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Sample records for absorption electron paramagnetic

  1. Electron paramagnetic resonance and optical absorption spectral studies on chalcocite

    NASA Astrophysics Data System (ADS)

    Reddy, S. Lakshmi; Fayazuddin, Md.; Frost, Ray L.; Endo, Tamio

    2007-11-01

    A chalcocite mineral sample of Shaha, Congo is used in the present study. An electron paramagnetic resonance (EPR) study on powdered sample confirms the presence of Mn(II), Fe(III) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. Mid-infrared results are due to water and sulphate fundamentals.

  2. Electron paramagnetic resonance and optical absorption spectral studies on chalcocite.

    PubMed

    Reddy, S Lakshmi; Fayazuddin, Md; Frost, Ray L; Endo, Tamio

    2007-11-01

    A chalcocite mineral sample of Shaha, Congo is used in the present study. An electron paramagnetic resonance (EPR) study on powdered sample confirms the presence of Mn(II), Fe(III) and Cu(II). Optical absorption spectrum indicates that Fe(III) impurity is present in octahedral structure whereas Cu(II) is present in rhombically distorted octahedral environment. Mid-infrared results are due to water and sulphate fundamentals. PMID:17324611

  3. Detection of electron paramagnetic resonance absorption using frequency modulation.

    PubMed

    Hirata, Hiroshi; Kuyama, Toshifumi; Ono, Mitsuhiro; Shimoyama, Yuhei

    2003-10-01

    A frequency modulation (FM) method was developed to measure electron paramagnetic resonance (EPR) absorption. The first-derivative spectrum of 1,1-diphenyl-2-picrylhydrazyl (DPPH) powder was measured with this FM method. Frequency modulation of up to 1.6 MHz (peak-to-peak) was achieved at a microwave carrier frequency of 1.1 GHz. This corresponds to a magnetic field modulation of 57microT (peak-to-peak) at 40.3 mT. By using a tunable microwave resonator and automatic control systems, we achieved a practical continuous-wave (CW) EPR spectrometer that incorporates the FM method. In the present experiments, the EPR signal intensity was proportional to the magnitude of frequency modulation. The background signal at the modulation frequency (1 kHz) for EPR detection was also proportional to the magnitude of frequency modulation. An automatic matching control (AMC) system reduced the amplitude of noise in microwave detection and improved the baseline stability. Distortion of the spectral lineshape was seen when the spectrometer settings were not appropriate, e.g., with a lack of the open-loop gain in automatic tuning control (ATC). FM is an alternative to field modulation when the side-effect of field modulation is detrimental for EPR detection. The present spectroscopic technique based on the FM scheme is useful for measuring the first derivative with respect to the microwave frequency in investigations of electron-spin-related phenomena. PMID:14511592

  4. Detection of electron paramagnetic resonance absorption using frequency modulation

    NASA Astrophysics Data System (ADS)

    Hirata, Hiroshi; Kuyama, Toshifumi; Ono, Mitsuhiro; Shimoyama, Yuhei

    2003-10-01

    A frequency modulation (FM) method was developed to measure electron paramagnetic resonance (EPR) absorption. The first-derivative spectrum of 1,1-diphenyl-2-picrylhydrazyl (DPPH) powder was measured with this FM method. Frequency modulation of up to 1.6 MHz (peak-to-peak) was achieved at a microwave carrier frequency of 1.1 GHz. This corresponds to a magnetic field modulation of 57 μT (peak-to-peak) at 40.3 mT. By using a tunable microwave resonator and automatic control systems, we achieved a practical continuous-wave (CW) EPR spectrometer that incorporates the FM method. In the present experiments, the EPR signal intensity was proportional to the magnitude of frequency modulation. The background signal at the modulation frequency (1 kHz) for EPR detection was also proportional to the magnitude of frequency modulation. An automatic matching control (AMC) system reduced the amplitude of noise in microwave detection and improved the baseline stability. Distortion of the spectral lineshape was seen when the spectrometer settings were not appropriate, e.g., with a lack of the open-loop gain in automatic tuning control (ATC). FM is an alternative to field modulation when the side-effect of field modulation is detrimental for EPR detection. The present spectroscopic technique based on the FM scheme is useful for measuring the first derivative with respect to the microwave frequency in investigations of electron-spin-related phenomena.

  5. Infrared absorption and electron paramagnetic resonance studies of vinyl radical in noble-gas matrices

    SciTech Connect

    Tanskanen, Hanna; Khriachtchev, Leonid; Raesaenen, Markku; Feldman, Vladimir I.; Sukhov, Fedor F.; Orlov, Aleksei Yu.; Tyurin, Daniil A.

    2005-08-08

    Vinyl radicals produced by annealing-induced reaction of mobilized hydrogen atoms with acetylene molecules in solid noble-gas matrices (Ar, Kr, and Xe) were characterized by Fourier transform infrared and electron paramagnetic resonance (EPR) spectroscopies. The hydrogen atoms were generated from acetylene by UV photolysis or fast electron irradiation. Two vibrational modes of the vinyl radical ({nu}{sub 7} and {nu}{sub 5}) were assigned in IR absorption studies. The assignment is based on data for various isotopic substitutions (D and {sup 13}C) and confirmed by comparison with the EPR measurements and density-functional theory calculations. The data on the {nu}{sub 7} mode is in agreement with previous experimental and theoretical results whereas the {nu}{sub 5} frequency agrees well with the computational data but conflicts with the gas-phase IR emission results.

  6. Optical Absorption and Electron Paramagnetic Resonance studies of two different solid solutions of Pyralspite Garnet

    NASA Astrophysics Data System (ADS)

    Watanabe, S.; Espinoza, S. R. Q.; Chubaci, J. F. D.; Cano, N. F.; Cornejo, D. R.

    2015-04-01

    Two different solid solutions of pyralspite garnet have been investigated as to their optical absorption and EPR properties. The absorption band around 9850 cm-1 is due to Fe2+. After heating above 950 °C we found this band diminishes considerably; which was interpreted as Fe2+ loosing an electron to become Fe3+. The EPR spectrum of sample consisted of a straight line with angular coefficient of about 176°. After 600°C/1hr annealing, the spectrum starts deviating from a straight line. A strong typical EPR signal is observed around g = 2.0 after annealing at 850°C. We assume that with high temperature annealing a large number of Fe2+ are converted to Fe3+ as the optical absorption has shown. These results were also confirmed by chemical reaction. The susceptibility vs. magnetic field measurement has shown that the samples annealed at temperatures below 850°C present normal paramagnetic behavior, however, annealed above 900 °C, they show hysteresis, namely ferromagnetic behavior.

  7. Electron paramagnetic resonance and optical absorption study of V4+ centres in YVO4 crystals

    NASA Astrophysics Data System (ADS)

    Garces, N. Y.; Stevens, K. T.; Foundos, G. K.; Halliburton, L. E.

    2004-10-01

    Electron paramagnetic resonance (EPR) has been used to characterize three distinct V4+ centres in undoped Czochralski-grown yttrium orthovanadate (YVO4) crystals. These EPR signals are observed at low temperatures, and their average c-axis splittings between adjacent 51V hyperfine lines are 40 G, 123 G, and 140 G. We refer to these centres as [V4+]A, [V4+]B, and [V4+]C, respectively. The [V4+]A and [V4+]B centres are present in as-grown crystals. Exposure at 77 K to ionizing radiation (x-rays or an ultraviolet laser beam) destroys these centres and creates the [V4+]C centres. The as-grown state of the crystal is restored upon returning to room temperature. Angular dependence data are used to determine the principal values and principal directions of the g tensor and the 51V hyperfine tensor for each of the centres. We suggest that the [V4+]A centre is a V4+ ion adjacent to an oxygen vacancy and that the [V4+]B centre is a V4+ ion substituting for a Y3+ ion (i.e. a vanadium antisite defect). The [V4+]C centre is assigned to a V4+ ion at a regular vanadium site with a nearby stabilizing defect, possibly a Zr4+ on a Y3+ site. In as-grown crystals, there is a correlation between the number of [V4+]A centres and the intensity (at 380 nm) of a broad near-edge optical absorption band. This band, now associated with oxygen vacancies, gives YVO4 a 'yellow' appearance.

  8. An electron paramagnetic resonance and magnetically modulated microwave absorption characterization of thermochromic (Ba, Li)-Mn oxides

    NASA Astrophysics Data System (ADS)

    Alvarez, G.; Zamorano, R.; Heiras, J.; Castellanos, M.; Valenzuela, R.

    2007-09-01

    We report electron paramagnetic resonance (EPR) and magnetically modulated microwave absorption spectroscopy (MAMMAS) studies on powdered BaMnO 3 and Li 2MnO 3 in the 77-300 K temperature range. The two oxides showed one single-line EPR spectra at room temperature. For Li 2MnO 3 the absorption line changed continuously with temperature, and showed a paramagnetic behavior in the whole temperature range. For BaMnO 3 an additional signal was observed below ˜196 K; at low temperature (<135 K) the original signal has practically vanished. The changes in the g-factor, peak-to-peak linewidth (Δ Hpp) and integrated intensity ( IEPR) as a function of temperature are studied. The MAMMAS spectrum for Li 2Mn0 3 showed a monotonic increase with temperature; this result confirmed its paramagnetic behavior. For BaMnO 3 the MAMMAS signal exhibited a maximum at Tmax=139 K, approximately the temperature for the color change.

  9. Electron paramagnetic resonance, optical absorption and Raman spectral studies on a pyrite/chalcopyrite mineral

    NASA Astrophysics Data System (ADS)

    Udayabhaskar Reddy, G.; Seshamaheswaramma, K.; Nakamura, Yoshinobu; Lakshmi Reddy, S.; Frost, Ray L.; Endo, Tamio

    2012-10-01

    Pyrite and chalcopyrite mineral samples from Mangampet barite mine, Kadapa, Andhra Pradesh, India are used in the present study. XRD data indicate that the pyrite mineral has a face centered cubic lattice structure with lattice constant 5.4179 Å. Also it possesses an average particle size of 91.9 nm. An EPR study on the powdered samples confirms the presence of iron in pyrite and iron and Mn(II) in chalcopyrite. The optical absorption spectrum of chalcopyrite indicates presence of copper which is in a distorted octahedral environment. NIR results confirm the presence of water fundamentals and Raman spectrum reveals the presence of water and sulfate ions.

  10. Electronic structure of four-coordinate C3v nickel(II) scorpionate complexes: investigation by high-frequency and -field electron paramagnetic resonance and electronic absorption spectroscopies.

    PubMed

    Desrochers, Patrick J; Telser, Joshua; Zvyagin, S A; Ozarowski, Andrew; Krzystek, J; Vicic, David A

    2006-10-30

    A series of complexes of formula TpNiX, where Tp*- = hydrotris(3,5-dimethylpyrazole)borate and X = Cl, Br, I, has been characterized by electronic absorption spectroscopy in the visible and near-infrared (NIR) region and by high-frequency and -field electron paramagnetic resonance (HFEPR) spectroscopy. The crystal structure of TpNiCl has been previously reported; that for TpNiBr is given here: space group = Pmc2(1), a = 13.209(2) A, b = 8.082(2) A, c = 17.639(4) A, alpha = beta = gamma = 90 degrees , Z = 4. TpNiX contains a four-coordinate nickel(II) ion (3d8) with approximate C3v point group symmetry about the metal and a resulting S = 1 high-spin ground state. As a consequence of sizable zero-field splitting (zfs), TpNiX complexes are "EPR silent" with use of conventional EPR; however, HFEPR allows observation of multiple transitions. Analysis of the resonance field versus the frequency dependence of these transitions allows extraction of the full set of spin Hamiltonian parameters. The axial zfs parameter for TpNiX displays pronounced halogen contributions down the series: D = +3.93(2), -11.43(3), -22.81(1) cm(-1), for X = Cl, Br, I, respectively. The magnitude and change in sign of D observed for TpNiX reflects the increasing bromine and iodine spin-orbit contributions facilitated by strong covalent interactions with nickel(II). These spin Hamiltonian parameters are combined with estimates of 3d energy levels based on the visible-NIR spectra to yield ligand-field parameters for these complexes following the angular overlap model (AOM). This description of electronic structure and bonding in a pseudotetrahedral nickel(II) complex can enhance the understanding of similar sites in metalloproteins, both native nickel enzymes and nickel-substituted zinc enzymes. PMID:17054352

  11. Electron Paramagnetic Resonance Retrospective Dosimetry

    SciTech Connect

    Romanyukha, Alex; Trompier, Francois

    2011-05-05

    Necessity for, principles of, and general concepts of the electron paramagnetic resonance (EPR) retrospective dosimetry are presented. Also presented and given in details are examples of EPR retrospective dosimetry applications in tooth enamel, bone, and fingernails with focus on general approaches for solving technical and methodological problems. Advantages, drawbacks, and possible future developments are discussed and an extensive bibliography on EPR retrospective dosimetry is provided.

  12. Paramagnetic Materials for PASER and Tunable RF Absorption

    SciTech Connect

    Antipov, Sergey P.; Schoessow, Paul; Kanareykin, Alexei; Jing Chunguang; Poluektov, Oleg; Gai Wei

    2010-11-04

    We report on the use of paramagnetic active media for the PASER (Particle Acceleration by Stimulated Emission of Radiation) and for dielectric loaded accelerating structures with tunable absorption for high order modes. The dielectric is doped with a material exhibiting high paramagnetic resonance, e.g. ruby with Cr{sup 3+}. The absorption frequency can be tuned by a magnetic field.

  13. Demonstrations on Paramagnetism with an Electronic Balance.

    ERIC Educational Resources Information Center

    Cortel, Adolf

    1998-01-01

    A paramagnetic substance is attracted by a magnetic field with a force proportional to its magnetic susceptibility which is related to the number of unpaired electrons in the atoms. Data are used to establish oxidation states and bonding properties. Describes a simple setup to demonstrate the paramagnetism of common inorganic compounds. (DKM)

  14. Electron Paramagnetic Resonance Study of Pr

    SciTech Connect

    Tezuka, Keitaro; Hinatsu, Yukio

    2001-01-01

    Electron paramagnetic resonance (EPR) spectra of tetravalent praseodymium ions doped in the cubic perovskite compound BaHfO{sub 3} have been measured at 4.2 K. A very large hyperfine interaction with the {sup 141}Pr nucleus was observed in the spectrum of Pr{sup 4+}/ BaHfO{sub 3}. The results were analyzed based on the weak field approximation, and the g value (|g|=0.619) and a hyperfine coupling constant (A=0.0589 cm{sup {minus}1}) were obtained. The measured g value is much smaller than |-10/7|, which indicates that the crystal field effect on the behavior of a 4f electron is large. These g and A values were compared with the EPR results for other f{sup 1} ions in an octahedral crystal field.

  15. Electron injection at the PTCDA/metal interface detected by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Gerardi, G. J.; Domenico, J.; Muraca, A.; Gerardi, H. K.

    2014-02-01

    Electron paramagnetic resonance absorption was observed for samples prepared by vacuum vapor deposition of thin films of 3,4,9,10-perylenetetracarboxylic-dianhydride (PTCDA) on metal films of magnesium (Mg), aluminum (Al) and silver (Ag) but not on gold (Au) or PTCDA on quartz. The resonance absorption is seen as a Lorentzian line with g-value of 2.0030 and a linewidth of 0.19 mT. The signal is attributed to PTCDA anions at the metal organic interface. The relative values of the metal work function and the PTCDA electron affinity appear to determine the occurrence of the EPR absorption.

  16. Electron paramagnetic resonance at dislocations in germanium

    SciTech Connect

    Pakulis, E.J.

    1982-06-01

    The first observation of the paramagnetic resonance of electrons at dislocations in germanium single crystals is reported. Under subband gap optical excitation, two sets of lines are detected: four lines about the <111> axes with g/sub perpendicular to/ = 0.34 and g/sub parallel/ = 1.94, and 24 lines with g/sub perpendicular to/ = 0.73 and g/sub parallel/ = 1.89 about <111> axes with the six-fold 1.2/sup 0/ distortion. This represents the first measurement of the disortion angle of a dislocation dangling bond. The possibility that the distortion results from a Peierls transition along the dislocation line is discussed.

  17. Electron paramagnetic resonance in Cu-doped ZnO

    NASA Astrophysics Data System (ADS)

    Buchheit, R.; Acosta-Humánez, F.; Almanza, O.

    2016-04-01

    In this work, ZnO and Cu-doped ZnO nanoparticles (Zn1‑xCuxO, x = 3%), with a calcination temperature of 500∘C were synthesized using the sol-gel method. The particles were analyzed using atomic absorption spectroscopy (AAS), X-ray diffraction (XRD) and electron paramagnetic resonance (EPR) at X-band, measurement in a temperature range from 90 K to room temperature. AAS confirmed a good correspondence between the experimental doping concentration and the theoretical value. XRD reveals the presence of ZnO phase in hexagonal wurtzite structure and a nanoparticle size for the samples synthesized. EPR spectroscopy shows the presence of point defects in both samples with g-values of g = 1.959 for shallow donors and g = 2.004 for ionized vacancies. It is important when these materials are required have been used as catalysts, as suggested that it is not necessary prepare them at higher temperature. A simulation of the Cu EPR signal using an anisotropic spin Hamiltonian was performed and showed good coincidence with the experimental spectra. It was shown that Cu2+ ions enter interstitial octahedral sites of orthorhombic symmetry in the wurtzite crystal structure. Temperature dependence of the EPR linewidth and signal intensity shows a paramagnetic behavior of the sample in the measurement range. A Néel temperature TN = 78 ± 19 K was determined.

  18. Combined Electron Paramagnetic Resonance and Atomic Absorption Spectroscopy/Inductively Coupled Plasma Analysis As Diagnostics for Soluble Manganese Species from Mn-Based Positive Electrode Materials in Li-ion Cells.

    PubMed

    Shilina, Yuliya; Ziv, Baruch; Meir, Aviv; Banerjee, Anjan; Ruthstein, Sharon; Luski, Shalom; Aurbach, Doron; Halalay, Ion C

    2016-04-19

    Manganese dissolution from positive electrodes significantly reduces the durability of lithium-ion batteries. Knowledge of dissolution rates and oxidation states of manganese ions is essential for designing effective mitigation measures for this problem. We show that electron paramagnetic resonance (EPR) combined with atomic absorption spectroscopy (AAS) or inductively coupled plasma (ICP) can determine both manganese dissolution rates and relative Mn(3+) amounts, by comparing the correlation between EPR and AAS/ICP data for Mn(2+) standards with that for samples containing manganese cations dissolved from active materials (LiMn2O4 (LMO) and LiNi0.5Mn1.5O4 (LNMO)) into the same electrolyte solution. We show that Mn(3+), and not Mn(2+), is the dominant species dissolved from LMO, while Mn(2+) is predominant for LNMO. Although the dissolution rate of LMO varies significantly for the two investigated materials, due to particle morphology and the presence of Cr in one of them, the Mn speciation appears independent of such details. Thus, the relative abundance of dissolved manganese ions in various oxidation states depends mainly on the overall chemical identity of the active material (LMO vs LNMO). We demonstrate the relevance of our methodology for practical batteries with data for graphite-LMO cells after high-temperature cycling or stand at 4.2 V. PMID:27018717

  19. Electron paramagnetic resonance of a donor in aluminum nitride crystals

    NASA Astrophysics Data System (ADS)

    Evans, S. M.; Giles, N. C.; Halliburton, L. E.; Slack, G. A.; Schujman, S. B.; Schowalter, L. J.

    2006-02-01

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectra are obtained from a donor in aluminum nitride (AlN) crystals. Although observed in as-grown crystals, exposure to x rays significantly increases the concentration of this center. ENDOR identifies a strong hyperfine interaction with one aluminum neighbor along the c axis and weaker equivalent hyperfine interactions with three additional aluminum neighbors in the basal plane. These aluminum interactions indicate that the responsible center is a deep donor at a nitrogen site. The observed paramagnetic defect is either a neutral oxygen substituting for nitrogen (ON0) or a neutral nitrogen vacancy (VN0).

  20. Introduction to Spin Label Electron Paramagnetic Resonance Spectroscopy of Proteins

    ERIC Educational Resources Information Center

    Melanson, Michelle; Sood, Abha; Torok, Fanni; Torok, Marianna

    2013-01-01

    An undergraduate laboratory exercise is described to demonstrate the biochemical applications of electron paramagnetic resonance (EPR) spectroscopy. The beta93 cysteine residue of hemoglobin is labeled by the covalent binding of 3-maleimido-proxyl (5-MSL) and 2,2,5,5-tetramethyl-1-oxyl-3-methyl methanethiosulfonate (MTSL), respectively. The excess…

  1. Intracellular hypoxia of tumor tissue estimated by noninvasive electron paramagnetic resonance oximetry technique using paramagnetic probes.

    PubMed

    Matsumoto, Atsuko; Matsumoto, Ken-ichiro; Matsumoto, Shingo; Hyodo, Fuminori; Sowers, Anastasia L; Koscielniak, Janusz W; Devasahayam, Nallathamby; Subramanian, Sankaran; Mitchell, James B; Krishna, Murali C

    2011-01-01

    Electron paramagnetic resonance (EPR) oximetry at 700 MHz operating frequency employing a surface coil resonator is used to assess tissue partial pressure of oxygen (pO(2)) using paramagnetic media whose linewidth and decay constant are related to oxygen concentration. Differences in extracellular and intracellular pO(2) in squamous cell carcinoma (SCC) tumor tissue were tested using several types of water-soluble paramagnetic media, which localize extracellularly or permeate through the cell membrane. The nitroxide carboxy-PROXYL (CxP) can only be distributed in blood plasma and extracellular fluids whereas the nitroxides carbamoyl-PROXYL (CmP) and TEMPOL (TPL) can permeate cell membranes and localize intracellularly. EPR signal decay constant and the linewidth of the intravenously administered nitroxides in SCC tumor tissues implanted in mouse thigh and the contralateral normal muscle of healthy mice breathing gases with different pO(2) were compared. The pO(2) in the blood can depend on the oxygen content in the breathing gas while tissue pO(2) was not directly influenced by pO(2) in the breathing gas. The decay constants of CmP and TPL in tumor tissue were significantly larger than in the normal muscles, and lower linewidths of CmP and TPL in tumor tissue was observed. The SCC tumor showed intracellular hypoxia even though the extracellular pO(2) is similar to normal tissue in the peripheral region. PMID:21212532

  2. Electron paramagnetic resonance of material properties and processes

    SciTech Connect

    Brower, K. L.

    1980-01-01

    This paper demonstrates, primarily for the non-specialist and within the context of new and recent achievements, the diagnostic value of electron paramagnetic resonance (EPR) in the study of material properties and processes. I have selected three EPR studies which demonstrate the elegance and uniqueness of EPR in atomic defect studies and exemplify unusual achievements through the use of new techniques for material measurement and preparation. A brief introduction into the origin, interaction, and detection of unpaired electrons is included.

  3. In vivo imaging of a stable paramagnetic probe by pulsed-radiofrequency electron paramagnetic resonance spectroscopy.

    PubMed

    Murugesan, R; Cook, J A; Devasahayam, N; Afeworki, M; Subramanian, S; Tschudin, R; Larsen, J A; Mitchell, J B; Russo, A; Krishna, M C

    1997-09-01

    Imaging of free radicals by electron paramagnetic resonance (EPR) spectroscopy using time domain acquisition as in nuclear magnetic resonance (NMR) has not been attempted because of the short spin-spin relaxation times, typically under 1 microsecond, of most biologically relevant paramagnetic species. Recent advances in radiofrequency (RF) electronics have enabled the generation of pulses of the order of 10-50 ns. Such short pulses provide adequate spectral coverage for EPR studies at 300 MHz resonant frequency. Acquisition of free induction decays (FID) of paramagnetic species possessing inhomogenously broadened narrow lines after pulsed excitation is feasible with an appropriate digitizer/averager. This report describes the use of time-domain RF EPR spectrometry and imaging for in vivo applications. FID responses were collected from a water-soluble, narrow line width spin probe within phantom samples in solution and also when infused intravenously in an anesthetized mouse. Using static magnetic field gradients and back-projection methods of image reconstruction, two-dimensional images of the spin-probe distribution were obtained in phantom samples as well as in a mouse. The resolution in the images was better than 0.7 mm and devoid of motional artifacts in the in vivo study. Results from this study suggest a potential use for pulsed RF EPR imaging (EPRI) for three-dimensional spatial and spectral-spatial imaging applications. In particular, pulsed EPRI may find use in vivo studies to minimize motional artifacts from cardiac and lung motion that cause significant problems in frequency-domain spectral acquisition, such as in continuous wave (cw) EPR techniques. PMID:9339442

  4. Electron-paramagnetic resonance detection with software time locking

    NASA Astrophysics Data System (ADS)

    Aloisi, Giovanni; Mannini, Matteo; Caneschi, Andrea; Dolci, David; Carlà, Marcello

    2014-02-01

    A setup for electron paramagnetic resonance with narrow band digital detection is described. A low frequency reference tone is added to the radio frequency signal. This reference signal, after digital detection, is used to lock the resonance signal, even in the absence of hardware time locking among the radio frequency generator, the conversion local oscillators, and the sampling stage. Results obtained with 2,2-Diphenyl-1-Pycryl-Hydrazil are presented and discussed.

  5. Investigation of electron paramagnetic resonance in carbon tubes

    NASA Astrophysics Data System (ADS)

    Byszewski, P.; Nabialek, A.

    1996-04-01

    Electron paramagnetic resonance (EPR) on carbon nanotubes was measured in a wide range of temperatures, the resonance disappeared after oxidizing the tubes. The results are discussed in terms of graphite properties and a model introducing a deformation potential to describe tubular structure. It leads to persistent ring currents in the magnetic field due to the carriers circular motion around a tube. A spin angular-momentum interaction is discussed in an attempt to explain the lack of EPR in purified carbon nanotubes.

  6. The role of spinning electrons in paramagnetic phenomena

    NASA Technical Reports Server (NTRS)

    Bose, D. M.

    1986-01-01

    An attempt is made to explain paramagnetic phenomena without assuming the orientation of a molecule or ion in a magnetic field. Only the spin angular momentum is assumed to be responsible. A derivative of the Gurie-Langevin law and the magnetic moments of ions are given as a function of the number of electrons in an inner, incomplete shell. An explanation of Gerlach's experiments with iron and nickel vapors is attempted. An explanation of magnetomechanical experiments with ferromagne elements is given.

  7. Detection of Nitric Oxide by Electron Paramagnetic Resonance Spectroscopy

    PubMed Central

    Hogg, Neil

    2010-01-01

    Electron paramagnetic resonance (EPR) spectroscopy has been used in a number of ways to study nitric oxide chemistry and biology. As an intrinsically stable and relatively unreactive diatomic free radical, the challenges for detecting this species by EPR are somewhat different than those for transient radical species. This review gives a basic introduction to EPR spectroscopy and discusses its uses to assess and quantify nitric oxide formation in biological systems. PMID:20304044

  8. Towards Human Oxygen Images with Electron Paramagnetic Resonance Imaging

    PubMed Central

    Epel, Boris; Redler, Gage; Tormyshev, Victor; Halpern, Howard J.

    2016-01-01

    Electron paramagnetic resonance imaging (EPRI) has been used to noninvasively provide 3D images of absolute oxygen concentration (pO2) in small animals. These oxygen images are well resolved both spatially (∼1mm) and in pO2 (1-3 torr). EPRI preclinical images of pO2 have demonstrated extremely promising results for various applications investigating oxygen related physiologic and biologic processes as well as the dependence of various disease states on pO2, such as the role of hypoxia in cancer. Recent developments have been made that help to progress EPRI towards the eventual goal of human application. For example, a bimodal crossed-wire surface coil has been developed. Very preliminary tests demonstrated a 20 dB isolation between transmit and receive for this coil, with an anticipated additional 20dB achievable. This could potentially be used to image local pO2 in human subjects with superficial tumors with EPRI. Local excitation and detection will reduce the specific absorption rate limitations on images and eliminate any possible power deposition concerns. Additionally, a large 9 mT EPRI magnet has been constructed which can fit and provide static main and gradient fields for imaging local anatomy in an entire human. One potential obstacle that must be overcome in order to use EPRI to image humans is the approved use of the requisite EPRI spin probe imaging agent (trityl). While nontoxic, EPRI trityl spin probes have been injected intravenously when imaging small animals, which results in relatively high total body injection doses that would not be suitable for human imaging applications. Work has been done demonstrating the alternative use of intratumoral (IT) injections, which can reduce the amount of trityl required for imaging by a factor of 2000- relative to a whole body intravenous injection. The development of a large magnet that can accommodate human subjects, the design of a surface coil for imaging of superficial pO2, and the reduction of required

  9. Electron Paramagnetic Resonance -- Nuclear Magnetic Resonance Three Axis Vector Magnetometer

    NASA Astrophysics Data System (ADS)

    Bulatowicz, Michael; Clark, Philip; Griffith, Robert; Larsen, Michael; Mirijanian, James

    2012-06-01

    The Northrop Grumman Corporation is leveraging the technology developed for the Nuclear Magnetic Resonance Gyroscope (NMRG) to build a combined Electron Paramagnetic Resonance -- Nuclear Magnetic Resonance (EPR-NMR) magnetometer. The EPR-NMR approach provides a high bandwidth and high sensitivity simultaneous measurement of all three vector components of the magnetic field averaged over the small volume of the sensor's one vapor cell. This poster will describe the history, operational principles, and design basics of the EPR-NMR magnetometer including an overview of the NSD designs developed and demonstrated to date. General performance results will also be presented.

  10. General magnetic transition dipole moments for electron paramagnetic resonance.

    PubMed

    Nehrkorn, Joscha; Schnegg, Alexander; Holldack, Karsten; Stoll, Stefan

    2015-01-01

    We present general expressions for the magnetic transition rates in electron paramagnetic resonance (EPR) experiments of anisotropic spin systems in the solid state. The expressions apply to general spin centers and arbitrary excitation geometry (Voigt, Faraday, and intermediate). They work for linear and circular polarized as well as unpolarized excitation, and for crystals and powders. The expressions are based on the concept of the (complex) magnetic transition dipole moment vector. Using the new theory, we determine the parities of ground and excited spin states of high-spin (S=5/2) Fe(III) in hemin from the polarization dependence of experimental EPR line intensities. PMID:25615456

  11. Electron paramagnetic resonance in Zn1-xCoxO

    NASA Astrophysics Data System (ADS)

    Acosta-Humánez, F.; Cogollo Pitalúa, R.; Almanza, O.

    2013-03-01

    In this paper is reported the Electron Paramagnetic Resonance (EPR) studies in Zn1-xCoxO powder, with 0.01≤x≤0.05, at many temperatures (105-250 K). These samples were synthesized by the sol-gel method (citrate route). Results suggest that the ferromagnetism behavior of the materials is governed by ferromagnetic coupling among cobalt ions. For cobalt concentration higher than 3% were obtained mean size particle higher than 25 nm, measured by X-ray diffraction, and for this were also observed shallow free radical.

  12. Electron paramagnetic resonance of nitroxide-doped magnetic fluids

    NASA Astrophysics Data System (ADS)

    Morais, P. C.; Alonso, A.; Silva, O.; Buske, N.

    2002-11-01

    Electron paramagnetic resonance was used to investigate surface-coated magnetite-based magnetic fluids doped with TEMPOL. Two magnetic fluid samples, having magnetite nanoparticles with average diameter of 94 Å and coated with different coating layers (lauric acid plus ethoxylated polyalcohol in one case and oleoylsarcosine in the other case), were doped with TEMPOL (6 mM and pH 7.4) and investigated as a function of the nanoparticle concentration. The resonance field and the resonance linewidth both scale linearly with the nanoparticle concentration.

  13. Electron paramagnetic resonance study of paramagnetic centers in carbon-fumed silica adsorbent

    SciTech Connect

    Savchenko, D. V.; Shanina, B. D.; Kalabukhova, E. N.; Sitnikov, A. A.; Lysenko, V. S.; Tertykh, V. A.

    2014-04-07

    Fumed silica A-300 was carbonized by means of pyrolysis of CH{sub 2}Cl{sub 2}. The obtained initial SiO{sub 2}:C nanopowders of black color, with an average diameter of 14–16 nm and carbon (C) concentration 7 wt. %, subjected to the oxidation and passivation treatment were studied by electron paramagnetic resonance (EPR) in the temperature range 4–400 K. Two EPR signals of Lorentzian lineshape with nearly equal g-factors and different linewidth were observed in the initial, oxidized, and passivated SiO{sub 2}:C nanopowders. The two-component EPR spectrum was explained by the presence of C in two electronic states. The intensive narrow EPR signal, which has a temperature-dependent intensity, linewidth, and resonance field position, was attributed to the carbon-related defect with non-localized electron hopping between neighboring C-dangling bonds. The striking effect is that the temperature dependence of the EPR linewidth demonstrates the motional narrowing of the EPR signal at very low temperatures from 4 K to 20 K, which is not typically for nonmetallic materials and was explained by the quantum character of C layer conductivity in the SiO{sub 2}:C. The observed peaks in the temperature dependence of the conduction electron EPR signal integral intensity in the high-temperature range 200–440 K was explained by the presence of the C nanodots at the surface of SiO{sub 2} nanoparticles and the ejection of electrons from the confinement energy levels of C quantum dot when the temperature becomes comparable to the confinement energy.

  14. Electron paramagnetic resonance study of paramagnetic centers in carbon-fumed silica adsorbent

    NASA Astrophysics Data System (ADS)

    Savchenko, D. V.; Shanina, B. D.; Kalabukhova, E. N.; Sitnikov, A. A.; Lysenko, V. S.; Tertykh, V. A.

    2014-04-01

    Fumed silica A-300 was carbonized by means of pyrolysis of CH2Cl2. The obtained initial SiO2:C nanopowders of black color, with an average diameter of 14-16 nm and carbon (C) concentration 7 wt. %, subjected to the oxidation and passivation treatment were studied by electron paramagnetic resonance (EPR) in the temperature range 4-400 K. Two EPR signals of Lorentzian lineshape with nearly equal g-factors and different linewidth were observed in the initial, oxidized, and passivated SiO2:C nanopowders. The two-component EPR spectrum was explained by the presence of C in two electronic states. The intensive narrow EPR signal, which has a temperature-dependent intensity, linewidth, and resonance field position, was attributed to the carbon-related defect with non-localized electron hopping between neighboring C-dangling bonds. The striking effect is that the temperature dependence of the EPR linewidth demonstrates the motional narrowing of the EPR signal at very low temperatures from 4 K to 20 K, which is not typically for nonmetallic materials and was explained by the quantum character of C layer conductivity in the SiO2:C. The observed peaks in the temperature dependence of the conduction electron EPR signal integral intensity in the high-temperature range 200-440 K was explained by the presence of the C nanodots at the surface of SiO2 nanoparticles and the ejection of electrons from the confinement energy levels of C quantum dot when the temperature becomes comparable to the confinement energy.

  15. Electron paramagnetic resonance in positively charged Au25 molecular nanoclusters.

    PubMed

    Akbari-Sharbaf, Arash; Hesari, Mahdi; Workentin, Mark S; Fanchini, Giovanni

    2013-01-14

    In this study, we investigated the unpaired electrons and singly occupied molecular orbitals (SOMO) of positively charged Au(25) molecular clusters using solid-state electron paramagnetic resonance (EPR). The EPR powder spectra of the positively charged (Au(25) (+)) and neutral (Au(25) (0)) species of Au(25) are discussed and compared. Our study demonstrates that Au(25) (+) is paramagnetic with a SOMO that is mostly localized about the central gold atom in the core of the molecule and possesses a strong p-type atomic character. The unpaired electron spin is demonstrated to strongly interact with the nuclear spins from other (197)Au nuclei in the core of Au(25) (+) molecules and the hyperfine tensor describing such interaction was extracted from the comparison of the EPR spectra with quantum mechanical simulations assuming an anisotropic structure of the core. Our simulations suggest that the core of Au(25) (+) molecular clusters is more distorted than in the corresponding neutral counterpart. They also confirm previous hypotheses suggesting that the icosahedral core of Au(25) (+) experiences contraction with decreasing temperature. PMID:23320681

  16. Electron paramagnetic resonance of a donor in aluminum nitride crystals.

    NASA Astrophysics Data System (ADS)

    Evans, Sean; Giles, Nancy; Halliburton, Larry; Slack, Glen; Schujman, Sandra; Schowalter, Leo

    2006-03-01

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) have been used to characterize a dominant donor in single crystals of aluminum nitride (AlN). A broad EPR signal, with g (parallel) = 2.002 and g (perpendicular) = 2.006, is observed in the as-grown crystals. Exposure to x-rays (i.e., ionizing radiation) increases the concentration of this center by a factor of five to ten (depending on sample), thus indicating that most of these centers are initially present in the crystals in a nonparamagnetic charge state. ENDOR identifies a strong hyperfine interaction with one aluminum neighbor along the c axis (described by A (parallel) = 111.30 MHz, A (perpendicular) = 54.19 MHz, and P = 0.289 MHz) and weaker equivalent hyperfine interactions with three additional aluminum neighbors in the basal plane. These aluminum interactions indicate that the responsible center is a deep donor at a nitrogen site. The observed paramagnetic defect is either a neutral oxygen substituting for nitrogen or a neutral nitrogen vacancy. This work was supported at West Virginia University by the National Science Foundation (Grant DMR-0508140). One of the authors (SME) received support from the WV EPSCoR STEM fellowship program.

  17. Electron paramagnetic resonance of individual atoms on a surface.

    PubMed

    Baumann, Susanne; Paul, William; Choi, Taeyoung; Lutz, Christopher P; Ardavan, Arzhang; Heinrich, Andreas J

    2015-10-23

    We combined the high-energy resolution of conventional spin resonance (here ~10 nano-electron volts) with scanning tunneling microscopy to measure electron paramagnetic resonance of individual iron (Fe) atoms placed on a magnesium oxide film. We drove the spin resonance with an oscillating electric field (20 to 30 gigahertz) between tip and sample. The readout of the Fe atom's quantum state was performed by spin-polarized detection of the atomic-scale tunneling magnetoresistance. We determine an energy relaxation time of T1 ≈ 100 microseconds and a phase-coherence time of T2 ≈ 210 nanoseconds. The spin resonance signals of different Fe atoms differ by much more than their resonance linewidth; in a traditional ensemble measurement, this difference would appear as inhomogeneous broadening. PMID:26494753

  18. Magnetic nanoparticle imaging using multiple electron paramagnetic resonance activation sequences

    SciTech Connect

    Coene, A. Dupré, L.; Crevecoeur, G.

    2015-05-07

    Magnetic nanoparticles play an important role in several biomedical applications such as hyperthermia, drug targeting, and disease detection. To realize an effective working of these applications, the spatial distribution of the particles needs to be accurately known, in a non-invasive way. Electron Paramagnetic Resonance (EPR) is a promising and sensitive measurement technique for recovering these distributions. In the conventional approach, EPR is applied with a homogeneous magnetic field. In this paper, we employ different heterogeneous magnetic fields that allow to stabilize the solution of the associated inverse problem and to obtain localized spatial information. A comparison is made between the two approaches and our novel adaptation shows an average increase in reconstruction quality by 5% and is 12 times more robust towards noise. Furthermore, our approach allows to speed up the EPR measurements while still obtaining reconstructions with an improved accuracy and noise robustness compared to homogeneous EPR.

  19. Electron paramagnetic resonance investigation of metalloendofullerene derived carbon nanotube peapods

    NASA Astrophysics Data System (ADS)

    Jakes, P.; Gembus, A.; Dinse, K.-P.; Hata, K.

    2008-02-01

    Single Wall Carbon Nanotubes (SWCNT) prepared by the "super growth" method and arc-grown material were used as templates for peapod preparation with La@C82. A qualitative change of the electron paramagnetic resonance (EPR) properties of La@C82 is observed after incorporation into SWNT. The loss of lanthanum hyperfine interaction in combination with the observed increase of EPR susceptibility by two orders of magnitude after peapod preparation when comparing with signals from "empty" tubes is indicative for the generation of itinerant spins by charge and spin transfer from La@C82 to the tubes. This interpretation is supported by the observation of fast spin dephasing, detected with pulsed EPR techniques.

  20. Electron paramagnetic resonance investigation of metalloendofullerene derived carbon nanotube peapods.

    PubMed

    Jakes, P; Gembus, A; Dinse, K-P; Hata, K

    2008-02-01

    Single Wall Carbon Nanotubes (SWCNT) prepared by the "super growth" method and arc-grown material were used as templates for peapod preparation with La@C(82). A qualitative change of the electron paramagnetic resonance (EPR) properties of La@C(82) is observed after incorporation into SWNT. The loss of lanthanum hyperfine interaction in combination with the observed increase of EPR susceptibility by two orders of magnitude after peapod preparation when comparing with signals from "empty" tubes is indicative for the generation of itinerant spins by charge and spin transfer from La@C(82) to the tubes. This interpretation is supported by the observation of fast spin dephasing, detected with pulsed EPR techniques. PMID:18266423

  1. High field electron paramagnetic resonance spectroscopy under ultrahigh vacuum conditions—A multipurpose machine to study paramagnetic species on well defined single crystal surfaces

    NASA Astrophysics Data System (ADS)

    Rocker, J.; Cornu, D.; Kieseritzky, E.; Seiler, A.; Bondarchuk, O.; Hänsel-Ziegler, W.; Risse, T.; Freund, H.-J.

    2014-08-01

    A new ultrahigh vacuum (UHV) electron paramagnetic resonance (EPR) spectrometer operating at 94 GHz to investigate paramagnetic centers on single crystal surfaces is described. It is particularly designed to study paramagnetic centers on well-defined model catalysts using epitaxial thin oxide films grown on metal single crystals. The EPR setup is based on a commercial Bruker E600 spectrometer, which is adapted to ultrahigh vacuum conditions using a home made Fabry Perot resonator. The key idea of the resonator is to use the planar metal single crystal required to grow the single crystalline oxide films as one of the mirrors of the resonator. EPR spectroscopy is solely sensitive to paramagnetic species, which are typically minority species in such a system. Hence, additional experimental characterization tools are required to allow for a comprehensive investigation of the surface. The apparatus includes a preparation chamber hosting equipment, which is required to prepare supported model catalysts. In addition, surface characterization tools such as low energy electron diffraction (LEED)/Auger spectroscopy, temperature programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS) are available to characterize the surfaces. A second chamber used to perform EPR spectroscopy at 94 GHz has a room temperature scanning tunneling microscope attached to it, which allows for real space structural characterization. The heart of the UHV adaptation of the EPR experiment is the sealing of the Fabry-Perot resonator against atmosphere. To this end it is possible to use a thin sapphire window glued to the backside of the coupling orifice of the Fabry Perot resonator. With the help of a variety of stabilization measures reducing vibrations as well as thermal drift it is possible to accumulate data for a time span, which is for low temperature measurements only limited by the amount of liquid helium. Test measurements show that the system can detect paramagnetic

  2. High field electron paramagnetic resonance spectroscopy under ultrahigh vacuum conditions—A multipurpose machine to study paramagnetic species on well defined single crystal surfaces

    SciTech Connect

    Rocker, J.; Cornu, D.; Kieseritzky, E.; Hänsel-Ziegler, W.; Freund, H.-J.; Seiler, A.; Bondarchuk, O.

    2014-08-01

    A new ultrahigh vacuum (UHV) electron paramagnetic resonance (EPR) spectrometer operating at 94 GHz to investigate paramagnetic centers on single crystal surfaces is described. It is particularly designed to study paramagnetic centers on well-defined model catalysts using epitaxial thin oxide films grown on metal single crystals. The EPR setup is based on a commercial Bruker E600 spectrometer, which is adapted to ultrahigh vacuum conditions using a home made Fabry Perot resonator. The key idea of the resonator is to use the planar metal single crystal required to grow the single crystalline oxide films as one of the mirrors of the resonator. EPR spectroscopy is solely sensitive to paramagnetic species, which are typically minority species in such a system. Hence, additional experimental characterization tools are required to allow for a comprehensive investigation of the surface. The apparatus includes a preparation chamber hosting equipment, which is required to prepare supported model catalysts. In addition, surface characterization tools such as low energy electron diffraction (LEED)/Auger spectroscopy, temperature programmed desorption (TPD), and infrared reflection absorption spectroscopy (IRAS) are available to characterize the surfaces. A second chamber used to perform EPR spectroscopy at 94 GHz has a room temperature scanning tunneling microscope attached to it, which allows for real space structural characterization. The heart of the UHV adaptation of the EPR experiment is the sealing of the Fabry-Perot resonator against atmosphere. To this end it is possible to use a thin sapphire window glued to the backside of the coupling orifice of the Fabry Perot resonator. With the help of a variety of stabilization measures reducing vibrations as well as thermal drift it is possible to accumulate data for a time span, which is for low temperature measurements only limited by the amount of liquid helium. Test measurements show that the system can detect paramagnetic

  3. Electron Paramagnetic Resonance studies of x-ray irradiated Nafion

    NASA Astrophysics Data System (ADS)

    Fragoso, Juan; Usher, Timothy

    2007-03-01

    Fuel cells promise a bright future as power sources for a variety of electronic equipment as well as more power demanding elements. Nafion (DuPont's trademark of a sulfonated tetrafluorethylene polymer modified from Teflon) is the heart of Proton Exchange Membrane Fuel Cells (PEMFCs) as well as Direct Methanol Fuel Cells (DMFCs). Fuel cells are used to power electronic equipment on spacecraft, satellites and unpiloted high altitude aircraft, where ionizing radiation can be a concern. Electron Paramagnetic Resonance (EPR) is a spectroscopic technique that is very sensitive to free radicals such as those produced by ionizing radiation therefore EPR can give us a window into the degradation of the Nafion membranes due to the ionizing radiation. Nafion samples were irradiated using a x-ray diffractometer with a copper target operating at 40kV and 55mA for at least 3hrs. X-Band EPR spectroscopy of the irradiated nafion reveals a peak at 3400G with a width of 10G, which decays over time, completely diminishing in a couple of weeks. Preliminary results from the polarization studies on the effects of ionizing radiation will also be presented.

  4. 76 FR 67200 - Prospective Grant of Exclusive License: Electron Paramagnetic Resonance Devices and Systems for...

    Federal Register 2010, 2011, 2012, 2013, 2014

    2011-10-31

    ... From the Federal Register Online via the Government Publishing Office DEPARTMENT OF HEALTH AND HUMAN SERVICES National Institutes of Health Prospective Grant of Exclusive License: Electron... of use limited to electron paramagnetic resonance devices and systems for oximetry. DATES:...

  5. Maximally spaced projection sequencing in electron paramagnetic resonance imaging

    PubMed Central

    Redler, Gage; Epel, Boris; Halpern, Howard J.

    2015-01-01

    Electron paramagnetic resonance imaging (EPRI) provides 3D images of absolute oxygen concentration (pO2) in vivo with excellent spatial and pO2 resolution. When investigating such physiologic parameters in living animals, the situation is inherently dynamic. Improvements in temporal resolution and experimental versatility are necessary to properly study such a system. Uniformly distributed projections result in efficient use of data for image reconstruction. This has dictated current methods such as equal-solid-angle (ESA) spacing of projections. However, acquisition sequencing must still be optimized to achieve uniformity throughout imaging. An object-independent method for uniform acquisition of projections, using the ESA uniform distribution for the final set of projections, is presented. Each successive projection maximizes the distance in the gradient space between itself and prior projections. This maximally spaced projection sequencing (MSPS) method improves image quality for intermediate images reconstructed from incomplete projection sets, enabling useful real-time reconstruction. This method also provides improved experimental versatility, reduced artifacts, and the ability to adjust temporal resolution post factum to best fit the data and its application. The MSPS method in EPRI provides the improvements necessary to more appropriately study a dynamic system. PMID:26185490

  6. Electron paramagnetic resonance of Er3+ ions in aluminum nitride

    NASA Astrophysics Data System (ADS)

    Yang, Shan; Evans, S. M.; Halliburton, L. E.; Slack, G. A.; Schujman, S. B.; Morgan, K. E.; Bondokov, R. T.; Mueller, S. G.

    2009-01-01

    An electron paramagnetic resonance (EPR) spectrum from Er3+ ions has been observed in a bulk single crystal of aluminum nitride (AlN). These Er3+ ions were introduced into the crystal during growth and had a concentration of approximately 2×1016 cm-3. The Er3+ EPR signal, monitored at 4.5 K, exhibits axial symmetry (the unique axis is parallel to the c axis in this wurtzite lattice) and shows well-resolved hyperfine splittings due to E167r nuclei. An absence of site splittings in the EPR angular dependence indicates that these erbium ions, replacing aluminum ions in the AlN crystal, have no nearby defects. Principal values for the g and hyperfine matrices are g∥=4.337, g⊥=7.647, |A∥|=454 MHz, and |A⊥|=796 MHz. Forbidden transitions, appearing in the low-field portion of the hyperfine spectrum when the magnetic field is rotated a few degrees away from the c axis, give |P|=7.8 MHz for the nuclear electric quadrupole parameter.

  7. Single Acquisition Quantitative Single Point Electron Paramagnetic Resonance Imaging

    PubMed Central

    Jang, Hyungseok; Subramanian, Sankaran; Devasahayam, Nallathamby; Saito, Keita; Matsumoto, Shingo; Krishna, Murali C; McMillan, Alan B

    2013-01-01

    Purpose Electron paramagnetic resonance imaging (EPRI) has emerged as a promising non-invasive technology to dynamically image tissue oxygenation. Due to its extremely short spin-spin relaxation times, EPRI benefits from a single-point imaging (SPI) scheme where the entire FID signal is captured using pure phase encoding. However, direct T2*/pO2 quantification is inhibited due to constant magnitude gradients which result in time-decreasing FOV. Therefore, conventional acquisition techniques require repeated imaging experiments with differing gradient amplitudes (typically 3), which results in long acquisition time. Methods In this study, gridding was evaluated as a method to reconstruct images with equal FOV to enable direct T2*/pO2 quantification within a single imaging experiment. Additionally, an enhanced reconstruction technique that shares high spatial k-space regions throughout different phase encoding time delays was investigated (k-space extrapolation). Results The combined application of gridding and k-space extrapolation enables pixelwise quantification of T2* from a single acquisition with improved image quality across a wide range of phase encoding delay times. The calculated T2*/pO2 does not vary across this time range. Conclusion By utilizing gridding and k-space extrapolation, accurate T2*/pO2 quantification can be achieved within a single dataset to allow enhanced temporal resolution (by a factor of 3). PMID:23913515

  8. Uniform Spinning Sampling Gradient Electron Paramagnetic Resonance Imaging

    PubMed Central

    Johnson, David H.; Ahmad, Rizwan; Liu, Yangping; Chen, Zhiyu; Samouilov, Alexandre; Zweier, Jay L.

    2014-01-01

    Purpose To improve the quality and speed of electron paramagnetic resonance imaging (EPRI) acquisition by combining a uniform sampling distribution with spinning gradient acquisition. Theory and Methods A uniform sampling distribution was derived for spinning gradient EPRI acquisition (Uniform Spinning Sampling, USS) and compared to the existing (Equilinear Spinning Sampling, ESS) acquisition strategy. Novel corrections were introduced to reduce artifacts in experimental data. Results Simulations demonstrated that USS puts an equal number of projections near each axis whereas ESS puts excessive projections at one axis, wasting acquisition time. Artifact corrections added to the magnetic gradient waveforms reduced noise and correlation between projections. USS images had higher SNR (85.9±0.8 vs. 56.2±0.8) and lower mean-squared error than ESS images. The quality of the USS images did not vary with the magnetic gradient orientation, in contrast to ESS images. The quality of rat heart images was improved using USS compared to that with ESS or traditional fast-scan acquisitions. Conclusion A novel EPRI acquisition which combines spinning gradient acquisition with a uniform sampling distribution was developed. This USS spinning gradient acquisition offers superior SNR and reduced artifacts compared to prior methods enabling potential improvements in speed and quality of EPR imaging in biological applications. PMID:23475830

  9. The Contribution of Electron Paramagnetic Resonance to Melanoma Research

    PubMed Central

    Godechal, Quentin; Gallez, Bernard

    2011-01-01

    The incidence of malignant melanoma, the most dangerous form of skin cancer, is rising each year. However, some aspects of the tumor initiation and development are still unclear, and the current method of diagnosis, based on the visual aspect of the tumor, shows limitations. For these reasons, developments of new techniques are ongoing to improve basic knowledge on the disease and diagnosis of tumors in individual patients. This paper shows how electron paramagnetic resonance (EPR), a method able to detect free radicals trapped in melanin pigments, has recently brought its unique value to this specific field. The general principles of the method and the convenience of melanin as an endogenous substrate for EPR measurements are explained. Then, the way by which EPR has recently helped to assess the contribution of ultraviolet rays (UVA and UVB) to the initiation of melanoma is described. Finally, we describe the improvements of EPR spectrometry and imaging in the detection and mapping of melanin pigments inside ex vivo and in vivo melanomas. We discuss how these advances might improve the diagnosis of this skin cancer and point out the present capabilities and limitations of the method. PMID:21941659

  10. Dating Carbonaceous Matter in Archean Cherts by Electron Paramagnetic Resonance

    PubMed Central

    Bourbin, M.; Derenne, S.; Binet, L.; Le Du, Y.; Westall, F.; Kremer, B.; Gautret, P.

    2013-01-01

    Abstract Ancient geological materials are likely to be contaminated through geological times. Thus, establishing the syngeneity of the organic matter embedded in a mineral matrix is a crucial step in the study of very ancient rocks. This is particularly the case for Archean siliceous sedimentary rocks (cherts), which record the earliest traces of life. We used electron paramagnetic resonance (EPR) for assessing the syngeneity of organic matter in cherts that have a metamorphic grade no higher than greenschist. A correlation between the age of Precambrian samples and the shape of their EPR signal was established and statistically tested. As thermal treatments impact organic matter maturity, the effect of temperature on this syngeneity proxy was studied; cyanobacteria were submitted to cumulative short thermal treatment at high temperatures followed by an analysis of their EPR parameters. The resulting carbonaceous matter showed an evolution similar to that of a thermally treated young chert. Furthermore, the possible effect of metamorphism, which is a longer thermal event at lower temperatures, was ruled out for cherts older than 2 Gyr, based on the study of Silurian cherts of the same age and same precursors but various metamorphic grades. We determined that even the most metamorphosed sample did not exhibit the lineshape of an Archean sample. In the hope of detecting organic contamination in Archean cherts, a “contamination-like” mixture was prepared and studied by EPR. It resulted that the lineshape analysis alone does not allow contamination detection and that it must be performed along with cumulative thermal treatments. Such treatments were applied to three Archean chert samples, making dating of their carbonaceous matter possible. We concluded that EPR is a powerful tool to study primitive organic matter and could be used in further exobiology studies on low-metamorphic grade samples (from Mars for example). Key Words: Kerogen—Sedimentary rocks

  11. Dating carbonaceous matter in archean cherts by electron paramagnetic resonance.

    PubMed

    Bourbin, M; Gourier, D; Derenne, S; Binet, L; Le Du, Y; Westall, F; Kremer, B; Gautret, P

    2013-02-01

    Ancient geological materials are likely to be contaminated through geological times. Thus, establishing the syngeneity of the organic matter embedded in a mineral matrix is a crucial step in the study of very ancient rocks. This is particularly the case for Archean siliceous sedimentary rocks (cherts), which record the earliest traces of life. We used electron paramagnetic resonance (EPR) for assessing the syngeneity of organic matter in cherts that have a metamorphic grade no higher than greenschist. A correlation between the age of Precambrian samples and the shape of their EPR signal was established and statistically tested. As thermal treatments impact organic matter maturity, the effect of temperature on this syngeneity proxy was studied; cyanobacteria were submitted to cumulative short thermal treatment at high temperatures followed by an analysis of their EPR parameters. The resulting carbonaceous matter showed an evolution similar to that of a thermally treated young chert. Furthermore, the possible effect of metamorphism, which is a longer thermal event at lower temperatures, was ruled out for cherts older than 2 Gyr, based on the study of Silurian cherts of the same age and same precursors but various metamorphic grades. We determined that even the most metamorphosed sample did not exhibit the lineshape of an Archean sample. In the hope of detecting organic contamination in Archean cherts, a "contamination-like" mixture was prepared and studied by EPR. It resulted that the lineshape analysis alone does not allow contamination detection and that it must be performed along with cumulative thermal treatments. Such treatments were applied to three Archean chert samples, making dating of their carbonaceous matter possible. We concluded that EPR is a powerful tool to study primitive organic matter and could be used in further exobiology studies on low-metamorphic grade samples (from Mars for example). PMID:23397956

  12. Electron Paramagnetic Resonance Spectroscopy of Nitroxide-Labeled Calmodulin

    PubMed Central

    Bowman, Paula B.; Puett, David

    2014-01-01

    Calmodulin (CaM) is a highly conserved calcium-binding protein consisting of two homologous domains, each of which contains two EF-hands, that is known to bind well over 300 proteins and peptides. In most cases the (Ca2+)4-form of CaM leads to the activation of a key regulatory enzyme or protein in a myriad of biological processes. Using the nitroxide spin-labeling reagent, 3-(2-iodoacetamido)-2,2,5,5-tetramethyl-1-pyrrolidinyl oxyl, bovine brain CaM was modified at 2-3 methionines with retention of activity as judged by the activation of cyclic nucleotide phosphodiesterase. X-band electron paramagnetic resonance (EPR) spectroscopy was used to measure the spectral changes upon addition of Ca2+ to the apo-form of spin-labeled protein. A significant loss of spectral intensity, arising primarily from reductions in the heights of the low, intermediate, and high field peaks, accompanied Ca2+ binding. The midpoint of the Ca2+-mediated transition determined by EPR occurred at a higher Ca2+ concentration than that measured with circular dichroic spectroscopy and enzyme activation. Recent data have indicated that the transition from the apo-state of CaM to the fully saturated form, [Ca2+)4-CaM], contains a compact intermediate corresponding to [Ca2+)2-CaM], and the present results suggest that the spin probes are reporting on Ca2+ binding to the last two sites in the N-terminal domain, i.e. for the [Ca2+)2-CaM] → [Ca2+)4-CaM] transition in which the compact structure becomes more extended. EPR of CaM, spin-labeled at methionines, offers a different approach for studying Ca2+-mediated conformational changes and may emerge as a useful technique for monitoring interactions with target proteins. PMID:24718677

  13. Electron paramagnetic resonance dosimetry: Methodology and material characterization

    NASA Astrophysics Data System (ADS)

    Hayes, Robert Bruce

    Electron Paramagnetic Resonance (EPR) methodologies for radiation dose reconstruction are investigated using various dosimeter materials. Specifically, methodologies were developed and used that were intended to improve the accuracy and precision of EPR dosimetric techniques, including combining specimen rotation during measurement, use of an internal manganese standard, instrument stabilization techniques and strict measurement protocols. Characterization and quantification of these improvements were preformed on three specific EPR dosimeter materials. The dosimeter materials investigated using these optimized EPR techniques were Walrus teeth, human tooth enamel and alanine dosimeters. Walrus teeth showed the least desirable properties for EPR dosimetry yielding large native signals and low sensitivity (EPR signal per unit dose). The methods for tooth enamel and alanine resulted in large improvements in precision and accuracy. The minimum detectable dose (MDD) found for alanine was approximately 30 mGy (three standard deviations from the measured zero dose value). This is a sensitivity improvement of 5 to 10 over other specialized techniques published in the literature that offer MDD's in the range of 150 mGy to 300 mGy. The accuracy of the method on tooth enamel was comparable to that typically reported in the literature although the measurement precision was increased by about 7. This improvement in measurement precision enables various applications including dose vs. depth profile analysis and a more nondestructive testing evaluation (where the whole sample need not be additively irradiated in order to calibrate its radiation response). A nondestructive evaluation of numerous samples showed that the method could reconstruct the same doses to within 10 mGy of those evaluated destructively. Doses used for this assessment were in the range of 100 to 250 mGy. The method had sufficient stability to measure tooth enamel samples exhibiting extreme anisotropy with a

  14. Semiquinone Radicals from Oxygenated Polychlorinated Biphenyls: Electron Paramagnetic Resonance Studies

    PubMed Central

    2008-01-01

    Polychlorinated biphenyls (PCBs) can be oxygenated to form very reactive hydroquinone and quinone products. A guiding hypothesis in the PCB research community is that some of the detrimental health effects of some PCBs are a consequence of these oxygenated forms undergoing one-electron oxidation or reduction, generating semiquinone radicals (SQ•−). These radicals can enter into a futile redox cycle resulting in the formation of reactive oxygen species, that is, superoxide and hydrogen peroxide. Here, we examine some of the properties and chemistry of these semiquinone free radicals. Using electron paramagnetic resonance (EPR) to detect SQ•− formation, we observed that (i) xanthine oxidase can reduce quinone PCBs to the corresponding SQ•−; (ii) the heme-containing peroxidases (horseradish and lactoperoxidase) can oxidize hydroquinone PCBs to the corresponding SQ•−; (iii) tyrosinase acting on PCB ortho-hydroquinones leads to the formation of SQ•−; (iv) mixtures of PCB quinone and hydroquinone form SQ•− via a comproportionation reaction; (v) SQ•− are formed when hydroquinone-PCBs undergo autoxidation in high pH buffer (≈>pH 8); and, surprisingly, (vi) quinone-PCBs in high pH buffer can also form SQ•−; (vii) these observations along with EPR suggest that hydroxide anion can add to the quinone ring; (viii) H2O2 in basic solution reacts rapidly with PCB-quinones; and (ix) at near-neutral pH SOD can catalyze the oxidization of PCB-hydroquinone to quinone, yielding H2O2. However, using 5,5-dimethylpyrroline-1-oxide (DMPO) as a spin-trapping agent, we did not trap superoxide, indicating that generation of superoxide from SQ•− is not kinetically favorable. These observations demonstrate multiple routes for the formation of SQ•− from PCB-quinones and hydroquinones. Our data also point to futile redox cycling as being one mechanism by which oxygenated PCBs can lead to the formation of reactive oxygen species, but this is most efficient

  15. Electron paramagnetic resonance study of two smectic A liquid crystals.

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Gelerinter, E.; Fishel, D. L.

    1972-01-01

    Study of the molecular ordering in two smectic A liquid crystals using vanadyl acetylacetonate as a paramagnetic probe. The average hyperfine splitting of the spectrum in the smectic A mesophase is measured as a function of the orientation relative to the dc magnetic field of the spectrometer after alignment of the molecules of the liquid crystal.

  16. Enhanced dynamic electron paramagnetic resonance imaging of in vivo physiology

    NASA Astrophysics Data System (ADS)

    Redler, Gage

    It is well established that low oxygen concentration (hypoxia) in tumors strongly affects their malignant state and resistance to therapy. The importance of tumor oxygenation status has led to increased interest in the development of robust oxygen imaging modalities. One such method is electron paramagnetic resonance imaging (EPRI). EPRI has provided a non-invasive, quantitative imaging modality with sensitivity deep in tissues, capable of investigating static oxygen concentration (pO2) in vivo and has helped to corroborate the correlation between chronic states of hypoxia and tumor malignancy. However, when studying the complicated physiology of a living animal, the situation tends to be inherently dynamic. It has been found that in certain tumor regions there may exist steady states of hypoxia, or chronic hypoxia, whereas in other regions there may exist transient states of hypoxia, or acute hypoxia. It has been postulated that the negative prognostic implications associated with hypoxic tumors may be amplified for acutely hypoxic tumors. However, controversial data and a current lack in methods with the capability to noninvasively image tumor pO2 in vivo with sufficient spatial, temporal, and pO 2 resolution preclude definitive conclusions on the relationships between the different forms of hypoxia and the differences in their clinical implications. A particularly promising oxygen imaging modality that can help to study both chronic and acute hypoxia and elucidate important physiological and clinical differences is rapid Dynamic EPRI. The focus of this work is the development of methods enabling Dynamic EPRI of in vivo physiology as well as its potential applications. This work describes methods which enhance various aspects of EPRI in order to establish a more robust Dynamic EPRI capable of noninvasively studying and quantifying acute hypoxia in vivo. These enhancements are achieved through improvements that span from methods for the acquisition of individual

  17. Simultaneous electrochemical and electron paramagnetic resonance studies of carotenoids. Effect of electron donating and accepting substituents

    SciTech Connect

    Jeevarajan, A.S.; Khaled, M.; Kispert, L.D. )

    1994-08-11

    A series of substituted phenyl-7[prime]-apocarotenoids with varying electron donating and accepting substituents was examined by cyclic voltammogram (CV) and simultaneous electrochemical electron paramagnetic resonance (SEEPR). Carotenoids substituted with electron donating groups are more easily oxidized than those with electron accepting substituents. Comproportionation constants for the dication and the neutral species were measured by SEEPR techniques and by simulation of the CVs. The [Delta]H[sub pp] of the SEEPR spectrum of the cation radicals varies from 13.2 to 15.6 G, and the g factors are 2.0027 [+-] 0.0002. These EPR parameters suggest a polyene [pi]-cation radical structure. The CVs are calculated using DigiSim, a CV simulation program, and the proposed mechanism involves three electrode reactions and two homogeneous reactions. 24 refs., 3 figs., 2 tabs.

  18. High field electron paramagnetic resonance characterization of electronic and structural environments for paramagnetic metal ions and organic free radicals in Deepwater Horizon oil spill tar balls.

    PubMed

    Ramachandran, Vasanth; van Tol, Johan; McKenna, Amy M; Rodgers, Ryan P; Marshall, Alan G; Dalal, Naresh S

    2015-02-17

    In the first use of high-field electron paramagnetic resonance (EPR) spectroscopy to characterize paramagnetic metal-organic and free radical species from tar balls and weathered crude oil samples from the Gulf of Mexico (collected after the Deepwater Horizon oil spill) and an asphalt volcano sample collected off the coast of Santa Barbara, CA, we are able to identify for the first time the various paramagnetic species present in the native state of these samples and understand their molecular structures and bonding. The two tar ball and one asphalt volcano samples contain three distinct paramagnetic species: (i) an organic free radical, (ii) a [VO](2+) containing porphyrin, and (iii) a Mn(2+) containing complex. The organic free radical was found to have a disc-shaped or flat structure, based on its axially symmetric spectrum. The characteristic spectral features of the vanadyl species closely resemble those of pure vanadyl porphyrin; hence, its nuclear framework around the vanadyl ion must be similar to that of vanadyl octaethyl porphyrin (VOOEP). The Mn(2+) ion, essentially undetected by low-field EPR, yields a high-field EPR spectrum with well-resolved hyperfine features devoid of zero-field splitting, characteristic of tetrahedral or octahedral Mn-O bonding. Although the lower-field EPR signals from the organic free radicals in fossil fuel samples have been investigated over the last 5 decades, the observed signal was featureless. In contrast, high-field EPR (up to 240 GHz) reveals that the species is a disc-shaped hydrocarbon molecule in which the unpaired electron is extensively delocalized. We envisage that the measured g-value components will serve as a sensitive basis for electronic structure calculations. High-field electron nuclear double resonance experiments should provide an accurate picture of the spin density distribution for both the vanadyl-porphyrin and Mn(2+) complexes, as well as the organic free radical, and will be the focus of follow

  19. Electron paramagnetic resonance investigation of purified catalyst-free single-walled carbon nanotubes.

    PubMed

    Zaka, Mujtaba; Ito, Yasuhiro; Wang, Huiliang; Yan, Wenjing; Robertson, Alex; Wu, Yimin A; Rümmeli, Mark H; Staunton, David; Hashimoto, Takeshi; Morton, John J L; Ardavan, Arzhang; Briggs, G Andrew D; Warner, Jamie H

    2010-12-28

    Electron paramagnetic resonance of single-walled carbon nanotubes (SWCNTs) has been bedevilled by the presence of paramagnetic impurities. To address this, SWCNTs produced by laser ablation with a nonmagnetic PtRhRe catalyst were purified through a multiple step centrifugation process in order to remove amorphous carbon and catalyst impurities. Centrifugation of a SWCNT solution resulted in sedimentation of carbon nanotube bundles containing clusters of catalyst particles, while isolated nanotubes with reduced catalyst particle content remained in the supernatant. Further ultracentrifugation resulted in highly purified SWCNT samples with a narrow diameter distribution and almost no detectable catalyst particles. Electron paramagnetic resonance (EPR) signals were detected only for samples which contained catalyst particles, with the ultracentrifuged SWCNTs showing no EPR signal at X-band (9.4 GHz) and fields < 0.4 T. PMID:21082779

  20. Magic-angle sample spinning electron paramagnetic resonance--instrumentation, performance, and limitations.

    PubMed

    Hessinger, D; Bauer, C; Hubrich, M; Jeschke, G; Spiess, H W

    2000-12-01

    An electron paramagnetic resonance (EPR) setup for line narrowing experiments with fast sample spinning at variable angles between the rotation axis and the static magnetic field is described and applied in the magic-angle sample spinning (MAS) EPR experiment at X-band frequencies (9.5 GHz). Sample spinning speeds up to 17 kHz at temperatures down to 200 K can be achieved with rotors of 4-mm outer and 2.5-mm inner diameter without severe losses in microwave amplitude compared to standard pulse EPR probeheads. A phase cycle is introduced that provides pure absorption MAS EPR spectra and allows one to distinguish between positive and negative frequency offsets (pseudo-quadrature detection). Possible broadening mechanisms in MAS EPR spectra are discussed. It is demonstrated both by theory and by experiment that the MAS EPR experiment requires excitation bandwidths that are comparable to the total spectral width, since otherwise destructive interference between contributions of spins with similar resonance offsets suppresses the signal. Experimental observations on the E(1) center in gamma-irradiated silica glass and on the SO(-)(3) radical in gamma-irradiated sulfamic acid are reported. PMID:11097812

  1. Electron Paramagnetic Resonance: A High-Resolution Tool for Muscle Physiology

    PubMed Central

    Thompson, LaDora V.; Lowe, Dawn A.; Ferrington, Deborah A.; Thomas, David D.

    2015-01-01

    Skeletal muscle function can be altered by changes in protein structure and motion. Electron paramagnetic resonance (EPR) paired with site-directed spin labeling has been used to study the relationships between (a) muscle force and myosin structure and (b) muscle relaxation and Ca-ATPase motion and structure. PMID:11210444

  2. The Effect of Electronic Paramagnetism on Nuclear Magnetic Resonance Frequencies in Metals

    DOE R&D Accomplishments Database

    Townes, C. H.; Herring, C.; Knight, W. D.

    1950-09-22

    Observations on the shifts of nuclear resonances in metals ( Li{sup 7}, Na{sup 23}, Cu {sup 63}, Be{sup 9}, Pb{sup 207}, Al{sup 27}, and Ca{sup 69} ) due to free electron paramagnetism; comparison with theoretical values.

  3. Radiation-induced electron paramagnetic resonance signal and soybean isoflavones content

    NASA Astrophysics Data System (ADS)

    de Oliveira, Marcos R. R.; Mandarino, José M. G.; del Mastro, Nelida L.

    2012-09-01

    Electron Paramagnetic Resonance (EPR) is a well-known spectroscopic technique that detects paramagnetic centers and can detect free radicals with high sensitivity. In food, free radicals can be generated by several commonly used industrial processes, such as radiosterilization or heat treatment. EPR spectroscopy is used to detect radioinduced free radicals in food. In this work the relation between EPR signal induced by gamma irradiation treatment and soybean isoflavones content was investigated. Present results did not show correlation between total isoflavones content and the EPR signal. Nevertheless, some isoflavone contents had a negative correlation with the radiation-induced EPR signal.

  4. Effects of Paramagnetism and Electron Correlations on the Electronic Structure of MnO: Ab Initio Study

    NASA Astrophysics Data System (ADS)

    Yoon, Sangmoon; Jin, Kyoungsuk; Kang, Seoung-Hun; Nam, Ki Tae; Kim, Miyoung; Kwon, Young-Kyun

    Manganese oxide nanoparticles have attracted a lot of attentions as a promising candidate for next-generation catalyst. Therefore, understanding the electronic structure of manganese oxide in room temperature is highly required for the rational design of catalysts. We study the effects of paramagnetism and electron correlations on the electronic structure of MnO using ab initio density functional theory. Spin configurations of paramagnetism are postulated as the ensemble average of various spin disorders. Each initial disordered spin configuration is randomly generated with two constraints on magnetic local moments. We first investigate the influence of magnetic ordering on the elctronic structure of MnO using noncollinear spin calculations and find that the magnetic disorders make valence band maximum more delocalized. Moreover, we examine the role of electron correlations in the electronic structure of paramagnetic MnO using DFT +U calculations. Strong electron correlations modify not only the size of band gap but also the magnitude of local moments as in the antiferromagnetic MnO. Besides, the initialized spin disorder remains almost unchanged as electron correlation get stronger. Furthermore, our results obtained by considering both strong electron correlation and paramagnetism confirm experimentally-observed oxygen K edge X-ray emission spectra [1] reflecting the feature of valence bands. [1] E. Z. Kurmaev et al., Phys. Rev. B. 77, 165127 (2008).

  5. ELECTRON PARAMAGNETIC RESONANCE DOSIMETRY FOR A LARGE-SCALE RADIATION INCIDENT

    PubMed Central

    Swartz, Harold M.; Flood, Ann Barry; Williams, Benjamin B.; Dong, Ruhong; Swarts, Steven G.; He, Xiaoming; Grinberg, Oleg; Sidabras, Jason; Demidenko, Eugene; Gui, Jiang; Gladstone, David J.; Jarvis, Lesley A.; Kmiec, Maciej M.; Kobayashi, Kyo; Lesniewski, Piotr N.; Marsh, Stephen D.P.; Matthews, Thomas P.; Nicolalde, Roberto J.; Pennington, Patrick M.; Raynolds, Timothy; Salikhov, Ildar; Wilcox, Dean E.; Zaki, Bassem I.

    2013-01-01

    With possibilities for radiation terrorism and intensified concerns about nuclear accidents since the recent Fukushima Daiichi event, the potential exposure of large numbers of individuals to radiation that could lead to acute clinical effects has become a major concern. For the medical community to cope with such an event and avoid overwhelming the medical care system, it is essential to identify not only individuals who have received clinically significant exposures and need medical intervention but also those who do not need treatment. The ability of electron paramagnetic resonance to measure radiation-induced paramagnetic species, which persist in certain tissues (e.g., teeth, fingernails, toenails, bone, and hair), has led this technique to become a prominent method for screening significantly exposed individuals. Although the technical requirements needed to develop this method for effective application in a radiation event are daunting, remarkable progress has been made. In collaboration with General Electric, and through funding committed by the Biomedical Advanced Research and Development Authority, electron paramagnetic resonance tooth dosimetry of the upper incisors is being developed to become a Food and Drug Administration-approved and manufacturable device designed to carry out triage for a threshold dose of 2 Gy. Significant progress has also been made in the development of electron paramagnetic resonance nail dosimetry based on measurements of nails in situ under point-of-care conditions, and in the near future this may become a second field-ready technique. Based on recent progress in measurements of nail clippings, we anticipate that this technique may be implementable at remotely located laboratories to provide additional information when the measurements of dose on site need to be supplemented. We conclude that electron paramagnetic resonance dosimetry is likely to be a useful part of triage for a large-scale radiation incident. PMID:22850230

  6. Tetrachloridocuprates(II)—Synthesis and Electron Paramagnetic Resonance (EPR) Spectroscopy

    PubMed Central

    Winter, Alette; Zabel, André; Strauch, Peter

    2012-01-01

    Ionic liquids (ILs) on the basis of metal containing anions and/or cations are of interest for a variety of technical applications e.g., synthesis of particles, magnetic or thermochromic materials. We present the synthesis and the results of electron paramagnetic resonance (EPR) spectroscopic analyses of a series of some new potential ionic liquids based on tetrachloridocuprates(II), [CuCl4]2−, with different sterically demanding cations: hexadecyltrimethylammonium 1, tetradecyltrimethylammonium 2, tetrabutylammonium 3 and benzyltriethylammonium 4. The cations in the new compounds were used to achieve a reasonable separation of the paramagnetic Cu(II) ions for EPR spectroscopy. The EPR hyperfine structure was not resolved. This is due to the exchange broadening, resulting from still incomplete separation of the paramagnetic Cu(II) centers. Nevertheless, the principal values of the electron Zeemann tensor (g║ and g┴) of the complexes could be determined. Even though the solid substances show slightly different colors, the UV/Vis spectra are nearly identical, indicating structural changes of the tetrachloridocuprate moieties between solid state and solution. The complexes have a promising potential e.g., as high temperature ionic liquids, as precursors for the formation of copper chloride particles or as catalytic paramagnetic ionic liquids. PMID:22408411

  7. Electron Paramagnetic Resonance of Single Magnetic Moment on a Surface.

    PubMed

    Berggren, P; Fransson, J

    2016-01-01

    We address electron spin resonance of single magnetic moments in a tunnel junction using time-dependent electric fields and spin-polarized current. We show that the tunneling current directly depends on the local magnetic moment and that the frequency of the external electric field mixes with the characteristic Larmor frequency of the local spin. The importance of the spin-polarized current induced anisotropy fields acting on the local spin moment is, moreover, demonstrated. Our proposed model thus explains the absence of an electron spin resonance for a half integer spin, in contrast with the strong signal observed for an integer spin. PMID:27156935

  8. Electron Paramagnetic Resonance of Single Magnetic Moment on a Surface

    PubMed Central

    Berggren, P.; Fransson, J.

    2016-01-01

    We address electron spin resonance of single magnetic moments in a tunnel junction using time-dependent electric fields and spin-polarized current. We show that the tunneling current directly depends on the local magnetic moment and that the frequency of the external electric field mixes with the characteristic Larmor frequency of the local spin. The importance of the spin-polarized current induced anisotropy fields acting on the local spin moment is, moreover, demonstrated. Our proposed model thus explains the absence of an electron spin resonance for a half integer spin, in contrast with the strong signal observed for an integer spin. PMID:27156935

  9. Electron paramagnetic resonance examination of aqueous anthrasemiquinone radical anion

    NASA Astrophysics Data System (ADS)

    Hocking, M. B.; Mattar, S. M.

    Anthrasemiquinone radical anion (AQ -·) was prepared in strictly aqueous alkaline solutions using reducing sugars. It was found to be stable in this medium at room temperature in the absence of air for periods exceeding 1 year. Reduction using an equivalent of sodium dithionite required brief exposure of the solution of dianion to air to obtain AQ -. EPR observations are reported for these solutions over the temperature range -50 to +90°C in basic ethanol, aqueous ethanol, and water and are related to redox potential measurements and electron exchange processes operating under these conditions.

  10. Electron paramagnetic resonance of spin-variable metallomesogens [Fe L 2] X ( X = PF6, SCN)

    NASA Astrophysics Data System (ADS)

    Ovchinnikov, I. V.; Ivanova, T. A.; Turanov, A. N.; Garipov, R. R.

    2009-10-01

    Significant differences in the manifestation of spin-crossover properties of the mesogen compounds [Fe L 2] X with oxysalicylidene- N'-ethyl- N-ethylenediamine ligands L and anions X = PF{6/-} and SCH- have been found by means of electron paramagnetic resonance. The electron paramagnetic resonance data and the quantum-chemical calculation within the density functional theory enables us to establish that the observed specific features are associated with the incorporation of the SCH- ion into the first coordination sphere of the Fe(III) ion. The role of the transition of the material to the liquid-state phase in the formation of a low-dimensional (two-dimensional) structure with stronger intermolecular interactions has been revealed.

  11. Electron paramagnetic resonance and FT-IR spectroscopic studies of glycine anhydride and betaine hydrochloride

    NASA Astrophysics Data System (ADS)

    Halim Başkan, M.; Kartal, Zeki; Aydın, Murat

    2015-12-01

    Gamma irradiated powders of glycine anhydride and betaine hydrochloride have been investigated at room temperature by electron paramagnetic resonance (EPR). In these compounds, the observed paramagnetic species were attributed to the R1 and R2 radicals, respectively. It was determined that the free electron interacted with environmental protons and 14N nucleus in both radicals. The EPR spectra of gamma irradiated powder samples remained unchanged at room temperature for two weeks after irradiation. Also, the Fourier Transform Infrared (FT-IR), FT-Raman and thermal analyses of both compounds were investigated. The functional groups in the molecular structures of glycine anhydride and betaine hydrochloride were identified by vibrational spectroscopies (FT-IR and FT-Raman).

  12. Cavity- and waveguide-resonators in electron paramagnetic resonance, nuclear magnetic resonance, and magnetic resonance imaging.

    PubMed

    Webb, Andrew

    2014-11-01

    Cavity resonators are widely used in electron paramagnetic resonance, very high field magnetic resonance microimaging and also in high field human imaging. The basic principles and designs of different forms of cavity resonators including rectangular, cylindrical, re-entrant, cavity magnetrons, toroidal cavities and dielectric resonators are reviewed. Applications in EPR and MRI are summarized, and finally the topic of traveling wave MRI using the magnet bore as a waveguide is discussed. PMID:25456314

  13. EPR and electronic absorption spectra of copper bearing turquoise mineral

    NASA Astrophysics Data System (ADS)

    Sharma, K. B. N.; Moorthy, L. R.; Reddy, B. J.; Vedanand, S.

    1988-10-01

    Electron paramagnetic resonance and optical absorption spectra of turquoise have been studied both at room and low temperatures. It is concluded from the EPR spectra that the ground state of Cu 2+ ion in turquoise is 2A g(d x2- y2) and it is sited in an elongated rhombic octahedron (D 2π). The observed absorption bands at 14970 and 18354 cm -1 are assigned at 2A g→ 2B 1 g( dx2- y2→ xy) and 2A g→[ su2B 3g(d x 2-y 2→d yz) respectively assuming D 2π symmetry which are inconsistent with EPR studies. The three bands in the NIR region are attributed to combinations of fundamental modes of the H 2O molecule present in the sample.

  14. Hysteresis loops of spin-dependent electronic current in a paramagnetic resonant tunnelling diode

    NASA Astrophysics Data System (ADS)

    Wójcik, P.; Spisak, B. J.; Wołoszyn, M.; Adamowski, J.

    2012-11-01

    Nonlinear properties of the spin-dependent electronic transport through a semiconductor resonant tunnelling diode with a paramagnetic quantum well are considered. The spin-dependent Wigner-Poisson model of the electronic transport and the two-current Mott’s formula for the independent spin channels are applied to determine the current-voltage curves of the nanodevice. Two types of the electronic current hysteresis loops are found in the current-voltage characteristics for both the spin components of the electronic current. The physical interpretation of these two types of the electronic current hysteresis loops is given based on the analysis of the spin-dependent electron densities and the potential energy profiles. The differences between the current-voltage characteristics for both the spin components of the electronic current allow us to explore the changes of the spin polarization of the current for different electric fields and determine the influence of the electronic current hysteresis on the spin polarization of the current flowing through the paramagnetic resonant tunnelling diode.

  15. Electron paramagnetic resonance spectroscopy using a direct current-SQUID magnetometer directly coupled to an electron spin ensemble

    NASA Astrophysics Data System (ADS)

    Toida, Hiraku; Matsuzaki, Yuichiro; Kakuyanagi, Kosuke; Zhu, Xiaobo; Munro, William J.; Nemoto, Kae; Yamaguchi, Hiroshi; Saito, Shiro

    2016-02-01

    We demonstrate electron spin polarization detection and electron paramagnetic resonance (EPR) spectroscopy using a direct current superconducting quantum interference device (dc-SQUID) magnetometer. Our target electron spin ensemble is directly bonded to the dc-SQUID magnetometer that detects electron spin polarization induced by an external magnetic field or EPR in a micrometer-sized area. The minimum distinguishable number of polarized spins and sensing volume of the electron spin polarization detection and the EPR spectroscopy are estimated to be ˜106 and ˜10-10 cm3 (˜0.1 pl), respectively.

  16. Electron paramagnetic resonance imaging for real-time monitoring of Li-ion batteries

    PubMed Central

    Sathiya, M.; Leriche, J.-B.; Salager, E.; Gourier, D.; Tarascon, J.-M.; Vezin, H.

    2015-01-01

    Batteries for electrical storage are central to any future alternative energy paradigm. The ability to probe the redox mechanisms occurring at electrodes during their operation is essential to improve battery performances. Here we present the first report on Electron Paramagnetic Resonance operando spectroscopy and in situ imaging of a Li-ion battery using Li2Ru0.75Sn0.25O3, a high-capacity (>270 mAh g−1) Li-rich layered oxide, as positive electrode. By monitoring operando the electron paramagnetic resonance signals of Ru5+ and paramagnetic oxygen species, we unambiguously prove the formation of reversible (O2)n− species that contribute to their high capacity. In addition, we visualize by imaging with micrometric resolution the plating/stripping of Li at the negative electrode and highlight the zones of nucleation and growth of Ru5+/oxygen species at the positive electrode. This efficient way to locate ‘electron’-related phenomena opens a new area in the field of battery characterization that should enable future breakthroughs in battery research. PMID:25662295

  17. 4 f-4 f hypersensitivity in the absorption spectra and NMR studies on paramagnetic lanthanide chloride complexes with 1,10-phenanthroline in non-aqueous solutions

    NASA Astrophysics Data System (ADS)

    Hussain, H. A.; Iftikhar, K.

    2003-03-01

    The optical absorption and NMR studies of trivalent lanthanide chloride complexes with 1,10-phenanthroline (phen) are presented and discussed. The 1H NMR spectra of the complexes of La, Pr, Nd, Eu and Yb have been studied in methanol- d4. The resonances of phen in the NMR spectra of the paramagnetic complexes have been shifted to lower as well as higher fields, which is a manifestation of dipolar interaction. The H (2) protons of the heterocyclic amine display broad resonances. The degree of broadening in Pr, Nd, and Yb complexes follows the order Prparamagnetic shift is predominantly due to dipolar interaction. The electronic spectra of Pr, Nd, Ho and Er complexes have been investigated in methanol, pyridine, DMSO and DMF, which reveal that the hypersensitive transitions exhibit larger variation in oscillator strength values and band shapes. The change in the coordination geometry of the complexes and relative basicity of ligand are found responsible for oscillator strength and band shape variation. The interelectronic repulsion and covalency parameters show covalent nature of bonding between the metal and the ligand.

  18. Feasibility study of superresolution continuous-wave electron paramagnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Hirata, Hiroshi; Wakana, Michi; Susaki, Hitoshi

    2006-06-01

    In this letter, we report that superresolution continuous-wave electron paramagnetic resonance (cw-EPR) imaging is feasible for enhancing spatial resolution in images of unpaired electrons. We demonstrate one-dimensional superresolution EPR imaging for phantoms of 1,1-diphenyl-2-picrylhydrazyl (DPPH) powder with a 650MHz cw-EPR imager. The spatial resolution was improved up to fivefold with iterative deconvolution techniques. Our superresolution EPR imaging includes two-stage postprocessing, i.e., noniterative deconvolution for measured EPR spectra and iterative deconvolution processing for a blurred EPR image profile with the point spread function of the low-pass window function being applied.

  19. Paramagnetic defects in electron-irradiated yttria-stabilized zirconia: Effect of yttria content

    SciTech Connect

    Costantini, Jean-Marc; Beuneu, Francois; Morrison-Smith, Sarah E.; Devanathan, Ramaswami; Weber, William J.

    2011-12-20

    We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are strongly enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. It is concluded that F+-type centres might be actually oxygen divacancies (F2+-type centres). Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 ± 1 eV with subsequent defect re-arrangement.

  20. Paramagnetic Defects in Electron-Irradiated Yttria-Stabilized Zirconia: Effect of Yttria Content

    SciTech Connect

    Costantini, Jean-Marc; Beuneu, Francois; Morrison-Smith, Sarah; Devanathan, Ram; Weber, William J

    2011-01-01

    We have studied the effect of the yttria content on the paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+) or YSZ. Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. The paramagnetic centre production was studied by X-band EPR spectroscopy. The same paramagnetic centres were identified for both chemical compositions, namely two electron centres, i.e. i) F+-type centres (involving singly ionized oxygen vacancies), and ii) so-called T centres (Zr3+ in a trigonal symmetry site), and hole-centres. A strong effect is observed on the production of hole-centres which are strongly enhanced when doubling the yttria content. However, no striking effect is found on the electron centres (except the enhancement of an extra line associated to the F+-type centres). It is concluded that hole-centres are produced by inelastic interactions, whereas F+-type centres are produced by elastic collisions with no effect of the yttria content on the defect production rate. In the latter case, the threshold displacement energy (Ed) of oxygen is estimated from the electron-energy dependence of the F+-type centre production rate, with no significant effect of the yttria content on Ed. An Ed value larger than 120 eV is found. Accordingly, classical molecular dynamics (MD) simulations with a Buckingham-type potential show that Ed values for Y and O are likely to be in excess of 200 eV. Due to the difficulty in displacing O or Y atoms, the radiation-induced defects may alternatively be a result of Zr atom displacements for Ed = 80 1 eV with subsequent defect re-arrangement.

  1. Comparative studies of microwave absorption in the singlet paramagnets HoVO{sub 4} and HoBa{sub 2}Cu{sub 3}O{sub x} in strong pulsed magnetic fields

    SciTech Connect

    Kazei, Z. A. Snegirev, V. V.; Goaran, M.; Kozeeva, L. P.; Kameneva, M. Yu.

    2008-03-15

    Microwave absorption in the tetragonal singlet paramagnets HoVO{sub 4} (zircon structure) and HoBa{sub 2}Cu{sub 3}O{sub x} (x {approx} 6, layered perovskite structure) is studied and compared in pulsed magnetic fields up to 40 T at low temperatures. These paramagnets are characterized by a singlet-doublet scheme of the low-lying levels of the Ho{sup 3+} ion in a crystal field. In a magnetic field directed along the tetragonal axis, HoVO{sub 4} exhibits resonance absorption lines at wavelengths of 871, 406, and 305 {mu}m, which correspond to electron transitions between the low-lying levels of the Ho{sup 3+} ion in the crystal field. The positions and intensities of these absorption lines in HoVO{sub 4} are well described in terms of the crystal-field formalism with the well-known interaction parameters. The absorption spectra of HoBa{sub 2}Cu{sub 3}O{sub x} at a wavelength of 871 {mu}m exhibit broad resonance absorption lines against the background of strong nonresonance absorption. The effects of low-symmetry (orthorhombic, monoclinic) crystal-field components, the deviation of a magnetic field from a symmetry axis, and various pair interactions on the absorption spectra of the HoVO{sub 4} and HoBa{sub 2}Cu{sub 3}O{sub x} crystals are discussed.

  2. Biophysical Characterisation of Globins and Multi-Heme Cytochromes Using Electron Paramagnetic Resonance and Optical Spectroscopy

    NASA Astrophysics Data System (ADS)

    Desmet, Filip

    Heme proteins of different families were investigated in this work, using a combination of pulsed and continuous-wave electron paramagnetic resonance (EPR) spectroscopy, optical absorption spectroscopy, resonance Raman spectroscopy and laser flash photolysis. The first class of proteins that were investigated, were the globins. The globin-domain of the globin-coupled sensor of the bacterium Geobacter sulfurreducens was studied in detail using different pulsed EPR techniques (HYSCORE and Mims ENDOR). The results of this pulsed EPR study are compared with the results of the optical investigation and the crystal structure of the protein. The second globin, which was studied, is the Protoglobin of Methanosarcina acetivorans, various mutants of this protein were studied using laser flash photolysis and Raman spectroscopy to unravel the link between this protein's unusual structure and its ligand-binding kinetics. In addition to this, the CN -bound form of this protein was investigated using EPR and the influence of the strong deformation of the heme on the unusual low gz values is discussed. Finally, the neuroglobins of three species of fishes, Danio rerio, Dissostichus mawsoni and Chaenocephalus aceratus are studied. The influence of the presence or absence of two cysteine residues in the C-D and D-region of the protein on the EPR spectrum, and the possible formation of a disulfide bond is studied. The second group of proteins that were studied in this thesis belong to the family of the cytochromes. First the Mouse tumor suppressor cytochrome b561 was studied, the results of a Raman and EPR investigation are compared to the Human orthologue of the protein. Secondly, the tonoplast cytochrome b561 of Arabidopsis was investigated in its natural form and in two double-mutant forms, in which the heme at the extravesicular side was removed. The results of this investigation are then compared with two models in literature that predict the localisation of the hemes in this

  3. Study of ultrasonic attenuation in f-electron systems in the paramagnetic limit of Coulomb interaction

    SciTech Connect

    Shadangi, Asit Ku.; Rout, G. C.

    2015-05-15

    We report here a microscopic model study of ultrasonic attenuation in f-electron systems based on Periodic Anderson Model in which Coulomb interaction is considered within a mean-field approximation for a weak interaction. The Phonon is coupled to the conduction band and f-electrons. The phonon Green's function is calculated by Zubarev's technique of the Green's function method. The temperature dependent ultrasonic attenuation co-efficient is calculated from the imaginary part of the phonon self-energy in the dynamic and long wave length limit. The f-electron occupation number is calculated self-consistently in paramagnetic limit of Coulomb interaction. The effect of the Coulomb interaction on ultrasonic attenuation is studied by varying the phonon coupling parameters to the conduction and f-electrons, hybridization strength, the position of f-level and the Coulomb interaction Strength. Results are discussed on the basis of experimental results.

  4. Environmental Factors Influencing the Hyperfine Structure of Manganous Low-Temperature Electron Paramagnetic Resonance Spectra

    PubMed Central

    Nebert, D. W.; Allen, B. T.

    1966-01-01

    Hyperfine structure is observed in low temperature (T = -180°C) EPR (electron paramagnetic resonance) spectra of a number of solutions containing Mn++ ions 13, 15) which have characteristics in common with low temperature EPR spectra from biological substances such as mitochondria and microsomes (1-4). This investigation is an attempt to understand the features of these signals in terms of the molecular environment of the manganous ion, and a qualitative explanation for the observations reported here is advanced in terms of the amount of axial distortion of a manganese hydrate in different environments. PMID:4289642

  5. Nondestructive measurement of large objects with electron paramagnetic resonance: Pottery, sculpture, and jewel ornament

    NASA Astrophysics Data System (ADS)

    Ikeya, Motoji; Yamamoto, Masahiro; Ishii, Hiroshi

    1994-12-01

    A cylindicral cavity of TE111 mode with an aperture of 3 mm in diameter has been used to measure the electron paramagnetic resonance (EPR) spectrum of a large object placed over the aperture. EPR spectra of a precious fossil of a dinosaur tooth piece and a fossil bone of the Machikane Alligator were measured nondestructively in addition to a jadeite sculpture, a pearl and turquoise necklace, a large turmaline, a star ruby, and ceramic pottery. Thus, EPR can be a nondestructive tool to detect forgery and to test the authenticity in art as well as to allocate ancient objects in archaeological provenance study.

  6. Improvement of temporal resolution for three-dimensional continuous-wave electron paramagnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Sato-Akaba, Hideo; Fujii, Hirotada; Hirata, Hiroshi

    2008-12-01

    This paper describes improved temporal resolution for three-dimensional (3D) continuous-wave electron paramagnetic resonance (EPR) imaging. To improve temporal resolution, the duration of magnetic filed scanning that is used to obtain an EPR spectrum for each projection was reduced to 40 ms. The Helmholtz coil pair for field scanning was driven by triangular waves. The uniform distribution of projections was also used to reduce the number of projections for 3D image reconstruction. The reduction reaction of 4-hydroxy-2,2,6,6-tetramethyl-piperidinooxy with ascorbic acid was visualized by improved 3D EPR imaging techniques with a temporal resolution of 5.8 s.

  7. Al-doped MgB2 materials studied using electron paramagnetic resonance and Raman spectroscopy

    NASA Astrophysics Data System (ADS)

    Bateni, Ali; Erdem, Emre; Repp, Sergej; Weber, Stefan; Somer, Mehmet

    2016-05-01

    Undoped and aluminum (Al) doped magnesium diboride (MgB2) samples were synthesized using a high-temperature solid-state synthesis method. The microscopic defect structures of Al-doped MgB2 samples were systematically investigated using X-ray powder diffraction, Raman spectroscopy, and electron paramagnetic resonance. It was found that Mg-vacancies are responsible for defect-induced peculiarities in MgB2. Above a certain level of Al doping, enhanced conductive properties of MgB2 disappear due to filling of vacancies or trapping of Al in Mg-related vacancy sites.

  8. Degradation of edible oil during food processing by ultrasound: electron paramagnetic resonance, physicochemical, and sensory appreciation.

    PubMed

    Pingret, Daniella; Durand, Grégory; Fabiano-Tixier, Anne-Sylvie; Rockenbauer, Antal; Ginies, Christian; Chemat, Farid

    2012-08-01

    During ultrasound processing of lipid-containing food, some off-flavors can be detected, which can incite depreciation by consumers. The impacts of ultrasound treatment on sunflower oil using two different ultrasound horns (titanium and pyrex) were evaluated. An electron paramagnetic resonance study was performed to identify and quantify the formed radicals, along with the assessment of classical physicochemical parameters such as peroxide value, acid value, anisidine value, conjugated dienes, polar compounds, water content, polymer quantification, fatty acid composition, and volatiles profile. The study shows an increase of formed radicals in sonicated oils, as well as the modification of physicochemical parameters evidencing an oxidation of treated oils. PMID:22804736

  9. Electron paramagnetic resonance of Fe3+ in near-stoichiometric LiTaO3

    NASA Astrophysics Data System (ADS)

    Loyo-Menoyo, M.; Keeble, D. J.; Furukawa, Y.; Kitamura, K.

    2004-12-01

    Electron paramagnetic resonance (EPR) experiments on the dominant Fe3+ centre in near-stoichiometric LiTaO3 crystals grown by the double crucible Czochralski method are reported. A near complete roadmap of EPR positions was obtained, and transitions from two magnetically non-equivalent sites clearly resolved in the zx plane, perpendicular to the glide plane. This allowed accurate determination of C3 symmetry spin Hamiltonian parameters. Newman superposition model analyses of second and fourth order zero field splitting term parameters were performed to give further insight into the site of incorporation. The second order calculations provide evidence for Fe3+ substitution within the Li octahedron.

  10. Spin label electron paramagnetic resonance (EPR) studies of Huntington disease erythrocyte membranes.

    PubMed Central

    Fung, L W; Ostrowski, M S

    1982-01-01

    Several spin-label electron paramagnetic resonance (EPR) studies of red cell membranes appear to show abnormalities in some Huntington disease (HD) patients, but not in others. Both studies measure the W/S ratios, presumably under similar conditions, but have different results. We have studied the W/S ratio in some detail to gain a better understanding of this experimental parameter and to determine its potential application in detecting HD abnormalities. Our results offer little encouragement for continued use of W/S as an indication of membrane defect in HD. PMID:6282120

  11. The electronic absorption edge of petroleum

    SciTech Connect

    Mullins, O.C.; Mitra-Kirtley, S.; Zhu, Yifu

    1992-09-01

    The electronic absorption spectra of more than 20 crude oils and asphaltenes are examined. The spectral location of the electronic absorption edge varies over a wide range, from the near-infrared for heavy oils and asphaltenes to the near-UV for gas condensates. The functional form of the electronic absorption edge for all crude oils (measured) is characteristic of the {open_quotes}Urbach tail,{close_quotes} a phenomenology which describes electronic absorption edges in wide-ranging materials. The crude oils all show similar Urbach widths, which are significantly larger than those generally found for various materials but are similar to those previously reported for asphaltenes. Monotonically increasing absorption at higher photon energy continues for all crude oils until the spectral region is reached where single-ring aromatics dominate absorption. However, the rate of increasing absorption at higher energies moderates, thereby deviating from the Urbach behavior. Fluorescence emission spectra exhibit small red shifts from the excitation wavelength and small fluorescence peak widths in the Urbach regions of different crude oils, but show large red shifts and large peak widths in spectral regions which deviate from the Urbach behavior. This observation implies that the Urbach spectral region is dominated by lowest-energy electronic absorption of corresponding chromophores. Thus, the Urbach tail gives a direct measure of the population distribution of chromophores in crude oils. Implied population distributions are consistent with thermally activated growth of large chromophores from small ones. 12 refs., 8 figs.

  12. Combustion Synthesized Cr3+-doped-BaMgAl10O17 Phosphor: An Electron Paramagnetic Resonance and Optical Study

    NASA Astrophysics Data System (ADS)

    Singh, Vijay; Sivaramaiah, G.; Rao, J. L.; Srivastava, Anoop K.; Ravikumar, R. V. S. S. N.; Dhoble, S. J.; Singh, P. K.; Mohapatra, Manoj

    2016-01-01

    BaMgAl10O17 phosphors doped with Cr3+ ions were prepared by a combustion route at a furnace temperature of 773 K. The X-ray diffraction pattern revealed that the BaMgAl10O17 phosphor was in a hexagonal phase. Energy-dispersive X-ray mapping images demonstrated the presence of the dopant ion in the BaMgAl10O17 matrix. The bands observed in the optical absorption spectrum were characteristic of Cr3+ ions in octahedral geometry. Upon 555-nm excitation, an intense narrow red emission line centred at 690 nm due to the 2Eg → 4A2g transition of Cr3+ ions was observed. The electron paramagnetic resonance (EPR) spectrum of Cr3+ ions in BaMgAl10O17 phosphor showed multiple absorption bands having at least 6 g values. Based on the EPR data, various parameters such as the absolute number of spins, Gibbs potential, magnetic susceptibility and magnetic moments, Curie constant, etc., for the system were evaluated.

  13. Bulk Quantum Computation with Pulsed Electron Paramagnetic Resonance: Simulations of Single-Qubit Error Correction Schemes

    NASA Astrophysics Data System (ADS)

    Ishmuratov, I. K.; Baibekov, E. I.

    2015-12-01

    We investigate the possibility to restore transient nutations of electron spin centers embedded in the solid using specific composite pulse sequences developed previously for the application in nuclear magnetic resonance spectroscopy. We treat two types of systematic errors simultaneously: (i) rotation angle errors related to the spatial distribution of microwave field amplitude in the sample volume, and (ii) off-resonance errors related to the spectral distribution of Larmor precession frequencies of the electron spin centers. Our direct simulations of the transient signal in erbium- and chromium-doped CaWO4 crystal samples with and without error corrections show that the application of the selected composite pulse sequences can substantially increase the lifetime of Rabi oscillations. Finally, we discuss the applicability limitations of the studied pulse sequences for the use in solid-state electron paramagnetic resonance spectroscopy.

  14. Study of the effects of hydroxyapatite nanocrystal codoping by pulsed electron paramagnetic resonance methods

    NASA Astrophysics Data System (ADS)

    Gafurov, M. R.; Biktagirov, T. B.; Mamin, G. V.; Shurtakova, D. V.; Klimashina, E. S.; Putlyaev, V. I.; Orlinskii, S. B.

    2016-03-01

    The effect of codoping of hydroxyapatite (HAP) nanocrystals with average sizes of 35 ± 15 nm during "wet" synthesis by CO 3 2- carbonate anions and Mn2+ cations on relaxation characteristics (for the times of electron spin-spin relaxation) of the NO 3 2- nitrate radical anion has been studied. By the example of HAP, it has been demonstrated that the electron paramagnetic resonance (EPR) is an efficient method for studying anion-cation (co)doping of nanoscale particles. It has been shown experimentally and by quantummechanical calculations that simultaneous introduction of several ions can be energetically more favorable than their separate inclusion. Possible codoping models have been proposed, and their energy parameters have been calculated.

  15. Electrochemical electron paramagnetic resonance utilizing loop gap resonators and micro-electrochemical cells.

    PubMed

    Tamski, Mika A; Macpherson, Julie V; Unwin, Patrick R; Newton, Mark E

    2015-09-28

    A miniaturised electrochemical cell design for Electron Paramagnetic Resonance (EPR) studies is reported. The cell incorporates a Loop Gap Resonator (LGR) for EPR investigation of electrochemically generated radicals in aqueous (and other large dielectric loss) samples and achieves accurate potential control for electrochemistry by using micro-wires as working electrodes. The electrochemical behaviour of the cell is analysed with COMSOL finite element models and the EPR sensitivity compared to a commercial TE011 cavity resonator using 4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPOL) as a reference. The electrochemical EPR performance is demonstrated using the reduction of methyl viologen as a redox probe in both water and acetonitrile. The data reported herein suggest that sub-micromolar concentrations of radical species can be detected in aqueous samples with accurate potential control, and that subtle solution processes coupled to electron transfer, such as comproportionation reactions, can be studied quantitatively using EPR. PMID:26291423

  16. Electron paramagnetic resonance study of Fe3+ in α-quartz: Hydrogen-compensated center

    NASA Astrophysics Data System (ADS)

    Mombourquette, M. J.; Minge, J.; Hantehzadeh, M. R.; Weil, J. A.; Halliburton, L. E.

    1989-03-01

    Electron paramagnetic resonance and proton electron-nuclear double-resonance studies of a hydrogen-compensated Fe3+ (S=(5/2) center in synthetic iron-doped α-quartz have been carried out at 20 and 15 K, respectively. The spin-Hamiltonian parameters were determined, allowing anisotropy of the g matrix as well as [g,D,A(1H)]-matrix noncoaxiality, and including high-spin terms of the form S4. Evaluation of the results gives strong evidence that the center (called S2 by some workers) consists of a Fe3+ ion occurring substitutionally at a Si4+ site, charge compensated by an interstitial hydrogen ion. The label [FeO4/H+]0 is proposed for the center.

  17. Calculation of electron paramagnetic resonance spectra from Brownian dynamics trajectories: application to nitroxide side chains in proteins.

    PubMed Central

    Steinhoff, H J; Hubbell, W L

    1996-01-01

    We present a method to simulate electron paramagnetic resonance spectra of spin-labeled proteins that explicitly includes the protein structure in the vicinity of the attached spin label. The method is applied to a spin-labeled polyleucine alpha-helix trimer. From short (6 ns) stochastic dynamics simulations of this trimer, an effective potential energy function is calculated. Interaction with secondary and tertiary structures determine the reorientational motion of the spin label side chains. After reduction to a single particle problem, long stochastic dynamic trajectories (700 ns) of the spin label side-chain reorientation are calculated from which the Lamor frequency trajectory and subsequently the electron paramagnetic resonance spectrum is determined. The simulated spectra agree well with experimental electron paramagnetic resonance spectra of bacteriorhodopsin mutants with spin labels in similar secondary and tertiary environments as in the polyleucine. Images FIGURE 1 PMID:8889196

  18. Electronic structure and spectral properties of paramagnetic point defects in Si3N4

    NASA Astrophysics Data System (ADS)

    Pacchioni, Gianfranco; Erbetta, Davide

    1999-11-01

    The geometric and electronic structure and the optical, vibrational, and magnetic properties of paramagnetic point defects in Si3N4 have been studied by means of ab initio quantum-chemical methods. Using cluster models and gradient-corrected density functional theory or configuration interaction (CI) wave functions, we have studied the N3≡Si• and Si2=N• paramagnetic point defects, also known as K0 and N0 centers, respectively. The computed ground-state properties, in particular the hyperfine coupling constants of N3≡Si• and Si2=N•, the vibrational spectra of the corresponding hydrogenated centers, N3≡Si-H and Si2=N-H, and the valence density of states are correctly described, showing the adequacy of the cluster models used for the study of point defects in silicon nitride. The optical transitions associated with N and K centers have been computed by means of CI calculations. The results are compared with those of the analogous defects in SiO2, the nonbridging oxygen and the E' center, respectively.

  19. Electron Paramagnetic Resonance of a Single NV Nanodiamond Attached to an Individual Biomolecule.

    PubMed

    Teeling-Smith, Richelle M; Jung, Young Woo; Scozzaro, Nicolas; Cardellino, Jeremy; Rampersaud, Isaac; North, Justin A; Šimon, Marek; Bhallamudi, Vidya P; Rampersaud, Arfaan; Johnston-Halperin, Ezekiel; Poirier, Michael G; Hammel, P Chris

    2016-05-10

    Electron paramagnetic resonance (EPR), an established and powerful methodology for studying atomic-scale biomolecular structure and dynamics, typically requires in excess of 10(12) labeled biomolecules. Single-molecule measurements provide improved insights into heterogeneous behaviors that can be masked in ensemble measurements and are often essential for illuminating the molecular mechanisms behind the function of a biomolecule. Here, we report EPR measurements of a single labeled biomolecule. We selectively label an individual double-stranded DNA molecule with a single nanodiamond containing nitrogen-vacancy centers, and optically detect the paramagnetic resonance of nitrogen-vacancy spins in the nanodiamond probe. Analysis of the spectrum reveals that the nanodiamond probe has complete rotational freedom and that the characteristic timescale for reorientation of the nanodiamond probe is slow compared with the transverse spin relaxation time. This demonstration of EPR spectroscopy of a single nanodiamond-labeled DNA provides the foundation for the development of single-molecule magnetic resonance studies of complex biomolecular systems. PMID:27166812

  20. Heteroatom-containing organic electronic oligomers and polymers: Electron paramagnetic resonance studies

    NASA Astrophysics Data System (ADS)

    Brenneman, Keith Richard

    Conjugated conducting polymers are organic materials which can be chemically modified or "doped" to exhibit the property of electrical conduction normally seen only in inorganic materials such as metals. Polyaniline (PAN) is of interest due to the fact that it can be switched between conducting and non-conducting forms without changing its oxidation state. Polythiophene (PT) and polypyrrole (PPy) have a conjugated structure, only the heteroatom (sulfur (S) or nitrogen (N)) is not part of the conducting backbone. However, the morphology and optimal chain length of these polymers are still matters of controversy. In order to explore these issues, X-band (9.5 GHz) electron paramagnetic resonance (EPR) susceptibility (X) and linewidth measurements of the undoped and aqueously camphor sulfonic acid (HCSA)-doped tetramer, octamer, and hexadecamer (oligomers) of aniline, the hexafluorophosphate (PF 6)- and trifluoromethylsulfonate (CF3SO3)-doped polymers of 3,4-ethylenedioxy-thiophene (EDOT) and 3,4-propylenedioxythiophene (ProDOT), and the PF6-doped polymer of 3,4-propylenedioxypyrrole (ProDOP) were undertaken. The undoped oligomer systems exhibit a spin density of ˜1 spin per 500 2-ring repeat units. The doped systems have both Pauli- and Curie-like susceptibility with chiPauli ˜ 40 x 10-6 emu/mole 2-ring repeat units and a localized spin density (nCurie) of ˜1 spin per 50 2-ring repeat units. It also is observed that both the undoped and doped oligomer samples exhibit a decreasing EPR DeltaHPP linewidth with increasing temperature and length, implying increasing delocalization with increasing temperature (intrachain motion) and oligomer length (interchain motion). The aniline oligomer data are compared to results for the undoped and the doped state of PAN. The PT and PPy systems also exhibit both Pauli- and Curie-like susceptibilities. In contrast to the aniline oligomers, it also is observed that both the PT and PPy samples exhibit an increasing EPR Delta

  1. Time-resolved electron paramagnetic resonance of radical pair intermediates in cryptochromes

    NASA Astrophysics Data System (ADS)

    Biskup, Till

    2013-12-01

    Electron transfer plays a key role in many biological systems, including core complexes of photosynthesis and respiration. As this involves unpaired electron spins, electron paramagnetic resonance (EPR) is the method of choice to investigate such processes. Systems that show photo-induced charge separation and electron transfer are of particular interest, as here the processes can easily be synchronised to the experiment and therefore followed directly over its time course. One particular class of proteins, the cryptochromes, showing charge separation and in turn spin-correlated radical pairs upon excitation with blue light, have been investigated by time-resolved EPR spectroscopy in great detail and the results obtained so far are summarised in this contribution. Highlights include the first observation of spin-correlated radical pairs in these proteins, a fact with great impact on the proposed role as key part of a magnetic compass of migratory birds, as well as the assignment of the radical-pair partners and the unravelling of alternative and unexpected electron transfer pathways in these proteins, giving new insights into aspects of biological electron transfer itself.

  2. First-principles calculation of parameters of electron paramagnetic resonance spectroscopy in solids.

    PubMed

    Kadantsev, Eugene S; Ziegler, Tom

    2010-12-01

    The hyperfine A-tensor and Zeeman g-tensor parameterize the interaction of an 'effective' electron spin with the magnetic field due to the nuclear spin and the homogeneous external magnetic field, respectively. The A- and g-tensors are the quantities of primary interest in electron paramagnetic resonance (EPR) spectroscopy. In this paper, we review our work [E.S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2008, 112, 4521; E. S. Kadantsev, T. Ziegler, J. Phys. Chem. A 2009, 113, 1327] on the calculation of these EPR parameters under periodic boundary conditions (PBC) from first-principles. Our methodology is based on the Kohn-Sham DFT (KS DFT), explicit usage of Bloch basis set made up of numerical and Slater-type atomic orbitals (NAOs/STOs), and is implemented in the 'full potential' program BAND. Our implementation does not rely on the frozen core approximation. The NAOs/STOs basis is well suited for the accurate representation of the electron density near the nuclei, a prerequisite for the calculation of highly accurate hyperfine parameters. In the case of g-tensor, our implementation is based on the method of Van Lenthe et al. [E. van Lenthe, P. E. S. Wormer, A. van der Avoird, J. Chem. Phys. 1997, 107, 2488] in which the spin-orbital coupling is taken into account variationally. We demonstrate the viability of our scheme by calculating EPR parameters of paramagnetic defects in solids. We consider the A-tensor of 'normal' and 'anomalous' muonium defect in IIIA-VA semiconductors as well as the S2 anion radical in KCl host crystal lattice. PMID:20821407

  3. Denaturation studies of active-site labeled papain using electron paramagnetic resonance and fluorescence spectroscopy.

    PubMed Central

    Ping, Z A; Butterfiel, D A

    1991-01-01

    A spin-labeled p-chloromercuribenzoate (SL-PMB) and a fluorescence probe, 6-acryloyl-2-dimethylaminonaphthalene (Acrylodan), both of which bind to the single SH group located in the active site of papain, were used to investigate the interaction of papain (EC 3.4.22.2) with two protein denaturants. It was found that the active site of papain was highly stable in urea solution, but underwent a large conformational change in guanidine hydrochloride solution. Electron paramagnetic resonance and fluorescence results were in agreement and both paralleled enzymatic activity of papain with respect to both the variation in pH and denaturation. These results strongly suggest that SL-PMB and Acrylodan labels can be used to characterize the physical state of the active site of the enzyme. PMID:1657229

  4. Electron paramagnetic resonance studies of the tungsten-containing formate dehydrogenase from Clostridium thermoaceticum.

    PubMed

    Deaton, J C; Solomon, E I; Watt, G D; Wetherbee, P J; Durfor, C N

    1987-12-16

    The redox centers in the tungsten-containing formate dehydrogenase from Clostridium thermoaceticum were examined by potentiometric titration and electron paramagnetic resonance spectroscopy. At low temperature two overlapping iron-sulfur signals which correlated with enzymatic activity were observed with formal potentials near -400 mV vs. SHE. Based on their temperature dependences, one signal is assigned to a reduced Fe2S2 cluster and one to a reduced Fe4S4 cluster. Quantitation of signal intensity suggests two Fe2S2 and two Fe4S4 clusters per formate dehydrogenase molecule. Another signal (g = 2.101, 1.980, 1.950) present in low concentrations at more negative potentials was observable up to 200 degrees K and is not attributed to any iron-sulfur cluster. The possible origin of this signal is analyzed using ligand field theory, and the redox behavior is considered with respect to possible ligation at the active site. PMID:2827642

  5. Growth Kinetics of the S Sub H Center on Magnesium Oxide Using Electron Paramagnetic Resonance

    NASA Technical Reports Server (NTRS)

    Jayne, J. P.

    1971-01-01

    Electron paramagnetic resonance spectroscopy was used to study the growth of S sub H centers on magnesium oxide powder which had hydrogen adsorbed on its surface. The centers were produced by ultraviolet radiation. The effects of both radiation intensity and hydrogen pressure were also studied. At constant hydrogen pressure and radiation dose, the initial S sub H center growth rate was found to be zero order. Beyond the initial region the growth rate deviated from zero order and finally approached saturation. The results are interpreted in terms of a model which assumes that the S sub H center is a hydrogen atom associated with a surface vacancy. Saturation appears to result from a limited supply of surface vacancies.

  6. Direct electron paramagnetic resonance study of tobacco. 1. Manganese(ii) as a marker.

    PubMed

    Morsy, M A; Khaled, M M

    2001-02-01

    Three categories of tobacco products were studied using electron paramagnetic resonance (EPR) spectroscopy: Cuban cigar brand name Montecristo, four international trademark cigarettes, and three types of Middle Eastern tobacco blends called Al-Moassal or Jurak. The Montecristo Cuban cigar is used as standard of high-quality tobacco. Mainly two EPR signals from all of the studied samples are observed: a very weak sharp EPR signal superimposed on a broad signal. The broad EPR signal is attributed to a manganese(II) complex. The intensity of the manganese(II) EPR signal is found to be related to the quality of the tobacco content. The sharp signal, which is characteristic of semiquinone radicals, is observed at room temperature, and its intensity increases drastically with temperature. PMID:11262012

  7. Electron Paramagnetic Resonance and DTA Investigation of Cr3+ in Tris(guanidinium) Hexafluoroaluminate Single Crystals

    NASA Astrophysics Data System (ADS)

    Lakshmi Kasturi, T.; Krishnan, V. G.

    1998-05-01

    Electron Paramagnetic Resonance (EPR) studies of Cr 3+ in single crystals of tris(guanidinium) hexafluoroaluminate, [C(NH2)3]3 AlF6 , have been carried out in the X-band region. A temperature dependent study of the zero-field splitting parameter D in the range 77-398 K shows the presence of a phase transition, which is supported by Differential Thermal Analysis. In addition, 19F superhyperfine struc-ture has been observed in the 9.3% naturally abundant 53Cr isotope hyperfine structure. D shows a large decrease with increasing temperature. The phase transition brings about a chemical inequivalence in the two chemically equivalent but magnetically inequivalent room temperature (CrF6)3- species. Compar-ison is made with the alums AlCl3 • 6H20, as well as other guanidinium aluminum salts.

  8. Electron paramagnetic resonance as a quantitative tool for the study of multiwalled carbon nanotubes

    NASA Astrophysics Data System (ADS)

    Coleman, J. N.; O'Brien, D. F.; Dalton, A. B.; McCarthy, B.; Lahr, B.; Barklie, R. C.; Blau, W. J.

    2000-12-01

    We have described a method that maximizes the phase separation of graphitic particles (GP) and multiwalled carbon nanotubes (MWNT) in solutions of various organic polymeric hosts. This involves the formation of sediment and a solute. These components were characterized for MWNT and GP content using electron paramagnetic resonance (EPR) measurements. All EPR signals could be deconvoluted into nanotube and GP components. When normalized, these components are representative of the mass of MWNT and GP present. This allows us to make quantitative measurements of nanotube and GP content in different environments. The most successful polymer host was poly (m-phenylenevinylene-co-2,5-dioctyloxy-p-phenylenevinylene) (PmPV). In this case the solute contained 63% of the added nanotubes with only 2% of the added graphite remaining.

  9. Optically detected electron paramagnetic resonance of AlN single crystals

    NASA Astrophysics Data System (ADS)

    Mason, P. M.; Przybylinska, H.; Watkins, G. D.; Choyke, W. J.; Slack, G. A.

    1999-01-01

    AlN single crystals have been investigated using photoluminescence (PL) and optical detection of electron paramagnetic resonance in the PL (ODEPR). All crystals were found to exhibit intense PL extending from the visible into the near infrared. Several S=1 centers, each with its own distinct emission spectrum, and distant S=1/2 pair recombination centers have been observed via ODEPR. In all except one center, D5, no hyperfine structure was observed preventing chemical identification of the impurity involved. In the case of D5 the partially resolved hyperfine structure suggests interaction with a 100% abundant nucleus of I~5/2. We present arguments to associate it with a displaced host aluminum atom.

  10. Comparison of pulse sequences for R1-based electron paramagnetic resonance oxygen imaging.

    PubMed

    Epel, Boris; Halpern, Howard J

    2015-05-01

    Electron paramagnetic resonance (EPR) spin-lattice relaxation (SLR) oxygen imaging has proven to be an indispensable tool for assessing oxygen partial pressure in live animals. EPR oxygen images show remarkable oxygen accuracy when combined with high precision and spatial resolution. Developing more effective means for obtaining SLR rates is of great practical, biological and medical importance. In this work we compared different pulse EPR imaging protocols and pulse sequences to establish advantages and areas of applicability for each method. Tests were performed using phantoms containing spin probes with oxygen concentrations relevant to in vivo oxymetry. We have found that for small animal size objects the inversion recovery sequence combined with the filtered backprojection reconstruction method delivers the best accuracy and precision. For large animals, in which large radio frequency energy deposition might be critical, free induction decay and three pulse stimulated echo sequences might find better practical usage. PMID:25828242

  11. Study of free radicals in gamma irradiated cellulose of cultural heritage materials using Electron Paramagnetic Resonance

    NASA Astrophysics Data System (ADS)

    Kodama, Yasko; Rodrigues, Orlando, Jr.; Garcia, Rafael Henrique Lazzari; Santos, Paulo de Souza; Vasquez, Pablo A. S.

    2016-07-01

    Main subject of this article was to study room temperature stable radicals in Co-60 gamma irradiated contemporary paper using Electron Paramagnetic Resonance spectrometer (EPR). XRD was used to study the effect of ionizing radiation on the morphology of book paper. SEM images presented regions with cellulose fibers and regions with particles agglomeration on the cellulose fibers. Those agglomerations were rich in calcium, observed by EDS. XRD analysis confirmed presence of calcium carbonate diffraction peaks. The main objective of this study was to propose a method using conventional kinetics chemical reactions for the observed radical formed by ionizing radiation. Therefore, further analyses were made to study the half-life and the kinetics of the free radical created. This method can be suitably applied to study radicals on cultural heritage objects.

  12. Detection of Nitric Oxide by Electron Paramagnetic Resonance Spectroscopy: Spin-Trapping with Iron-Dithiocarbamates.

    PubMed

    Maia, Luisa B; Moura, José J G

    2016-01-01

    Electron paramagnetic resonance (EPR) spectroscopy is the ideal methodology to identify radicals (detection and characterization of molecular structure) and to study their kinetics, in both simple and complex biological systems. The very low concentration and short life-time of NO and of many other radicals do not favor its direct detection and spin-traps are needed to produce a new and persistent radical that can be subsequently detected by EPR spectroscopy.In this chapter, we present the basic concepts of EPR spectroscopy and of some spin-trapping methodologies to study NO. The "strengths and weaknesses" of iron-dithiocarbamates utilization, the NO traps of choice for the authors, are thoroughly discussed and a detailed description of the method to quantify the NO formation by molybdoenzymes is provided. PMID:27094413

  13. Temperature dependent electron paramagnetic resonance (EPR) of SrZrO3

    NASA Astrophysics Data System (ADS)

    Gupta, Santosh K.; Pathak, Nimai; Ghosh, P. S.; Rajeshwari, B.; Natarajan, V.; Kadam, R. M.

    2015-10-01

    SrZrO3 (SZO), a distorted perovskite was synthesized using gel-combustion route employing citric acid as a fuel and ammonium nitrate as oxidizer followed by characterization using X-ray diffraction (XRD) and electron paramagnetic resonance (EPR). Purity of the sample is confirmed by inductively coupled plasma atomic emission spectroscopy (ICP-AES) analysis. Broadening and shift of the resonance field position in EPR spectrum to the lower field was observed as the temperature is lowered; which is the characteristic of ferromagnetic resonance spectra. The value of Curie-Weiss temperature obtained for SZO particles is 8.7 K. The positive sign of the Curie-Weiss temperature indicates that some of the spins are ferromagnetically coupled in this sample. Theoretical investigation using density functional theory (DFT) calculation revealed that Vacancy at zirconium site contribute maximum to the magnetic moment.

  14. An alternative method using microwave power saturate in fingernail/electron paramagnetic resonance dosimetry.

    PubMed

    Choi, Hoon; Park, Byeongryong; Choi, Muhyun; Lee, Byungil; Lee, Cheol Eui

    2014-06-01

    An alternative method for fingernail/electron paramagnetic resonance (EPR) dosimetry valid at low doses (0-3 Gy) is suggested in this paper. The method consisted of two steps. The first step involved dehydrating fingernail clippings to remove their water content by heating them at 70 °C for 72 h. As the water content in the fingernails decreased, the variability of the EPR signals improved. The second step involved measuring and fitting the EPR signals at successive microwave power levels. A newly derived value known as 'curvature', which was based on the conventional peak-to-peak amplitudes of the EPR signals, was applied for the dosimetry. This method could be used as an alternative method in cases of low-radiation exposure doses (<3 Gy) or where use of the conventional dosimetry method is not proper for a fingernail sample. PMID:24876339

  15. Comparison of pulse sequences for R1-based electron paramagnetic resonance oxygen imaging

    NASA Astrophysics Data System (ADS)

    Epel, Boris; Halpern, Howard J.

    2015-05-01

    Electron paramagnetic resonance (EPR) spin-lattice relaxation (SLR) oxygen imaging has proven to be an indispensable tool for assessing oxygen partial pressure in live animals. EPR oxygen images show remarkable oxygen accuracy when combined with high precision and spatial resolution. Developing more effective means for obtaining SLR rates is of great practical, biological and medical importance. In this work we compared different pulse EPR imaging protocols and pulse sequences to establish advantages and areas of applicability for each method. Tests were performed using phantoms containing spin probes with oxygen concentrations relevant to in vivo oxymetry. We have found that for small animal size objects the inversion recovery sequence combined with the filtered backprojection reconstruction method delivers the best accuracy and precision. For large animals, in which large radio frequency energy deposition might be critical, free induction decay and three pulse stimulated echo sequences might find better practical usage.

  16. Electron paramagnetic resonance linewidths and line shapes for the molecular magnets Fe8 and Mn12

    NASA Astrophysics Data System (ADS)

    Park, Kyungwha; Novotny, M. A.; Dalal, N. S.; Hill, S.; Rikvold, P. A.

    2002-05-01

    We study theoretically electron paramagnetic resonance (EPR) linewidths for single crystals of the molecular magnets Fe8 and Mn12 as functions of energy eigenstates Ms, frequency, and temperature when a magnetic field along the easy axis is swept at fixed excitation frequency. This work was motivated by recent EPR experiments. To calculate the linewidths, we use density-matrix equations, including dipolar interactions and distributions of the uniaxial anisotropy parameter D and the Landé g factor. Our calculated linewidths agree well with the experimental data. We also examine the line shapes of the EPR spectra due to local rotations of the magnetic anisotropy axes caused by defects in samples. Our preliminary results predict that this effect leads to asymmetry in the EPR spectra.

  17. Imaging of Nitroxides at 250 MHz using Rapid-Scan Electron Paramagnetic Resonance

    PubMed Central

    Biller, Joshua R.; Tseitlin, Mark; Quine, Richard W.; Rinard, George A.; Weismiller, Hilary A.; Elajaili, Hanan; Rosen, Gerald M.; Kao, Joseph P. Y.; Eaton, Sandra S.; Eaton, Gareth R.

    2014-01-01

    Projections for 2D spectral-spatial images were obtained by continuous wave and rapid-scan electron paramagnetic resonance using a bimodal cross-loop resonator at 251 MHz. The phantom consisted of three 4 mm tubes containing different 15N,2H-substituted nitroxides. Rapid-scan and continuous wave images were obtained with 5 min total acquisition times. For comparison, images also were obtained with 29 s acquisition time for rapid scan and 15 min for continuous wave. Relative to continuous wave projections obtained for the same data acquisition time, rapid-scan projections had significantly less low-frequency noise and substantially higher signal-to-noise at higher gradients. Because of the improved image quality for the same data acquisition time, linewidths could be determined more accurately from the rapid-scan images than from the continuous wave images. PMID:24650729

  18. Vector electron paramagnetic resonance spectroscopy with first and second harmonic displays of ferrihemoglobin.

    PubMed

    Watari, H; Murakami, M; Seo, Y; Shimoyama, Y

    1989-07-31

    Superimposed plots of electron paramagnetic resonance spectra with the first and second harmonic displays of ferrihemoglobin at pH 9.1 and 90 K were measured at 20 degree intervals of phase angle using a phase-sensitive detector. The high spin signal in the g = 6 region was observed in both displays, and a small splitting of the signal was found in the calculated amplitude spectrum of the second harmonic display, with g values of 5.95 and 6.05. Low spin signals were observed at g = 2.55, 2.25 and 1.82 in both harmonic displays. A signal in the g = 2.05 region was observed only in the second harmonic display. The signal is probably associated with the low spin spectrum; however, its origin is obscure. PMID:2547369

  19. Evaluation of adriamycin nephropathy by an in vivo electron paramagnetic resonance

    SciTech Connect

    Oteki, Takaaki; Nagase, Sohji . E-mail: sohji-n@md.tsukuba.ac.jp; Yokoyama, Hidekatsu; Ohya, Hiroaki; Akatsuka, Takao; Tada, Mika; Ueda, Atsushi; Hirayama, Aki; koyama, Akio

    2005-07-01

    A rat model for human minimal change nephropathy was obtained by the intravenous injection of adriamycin (ADR) at 5 mg/kg. By using an in vivo electron paramagnetic resonance (EPR) spectrometer operating at 700 MHz, the temporal changes in signal intensities of a nitroxide radical, 4-hydroxyl-2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPOL), in the kidneys of rats with ADR nephropathy were investigated. The decay rate of the EPR signal intensity obtained in the kidney is indicative of the renal reducing ability. It was found that the reducing ability in the kidney declined on the 7th day after ADR administration and recovered after the 14th day. Impairment of the reducing ability occurred before the appearance of continuous urinary protein. The in vitro EPR study showed that this impairment of in vivo renal reducing ability is related to impairment of the reducing ability in the mitochondria.

  20. Age of an Indonesian Fossil Tooth Determined by Electron Paramagnetic Resonance

    SciTech Connect

    Bogard, JS

    2004-04-07

    The first fossil hominid tooth recovered during 1999 excavations from the Cisanca River region in West Java, Indonesia, was associated with a series of bovid teeth from a single individual that was recovered 190 cm beneath the hominid tooth. The age of the fossil bovid teeth was determined using electron paramagnetic resonance (EPR) analysis as part of an effort to bracket the age of the hominid tooth. The EPR-derived age of the bovid teeth is (5.16 {+-} 2.01) x 10{sup 5} years. However, the age estimate reported here is likely an underestimate of the actual age of deposition since evidence of heating was detected in the EPR spectra of the bovid teeth, and the heating may have caused a decrease in the intensity of EPR components on which the age calculation is based.

  1. Electron paramagnetic resonance spectroscopy in radiation research: Current status and perspectives

    PubMed Central

    Rana, Sudha; Chawla, Raman; Kumar, Raj; Singh, Shefali; Zheleva, Antoaneta; Dimitrova, Yanka; Gadjeva, Veselina; Arora, Rajesh; Sultana, Sarwat; Sharma, Rakesh Kumar

    2010-01-01

    Exposure to radiation leads to a number of health-related malfunctions. Ionizing radiation is more harmful than non-ionizing radiation, as it causes both direct and indirect effects. Irradiation with ionizing radiation results in free radical-induced oxidative stress. Free radical-mediated oxidative stress has been implicated in a plethora of diseased states, including cancer, arthritis, aging, Parkinson's disease, and so on. Electron Paramagnetic Resonance (EPR) spectroscopy has various applications to measure free radicals, in radiation research. Free radicals disintegrate immediately in aqueous environment. Free radicals can be detected indirectly by the EPR spin trapping technique in which these forms stabilize the radical adduct and produce characteristic EPR spectra for specific radicals. Ionizing radiation-induced free radicals in calcified tissues, for example, teeth, bone, and fingernail, can be detected directly by EPR spectroscopy, due to their extended stability. Various applications of EPR in radiation research studies are discussed in this review. PMID:21814437

  2. Electron paramagnetic resonance of Cr3+ in near-stoichiometric LiTaO3

    NASA Astrophysics Data System (ADS)

    Loyo-Menoyo, M.; Keeble, D. J.; Furukawa, Y.; Kitamura, K.

    2005-06-01

    Electron-paramagnetic-resonance (EPR) experiments on the dominant Cr3+ center in near-stoichiometric LiTaO3 crystals, grown by the double crucible Czochralski method, are reported. A near complete roadmap of EPR positions was obtained allowing an accurate determination of the spin-Hamiltonian parameters. Newman superposition model calculations of zero-field splitting term were performed and support the model of Cr3+ incorporation within the Li octahedron. Calculations were also made for Cr3+ in LiNbO3, again good agreement with a Li site model was obtained for the main EPR center. The temperature dependence of the zero-field splitting parameter for Cr3+ in LiTaO3 was found to show anomalous behavior in the region of 40 K, suggesting the presence local structural instability at the ion site.

  3. Electron Paramagnetic Resonance (EPR) Studies of Near-Surface Magnetic Properties of YBCO Thin Films

    NASA Astrophysics Data System (ADS)

    Pugel, D. E.; Xia, Y.-M.; Salamon, M. B.; Greene, L. H.

    2000-03-01

    Several thin film planar tunneling experiments are consistent with a broken time-reversal symmetry (BTRS) state [1-4].To compliment tunneling measurements, we have developed a technique to measure electron paramagnetic resonance (EPR) effects of the near-surface region of a superconductor. Preliminary data are consistent with the spontaneous formation of magnetic moments at low temperature on YBCO thin films and may prove to be an important confirmation of BTRS. 1. Covington,M. et al., Phys. Rev. Lett., 79, 277, (1997). 2. Kashiwaya, S. et al., J. Phys. Chem. Solids, 59, 2034, (1997). 3. Krupke, R. and Deutscher,G., Phys. Rev. Lett., 83, 4634, (1999). 4. Lesueur,J., Grison,X., Aprili,M. and Kontos,T., cond-mat/9909212. -------------------------------------------------------------

  4. Comparison of Pulse Sequences for R1–based Electron Paramagnetic Resonance Oxygen Imaging

    PubMed Central

    Epel, Boris; Halpern, Howard J.

    2015-01-01

    Electron paramagnetic resonance (EPR) spin-lattice relaxation (SLR) oxygen imaging has proven to be an indispensable tool for assessing oxygen partial pressure in live animals. EPR oxygen images show remarkable oxygen accuracy when combined with high precision and spatial resolution. Developing more effective means for obtaining SLR rates is of great practical, biological and medical importance. In this work we compared different pulse EPR imaging protocols and pulse sequences to establish advantages and areas of applicability for each method. Tests were performed using phantoms containing spin probes with oxygen concentrations relevant to in vivo oxymetry. We have found that for small animal size objects the inversion recovery sequence combined with the filtered backprojection reconstruction method delivers the best accuracy and precision. For large animals, in which large radio frequency energy deposition might be critical, free induction decay and three pulse stimulated echo sequences might find better practical usage. PMID:25828242

  5. Characterization of radiation-induced damage in high performance polymers by electron paramagnetic resonance imaging spectroscopy

    NASA Technical Reports Server (NTRS)

    Suleman, Naushadalli K.

    1992-01-01

    The potential for long-term human activity beyond the Earth's protective magnetosphere is limited in part by the lack of detailed information on the effectiveness and performance of existing structural materials to shield the crew and spacecraft from highly penetrating space radiations. The two radiations of greatest concern are high energy protons emitted during solar flares and galactic cosmic rays which are energetic ions ranging from protons to highly oxidized iron. Although the interactions of such high-energy radiations with matter are not completely understood at this time, the effects of the incident radiation are clearly expected to include the formation of paramagnetic spin centers via ionization and bond-scission reactions in the molecular matrices of structural materials. Since this type of radiation damage is readily characterized by Electron Paramagnetic Resonance (EPR) spectroscopy, the NASA Langley Research Center EPR system was repaired and brought on-line during the 1991 ASEE term. A major goal of the 1992 ASEE term was to adapt the existing core of the LaRC EPR system to meet the requirements for EPR Imaging--a powerful new technique which provides detailed information on the internal structure of materials by mapping the spatial distribution of unpaired spin density in bulk media. Major impetus for this adaptation arises from the fact that information derived from EPRI complements other methods such as scanning electron microscopy which primarily characterize surface phenomena. The modification of the EPR system has been initiated by the construction of specially designed, counterwound Helmholtz coils which will be mounted on the main EPR electromagnet. The specifications of the coils have been set to achieve a static linear magnetic field gradient of 10 gauss/mm/amp along the principal (Z) axis of the Zeeman field. Construction is also in progress of a paramagnetic standard in which the spin distribution is known in all three dimensions. This

  6. A Spectrometer for Dynamic Nuclear Polarization and Electron Paramagnetic Resonance at High Frequencies

    NASA Astrophysics Data System (ADS)

    Becerra, L. R.; Gerfen, G. J.; Bellew, B. F.; Bryant, J. A.; Hall, D. A.; Inati, S. J.; Weber, R. T.; Un, S.; Prisner, T. F.; McDermott, A. E.; Fishbein, K. W.; Kreischer, K. E.; Temkin, R. J.; Singel, D. J.; Griffin, R. G.

    A high-frequency dynamic nuclear polarization (DNP)/electron paramagnetic resonance spectrometer operating at 211 MHz for 1H and 140 GHz for g= 2 paramagnetic centers (5 T static field) is described. The salient feature of the instrument is a cyclotron-resonance maser (gyrotron) which generates high-frequency, high-power microwave radiation. This gyrotron, which under conventional operation produces millisecond pulses at kilowatt powers, has been adapted to operate at ˜100 W for 1 to 20 s pulses and in the continuous wave mode at the 10 W power level. Experiments combining DNP with magic-angle spinning (MAS) nuclear magnetic resonance were performed on samples consisting of 2% by weight of the free radical BDPA doped into polystyrene. Room-temperature DNP enhancement factors of 10 for 1H and 40 for 13C were obtained in the NMR-MAS spectra. Static DNP NMR has also been performed on samples containing nitroxides dissolved in water:glycerol solvent mixtures. Enhancements of approximately 200 have been obtained for low-temperature (14 K) 1H NMR. A pulsed/CW EPR spectrometer operating at 140 GHz has been developed in conjunction with the DNP spectrometer. Microwave sources include Gunn-diode oscillators which provide low-power (20 mW) radiation, and the gyrotron, which has been used to deliver higher power levels in pulsed experiments. Results using this spectrometer are presented for continuous-wave and echo-detected EPR, electron spin-echo-envelope modulation (ESEEM), and Fourier-transform EPR.

  7. Combustion Synthesized Europium Doped LaAI₁₁O₁₈ Phosphors--An Electron Paramagnetic Resonance and Optical Study.

    PubMed

    Singh, Vijay; Sivaramaiah, G; Rao, J L; Kumaran, R Senthil; Dhoble, S J

    2016-01-01

    By adopting a facile solution combustion synthesis, crystallized europium doped blue phosphors were successfully prepared. These phosphors were characterized by X-ray diffraction (XRD), Fourier transform infrared absorption (FT-IR), energy dispersive analysis of X-ray, Electron Paramagnetic Resonance (EPR) and Photoluminescence (PL) experimental methods. The photoluminescence spectrum indicates Eu²⁺ and Eu³⁺ ions in these phosphors. The band at around 442 nm is attributed to the spin-allowed 4f⁶5d¹ (2D) --> 4f⁷(⁸S₇/2) transition of Eu²⁺ ions. The sharp bands at 591 (⁵D₀ --> ⁷F₁) and 616 (⁵D₀ --> ⁷F₂) nm are attributed to the spin-forbidden transitions of Eu³⁺ ions. The EPR spectra of as-prepared and post-treated LaAl₁₁O₁₈:Eu phosphors exhibit signals characteristic of La²⁺ and Eu²⁺ ions. The number of spins, Gibbs energy, magnetic susceptibility, Curie constant and effective magnetic moment values were calculated and compared at 296 and 110 K. PMID:27398524

  8. Strong impact of lattice vibrations on electronic and magnetic properties of paramagnetic Fe revealed by disordered local moments molecular dynamics

    NASA Astrophysics Data System (ADS)

    Alling, B.; Körmann, F.; Grabowski, B.; Glensk, A.; Abrikosov, I. A.; Neugebauer, J.

    2016-06-01

    We study the impact of lattice vibrations on magnetic and electronic properties of paramagnetic bcc and fcc iron at finite temperature, employing the disordered local moments molecular dynamics (DLM-MD) method. Vibrations strongly affect the distribution of local magnetic moments at finite temperature, which in turn correlates with the local atomic volumes. Without the explicit consideration of atomic vibrations, the mean local magnetic moment and mean field derived magnetic entropy of paramagnetic bcc Fe are larger compared to paramagnetic fcc Fe, which would indicate that the magnetic contribution stabilizes the bcc phase at high temperatures. In the present study we show that this assumption is not valid when the coupling between vibrations and magnetism is taken into account. At the γ -δ transition temperature (1662 K), the lattice distortions cause very similar magnetic moments of both bcc and fcc structures and hence magnetic entropy contributions. This finding can be traced back to the electronic densities of states, which also become increasingly similar between bcc and fcc Fe with increasing temperature. Given the sensitive interplay of the different physical excitation mechanisms, our results illustrate the need for an explicit consideration of vibrational disorder and its impact on electronic and magnetic properties to understand paramagnetic Fe. Furthermore, they suggest that at the γ -δ transition temperature electronic and magnetic contributions to the Gibbs free energy are extremely similar in bcc and fcc Fe.

  9. Assessment of melanoma extent and melanoma metastases invasion using electron paramagnetic resonance and bioluminescence imaging.

    PubMed

    Godechal, Quentin; Defresne, Florence; Danhier, Pierre; Leveque, Philippe; Porporato, Paolo Ettore; Sonveaux, Pierre; Baurain, Jean-François; Feron, Olivier; Gallez, Bernard

    2011-01-01

    The clinical outcome of melanoma depends on the local and distant spread of the disease at the time of diagnosis, as the estimated 5-year survival rate is about 100% for superficial melanoma diagnosed early, but less than 10% for melanoma that has disseminated to major organs such as lungs. There is a crucial need for new effective methods for the detection and the characterization of melanomas. In the pre-clinical setting, this will help to understand the factors that contribute to the malignancy while the transfer into the clinic will contribute to an early effective treatment of patients. Melanoma lesions can be detected by electron paramagnetic resonance (EPR) using paramagnetic properties of melanin pigments. As part of the development of EPR imaging to characterize melanomas, we evaluated in the present study the usefulness of EPR to report on the extension of lung metastases by comparing the method with bioluminescence imaging using B16 melanoma cells expressing luciferase. B16 melanoma cells were injected subcutaneously or intravenously in C57/BL6 mice. The primary tumors or the lung colonization by melanoma cells was measured after several delay periods to obtain several degrees of invasiveness. The animals were measured in-vivo with bioluminescence after i.v. injection of luciferin. The primary tumors or lungs were then excised. After freeze-drying, the content of melanin in lungs was measured and imaged by EPR at 9 GHz. We observed a direct relationship between the EPR intensity and the bioluminescence intensity. Another tumor model (KHT sarcoma), non-pigmented but expressing luciferase, was used to confirm that the EPR signal was directly linked to the melanin pigment present in the tumors. PMID:21861288

  10. Temperature dependence on the electron paramagnetic resonance spectra of natural jasper from Taroko Gorge (Taiwan)

    NASA Astrophysics Data System (ADS)

    Hemantha Kumar, G. N.; Parthasarathy, G.; Chakradhar, R. P. S.; Rao, J. Lakshmana; Ratnakaram, Y. C.

    2010-04-01

    Structural properties of natural jasper from Taroko Gorge (Taiwan) have been investigated by means of powder X-ray diffraction, electron paramagnetic resonance (EPR) and Fourier transform infrared spectroscopic techniques. The EPR spectrum at room temperature exhibits a sharp resonance signal at g = 2.007 and two more resonance signals centered at g ≈ 4.3 and 14.0. The resonance signal at g = 2.007 has been attributed to the E' center and is related to a natural radiation-induced paramagnetic defect. Two more resonance signals centered at g ≈ 4.3 and 14.0 are characteristic of Fe3+ ions. The EPR spectra recorded at room temperature of jasper samples, heat-treated at temperatures ranging from 473 to 1,473 K exhibit marked temperature dependence. The resonance signal corresponding to E' center disappears at elevated temperatures. A broad, intense resonance signal centered at g ≈ 2.0 appears at elevated temperatures. This resonance signal is a characteristic of Fe3+ ions, which are present as hematite in the jasper sample. The intensity of the resonance signal becomes dominant at elevated temperatures at ≥873 K, masking g ≈ 4.3 and g ≈ 14.0 resonance signals. The EPR spectra of jasper heat-treated at 673 K have been recorded at temperatures between 123 and 296 K. The population of spin levels ( N) has been calculated for the broad g ≈ 2.0 resonance signal. It is found that N decreases with decreasing temperature. The linewidth (ΔH) of g ≈ 2.0 resonance signal of the heat-treated jasper is found to increase with decreasing temperature. This has been attributed to spin-spin interaction of the Fe3+ ions present in the form of hematite in the studied jasper sample.

  11. Ageing and thermal recovery of paramagnetic centers induced by electron irradiation in yttria-stabilized zirconia

    NASA Astrophysics Data System (ADS)

    Costantini, J. M.; Beuneu, F.

    We have used electron spin resonance spectroscopy to study the defects induced in yttria-stabilized zirconia (YSZ) single crystals by 2.5-MeV electron irradiations. Two paramagnetic centers are produced: the first one with an axial <111> symmetry is similar to the trigonal Zr3+ electron center (T center) found after X-ray irradiation or thermo-chemical reduction, whereas the second one is a new oxygen hole center with an axial <100> symmetry different from the orthorhombic O- center induced by X-ray irradiation. At a fluence around 10(18) e/cm(2) , both centers are bleached out near 600 K, like the corresponding X-ray induced defects. At a fluence around 10(19) e/cm(2) , defects are much more stable, since complete thermal bleaching occurs near 1000 K. Accordingly, ageing of as-irradiated samples shows that high-dose defects at more stable than the low-dose ones.

  12. Polynuclear water-soluble dinitrosyl iron complexes with cysteine or glutathione ligands: electron paramagnetic resonance and optical studies.

    PubMed

    Vanin, Anatoly F; Poltorakov, Alexander P; Mikoyan, Vasak D; Kubrina, Lyudmila N; Burbaev, Dosymzhan S

    2010-09-15

    Electron paramagnetic resonance and optical spectrophotometric studies have demonstrated that low-molecular dinitrosyl iron complexes (DNICs) with cysteine or glutathione exist in aqueous solutions in the form of paramagnetic mononuclear (capital EM, Cyrillic-DNICs) and diamagnetic binuclear complexes (B-DNICs). The latter represent Roussin's red salt esters and can be prepared by treatment of aqueous solutions of Fe(2+) and thiols (small er, Cyrilliccapital EN, Cyrillic 7.4) with gaseous nitric oxide (NO) at the thiol:Fe(2+) ratio 1:1. capital EM, Cyrillic-DNICs are synthesized under identical conditions at the thiol:Fe(2+) ratios above 20 and produce an EPR signal with an electronic configuration {Fe(NO)(2)}(7) at g(aver.)=2.03. At neutral pH, aqueous solutions contain both M-DNICs and B-DNICs (the content of the latter makes up to 50% of the total DNIC pool). The concentration of B-DNICs decreases with a rise in pH; at small er, Cyrilliccapital EN, Cyrillic 9-10, the solutions contain predominantly M-DNICs. The addition of thiol excess to aqueous solutions of B-DNICs synthesized at the thiol:Fe(2+) ratio 1:2 results in their conversion into capital EM, Cyrillic-DNICs, the total amount of iron incorporated into M-DNICs not exceeding 50% of the total iron pool in B-DNICs. Air bubbling of cys-capital EM, Cyrillic-DNIC solutions results in cysteine oxidation-controlled conversion of capital EM, Cyrillic-DNICs first into cys-B-DNICs and then into the EPR-silent compound capital HA, Cyrillic able to generate a strong absorption band at 278 nm. In the presence of glutathione or cysteine excess, compound capital HA, Cyrillic is converted into B-DNIC/M-DNIC and is completely decomposed under effect of the Fe(2+) chelator small o, Cyrillic-phenanthroline or N-methyl-d-glucamine dithiocarbamate (MGD). Moreover, MGD initiates the synthesis of paramagnetic mononitrosyl iron complexes with MGD. It is hypothesized that compound capital HA, Cyrillic represents a polynuclear

  13. Coordination and ion-ion interactions of chromium centers in alkaline earth zinc borate glasses probed by electron paramagnetic resonance and optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Sumalatha, B.; Omkaram, I.; Rajavardana Rao, T.; Linga Raju, Ch

    2013-05-01

    Electron paramagnetic resonance (EPR), optical absorption and FT-IR studies have been carried out on chromium ions incorporated in alkaline earth zinc borate glasses. The EPR spectra exhibit two resonance signals with effective g values at g ≈ 1.99 and ≈1.97. The resonance signal at g ≈ 1.99 is attributed to the contribution from both the exchange coupled Cr3+-Cr3+ ion pairs and the isolated Cr3+ ions and the resonance signal at g ≈ 1.97 is due to Cr5+ ions. The paramagnetic susceptibility (χ) was calculated from the EPR data at various (123-303 K) temperatures and the Curie temperature (θp) was calculated from the 1/χ-T graph. The optical absorption spectra exhibit three bands at ˜360 nm, ˜440 nm and a broad band at ˜615 nm characteristic of Cr3+ ions in an octahedral symmetry. From the observed band positions, the crystal-field splitting parameter Dq and the Racah parameters (B and C) have been evaluated. From the ultraviolet edges, the optical band gap energies (Eopt) and Urbach energy (ΔE) are calculated. The theoretical optical basicity (Λth) of these glasses has also been evaluated. Chromium ions doped alkaline earth zinc borate glasses show BO3 and BO4 structural units in the FT-IR studies.

  14. Electron paramagnetic resonance study of a photosynthetic microbial mat and comparison with Archean cherts.

    PubMed

    Bourbin, M; Derenne, S; Gourier, D; Rouzaud, J-N; Gautret, P; Westall, F

    2012-12-01

    Organic radicals in artificially carbonized biomass dominated by oxygenic and non-oxygenic photosynthetic bacteria, Microcoleus chthonoplastes-like and Chloroflexus-like bacteria respectively, were studied by Electron Paramagnetic Resonance (EPR) spectroscopy. The two bacteria species were sampled in mats from a hypersaline lake. They underwent accelerated ageing by cumulative thermal treatments to induce progressive carbonization of the biological material, mimicking the natural maturation of carbonaceous material of Archean age. For thermal treatments at temperatures higher than 620 °C, a drastic increase in the EPR linewidth is observed in the carbonaceous matter from oxygenic photosynthetic bacteria and not anoxygenic photosynthetic bacteria. This selective EPR linewidth broadening reflects the presence of a catalytic element inducing formation of radical aggregates, without affecting the molecular structure or the microstructure of the organic matter, as shown by Raman spectroscopy and Transmission Electron Microscopy. For comparison, we carried out an EPR study of organic radicals in silicified carbonaceous rocks (cherts) from various localities, of different ages (0.42 to 3.5 Gyr) and having undergone various degrees of metamorphism, i.e. various degrees of natural carbonization. EPR linewidth dispersion for the most primitive samples was quite significant, pointing to a selective dipolar broadening similar to that observed for carbonized bacteria. This surprising result merits further evaluation in the light of its potential use as a marker of past bacterial metabolisms, in particular oxygenic photosynthesis, in Archean cherts. PMID:23254854

  15. Defects in paramagnetic Co-doped ZnO films studied by transmission electron microscopy

    SciTech Connect

    Kovács, A.; Duchamp, M.; Boothroyd, C. B.; Dunin-Borkowski, R. E.; Ney, A.; Ney, V.; Galindo, P. L.; Kaspar, T. C.; Chambers, S. A.

    2013-12-28

    We study planar defects in epitaxial Co:ZnO dilute magnetic semiconductor thin films deposited on c-plane sapphire (Al{sub 2}O{sub 3}), as well as the Co:ZnO/Al{sub 2}O{sub 3} interface, using aberration-corrected transmission electron microscopy and electron energy-loss spectroscopy. Co:ZnO samples that were deposited using pulsed laser deposition and reactive magnetron sputtering are both found to contain extrinsic stacking faults, incoherent interface structures, and compositional variations within the first 3–4 Co:ZnO layers next to the Al{sub 2}O{sub 3} substrate. The stacking fault density is in the range of 10{sup 17} cm{sup −3}. We also measure the local lattice distortions around the stacking faults. It is shown that despite the relatively high density of planar defects, lattice distortions, and small compositional variation, the Co:ZnO films retain paramagnetic properties.

  16. Electron paramagnetic resonance and optical spectroscopy of Er-doped β-Ga2O3

    NASA Astrophysics Data System (ADS)

    Vincent, J.; Guillot-Noël, O.; Binet, L.; Aschehoug, P.; Le Du, Y.; Beaudoux, F.; Goldner, P.

    2008-08-01

    Conducting β-Ga2O3 single crystals doped with Er3+ were grown using the floating zone method. Electron paramagnetic resonance (EPR) showed that conduction electrons can coexist with the Er3+ dopant. Optical and EPR characterizations of samples nominally doped with 0.5% and 1.5% were performed at low temperature showing that erbium substitution into β-Ga2O3 can only be achieved effectively at the lower concentration because of the appearance of an erbium gallium garnet phase when the erbium concentration is increased. Despite the existence of two cationic sites in β-Ga2O3, EPR measurements demonstrate that Er incorporation occurs at a single crystallographic position. Optical spectroscopy of 0.5% doped samples of the 1.5μm transition allowed us to determine some crystal field levels of the I15/24 and I13/24 multiplets. A lifetime of about 12ms was found for the 1.5μm emission, indicating a high quantum yield for the I13/24 multiplet.

  17. Electron Paramagnetic Resonance Study of a Photosynthetic Microbial Mat and Comparison with Archean Cherts

    NASA Astrophysics Data System (ADS)

    Bourbin, M.; Derenne, S.; Gourier, D.; Rouzaud, J.-N.; Gautret, P.; Westall, F.

    2012-12-01

    Organic radicals in artificially carbonized biomass dominated by oxygenic and non-oxygenic photosynthetic bacteria, Microcoleus chthonoplastes-like and Chloroflexus-like bacteria respectively, were studied by Electron Paramagnetic Resonance (EPR) spectroscopy. The two bacteria species were sampled in mats from a hypersaline lake. They underwent accelerated ageing by cumulative thermal treatments to induce progressive carbonization of the biological material, mimicking the natural maturation of carbonaceous material of Archean age. For thermal treatments at temperatures higher than 620 °C, a drastic increase in the EPR linewidth is observed in the carbonaceous matter from oxygenic photosynthetic bacteria and not anoxygenic photosynthetic bacteria. This selective EPR linewidth broadening reflects the presence of a catalytic element inducing formation of radical aggregates, without affecting the molecular structure or the microstructure of the organic matter, as shown by Raman spectroscopy and Transmission Electron Microscopy. For comparison, we carried out an EPR study of organic radicals in silicified carbonaceous rocks (cherts) from various localities, of different ages (0.42 to 3.5 Gyr) and having undergone various degrees of metamorphism, i.e. various degrees of natural carbonization. EPR linewidth dispersion for the most primitive samples was quite significant, pointing to a selective dipolar broadening similar to that observed for carbonized bacteria. This surprising result merits further evaluation in the light of its potential use as a marker of past bacterial metabolisms, in particular oxygenic photosynthesis, in Archean cherts.

  18. Determination of very rapid molecular rotation by using the central electron paramagnetic resonance line.

    PubMed

    Kurban, Mark R

    2013-02-21

    Picosecond rotational correlation times of perdeuterated tempone (PDT) are found in alkane and aromatic liquids by directly using the spectral width of the central electron paramagnetic resonance line. This is done by mathematically eliminating the nonsecular spectral density from the spectral parameter equations, thereby removing the need to assume a particular form for it. This is preferable to fitting a constant correction factor to the spectral density, because such a factor does not fit well in the low picosecond range. The electron-nuclear spin dipolar interaction between the probe and solvent is shown to be negligible for the very rapid rotation of PDT in these liquids at the temperatures of the study. The rotational correlation times obtained with the proposed method generally agree to within experimental uncertainty with those determined by using the traditional parameters. Using the middle line width offers greater precision and smoother trends. Previous work with the central line width is discussed, and past discrepancies are explained as possibly resulting from residual inhomogeneous broadening. The rotational correlation time almost forms a common curve across all of the solvents when plotted with respect to isothermal compressibility, which shows the high dependence of rotation on liquid free volume. PMID:23320940

  19. Formation and reactions of paramagnetic species in irradiated microheterogeneous copolymer systems with different electronic characteristics of components

    NASA Astrophysics Data System (ADS)

    Zezin, A. A.; Feldman, V. I.

    2002-01-01

    The formation of paramagnetic species in the radiolysis of styrene-butadiene block copolymers and interpolymers of polystyrene and polytrichlorobutadiene was studied at 77 K using ESR spectroscopy. The results obtained reveal substantial non-additive effects in the radical yields. In the case of interpolymers, the observed yields are higher than the expected additive values (sensitization), whereas in the case of block copolymers the effect has the opposite sign (protection). The analysis of paramagnetic species demonstrates that the observed peculiarities result from interphase migration of electrons followed by their reactions with chemical traps (chlorinated groups or neutral radicals). It was concluded that the long-range reactions of electrons were controlled by electronic characteristics of microphases.

  20. Use of Electron Paramagnetic Resonance Spectroscopy to Evaluate the Redox State In Vivo

    PubMed Central

    SWARTZ, HAROLD M.; KHAN, NADEEM; KHRAMTSOV, VALERY V.

    2009-01-01

    The aim of this article is to provide an overview of how electron paramagnetic resonance (EPR) can be used to measure redox-related parameters in vivo. The values of this approach include that the measurements are made under fully physiological conditions, and some of the measurements cannot be made by other means. Three complementary approaches are used with in vivo EPR: the rate of reduction or reactions of nitroxides, spin trapping of free radicals, and measurements of thiols. All three approaches already have produced unique and useful information. The measurement of the rate of decrease of nitroxides technically is the simplest, but difficult to interpret because the measured parameter, reduction in the intensity of the nitroxide signal, can occur by several different mechanisms. In vivo spin trapping can provide direct evidence for the occurrence of specific free radicals in vivo and reflect relative changes, but accurate absolute quantification remains challenging. The measurement of thiols in vivo also appears likely to be useful, but its development as an in vivo technique is at an early stage. It seems likely that the use of in vivo EPR to measure redox processes will become an increasingly utilized and valuable tool. PMID:17678441

  1. Training effects on ROS production determined by electron paramagnetic resonance in master swimmers.

    PubMed

    Mrakic-Sposta, Simona; Gussoni, Maristella; Porcelli, Simone; Pugliese, Lorenzo; Pavei, Gaspare; Bellistri, Giuseppe; Montorsi, Michela; Tacchini, Philippe; Vezzoli, Alessandra

    2015-01-01

    Acute exercise induces an increase in Reactive Oxygen Species (ROS) production dependent on exercise intensity with highest ROS amount generated by strenuous exercise. However, chronic repetition of exercise, that is, exercise training, may reduce exercise-induced oxidative stress. Aim of this study was to evaluate the effects of 6-weeks high-intensity discontinuous training (HIDT), characterized by repeated variations of intensity and changes of redox potential, on ROS production and antioxidant capacity in sixteen master swimmers. Time course changes of ROS generation were assessed by Electron Paramagnetic Resonance in capillary blood by a microinvasive approach. An incremental arm-ergometer exercise (IE) until exhaustion was carried out at both before (PRE) and after (POST) training (Trg) period. A significant (P < 0.01) increase of ROS production from REST to the END of IE in PRE Trg (2.82 ± 0.66 versus 3.28 ± 0.66 µmol·min(-1)) was observed. HIDT increased peak oxygen consumption (36.1 ± 4.3 versus 40.6 ± 5.7 mL·kg(-1)·min(-1) PRE and POST Trg, resp.) and the antioxidant capacity (+13%) while it significantly decreased the ROS production both at REST (-20%) and after IE (-25%). The observed link between ROS production, adaptive antioxidant defense mechanisms, and peak oxygen consumption provides new insight into the correlation between ROS response pathways and muscle metabolic function. PMID:25874024

  2. Electron Paramagnetic Resonance Imaging of the Spatial Distribution of Free Radicals in PMR-15 Polyimide Resins

    NASA Technical Reports Server (NTRS)

    Ahn, Myong K.; Eaton, Sandra S.; Eaton, Gareth R.; Meador, Mary Ann B.

    1997-01-01

    Prior studies have shown that free radicals generated by heating polyimides above 300 C are stable at room temperature and are involved in thermo-oxidative degradation in the presence of oxygen gas. Electron paramagnetic resonance imaging (EPRI) is a technique to determine the spatial distribution of free radicals. X-band (9.5 GHz) EPR images of PMR-15 polyimide were obtained with a spatial resolution of approximately 0.18 mm along a 2-mm dimension of the sample. In a polyimide sample that was not thermocycled, the radical distribution was uniform along the 2-mm dimension of the sample. For a polyimide sample that was exposed to thermocycling in air for 300 1-h cycles at 335 C, one-dimensional EPRI showed a higher concentration of free radicals in the surface layers than in the bulk sample. A spectral-spatial two-dimensional image showed that the EPR lineshape of the surface layer remained the same as that of the bulk. These EPRI results suggest that the thermo-oxidative degradation of PMR-15 resin involves free radicals present in the oxygen-rich surface layer.

  3. Novel antioxidant capacity assay for lipophilic compounds using electron paramagnetic resonance spectroscopy

    PubMed Central

    Takahashi, Yushi; Ichimori, Kohji; Okano, Masahito; Goto, Hirofumi

    2015-01-01

    A novel antioxidant capacity assay for lipophilic compounds was developed using electron paramagnetic resonance (EPR) spectroscopy. The assay is based on antioxidant’s scavenging ability against the tert-butoxyl radical generated photolytically from di-tert-butyl peroxide in ethyl acetate, and named the tert-butoxyl-based antioxidant capacity (BAC) assay. The radical was trapped by spin trap, 5,5-dimethyl-1-pyrroline-N-oxide, and EPR signal intensity of the spin adduct was used as a quantitative marker of radical levels. Signal intensity decreased in a dose-dependent manner in the presence of an antioxidant that competitively reacts with the radical, which was utilized to evaluate BAC values. The BAC method enabled the accurate estimation of antioxidant capacity for lipophilic materials that may counteract lipid peroxidation in biological membranes. The BAC values for quercetin and caffeic acid are 0.639 ± 0.020 and 0.118 ± 0.012 trolox equivalents, respectively, which are much smaller than values obtained by other aqueous methods such as H-ORAC and ORAC-EPR. Thus, antioxidants present in a non-aqueous environment should be evaluated using a non-aqueous system. In combination with in situ ascorbate reduction, the BAC method was capable of accurately determining the antioxidant capacity of water-insoluble materials that may be reduced in living cells. PMID:25759515

  4. The fate of free radicals in a cellulose based hydrogel: detection by electron paramagnetic resonance spectroscopy.

    PubMed

    Basumallick, Lipika; Ji, J Andrea; Naber, Nariman; Wang, Y John

    2009-07-01

    Cellulose derivatives are commonly used as gelling agents in topical and ophthalmic drug formulations. During the course of manufacturing, cellulose derivatives are believed to generate free radicals. These free radicals may degrade the gelling agent, leading to lower viscosity. Free radicals also may react with the active ingredient in the product. The formation of radicals in a 3% hydrogel of hypromellose (hydroxypropyl methylcellulose) was monitored by electron paramagnetic resonance (EPR) spectroscopy and spin trapping techniques. Radicals were trapped with 5,5-dimethyl-1-pyrroline-N-oxide (DMPO) and quantitated by comparing the EPR intensity with 4-hydroxy-2,2,6,6-tetramethylpiperidinyloxy (TEMPOL), a stable free radical. Typically, the hydrogels showed an initial increase in the radical concentration within 2 days after autoclaving, followed by a drop in radical concentration in 7 days. EDTA prevented the formation of free radicals in the hypromellose (HPMC) hydrogel, suggesting the involvement of metal ions in the generation of free radicals. The oxidizing potential of the hydrogel was estimated by measuring the rate at which methionine (a model for the protein active pharmaceutical ingredient) was degraded, and was consistent with the amount of radicals present in the gel. This study is the first report investigating the application of EPR spectroscopy in detecting and estimating free radical concentration in cellulose based hydrogels. PMID:19090570

  5. Evaluation of sub-microsecond recovery resonators for in vivo electron paramagnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Hyodo, F.; Subramanian, S.; Devasahayam, N.; Murugesan, R.; Matsumoto, K.; Mitchell, J. B.; Krishna, M. C.

    2008-02-01

    Time-domain (TD) electron paramagnetic resonance (EPR) imaging at 300 MHz for in vivo applications requires resonators with recovery times less than 1 μs after pulsed excitation to reliably capture the rapidly decaying free induction decay (FID). In this study, we tested the suitability of the Litz foil coil resonator (LCR), commonly used in MRI, for in vivo EPR/EPRI applications in the TD mode and compared with parallel coil resonator (PCR). In TD mode, the sensitivity of LCR was lower than that of the PCR. However, in continuous wave (CW) mode, the LCR showed better sensitivity. The RF homogeneity was similar in both the resonators. The axis of the RF magnetic field is transverse to the cylindrical axis of the LCR, making the resonator and the magnet co-axial. Therefore, the loading of animals, and placing of the anesthesia nose cone and temperature monitors was more convenient in the LCR compared to the PCR whose axis is perpendicular to the magnet axis.

  6. Disulfide-Linked Dinitroxides for Monitoring Cellular Thiol Redox Status through Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Legenzov, Eric A; Sims, Stephen J; Dirda, Nathaniel D A; Rosen, Gerald M; Kao, Joseph P Y

    2015-12-01

    Intracellular thiol-disulfide redox balance is crucial to cell health, and may be a key determinant of a cancer's response to chemotherapy and radiation therapy. The ability to assess intracellular thiol-disulfide balance may thus be useful not only in predicting responsiveness of cancers to therapy, but in assessing predisposition to disease. Assays of thiols in biology have relied on colorimetry or fluorimetry, both of which require UV-visible photons, which do not penetrate the body. Low-frequency electron paramagnetic resonance imaging (EPRI) is an emerging magnetic imaging technique that uses radio waves, which penetrate the body well. Therefore, in combination with tailored imaging agents, EPRI affords the opportunity to image physiology within the body. In this study, we have prepared water-soluble and membrane-permeant disulfide-linked dinitroxides, at natural isotopic abundance, and with D,(15)N-substitution. Thiols such as glutathione cleave the disulfides, with simple bimolecular kinetics, to yield the monomeric nitroxide species, with distinctive changes in the EPR spectrum. Using the D,(15)N-substituted disulfide-dinitroxide and EPR spectroscopy, we have obtained quantitative estimates of accessible intracellular thiol in cultured human lymphocytes. Our estimates are in good agreement with published measurements. This suggests that in vivo EPRI of thiol-disulfide balance is feasible. Finally, we discuss the constraints on the design of probe molecules that would be useful for in vivo EPRI of thiol redox status. PMID:26523485

  7. Spin treatment-based approach for electronic transport in paramagnetic liquid transition metals

    NASA Astrophysics Data System (ADS)

    Grosdidier, B.; Ben Abdellah, A.; Bouziane, K.; Mujibur Rahman, S. M.; Gasser, J. G.

    2013-09-01

    A novel concept is proposed to calculate both the electrical resistivity and thermoelectric power (TEP) of liquid transition metals (Mn, Fe, Co and Ni) characterized by a paramagnetic state in the liquid phase. By contrast to a previous work (PRB64, 094202 (2001)), where the resistivity was calculated by treating separately the interactions between spin up and spin down using the Matthiessen rule, our current approach is based on two types of muffin tin potentials in the t-matrix, namely spin up and spin down. The resistivity is treated as the result of the interference of the two kinds of spin states of electrons including a cross-contribution. The calculated resistivity values agree reasonably well with the available experimental ones for all the metals considered. Moreover, the calculated TEP, as deduced from the slope of resistivity vs. energy, has been found to be positive for Mn and Fe but negative for Co and Ni. Besides that, this formalism for resistivity calculation may be generalized to a system that may exist in different atomic states. It is worth mentioning that this concept is analogous to the one used in the process of neutron scattering on a metal composed of multiple isotopes.

  8. Stabilization of reactive nitroxides using invasomes to allow prolonged electron paramagnetic resonance measurements.

    PubMed

    Haag, S F; Taskoparan, B; Bittl, R; Teutloff, C; Wenzel, R; Fahr, A; Chen, M; Lademann, J; Schäfer-Korting, M; Meinke, M C

    2011-01-01

    The detection of the antioxidative capacity of the skin is of great practical relevance since free radicals are involved in many skin damaging processes, including aging and inflammation. The nitroxide TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxyl) in combination with electron paramagnetic resonance spectroscopy was found suitable for measuring the antioxidative capacity since its reaction with reducing agents is considerably fast. Yet, in order to achieve longer measurement times, e.g. in inflammatory skin diseases, the stabilizing effect of an invasome (ultraflexible vesicle/liposome) suspension with TEMPO was investigated ex vivo on porcine skin and in vivo on human skin. Invasomes increased the measurement time ex vivo 2-fold and the reduction was significantly slowed down in vivo, which is due to membrane-associated and therefore protected TEMPO. Furthermore, TEMPO accumulation in the membrane phase as well as the decreasing polarity of the ultimate surroundings of TEMPO during skin penetration explains the stabilizing effect. Thus, an invasome suspension with TEMPO exhibits stabilizing effects ex vivo and in vivo. PMID:21822032

  9. Integration of digital signal processing technologies with pulsed electron paramagnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Pursley, Randall H.; Salem, Ghadi; Devasahayam, Nallathamby; Subramanian, Sankaran; Koscielniak, Janusz; Krishna, Murali C.; Pohida, Thomas J.

    2006-02-01

    The integration of modern data acquisition and digital signal processing (DSP) technologies with Fourier transform electron paramagnetic resonance (FT-EPR) imaging at radiofrequencies (RF) is described. The FT-EPR system operates at a Larmor frequency ( Lf) of 300 MHz to facilitate in vivo studies. This relatively low frequency Lf, in conjunction with our ˜10 MHz signal bandwidth, enables the use of direct free induction decay time-locked subsampling (TLSS). This particular technique provides advantages by eliminating the traditional analog intermediate frequency downconversion stage along with the corresponding noise sources. TLSS also results in manageable sample rates that facilitate the design of DSP-based data acquisition and image processing platforms. More specifically, we utilize a high-speed field programmable gate array (FPGA) and a DSP processor to perform advanced real-time signal and image processing. The migration to a DSP-based configuration offers the benefits of improved EPR system performance, as well as increased adaptability to various EPR system configurations (i.e., software configurable systems instead of hardware reconfigurations). The required modifications to the FT-EPR system design are described, with focus on the addition of DSP technologies including the application-specific hardware, software, and firmware developed for the FPGA and DSP processor. The first results of using real-time DSP technologies in conjunction with direct detection bandpass sampling to implement EPR imaging at RF frequencies are presented.

  10. Three-dimensional electron paramagnetic resonance imaging technique for mapping porosity in ceramics

    SciTech Connect

    Kordas, G.; Kang, Y.H. )

    1991-04-01

    This paper reports on a three-dimensional (3D) electron paramagnetic resonance imaging (EPRI) method which was developed to probe the structure and size of pores in ceramic materials. The imaging device that was added to the EPR instrument consisted of a computer-controlled current source and magnetic field gradient. This add-on facility was tested using a well-defined diphenlpicrylhydrazzyl phantom sample. Pumice was then used to demonstrate the potential of the technique. This stone was immersed in a 0.5 mm {sup 15}N-substituted per-deutereted tempone water solution to fill the pores with spin labels. Images were reconstructed using a filtered back-projection technique. A two-dimensional (2D) imaging plane was constructed by collecting 33 projection planes over 180 {degrees}. A 3D image was derived from 22 planes each constructed by 22 projections. At present, the facility allows a resolution of 69 and 46 {mu}m for 2D and 3D imaging, respectively. Advancements of the imaging apparatus, software, and line width of the spin labels will be needed to enhance the resolution of this technique.

  11. Training Effects on ROS Production Determined by Electron Paramagnetic Resonance in Master Swimmers

    PubMed Central

    Mrakic-Sposta, Simona; Gussoni, Maristella; Porcelli, Simone; Pugliese, Lorenzo; Pavei, Gaspare; Bellistri, Giuseppe; Montorsi, Michela; Tacchini, Philippe; Vezzoli, Alessandra

    2015-01-01

    Acute exercise induces an increase in Reactive Oxygen Species (ROS) production dependent on exercise intensity with highest ROS amount generated by strenuous exercise. However, chronic repetition of exercise, that is, exercise training, may reduce exercise-induced oxidative stress. Aim of this study was to evaluate the effects of 6-weeks high-intensity discontinuous training (HIDT), characterized by repeated variations of intensity and changes of redox potential, on ROS production and antioxidant capacity in sixteen master swimmers. Time course changes of ROS generation were assessed by Electron Paramagnetic Resonance in capillary blood by a microinvasive approach. An incremental arm-ergometer exercise (IE) until exhaustion was carried out at both before (PRE) and after (POST) training (Trg) period. A significant (P < 0.01) increase of ROS production from REST to the END of IE in PRE Trg (2.82 ± 0.66 versus 3.28 ± 0.66 µmol·min−1) was observed. HIDT increased peak oxygen consumption (36.1 ± 4.3 versus 40.6 ± 5.7 mL·kg−1·min−1 PRE and POST Trg, resp.) and the antioxidant capacity (+13%) while it significantly decreased the ROS production both at REST (−20%) and after IE (−25%). The observed link between ROS production, adaptive antioxidant defense mechanisms, and peak oxygen consumption provides new insight into the correlation between ROS response pathways and muscle metabolic function. PMID:25874024

  12. Structural investigation and electron paramagnetic resonance of vanadyl doped alkali niobium borate glasses.

    PubMed

    Agarwal, A; Sheoran, A; Sanghi, S; Bhatnagar, V; Gupta, S K; Arora, M

    2010-03-01

    Glasses with compositions xNb(2)O(5).(30-x)M(2)O.69B(2)O(3) (where M=Li, Na, K; x=0, 4, 8 mol%) doped with 1 mol% V(2)O(5) have been prepared using normal melt quench technique. The IR transmission spectra of the glasses have been studied over the range 400-4000 cm(-1). The changes caused by the addition of Nb(2)O(5) on the structure of these glasses have been reported. The electron paramagnetic resonance spectra of VO(2+) ions in these glasses have been recorded in X-band (9.14 GHz) at room temperature (300 K). The spin Hamiltonian parameters, dipolar hyperfine coupling parameter and Fermi contact interaction parameter have been calculated. It is observed that the resultant resonance spectra contain hyperfine structures (hfs) due to V(4+) ions which exist as VO(2+) ions in octahedral coordination with a tetragonal compression in the present glasses. The tetragonality of V(4+)O(6) complex decreases with increasing concentration of Nb(2)O(5). The 3d(xy) orbit contracts with increase in Nb(2)O(5):M(2)O ratio. Values of the theoretical optical basicity, Lambda(th), have also been reported. PMID:20060775

  13. Electronic paramagnetic resonance (EPR) for the study of ascorbyl radical and lipid radicals in marine organisms.

    PubMed

    González, Paula Mariela; Aguiar, María Belén; Malanga, Gabriela; Puntarulo, Susana

    2013-08-01

    Electron paramagnetic resonance (EPR) spectroscopy detects the presence of radicals of biological interest, such as ascorbyl radical (A(•)) and lipid radicals. A(•) is easily detectable by EPR even in aqueous solution at room-temperature. Under oxidative conditions leading to changes in total ascorbate (AH(-)) content, the A(•)/AH(-) ratio could be used to estimate early oxidative stress in the hydrophilic milieu. This methodology was applied to a wide range of aquatic systems including algae, sea urchin, limpets, bivalves and fish, under physiological and oxidative stress conditions as well. The A(•)/AH(-) ratio reflected the state of one part of the oxidative defense system and provided an early and simple diagnosis of environmental stressing conditions. Oxidative damage to lipids was assessed by the EPR-sensitive adduct formation that correlates well with cell membrane damage with no interference from other biological compounds. Probe instability, tissue metabolism, and lack of spin specificity are drawback factors for employing EPR for in vivo determination of free radicals. However, the dependability of this technique, mostly by combining it with other biochemical strategies, enhances the value of these procedures as contributors to the knowledge of oxidative condition in aquatic organisms. PMID:23485428

  14. Integration of digital signal processing technologies with pulsed electron paramagnetic resonance imaging.

    PubMed

    Pursley, Randall H; Salem, Ghadi; Devasahayam, Nallathamby; Subramanian, Sankaran; Koscielniak, Janusz; Krishna, Murali C; Pohida, Thomas J

    2006-02-01

    The integration of modern data acquisition and digital signal processing (DSP) technologies with Fourier transform electron paramagnetic resonance (FT-EPR) imaging at radiofrequencies (RF) is described. The FT-EPR system operates at a Larmor frequency (L(f)) of 300MHz to facilitate in vivo studies. This relatively low frequency L(f), in conjunction with our approximately 10MHz signal bandwidth, enables the use of direct free induction decay time-locked subsampling (TLSS). This particular technique provides advantages by eliminating the traditional analog intermediate frequency downconversion stage along with the corresponding noise sources. TLSS also results in manageable sample rates that facilitate the design of DSP-based data acquisition and image processing platforms. More specifically, we utilize a high-speed field programmable gate array (FPGA) and a DSP processor to perform advanced real-time signal and image processing. The migration to a DSP-based configuration offers the benefits of improved EPR system performance, as well as increased adaptability to various EPR system configurations (i.e., software configurable systems instead of hardware reconfigurations). The required modifications to the FT-EPR system design are described, with focus on the addition of DSP technologies including the application-specific hardware, software, and firmware developed for the FPGA and DSP processor. The first results of using real-time DSP technologies in conjunction with direct detection bandpass sampling to implement EPR imaging at RF frequencies are presented. PMID:16243552

  15. Electron Paramagnetic Resonance Imaging of the Spatial Distribution of Free Radicals in PMR-15 Polyimide Resins

    NASA Technical Reports Server (NTRS)

    Ahn, Myong K.; Eaton, Sandra S.; Eaton, Gareth R.; Meador, Mary Ann B.

    1997-01-01

    Prior studies have shown that free radicals generated by heating polyimides above 300 C are stable at room temperature and are involved in thermo-oxidative degradation in the presence of oxygen gas. Electron Paramagnetic Resonance Imaging (EPRI) is a technique to determine the spatial distribution of free radicals. X-band (9.5 GHz) EPR images of PMR-15 polyimide were obtained with a spatial resolution of about 0.18 mm along a 2 mm dimension of the sample. In a polyimide sample that was not thermocycled, the radical distribution was uniform along the 2 mm dimension of the sample. For a polyimide sample that was exposed to thermocycling in air for 300 one-hour cycles at 335 C, one-dimensional EPRI showed a higher concentration of free radicals in the surface layers than in the bulk sample. A spectral-spatial two-dimensional image showed that the EPR lineshape of the surface layer remained the same as that of the bulk. These EPRI results suggest that the thermo-oxidative degradation of PMR-15 resin involves free radicals present in the oxygen-rich surface layer.

  16. Electron paramagnetic resonance measurements of absorbed dose in teeth from citizens of Ozyorsk.

    PubMed

    Wieser, A; Vasilenko, E; Aladova, E; Fattibene, P; Semiochkina, N; Smetanin, M

    2014-05-01

    In 1945, within the frame of the Uranium Project for the production of nuclear weapons, the Mayak nuclear facilities were constructed at the Lake Irtyash in the Southern Urals, Russia. The nuclear workers of the Mayak Production Association (MPA), who lived in the city of Ozyorsk, are the focus of epidemiological studies for the assessment of health risks due to protracted exposure to ionising radiation. Electron paramagnetic resonance measurements of absorbed dose in tooth enamel have already been used in the past, in an effort to validate occupational external doses that were evaluated in the Mayak Worker Dosimetry System. In the present study, 229 teeth of Ozyorsk citizens not employed at MPA were investigated for the assessment of external background exposure in Ozyorsk. The annually absorbed dose in tooth enamel from natural background radiation was estimated to be (0.7 ± 0.3) mGy. For citizens living in Ozyorsk during the time of routine noble gas releases of the MPA, which peaked in 1953, the average excess absorbed dose in enamel above natural background was (36 ± 29) mGy, which is consistent with the gamma dose obtained by model calculations. In addition, there were indications of possible accidental gaseous MPA releases that affected the population of Ozyorsk, during the early and late MPA operation periods, before 1951 and after 1960. PMID:24604722

  17. Identification of free radical intermediates in oxidized wine using electron paramagnetic resonance spin trapping.

    PubMed

    Elias, Ryan J; Andersen, Mogens L; Skibsted, Leif H; Waterhouse, Andrew L

    2009-05-27

    Free radicals are thought to be key intermediates in the oxidation of wine, but their nature has not been established. Electron paramagnetic resonance spectroscopy was used to detect and identify several free radical species in wine under oxidative conditions with the aid of spin traps. The 1-hydroxylethyl radical was the sole radical species observed when α-(4-pyridyl-1-oxide)-N-tert-butylnitrone was used as a spin trap in a heated (55 °C), low-sulfite (15 mg L(-1)) red wine. This radical appears to arise from ethanol oxidation via the hydroxyl radical, and this latter species was confirmed by using a high concentration (1.5 M) of the 5,5-dimethylpyrroline-N-oxide spin trap, thus providing the first direct evidence of the Fenton reaction in wine. Hydroxyl radical formation in wine was corroborated by converting hydroxyl radicals to methyl radicals by its reaction with dimethyl sulfoxide. The novel spin trap 5-tert-butoxycarbonyl 5-methyl-1-pyrroline N-oxide was also used in this study to identify sulfite radicals in wine for the first time. This spin trap has also been shown to trap hydroperoxyl radicals, the generation of which is predicted in wine; however, no evidence of this species was observed. PMID:19358607

  18. Integration of digital signal processing technologies with pulsed electron paramagnetic resonance imaging

    PubMed Central

    Pursley, Randall H.; Salem, Ghadi; Devasahayam, Nallathamby; Subramanian, Sankaran; Koscielniak, Janusz; Krishna, Murali C.; Pohida, Thomas J.

    2006-01-01

    The integration of modern data acquisition and digital signal processing (DSP) technologies with Fourier transform electron paramagnetic resonance (FT-EPR) imaging at radiofrequencies (RF) is described. The FT-EPR system operates at a Larmor frequency (Lf) of 300 MHz to facilitate in vivo studies. This relatively low frequency Lf, in conjunction with our ~10 MHz signal bandwidth, enables the use of direct free induction decay time-locked subsampling (TLSS). This particular technique provides advantages by eliminating the traditional analog intermediate frequency downconversion stage along with the corresponding noise sources. TLSS also results in manageable sample rates that facilitate the design of DSP-based data acquisition and image processing platforms. More specifically, we utilize a high-speed field programmable gate array (FPGA) and a DSP processor to perform advanced real-time signal and image processing. The migration to a DSP-based configuration offers the benefits of improved EPR system performance, as well as increased adaptability to various EPR system configurations (i.e., software configurable systems instead of hardware reconfigurations). The required modifications to the FT-EPR system design are described, with focus on the addition of DSP technologies including the application-specific hardware, software, and firmware developed for the FPGA and DSP processor. The first results of using real-time DSP technologies in conjunction with direct detection bandpass sampling to implement EPR imaging at RF frequencies are presented. PMID:16243552

  19. An improved coupling design for high-frequency TE011 electron paramagnetic resonance cavities

    NASA Astrophysics Data System (ADS)

    Savitsky, A.; Grishin, Yu.; Rakhmatullin, R.; Reijerse, E.; Lubitz, W.

    2013-01-01

    In high-frequency electron paramagnetic resonance (EPR) spectroscopy the sample is usually accommodated in a single-mode cylindrical TE011 microwave cavity. This cavity stands out in terms of flexibility for various types of EPR experiments due to convenient control of its resonance frequency and easy waveguide-to-cavity microwave coupling. In continuous wave and in pulsed EPR it is, however, essential to be able to vary the coupling efficiency over a large range. We present a new mechanical design to vary the microwave coupling to the cavity using a movable metal sphere. This coupling sphere is shifted in the plane of the iris wall inside the coupling waveguide. The design allows for a compact and robust construction of the EPR probehead that can be easily accommodated inside a limited space of helium flow cryostat. The construction details and characterization of the coupling element for 95 GHz (W-band) EPR as well as for 34 GHz (Q-band) are presented.

  20. Orthogonal resonators for pulse in vivo electron paramagnetic imaging at 250 MHz

    PubMed Central

    Sundramoorthy, Subramanian V.; Epel, Boris; Halpern, Howard J.

    2014-01-01

    A 250 MHz bimodal resonator with a 19 mm internal diameter for in vivo pulse electron paramagnetic resonance (EPR) imaging is presented. Two separate coaxial cylindrical resonators inserted one into another were used for excitation and detection. The Alderman-Grant excitation resonator (AGR) showed the highest efficiency among all the excitation resonators tested. The magnetic field of AGR is confined to the volume of the detection resonator, which results in highly efficient use of the radio frequency power. A slotted inner single loop single gap resonator (SLSG LGR), coaxial to the AGR, was used for signal detection. The resulting bimodal resonator (AG/LGR) has two mutually orthogonal magnetic field modes; one of them has the magnetic field in the axial direction. The resonator built in our laboratory achieved 40dB isolation over 20 MHz bandwidth with quality factors of detection and excitation resonators of 36 and 11 respectively. Considerable improvement of the B1 homogeneity and EPR image quality in comparison with reflection loop-gap resonator of similar size and volume was observed. PMID:24530507

  1. Antioxidant and radical-scavenging activities of Slovak honeys - An electron paramagnetic resonance study.

    PubMed

    Zalibera, Michal; Staško, Andrej; Šlebodová, Anna; Jančovičová, Viera; Čermáková, Tatiana; Brezová, Vlasta

    2008-09-15

    The antioxidant properties of 15 honey samples from different floral sources and various Slovak regions were investigated by means of electron paramagnetic resonance spectroscopy. Cation radical of ABTS (2,2'-azino-bis(3-ethylbenzothiazoline-6-sulfonate) diammonium salt), DPPH (1,1-diphenyl-2-picrylhydrazyl) and hydroxyl radicals generated by the photochemical decomposition of hydrogen peroxide were used as oxidants. The antioxidant activities found with ABTS(+), expressed as trolox equivalent antioxidant capacity (TEAC), ranged from 0.15 to 1.14mmolkg(-1), and those determined with DPPH, from 0.04 to 0.32mmolkg(-1). TEAC values correlated well with results found by elimination of DPPH, and both values revealed a linear relationship with the concentration of phenolics obtained with the Folin-Ciocalteu phenol test (expressed as gallic acid equivalents, GAE). The colour coordinates (CIE L(∗)a(∗)b(∗)), as well as reflectance spectra determined for original honeys using a white background, demonstrated that the colour difference (ΔE(∗)) and coordinate b(∗) interrelate with TEAC values. The radical-scavenging capacities (RSC) of the honey samples determined in the experiments with photochemically decomposed hydrogen peroxide, generating reactive OH radicals in the presence of spin trapping agent, differ from those found with ABTS(+) and DPPH. Here, probably, the reactive OH radicals, having higher redox potential, are scavenged by a variety of compounds not effective with ABTS(+) and DPPH (e.g., saccharides, proteins). PMID:26049247

  2. A study of the antioxidant properties of beers using electron paramagnetic resonance.

    PubMed

    Polak, Justyna; Bartoszek, Mariola; Stanimirova, Ivana

    2013-12-01

    The antioxidant properties of various kinds of beers were investigated using electron paramagnetic resonance (EPR) spectroscopy. This was possible by measuring the changes in the intensity of the EPR spectrum that resulted from the interaction of the stable radical DPPH (1,1-diphenyl-2-picrylhydrazyl) with the antioxidants found in a beer sample. The antioxidant capacity was then presented in Trolox Equivalents, e.g. μM trolox in a beer sample of 100ml. The influence of the type, colour, the content of the extract and alcohol on the antioxidant activities of commercial beer samples was investigated using two-way hierarchical clustering and analysis of variance. The results showed that all of the beers investigated exhibit antioxidant properties. By performing an analysis of variance, it was found that the value of the antioxidant capacity significantly (0.05 level of significance) depends on the content of the extract and the colour of the beer. It seems that additives also influence the antioxidant properties to some extent, but neither the alcohol content nor the kind of fermentation affects the antioxidant properties of beer. PMID:23871057

  3. Antioxidant activity in hepatopancreas of the shrimp (Pleoticus muelleri) by electron paramagnetic spin resonance spectrometry.

    PubMed

    Díaz, Ana C; Fernández Gimenez, Analía V; Mendiara, Sara N; Fenucci, Jorge L

    2004-05-19

    Free radical scavenging properties of hepatopancreas extracts of Pleoticus muelleri were evaluated by electron paramagnetic spin resonance spectrometry methods (EPR) against the stable 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical. The present study was carried out to characterize different physiological stages of the shrimp under environmental and nutritional stress, evaluating the effect on growth, survival, and functional morphology of the hepatopancreas. Feeding trials were carried out on juveniles (1 g initial weight) held in aquaria. Each diet, with different concentrations of vitamins A and E, was tested in triplicate groups during 25 days. The control groups were fed with fresh squid mantle and with a vitamin-free diet. For all of the diets, the extracts exhibited strong DPPH radical scavenging activity, suggesting that the tissue is a powerful natural antioxidant. Individuals fed with different concentrations of vitamin E showed the strongest effect on the DPPH radicals, reducing the DPPH radicals to 50%, after an incubation period of 3 min. In contrast, the extracts of control animals, fed with squid mantle, had the weakest antioxidant activity (4%). These data indicated that the presence of vitamin E in the diet can provide immediate protection against free radicals. PMID:15137874

  4. Anthocyanin composition of wild Colombian fruits and antioxidant capacity measurement by electron paramagnetic resonance spectroscopy.

    PubMed

    Santacruz, Liliana; Carriazo, José G; Almanza, Ovidio; Osorio, Coralia

    2012-02-15

    The qualitative and quantitative anthocyanin composition of four wild tropical fruits from Colombia was studied. Compounds of "mora pequeña" ( Rubus megalococcus Focke.), "uva de árbol" ( Myrciaria aff. cauliflora O. Berg), coral, and motilón ( Hyeronima macrocarpa Mull. Arg.) fruits were separately extracted with methanol-acetic acid (95:5, v/v). The anthocyanin-rich extracts (AREs) were obtained by selective adsorption on Amberlite XAD-7. Each extract was analyzed by HPLC-PDA and HPLC-HRESI-MS(n) with LCMS-IT-TOF equipment in order to characterize the anthocyanin pigments and the coinjection in HPLC using standards allowed identifying the major constituents in each extract. The antioxidant activity was measured by electron paramagnetic resonance (EPR) and UV-vis spectroscopy, using ABTS and DPPH free radicals. The ARE of motilón ( H. macrocarpa Müll. Arg) exhibited the highest radical scavenging activity in comparison to the other extracts. A second-order kinetic model was followed in all of the cases. These results suggested that the studied fruits are promising not only as source of natural pigments but also as antioxidant materials for food industry. PMID:22242913

  5. Electron Paramagnetic Resonance of Nitrogenase and Nitrogenase Components from Clostridium pasteurianum W5 and Azotobacter vinelandii OP

    PubMed Central

    Orme-Johnson, W. H.; Hamilton, W. D.; Jones, T. L.; Tso, M.-Y. W.; Burris, R. H.; Shah, V. K.; Brill, W. J.

    1972-01-01

    The electron paramagnetic resonance of nitrogenase components, separately and together with the other reactants in the nitrogenase system (namely, reductant and Mg·ATP), have been examined at low temperatures (<20°K). The MoFe protein, component I or molybdoferredoxin, in the oxidized (but not oxygen-inactivated) state yields signals with g-values of 4.3, 3.7, and 2.01, and when reduced has no observable electron paramagnetic resonance. The Fe protein, component II, or azoferredoxin, yields a signal with g-values of 2.05, 1.94, and 1.89 in the reduced state that is converted by Mg·ATP into an axial signal with g-values near 2.05 and 1.94, and a second split signal near g = 4.3. The Fe protein has no definite electron paramagnetic resonance in the oxidized (not oxygen-denatured) state under these conditions. The Mg·ATP complex of reduced Fe protein reduces the MoFe protein, whereas dithionite alone does not reduce the MoFe protein. Reoxidation of the system by substrate leads to disappearance of the Fe protein signal and the reappearance of the MoFe protein signal. Thus Mg·ATP, which is hydrolyzed during substrate reduction, converts the Fe protein to a reductant capable of transferring electrons to MoFe protein, after which substrate reduction occurs. PMID:4343957

  6. Triplet State Delocalization in a Conjugated Porphyrin Dimer Probed by Transient Electron Paramagnetic Resonance Techniques

    PubMed Central

    2015-01-01

    The delocalization of the photoexcited triplet state in a linear butadiyne-linked porphyrin dimer is investigated by time-resolved and pulse electron paramagnetic resonance (EPR) with laser excitation. The transient EPR spectra of the photoexcited triplet states of the porphyrin monomer and dimer are characterized by significantly different spin polarizations and an increase of the zero-field splitting parameter D from monomer to dimer. The proton and nitrogen hyperfine couplings, determined using electron nuclear double resonance (ENDOR) and X- and Q-band HYSCORE, are reduced to about half in the porphyrin dimer. These data unequivocally prove the delocalization of the triplet state over both porphyrin units, in contrast to the conclusions from previous studies on the triplet states of closely related porphyrin dimers. The results presented here demonstrate that the most accurate estimate of the extent of triplet state delocalization can be obtained from the hyperfine couplings, while interpretation of the zero-field splitting parameter D can lead to underestimation of the delocalization length, unless combined with quantum chemical calculations. Furthermore, orientation-selective ENDOR and HYSCORE results, in combination with the results of density functional theory (DFT) calculations, allowed determination of the orientations of the zero-field splitting tensors with respect to the molecular frame in both porphyrin monomer and dimer. The results provide evidence for a reorientation of the zero-field splitting tensor and a change in the sign of the zero-field splitting D value. The direction of maximum dipolar coupling shifts from the out-of-plane direction in the porphyrin monomer to the vector connecting the two porphyrin units in the dimer. This reorientation, leading to an alignment of the principal optical transition moment and the axis of maximum dipolar coupling, is also confirmed by magnetophotoselection experiments. PMID:25914154

  7. Electron Paramagnetic Resonance and Photoluminescence Studies of LaMgAl11O19:Mn2+ Green Phosphors

    NASA Astrophysics Data System (ADS)

    Singh, Vijay; Chakradhar, R. P. S.; Rao, J. L.; Dhoble, S. J.; Kim, S. H.

    2014-09-01

    Manganese-doped LaMgAl11O19 powder has been prepared by an easy combustion method. Powder x-ray diffraction and scanning electron microscopy have been used to characterize the as-prepared phosphor. The electron paramagnetic resonance (EPR) spectrum of LaMgAl11O19:Mn2+ phosphor exhibits six-line hyperfine structure centered at g ≈ 1.973. The number of spins participating in resonance (N) and the paramagnetic susceptibility (χ) for the resonance signal at g ≈ 1.973 have been calculated as a function of temperature. The photoluminescence spectrum exhibits green emission at 516 nm, which is attributed to 4T1 → 6A1 transition of Mn2+ ions. From EPR and luminescence studies, it is observed that Mn2+ ions occupy Mg2+ sites and Mn2+ ions are located at tetrahedral sites in the prepared phosphors.

  8. Fine structure of the electron paramagnetic resonance spectrum of Fe3+ centres in LiTaO3

    NASA Astrophysics Data System (ADS)

    Vazhenin, V. A.; Guseva, V. B.; Artyomov, M. Yu; Route, R. K.; Fejer, M. M.; Byer, R. L.

    2003-01-01

    The electron paramagnetic resonance spectrum of trigonal Fe3+ centres has been investigated and parameters of the spin Hamiltonian obtained for nominally pure congruent LiTaO3 crystals annealed at ~1500 K under Li2O vapour pressure corresponding to the pressure over the stoichiometric lithium tantalate. The possibility of calculating the zero-field splitting of the ground state of the impurity ion on the basis of the superposition model is discussed.

  9. Advanced Paramagnetic Resonance Spectroscopies of Iron-Sulfur Proteins: Electron Nuclear Double Resonance (ENDOR) and Electron Spin Echo Envelope Modulation (ESEEM)

    PubMed Central

    Cutsail, George E.; Telser, Joshua; Hoffman, Brian M.

    2015-01-01

    The advanced electron paramagnetic resonance (EPR) techniques, electron nuclear double resonance (ENDOR) and electron spin echo envelope modulation (ESEEM) spectroscopies, provide unique insights into the structure, coordination chemistry, and biochemical mechanism of Nature’s widely distributed iron-sulfur cluster (FeS) proteins. This review describes the ENDOR and ESEEM techniques and then provides a series of case studies on their application to a wide variety of FeS proteins including ferredoxins, nitrogenase, and radical SAM enzymes. PMID:25686535

  10. Electron paramagnetic resonance studies on conformation states and metal ion exchange properties of vanadium bromoperoxidase

    SciTech Connect

    de Boer, E.; Boon, K.; Wever, R.

    1988-03-08

    An electron paramagnetic resonance (EPR) study was carried out to examine structural aspects of vanadium-containing bromoperoxidase from the brown seaweed Ascophyllum nodosum. At high pH, the reduced form of bromoperoxidase showed an apparently axially symmetric EPR signal with 16 hyperfine lines. When the pH was lowered, a new EPR spectrum was formed. When EPR spectra of the reduced enzyme were recorded in the pH range from 4.2 to 8.4, it appeared that these changes were linked to a functional group with an apparent pK/sub a/ of about 5.4. In D/sub 2/O this value for the pK/sub a/ was 5.3. It is suggested that these effects arise from protonation of histidine or aspartate/glutamate residues near the metal ion. The values for the isotropic hyperfine coupling constant of the reduced enzyme at both high and low pH are also consistent with a ligand field containing nitrogen and/or oxygen donor atoms. When reduced bromoperoxidase was dissolved in D/sub 2/O or H/sub 2//sup 17/O instead of H/sub 2//sup 16/O, vanadium (IV) hyperfine line widths were markedly affected, demonstrating that water is a ligand of the metal ion. Together with previous work these findings suggest that vanadium (IV) is not involved in catalytic turnover and confirm the model in which the vanadium (V) ion of the native enzyme only serves to bind both hydrogen peroxide and bromide. After excess vanadate was added to a homogeneous preparation of purified bromoperoxidase, the extent of vanadium bound to the protein increased from 0.5 to 1.1, with a concomitant enhancement of enzymic activity. Finally, it is demonstrated that both vanadate (VO/sub 4//sup 3 -/) and molybdate (MoO/sub 4//sup 2 -/) compete for the same site on apobromoperoxidase.

  11. Methodology for increased precision in saturation transfer electron paramagnetic resonance studies of rotational dynamics.

    PubMed Central

    Squier, T C; Thomas, D D

    1986-01-01

    Microsecond rotational motions of nitroxide spin labels are measured primarily with saturation transfer electron paramagnetic resonance (ST-EPR). In the present study we have used model system experiments to quantitatively evaluate different ST-EPR spectral parameters, both in-phase and out-of-phase, with an emphasis on techniques for suppressing the interference from weakly immobilized probes. Analyses of both systematic and random errors show that maximum sensitivity to small changes in correlation time and minimum ambiguity of interpretation are best achieved by combining measurements of both spectral line-shape, i.e., the ratio of line-heights, and spectral intensity, i.e., the absolute amplitude of either a position within a spectrum or a spectral integral. Errors in the measurement of correlation times for the two types of parameters tend to be complementary. Integrated intensity parameters are particularly useful in measuring microsecond probe motions in the presence of weakly immobilized components. We confirm that integrated intensity parameters are sometimes effective in rejecting signals from weakly immobilized probes, but the effectiveness of this rejection is more limited than previously supposed and depends on the type of parameter being measured. We describe procedures for evaluating and minimizing errors due to weakly immobilized probes, emphasizing the advantages of a new kind of intensity parameter obtained from integrated in-phase spectra. We provide detailed descriptions of experimental procedures, along with calibration plots of the most useful spectral parameters vs. rotational correlation time, which should make it possible for workers in other laboratories, using different instruments and sample geometries, to reproduce spectra quantitatively and to make accurate correlation time measurements. PMID:3013330

  12. Tooth Retrospective Dosimetry Using Electron Paramagnetic Resonance: Influence of Irradiated Dental Composites

    PubMed Central

    Desmet, Céline M.; Djurkin, Andrej; Dos Santos-Goncalvez, Ana Maria; Dong, Ruhong; Kmiec, Maciej M.; Kobayashi, Kyo; Rychert, Kevin; Beun, Sébastien; Leprince, Julian G.; Leloup, Gaëtane; Levêque, Philippe; Gallez, Bernard

    2015-01-01

    In the aftermath of a major radiological accident, the medical management of overexposed individuals will rely on the determination of the dose of ionizing radiations absorbed by the victims. Because people in the general population do not possess conventional dosimeters, after the fact dose reconstruction methods are needed. Free radicals are induced by radiations in the tooth enamel of victims, in direct proportion to dose, and can be quantified using Electron Paramagnetic Resonance (EPR) spectrometry, a technique that was demonstrated to be very appropriate for mass triage. The presence of dimethacrylate based restorations on teeth can interfere with the dosimetric signal from the enamel, as free radicals could also be induced in the various composites used. The aim of the present study was to screen irradiated composites for a possible radiation-induced EPR signal, to characterize it, and evaluate a possible interference with the dosimetric signal of the enamel. We investigated the most common commercial composites, and experimental compositions, for a possible class effect. The effect of the dose was studied between 10 Gy and 100 Gy using high sensitivity X-band spectrometer. The influence of this radiation-induced signal from the composite on the dosimetric signal of the enamel was also investigated using a clinical L-Band EPR spectrometer, specifically developed in the EPR center at Dartmouth College. In X-band, a radiation-induced signal was observed for high doses (25-100 Gy); it was rapidly decaying, and not detected after only 24h post irradiation. At 10 Gy, the signal was in most cases not measurable in the commercial composites tested, with the exception of 3 composites showing a significant intensity. In L-band study, only one irradiated commercial composite influenced significantly the dosimetric signal of the tooth, with an overestimation about 30%. In conclusion, the presence of the radiation-induced signal from dental composites should not

  13. Application of Electron Paramagnetic Resonance (EPR) Oximetry to Monitor Oxygen in Wounds in Diabetic Models

    PubMed Central

    Desmet, Céline M.; Lafosse, Aurore; Vériter, Sophie; Porporato, Paolo E.; Sonveaux, Pierre; Dufrane, Denis; Levêque, Philippe; Gallez, Bernard

    2015-01-01

    A lack of oxygen is classically described as a major cause of impaired wound healing in diabetic patients. Even if the role of oxygen in the wound healing process is well recognized, measurement of oxygen levels in a wound remains challenging. The purpose of the present study was to assess the value of electron paramagnetic resonance (EPR) oximetry to monitor pO2 in wounds during the healing process in diabetic mouse models. Kinetics of wound closure were carried out in streptozotocin (STZ)-treated and db/db mice. The pO2 was followed repeatedly during the healing process by 1 GHz EPR spectroscopy with lithium phthalocyanine (LiPc) crystals used as oxygen sensor in two different wound models: a full-thickness excisional skin wound and a pedicled skin flap. Wound closure kinetics were dramatically slower in 12-week-old db/db compared to control (db/+) mice, whereas kinetics were not statistically different in STZ-treated compared to control mice. At the center of excisional wounds, measurements were highly influenced by atmospheric oxygen early in the healing process. In pedicled flaps, hypoxia was observed early after wounding. While reoxygenation occurred over time in db/+ mice, hypoxia was prolonged in the diabetic db/db model. This observation was consistent with impaired healing and microangiopathies observed using intravital microscopy. In conclusion, EPR oximetry using LiPc crystals as the oxygen sensor is an appropriate technique to follow wound oxygenation in acute and chronic wounds, in normal and diabetic animals. Nevertheless, the technique is limited for measurements in pedicled skin flaps and cannot be applied to excisional wounds in which diffusion of atmospheric oxygen significantly affects the measurements. PMID:26659378

  14. A microwave resonator for limiting depth sensitivity for electron paramagnetic resonance spectroscopy of surfaces

    PubMed Central

    Sidabras, Jason W.; Varanasi, Shiv K.; Mett, Richard R.; Swarts, Steven G.; Swartz, Harold M.; Hyde, James S.

    2014-01-01

    A microwave Surface Resonator Array (SRA) structure is described for use in Electron Paramagnetic Resonance (EPR) spectroscopy. The SRA has a series of anti-parallel transmission line modes that provides a region of sensitivity equal to the cross-sectional area times its depth sensitivity, which is approximately half the distance between the transmission line centers. It is shown that the quarter-wave twin-lead transmission line can be a useful element for design of microwave resonators at frequencies as high as 10 GHz. The SRA geometry is presented as a novel resonator for use in surface spectroscopy where the region of interest is either surrounded by lossy material, or the spectroscopist wishes to minimize signal from surrounding materials. One such application is in vivo spectroscopy of human finger-nails at X-band (9.5 GHz) to measure ionizing radiation dosages. In order to reduce losses associated with tissues beneath the nail that yield no EPR signal, the SRA structure is designed to limit depth sensitivity to the thickness of the fingernail. Another application, due to the resonator geometry and limited depth penetration, is surface spectroscopy in coating or material science. To test this application, a spectrum of 1.44 μM of Mg2+ doped polystyrene 1.1 mm thick on an aluminum surface is obtained. Modeling, design, and simulations were performed using Wolfram Mathematica (Champaign, IL; v. 9.0) and Ansys High Frequency Structure Simulator (HFSS; Canonsburg, PA; v. 15.0). A micro-strip coupling circuit is designed to suppress unwanted modes and provide a balanced impedance transformation to a 50 Ω coaxial input. Agreement between simulated and experimental results is shown. PMID:25362434

  15. Characterization of iron, manganese, and copper synthetic hydroxyapatites by electron paramagnetic resonance spectroscopy

    NASA Technical Reports Server (NTRS)

    Sutter, B.; Wasowicz, T.; Howard, T.; Hossner, L. R.; Ming, D. W.

    2002-01-01

    The incorporation of micronutrients (e.g., Fe, Mn, Cu) into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in NASA's Advanced Life Support (ALS) program for long-duration space missions. Separate Fe3+ (Fe-SHA), Mn2+ (Mn-SHA), and Cu2+ (Cu-SHA) containing SHA materials were synthesized by a precipitation method. Electron paramagnetic resonance (EPR) spectroscopy was used to determine the location of Fe3+, Mn2+, and Cu2+ ions in the SHA structure and to identify other Fe(3+)-, Mn(2+)-, and Cu(2+)-containing phases that formed during precipitation. The EPR parameters for Fe3+ (g=4.20 and 8.93) and for Mn2+ (g=2.01, A=9.4 mT, D=39.0 mT and E=10.5 mT) indicated that Fe3+ and Mn2+ possessed rhombic ion crystal fields within the SHA structure. The Cu2+ EPR parameters (g(z)=2.488, A(z)=5.2 mT) indicated that Cu2+ was coordinated to more than six oxygens. The rhombic environments of Fe3+ and Mn2+ along with the unique Cu2+ environment suggested that these metals substituted for the 7 or 9 coordinate Ca2+ in SHA. The EPR analyses also detected poorly crystalline metal oxyhydroxides or metal-phosphates associated with SHA. The Fe-, Mn-, and Cu-SHA materials are potential slow release sources of Fe, Mn, and Cu for ALS and terrestrial cropping systems.

  16. Application of Electron Paramagnetic Resonance (EPR) Oximetry to Monitor Oxygen in Wounds in Diabetic Models.

    PubMed

    Desmet, Céline M; Lafosse, Aurore; Vériter, Sophie; Porporato, Paolo E; Sonveaux, Pierre; Dufrane, Denis; Levêque, Philippe; Gallez, Bernard

    2015-01-01

    A lack of oxygen is classically described as a major cause of impaired wound healing in diabetic patients. Even if the role of oxygen in the wound healing process is well recognized, measurement of oxygen levels in a wound remains challenging. The purpose of the present study was to assess the value of electron paramagnetic resonance (EPR) oximetry to monitor pO2 in wounds during the healing process in diabetic mouse models. Kinetics of wound closure were carried out in streptozotocin (STZ)-treated and db/db mice. The pO2 was followed repeatedly during the healing process by 1 GHz EPR spectroscopy with lithium phthalocyanine (LiPc) crystals used as oxygen sensor in two different wound models: a full-thickness excisional skin wound and a pedicled skin flap. Wound closure kinetics were dramatically slower in 12-week-old db/db compared to control (db/+) mice, whereas kinetics were not statistically different in STZ-treated compared to control mice. At the center of excisional wounds, measurements were highly influenced by atmospheric oxygen early in the healing process. In pedicled flaps, hypoxia was observed early after wounding. While reoxygenation occurred over time in db/+ mice, hypoxia was prolonged in the diabetic db/db model. This observation was consistent with impaired healing and microangiopathies observed using intravital microscopy. In conclusion, EPR oximetry using LiPc crystals as the oxygen sensor is an appropriate technique to follow wound oxygenation in acute and chronic wounds, in normal and diabetic animals. Nevertheless, the technique is limited for measurements in pedicled skin flaps and cannot be applied to excisional wounds in which diffusion of atmospheric oxygen significantly affects the measurements. PMID:26659378

  17. A microwave resonator for limiting depth sensitivity for electron paramagnetic resonance spectroscopy of surfaces

    SciTech Connect

    Sidabras, Jason W.; Varanasi, Shiv K.; Hyde, James S.; Mett, Richard R.; Swarts, Steven G.; Swartz, Harold M.

    2014-10-15

    A microwave Surface Resonator Array (SRA) structure is described for use in Electron Paramagnetic Resonance (EPR) spectroscopy. The SRA has a series of anti-parallel transmission line modes that provides a region of sensitivity equal to the cross-sectional area times its depth sensitivity, which is approximately half the distance between the transmission line centers. It is shown that the quarter-wave twin-lead transmission line can be a useful element for design of microwave resonators at frequencies as high as 10 GHz. The SRA geometry is presented as a novel resonator for use in surface spectroscopy where the region of interest is either surrounded by lossy material, or the spectroscopist wishes to minimize signal from surrounding materials. One such application is in vivo spectroscopy of human finger-nails at X-band (9.5 GHz) to measure ionizing radiation dosages. In order to reduce losses associated with tissues beneath the nail that yield no EPR signal, the SRA structure is designed to limit depth sensitivity to the thickness of the fingernail. Another application, due to the resonator geometry and limited depth penetration, is surface spectroscopy in coating or material science. To test this application, a spectrum of 1.44 μM of Mg{sup 2+} doped polystyrene 1.1 mm thick on an aluminum surface is obtained. Modeling, design, and simulations were performed using Wolfram Mathematica (Champaign, IL; v. 9.0) and Ansys High Frequency Structure Simulator (HFSS; Canonsburg, PA; v. 15.0). A micro-strip coupling circuit is designed to suppress unwanted modes and provide a balanced impedance transformation to a 50 Ω coaxial input. Agreement between simulated and experimental results is shown.

  18. Dielectric microwave resonators in TE011 cavities for electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Mett, Richard R.; Sidabras, Jason W.; Golovina, Iryna S.; Hyde, James S.

    2008-09-01

    The coupled system of the microwave cylindrical TE011 cavity and the TE01δ dielectric modes has been analyzed in order to determine the maximum achievable resonator efficiency parameter of a dielectric inserted into a cavity, and whether this value can exceed that of a dedicated TE01δ mode dielectric resonator. The frequency, Q value, and resonator efficiency parameter Λ for each mode of the coupled system were calculated as the size of the dielectric was varied. Other output parameters include the relative field magnitudes and phases. Two modes are found: one with fields in the dielectric parallel to the fields in the cavity center and the other with antiparallel fields. Results closely match those from a computer program that solves Maxwell's equations by finite element methods. Depending on the relative natural resonance frequencies of the cavity and dielectric, one mode has a higher Q value and correspondingly lower Λ than the other. The mode with the higher Q value is preferentially excited by a coupling iris or loop in or near the cavity wall. However, depending on the frequency separation between modes, either can be excited in this way. A relatively narrow optimum is found for the size of the insert that produces maximum signal for both modes simultaneously. It occurs when the self-resonance frequencies of the two resonators are nearly equal. The maximum signal is almost the same as that of the dedicated TE01δ mode dielectric resonator alone, Λ ≅40 G/W1/2 at X-band for a KTaO3 crystal. The cavity is analogous to the second stage of a two-stage coupler. In general, there is no electron paramagnetic resonance (EPR) signal benefit by use of a second stage. However, there is a benefit of convenience. A properly designed sample-mounted resonator inserted into a cavity can give EPR signals as large as what one would expect from the dielectric resonator alone.

  19. Dielectric microwave resonators in TE(011) cavities for electron paramagnetic resonance spectroscopy.

    PubMed

    Mett, Richard R; Sidabras, Jason W; Golovina, Iryna S; Hyde, James S

    2008-09-01

    The coupled system of the microwave cylindrical TE(011) cavity and the TE(01delta) dielectric modes has been analyzed in order to determine the maximum achievable resonator efficiency parameter of a dielectric inserted into a cavity, and whether this value can exceed that of a dedicated TE(01delta) mode dielectric resonator. The frequency, Q value, and resonator efficiency parameter Lambda for each mode of the coupled system were calculated as the size of the dielectric was varied. Other output parameters include the relative field magnitudes and phases. Two modes are found: one with fields in the dielectric parallel to the fields in the cavity center and the other with antiparallel fields. Results closely match those from a computer program that solves Maxwell's equations by finite element methods. Depending on the relative natural resonance frequencies of the cavity and dielectric, one mode has a higher Q value and correspondingly lower Lambda than the other. The mode with the higher Q value is preferentially excited by a coupling iris or loop in or near the cavity wall. However, depending on the frequency separation between modes, either can be excited in this way. A relatively narrow optimum is found for the size of the insert that produces maximum signal for both modes simultaneously. It occurs when the self-resonance frequencies of the two resonators are nearly equal. The maximum signal is almost the same as that of the dedicated TE(01delta) mode dielectric resonator alone, Lambda congruent with40 G/W(1/2) at X-band for a KTaO(3) crystal. The cavity is analogous to the second stage of a two-stage coupler. In general, there is no electron paramagnetic resonance (EPR) signal benefit by use of a second stage. However, there is a benefit of convenience. A properly designed sample-mounted resonator inserted into a cavity can give EPR signals as large as what one would expect from the dielectric resonator alone. PMID:19044441

  20. A microwave resonator for limiting depth sensitivity for electron paramagnetic resonance spectroscopy of surfaces.

    PubMed

    Sidabras, Jason W; Varanasi, Shiv K; Mett, Richard R; Swarts, Steven G; Swartz, Harold M; Hyde, James S

    2014-10-01

    A microwave Surface Resonator Array (SRA) structure is described for use in Electron Paramagnetic Resonance (EPR) spectroscopy. The SRA has a series of anti-parallel transmission line modes that provides a region of sensitivity equal to the cross-sectional area times its depth sensitivity, which is approximately half the distance between the transmission line centers. It is shown that the quarter-wave twin-lead transmission line can be a useful element for design of microwave resonators at frequencies as high as 10 GHz. The SRA geometry is presented as a novel resonator for use in surface spectroscopy where the region of interest is either surrounded by lossy material, or the spectroscopist wishes to minimize signal from surrounding materials. One such application is in vivo spectroscopy of human finger-nails at X-band (9.5 GHz) to measure ionizing radiation dosages. In order to reduce losses associated with tissues beneath the nail that yield no EPR signal, the SRA structure is designed to limit depth sensitivity to the thickness of the fingernail. Another application, due to the resonator geometry and limited depth penetration, is surface spectroscopy in coating or material science. To test this application, a spectrum of 1.44 μM of Mg(2+) doped polystyrene 1.1 mm thick on an aluminum surface is obtained. Modeling, design, and simulations were performed using Wolfram Mathematica (Champaign, IL; v. 9.0) and Ansys High Frequency Structure Simulator (HFSS; Canonsburg, PA; v. 15.0). A micro-strip coupling circuit is designed to suppress unwanted modes and provide a balanced impedance transformation to a 50 Ω coaxial input. Agreement between simulated and experimental results is shown. PMID:25362434

  1. Study of nanostructural organization of ionic liquids by electron paramagnetic resonance spectroscopy.

    PubMed

    Merunka, Dalibor; Peric, Mirna; Peric, Miroslav

    2015-02-19

    The X-band electron paramagnetic resonance spectroscopy (EPR) of a stable, spherical nitroxide spin probe, perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDTO) has been used to study the nanostructural organization of a series of 1-alkyl-3-methylimidazolium tetrafluoroborate ionic liquids (ILs) with alkyl chain lengths from two to eight carbons. By employing nonlinear least-squares fitting of the EPR spectra, we have obtained values of the rotational correlation time and hyperfine coupling splitting of pDTO to high precision. The rotational correlation time of pDTO in ILs and squalane, a viscous alkane, can be fit very well to a power law functionality with a singular temperature, which often describes a number of physical quantities measured in supercooled liquids. The viscosity of the ILs and squalane, taken from the literature, can also be fit to the same power law expression, which means that the rotational correlation times and the ionic liquid viscosities have similar functional dependence on temperature. The apparent activation energy of both the rotational correlation time of pDTO and the viscous flow of ILs and squalane increases with decreasing temperature; in other words, they exhibit strong non-Arrhenius behavior. The rotational correlation time of pDTO as a function of η/T, where η is the shear viscosity and T is the temperature, is well described by the Stokes-Einstein-Debye (SED) law, while the hydrodynamic probe radii are solvent dependent and are smaller than the geometric radius of the probe. The temperature dependence of hyperfine coupling splitting is the same in all four ionic liquids. The value of the hyperfine coupling splitting starts decreasing with increasing alkyl chain length in the ionic liquids in which the number of carbons in the alkyl chain is greater than four. This decrease together with the decrease in the hydrodynamic radius of the probe indicates a possible existence of nonpolar nanodomains. PMID:25594422

  2. Paramagnetic dipole centers in KTaO3: Electron-spin-resonance and dielectric spectroscopy study

    NASA Astrophysics Data System (ADS)

    Laguta, V. V.; Glinchuk, M. D.; Bykov, I. P.; Rosa, J.; Jastrabík, L.; Savinov, M.; Trybuła, Z.

    2000-02-01

    Electron-spin-resonance (ESR) and dielectric spectroscopy techniques have been applied to study the dipole centers connected with Mn2+ and Fe3+ impurity ions substituted for K+ in the incipient ferroelectric KTaO3. It was shown that the reorientations of paramagnetic dipole complexes Fe3+-OI (OI is the interstitial oxygen) give rise to dielectric losses near T~=185 K at the frequency 1 kHz. Their activation energy Er=0.34 eV was obtained both from dielectric and ESR measurements. The peak of dielectric losses at T~=55 K was observed in KTaO3 doped by low concentrations of Mn2+(n~0.01 at. %). At n>~0.3 at. % a pronounced peak of dielectric susceptibility similar to that in KTaO3:Li was revealed in addition to the aforementioned losses peak. The studies of electric field and temperature dependence of Mn2+ ESR intensities with respect to the local Lorentz field had shown that the dipole moment 1.4 eÅ can be associated with Mn2+ ion. The origin of this dipole moment was shown to be off-center displacement Δ~=0.9 Å of Mn2+ from the K+ site in one of six [001]-type directions. The relaxation rate of these dipoles after the polarizing electric field switching off was directly measured by the ESR method. It was described by Arrhenius law with activation energy Er=0.104 eV, which is close to the value obtained from dielectric measurements. Possible sources of dielectric losses in nominally pure KTaO3 single crystals in the vicinity of T~40 K are analyzed and discussed on the basis of both present work data and earlier results collected from the literature.

  3. Multiharmonic electron paramagnetic resonance for extended samples with both narrow and broad lines

    NASA Astrophysics Data System (ADS)

    Yu, Zhelin; Tseytlin, Mark; Eaton, Sandra S.; Eaton, Gareth R.

    2015-05-01

    Multiharmonic electron paramagnetic resonance spectroscopy was demonstrated for two samples with both narrow and broad lines: (i) α,γ-Bisdiphenylene-β-phenylallyl (BDPA) with ΔBpp of 0.85 G plus ultramarine blue with ΔBpp of 17 G, and (ii) a nitroxide radical immobilized in sucrose octaacetate. Modulation amplitudes up to 17 G at 41 kHz were generated with a rapid scan coil driver and Litz wire coils that provide uniform magnetic field sweeps over samples with heights of 5 mm. Data were acquired with a 2-D experiment in the Xepr software through the transient signal path of a Bruker E500T and digitized in quadrature with a Bruker SpecJet II. Signals at the modulation frequency and its harmonics were calculated by digital phase-sensitive detection. The number of harmonics with signal intensity greater than noise increases as the ratio of the modulation amplitude to the narrowest peak increases. Spectra reconstructed by the multiharmonic method from data obtained with modulation amplitudes up to five times the peak-to-peak linewidths of the narrowest features have linewidths that are broadened by up to only about 10% relative to linewidths in spectra obtained at low modulation amplitudes. The signal-to-noise improves with increasing modulation amplitude up to the point where the modulation amplitude is slightly larger than the linewidth of the narrowest features. If this high a modulation amplitude had been used in conventional methodology the linewidth of the narrowest features would have been severely broadened. The multiharmonic reconstruction methodology means that the selection of the modulation amplitude that can be used without spectral distortion is no longer tightly tied to the linewidth of the narrowest line.

  4. A microwave resonator for limiting depth sensitivity for electron paramagnetic resonance spectroscopy of surfaces

    NASA Astrophysics Data System (ADS)

    Sidabras, Jason W.; Varanasi, Shiv K.; Mett, Richard R.; Swarts, Steven G.; Swartz, Harold M.; Hyde, James S.

    2014-10-01

    A microwave Surface Resonator Array (SRA) structure is described for use in Electron Paramagnetic Resonance (EPR) spectroscopy. The SRA has a series of anti-parallel transmission line modes that provides a region of sensitivity equal to the cross-sectional area times its depth sensitivity, which is approximately half the distance between the transmission line centers. It is shown that the quarter-wave twin-lead transmission line can be a useful element for design of microwave resonators at frequencies as high as 10 GHz. The SRA geometry is presented as a novel resonator for use in surface spectroscopy where the region of interest is either surrounded by lossy material, or the spectroscopist wishes to minimize signal from surrounding materials. One such application is in vivo spectroscopy of human finger-nails at X-band (9.5 GHz) to measure ionizing radiation dosages. In order to reduce losses associated with tissues beneath the nail that yield no EPR signal, the SRA structure is designed to limit depth sensitivity to the thickness of the fingernail. Another application, due to the resonator geometry and limited depth penetration, is surface spectroscopy in coating or material science. To test this application, a spectrum of 1.44 μM of Mg2+ doped polystyrene 1.1 mm thick on an aluminum surface is obtained. Modeling, design, and simulations were performed using Wolfram Mathematica (Champaign, IL; v. 9.0) and Ansys High Frequency Structure Simulator (HFSS; Canonsburg, PA; v. 15.0). A micro-strip coupling circuit is designed to suppress unwanted modes and provide a balanced impedance transformation to a 50 Ω coaxial input. Agreement between simulated and experimental results is shown.

  5. Optimal dielectric and cavity configurations for improving the efficiency of electron paramagnetic resonance probes.

    PubMed

    Elnaggar, Sameh Y; Tervo, Richard; Mattar, Saba M

    2014-08-01

    An electron paramagnetic resonance (EPR) spectrometer's lambda efficiency parameter (Λ) is one of the most important parameters that govern its sensitivity. It is studied for an EPR probe consisting of a dielectric resonator (DR) in a cavity (CV). Expressions for Λ are derived in terms of the probe's individual DR and CV components, Λ1 and Λ2 respectively. Two important cases are considered. In the first, a probe consisting of a CV is improved by incorporating a DR. The sensitivity enhancement depends on the relative rather than the absolute values of the individual components. This renders the analysis general. The optimal configuration occurs when the CV and DR modes are nearly degenerate. This configuration guarantees that the probe can be easily coupled to the microwave bridge while maintaining a large Λ. It is shown that for a lossy CV with a small quality factor Q2, one chooses a DR that has the highest filling factor, η1, regardless of its Λ1 and Q1. On the other hand, if the CV has a large Q2, the optimum DR is the one which has the highest Λ1. This is regardless of its η1 and relative dielectric constant, ɛr. When the quality factors of both the CV and DR are comparable, the lambda efficiency is reduced by a factor of 2. Thus the signal intensity for an unsaturated sample is cut in half. The second case is the design of an optimum shield to house a DR. Besides preventing radiation leakage, it is shown that for a high loss DR, the shield can actually boost Λ above the DR value. This can also be very helpful for relatively low efficiency dielectrics as well as lossy samples, such as polar liquids. PMID:24937043

  6. Cobalt(II) "scorpionate" complexes as models for cobalt-substituted zinc enzymes: electronic structure investigation by high-frequency and -field electron paramagnetic resonance spectroscopy.

    PubMed

    Krzystek, J; Swenson, Dale C; Zvyagin, S A; Smirnov, Dmitry; Ozarowski, Andrew; Telser, Joshua

    2010-04-14

    A series of complexes of formula Tp(R,R')CoL, where Tp(R,R'-) = hydrotris(3-R,5-R'-pyrazol-1-yl)borate ("scorpionate") anion (R = tert-butyl, R' = H, Me, 2'-thienyl (Tn), L = Cl(-), NCS(-), NCO(-), N(3)(-)), has been characterized by electronic absorption spectroscopy in the visible and near-infrared (near-IR) region and by high-frequency and -field electron paramagnetic resonance (HFEPR). Reported here are also crystal structures of seven members of the series that have not been reported previously: R' = H, L = NCO(-), N(3)(-); R' = Me, L = Cl(-), NCS(-), NCO(-), N(3)(-); R' = Tn, L = Cl(-), NCS(-). These include a structure for Tp(t-Bu,Me)CoCl different from that previously reported. All of the investigated complexes contain a four-coordinate cobalt(II) ion (3d(7)) with approximate C(3v) point group symmetry about the metal ion and exhibit an S = (3)/(2) high-spin ground state. The use of HFEPR allows extraction of the full set of intrinsic S = (3)/(2) spin Hamiltonian parameters (D, E, and g values). The axial zero-field splitting parameter, D, for all investigated Tp(R,R')CoL complexes is always positive, a fact not easily determined by other methods. However, the magnitude of this parameter varies widely: 2.4 cm(-1) electronic structure and bonding in pseudotetrahedral cobalt(II) complexes can enhance the understanding of similar sites in metalloproteins, specifically cobalt-substituted zinc enzymes. PMID:20329727

  7. [The evaluation of mineral crystallinity of mandibular bone tissue using electron paramagnetic resonance (EPR) in patients suffering from renal osteodystrophy].

    PubMed

    Wojtowicz, Andrzej; Dijakiewicz, Maciej; Wandzel, Barbara; Wesołowski, Piotr; Rutkowski, Bolesław; Fiedor, Piotr; Stachowicz, Wacław; Ostrowski, Kazimierz

    2006-01-01

    Mineral crystallinity of bone tissue is subject to changes during one's development, as well as in many systemic diseases, especially renal osteodystrophy. The aim of the study was qualitative evaluation of the mandibular bone tissue in patients suffering from renal osteodytrophy, treated with renal-replacement therapy: hemo-dialysis or allogeneic kidney transplantation. The mineral crystallinity coefficient was evaluated using electron paramagnetic resonance (EPR) based on the observation that ionizing radiation induces paramagnetic centers in hydroxyapatites. The concentration of these centers was used to establish an indicator of crystallinity rate which is a measure of the crystallinity of tissue mineral. On the basis of these results, it is possible to widen the indications for implantological treatment in specific clinical cases. PMID:17479865

  8. Photodynamic treatment of the RIF-1 tumor with verteporfin with online monitoring of tissue oxygen using electron paramagnetic resonance oximetry

    NASA Astrophysics Data System (ADS)

    Pogue, Brian W.; O'Hara, Julia A.; Liu, Ke J.; Hasan, Tayyaba; Swartz, Harold

    1999-06-01

    In this study, treatment of the RIF-1 tumor was examined with photodynamic therapy using Verteprofin (formerly benzoporphyrin derivative, BPD). The effects of two different optical dose rates were examined, with no detectable difference in the tumor regrowth time. Oxygen consumption during PDT could reliably be monitored with electron paramagnetic resonance (EPR) oximetry using an implanted paramagnetic material within the tumor. A reduction of the tumor pO2 was detected in the animals that were followed after treatment, suggesting that there was a compromise to the tumor vasculature that persisted throughout the measurements. At high total doses some of the tumors did not regrow. Altogether these results are indicative of the tumor destruction being caused by destruction of the blood vessels from the treatment.

  9. Structure and dynamics in B12 enzyme catalysis revealed by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Warncke, Kurt

    2009-03-01

    Challenges to the understanding of how protein structure and dynamics contribute to catalysis in enzymes, and the use of time-resolved electron paramagnetic resonance (EPR) spectroscopic techniques to address the challenges, are examined in the context of the coenzyme B12-dependent enzyme, ethanolamine ammonia-lyase (EAL), from Salmonella typhimurium. EAL conducts the homolytic cleavage of the coenzyme cobalt-carbon bond, intraprotein radical migration (5-6 å), and hydrogen atom transfers, which enable the core radical-mediated rearrangement reaction. Thermodynamic and activation parameters are measured in two experimental systems, which were developed to isolate sub-sequences from the multi-step catalytic cycle, as follows: (1) A dimethylsulfoxide (DMSO)/water cryosolvent system is used to prepare the kinetically-arrested enzyme/coenzyme/substrate ternary complex in fluid solution at 230 K.[1] Temperature-step initiated cobalt-carbon bond cleavage and radical pair separation to form the Co(II)-substrate radical pair are monitored by using time-resolved, full-spectrum EPR spectroscopy (234<=T<=250 K).[1] (2) The Co(II)-substrate radical pair is cryotrapped in frozen aqueous solution at T<150 K, and then promoted to react by a temperature step. The reaction of the substrate radical along the native pathway to form the diamagnetic bound products is monitored by using time-resolved, full-spectrum EPR spectroscopy (187<=T<=217 K).[2] High temporal resolution is achieved, because the reactions are dramatically slowed at the low temperatures, relative to the initiation and spectrum acquistion times. The results are combined with high resolution structures of the reactant centers, obtained by pulsed-EPR spectroscopies,[3] and the protein, obtained by structural proteomics[4] and EPR and electron spin echo envelope modulation (ESEEM) in combination with site directed mutagenesis,[5] to approach a molecular level description of protein contributions to catalysis in EAL. [4

  10. Unravelling electronic and structural requisites of triplet-triplet energy transfer by advanced electron paramagnetic resonance and density functional theory

    NASA Astrophysics Data System (ADS)

    Di Valentin, M.; Salvadori, E.; Barone, V.; Carbonera, D.

    2013-10-01

    Advanced electron paramagnetic resonance (EPR) techniques, in combination with Density Functional theory (DFT), have been applied to the comparative study of carotenoid triplet states in two major photosynthetic antenna complexes, the Peridinin-chlorophyll a-protein of dinoflagellates and the light-harvesting complex II of higher plants. Carotenoid triplet states are populated by triplet-triplet energy transfer (TTET) from chlorophyll molecules to photoprotect the system from singlet oxygen formation under light-stress conditions. The TTET process is strongly dependent on the relative arrangement and on the electronic properties of the triplet states involved. The proposed spectroscopic approach exploits the concept of spin conservation during TTET, which leads to recognisable spin polarisation effects in the time-resolved and field-swept echo-detected EPR spectra. The electron spin polarisation produced at the carotenoid acceptor site depends on the initial polarisation of the chlorophyll donor and on the relative geometrical arrangement of the donor-acceptor zero-field splitting axes. We have demonstrated that a proper analysis of the spectra in the framework of spin angular momentum conservation allows to derive the pathways of TTET and to gain insight into the structural requirements of this mechanism for those antenna complexes, whose X-ray structure is available. We have further proved that this method, developed for natural antenna complexes of known X-ray structure, can be extended to systems lacking structural information in order to derive the relative arrangement of the partners in the energy transfer process. The structural requirements for efficient TTET, obtained from time-resolved and pulse EPR, have been complemented by a detailed description of the electronic structure of the carotenoid triplet state, provided by pulse Electron-Nuclear DOuble Resonance (ENDOR) experiments. Triplet-state hyperfine couplings of the α- and β-protons of the

  11. Optical and time-resolved electron paramagnetic resonance studies of the excited states of a UV-B absorber (4-methylbenzylidene)camphor.

    PubMed

    Kikuchi, Azusa; Shibata, Kenji; Kumasaka, Ryo; Yagi, Mikio

    2013-02-21

    The excited states of UV-B absorber (4-methylbenzylidene)camphor (MBC) have been studied through measurements of UV absorption, phosphorescence, triplet-triplet (T-T) absorption, and steady-state and time-resolved electron paramagnetic resonance spectra in ethanol. The energy level and lifetime of the lowest excited triplet (T(1)) state of MBC were determined. The energy level of the T(1) state of MBC is much lower than that of photolabile 4-tert-butyl-4'-methoxydibenzoylmethane. The weak phosphorescence and strong time-resolved EPR signals, and T-T absorption band of MBC were observed. These facts suggest that the significant proportion of the lowest excited singlet (S(1)) molecules undergoes intersystem crossing to the T(1) state and the deactivation process from the T(1) state is predominantly radiationless. The quantum yields of singlet oxygen production by MBC determined by time-resolved near-IR luminescence measurements are 0.05 ± 0.01 and 0.06 ± 0.01 in ethanol and in acetonitrile, respectively. The photostability of MBC arises from the (3)ππ* character in the T(1) state. The zero-field splitting parameters in the T(1) state are D = 0.0901 cm(-1) and E = -0.0498 cm(-1). The sublevel preferentially populated by intersystem crossing is T(y) (y close to in-plane short axis and to the C═O direction). PMID:23320917

  12. Electron paramagnetic resonance and electron-nuclear double resonance study of trapped-hole centers in LiB3O5 crystals

    NASA Astrophysics Data System (ADS)

    Hong, Wei; Chirila, M. M.; Garces, N. Y.; Halliburton, L. E.; Lupinski, D.; Villeval, P.

    2003-09-01

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) have been used to characterize two distinct hole centers in single crystals of LiB3O5 (commonly referred to as LBO). Irradiating a crystal at 77 K with x rays produces an intense four-line holelike EPR signal, with the structure arising from the hyperfine interaction with one 11B nucleus. Warming the crystal to approximately 130 K destroys the first hole center and allows a second less intense four-line holelike EPR signal to be observed (also interacting with one 11B nucleus). The second hole center decays between 150 and 200 K. EPR and ENDOR angular dependence data were used to determine the g matrix and the 11B hyperfine and nuclear quadrupole matrices for each hole center. We suggest that the first (less thermally stable) center is a self-trapped hole. In this defect, the hole is localized primarily on an oxygen ion between a threefold bonded boron and a fourfold bonded boron, and the self-trapping occurs because of a significant relaxation of the neighboring fourfold boron away from the hole. GAUSSIAN 98 calculations, using a (B3O7H4)0 cluster to represent the defect and the nearby lattice, support this self-trapping mechanism. A similar model is suggested for the second hole center, except in this case a neighboring lithium vacancy is included to provide the increased thermal stability. These trapped-hole centers are of interest because of their possible role in the unwanted transient optical absorption produced in LiB3O5 crystals at room temperature by high-power pulsed ultraviolet lasers.

  13. Scaling craters in carbonates: Electron paramagnetic resonance analysis of shock damage

    NASA Technical Reports Server (NTRS)

    Polanskey, Carol A.; Ahrens, Thomas J.

    1994-01-01

    Carbonate samples from the 8.9-Mt nuclear (near-surface explosion) crater, OAK, and a terrestrial impact crater, Meteor Crater, were analyzed for shock damage using electron paramagnetic resonance (EPR). Samples from below the OAK apparent crater floor were obtained from six boreholes, as well as ejecta recovered from the crater floor. The degree of shock damage in the carbonate material was assessed by comparing the sample spectra to the spectra of Solenhofen and Kaibab limestone, which had been skocked to known pressures. Analysis of the OAK Crater borehole samples has identified a thin zone of allocthonous highly shocked (10-13 GPa) carbonate material underneath the apparent crater floor. This approx. 5- to 15-m-thick zone occurs at a maximum depth of approx. 125 m below current seafloor at the borehole, sited at the initial position of the OAK explosive, and decreases in depth towards the apparent crater edge. Because this zone of allocthonous shocked rock delineates deformed rock below, and a breccia of mobilized sand and collapse debris above, it appears to outline the transient crater. The transient crater volume inferred in this way is found to by 3.2 +/- 0.2 times 10(exp 6)cu m, which is in good agreement with a volume of 5.3 times 10(exp 6)cu m inferred from gravity scaling of laboratory experiments. A layer of highly shocked material is also found near the surface outside the crater. The latter material could represent a fallout ejecta layer. The ejecta boulders recovered from the present crater floor experienced a range of shock pressures from approx. 0 to 15 GPa with the more heavily shocked samples all occurring between radii of 360 and approx. 600 m. Moreover, the fossil content, lithology and Sr isotopic composition all demonstrate that the initial position of the bulk of the heavily shocked rock ejecta sampled was originally near surface rock at initial depths in the 32 to 45-m depth (below sea level) range. The EPR technique is also sensitive to

  14. Location of Trapped Electron Centers in the Bulk of Epitaxial MgO(001) Films Grown on Mo(001) Using in situ W -band Electron Paramagnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Cornu, Damien; Rocker, Jan; Gonchar, Anastasia; Risse, Thomas; Freund, Hans-Joachim

    2016-07-01

    We present the first in situ W -band (94-GHz) electron paramagnetic resonance (EPR) study of a trapped electron center in thin MgO(001) films. The improved resolution of the high-field EPR experiments proves that the signal originate from a well-defined species present in the bulk of the films, whose projection of the principal g -tensor components onto the (001) plane are oriented along the [110] direction of the MgO lattice. Based on a comparison between the structural properties of the films, knowledge of the ability of bulk defects to trap electrons, and the properties of the EPR signal, it is possible to propose that the paramagnetic species are located at the origin of a screw dislocation in the bulk of the film.

  15. On the Electron Paramagnetic Resonance Studies in Mixed Alkali Borate Glasses

    SciTech Connect

    Padmaja, G.; Reddy, T. Goverdhan; Kistaiah, P.

    2011-10-20

    Mixed alkali effect in oxide based glasses is one of the current research activity and studies on the behavior of spectroscopic parameters in these systems are quite important to understand the basic nature of this phenomenon. EPR studies of mixed alkali glasses Li{sub 2}O-K{sub 2}O-ZnO-B{sub 2}O{sub 3} doped with Fe{sup 3+} and Mn{sup 2+} were carried out at room temperature. The EPR spectra show typical resonances of d{sup 5} system (Fe{sup 3+} and Mn{sup 2+}) in all the measured glass specimens. Evaluated hyperfine constant, number of paramagnetic centers and paramagnetic susceptibility values show deviation from the linearity with the progressive substitution of the Li ion with K in glass network.

  16. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment

    NASA Astrophysics Data System (ADS)

    Pham, Chuyen V.; Krueger, Michael; Eck, Michael; Weber, Stefan; Erdem, Emre

    2014-03-01

    Electron paramagnetic resonance (EPR) spectroscopy has been applied to different chemically treated reduced graphene oxide (rGO) and multiwalled carbon nanotubes (CNTs). A narrow EPR signal is visible at g = 2.0029 in both GO and CNT-Oxide from carbon-related dangling bonds. EPR signals became broader and of lower intensity after oxygen-containing functionalities were reduced and partially transformed into thiol groups to obtain thiol-functionalized reduced GO (TrGO) and thiol-functionalized CNT (CNT-SH), respectively. Additionally, EPR investigation of CdSe quantum dot-TrGO hybrid material reveals complete quenching of the TrGO EPR signal due to direct chemical attachment and electronic coupling. Our work confirms that EPR is a suitable tool to detect spin density changes in different functionalized nanocarbon materials and can contribute to improved understanding of electronic coupling effects in nanocarbon-nanoparticle hybrid nano-composites promising for various electronic and optoelectronic applications.

  17. Electron Paramagnetic Resonance and Electron-Nuclear Double Resonance Studies of the Reactions of Cryogenerated Hydroperoxoferric–Hemoprotein Intermediates

    PubMed Central

    2015-01-01

    The fleeting ferric peroxo and hydroperoxo intermediates of dioxygen activation by hemoproteins can be readily trapped and characterized during cryoradiolytic reduction of ferrous hemoprotein–O2 complexes at 77 K. Previous cryoannealing studies suggested that the relaxation of cryogenerated hydroperoxoferric intermediates of myoglobin (Mb), hemoglobin, and horseradish peroxidase (HRP), either trapped directly at 77 K or generated by cryoannealing of a trapped peroxo-ferric state, proceeds through dissociation of bound H2O2 and formation of the ferric heme without formation of the ferryl porphyrin π-cation radical intermediate, compound I (Cpd I). Herein we have reinvestigated the mechanism of decays of the cryogenerated hydroperoxyferric intermediates of α- and β-chains of human hemoglobin, HRP, and chloroperoxidase (CPO). The latter two proteins are well-known to form spectroscopically detectable quasistable Cpds I. Peroxoferric intermediates are trapped during 77 K cryoreduction of oxy Mb, α-chains, and β-chains of human hemoglobin and CPO. They convert into hydroperoxoferric intermediates during annealing at temperatures above 160 K. The hydroperoxoferric intermediate of HRP is trapped directly at 77 K. All studied hydroperoxoferric intermediates decay with measurable rates at temperatures above 170 K with appreciable solvent kinetic isotope effects. The hydroperoxoferric intermediate of β-chains converts to the S = 3/2 Cpd I, which in turn decays to an electron paramagnetic resonance (EPR)-silent product at temperature above 220 K. For all the other hemoproteins studied, cryoannealing of the hydroperoxo intermediate directly yields an EPR-silent majority product. In each case, a second follow-up 77 K γ-irradiation of the annealed samples yields low-spin EPR signals characteristic of cryoreduced ferrylheme (compound II, Cpd II). This indicates that in general the hydroperoxoferric intermediates relax to Cpd I during cryoanealing at low temperatures, but

  18. Cathodoluminescence, laser ablasion inductively coupled plasma mass spectrometry, electron probe microanalysis and electron paramagnetic resonance analyses of natural sphalerite

    USGS Publications Warehouse

    Karakus, M.; Hagni, R.D.; Koenig, A.; Ciftc, E.

    2008-01-01

    Natural sphalerite associated with copper, silver, lead-zinc, tin and tungsten deposits from various world-famous mineral deposits have been studied by cathodoluminescence (CL), laser ablasion inductively coupled plasma mass spectrometry (LA-ICP-MS), electron probe microanalysis (EPMA) and electron paramagnetic resonance (EPR) to determine the relationship between trace element type and content and the CL properties of sphalerite. In general, sphalerite produces a spectrum of CL colour under electron bombardment that includes deep blue, turquoise, lime green, yellow-orange, orange-red and dull dark red depending on the type and concentration of trace quantities of activator ions. Sphalerite from most deposits shows a bright yellow-orange CL colour with ??max centred at 585 nm due to Mn2+ ion, and the intensity of CL is strongly dependent primarily on Fe2+ concentration. The blue emission band with ??max centred at 470-490 nm correlates with Ga and Ag at the Tsumeb, Horn Silver, Balmat and Kankoy mines. Colloform sphalerite from older well-known European lead-zinc deposits and late Cretaceous Kuroko-type VMS deposits of Turkey shows intense yellowish CL colour and their CL spectra are characterised by extremely broad emission bands ranging from 450 to 750 nm. These samples are characterised by low Mn (<10 ppm) and Ag (<1 ppm), and they are enriched in Tl (1-30 ppm) and Pb (80-1500 ppm). Strong green CL is produced by sphalerite from the Balmat-Edwards district. Amber, lime-green and red-orange sphalerite produced weak orange-red CL at room temperatures, with several emission bands centred at 490, 580, 630, 680, 745, with ??max at 630 nm being the strongest. These emission bands are well correlated with trace quantities of Sn, In, Cu and Mn activators. Sphalerite from the famous Ogdensburg and Franklin mines exhibited brilliant deep blue and orange CL colours and the blue CL may be related to Se. Cathodoluminescence behaviour of sphalerite serves to characterise ore

  19. Cryogen-free superconducting magnet system for multifrequency electron paramagnetic resonance up to 12.1 T

    NASA Astrophysics Data System (ADS)

    Smirnov, Alex I.; Smirnova, Tatyana I.; MacArthur, Ryan L.; Good, Jeremy A.; Hall, Renny

    2006-03-01

    Multifrequency and high field/high frequency (HF) electron paramagnetic resonance (EPR) is a powerful spectroscopy for studying paramagnetic spin systems ranging from organic-free radicals to catalytic paramagnetic metal ion centers in metalloproteins. Typically, HF EPR experiments are carried out at resonant frequencies ν =95-300GHz and this requires magnetic fields of 3.4-10.7T for electronic spins with g ≈2.0. Such fields could be easily achieved with superconducting magnets, but, unlike NMR, these magnets cannot operate in a persistent mode in order to satisfy a wide range of resonant fields required by the experiment. Operating and maintaining conventional passively cooled superconducting magnets in EPR laboratories require frequent transfer of cryogens by trained personnel. Here we describe and characterize a versatile cryogen-free magnet system for HF EPR at magnetic fields up to 12.1T that is suitable for ramping the magnetic field over the entire range, precision scans around the target field, and/or holding the field at the target value. We also demonstrate that in a nonpersistent mode of operation the magnetic field can be stabilized to better than 0.3ppm/h over 15h period by employing a transducer-controlled power supply. Such stability is sufficient for many HF EPR experiments. An important feature of the system is that it is virtually maintenance-free because it is based on a cryogen-free technology and therefore does not require any liquid cryogens (liquid helium or nitrogen) for operation. We believe that actively cooled superconducting magnets are ideally suited for a wide range of HF EPR experiments including studies of spin-labeled nucleic acids and proteins, single-molecule magnets, and metalloproteins.

  20. Reactive oxygen species' role in endothelial dysfunction by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Wassall, Cynthia D.

    The endothelium is a single layer of cells lining the arteries and is involved in many physiological reactions which are responsible for vascular tone. Free radicals are important participants in these chemical reactions in the endothelium. Here we quantify free radicals, ex vivo, in biological tissue with continuous wave electron paramagnetic resonance (EPR). In all of the experiments in this thesis, we use a novel EPR spin trapping technique that has been developed for tissue segments. EPR spin trapping is often considered the 'gold standard' in reactive oxygen species (ROS) detection because of its sensitivity and non-invasive nature. In all experiments, tissue was placed in physiological saline solution with 190-mM PBN (N-tert -butyl-α-phenylnitrone), 10% by volume dimethyl-sulphoxide (DMSO) for cryopreservation, and incubated in the dark for between 30 minutes up to 2 hours at 37°C while gently being stirred. Tissue and supernatant were then loaded into a syringe and frozen at -80°C until EPR analysis. In our experiments, the EPR spectra were normalized with respect to tissue volume. Conducting experiments at liquid nitrogen temperature leads to some experimental advantages. The freezing of the spin adducts renders them stable over a longer period, which allows ample time to analyze tissue samples for ROS. The dielectric constant of ice is greatly reduced over its liquid counterpart; this property of water enables larger sample volumes to be inserted into the EPR cavity without overloading it and leads to enhanced signal detection. Due to Maxwell-Boltzmann statistics, the population difference goes up as the temperature goes down, so this phenomenon enhances the signal intensity as well. With the 'gold standard' assertion in mind, we investigated whether slicing tissue to assay ROS that is commonly used in fluorescence experiments will show more free radical generation than tissue of a similar volume that remains unsliced. Sliced tissue exhibited a 76

  1. Reactive oxygen species' role in endothelial dysfunction by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Wassall, Cynthia D.

    The endothelium is a single layer of cells lining the arteries and is involved in many physiological reactions which are responsible for vascular tone. Free radicals are important participants in these chemical reactions in the endothelium. Here we quantify free radicals, ex vivo, in biological tissue with continuous wave electron paramagnetic resonance (EPR). In all of the experiments in this thesis, we use a novel EPR spin trapping technique that has been developed for tissue segments. EPR spin trapping is often considered the 'gold standard' in reactive oxygen species (ROS) detection because of its sensitivity and non-invasive nature. In all experiments, tissue was placed in physiological saline solution with 190-mM PBN (N-tert -butyl-α-phenylnitrone), 10% by volume dimethyl-sulphoxide (DMSO) for cryopreservation, and incubated in the dark for between 30 minutes up to 2 hours at 37°C while gently being stirred. Tissue and supernatant were then loaded into a syringe and frozen at -80°C until EPR analysis. In our experiments, the EPR spectra were normalized with respect to tissue volume. Conducting experiments at liquid nitrogen temperature leads to some experimental advantages. The freezing of the spin adducts renders them stable over a longer period, which allows ample time to analyze tissue samples for ROS. The dielectric constant of ice is greatly reduced over its liquid counterpart; this property of water enables larger sample volumes to be inserted into the EPR cavity without overloading it and leads to enhanced signal detection. Due to Maxwell-Boltzmann statistics, the population difference goes up as the temperature goes down, so this phenomenon enhances the signal intensity as well. With the 'gold standard' assertion in mind, we investigated whether slicing tissue to assay ROS that is commonly used in fluorescence experiments will show more free radical generation than tissue of a similar volume that remains unsliced. Sliced tissue exhibited a 76

  2. Advanced paramagnetic resonance spectroscopies of iron-sulfur proteins: Electron nuclear double resonance (ENDOR) and electron spin echo envelope modulation (ESEEM).

    PubMed

    Cutsail, George E; Telser, Joshua; Hoffman, Brian M

    2015-06-01

    The advanced electron paramagnetic resonance (EPR) techniques, electron nuclear double resonance (ENDOR) and electron spin echo envelope modulation (ESEEM) spectroscopies, provide unique insights into the structure, coordination chemistry, and biochemical mechanism of nature's widely distributed iron-sulfur cluster (FeS) proteins. This review describes the ENDOR and ESEEM techniques and then provides a series of case studies on their application to a wide variety of FeS proteins including ferredoxins, nitrogenase, and radical SAM enzymes. This article is part of a Special Issue entitled: Fe/S proteins: Analysis, structure, function, biogenesis and diseases. PMID:25686535

  3. Annealing of paramagnetic centres in electron- and ion-irradiated yttria-stabilized zirconia: effect of yttria content

    SciTech Connect

    Costantini, Jean-Marc; Beuneu, Francois; Weber, William J

    2014-01-01

    We have studied the effect of the yttria content on the recovery of paramagnetic centres in electron-irradiated yttria-stabilized zirconia (ZrO2: Y3+). Single crystals with 9.5 mol% or 18 mol% Y2O3 were irradiated with electrons of 1.0, 1.5, 2.0 and 2.5 MeV. Paramagnetic centre thermal annealing was studied by X-band EPR spectroscopy. Hole-centres are found to be annealed more quickly, or at a lower temperature, for 18 mol% than for 9.5 mol% Y2O3. At long annealing times, a non-zero asymptotic behaviour is observed in the isothermal annealing curves of hole-centres and F+-type centres between 300 and 500 K. The normalized asymptotic concentration of both defects has a maximum value of about 0.5 for annealing temperatures near 375 K, below the onset of the (isochronal) recovery stage, regardless of the yttria content. Such an uncommon behaviour is analyzed on the basis of either kinetic rate equations of charge transfer or equilibria between point defects with different charge states.

  4. High-resolution mapping of 1D and 2D dose distributions using X-band electron paramagnetic resonance imaging.

    PubMed

    Kolbun, N; Adolfsson, E; Gustafsson, H; Lund, E

    2014-06-01

    Electron paramagnetic resonance imaging (EPRI) was performed to visualise 2D dose distributions of homogenously irradiated potassium dithionate tablets and to demonstrate determination of 1D dose profiles along the height of the tablets. Mathematical correction was applied for each relative dose profile in order to take into account the inhomogeneous response of the resonator using X-band EPRI. The dose profiles are presented with the spatial resolution of 0.6 mm from the acquired 2D images; this value is limited by pixel size, and 1D dose profiles from 1D imaging with spatial resolution of 0.3 mm limited by the intrinsic line-width of potassium dithionate. In this paper, dose profiles from 2D reconstructed electron paramagnetic resonance (EPR) images using the Xepr software package by Bruker are focussed. The conclusion is that using potassium dithionate, the resolution 0.3 mm is sufficient for mapping steep dose gradients if the dosemeters are covering only ±2 mm around the centre of the resonator. PMID:24748487

  5. Direct evidence of complete charge separation in the excited triplet state of 1,2-( N-arylaziridino)-[60] fullerenes by means of time-resolved electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Yamauchi, Seigo; Iwasaki, Yohei; Ohba, Yasunori; Awen, Bahlul Z. S.; Ouchi, Akihiko

    2005-08-01

    Some of 1,6-( N-substituted) aza-[60] fulleroids ( 1) and their corresponding photochemical reaction products, 1,2-( N-substituted) aziridino-[60] fullerenes ( 2) showed peculiar transient absorption peaks depending on the N-substituents. Although these bands are considered to concern with very slow photochemical rearrangements 1 → 2 in the excited triplet state, no definitive evidence has been obtained yet. We report on the character of the excited triplet states in these compounds by means of a time-resolved electron paramagnetic resonance technique. Definitive evidence on the involvement of intra-molecular charge transfer states is shown in this Letter.

  6. Me{sup 5}C{sup 5}Ni(acac): A monomeric, paramagnetic, 18-electron, spin-equilibrium molecule

    SciTech Connect

    Smith, M.E.; Anderson, R.A. |

    1996-11-13

    New synthetic procedures have been developed for Me{sup 5}C{sup 5}M(acac), M = Co or Ni. The crystal structures of these 17- or 18-electron monomers show that the compounds are isomorphous and in space group P1{bar O}, with the planes defined by the Me{sup 5}C{sup 5} ring and the M(acac) fragment perpendicular to within 5{degree}. The Me{sup 5}C{sup 5} ring in both molecules has an ene-allyl distortion which is rationalized by the low molecular symmetry (C{sup s}), which removes the degeneracy in the e{sup +} and e{sup -} ring orbitals. The electronic structure of the cobalt compound is {sup 2}A, as deduced from magnetic susceptibility and EPR spectroscopy. The electronic structure of the nickel compound depends upon the temperature. In the solid state, the compound is diamagnetic below 150 K, but it becomes paramagnetic with increasing temperature. The {sup 1}H NMR chemical shift of the compound in solution are nonlinear in temperature, and a plot of {delta} vs T{sup -1} yields an equilibrium constant of 0.47 at 303 K for the low spin high spin equilibrium. The 20-electron phosphine complexes of nickel can be isolated; Me{sup 5}C{sup 5}Ni(acac)(PMe{sup 3}) is a simple paramagnet with two unpaired spins, but the PEt{sup 3} complex exists in equilibrium with its base-free compound in solution. The cobalt compound does not give an isolable phosphine complex. A simple symmetry orbital model is proposed that accounts for the electronic and molecular structures of these organometallic compounds. 34 refs., 7 figs., 5 tabs.

  7. Applications of electron paramagnetic resonance spectroscopy to study interactions of iron proteins in cells with nitric oxide

    NASA Astrophysics Data System (ADS)

    Cammack, R.; Shergill, J. K.; Ananda Inalsingh, V.; Hughes, Martin N.

    1998-12-01

    Nitric oxide and species derived from it have a wide range of biological functions. Some applications of electron paramagnetic resonance (EPR) spectroscopy are reviewed, for observing nitrosyl species in biological systems. Nitrite has long been used as a food preservative owing to its bacteriostatic effect on spoilage bacteria. Nitrosyl complexes such as sodium nitroprusside, which are added experimentally as NO-generators, themselves produce paramagnetic nitrosyl species, which may be seen by EPR. We have used this to observe the effects of nitroprusside on clostridial cells. After growth in the presence of sublethal concentrations of nitroprusside, the cells show they have been converted into other, presumably less toxic, nitrosyl complexes such as (RS) 2Fe(NO) 2. Nitric oxide is cytotoxic, partly due to its effects on mitochondria. This is exploited in the destruction of cancer cells by the immune system. The targets include iron-sulfur proteins. It appears that species derived from nitric oxide such as peroxynitrite may be responsible. Addition of peroxynitrite to mitochondria led to depletion of the EPR-detectable iron-sulfur clusters. Paramagnetic complexes are formed in vivo from hemoglobin, in conditions such as experimental endotoxic shock. This has been used to follow the course of production of NO by macrophages. We have examined the effects of suppression of NO synthase using biopterin antagonists. Another method is to use an injected NO-trapping agent, Fe-diethyldithiocarbamate (Fe-DETC) to detect accumulated NO by EPR. In this way we have observed the effects of depletion of serum arginine by arginase. In brains from victims of Parkinson's disease, a nitrosyl species, identified as nitrosyl hemoglobin, has been observed in substantia nigra. This is an indication for the involvement of nitric oxide or a derived species in the damage to this organ.

  8. Experimental and theoretical Electron Paramagnetic Resonance (EPR) study on the temperature-dependent structural changes of methylsulfanylmethane.

    PubMed

    Tapramaz, Recep; Türkkan, Ercan; Dereli, Ömer

    2011-01-01

    Methylsulfonylmethane (or dimethyl sulfone), a naturally produced and vitally important organosulfur compound in living organisms, was irradiated with gamma rays, and the produced radicals were investigated using electron paramagnetic resonance spectroscopy at different temperatures. The structure and behavior of the radical changed when the temperatures varied. The hyperfine splitting of the CH(3) group was small, and the (33)S splitting was relatively high between 80 and -50 °C. When the temperature was between -50 and -160 °C, the (33)S splitting became small and the CH(3) splitting was higher. However, the group kept rotating; therefore, only the isotropic splitting values were measured, and the g-values were anisotropic. When the temperature decreased below -180 °C, the CH(3) group stopped rotating, and the hydrogen splitting values became nonequivalent due to an inhomogeneous electron distribution. The observed structures can be explained by referring to both the experimental and theoretically calculated values reported. PMID:21954334

  9. Electrical and electron paramagnetic resonance spectroscopy characterization of Mn-doped nanostructured TiO2 for capacitor applications

    NASA Astrophysics Data System (ADS)

    Vazquez-Reina, Rafael; Chao, Sheng; Petrovsky, Vladimir; Dogan, Fatih; Greenbaum, Steven

    2012-07-01

    Nanostructured TiO2 has shown promise as a dielectric material for high energy density ceramic capacitors because of its high dielectric breakdown strength and dielectric constant. Strategies to increase the insulation resistance or to reduce the leakage current of TiO2 include doping with transition metal ions. It is shown that Mn doping followed by an appropriate thermal treatment increases the grain boundary resistivity significantly and lowers the dielectric loss. Electrical measurements along with electron paramagnetic resonance and scanning electron microscopy of Mn-doped nanoscopic TiO2 demonstrate that sintering at 900 °C leads to optimal electrical properties that are correlated with a non-uniform distribution of dopant ions, concentrated at the grain boundaries. Nanostructured TiO2 dielectrics with improved insulation resistance are promising for the development of higher energy density capacitors.

  10. Synthesis and EPR Characterization of Exohedrally Perfluoroalkylated Paramagnetic Lanthanum Metallofullerenes: A Fluorous Phase Approach

    NASA Astrophysics Data System (ADS)

    Tagmatarchis, Nikos; Taninaka, Atsushi; Shinohara, Hisanori; Prato, Maurizio

    2002-10-01

    A strategy to chemically derivatize the outer sphere of endohedral metallofullerenes by using a modern organic technique that utilizes a fluorous synthesis-partitioning approach has been developed. The newly synthesized materials were found to be paramagnetic species and were characterized by electron paramagnetic resonance spectroscopy (EPR), laser desorption time-of-flight spectrometry (LD-TOF) and electronic absorption spectroscopy (UV-VIS-NIR). The systematic study of exohedrally derivatized endohedral metallofullerenes should ultimately provide technologically intriguing novel nano-materials.

  11. Electron paramagnetic resonance (EPR) study of spin-labeled camptothecin derivatives: a different look of the ternary complex.

    PubMed

    Ricci, Antonio; Marinello, Jessica; Bortolus, Marco; Sánchez, Albert; Grandas, Anna; Pedroso, Enrique; Pommier, Yves; Capranico, Giovanni; Maniero, Anna Lisa; Zagotto, Giuseppe

    2011-02-24

    Camptothecin (CPT) derivatives are clinically effective poisons of DNA topoisomerase I (Top1) able to form a ternary complex with the Top1-DNA complex. The aim of this investigation was to examine the dynamic aspects of the ternary complex formation by means of site-directed spin labeling electron paramagnetic resonance (SDSL-EPR). Two semisynthetic CPT derivatives bearing the paramagnetic moiety were synthesized, and their biological activity was tested. A 22-mer DNA oligonucleotide sequence with high affinity cleavage site for Top1 was also synthesized. EPR experiments were carried out on modified CPT in the presence of DNA, of Top1, or of both. In the last case, a slow motion component in the EPR signal appeared, indicating the formation of the ternary complex. Deconvolution of the EPR spectrum allowed to obtain the relative drug amounts in the complex. It was also possible to demonstrate that the residence time of CPT "trapped" in the ternary complex is longer than hundreds of microseconds. PMID:21254781

  12. High-frequency (95 GHz) electron paramagnetic resonance study of the photoinduced charge transfer in conjugated polymer-fullerene composites

    NASA Astrophysics Data System (ADS)

    Ceuster, J. De; Goovaerts, E.; Bouwen, A.; Hummelen, J. C.; Dyakonov, V.

    2001-11-01

    Light-induced electron paramagnetic resonance (LEPR) measurements are reported in composites of poly(2-methoxy-5-(3-,7-dimethyloctyloxy)-1,4-phenylenevinylene) (MDMO-PPV) and [6,6]-phenyl-C61-butyric acid methyl ester (PCBM), a soluble derivative of C60. Under illumination of the sample, two paramagnetic species are formed due to photoinduced charge transfer between conjugated polymer and fullerene. One is the positive polaron P+ on the polymer backbone and the other is the radical anion on the methanofullerene. Using high-frequency (95 GHz) LEPR it was possible to separate these two contributions to the spectrum on the basis of their g factors, and moreover to resolve the g anisotropy for both radicals. The positive polaron on the conjugated polymer chain possesses axial symmetry with g values g||=2.0034(1) and g⊥=2.0024(1). EPR on low doped polymer gave extra proof for the assignment to the positive polaron. The negatively charged methanofullerene has a lower, rhombic symmetry with gx=2.0003(1), gy=2.0001(1), and gz=1.9982(1). Different spin-lattice relaxation of both species gives rise to a rapid passage effect for the positive polaron spectrum.

  13. Site selective substitution Pt for Ti in KTiOPO{sub 4}:Ga crystals revealed by electron paramagnetic resonance

    SciTech Connect

    Grachev, V.; Meyer, M.; Jorgensen, J.; Malovichko, G.; Hunt, A. W.

    2014-07-28

    Electron Paramagnetic Resonance at low temperatures has been used to characterize potassium titanyl phosphate (KTiOPO{sub 4}) single crystals grown by different techniques. Irradiation with 20 MeV electrons performed at room temperature and liquid nitrogen temperature caused an appearance of electrons and holes. Platinum impurities act as electron traps in KTiOPO{sub 4} creating Pt{sup 3+} centers. Two different Pt{sup 3+} centers were observed, Pt(A) and Pt(D). The Pt(A) centers are dominant in undoped samples, whereas Pt(D)—in Ga-doped KTP crystals. Superhyperfine structure registered for Pt(D) centers was attributed to interactions of platinum electrons with {sup 39}K and two {sup 31}P nuclei in their surroundings. In both Pt(A) and Pt(D) centers, Pt{sup 3+} ions substitute for Ti{sup 4+} ions, but with a preference to one of two electrically distinct crystallographic positions. The site selective substitution can be controlled by the Ga-doping.

  14. Effect of electron scavengers on the formation of paramagnetic species upon radiolysis of polystyrene and its low-molecular-weight analogs

    SciTech Connect

    Zezin, A.A.; Fel`dman, V.I.; Sukhov, F.F.

    1995-05-01

    The effect of electron scavengers on the composition and the yields of paramagnetic species upon the radiolysis of polystyrene was examined. Various mechanisms of the reactions of radical cations (holes) in low-molecular-weight aromatic hydrocarbons and polystyrene are discussed. The dimeric radical cations were found to be trapped in polystyrene and benzene irradiated in the presence of electron scavengers at 77 K. The yield of paramagnetic species was shown to increase markedly in the presence of small amounts (<1%) of chloroform of benzyl chloride. The results obtained show that the ionic processes make a large contribution to the formation of paramagnetic species. It is concluded that the radiation resistance of polystyrene is due not only to its chemical structure, but to the association of phenyl rings in the solid polymer.

  15. Itinerant 5 f Electrons and the Fermi Surface Properties in an Enhanced Pauli Paramagnet NpGe3

    NASA Astrophysics Data System (ADS)

    Aoki, Dai; Yamagami, Hiroshi; Homma, Yoshiya; Shiokawa, Yoshinobu; Yamamoto, Etsuji; Nakamura, Akio; Haga, Yoshinori; Settai, Rikio; Ōnuki, Yoshichika

    2005-08-01

    We succeeded in growing a high-quality single crystal of an enhanced Pauli paramagnet, NpGe3, by the Bi-flux method, and observed the de Haas-van Alphen (dHvA) effect. The topology of a Fermi surface is well explained by the relativistic linear augmented-plane-wave (LAPW) band calculations based on the 5 f itinerant band model. The Fermi surface consists of a nearly spherical electron-Fermi surface with necks along the < 100 > direction, forming a hollow ball, centered at the R point, which is derived from the single band. The cyclotron effective mass is in the range from 2.6 to 16 m0, which is enhanced approximately 3.5 times from the corresponding band mass.

  16. Investigation of the generation of singlet oxygen in ensembles of photoexcited silicon nanocrystals by electron paramagnetic resonance spectroscopy

    SciTech Connect

    Konstantinova, E. A. Demin, V. A.; Timoshenko, V. Yu.

    2008-09-15

    The generation of singlet oxygen is investigated and its concentration upon photoexcitation of silicon nanocrystals in porous silicon layers is determined using electron paramagnetic resonance spectroscopy. The relaxation times of spin centers, i.e., silicon dangling bonds, in vacuum and in an oxygen atmosphere in the dark and under illumination of the samples are measured for the first time. It is revealed that the spin-lattice relaxation in porous silicon is retarded as compared to that in a single-crystal substrate. From analyzing experimental data, a microscopic model is proposed for interaction of oxygen molecules in the triplet state and spin centers at the surface of silicon nanocrystals. The results obtained have demonstrated that porous silicon holds promise for the use as a photosensitizer of molecular oxygen in biomedical applications.

  17. Determination of S-nitrosothiols in biological and clinical samples using electron paramagnetic resonance spectrometry with spin trapping.

    PubMed

    Winyard, Paul G; Knight, Iona A; Shaw, Frances L; Rocks, Sophie A; Davies, Claire A; Eggleton, Paul; Haigh, Richard; Whiteman, Matthew; Benjamin, Nigel

    2008-01-01

    S-Nitroso moieties, such as the S-nitroso group within S-nitrosated albumin, constitute a potential endogenous reservoir of nitric oxide (NO.) in human tissues and other biological systems. Moreover, S-nitroso compounds are under investigation as therapeutic agents in humans. Therefore, it is important to be able to detect S-nitrosothiols (RSNOs) in human extracellular fluids, such as plasma and synovial fluid, as well as other biological samples. This chapter describes a method for the determination of S-nitrosothiols in biofluids. The method is based on electron paramagnetic resonance (EPR) spectrometry, in combination with spin trapping using a ferrous ion complex of the iron chelator N-methyl-d-glucamine dithiocarbamate under alkaline conditions. This iron complex mediates the decomposition of RSNO to NO., as well as spin trapping the generated NO.. The resulting spin adduct has a unique EPR signal that can be quantified. PMID:18554533

  18. In vivo pO2 imaging of tumors: Oxymetry with very low frequency Electron Paramagnetic Resonance

    PubMed Central

    Epel, Boris; Halpern, Howard J.

    2016-01-01

    For over a century it has been known that tumor hypoxia, regions of a tumor with low levels of oxygenation, are important contributors to tumor resistance to radiation therapy and failure of radiation treatment of cancer. Recently, using novel pulse electron paramagnetic resonance (EPR) oxygen imaging, near absolute images of the partial pressure of oxygen (pO2) in tumors of living animals have been obtained. We discuss here the means by which EPR signals can be obtained in living tissues and tumors. We review development of EPR methods to image the pO2 in tumors and the potential for the pO2 image acquisition in human subjects. PMID:26477263

  19. Fluorescence properties and electron paramagnetic resonance studies of {gamma}-irradiated Sm{sup 3+}-doped oxyfluoroborate glasses

    SciTech Connect

    Babu, B. Hari; Ravi Kanth Kumar, V. V.

    2012-11-01

    The permanent photoinduced valence manipulation of samarium doped oxyfluoroborate glasses as a function of {gamma}-ray irradiation has been investigated using a steady-state fluorescence and electron paramagnetic resonance techniques. An increase in SrF{sub 2} content in the glass led to the red shift of the peaks in as prepared glass, while in irradiated glasses this led to the decrease in defect formation as well as increase in photoreduction of Sm{sup 3+} to Sm{sup 2+} ion. The energy transfer mechanism of induced permanent photoreduction of Sm{sup 3+} to Sm{sup 2+} ions in oxyfluoroborate glasses has been discussed. The decay analysis shows exponential behavior before irradiation and non-exponential behavior after irradiation. The energy transfer in irradiated glasses increases with the increase in SrF{sub 2} content in the glass and also with the irradiation dose.

  20. Theoretical and electron paramagnetic resonance studies of hyperfine interaction in nitrogen doped 4H and 6H SiC

    SciTech Connect

    Szász, K.; Gali, A.

    2014-02-21

    Motivated by recent experimental findings on the hyperfine signal of nitrogen donor (N{sub C}) in 4 H and 6 H SiC, we calculate the hyperfine tensors within the framework of density functional theory. We find that there is negligible hyperfine coupling with {sup 29}Si isotopes when N{sub C} resides at h site both in 4 H and 6 H SiC. We observe measurable hyperfine coupling to a single {sup 29}Si at k site in 4 H SiC and k{sub 1} site in 6 H SiC. Our calculations unravel that such {sup 29}Si hyperfine coupling does not occur at k{sub 2} site in 6 H SiC. Our findings are well corroborated by our new electron paramagnetic resonance studies in nitrogen doped 6 H SiC.

  1. Electron paramagnetic resonance and Raman spectroscopy studies on carbon-doped MgB{sub 2} superconductor nanomaterials

    SciTech Connect

    Bateni, Ali; Somer, Mehmet E-mail: msomer@ku.edu.tr; Erdem, Emre E-mail: msomer@ku.edu.tr; Repp, Sergej; Weber, Stefan; Acar, Selcuk; Kokal, Ilkin; Häßler, Wolfgang

    2015-04-21

    Undoped and carbon-doped magnesium diboride (MgB{sub 2}) samples were synthesized using two sets of mixtures prepared from the precursors, amorphous nanoboron, and as-received amorphous carbon-doped nanoboron. The microscopic defect structures of carbon-doped MgB{sub 2} samples were systematically investigated using X-ray powder diffraction, Raman and electron paramagnetic resonance spectroscopy. Mg vacancies and C-related dangling-bond active centers could be distinguished, and sp{sup 3}-hybridized carbon radicals were detected. A strong reduction in the critical temperature T{sub c} was observed due to defects and crystal distortion. The symmetry effect of the latter is also reflected on the vibrational modes in the Raman spectra.

  2. X-Band Rapid-Scan Electron Paramagnetic Resonance of Radiation-Induced Defects in Tooth Enamel

    PubMed Central

    Yu, Zhelin; Romanyukha, Alexander; Eaton, Sandra S.; Eaton, Gareth R.

    2015-01-01

    X-band rapid-scan electron paramagnetic resonance (EPR) spectra from tooth enamel samples irradiated with doses of 0.5, 1 and 10 Gy had substantially improved signal-to-noise relative to conventional continuous wave EPR. The radiation-induced signal in 60 mg of a tooth enamel sample irradiated with a 0.5 Gy dose was readily characterized in spectra recorded with 34 min data acquisition times. The coefficient of variance of the calculated dose for a 1 Gy irradiated sample, based on simulation of the first-derivative spectra for three replicates as the sum of native and radiation-induced signals, was 3.9% for continuous wave and 0.4% for rapid scan. PMID:26207683

  3. Electron paramagnetic resonance spectral study of [Mn(acs)2(2-pic)2(H2O)2] single crystals

    NASA Astrophysics Data System (ADS)

    Kocakoç, Mehpeyker; Tapramaz, Recep

    2016-03-01

    Acesulfame potassium salt is a synthetic and non-caloric sweetener. It is also important chemically for its capability of being ligand in coordination compounds, because it can bind over Nitrogen and Oxygen atoms of carbonyl and sulfonyl groups and ring oxygen. Some acesulfame containing transition metal ion complexes with mixed ligands exhibit solvato and thermo chromic properties and these properties make them physically important. In this work single crystals of Mn+2 ion complex with mixed ligand, [Mn(acs)2(2-pic)2(H2O)2], was studied with electron paramagnetic resonance (EPR) spectroscopy. EPR parameters were determined. Zero field splitting parameters indicated that the complex was highly symmetric. Variable temperature studies showed no detectable chance in spectra.

  4. Antioxidant activity of grape skin aqueous extracts from pressurized hot water extraction combined with electron paramagnetic resonance spectroscopy.

    PubMed

    Sťavíková, Lenka; Polovka, Martin; Hohnová, Barbora; Karásek, Pavel; Roth, Michal

    2011-09-30

    Pressurized hot water extraction (PHWE) was employed to prepare extracts from dried grape skin of two wine grape varieties (St. Laurent and Alibernet) at various temperatures (from 40 up to 120°C) and amounts of sample (0.5, 1.0 and 1.5 g). To assess the antioxidant activity of the extracts, electron paramagnetic resonance (EPR) spectroscopy was applied involving DPPH and ABTS(+) assays. Other extract characteristics including HPLC profile of anthocyanins and total phenolic compound content were obtained as well. PHWE has also been compared with earlier results of extractions of the same grape skin samples with compressed methanol and compressed ethanol under the conditions of pressurized fluid extraction (PFE). From this comparison, PHWE emerges as the more benign and efficient extraction method to recover valuable phenolic antioxidants from grape skins for the prospective use in functional food supplements. PMID:21872083

  5. Comparative identification of irradiated herbs by the methods of electron paramagnetic resonance and thermoluminescence

    NASA Astrophysics Data System (ADS)

    Yordanov, N. D.; Gancheva, V.; Radicheva, M.; Hristova, B.; Guelev, M.; Penchev, O.

    1998-12-01

    Non irradiated and γ-irradiated dry herbs savoury ( Savoury), wild thyme ( Thymus serpollorium) and marjoram ( Origanum) with absorbed dose of 8 kGy have been investigated by the methods of elecrtron paramagnetic resonance (EPR) and thermoluminescence (TL). Non-irradiated herbs exhibit only one weak siglet EPR signal whereas in irradiated samples its intensity increase and in addition two satelite lines are recorded. This triplet EPR spectrum is attributed to cellulose free radical generated by irradiation. It has been found that upon keeping the samples under the normal stock conditions the life-time of the cellulose free radical in the examined samples is ˜60-80 days. Thus the conclusion has been made that the presence of the EPR signal of cellulose free radical is unambiguous indication that the sample under study has been irradiated but its absence can not be considered as the opposite evidence. In the case when EPR signal was absent the method of TL has been used to give the final decision about the previous radiation treatment of the sample.

  6. Detection of undistorted continuous wave (CW) electron paramagnetic resonance (EPR) spectra with non-adiabatic rapid sweep (NARS) of the magnetic field

    PubMed Central

    Kittell, Aaron W.; Camenisch, Theodore G.; Ratke, Joseph J.; Sidabras, Jason W.; Hyde, James S.

    2011-01-01

    A continuous wave (CW) electron paramagnetic resonance (EPR) spectrum is typically displayed as the first harmonic response to the application of 100 kHz magnetic field modulation, which is used to enhance sensitivity by reducing the level of 1/f noise. However, magnetic field modulation of any amplitude causes spectral broadening and sacrifices EPR spectral intensity by at least a factor of two. In the work presented here, a CW rapid-scan spectroscopic technique that avoids these compromises and also provides a means of avoiding 1/f noise is developed. This technique, termed non-adiabatic rapid sweep (NARS) EPR, consists of repetitively sweeping the polarizing magnetic field in a linear manner over a spectral fragment with a small coil at a repetition rate that is sufficiently high that receiver noise, microwave phase noise, and environmental microphonics, each of which has 1/f characteristics, are overcome. Nevertheless, the rate of sweep is sufficiently slow that adiabatic responses are avoided and the spin system is always close to thermal equilibrium. The repetitively acquired spectra from the spectral fragment are averaged. Under these conditions, undistorted pure absorption spectra are obtained without broadening or loss of signal intensity. A digital filter such as a moving average is applied to remove high frequency noise, which is approximately equivalent in bandwidth to use of an integrating time constant in conventional field modulation with lock-in detection. Nitroxide spectra at L- and X-band are presented. PMID:21741868

  7. Comparative electron paramagnetic resonance investigation of reduced graphene oxide and carbon nanotubes with different chemical functionalities for quantum dot attachment

    SciTech Connect

    Pham, Chuyen V.; Krueger, Michael E-mail: emre.erdem@physchem.uni-freiburg.de; Eck, Michael; Weber, Stefan; Erdem, Emre E-mail: emre.erdem@physchem.uni-freiburg.de

    2014-03-31

    Electron paramagnetic resonance (EPR) spectroscopy has been applied to different chemically treated reduced graphene oxide (rGO) and multiwalled carbon nanotubes (CNTs). A narrow EPR signal is visible at g = 2.0029 in both GO and CNT-Oxide from carbon-related dangling bonds. EPR signals became broader and of lower intensity after oxygen-containing functionalities were reduced and partially transformed into thiol groups to obtain thiol-functionalized reduced GO (TrGO) and thiol-functionalized CNT (CNT-SH), respectively. Additionally, EPR investigation of CdSe quantum dot-TrGO hybrid material reveals complete quenching of the TrGO EPR signal due to direct chemical attachment and electronic coupling. Our work confirms that EPR is a suitable tool to detect spin density changes in different functionalized nanocarbon materials and can contribute to improved understanding of electronic coupling effects in nanocarbon-nanoparticle hybrid nano-composites promising for various electronic and optoelectronic applications.

  8. Electron paramagnetic resonance studies of gamma-irradiated DL-alanine ethyl ester hydrochloride, L-theanine and L-glutamic acid dimethyl ester hydrochloride.

    PubMed

    Başkan, M Halim; Aydın, Murat

    2013-08-01

    The electron paramagnetic resonance (EPR) of gamma irradiated powders of DL-alanine ethyl ester hydrochloride, L-theanine and L-glutamic acid dimethyl ester hydrochloride were investigated at room temperature. The observed paramagnetic species were attributed to the CH3ĊHCOOC2H5, -CH2ĊHCOOH and -CH2ĊHCOOCH3 radicals, respectively. Hyperfine structure constants and g-values were determined for these three radicals. Some spectroscopic properties and suggestions concerning the possible structure of the radicals were also discussed. PMID:23680512

  9. Electron paramagnetic resonance studies of gamma-irradiated DL-alanine ethyl ester hydrochloride, L-theanine and L-glutamic acid dimethyl ester hydrochloride

    NASA Astrophysics Data System (ADS)

    Başkan, M. Halim; Aydın, Murat

    2013-08-01

    The electron paramagnetic resonance (EPR) of gamma irradiated powders of DL-alanine ethyl ester hydrochloride, L-theanine and L-glutamic acid dimethyl ester hydrochloride were investigated at room temperature. The observed paramagnetic species were attributed to the CH3ĊHCOOC2H5, -CH2ĊHCOOH and -CH2ĊHCOOCH3 radicals, respectively. Hyperfine structure constants and g-values were determined for these three radicals. Some spectroscopic properties and suggestions concerning the possible structure of the radicals were also discussed.

  10. A QUANTUM MECHANICAL STUDY OF STRUCTURAL AND ELECTRONIC DILUTION EFFECTS IN PARAMAGNETIC CHEMICAL EXCHANGE SATURATION TRANSFER AGENTS

    PubMed Central

    Miller, Whelton A.; Moore, Preston B.

    2014-01-01

    We present a computational study of the effect of chemical modifications of the meta and para substituents in the coordinating pendant arm of a modified 1,4,7,10-tetraazacyclododecane-N, N’, N″, N‴-tetraamide (DOTAM) ligand on the Chemical Exchange Saturation Transfer (CEST) signal. Magnetic Resonance Imaging (MRI) is currently one of the most widely used techniques available. MRI has led to a new class of pharmaceuticals termed “imagining” or “contrast” agents. These agents usually work by incorporating lanthanide metals such as Gadolinium (Gd) and Europium (Eu). This allows the contrast agents to take advantage of the paramagnetic properties of the metals, which in turn enhances the signal detectable by MRI. The effect of simple electron-withdrawing (e.g., nitro) and electron-donating (e.g., methyl) substituents chemically attached to a modified chelate arm (pendant arm) is quantified by charge transfer interactions in the coordinated water-chelate system computed from quantum mechanics. This study attempts to reveal the origin of the substituent effect on the CEST signal and the electronic structure of the complex. We find that the extent of Charge Transfer (CT) depends on orbital orientations and overlaps. However, CT interactions occur simultaneously from all arms, which causes a dilution effect with respect to the pendant arm. PMID:25485283

  11. Molecular shock response of explosives: electronic absorption spectroscopy

    SciTech Connect

    Mcgrne, Shawn D; Moore, David S; Whitley, Von H; Bolme, Cindy A; Eakins, Daniel E

    2009-01-01

    Electronic absorption spectroscopy in the range 400-800 nm was coupled to ultrafast laser generated shocks to begin addressing the question of the extent to which electronic excitations are involved in shock induced reactions. Data are presented on shocked polymethylmethacrylate (PMMA) thin films and single crystal pentaerythritol tetranitrate (PETN). Shocked PMMA exhibited thin film interference effects from the shock front. Shocked PETN exhibited interference from the shock front as well as broadband increased absorption. Relation to shock initiation hypotheses and the need for time dependent absorption data (future experiments) is briefly discussed.

  12. A Ku band pulsed electron paramagnetic resonance spectrometer using an arbitrary waveform generator for quantum control experiments at millikelvin temperatures.

    PubMed

    Yap, Yung Szen; Tabuchi, Yutaka; Negoro, Makoto; Kagawa, Akinori; Kitagawa, Masahiro

    2015-06-01

    We present a 17 GHz (Ku band) arbitrary waveform pulsed electron paramagnetic resonance spectrometer for experiments down to millikelvin temperatures. The spectrometer is located at room temperature, while the resonator is placed either in a room temperature magnet or inside a cryogen-free dilution refrigerator; the operating temperature range of the dilution unit is from ca. 10 mK to 8 K. This combination provides the opportunity to perform quantum control experiments on electron spins in the pure-state regime. At 0.6 T, spin echo experiments were carried out using γ-irradiated quartz glass from 1 K to 12.3 mK. With decreasing temperatures, we observed an increase in spin echo signal intensities due to increasing spin polarizations, in accordance with theoretical predictions. Through experimental data fitting, thermal spin polarization at 100 mK was estimated to be at least 99%, which was almost pure state. Next, to demonstrate the ability to create arbitrary waveform pulses, we generate a shaped pulse by superposing three Gaussian pulses of different frequencies. The resulting pulse was able to selectively and coherently excite three different spin packets simultaneously-a useful ability for analyzing multi-spin system and for controlling a multi-qubit quantum computer. By applying this pulse to the inhomogeneously broadened sample, we obtain three well-resolved excitations at 8 K, 1 K, and 14 mK. PMID:26133831

  13. A Ku band pulsed electron paramagnetic resonance spectrometer using an arbitrary waveform generator for quantum control experiments at millikelvin temperatures

    SciTech Connect

    Yap, Yung Szen; Tabuchi, Yutaka; Negoro, Makoto; Kagawa, Akinori; Kitagawa, Masahiro

    2015-06-15

    We present a 17 GHz (Ku band) arbitrary waveform pulsed electron paramagnetic resonance spectrometer for experiments down to millikelvin temperatures. The spectrometer is located at room temperature, while the resonator is placed either in a room temperature magnet or inside a cryogen-free dilution refrigerator; the operating temperature range of the dilution unit is from ca. 10 mK to 8 K. This combination provides the opportunity to perform quantum control experiments on electron spins in the pure-state regime. At 0.6 T, spin echo experiments were carried out using γ-irradiated quartz glass from 1 K to 12.3 mK. With decreasing temperatures, we observed an increase in spin echo signal intensities due to increasing spin polarizations, in accordance with theoretical predictions. Through experimental data fitting, thermal spin polarization at 100 mK was estimated to be at least 99%, which was almost pure state. Next, to demonstrate the ability to create arbitrary waveform pulses, we generate a shaped pulse by superposing three Gaussian pulses of different frequencies. The resulting pulse was able to selectively and coherently excite three different spin packets simultaneously—a useful ability for analyzing multi-spin system and for controlling a multi-qubit quantum computer. By applying this pulse to the inhomogeneously broadened sample, we obtain three well-resolved excitations at 8 K, 1 K, and 14 mK.

  14. Design and implementation of an FPGA-based timing pulse programmer for pulsed-electron paramagnetic resonance applications

    PubMed Central

    Sun, Li; Savory, Joshua J.; Warncke, Kurt

    2014-01-01

    The design, construction and implementation of a field-programmable gate array (FPGA) -based pulse programmer for pulsed-electron paramagnetic resonance (EPR) experiments is described. The FPGA pulse programmer offers advantages in design flexibility and cost over previous pulse programmers, that are based on commercial digital delay generators, logic pattern generators, and application-specific integrated circuit (ASIC) designs. The FPGA pulse progammer features a novel transition-based algorithm and command protocol, that is optimized for the timing structure required for most pulsed magnetic resonance experiments. The algorithm was implemented by using a Spartan-6 FPGA (Xilinx), which provides an easily accessible and cost effective solution for FPGA interfacing. An auxiliary board was designed for the FPGA-instrument interface, which buffers the FPGA outputs for increased power consumption and capacitive load requirements. Device specifications include: Nanosecond pulse formation (transition edge rise/fall times, ≤3 ns), low jitter (≤150 ps), large number of channels (16 implemented; 48 available), and long pulse duration (no limit). The hardware and software for the device were designed for facile reconfiguration to match user experimental requirements and constraints. Operation of the device is demonstrated and benchmarked by applications to 1-D electron spin echo envelope modulation (ESEEM) and 2-D hyperfine sublevel correlation (HYSCORE) experiments. The FPGA approach is transferrable to applications in nuclear magnetic resonance (NMR; magnetic resonance imaging, MRI), and to pulse perturbation and detection bandwidths in spectroscopies up through the optical range. PMID:25076864

  15. A Ku band pulsed electron paramagnetic resonance spectrometer using an arbitrary waveform generator for quantum control experiments at millikelvin temperatures

    NASA Astrophysics Data System (ADS)

    Yap, Yung Szen; Tabuchi, Yutaka; Negoro, Makoto; Kagawa, Akinori; Kitagawa, Masahiro

    2015-06-01

    We present a 17 GHz (Ku band) arbitrary waveform pulsed electron paramagnetic resonance spectrometer for experiments down to millikelvin temperatures. The spectrometer is located at room temperature, while the resonator is placed either in a room temperature magnet or inside a cryogen-free dilution refrigerator; the operating temperature range of the dilution unit is from ca. 10 mK to 8 K. This combination provides the opportunity to perform quantum control experiments on electron spins in the pure-state regime. At 0.6 T, spin echo experiments were carried out using γ-irradiated quartz glass from 1 K to 12.3 mK. With decreasing temperatures, we observed an increase in spin echo signal intensities due to increasing spin polarizations, in accordance with theoretical predictions. Through experimental data fitting, thermal spin polarization at 100 mK was estimated to be at least 99%, which was almost pure state. Next, to demonstrate the ability to create arbitrary waveform pulses, we generate a shaped pulse by superposing three Gaussian pulses of different frequencies. The resulting pulse was able to selectively and coherently excite three different spin packets simultaneously—a useful ability for analyzing multi-spin system and for controlling a multi-qubit quantum computer. By applying this pulse to the inhomogeneously broadened sample, we obtain three well-resolved excitations at 8 K, 1 K, and 14 mK.

  16. Quantitative determination of copper in a glass matrix using double pulse laser induced breakdown and electron paramagnetic resonance spectroscopic techniques.

    PubMed

    Khalil, Ahmed A I; Morsy, Mohamed A

    2016-07-01

    A series of lithium-lead-borate glasses of a variable copper oxide loading were quantitatively analyzed in this work using two distinct spectroscopic techniques, namely double pulse laser induced breakdown spectroscopy (DP-LIBS) and electron paramagnetic resonance (EPR). DP-LIBS results measured upon a combined nanosecond lasers irradiation running at 266nm and 1064nm pulses of a collinear configuration directed to the surface of borate glass samples with a known composition. This arrangement was employed to predict the electron's temperature (Te) and density (Ne) of the excited plasma from the recorded spectra. The intensity of elements' responses using this scheme is higher than that of single-pulse laser induced breakdown spectroscopy (SP-LIBS) setup under the same experimental conditions. On the other hand, the EPR data shows typical Cu (II) EPR-signals in the borate glass system that is networked at a distorted tetragonal Borate-arrangement. The signal intensity of the Cu (II) peak at g⊥=2.0596 has been used to quantify the Cu-content accurately in the glass matrix. Both techniques produced linear calibration curves of Cu-metals in glasses with excellent linear regression coefficient (R(2)) values. This study establishes a good correlation between DP-LIBS analysis of glass and the results obtained using EPR spectroscopy. The proposed protocols prove the great advantage of DP-LIBS system for the detection of a trace copper on the surface of glasses. PMID:27154655

  17. Design and implementation of an FPGA-based timing pulse programmer for pulsed-electron paramagnetic resonance applications.

    PubMed

    Sun, Li; Savory, Joshua J; Warncke, Kurt

    2013-08-01

    The design, construction and implementation of a field-programmable gate array (FPGA) -based pulse programmer for pulsed-electron paramagnetic resonance (EPR) experiments is described. The FPGA pulse programmer offers advantages in design flexibility and cost over previous pulse programmers, that are based on commercial digital delay generators, logic pattern generators, and application-specific integrated circuit (ASIC) designs. The FPGA pulse progammer features a novel transition-based algorithm and command protocol, that is optimized for the timing structure required for most pulsed magnetic resonance experiments. The algorithm was implemented by using a Spartan-6 FPGA (Xilinx), which provides an easily accessible and cost effective solution for FPGA interfacing. An auxiliary board was designed for the FPGA-instrument interface, which buffers the FPGA outputs for increased power consumption and capacitive load requirements. Device specifications include: Nanosecond pulse formation (transition edge rise/fall times, ≤3 ns), low jitter (≤150 ps), large number of channels (16 implemented; 48 available), and long pulse duration (no limit). The hardware and software for the device were designed for facile reconfiguration to match user experimental requirements and constraints. Operation of the device is demonstrated and benchmarked by applications to 1-D electron spin echo envelope modulation (ESEEM) and 2-D hyperfine sublevel correlation (HYSCORE) experiments. The FPGA approach is transferrable to applications in nuclear magnetic resonance (NMR; magnetic resonance imaging, MRI), and to pulse perturbation and detection bandwidths in spectroscopies up through the optical range. PMID:25076864

  18. Electron Paramagnetic Resonance: a tool for in situ detection, imaging and dating of biosignatures in primitive organic matter

    NASA Astrophysics Data System (ADS)

    Gourier, D.; Binet, L.; Vezin, H.

    2012-04-01

    Electron Paramagnetic Resonance (EPR) spectroscopy and imaging are based on the interaction of a microwave electromagnetic field (typically in the GHz range) with electron spins in presence of an external magnetic field. Contrary to UV-visible and Infrared light, microwave radiation can penetrate in most non conducting materials, so that EPR is sensitive to the bulk (and not to the surface) of samples. All the paramagnetic defects, impurities, point defects in the mineral matrix, radicals in carbonaceous matter of an ancient rock can be detected by this technique. As the most ancient traces of life, as old as 3.5 Gy, are recorded as carbonaceous microstructures in siliceous sedimentary structures (cherts), the radical defects of these microstructures can be probed in situ without sample preparation. By using continuous-wave EPR, the fossilized carbonaceous matter can be mapped at the sub-millimeter scale (EPR imaging)[1], and can be dated with respect to the host rock (evolution of the EPR lineshape)[2]. Thus this method could be used for contamination detection (endolithic bacteria, infiltration etc…). By using pulsed-EPR spectroscopy (instead of continuous wave), nuclear magnetic transitions of elements in and around radicals can be detected with a high resolution and sensitivity. We show that specific nuclear transitions for hydrogen (1H and 2D) and 13C (and other nuclei such as 29Si and 31P) can be identified in extraterrestrial carbonaceous matter (meteorites) and in Precambrian and younger cherts. These pulsed techniques provide molecular scale biosignatures for primitive life detection and internal probes to study the history of organic matter in the early solar system [3,4]. Paramagnetic biosignatures are not limited to the organic component of cherts. Specific EPR biosignatures of metal ions can be detected in biominerals such as MnO2 [5] or in molecular V4+ complexes [6]. EPR is thus a potential technique for the search of primitive life on Earth and

  19. Accurate prediction of electron-paramagnetic-resonance tensors for spin probes dissolved in liquid crystals.

    PubMed

    Benzi, Caterina; Cossi, Maurizio; Barone, Vincenzo

    2005-11-15

    High-level ab initio g and A tensor components have been calculated for PD-tempone and tempo-palmitate (TP) radical spin probes dissolved in n-pentyl and n-hexyl cyanobiphenyl liquid crystals. Solvent effects have been included in the proposed approach by means of the polarizable continuum model, allowing for solvent anisotropy. An in-depth analysis of the electronic structure of probes was performed to choose a suitable model for TP and make the calculations more accessible. Computed magnetic tensor components have been compared with corresponding values measured in the rigid limit. The quality of the results suggests the use of quantum-mechanical data to determine the order parameter of the nematic from experimental electron-spin resonance measurements. PMID:16321115

  20. Free radicals generated during oxidation of green tea polyphenols: electron paramagnetic resonance spectroscopy combined with density functional theory calculations.

    PubMed

    Severino, Joyce Ferreira; Goodman, Bernard A; Kay, Christopher W M; Stolze, Klaus; Tunega, Daniel; Reichenauer, Thomas G; Pirker, Katharina F

    2009-04-15

    Electron paramagnetic resonance spectroscopy and density functional theory calculations have been used to investigate the redox properties of the green tea polyphenols (GTPs) (-)-epigallocatechin gallate (EGCG), (-)-epigallocatechin (EGC), and (-)-epicatechin gallate (ECG). Aqueous extracts of green tea and these individual phenols were autoxidized at alkaline pH and oxidized by superoxide anion (O(2)(-)) radicals in dimethyl sulfoxide. Several new aspects of the free radical chemistry of GTPs were revealed. EGCG can be oxidized on both the B and the D ring. The B ring was the main oxidation site during autoxidation, but the D ring was the preferred site for O(2)(-) oxidation. Oxidation of the D ring was followed by structural degradation, leading to generation of a radical identical to that of oxidized gallic acid. Alkaline autoxidation of green tea extracts produced four radicals that were related to products of the oxidation of EGCG, EGC, ECG, and gallic acid, whereas the spectra from O(2)(-) oxidation could be explained solely by radicals generated from EGCG. Assignments of hyperfine coupling constants were made by DFT calculations, allowing the identities of the radicals observed to be confirmed. PMID:19439236

  1. A quantitative method to monitor reactive oxygen species production by electron paramagnetic resonance in physiological and pathological conditions.

    PubMed

    Mrakic-Sposta, Simona; Gussoni, Maristella; Montorsi, Michela; Porcelli, Simone; Vezzoli, Alessandra

    2014-01-01

    The growing interest in the role of Reactive Oxygen Species (ROS) and in the assessment of oxidative stress in health and disease clashes with the lack of consensus on reliable quantitative noninvasive methods applicable. The study aimed at demonstrating that a recently developed Electron Paramagnetic Resonance microinvasive method provides direct evidence of the "instantaneous" presence of ROS returning absolute concentration levels that correlate with "a posteriori" assays of ROS-induced damage by means of biomarkers. The reliability of the choice to measure ROS production rate in human capillary blood rather than in plasma was tested (step I). A significant (P < 0.01) linear relationship between EPR data collected on capillary blood versus venous blood (R (2) = 0.95), plasma (R (2) = 0.82), and erythrocytes (R (2) = 0.73) was found. Then (step II) ROS production changes of various subjects' categories, young versus old and healthy versus pathological at rest condition, were found significantly different (range 0.0001-0.05 P level). The comparison of the results with antioxidant capacity and oxidative damage biomarkers concentrations showed that all changes indicating increased oxidative stress are directly related to ROS production increase. Therefore, the adopted method may be an automated technique for a lot of routine in clinical trials. PMID:25374651

  2. One-dimensional quantum antiferromagnetism in the p -orbital CsO2 compound revealed by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Knaflič, Tilen; Klanjšek, Martin; Sans, Annette; Adler, Peter; Jansen, Martin; Felser, Claudia; Arčon, Denis

    2015-05-01

    Recently, it was proposed that the orbital ordering of πx,y * molecular orbitals in the superoxide CsO2 compound leads to the formation of spin-1/2 chains below the structural phase transition occurring at Ts 1=61 K on cooling. Here we report a detailed X -band electron paramagnetic resonance (EPR) study of this phase in CsO2 powder. The EPR signal appears as a broad line below Ts 1, which is replaced by the antiferromagnetic resonance below the Néel temperature TN=8.3 K . The temperature dependence of the EPR linewidth between Ts 1 and TN agrees with the predictions for the one-dimensional Heisenberg antiferromagnetic chain of S =1 /2 spins in the presence of symmetric anisotropic exchange interaction. Complementary analysis of the EPR line shape, linewidth, and the signal intensity within the Tomonaga-Luttinger liquid (TLL) framework allows for a determination of the TLL exponent K =0.48 . Present EPR data thus fully comply with the quantum antiferromagnetic state of spin-1/2 chains in the orbitally ordered phase of CsO2, which is therefore a unique p -orbital system where such a state could be studied.

  3. Molecular distances from dipolar coupled spin-labels: the global analysis of multifrequency continuous wave electron paramagnetic resonance data.

    PubMed Central

    Hustedt, E J; Smirnov, A I; Laub, C F; Cobb, C E; Beth, A H

    1997-01-01

    For immobilized nitroxide spin-labels with a well-defined interprobe geometry, resolved dipolar splittings can be observed in continuous wave electron paramagnetic resonance (CW-EPR) spectra for interelectron distances as large as 30 A using perdeuterated probes. In this work, algorithms are developed for calculating CW-EPR spectra of immobilized, dipolar coupled nitroxides, and then used to define the limits of sensitivity to the interelectron distance as a function of geometry and microwave frequency. Secondly, the CW-EPR spectra of N epsilon-spin-labeled coenzyme NAD+ bound to microcrystalline, tetrameric glyceraldehyde-3-phosphate dehydrogenase (GAPDH) have been collected at 9.8, 34, and 94 GHz. These data have been analyzed, using a combination of simulated annealing and global analysis, to obtain a unique fit to the data. The values of the intermitroxide distance and the five angles defining the relative orientation of the two nitroxides are in reasonable agreement with a molecular model built from the known crystal structure. Finally, the effect of rigid body isotropic rotational diffusion on the CW-EPR spectra of dipolar coupled nitroxides has been investigated using an algorithm based on Brownian dynamics trajectories. These calculations demonstrate the sensitivity of CW-EPR spectra to dipolar coupling in the presence of rigid body rotational diffusion. PMID:9083690

  4. Investigation of Antioxidant Activity of Pomegranate Juices by Means of Electron Paramagnetic Resonance and UV-Vis Spectroscopy.

    PubMed

    Kozik, Violetta; Jarzembek, Krystyna; Jędrzejowska, Agnieszka; Bąk, Andrzej; Polak, Justyna; Bartoszek, Mariola; Pytlakowska, Katarzyna

    2015-01-01

    Pomegranate fruit (Punica granatum L.) is a source of numerous phenolic compounds, and it contains flavonoids such as anthocyanins, anthocyanidins, cyanidins, catechins and other complexes of flavonoids, ellagitannins, and hydrolyzed tannins. Pomegranate juice shows antioxidant, antiproliferative, and anti-atherosclerotic properties. The antioxidant capacity (TEAC) of the pomegranate juices was measured using electron paramagnetic resonance (EPR) spectroscopy and 1,1-diphenyl-2-picrylhydrazyl (DPPH•) as a source of free radicals, and the total phenolic (TP) content was measured using UV-Vis spectroscopy. All the examined pomegranate juices exhibited relatively high antioxidant properties. The TEAC values determined by means of EPR spectroscopy using Trolox (TE) as a free radical scavenger were in the range of 463.12 to 1911.91 μmol TE/100 mL juice. The TP content measured by the Folin-Ciocalteu method, using gallic acid (GA) as a free radical scavenger, widely varied in the investigated pomegranate juice samples and ranged from 1673.62 to 5263.87 mg GA/1 L juice. The strongest antioxidant properties were observed with the fresh pomegranate juices obtained from the fruits originating from Israel, Lebanon, and Azerbaijan. Correlation analysis of numerical data obtained by means of EPR spectroscopy (TEAC) and UV-Vis spectroscopy (TP) gave correlation coefficient (r)=0.90 and determination coefficient (r2)=0.81 (P<0.05). PMID:26268964

  5. Evaluation of synergistic antioxidant potential of complex mixtures using oxygen radical absorbance capacity (ORAC) and electron paramagnetic resonance (EPR).

    PubMed

    Parker, Tory L; Miller, Samantha A; Myers, Lauren E; Miguez, Fernando E; Engeseth, Nicki J

    2010-01-13

    Previous research has demonstrated that certain combinations of compounds result in a decrease in toxic or pro-oxidative effects, previously noted when compounds were administered singly. Thus, there is a need to study many complex interactions further. Two in vitro techniques [electron paramagnetic resonance (EPR) and oxygen radical absorbance capacity (ORAC) assays] were used in this study to assess pro- and antioxidant capacity and synergistic potential of various compounds. Rutin, p-coumaric acid, abscisic acid, ascorbic acid, and a sugar solution were evaluated individually at various concentrations and in all 26 possible combinations at concentrations found in certain foods (honey or papaya), both before and after simulated digestion. EPR results indicated sugar-containing combinations provided significantly higher antioxidant capacity; those combinations containing sugars and ascorbic acid demonstrated synergistic potential. The ORAC assay suggested additive effects, with some combinations having synergistic potential, although fewer combinations were significantly synergistic after digestion. Finally, ascorbic acid, caffeic acid, quercetin, and urate were evaluated at serum-achievable levels. EPR analysis did not demonstrate additive or synergistic potential, although ORAC analysis did, principally in combinations containing ascorbic acid. PMID:19957934

  6. Design and evaluation of a 1.1-GHz surface coil resonator for electron paramagnetic resonance-based tooth dosimetry.

    PubMed

    Sugawara, Hirotaka; Hirata, Hiroshi; Petryakov, Sergey; Lesniewski, Piotr; Williams, Benjamin B; Flood, Ann Barry; Swartz, Harold M

    2014-06-01

    This paper describes an optimized design of a surface coil resonator for in vivo electron paramagnetic resonance (EPR)-based tooth dosimetry. Using the optimized resonator, dose estimates with the standard error of the mean of approximately 0.5 Gy were achieved with irradiated human teeth. The product of the quality factor and the filling factor of the resonator was computed as an index of relative signal intensity in EPR tooth dosimetry by the use of 3-D electromagnetic wave simulator and radio frequency circuit design environment (ANSYS HFSS and Designer). To verify the simulated results of the signal intensity in our numerical model of the resonator and a tooth sample, we experimentally measured the radiation-induced signals from an irradiated tooth with an optimally designed resonator. In addition to the optimization of the resonator design, we demonstrated the improvement of the stability of EPR spectra by decontamination of the surface coil resonator using an HCl solution, confirming that contamination of small magnetic particles on the silver wire of the surface coil had degraded the stability of the EPR spectral baseline. PMID:24845300

  7. Identifying the Constituents of and Transformations in Diatomaceous Earth and Polysiloxane Foams Through the Use of Electron Paramagnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Blair, Michael; Muenchausen, Ross; Bennett, Bryan; Smith, James; Stephens, Thomas; Cooke, Wayne

    2007-03-01

    The chemical aging of polymeric materials is largely governed by the characteristics of the storage environment. For polysiloxane foams, the diatomaceous earth (DE) filler is a small component of the foam, but it plays a large role in the handling of water in the system. The DE filler can act as either a ``source'' or a ``sink'' for water via both chemical hydroxylation/ dehydroxylation and physical adsorption/ desorption processes, depending on the processing history and storage conditions. We have used electron paramagnetic resonance (EPR) spectroscopy to examine composite foam material as well as the DE filler alone. Intense, broad (400 Gauss) resonances were recorded at room temperature as a function of the microwave power at X-band frequency. The observed spectra have been assigned to the iron oxide compounds goethite, lepidocrocite, hematite, and magnetite based upon the measured EPR spectra of these minerals. As the presence or absence of free H2O and the temperature of processing and storage also affects the interconversion of these various iron oxides, we indicate how this process can be followed by monitoring changes in the EPR spectra.

  8. Electron paramagnetic resonance studies of the soluble CuA protein from the cytochrome ba3 of Thermus thermophilus.

    PubMed Central

    Karpefors, M; Slutter, C E; Fee, J A; Aasa, R; Källebring, B; Larsson, S; Vänngård, T

    1996-01-01

    The electron paramagnetic resonance (EPR) spectrum of the binuclear CuA center in the water-soluble subunit II fragment from cytochrome ba3 of Thermus thermophilus was recorded at 3.93, 9.45, and 34.03 GHz, and the EPR parameters were determined by computer simulations. The frequency and M1 dependence of the linewidth was discussed in terms of g strain superimposed on a correlation between the A and g values. The g values were found to be gx = 1.996, gy = 2.011, gz = 2.187, and the two Cu ions contribute nearly equally to the hyperfine structure, with magnitude of Ax magnitude of approximately 15 G, magnitude of Ay magnitude = 29 G, and magnitude of Az magnitude of = 28.5 G (65Cu). Theoretical CNDO/S calculations, based on the x-ray structure of the Paracoccus denitrificans enzyme, yield a singly occupied antibonding orbital in which each Cu is pi*-bonded to one S and sigma*-bonded to the other. In contrast to the equal spin distribution suggested by the EPR simulations, the calculated contributions from the Cu ions differ by a factor of 2. However, only small changes in the ligand geometry are needed to reproduce the experimental results. PMID:8913619

  9. Electron paramagnetic resonance linewidth narrowing of Gd3+ ions in Y-doped ceria nanocrystals with decreasing crystallite size.

    PubMed

    Rakhmatullin, R M; Aminov, L K; Kurkin, I N; Böttcher, R; Pöppl, A; Avila-Paredes, H; Kim, S; Sen, S

    2009-09-28

    Electron paramagnetic resonance (EPR) spectra of Gd(3+) ions in crystalline Ce(1-x-y)Gd(x)Y(y)O(2-[0.5*(x+y)]) (x=0.0025, y=0.10, and 0.25) with crystallite sizes ranging from 600 nm down to 5 nm have been measured at X-band and at Q-band near liquid He and room temperatures. The EPR line shape is controlled by the low-symmetry surrounding of Gd(3+) ions in a coordination environment with one oxygen-vacancy and seven oxygen nearest-neighbors forming GdO(7) polyhedra. These coordination polyhedra are characterized by a wide distribution of crystal field parameters that primarily controls the EPR linewidth. The EPR linewidth of the central (-1/2 <--> +1/2) transition is observed to decrease systematically with decreasing crystallite size. This observation implies that the size of the crystallites in the nanoregime may have important influence on the energetics of vacancy distribution in crystalline materials. PMID:19791902

  10. A Quantitative Method to Monitor Reactive Oxygen Species Production by Electron Paramagnetic Resonance in Physiological and Pathological Conditions

    PubMed Central

    Mrakic-Sposta, Simona; Gussoni, Maristella; Montorsi, Michela; Porcelli, Simone; Vezzoli, Alessandra

    2014-01-01

    The growing interest in the role of Reactive Oxygen Species (ROS) and in the assessment of oxidative stress in health and disease clashes with the lack of consensus on reliable quantitative noninvasive methods applicable. The study aimed at demonstrating that a recently developed Electron Paramagnetic Resonance microinvasive method provides direct evidence of the “instantaneous” presence of ROS returning absolute concentration levels that correlate with “a posteriori” assays of ROS-induced damage by means of biomarkers. The reliability of the choice to measure ROS production rate in human capillary blood rather than in plasma was tested (step I). A significant (P < 0.01) linear relationship between EPR data collected on capillary blood versus venous blood (R2 = 0.95), plasma (R2 = 0.82), and erythrocytes (R2 = 0.73) was found. Then (step II) ROS production changes of various subjects' categories, young versus old and healthy versus pathological at rest condition, were found significantly different (range 0.0001–0.05 P level). The comparison of the results with antioxidant capacity and oxidative damage biomarkers concentrations showed that all changes indicating increased oxidative stress are directly related to ROS production increase. Therefore, the adopted method may be an automated technique for a lot of routine in clinical trials. PMID:25374651

  11. Early folding events during light harvesting complex II assembly in vitro monitored by pulsed electron paramagnetic resonance.

    PubMed

    Fehr, Niklas; García-Rubio, Inés; Jeschke, Gunnar; Paulsen, Harald

    2016-06-01

    Efficient energy transfer in the major light harvesting complex II (LHCII) of green plants is facilitated by the precise alignment of pigments due to the protein matrix they are bound to. Much is known about the import of the LHCII apoprotein into the chloroplast via the TOC/TIC system and its targeting to the thylakoid membrane but information is sparse about when and where the pigments are bound and how this is coordinated with protein folding. In vitro, the LHCII apoprotein spontaneously folds and binds its pigments if the detergent-solubilized protein is combined with a mixture of chlorophylls a and b and carotenoids. In the present work, we employed this approach to study apoprotein folding and pigment binding in a time-resolved manner by using pulsed electron paramagnetic resonance (EPR). Intra-molecular distances were measured before folding, after 255 ms and 40 s folding time in the absence of cryoprotectant, and in the fully folded and assembled LHCII. In accordance with earlier results, the most of the folding of the three membrane-spanning alpha helices precedes their apposition into the final tertiary structure. However, their formation follows different kinetics, partially extending into the final phase of LHCII formation during which much of the condensation of the pigment-protein structure occurs, presumably governed by the binding of chlorophyll b. A rough timetable is proposed to sort partial events into the LHCII formation process. PMID:27063475

  12. Electron paramagnetic resonance- (EPR-) resolved kinetics of cryogenic nitric oxide recombination to cytochrome c oxidase and myoglobin.

    PubMed Central

    LoBrutto, R; Wei, Y H; Yoshida, S; Van Camp, H L; Scholes, C P; King, T E

    1984-01-01

    By the electron paramagnetic resonance (EPR) technique, recovery kinetics for nitric oxide (NO) to heme following cryogenic photolysis were studied for the nitrosylferrocytochrome a3 center in cytochrome c oxidase and for myoglobin. The recovery was nonexponential, as has been observed in previous cryogenic CO and O2 rebinding to heme systems. NO rebinding to heme a3 started near a temperature of 50 K and was related to a distribution of thermal activation energies. At the peak of the distribution the activation energy was 3.1 kcal/mol, and the preexponential in the recovery rate was 10(9.9) s-1. For recovery of NO back to the a3 heme, the activation energy was threefold less than that for CO where CO binds to nearby Cua3 following photolysis from heme a3, but was larger than the activation energy for CO, O2, and probably NO rebinding to myoglobin. NO ligand rebinding to myoglobin occurred at a temperature as low as 15 K and in a temperature regime where tunneling could occur. However, the rate of NO rebinding to myoglobin did increase with temperature in the 15-25 K range. PMID:6320917

  13. Electron paramagnetic resonance study of partially oriented clay platelets intercalated with copper(II) 1,4,8,11-tetraazacyclotetradecane.

    PubMed

    So, Hyunsoo; Jung, Hyun; Choy, Jin-Ho; Belford, R Linn

    2005-03-01

    Electron paramagnetic resonance (EPR) spectra of powder and oriented films of montmorillonite, hectorite, and saponite intercalated with [Cu(cyclam)](2+) (cyclam = 1,4,8,11-tetraazacyclotetradecane) exhibit three components: an orientation-dependent component without hyperfine features, an orientation-dependent component with hyperfine features, and an orientation-independent component without hyperfine feature. EPR spectra of [Cu(cyclam)](2+)-saponite, which exhibit only two components and the best resolved hyperfine features, were simulated. The spectra indicate that a large portion of the saponite platelets are inclined to the glass surface, although they tend to align with their basal planes parallel to the glass surface. The orientation-dependent spectra could be simulated by introducing a Gaussian distribution with a standard deviation of 20 degrees for the inclination angle. The standard deviation may be used as a disorder parameter for the microcrystals assembled on glass plates. Spectral simulation also shows that the CuN(4) plane of [Cu(cyclam)](2+) is parallel to the clay layers. EPR spectra of some other partially oriented systems are also discussed. PMID:16851360

  14. Electron Paramagnetic Resonance Study of the Free Radical Scavenging Capacity of Curcumin and Its Demethoxy and Hydrogenated Derivatives.

    PubMed

    Morales, Noppawan Phumala; Sirijaroonwong, Srisuporn; Yamanont, Paveena; Phisalaphong, Chada

    2015-01-01

    The quantitative free radical scavenging capacity of curcumin and its demethoxy derivatives (demethoxycurcumin (Dmc) and bisdemethoxycurcumin (Bdmc)) and hydrogenated derivatives (tetrahydrocurcumin (THC), hexahydrocurcumin (HHC) and octahydrocurcumin (OHC)) towards 1,1-diphenyl-2-picryl hydrazyl (DPPH), nitric oxide radical (NO), hydroxyl radical (HO(·)) and superoxide anion radical (O2(·)) were investigated by electron paramagnetic resonance (EPR) spectroscopy. One mole of the hydrogenated derivatives scavenged about 4 mol of the DPPH radical, while curcumin and Dmc scavenged about 3 mol of the DPPH radical. Curcumin and THC showed moderate scavenging activity towards NO, yielding 200 mmol of NO scavenged per 1 mol of the scavenger. In contrast, curcumin and its derivatives showed very low scavenging activity towards HO(·) and O2(·), yielding approximately only 3-12 mmol scavenged per 1 mol of the tested compounds. Our results suggest that curcumin and its derivatives principally act as chain breaking antioxidants rather than as direct free radical scavengers. Furthermore, we showed that the ortho-methoxyphenolic group and the heptadione linkage of these molecules greatly contributed to their DPPH and NO scavenging activity. PMID:26424013

  15. Phenolic composition and related antioxidant properties in differently colored lettuces: a study by electron paramagnetic resonance (EPR) kinetics.

    PubMed

    Pérez-López, Usue; Pinzino, Calogero; Quartacci, Mike Frank; Ranieri, Annamaria; Sgherri, Cristina

    2014-12-10

    Differently colored lettuce (Lactuca sativa L.) cultivars (green, green/red, and red) were studied to correlate their phenolic composition with their antioxidant kinetic behavior. Electron paramagnetic resonance (EPR) was employed to monitor decay kinetics of 1,1-diphenyl-2-picrylhydrazyl (DPPH(•)), which allowed the identification of three differently paced antioxidants. The results showed that as long as lettuce had higher red pigmentation, the hydrophilic antioxidant capacity increased together with the contents in free and conjugated phenolic acids, free and conjugated flavonoids, and anthocyanins. EPR allowed the identification of slow-rate antioxidants in green and green/red cultivars, intermediate-rate antioxidants in green, green/red, and red cultivars, and fast-rate antioxidants in green/red and red cultivars. At present, the different kinetic behaviors cannot be attributed to a specific antioxidant, but it is suggested that the flavonoid quercetin accounted for the majority of the intermediate-rate antioxidants, whereas the anthocyanins accounted for the majority of the fast-rate antioxidants. PMID:25389053

  16. Electronic structure and optic absorption of phosphorene under strain

    NASA Astrophysics Data System (ADS)

    Duan, Houjian; Yang, Mou; Wang, Ruiqiang

    2016-07-01

    We studied the electronic structure and optic absorption of phosphorene (monolayer of black phosphorus) under strain. Strain was found to be a powerful tool for the band structure engineering. The in-plane strain in armchair or zigzag direction changes the effective mass components along both directions, while the vertical strain only has significant effect on the effective mass in the armchair direction. The band gap is narrowed by compressive in-plane strain and tensile vertical strain. Under certain strain configurations, the gap is closed and the energy band evolves to the semi-Dirac type: the dispersion is linear in the armchair direction and is gapless quadratic in the zigzag direction. The band-edge optic absorption is completely polarized along the armchair direction, and the polarization rate is reduced when the photon energy increases. Strain not only changes the absorption edge (the smallest photon energy for electron transition), but also the absorption polarization.

  17. Probing the donor side of photosystem II in spinach chloroplasts and algae using electron paramagnetic resonance

    SciTech Connect

    Boska, M.D.

    1985-11-01

    this work concerns electron transfer reactions in photosystem II (PS II). Investigations carried out in this work examine the redox reaction rates in PS II using EPR. In Tris-washed PS II preparations from spinach, it is observed that the oxidation kinetics of S II/sub f/, the EPR signal formed by Z/sup +/ after deactivation of oxygen evolution, mirror the reduction kinetics of P680/sup +/ seen by EPR in samples poised at a variety of pH's. These data agree with previous data on the optically measured reduction kinetics of P680/sup +/. The oxidation kinetics of S II/sub vf/, the EPR transient seen from Z/sup +/ in samples active in O/sub 2/ evolving samples, were instrument limited (t/sub 1/2/ less than 4 ..mu..s) and thus could not be directly measured. These results taken together support a model where Z donates electrons directly to P680/sup +/. The examination of the oxidation and reduction kinetics of S II in monovalent and divalent salt-washed PS II preparations from spinach correlated most of the change of Z oxidation and re-reduction kinetics seen upon Tris-treatment with the loss of a 33 kDa polypeptide associated with the donor side of PS II. These data coupled with observations of stead-state light-induced amplitude changes in S II give evidence for the existance of an electron carrier between the water-splitting enzyme and Z. Observation of S II amplitude and kinetics in highly resolved PS II protein complexes from Synechoccus sp., consisting of either a 5 polypeptide PS II core complex (E-1) or a 4 polypeptide PS II core complex (CP2b), localize Z and P680 within the 4 polypeptide complex. 187 refs., 17 figs., 7 tabs.

  18. Visible to deep ultraviolet range optical absorption of electron irradiated borosilicate glass

    NASA Astrophysics Data System (ADS)

    Wang, Tie-Shan; Duan, Bing-Huang; Tian, Feng; Peng, Hai-Bo; Chen, Liang; Zhang, Li-Min; Yuan, Wei

    2015-07-01

    To study the room-temperature stable defects induced by electron irradiation, commercial borosilicate glasses were irradiated by 1.2 MeV electrons and then ultraviolet (UV) optical absorption (OA) spectra were measured. Two characteristic bands were revealed before irradiation, and they were attributed to silicon dangling bond (E’-center) and Fe3+ species, respectively. The existence of Fe3+ was confirmed by electron paramagnetic resonance (EPR) measurements. After irradiation, the absorption spectra revealed irradiation-induced changes, while the content of E’-center did not change in the deep ultraviolet (DUV) region. The slightly reduced OA spectra at 4.9 eV was supposed to transform Fe3+ species to Fe2+ species and this transformation leads to the appearance of 4.3 eV OA band. By calculating intensity variation, the transformation of Fe was estimated to be about 5% and the optical absorption cross section of Fe2+ species is calculated to be 2.2 times larger than that of Fe3+ species. Peroxy linkage (POL, ≡Si-O-O-Si≡), which results in a 3.7 eV OA band, is speculated not to be from Si-O bond break but from Si-O-B bond, Si-O-Al bond, or Si-O-Na bond break. The co-presence defect with POL is probably responsible for 2.9-eV OA band. Project supported by the Fundamental Research Funds for the Central Universities of China (Grant No. lzujbky-2014-16).

  19. Electrochemical and electron paramagnetic resonance studies of a carotenoid cation radicals and dications: Effect of deuteration

    SciTech Connect

    Khaled, M.; Hadjipetrou, A.; Kispert, L. )

    1990-06-14

    The oxidation process involving the transfer of two electrons for {beta}-carotene is confirmed by bulk electrolysis in a CH{sub 2}Cl{sub 2} solvent and the observation of {Delta}E = 42 mV from cyclic voltammetric measurements. A similar process is also found to occur for {beta}-apo-8{prime}-carotenal and canthaxanthin. An additional cathodic peak between 0.2 0.5 relative to SCE is shown to be dependent on the initial formation of dications followed by the loss of H{sup +} as evidenced by a large isotope effect and most likely due to the reduction of a carotenoid cation. EPR evidence exists for the formation of radical cations by the reaction of diffusing carotenoid dictations with neutral carotenoids. The rate of formation is consistent with the differences in the diffusion coefficients of the carotenoids deduced by chronocoulometric measurements, being fastest for canthaxanthin.

  20. Multifrequency pulsed electron paramagnetic resonance study of the S2 state of the photosystem II manganese cluster.

    PubMed

    Yeagle, Gregory J; Gilchrist, M Lane; McCarrick, Robert M; Britt, R David

    2008-03-17

    Multifrequency electron spin-echo envelope modulation (ESEEM) spectroscopy is employed to measure the strength of the hyperfine coupling of magnetic nuclei to the paramagnetic (S = 1/2) S2 form of photosystem II (PSII). Previous X-band-frequency ESEEM studies indicated that one or more histidine nitrogens are electronically coupled to the tetranuclear manganese cluster in the S2 state of PSII. However, the spectral resolution was relatively poor at the approximately 9 GHz excitation frequency, precluding any in-depth analysis of the corresponding bonding interaction between the detected histidine and the manganese cluster. Here we report ESEEM experiments using higher X-, P-, and Ka-band microwave frequencies to target PSII membranes isolated from spinach. The X- to P-band ESEEM spectra suffer from the same poor resolution as that observed in previous experiments, while the Ka-band spectra show remarkably well-resolved features that allow for the direct determination of the nuclear quadrupolar couplings for a single I = 1(14)N nucleus. The Ka-band results demonstrate that at an applied field of 1.1 T we are much closer to the exact cancellation limit (alpha iso = 2nu(14)N) that optimizes ESEEM spectra. These results reveal hyperfine (alpha iso = 7.3 +/- 0.20 MHz and alpha dip = 0.50 +/- 0.10 MHz) and nuclear quadrupolar (e(2)qQ = 1.98 +/- 0.05 MHz and eta = 0.84 +/- 0.06) couplings for a single (14)N nucleus magnetically coupled to the manganese cluster in the S 2 state of PSII. These values are compared to the histidine imidazole nitrogen hyperfine and nuclear quadrupolar couplings found in superoxidized manganese catalase as well as (14)N couplings in relevant manganese model complexes. PMID:18330971

  1. Structural characterization of titania by X-ray diffraction, photoacoustic, Raman spectroscopy and electron paramagnetic resonance spectroscopy.

    PubMed

    Kadam, R M; Rajeswari, B; Sengupta, Arijit; Achary, S N; Kshirsagar, R J; Natarajan, V

    2015-02-25

    A titania mineral (obtained from East coast, Orissa, India) was investigated by X-ray diffraction (XRD), photoacoustic spectroscopy (PAS), Raman and Electron Paramagnetic Resonance (EPR) studies. XRD studies indicated the presence of rutile (91%) and anatase (9%) phases in the mineral. Raman investigation supported this information. Both rutile and anatase phases have tetragonal structure (rutile: space group P4(2)/mnm, a=4.5946(1) Å, c=2.9597(1) Å, V=62.48(1) (Å)(3), Z=2; anatase: space group I4(1)/amd, 3.7848(2) Å, 9.5098(11) Å, V=136.22(2) (Å)(3), Z=4). The deconvoluted PAS spectrum showed nine peaks around 335, 370, 415,485, 555, 605, 659, 690,730 and 785 nm and according to the ligand field theory, these peaks were attributed to the presence of V(4+), Cr(3+), Mn(4+) and Fe(3+) species. EPR studies revealed the presence of transition metal ions V(4+)(d(1)), Cr(3+)(d(3)), Mn(4+)(d(3)) and Fe(3+)(d(5)) at Ti(4+) sites. The EPR spectra are characterized by very large crystal filed splitting (D term) and orthorhombic distortion term (E term) for multiple electron system (s>1) suggesting that the transition metal ions substitute the Ti(4+) in the lattice which is situated in distorted octahedral coordination of oxygen. The possible reasons for observation of unusually large D and E term in the EPR spectra of transition metal ions (S=3/2 and 5/2) are discussed. PMID:25233027

  2. Structural characterization of titania by X-ray diffraction, photoacoustic, Raman spectroscopy and electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Kadam, R. M.; Rajeswari, B.; Sengupta, Arijit; Achary, S. N.; Kshirsagar, R. J.; Natarajan, V.

    2015-02-01

    A titania mineral (obtained from East coast, Orissa, India) was investigated by X-ray diffraction (XRD), photoacoustic spectroscopy (PAS), Raman and Electron Paramagnetic Resonance (EPR) studies. XRD studies indicated the presence of rutile (91%) and anatase (9%) phases in the mineral. Raman investigation supported this information. Both rutile and anatase phases have tetragonal structure (rutile: space group P42/mnm, a = 4.5946(1) Å, c = 2.9597(1) Å, V = 62.48(1) (Å)3, Z = 2; anatase: space group I41/amd, 3.7848(2) Å, 9.5098(11) Å, V = 136.22(2) (Å)3, Z = 4). The deconvoluted PAS spectrum showed nine peaks around 335, 370, 415,485, 555, 605, 659, 690,730 and 785 nm and according to the ligand field theory, these peaks were attributed to the presence of V4+, Cr3+, Mn4+ and Fe3+ species. EPR studies revealed the presence of transition metal ions V4+(d1), Cr3+(d3), Mn4+(d3) and Fe3+(d5) at Ti4+ sites. The EPR spectra are characterized by very large crystal filed splitting (D term) and orthorhombic distortion term (E term) for multiple electron system (s > 1) suggesting that the transition metal ions substitute the Ti4+ in the lattice which is situated in distorted octahedral coordination of oxygen. The possible reasons for observation of unusually large D and E term in the EPR spectra of transition metal ions (S = 3/2 and 5/2) are discussed.

  3. Binding of manganese(II) to a tertiary stabilized hammerhead ribozyme as studied by electron paramagnetic resonance spectroscopy

    PubMed Central

    KISSELEVA, NATALIA; KHVOROVA, ANASTASIA; WESTHOF, ERIC; SCHIEMANN, OLAV

    2005-01-01

    Electron paramagnetic resonance (EPR) spectroscopy is used to study the binding of MnII ions to a tertiary stabilized hammer-head ribozyme (tsHHRz) and to compare it with the binding to the minimal hammerhead ribozyme (mHHRz). Continuous wave EPR measurements show that the tsHHRz possesses a single high-affinity MnII binding site with a KD of ≤10 nM at an NaCl concentration of 0.1 M. This dissociation constant is at least two orders of magnitude smaller than the KD determined previously for the single high-affinity MnII site in the mHHRz. In addition, whereas the high-affinity MnII is displaced from the mHHRz upon binding of the aminoglycoside antibiotic neomycin B, it is not from the tsHHRz. Despite these pronounced differences in binding, a comparison between the electron spin echo envelope modulation and hyperfine sublevel correlation spectra of the minimal and tertiary stabilized HHRz demonstrates that the structure of both binding sites is very similar. This suggests that the MnII is located in both ribozymes between the bases A9 and G10.1 of the sheared G · A tandem base pair, as shown previously and in detail for the mHHRz. Thus, the much stronger MnII binding in the tsHHRz is attributed to the interaction between the two external loops, which locks in the RNA fold, trapping the MnII in the tightly bound conformation, whereas the absence of long-range loop–loop interactions in the mHHRz leads to more dynamical and open conformations, decreasing MnII binding. PMID:15611296

  4. On-chip integration of high-frequency electron paramagnetic resonance spectroscopy and Hall-effect magnetometry.

    PubMed

    Quddusi, H M; Ramsey, C M; Gonzalez-Pons, J C; Henderson, J J; del Barco, E; de Loubens, G; Kent, A D

    2008-07-01

    A sensor that integrates high-sensitivity micro-Hall effect magnetometry and high-frequency electron paramagnetic resonance spectroscopy capabilities on a single semiconductor chip is presented. The Hall-effect magnetometer (HEM) was fabricated from a two-dimensional electron gas GaAsAlGaAs heterostructure in the form of a cross, with a 50 x 50 microm2 sensing area. A high-frequency microstrip resonator is coupled with two small gaps to a transmission line with a 50 Omega impedance. Different resonator lengths are used to obtain quasi-TEM fundamental resonant modes in the frequency range 10-30 GHz. The resonator is positioned on top of the active area of the HEM, where the magnetic field of the fundamental mode is largest, thus optimizing the conversion of microwave power into magnetic field at the sample position. The two gaps coupling the resonator and transmission lines are engineered differently--the gap to the microwave source is designed to optimize the loaded quality factor of the resonator (Q

  5. Simulation of the S2 state multiline electron paramagnetic resonance signal of photosystem II: a multifrequency approach.

    PubMed

    Ahrling, K A; Pace, R J

    1995-05-01

    The S2 state electron paramagnetic resonance (EPR) multiline signal of Photosystem II has been simulated at Q-band (35 Ghz), X-band (9 GHz) and S-band (4 GHz) frequencies. The model used for the simulation assumes that the signal arises from an essentially magnetically isolated MnIII-MnIV dimer, with a ground state electronic spin ST = 1/2. The spectra are generated from exact numerical solution of a general spin Hamiltonian containing anisotropic hyperfine and quadrupolar interactions at both Mn nuclei. The features that distinguish the multiline from the EPR spectra of model manganese dimer complexes (additional width of the spectrum (195 mT), additional peaks (22), internal "superhyperfine" structure) are plausibly explained assuming an unusual ligand geometry at both Mn nuclei, giving rise to normally forbidden transitions from quadrupole interactions as well as hyperfine anisotropy. The fitted parameters indicate that the hyperfine and quadrupole interactions arise from Mn ions in low symmetry environments, corresponding approximately to the removal of one ligand from an octahedral geometry in both cases. For a quadrupole interaction of the magnitude indicated here to be present, the MnIII ion must be 5-coordinate and the MnIV 5-coordinate or possibly have a sixth, weakly bound ligand. The hyperfine parameters indicate a quasi-axial anisotropy at MnIII, which while consistent with Jahn-Teller distortion as expected for a d4 ion, corresponds here to the unpaired spin being in the ligand deficient, z direction of the molecular reference axis. The fitted parameters for MnIV are very unusual, showing a high degree of anisotropy not expected in a d3 ion. This degree of anisotropy could be qualitatively accounted for by a histidine ligand providing pi backbonding into the metal dxy orbital, together with a weakly bound or absent ligand in the x direction. PMID:7612851

  6. Photoluminescence, thermally stimulated luminescence and electron paramagnetic resonance investigations of Tb{sup 3+} doped SrBPO{sub 5}

    SciTech Connect

    Kumar, Mithlesh; Seshagiri, T.K.; Kadam, R.M.; Godbole, S.V.

    2011-09-15

    Graphical abstract: EPR spectra of BOHC's in 2 kGy {gamma}-irradiated SrBPO{sub 5}:Tb sample using Receiver Gain RG = 4 x 10{sup 4}, Modulation Amplitude MA = 0.25 G, Microwave power setting 6.3 mW: (A) un-annealed sample recorded at 300 K, (B) un-annealed sample recorded at 100 K and (C) sample annealed at 550 K for 10 min and recorded at 100 K. Highlights: {yields} PL studies on Tb doped SrBPO{sub 5} phosphor have shown emission due to Tb{sup 3+} associated with {sup 5}D{sub 3} {yields} {sup 7}F{sub J} and {sup 5}D{sub 4} {yields} {sup 7}F{sub J} (J = 3, 4, 5 and 6) transitions. {yields} The EPR studies on {gamma}-irradiated samples revealed formation of three types of boron oxygen hole trapped centres viz., BOHC{sub 1}, BOHC{sub 2} and BOHC{sub 3} and an electron trapped centre. {yields} The TSL peak at 475 K was associated with the thermal destruction of BOHC{sub 2}. -- Abstract: Trap level spectroscopic studies were carried out on {gamma}-irradiated Tb (1 mole%) doped SrBPO{sub 5} were carried out using photoluminescence (PL), thermally stimulated luminescence (TSL) and electron paramagnetic resonance (EPR) techniques. The incorporation of Tb in the 3+ oxidation state was ascertained from PL studies. Life time for Tb{sup 3+} emission corresponding to the intense transition {sup 5}D{sub 4} {yields} {sup 7}F{sub 5} at 543 nm was determined. The spectral characteristics of the TSL glows have shown that Tb{sup 3+} ions act as the emission center for the glow peak at 475 K. The trap parameters of the glow peak were determined. EPR investigations at room temperature/77 K revealed the stabilization of three boron oxygen hole trapped centers (BOHC's) and oxygen centered radicals such as O{sup -} and O{sub 2}{sup -} and trapped electrons in room temperature {gamma}-irradiated samples. TSL glow peak at 475 K was found to be associated with recombination of electron released from trapped electron center and the BOHC{sub 2} center.

  7. Electron paramagnetic resonance study of free radicals in γ-irradiated L-glutamine and L-glutamine-t-butyl ester hydrochloride

    NASA Astrophysics Data System (ADS)

    Yeşim Dicle, Işık; Osmanğolu, Şemsettin; İpek, Nazenin

    2015-01-01

    Electron paramagnetic resonance (EPR) spectra of γ-irradiated single crystals of l-glutamine (LG) and l-glutamine-t-butyl ester hydrochloride (LGBESHCI) powders were studied and analyzed for different orientations of the crystals in the magnetic field, after γ-irradiation. The spectra were observed to be independent of temperature down to 130 K. The hyperfine interaction tensors for one α proton and two β protons of radical have been determined at 295 K. An analysis of the EPR of γ-irradiated single crystals of LG and LGBESHCI powders shows that the paramagnetic species produced by the radiation damage is CH2ĊH. The g values of the radical and the hyperfine structure constants of the free electron with nearby protons and 14N nucleus were determined. The results were found to be in good agreement with the existing literature data.

  8. Assessment of a Standardized ROS Production Profile in Humans by Electron Paramagnetic Resonance

    PubMed Central

    Mrakic-Sposta, Simona; Gussoni, Maristella; Montorsi, Michela; Porcelli, Simone; Vezzoli, Alessandra

    2012-01-01

    Despite the growing interest in the role of reactive oxygen species (ROS) in health and disease, reliable quantitative noninvasive methods for the assessment of oxidative stress in humans are still lacking. EPR technique, coupled to a specific spin probe (CMH: 1-hydroxy-3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine) is here presented as the method of choice to gain a direct measurement of ROS in biological fluids and tissues. The study aimed at demonstrating that, differently from currently available “a posteriori” assays of ROS-induced damage by means of biomolecules (e.g., proteins and lipids) spin-trapping EPR provides direct evidence of the “instantaneous” presence of radical species in the sample and, as signal areas are proportional to the number of excited electron spins, lead to absolute concentration levels. Using a recently developed bench top continuous wave system (e-scan EPR scanner, Bruker) dealing with very low ROS concentration levels in small (50 μL) samples, we successfully monitored rapid ROS production changes in peripheral blood of athletes after controlled exercise and sedentary subjects after antioxidant supplementation. The correlation between EPR results and data obtained by various enzymatic assays (e.g., protein carbonyls and thiobarbituric acid reactive substances) was determined too. Synthetically, our method allows reliable, quick, noninvasive quantitative determination of ROS in human peripheral blood. PMID:22900129

  9. [Electron paramagnetic resonance study of the interactions between steroid hormones and binding proteins].

    PubMed

    Basset, M; Chambaz, E M; Defaye, G; Metz, B

    1978-01-01

    Interaction of a spin labeled corticosteroid (desoxycorticosterone nitroxyde: DOC -NO) with three purified proteins (albumin, transcortin, progesterone binding protein: PBG) was studied by electron spin resonance (ESR) spectroscopy. DOC-NO was competitive with natural corticosteroids and therefore bound at the same site to specific binding proteins. ESR spectra in the presence of each of the proteins showed an immobilized (bound) form of the spin labeled steroid and allowed the calculation of the corresponding association constant (Ka) at equilibrium. The three binding proteins could be characterized by the ESR parameters of the DOC-NO bound form. The thermodynamic parameters (deltaH, deltaS) of the steroid-protein interactions were calculated from the ESR data obtained within a wide temperature range (3--40 degrees C). The ESR spectra width (2T) was used to evaluate the polarity of the spin label environment within the steroid binding site: a hydrophobic character was observed for transcortin whereas PBG exhibited a more hydrophilic steroid binding sits. The rotational correlation time of the three protein DOC-NO complexes at equilibrium were calculated from ESR data; the results were correlated with the protein molecular size and suggested a non spherical shape for the binding macromolecule in solution. Spin labelling of biologically active steroids thus provides a novel approach for the study of the interaction of these hormones with their binding protein. Providing a suitable spin label, the ESR parameters may allow the characterization of several types of binding sites of different biological significance for the same hormone, in biological fluids as well as in target tissues. PMID:83166

  10. Electron paramagnetic resonance spectrum of Cu(CO)/sub 3/: an inorganic isolobal analogue of methyl

    SciTech Connect

    Howard, J.A.; Mile, B.; Morton, J.R.; Preston, K.F.; Sutcliffe, R.

    1986-03-13

    Copper tricarbonyl, Cu(CO)/sub 3/, has been prepared on a rotating cryostat by reacting /sup 63/Cu atoms with CO on either a cyclohexane or adamantane surface at 77 K. Its EPR spectrum (4-77 K) yielded the following parameters: g/sub xx/ = g/sub yy/ = 2.0028, g/sub zz/ = 2.0010; for /sup 63/Cu, a/sub xx/ = a/sub yy/ approx. = 0 MHz, a/sub zz/ = 225 MHz; for /sup 13/C, a/sub xx/ = a/sub yy/ = 29 MHz, a/sub zz/ = 8 MHz. The spectrum of Cu(CO)/sub 3/ in adamantane was isotropic at 223 K, yielding the following parameters: g/sub iso/ = 2.0014, a/sub 63/ = 93.9 MHz, a/sub 13/(3) = 22.0 MHz. Cu(CO)/sub 3/ is a planar molecule belonging to the A/sub 2/ representation in D/sub 3h/ symmetry. Most of the unpaired electron is in the Cu 4p/sub z/ orbital perpendicular to the molecular plane. There is a marked temperature dependence of the isotropic copper hyperfine interaction, which increases from 75 MHz at 4 K to 98 MHz at 250 K. This is attributed to an out-of-plane vibration of the radical which modulates the isotropic copper hyperfine interaction. An analysis of this effect yields a nu/sub 2/ vibration frequency of approx. 300 cm/sup -1/. Cu(CO)/sub 3/ is stable to decomposition or dimerization in adamantane up to at least 263 K and may provide a suitable vehicle for incorporating copper into inert supports for catalytic purposes. 23 references, 5 figures, 2 tables.

  11. Application of Electron Paramagnetic Resonance Spectroscopy to Comparative Examination of Different Groups of Free Radicals in Thermal Injuries Treated with Propolis and Silver Sulphadiazine

    PubMed Central

    Olczyk, Pawel; Ramos, Pawel; Bernas, Marcin; Komosinska-Vassev, Katarzyna; Stojko, Jerzy; Pilawa, Barbara

    2013-01-01

    Different groups of free radicals expressed in burn wounds treated with propolis and silver sulphadiazine were examined. The thermal effect forms major types of free radicals in a wound because of the breaking of chemical bonds. Free radicals, located in the heated skin, were tested after 21 days of treating by these two substances. The aim of this work was to find the method for determination of types and concentrations of different groups of free radicals in wound after high temperature impact during burning. The effects of the therapy by propolis and silver sulphadiazine on free radicals were studied. Since the chemical methods of free radicals studies are destructive, the usefulness of the electron paramagnetic resonance spectroscopy was tested in this work. The electron paramagnetic resonance spectra measured with the microwave power of 2.2 mW were numerically fitted by theoretical curves of Gaussian and Lorentzian shapes. The experimental electron paramagnetic resonance spectra of tissue samples are best fitted by the sum of one Gauss and two Lorentz lines. An innovatory numerical procedure of spectroscopic skin analysis was presented. It is very useful in the alternative medicine studies. PMID:23762162

  12. Consequences of partitioning the photon into its electrical and magnetic vectors upon absorption by an electron

    NASA Astrophysics Data System (ADS)

    Szumski, Daniel S.

    2013-10-01

    This research uses classical arguments to develop a blackbody spectral equation that provides useful insights into heat processes. The theory unites in a single equation, the heat radiation theory of Planck and the heat of molecular motion theory of Maxwell and Boltzmann. Light absorption is considered a two-step process. The first is an adiabatic reversible step, wherein one-dimensional light energy is absorbed in a quantum amount, ! h" , by an electron. The absorbed quanta is still 1-dimensional(1-D), and remains within the domain of reversible thermodynamics. There is no recourse to the Second Law during this first step. The absorption process' second step is a dimensional restructuring wherein the electrical and magnetic vectors evolve separately. The 1-D electrical quanta transforms into its 3-D equivalent, electrical charge density. The resulting displacement of the generalized coordinates translates to 3-D motion, the evolution of Joule heat, and irreversible thermodynamics. The magnetic vector has no 3-D equivalent, and can only transform to 1-D paramagnetic spin. Accordingly, photon decoupling distorts time's fabric, giving rise to the characteristic blackbody spectral emittance. This study's spectral equation introduces a new quantity to physics, the radiation temperature. Where it is identical to the classical thermodynamic temperature, the blackbody spectral curves are consistent with Planck's. However, by separating these two temperatures in a stable far-from-equilibrium manner, new energy storage modes become possible at the atomic level, something that could have profound implications in understanding matter's living state.

  13. Electron paramagnetic resonance study of the C e3 + pair centers in YAl O3 :Ce scintillator crystals

    NASA Astrophysics Data System (ADS)

    Buryi, M.; Laguta, V. V.; Mihóková, E.; Novák, P.; Nikl, M.

    2015-12-01

    Single crystals of YAl O3 doped with Ce have been studied by electron paramagnetic resonance (EPR) at the 9.4 and 34 GHz microwave bands. Besides the single-ion C e3 + spectrum, measurements have revealed many satellite lines which belong to the C e3 +-C e3 + pair centers. Their spectra have been fitted by a general effective spin Hamiltonian describing two interacting particles with the spin S =1 /2 . Corresponding g factors and spin-spin coupling constants have been determined. The spin-spin coupling constants are in the range from 0.1 up to 0.65 c m-1 for the nearest and next-nearest neighbors depending on the distance between Ce ions and their position. The exchange interaction between next-nearest neighbors (NNNs) is comparable to or even bigger than that between nearest neighbors (NNs), being in the range 0.4 -0.6 c m-1 . For a single C e3 + ion, crystal field parameters, energy sublevels of the 2F5 /2 and 2F7 /2 multiplets and principal g tensor components were obtained from the density functional theory calculation. They are in satisfactory agreement with those determined experimentally. The principal g tensor components of C e3 + pair centers are also calculated. Nevertheless, it was impossible to assign each of the satellite lines to actual positions of the six NN and 12 NNN Ce pairs in the lattice due to lack of valid information on the sign of the exchange interactions. The influence of C e3 + pairs on the luminescence efficiency is discussed as well.

  14. Models for Copper Dynamic Behavior in Doped Cadmium dl-Histidine Crystals: Electron Paramagnetic Resonance and Crystallographic Analysis.

    PubMed

    Colaneri, Michael J; Teat, Simon J; Vitali, Jacqueline

    2015-11-12

    Electron paramagnetic resonance and crystallographic studies of copper-doped cadmium dl-histidine, abbreviated as CdDLHis, were undertaken to gain further understanding on the relationship between site structure and dynamic behavior in biological model complexes. X-ray diffraction measurements determined the crystal structure of CdDLHis at 100 and 298 K. CdDLHis crystallizes in the monoclinic space group P21/c with two cadmium complexes per asymmetric unit. In each complex, the Cd is hexacoordinated to two histidine molecules. Both histidines are l in one complex and d in the other. Additionally, each complex contains multiple waters of varying disorder. Single crystal EPR spectroscopic splitting (g) and copper hyperfine (A(Cu)) tensors at room temperature (principal values: g = 2.249, 2.089, 2.050; A(Cu) = -453, -30.5, -0.08 MHz) were determined from rotational experiments. Alignments of the tensor directions with the host structure were used to position the copper unpaired dx(2)-y(2) orbital in an approximate plane made by four proposed ligand atoms: the N-imidazole and N-amino of one histidine, and the N-amino and O-carboxyl of the other. Each complex has two such planes related by noncrystallographic symmetry, which make an angle of 65° and have a 1.56 Å distance between their midpoints. These findings are consistent with three interpretations that can adequately explain previous temperature-dependent EPR powder spectra of this system: (1) a local structural distortion (static strain) at the copper site has a temperature dependence significant enough to affect the EPR pattern, (2) the copper can hop between the two sites in each complex at high temperature, and (3) there exists a dynamic Jahn-Teller effect involving the copper ligands. PMID:26501364

  15. Site-directed spin labeling electron paramagnetic resonance study of the ORF1 protein from a mouse L1 retrotransposon

    PubMed Central

    Januszyk, Kurt; Fleissner, Mark R; Atchabahian, Lara; Shieh, Fa-Kuen; Altenbach, Christian; Martin, Sandra L; Guo, Feng; Hubbell, Wayne L; Clubb, Robert T

    2011-01-01

    Long interspersed nuclear element-1 is a highly abundant mammalian retrotransposon that comprises 17% of the human genome. L1 retrotransposition requires the protein encoded by open reading frame-1 (ORF1p), which binds single-stranded RNA with high affinity and functions as a nucleic acid chaperone. ORF1p has been shown to adopt a homo-trimeric, asymmetric dumbbell-shaped structure. However, its atomic-level structure and mechanism of RNA binding remains poorly understood. Here, we report the results of a site-directed spin labeling electron paramagnetic resonance (SDSL-EPR) study of 27 residues within the RNA binding region of the full-length protein. The EPR data are compatible with the large RNA binding lobe of ORF1p containing a RNA recognition motif (RRM) domain and a carboxyl-terminal domain (CTD) that are predicted from crystallographic and NMR studies of smaller fragments of the protein. Interestingly, the EPR data indicate that residues in strands β3 and β4 of the RRM are structurally unstable, compatible with the previously observed sensitivity of this region to proteolysis. Affinity measurements and RNA-dependent EPR spectral changes map the RNA binding site on ORF1p to residues located in strands β3 and β4 of the RRM domain and to helix α1 of the CTD. Complementary in vivo studies also identify residues within the RRM domain that are required for retrotransposition. We propose that in the context of the full-length trimeric protein these distinct surfaces are positioned adjacent to one another providing a continuous surface that may interact with nucleic acids. PMID:21563223

  16. In Vivo Formation of Electron Paramagnetic Resonance-Detectable Nitric Oxide and of Nitrotyrosine Is Not Impaired during Murine Leishmaniasis

    PubMed Central

    Giorgio, Selma; Linares, Edlaine; Ischiropoulos, Harry; Von Zuben, Fernando José; Yamada, Aureo; Augusto, Ohara

    1998-01-01

    Recent studies have provided evidence for a dual role of nitric oxide (NO) during murine leishmaniasis. To explore this problem, we monitored the formation of NO and its derived oxidants during the course of Leishmania amazonensis infection in tissues of susceptible (BALB/c) and relatively resistant (C57BL/6) mice. NO production was detected directly by low-temperature electron paramagnetic resonance spectra of animal tissues. Both mouse strains presented detectable levels of hemoglobin nitrosyl (HbNO) complexes and of heme nitrosyl and iron-dithiol-dinitrosyl complexes in the blood and footpad lesions, respectively. Estimation of the nitrosyl complex levels demonstrated that most of the NO is synthesized in the footpad lesions. In agreement, immunohistochemical analysis of the lesions demonstrated the presence of nitrotyrosine in proteins of macrophage vacuoles and parasites. Since macrophages lack myeloperoxidase, peroxynitrite is likely to be the nitrating NO metabolite produced during the infection. The levels of HbNO complexes in the blood reflected changes occurring during the infection such as those in parasite burden and lesion size. The maximum levels of HbNO complexes detected in the blood of susceptible mice were higher than those of C57BL/6 mice but occurred at late stages of infection and were accompanied by the presence of bacteria in the cutaneous lesions. The results indicate that the local production of NO is an important mechanism for the elimination of parasites if it occurs before the parasite burden becomes too high. From then on, elevated production of NO and derived oxidants aggravates the inflammatory process with the occurrence of a hypoxic environment that may favor secondary infections. PMID:9453645

  17. Electron paramagnetic resonance and computational studies of radicals derived from boron-substituted N-heterocyclic carbene boranes.

    PubMed

    Walton, John C; Brahmi, Malika Makhlouf; Monot, Julien; Fensterbank, Louis; Malacria, Max; Curran, Dennis P; Lacôte, Emmanuel

    2011-07-01

    Fifteen second-generation NHC-ligated boranes with aryl and alkyl substituents on boron were prepared, and their radical chemistry was explored by electron paramagnetic resonance (EPR) spectroscopy and calculations. Hydrogen atom abstraction from NHC-BH(2)Ar groups produced boryl radicals akin to diphenylmethyl with spin extensively delocalized across the NHC, BH, and aryl units. All of the NHC-B·HAr radicals studied abstracted Br-atoms from alkyl bromides. Radicals with bulky N,N'-dipp substituents underwent dimerization about 2 orders of magnitude more slowly than first-generation NHC-ligated trihydroborates. The evidence favored head-to-head coupling yielding ligated diboranes. The first ligated diboranyl radical, with a structure intermediate between that of ligated diboranes and diborenes, was spectroscopically characterized during photolysis of di-t-butyl peroxide with N,N'-di-t-butyl-imidazol-2-ylidene phenylborane. The reactive site of B-alkyl-substituted NHC-boranes switched from the boron center to the alkyl substituent for both linear and branched alkyl groups. The β-borylalkyl radicals obtained from N,N'-dipp-substituted boranes underwent exothermic β-scissions with production of dipp-Imd-BH(2)· radicals and alkenes. The reverse additions of NHC-boryl radicals to alkenes are probably endothermic for alkyl-substituted alkenes, but exothermic for conjugated alkenes (addition of an NHC-boryl radical to 1,1-diphenylethene was observed). A cyclopropylboryl radical was observed, but, unlike other α-cyclopropyl-substituted radicals, this showed no propensity for ring-opening. PMID:21619055

  18. A versatile and modular quasi optics-based 200GHz dual dynamic nuclear polarization and electron paramagnetic resonance instrument.

    PubMed

    Siaw, Ting Ann; Leavesley, Alisa; Lund, Alicia; Kaminker, Ilia; Han, Songi

    2016-03-01

    Solid-state dynamic nuclear polarization (DNP) at higher magnetic fields (>3T) and cryogenic temperatures (∼ 2-90K) has gained enormous interest and seen major technological advances as an NMR signal enhancing technique. Still, the current state of the art DNP operation is not at a state at which sample and freezing conditions can be rationally chosen and the DNP performance predicted a priori, but relies on purely empirical approaches. An important step towards rational optimization of DNP conditions is to have access to DNP instrumental capabilities to diagnose DNP performance and elucidate DNP mechanisms. The desired diagnoses include the measurement of the "DNP power curve", i.e. the microwave (MW) power dependence of DNP enhancement, the "DNP spectrum", i.e. the MW frequency dependence of DNP enhancement, the electron paramagnetic resonance (EPR) spectrum, and the saturation and spectral diffusion properties of the EPR spectrum upon prolonged MW irradiation typical of continuous wave (CW) DNP, as well as various electron and nuclear spin relaxation parameters. Even basic measurements of these DNP parameters require versatile instrumentation at high magnetic fields not commercially available to date. In this article, we describe the detailed design of such a DNP instrument, powered by a solid-state MW source that is tunable between 193 and 201 GHz and outputs up to 140 mW of MW power. The quality and pathway of the transmitted and reflected MWs is controlled by a quasi-optics (QO) bridge and a corrugated waveguide, where the latter couples the MW from an open-space QO bridge to the sample located inside the superconducting magnet and vice versa. Crucially, the versatility of the solid-state MW source enables the automated acquisition of frequency swept DNP spectra, DNP power curves, the diagnosis of MW power and transmission, and frequency swept continuous wave (CW) and pulsed EPR experiments. The flexibility of the DNP instrument centered around the QO MW

  19. A versatile and modular quasi optics-based 200 GHz dual dynamic nuclear polarization and electron paramagnetic resonance instrument

    NASA Astrophysics Data System (ADS)

    Siaw, Ting Ann; Leavesley, Alisa; Lund, Alicia; Kaminker, Ilia; Han, Songi

    2016-03-01

    Solid-state dynamic nuclear polarization (DNP) at higher magnetic fields (>3 T) and cryogenic temperatures (∼2-90 K) has gained enormous interest and seen major technological advances as an NMR signal enhancing technique. Still, the current state of the art DNP operation is not at a state at which sample and freezing conditions can be rationally chosen and the DNP performance predicted a priori, but relies on purely empirical approaches. An important step towards rational optimization of DNP conditions is to have access to DNP instrumental capabilities to diagnose DNP performance and elucidate DNP mechanisms. The desired diagnoses include the measurement of the "DNP power curve", i.e. the microwave (MW) power dependence of DNP enhancement, the "DNP spectrum", i.e. the MW frequency dependence of DNP enhancement, the electron paramagnetic resonance (EPR) spectrum, and the saturation and spectral diffusion properties of the EPR spectrum upon prolonged MW irradiation typical of continuous wave (CW) DNP, as well as various electron and nuclear spin relaxation parameters. Even basic measurements of these DNP parameters require versatile instrumentation at high magnetic fields not commercially available to date. In this article, we describe the detailed design of such a DNP instrument, powered by a solid-state MW source that is tunable between 193 and 201 GHz and outputs up to 140 mW of MW power. The quality and pathway of the transmitted and reflected MWs is controlled by a quasi-optics (QO) bridge and a corrugated waveguide, where the latter couples the MW from an open-space QO bridge to the sample located inside the superconducting magnet and vice versa. Crucially, the versatility of the solid-state MW source enables the automated acquisition of frequency swept DNP spectra, DNP power curves, the diagnosis of MW power and transmission, and frequency swept continuous wave (CW) and pulsed EPR experiments. The flexibility of the DNP instrument centered around the QO MW

  20. Hyperfine Structure and Exchange Narrowing of Paramagnetic Resonance

    DOE R&D Accomplishments Database

    Townes, C. H.; Turkevich, J.

    1950-01-01

    Discussion of electronic paramagnetic resonance for the free radical á, á-diphenyl â-picryl hydrazyl as observed by its effect on the transmission of microwave through a TE{sub 01} cavity with a small amount of the free radical placed approximately on the axis of the cavity; the half-width of this resonance at half maximum absorption was 1.45 oersteds.

  1. The local environment of Cr3+ impurities in normal and x-rays irradiated carbon doped ruby: An electron paramagnetic resonance (EPR) study

    NASA Astrophysics Data System (ADS)

    Kazan, S.; Açıkgöz, M.; Yalçın, O.

    2015-01-01

    Local environment of substitutional paramagnetic point defect (impurity) in normal and x-ray irradiated commercially available α-Al2O3:C samples (commercial product of Landauer, Inc.) has been studied by using the electron paramagnetic resonance (EPR) technique at room temperature. In both samples the EPR spectra showed strongly angular dependent behavior. The zero-field splitting (ZFS) parameters (ZFSPs) have been determined for substitutional Cr3+ centers. The observed additional EPR signals for x-ray irradiated sample were attributed to another center with different spin Hamiltonian (SH) parameters. In addition to the experimental findings, the ZFSPs and the local structure of the Cr3+ ions were theoretically determined using superposition model (SPM) calculations.

  2. Magnetization detecting electron paramagnetic resonance spectroscopy using a dc-SQUID directly coupled to an electron spin ensemble

    NASA Astrophysics Data System (ADS)

    Toida, Hiraku; Matsuzaki, Yuichiro; Kakuyanagi, Kosuke; Zhu, Xiaobo; Munro, William; Nemoto, Kae; Yamaguchi, Hiroshi; Saito, Shiro

    Electron parametric resonance (EPR) spectroscopy is one of the most widely-used tool to characterize materials containing unpaired electrons. In the case of conventional EPR spectrometers, the resonance is detected as a change of microwave transmittance of a cavity. In our method, on the other hand, magnetization of the sample induced by the resonance is detected by a direct current superconducting quantum interference device (dc-SQUID) magnetometer, which is bonded to the sample. Here, we report detection of electron spin polarization and EPR spectroscopy using a micrometer-sized dc-SQUID magnetometer. We measure temperature and in-plane magnetic field dependence of spin polarization ratio and it has good agreement to the hyperbolic tangent law. We also successfully demonstrate EPR spectroscopy by applying a continuous microwave signal to the sample with a on-chip microstrip. We estimate the sensing volume and the minimum distinguishable number of electron spins to be ~ 10-10 cm3 (~ 0.1 pl) and ~ 106, respectively. This result paves the way towards realizing highly sensitive EPR spectroscopy in nanometer-sized area. This work was supported by Commissioned Research of NICT and in part by MEXT KAKENHI (Grant No. 15648489 and 15H05869).

  3. Visualizing, dating and determining the origin of the primitive carbonaceous matter in rocks: the potential of electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Binet, Laurent; Gourier, Didier; Delpoux, Olivier; Skrzypczak-Bonduelle, Audrey; Vezin, Herve; Derenne, Sylvie; Robert, Francois

    The study of primitive life on Earth is an essential task to determine the physical and chemical processes, which can lead to the emergence of life, and to devise methods to detect possible traces of life on Mars. Traces of primitive life should occur as residual fossil carbonaceous matter embedded in ancient rocks. However, on the early Earth or the early Mars, several sources, namely biological, chemical or extraplanetary, of carbonaceous matter must be considered. Besides, any fossilized carbonaceous matter, whether biological or abiotic, undergoes a complex evolution over geological times so that the memory of its precursors may be partially lost. Therefore the origin of ancient carbonaceous matter is difficult to assess on a chemical or structural basis. In addition, in the case of terrestrial rocks, unavoidable biogenic contamination by endolithic bacteria complicates the problem of proving the origin of primitive terrestrial organic matter. In the specific case of possible Martian rocks, it appears compelling to use techniques able to perform a non-destructive detection and analysis of the possible carbonaceous matter in such precious samples. Fossil carbonaceous matters contain radicals corresponding to unpaired electrons associated with broken chemical bonds or structural defects. These organic radicals are magnetic species, which can be detected and analyzed by Electron Paramagnetic Resonance (EPR). This technique is non-destructive, and sensitive enough to detect ideally 1 ppm of carbonaceous matter in a rock. To assess the potential of radicals to trace back the history and the origin of ancient carbonaceous matter, we performed an EPR study of a series of siliceous rocks (cherts) containing fossil carbonaceous matter with ages ranging from 45 Myr to 3.46 Byr. We showed that the distribution of the carbonaceous matter can be visualized within bulk sample by EPR imaging, with a submillimeter resolution, which may help detecting possible fossil bacterial

  4. Infrared electronic absorption in a single-component molecular metal.

    PubMed

    Kobayashi, Akiko; Sasa, Masaaki; Suzuki, Wakako; Fujiwara, Emiko; Tanaka, Hisashi; Tokumoto, Madoka; Okano, Yoshinori; Fujiwara, Hideki; Kobayashi, Hayao

    2004-01-21

    The infrared spectra of the crystal of transition metal complex molecules with extended-TTF ligands, Ni(tmdt)2, which is the first single-component molecular metal that has a stable metallic state even at low temperatures, exhibited an extremely low-energy electronic absorption around 2200 cm-1 (tmdt = trimethylenetetrathiafulvalenedithiolate). The systematic shift of the absorption peaks for molecules similar to Ni(tmdt)2, which range from metallic to semiconducting crystals, shows that the single-component molecular conductors are composed of molecules with unprecedentedly small HOMO-LUMO gaps. PMID:14719914

  5. Effects of MnO doping on the electronic properties of zinc oxide: 406 GHz electron paramagnetic resonance spectroscopy and Newman superposition model analysis

    NASA Astrophysics Data System (ADS)

    Yüksel Price, Berat; Hardal, Gökhan; Açıkgöz, Muhammed; Repp, Sergej; Erdem, Emre

    2015-11-01

    MnO-doped ZnO ceramics have been synthesized through the conventional ceramic processing route. Mn2+ ions have been incorporated into the ZnO lattice within the limits of solid solubility. By using X-band-frequency and high-field electron paramagnetic resonance (EPR), we have resolved some of the main electronic transitions for the S = 5/2, I = 5/2 high-spin system and have determined accurately the EPR spin-Hamiltonian parameters. By combining data from crystallographic X-ray diffraction and EPR with the semi-empirical Newman superposition model, we have found the local configurational position of Mn2+ and have confirmed the symmetry of the lattice. The results presented in this contribution indicate that Mn ions substitute at Zn sites in ZnO. The effect of Mn2+ ions on the intrinsic defects becomes remarkable, thus the vacancy related intrinsic defect signals cannot be visible in the EPR spectrum. MnO doping affects the band gap energy of ZnO system which was confirmed via UV-Vis spectroscopy.

  6. Effects of MnO doping on the electronic properties of zinc oxide: 406 GHz electron paramagnetic resonance spectroscopy and Newman superposition model analysis

    SciTech Connect

    Yüksel Price, Berat E-mail: muhammed.acikgoz@eng.bahcesehir.edu.tr Hardal, Gökhan; Açıkgöz, Muhammed E-mail: muhammed.acikgoz@eng.bahcesehir.edu.tr; Repp, Sergej; Erdem, Emre E-mail: muhammed.acikgoz@eng.bahcesehir.edu.tr

    2015-11-07

    MnO-doped ZnO ceramics have been synthesized through the conventional ceramic processing route. Mn{sup 2+} ions have been incorporated into the ZnO lattice within the limits of solid solubility. By using X-band-frequency and high-field electron paramagnetic resonance (EPR), we have resolved some of the main electronic transitions for the S = 5/2, I = 5/2 high-spin system and have determined accurately the EPR spin-Hamiltonian parameters. By combining data from crystallographic X-ray diffraction and EPR with the semi-empirical Newman superposition model, we have found the local configurational position of Mn{sup 2+} and have confirmed the symmetry of the lattice. The results presented in this contribution indicate that Mn ions substitute at Zn sites in ZnO. The effect of Mn{sup 2+} ions on the intrinsic defects becomes remarkable, thus the vacancy related intrinsic defect signals cannot be visible in the EPR spectrum. MnO doping affects the band gap energy of ZnO system which was confirmed via UV-Vis spectroscopy.

  7. Electronic structure of Q-A in reaction centers from Rhodobacter sphaeroides. I. Electron paramagnetic resonance in single crystals.

    PubMed Central

    Isaacson, R A; Lendzian, F; Abresch, E C; Lubitz, W; Feher, G

    1995-01-01

    The magnitude and orientation of the electronic g-tensor of the primary electron acceptor quinone radical anion, Q-A, has been determined in single crystals of zinc-substituted reaction centers of Rhodobacter sphaeroides R-26 at 275 K and at 80 K. To obtain high spectral resolution, EPR experiments were performed at 35 GHz and the native ubiquinone-10 (UQ10) in the reaction center was replaced by fully deuterated UQ10. The principal values and the direction cosines of the g-tensor axes with respect to the crystal axes a, b, c were determined. Freezing of the single crystals resulted in only minor changes in magnitude and orientation of the g-tensor. The orientation of Q-A as determined by the g-tensor axes deviates only by a few degrees (< or = 8 degrees) from the orientation of the neutral QA obtained from an average of four different x-ray structures of Rb. sphaeroides reaction centers. This deviation lies within the accuracy of the x-ray structure determinations. The g-tensor values measured in single crystals agree well with those in frozen solutions. Variations in g-values between Q-A, Q-B, and UQ10 radical ion in frozen solutions were observed and attributed to different environments. Images FIGURE 1 FIGURE 2 FIGURE 3 FIGURE 9 PMID:8527644

  8. SU-C-BRD-05: Non-Invasive in Vivo Biodosimetry in Radiotherapy Patients Using Electron Paramagnetic Resonance (EPR) Spectroscopy

    SciTech Connect

    Bahar, N; Roberts, K; Stabile, F; Mongillo, N; Decker, RD; Wilson, LD; Husain, Z; Contessa, J; Carlson, DJ; Williams, BB; Flood, AB; Swartz, HM

    2015-06-15

    Purpose: Medical intervention following a major, unplanned radiation event can elevate the human whole body exposure LD50 from 3 to 7 Gy. On a large scale, intervention cannot be achieved effectively without accurate and efficient triage. Current methods of retrospective biodosimetry are restricted in capability and applicability; published human data is limited. We aim to further develop, validate, and optimize an automated field-deployable in vivo electron paramagnetic resonance (EPR) instrument that can fill this need. Methods: Ionizing radiation creates highly-stable, carbonate-based free radicals within tooth enamel. Using a process similar to nuclear magnetic resonance, EPR directly measures the presence of radiation-induced free radicals. We performed baseline EPR measurements on one of the upper central incisors of total body irradiation (TBI) and head and neck (H&N) radiotherapy patients before their first treatment. Additional measurements were performed between subsequent fractions to examine the EPR response with increasing radiation dose. Independent dosimetry measurements were performed with optically-stimulated luminescent dosimeters (OSLDs) and diodes to more accurately establish the relationship between EPR signal and delivered radiation dose. Results: 36 EPR measurements were performed over the course of four months on two TBI and four H & N radiotherapy patients. We observe a linear increase in EPR signal with increasing dose across the entirety of the tested range. A linear least squares-weighted fit of delivered dose versus measured signal amplitude yields an adjusted R-square of 0.966. The standard error of inverse prediction (SEIP) is 1.77 Gy. For doses up to 7 Gy, the range most relevant to triage, we calculate an SEIP of 1.29 Gy. Conclusion: EPR spectroscopy provides a promising method of retrospective, non-invasive, in vivo biodosimetry. Our preliminary data show an excellent correlation between predicted signal amplitude and delivered

  9. Cerebral Oxygenation in Awake Rats during Acclimation and Deacclimation to Hypoxia: An In Vivo Electron Paramagnetic Resonance Study

    PubMed Central

    Khan, Mohammad N.; Hou, Huagang G.; Merlis, Jennifer; Abajian, Michelle A.; Demidenko, Eugene; Grinberg, Oleg Y.; Swartz, Harold M.

    2011-01-01

    Abstract Dunn, J. F., N. Khan, H. G. Hou, J. Merlis, M. A. Abajian, E. Demidenko, O.Y. Grinberg, and H. M. Swartz. Cerebral oxygenation in awake rats during acclimation and deacclimation to hypoxia: an in vivo EPR study. High Alt. Med. Biol. 12:71–77, 2011.— Exposure to high altitude or hypobaric hypoxia results in a series of metabolic, physiologic, and genetic changes that serve to acclimate the brain to hypoxia. Tissue Po2 (Pto2) is a sensitive index of the balance between oxygen delivery and utilization and can be considered to represent the summation of such factors as cerebral blood flow, capillary density, hematocrit, arterial Po2, and metabolic rate. As such, it can be used as a marker of the extent of acclimation. We developed a method using electron paramagnetic resonance (EPR) to measure Pto2 in unanesthetized subjects with a chronically implanted sensor. EPR was used to measure rat cortical tissue Pto2 in awake rats during acute hypoxia and over a time course of acclimation and deacclimation to hypobaric hypoxia. This was done to simulate the effects on brain Pto2 of traveling to altitude for a limited period. Acute reduction of inspired O2 to 10% caused a decline from 26.7 ± 2.2 to 13.0 ± 1.5 mmHg (mean ± SD). Addition of 10% CO2 to animals breathing 10% O2 returned Pto2 to values measured while breathing 21% O2, indicating that hypercapnia can reverse the effects of acute hypoxia. Pto2 in animals acclimated to 10% O2 was similar to that measured preacclimation when breathing 21% O2. Using a novel, individualized statistical model, it was shown that the T1/2 of the Pto2 response during exposure to chronic hypoxia was approximately 2 days. This indicates a capacity for rapid adaptation to hypoxia. When subjects were returned to normoxia, there was a transient hyperoxygenation, followed by a return to lower values with a T1/2 of deacclimation of 1.5 to 3 days. These data indicate that exposure to hypoxia results in significant

  10. Electron paramagnetic resonance of the excited triplet state of metal-free and metal-substituted cytochrome c.

    PubMed Central

    Angiolillo, P J; Vanderkooi, J M

    1995-01-01

    The photoactivated metastable triplate states of the porphyrin (free-base, i.e., metal-free) zinc and tin derivatives of horse cytochrome c were investigated using electron paramagnetic resonance. Zero-field splitting parameters, line shape, and Jahn-Teller distortion in the temperature range 3.8-150 K are discussed in terms of porphyrin-protein interactions. The zero-field splitting parameters D for the free-base, Zn and Sn derivatives are 465 x 10(-4), 342 x 10(-4) and 353 x 10(-4) cm-1, respectively, and are temperature invariant over the temperature ranges studied. AN E value at 4 K of 73 x 10(-4) cm-1 was obtained for Zn cytochrome c, larger than any previously found for Zn porphyrins derivatives of hemeproteins, showing that the heme site of cytochrome c imposes an asymmetric field. Though the E value for Zn cytochrome c is large, the geometry of the site appears quite constrained, as indicated by a spectral line shape showing a single species. Intersystem crossing occurred predominantly to the T2 > zero-field spin sublevel. EPR line shape changes with respect to temperature of Zn cyt c are interpreted in terms of vibronic coupling, and a maximum Jahn-Teller crystal-field splitting of approximately 180 cm-1 is obtained. Sn cytochrome c in comparison with the Zn protein exhibits a photoactivated triplet line shape that is less well resolved in the X-Y region. The magnitude of E value is approximately 60 x 10(-4) cm-1 at 4 K; its value rapidly tends toward zero with increasing temperature, from which a value for the Jahn-Teller crystal-field splitting of > or = 40 cm-1 is estimated. In contrast to those for the metal cytochromes, the magnitude of E value for the free-base derivative was essentially zero at all temperatures studied. This finding is discussed as a consequence of an excited-state tautomerization process that occurs even at 4 K. PMID:7647253

  11. Two-photon absorption of few-electron heavy ions

    SciTech Connect

    Surzhykov, A.; Indelicato, P.; Santos, J. P.; Amaro, P.; Fritzsche, S.

    2011-08-15

    The two-photon absorption of few-electron ions has been studied by using second-order perturbation theory and Dirac's relativistic equation. Within this framework, the general expressions for the excitation cross sections and rates are derived including a full account of the higher-order multipole terms in the expansion of the electron-photon interaction. While these expressions can be applied to any ion, independent of its particular shell structure, detailed computations are carried out for the two-photon absorption of hydrogen-, helium-, and berylliumlike ions and are compared with the available theoretical and experimental data. The importance of relativistic and nondipole effects in the analysis and computation of induced two-photon transitions is pointed out. Moreover, we discuss the potential of these transitions for atomic parity-violation studies in the high-Z domain.

  12. NASA three-laser airborne differential absorption lidar system electronics

    NASA Technical Reports Server (NTRS)

    Allen, R. J.; Copeland, G. D.

    1984-01-01

    The system control and signal conditioning electronics of the NASA three laser airborne differential absorption lidar (DIAL) system are described. The multipurpose DIAL system was developed for the remote measurement of gas and aerosol profiles in the troposphere and lower stratosphere. A brief description and photographs of the majority of electronics units developed under this contract are presented. The precision control system; which includes a master control unit, three combined NASA laser control interface/quantel control units, and three noise pulse discriminator/pockels cell pulser units; is described in detail. The need and design considerations for precision timing and control are discussed. Calibration procedures are included.

  13. Improved apparatus for trapped radical and other studies down to 1.5 K. [microwave cavity cryogenic equipment for electron paramagnetic resonance experiments

    NASA Technical Reports Server (NTRS)

    Woollam, J. A.; Sugawara, K.

    1978-01-01

    A Dewar system and associated equipment for electron paramagnetic resonance (EPR) studies of trapped free radicals and other optical or irradiation experiments are described. The apparatus is capable of reaching a temperature of 1.5 K and transporting on the order of 20 W per K temperature gradient; its principal advantages are for use at pumped cryogen temperatures and for experiments with large heat inputs. Two versions of the apparatus are discussed, one of which is designed for EPR in a rectangular cavity operating in a TE(102) mode and another in which EPR is performed in a cylindrical microwave cavity.

  14. Electron Paramagnetic Resonance: Elementary Theory and Practical Applications, Second Edition (John A. Weil and James R. Bolton)

    NASA Astrophysics Data System (ADS)

    Williams, Ffrancon

    2009-01-01

    The detection of electron magnetic resonance by Zavoiskii in the mid 1940s (1) ushered in a golden age of physical and chemical applications. Perhaps no single book did more to stimulate this development of EPR spectroscopy than the classic text by Wertz and Bolton (2) , which appeared in 1972. A revised version, with John A. Weil added as a co-author, was published by Wiley in 1994. This 2007 text is formally described as the second edition of the 1994 version. Wertz died shortly after the publication of the 1994 edition leaving Weil and Bolton as authors. In noting that the senior author (JAW) takes most of the responsibility for the content of this 2007 version, the Preface refers to it at one point as the "third edition", which of course is precisely how older readers will regard it. The main thrust of the book is decidedly on the physical aspects of EPR, so that it nicely complements the more chemical emphasis provided in the recent comprehensive text by Gerson and Hüber (3) . As the authors remark, the 2007 edition does not differ dramatically from the 1994 version. The titles of the 13 chapters remain the same except for chapter 11, which now refers to the "Noncontinuous" instead of the "Time-Dependent" Excitation of Spins. Recent developments are generally accommodated by a few extra pages in each chapter. Thus, chapter 1 on Basic Principles of Paramagnetic Resonance has been expanded from 31 to 36 pages to introduce the topics of parallel-field EPR, time-resolved EPR, "computerology", and EPR imaging. Chapter 2 on Magnetic Interactions is essentially unchanged while chapter 3 on Isotropic Hyperfine Effects has been expanded to include new sections on Deviations from the Simple Multinomial Scheme (3.7) and Some Interesting π-Type Free Radicals (3.9). Section 3.9 provides a useful corrective to the notion that the EPR method can detect and characterize almost any type of radical species. This welcome touch of realism is nicely illustrated by mentioning

  15. Electron Paramagnetic Resonance: Elementary Theory and Practical Applications, Second Edition (John A. Weil and James R. Bolton)

    NASA Astrophysics Data System (ADS)

    Williams, Ffrancon

    2009-01-01

    The detection of electron magnetic resonance by Zavoiskii in the mid 1940s (1) ushered in a golden age of physical and chemical applications. Perhaps no single book did more to stimulate this development of EPR spectroscopy than the classic text by Wertz and Bolton (2) , which appeared in 1972. A revised version, with John A. Weil added as a co-author, was published by Wiley in 1994. This 2007 text is formally described as the second edition of the 1994 version. Wertz died shortly after the publication of the 1994 edition leaving Weil and Bolton as authors. In noting that the senior author (JAW) takes most of the responsibility for the content of this 2007 version, the Preface refers to it at one point as the "third edition", which of course is precisely how older readers will regard it. The main thrust of the book is decidedly on the physical aspects of EPR, so that it nicely complements the more chemical emphasis provided in the recent comprehensive text by Gerson and Hüber (3) . As the authors remark, the 2007 edition does not differ dramatically from the 1994 version. The titles of the 13 chapters remain the same except for chapter 11, which now refers to the "Noncontinuous" instead of the "Time-Dependent" Excitation of Spins. Recent developments are generally accommodated by a few extra pages in each chapter. Thus, chapter 1 on Basic Principles of Paramagnetic Resonance has been expanded from 31 to 36 pages to introduce the topics of parallel-field EPR, time-resolved EPR, "computerology", and EPR imaging. Chapter 2 on Magnetic Interactions is essentially unchanged while chapter 3 on Isotropic Hyperfine Effects has been expanded to include new sections on Deviations from the Simple Multinomial Scheme (3.7) and Some Interesting π-Type Free Radicals (3.9). Section 3.9 provides a useful corrective to the notion that the EPR method can detect and characterize almost any type of radical species. This welcome touch of realism is nicely illustrated by mentioning

  16. Application of electron paramagnetic resonance imaging to the characterization of the Ultem(R) exposed to 1 MeV electrons. Correlation of radical density data to tiger code calculations

    SciTech Connect

    Suleman, N.K.

    1994-12-01

    A major long-term goal of the Materials Division at the NASA Langley Research Center is the characterization of new high-performance materials that have potential applications in the aircraft industry, and in space. The materials used for space applications are often subjected to a harsh and potentially damaging radiation environment. The present study constitutes the application of a novel technique to obtain reliable data for ascertaining the molecular basis for the resilience and durability of materials that have been exposed to simulated space radiations. The radiations of greatest concern are energetic electrons and protons, as well as galactic cosmic rays. Presently, the effects of such radiation on matter are not understood in their entirety. It is clear however, that electron radiation causes ionization and homolytic bond rupture, resulting in the formation of paramagnetic spin centers in the polymer matrices of the structural materials. Since the detection and structure elucidation of paramagnetic species are most readily accomplished using Electron Paramagnetic Resonance (EPR) Spectroscopy, the NASA LaRC EPR system was brought back on-line during the 1991 ASEE term. The subsequent 1992 ASEE term was devoted to the adaptation of the EPR core system to meet the requirements for EPR Imaging (EPRI), which provides detailed information on the spatial distribution of paramagnetic species in bulk media. The present (1994) ASEE term was devoted to the calibration of this EPR Imaging system, as well as to the application of this technology to study the effects of electron irradiation on Ultem(exp R), a high performance polymer which is a candidate for applications in aerospace. The Ultem was exposed to a dose of 2.4 x 10(exp 9) Rads (1-MeV energy/electron) at the LaRC electron accelerator facility. Subsequently, the exposed specimens were stored in liquid nitrogen, until immediately prior to analyses by EPRI.

  17. Role of the Proximal Cysteine Hydrogen Bonding Interaction in Cytochrome P450 2B4 Studied by Cryoreduction, Electron Paramagnetic Resonance, and Electron-Nuclear Double Resonance Spectroscopy.

    PubMed

    Davydov, Roman; Im, Sangchoul; Shanmugam, Muralidharan; Gunderson, William A; Pearl, Naw May; Hoffman, Brian M; Waskell, Lucy

    2016-02-16

    Crystallographic studies have shown that the F429H mutation of cytochrome P450 2B4 introduces an H-bond between His429 and the proximal thiolate ligand, Cys436, without altering the protein fold but sharply decreases the enzymatic activity and stabilizes the oxyferrous P450 2B4 complex. To characterize the influence of this hydrogen bond on the states of the catalytic cycle, we have used radiolytic cryoreduction combined with electron paramagnetic resonance (EPR) and (electron-nuclear double resonance (ENDOR) spectroscopy to study and compare their characteristics for wild-type (WT) P450 2B4 and the F429H mutant. (i) The addition of an H-bond to the axial Cys436 thiolate significantly changes the EPR signals of both low-spin and high-spin heme-iron(III) and the hyperfine couplings of the heme-pyrrole (14)N but has relatively little effect on the (1)H ENDOR spectra of the water ligand in the six-coordinate low-spin ferriheme state. These changes indicate that the H-bond introduced between His and the proximal cysteine decreases the extent of S → Fe electron donation and weakens the Fe(III)-S bond. (ii) The added H-bond changes the primary product of cryoreduction of the Fe(II) enzyme, which is trapped in the conformation of the parent Fe(II) state. In the wild-type enzyme, the added electron localizes on the porphyrin, generating an S = (3)/2 state with the anion radical exchange-coupled to the Fe(II). In the mutant, it localizes on the iron, generating an S = (1)/2 Fe(I) state. (iii) The additional H-bond has little effect on g values and (1)H-(14)N hyperfine couplings of the cryogenerated, ferric hydroperoxo intermediate but noticeably slows its decay during cryoannealing. (iv) In both the WT and the mutant enzyme, this decay shows a significant solvent kinetic isotope effect, indicating that the decay reflects a proton-assisted conversion to Compound I (Cpd I). (v) We confirm that Cpd I formed during the annealing of the cryogenerated hydroperoxy intermediate

  18. Electron paramagnetic resonance studies of a viscous nematic liquid crystal: Evidence counter to a second-order phase change

    NASA Technical Reports Server (NTRS)

    Shutt, W. E.; Gelerinter, E.; Fryburg, G. C.; Sheley, C. F.

    1972-01-01

    The ordering in a viscous, nematic, liquid crystal was studied using vanadyl acetyl acetonate and several nitroxides as paramagnetic probes. The ordering curve for VAAC at both K-band and X-band shows a slope discontinuity at a reduced temperature of 0.85. This discontinuity is caused by the tumbling time of the VAAC becoming comparable with the hyperfine splitting. The slope discontinuity is not present in the ordering curves of the nitroxides. The results are taken as evidence counter to the presence of a second-order phase transition.

  19. A tuneable doubly stacked dielectric resonator housed in an intact TE 102 cavity for electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Mattar, Saba M.; Emwas, Abdul H.

    2003-01-01

    An EPR resonator is constructed by inserting a pair of dielectric ceramic rings in an unmodified rectangular TE 102 cavity. It is tuneable over the range of 8.0-10.0 GHz. Therefore, existing EPR cavities can be easily converted to resonators with superior signal-to-noise ratios that are at least 24 times larger than the original ones in this extended frequency range. The resonator's performance is tested using DPPH, TEMPONE, MnO and Cu 2+ complexes and displays excellent resolution and sensitivity. Thus EPR spectra of small paramagnetic organic and inorganic samples and spin labeled biomolecules may be obtained without resorting to loop gap resonators.

  20. The Origin of the Multiline and g = 4.1 Electron Paramagnetic Resonance Signals from the Oxygen-Evolving System of Photosystem II

    PubMed Central

    Hansson, Örjan; Aasa, Roland; Vänngȧrd, Tore

    1987-01-01

    Continuous illumination at 200 K of photosystem (PS) II-enriched membranes generates two electron paramagnetic resonance (EPR) signals that both are connected with the S2 state: a multiline signal at g 2 and a single line at g = 4.1. From measurements at three different X-band frequencies and at 34 GHz, the g tensor of the multiline species was found to be isotropic with g = 1.982. It has an excited spin multiplet at ∼30 cm-1, inferred from the temperature-dependence of the linewidth. The intensity ratio of the g = 4.1 signal to the multiline signal was found to be almost constant from 5 to 23 K. Based on these findings and on spin quantitation of the two signals in samples with and without 4% ethanol, it is concluded that they arise from the ground doublets of paramagnetic species in different PS II centers. It is suggested that the two signals originate from separate PS II electron donors that are in a redox equilibrium with each other in the S2 state and that the g = 4.1 signal arises from monomeric Mn(IV). PMID:19431697

  1. Effects of thermal annealing on the radiation produced electron paramagnetic resonance spectra of bovine and equine tooth enamel: Fossil and modern

    NASA Astrophysics Data System (ADS)

    Weeks, Robert A.; Bogard, James S.; Elam, J. Michael; Weinand, Daniel C.; Kramer, Andrew

    2003-06-01

    The concentration of stable radiation-induced paramagnetic states in fossil teeth can be used as a measure of sample age. Temperature excursions >100 °C, however, can cause the paramagnetic state clock to differ from the actual postmortem time. We have heated irradiated enamel from both fossilized bovid and modern equine (MEQ) teeth for 30 min in 50 °C increments from 100 to 300 °C, measuring the electron paramagnetic resonance (EPR) spectrum after each anneal, to investigate such effects. Samples were irradiated again after the last anneal, with doses of 300-1200 Gy from 60Co photons, and measured. Two unirradiated MEQ samples were also annealed for 30 min at 300 °C, one in an evacuated EPR tube and the other in a tube open to the atmosphere, and subsequently irradiated. The data showed that hyperfine components attributed to the alanine radical were not detected in the irradiated MEQ sample until after the anneals. The spectrum of the MEQ sample heated in air and then irradiated was similar to that of the heat treated fossil sample. We conclude that the hyperfine components are due to sample heating to temperatures/times >100 °C/30 min and that similarities between fossil and MEQ spectra after the 300 °C/30 min MEQ anneal are also due to sample heating. We conclude that the presence of the hyperfine components in spectra of fossil tooth enamel indicate that such thermal events occurred either at the time of death, or during the postmortem history.

  2. Absorption effects in electron-sulfur-dioxide collisions

    SciTech Connect

    Machado, L. E.; Sugohara, R. T.; Santos, A. S. dos; Lee, M.-T.; Iga, I.; Souza, G. L. C. de; Homem, M. G. P.; Michelin, S. E.; Brescansin, L. M.

    2011-09-15

    A joint experimental-theoretical study on electron-SO{sub 2} collisions in the low and intermediate energy range is reported. More specifically, experimental elastic differential, integral, and momentum transfer cross sections in absolute scale are measured in the 100-1000 eV energy range using the relative-flow technique. Calculated elastic differential, integral, and momentum transfer cross sections as well as grand-total and total absorption cross sections are also presented in the 1-1000 eV energy range. A complex optical potential is used to represent the electron-molecule interaction dynamics, whereas the Schwinger variational iterative method combined with the distorted-wave approximation is used to solve the scattering equations. Comparison of the present results is made with the theoretical and experimental results available in the literature.

  3. Electron paramagnetic resonance and magnetization in Co doped La{sub 2/3}Ca{sub 1/3}MnO{sub 3}

    SciTech Connect

    Rivadulla, F.; Sande, P.; Causa, M. T.; Hueso, L. E.; Lopez-Quintela, M. A.; Rivas, J.

    2001-06-01

    Spin dynamics of the Mn-site substituted colossal magnetoresistance system were studied by means of electron paramagnetic resonance (EPR) and dc magnetic susceptibility in La{sub 2/3}Ca{sub 1/3}Mn{sub 1{minus}x}Co{sub x}O{sub 3} (0{le}x{le}0.1,{Delta}x=0.025). A dramatic increase in the high temperature limiting value for the EPR linewidth ({Delta}H{sub pp}({infinity})) was observed with doping. Structural analysis revealed that only negligible changes are produced in bond distances and angles at these low doping levels. On the other hand, dipolar contribution to {Delta}H{sub pp}({infinity}) was estimated in a few Gauss. To explain the effect of doping on {Delta}H{sub pp}({infinity}), we propose here a scenario including fast Mn-spin lattice relaxation through paramagnetic Co ions. {copyright} 2001 American Institute of Physics.

  4. Heterogeneous Ordered-Disordered Structure of the Mesodomain in Frozen Sucrose-Water Solutions Revealed by Multiple Electron Paramagnetic Resonance Spectroscopies

    PubMed Central

    Chen, Hanlin; Sun, Li; Warncke, Kurt

    2013-01-01

    The microscopic structure of frozen aqueous sucrose solutions, over concentrations of 0–75% (w/v), is characterized by using multiple continuous-wave and pulsed electron paramagnetic resonance (EPR) spectroscopic and relaxation techniques and the paramagnetic spin probe, TEMPOL. The temperature dependence of the TEMPOL EPR lineshape anisotropy reveals a mobility transition, specified at 205 K in pure water and 255 ±5 K for >1% (w/v) added sucrose. The transition temperature is >>Tg, where Tg is the homogeneous water glass transition temperature, which shows that TEMPOL resides in the mesoscopic domain (mesodomain) at water-ice crystallite boundaries, and that the mesodomain sucrose concentrations are comparable at >1% (w/v) added sucrose. Electron spin echo envelope modulation (ESEEM) spectroscopy of TEMPOL-2H2-sucrose hyperfine interactions also indicates comparable sucrose concentrations in mesodomains at >1% (w/v) added sucrose. Electron spin echo (ESE) – detected longitudinal and phase memory relaxation times (T1 and TM, respectively) at 6 K indicate a general trend of increased mesodomain volume with added sucrose, in three stages: 1-15, 20-50, and >50% (w/v). The calibrated TEMPOL concentrations indicate that the mesodomain volume is less than the predicted maximally freeze-concentrated value [80 (w/w); 120% (w/v)], with transitions at 15-20% and 50% (w/v) starting sucrose. An ordered sucrose hydrate phase, which excludes TEMPOL, and a disordered, amorphous sucrose-water glass phase, in which TEMPOL resides, are proposed to compose a heterogeneous mesodomain. The results show that the ratio of ordered and disordered volume fractions in the mesodomain is exquisitely sensitive to the starting sucrose concentration. PMID:23464733

  5. A paramagnetic molecular voltmeter.

    PubMed

    Surek, Jack T; Thomas, David D

    2008-01-01

    We have developed a general electron paramagnetic resonance (EPR) method to measure electrostatic potential at spin labels on proteins to millivolt accuracy. Electrostatic potential is fundamental to energy-transducing proteins like myosin, because molecular energy storage and retrieval is primarily electrostatic. Quantitative analysis of protein electrostatics demands a site-specific spectroscopic method sensitive to millivolt changes. Previous electrostatic potential studies on macromolecules fell short in sensitivity, accuracy and/or specificity. Our approach uses fast-relaxing charged and neutral paramagnetic relaxation agents (PRAs) to increase nitroxide spin label relaxation rate solely through collisional spin exchange. These PRAs were calibrated in experiments on small nitroxides of known structure and charge to account for differences in their relaxation efficiency. Nitroxide longitudinal (R(1)) and transverse (R(2)) relaxation rates were separated by applying lineshape analysis to progressive saturation spectra. The ratio of measured R(1) increases for each pair of charged and neutral PRAs measures the shift in local PRA concentration due to electrostatic potential. Voltage at the spin label is then calculated using the Boltzmann equation. Measured voltages for two small charged nitroxides agree with Debye-Hückel calculations. Voltage for spin-labeled myosin fragment S1 also agrees with calculation based on the pK shift of the reacted cysteine. PMID:17964835

  6. A Paramagnetic Molecular Voltmeter

    PubMed Central

    Surek, Jack T.; Thomas, David D.

    2008-01-01

    We have developed a general electron paramagnetic resonance (EPR) method to measure electrostatic potential at spin labels on proteins to millivolt accuracy. Electrostatic potential is fundamental to energy-transducing proteins like myosin, because molecular energy storage and retrieval is primarily electrostatic. Quantitative analysis of protein electrostatics demands a site-specific spectroscopic method sensitive to millivolt changes. Previous electrostatic potential studies on macromolecules fell short in sensitivity, accuracy and/or specificity. Our approach uses fast-relaxing charged and neutral paramagnetic relaxation agents (PRAs) to increase nitroxide spin label relaxation rate solely through collisional spin exchange. These PRAs were calibrated in experiments on small nitroxides of known structure and charge to account for differences in their relaxation efficiency. Nitroxide longitudinal (R1) and transverse (R2) relaxation rates were separated by applying lineshape analysis to progressive saturation spectra. The ratio of measured R1 increases for each pair of charged and neutral PRAs measures the shift in local PRA concentration due to electrostatic potential. Voltage at the spin label is then calculated using the Boltzmann equation. Measured voltages for two small charged nitroxides agree with Debye-Hückel calculations. Voltage for spin-labeled myosin fragment S1 also agrees with calculation based on the pK shift of the reacted cysteine. PMID:17964835

  7. A high-frequency electron paramagnetic resonance spectrometer for multi-dimensional, multi-frequency, and multi-phase pulsed measurements

    SciTech Connect

    Cho, F. H.; Stepanov, V.; Takahashi, S.

    2014-07-15

    We describe instrumentation for a high-frequency electron paramagnetic resonance (EPR) and pulsed electron-electron double resonance (PELDOR) spectroscopy. The instrumentation is operated in the frequency range of 107−120 GHz and 215−240 GHz and in the magnetic field range of 0−12.1 T. The spectrometer consisting of a high-frequency high-power solid-state source, a quasioptical system, a phase-sensitive detection system, a cryogenic-free superconducting magnet, and a {sup 4}He cryostat enables multi-frequency continuous-wave EPR spectroscopy as well as pulsed EPR measurements with a few hundred nanosecond pulses. Here we discuss the details of the design and the pulsed EPR sensitivity of the instrumentation. We also present performance of the instrumentation in unique experiments including PELDOR spectroscopy to probe correlations in an insulating electronic spin system and application of dynamical decoupling techniques to extend spin coherence of electron spins in an insulating solid-state system.

  8. Tuning of the spin distribution between ligand- and metal-based spin: electron paramagnetic resonance of mixed-ligand molybdenum tris(dithiolene) complex anions.

    PubMed

    Fekl, Ulrich; Sarkar, Biprajit; Kaim, Wolfgang; Zimmer-De Iuliis, Marco; Nguyen, Neilson

    2011-09-19

    Electron paramagnetic resonance spectra of homoleptic and mixed-ligand molybdenum tris(dithiolene) complex anions [Mo(tfd)(m)(bdt)(n)](-) (n + m = 3; bdt = S(2)C(6)H(4); tfd = S(2)C(2)(CF(3))(2)) reveal that the spin density has mixed metal-ligand character with more ligand-based spin for [Mo(tfd)(3)](-) and a higher degree of metal-based spin for [Mo(bdt)(3)](-): the magnitude of the isotropic (95,97)Mo hyperfine interaction increases continuously, by a factor of 2.5, on going from the former to the latter. The mixed complexes fall in between, and the metal character of the spin increases with the bdt content. The experiments were corroborated by density functional theory computations, which reproduce this steady increase in metal-based character. PMID:21853970

  9. Single-crystal electron paramagnetic resonance study of cytochrome c3 from Desulfovibrio desulfuricans Norway Strain. Assignment of the heme midpoint redox potentials.

    PubMed

    Guigliarelli, B; Bertrand, P; More, C; Haser, R; Gayda, J P

    1990-11-01

    A single crystal of cytochrome c3 from Desulfovibrio desulfuricans Norway is studied by electron paramagnetic resonance at low temperature. The orientation of the principal axis corresponding to the largest g value is determined for the 12 heme groups in the crystal unit cell. The comparison of these directions to the normals to the heme planes, determined from the crystallographic data at 2.5 A resolution, gives strong evidence for the following assignment of the midpoint redox potentials to the heme groups H1 to H4, defined in the three-dimensional structure: -150 mV is assigned to H3, -300 mV to H4, -330 mV to H1 and -355 mV to H2. This assignment is in agreement with a partial correspondence previously established from an independent study performed on cytochrome c3 in solution. PMID:2172551

  10. Characterization of oxygen vacancy defects in Ba1-xCaxTiO3 insulating ceramics using electron paramagnetic resonance technique

    NASA Astrophysics Data System (ADS)

    Lu, Da-Yong; Yuan, Long-Fei; Liang, Wei-Na; Zhu, Zhao-Bin

    2016-01-01

    The electron paramagnetic resonance (EPR) technique was employed to detect oxygen vacancy defects in the tetragonal Ba1-xCaxTiO3 (x = 0.03) ceramics (BCa3T) prepared via the mixed oxide route at 1300-1500 °C. In the rhombohedral phase below -100 °C, an EPR signal at g = 1.955 appeared in the insulating BCa3T with an electrical resistivity of 108 Ω cm and was assigned to ionized oxygen vacancy defects. BCa3T prepared at 1300 °C showed a temperature-stable X6S dielectric specification (ɛ‧ = 1750). Three types of vacancy defect, namely, Ba, Ti, and O vacances, could coexist in BCa3T owing to the partial Ti-site occupation by Ca2+.

  11. In vivo measurement of arterial and venous oxygenation in the rat using 3D spectral-spatial electron paramagnetic resonance imaging.

    PubMed

    Kuppusamy, P; Shankar, R A; Zweier, J L

    1998-07-01

    Electron paramagnetic resonance imaging (EPRI) instrumentation, enabling the performance of three-dimensional spectral-spatial images of free radicals, has been developed to study spatially defined differences in tissue metabolism and oxygenation. Using this instrumentation 3D images of nitroxides in rat tail were obtained. The images visualize the arterial and venous vasculature in the tail segment. Based on the exchange broadening influence of oxygen on the EPR linewidth of nitroxides, we performed localized oxygen measurements in the in vivo rat. An oxygen concentration of 300+/-30 microM was measured in the arteries and 50+/-20 microM in the veins. These results demonstrate the feasibility of performing in vivo, non-invasive measurements and mapping of localized oxygenation in small animals using spectral-spatial EPR imaging techniques. PMID:9703045

  12. Evaluation of the effect of dietary lycopene, the main carotenoid in tomato (Lycopersicon esculentum), on the in vivo renal reducing ability by a radiofrequency electron paramagnetic resonance method.

    PubMed

    Yoshida, Kazutaka; Yokoyama, Hidekatsu; Oteki, Takaaki; Matsumoto, Gaku; Aizawa, Koichi; Inakuma, Takahiro

    2011-04-13

    Although it has been reported that dietary lycopene, the main carotenoid in tomato, improved drug-induced nephropathy, there are no reports on the effect of orally administered lycopene on the in vivo renal reducing (i.e., antioxidant) ability. The radiofrequency electron paramagnetic resonance (EPR) method is a unique technique by which the in vivo reducing ability of an experimental animal can be studied. In this study, the in vivo changes in the renal reducing ability of rats orally administered lycopene were investigated using a 700 MHz EPR spectrometer equipped with a surface-coil-type resonator. Rats were fed either a control diet or a diet containing lycopene. After 2 weeks, in vivo EPR measurements were conducted. The renal reducing ability of lycopene-treated rats was significantly greater than that of the control. This is the first verification of in vivo antioxidant enhancement via dietary lycopene administration. PMID:21381743

  13. Application of electron paramagnetic resonance imaging to the characterization of the Ultem(R) exposed to 1 MeV electrons. Correlation of radical density data to tiger code calculations

    NASA Astrophysics Data System (ADS)

    Suleman, Naushadalli K.

    1994-12-01

    A major long-term goal of the Materials Division at the NASA Langley Research Center is the characterization of new high-performance materials that have potential applications in the aircraft industry, and in space. The materials used for space applications are often subjected to a harsh and potentially damaging radiation environment. The present study constitutes the application of a novel technique to obtain reliable data for ascertaining the molecular basis for the resilience and durability of materials that have been exposed to simulated space radiations. The radiations of greatest concern are energetic electrons and protons, as well as galactic cosmic rays. Presently, the effects of such radiation on matter are not understood in their entirety. It is clear however, that electron radiation causes ionization and homolytic bond rupture, resulting in the formation of paramagnetic spin centers in the polymer matrices of the structural materials. Since the detection and structure elucidation of paramagnetic species are most readily accomplished using Electron Paramagnetic Resonance (EPR) Spectroscopy, the NASA LaRC EPR system was brought back on-line during the 1991 ASEE term. The subsequent 1992 ASEE term was devoted to the adaptation of the EPR core system to meet the requirements for EPR Imaging (EPRI), which provides detailed information on the spatial distribution of paramagnetic species in bulk media. The present (1994) ASEE term was devoted to the calibration of this EPR Imaging system, as well as to the application of this technology to study the effects of electron irradiation on Ultem(exp R), a high performance polymer which is a candidate for applications in aerospace. The Ultem was exposed to a dose of 2.4 x 10(exp 9) Rads (1-MeV energy/electron) at the LaRC electron accelerator facility. Subsequently, the exposed specimens were stored in liquid nitrogen, until immediately prior to analyses by EPRI. The intensity and dimensions of the EPR Images that

  14. Application of electron paramagnetic resonance imaging to the characterization of the Ultem(R) exposed to 1 MeV electrons. Correlation of radical density data to tiger code calculations

    NASA Technical Reports Server (NTRS)

    Suleman, Naushadalli K.

    1994-01-01

    A major long-term goal of the Materials Division at the NASA Langley Research Center is the characterization of new high-performance materials that have potential applications in the aircraft industry, and in space. The materials used for space applications are often subjected to a harsh and potentially damaging radiation environment. The present study constitutes the application of a novel technique to obtain reliable data for ascertaining the molecular basis for the resilience and durability of materials that have been exposed to simulated space radiations. The radiations of greatest concern are energetic electrons and protons, as well as galactic cosmic rays. Presently, the effects of such radiation on matter are not understood in their entirety. It is clear however, that electron radiation causes ionization and homolytic bond rupture, resulting in the formation of paramagnetic spin centers in the polymer matrices of the structural materials. Since the detection and structure elucidation of paramagnetic species are most readily accomplished using Electron Paramagnetic Resonance (EPR) Spectroscopy, the NASA LaRC EPR system was brought back on-line during the 1991 ASEE term. The subsequent 1992 ASEE term was devoted to the adaptation of the EPR core system to meet the requirements for EPR Imaging (EPRI), which provides detailed information on the spatial distribution of paramagnetic species in bulk media. The present (1994) ASEE term was devoted to the calibration of this EPR Imaging system, as well as to the application of this technology to study the effects of electron irradiation on Ultem(exp R), a high performance polymer which is a candidate for applications in aerospace. The Ultem was exposed to a dose of 2.4 x 10(exp 9) Rads (1-MeV energy/electron) at the LaRC electron accelerator facility. Subsequently, the exposed specimens were stored in liquid nitrogen, until immediately prior to analyses by EPRI. The intensity and dimensions of the EPR Images that

  15. Native and induced triplet nitrogen-vacancy centers in nano- and micro-diamonds: Half-field electron paramagnetic resonance fingerprint

    SciTech Connect

    Shames, A. I.; Osipov, V. Yu.; Vul’, A. Ya.; Bardeleben, H.-J. von

    2014-02-10

    Multiple frequency electron paramagnetic resonance (EPR) study of small (4–25 nm) nanodiamonds obtained by various dynamic synthesis techniques reveals systematic presence in the half-field (HF) region a distinctive doublet fingerprint consisting of resolved g{sub HF1} = 4.26 and g{sub HF2} = 4.00 signals. This feature is attributed to “forbidden” ΔM{sub S} = 2 transitions in EPR spectra of two native paramagnetic centers of triplet (S = 1) origin designated as TR1 and TR2, characterized by zero field splitting values D{sub 1} = 0.0950 ± 0.002 cm{sup −1} and D{sub 2} = 0.030 ± 0.005 cm{sup −1}. Nanodiamonds of ∼50 nm particle size, obtained by crushing of Ib type nitrogen rich synthetic diamonds, show only HF TR2 signal whereas the same sample undergone high energy (20 MeV) electron irradiation and thermal annealing demonstrates rise of HF TR1 signal. The same HF TR1 signals appear in the process of fabrication of fluorescent nanodiamonds from micron-size synthetic diamond precursors. Results obtained allow unambiguous attribution of the half-field TR1 EPR signals with g{sub HF1} = 4.26, observed in nano- and micron-diamond powders, to triplet negatively charged nitrogen-vacancy centers. These signals are proposed as reliable and convenient fingerprints in both qualitative and quantitative study of fluorescent nano- and micron-diamonds.

  16. The effect of oxygen at physiological levels on the detection of free radical intermediates by electron paramagnetic resonance.

    PubMed

    Krishna, M C; Samuni, A

    1993-01-01

    It is well known that oxygen enhances the relaxation of free radical EPR probes through spin lattice and Heisenberg spin-spin interactions with consequent effect on the line height and width. The two relaxation processes have opposing effects on the signal heights and depend on the concentration of oxygen, the incident microwave power, and the presence of other paramagnetic species. During EPR studies of chemical, biochemical, and cellular processes involving free radicals, molecular oxygen has significant magnetic influence on the EPR signal intensity of the free radical species under investigation in addition to affecting the rates of production of the primary species and the stability of the spin adduct nitroxides. These effects are often overlooked and can cause artifacts and lead to erroneous interpretation. In the present study, the effects of oxygen and ferricyanide on the EPR signal height of stable and persistent spin adduct nitroxides at commonly employed microwave powers were examined. The results show that under commonly adopted EPR spectrometer instrumental conditions, artifactual changes in the EPR signal of spin adducts occur and the best way to avoid them is by keeping the oxygen level constant using a gas-permeable cell. PMID:8396553

  17. Electronic structure description of a [Co(III)3Co(IV)O4] cluster: a model for the paramagnetic intermediate in cobalt-catalyzed water oxidation.

    PubMed

    McAlpin, J Gregory; Stich, Troy A; Ohlin, C André; Surendranath, Yogesh; Nocera, Daniel G; Casey, William H; Britt, R David

    2011-10-01

    Multifrequency electron paramagnetic resonace (EPR) spectroscopy and electronic structure calculations were performed on [Co(4)O(4)(C(5)H(5)N)(4)(CH(3)CO(2))(4)](+) (1(+)), a cobalt tetramer with total electron spin S = 1/2 and formal cobalt oxidation states III, III, III, and IV. The cuboidal arrangement of its cobalt and oxygen atoms is similar to that of proposed structures for the molecular cobaltate clusters of the cobalt-phosphate (Co-Pi) water-oxidizing catalyst. The Davies electron-nuclear double resonance (ENDOR) spectrum is well-modeled using a single class of hyperfine-coupled (59)Co nuclei with a modestly strong interaction (principal elements of the hyperfine tensor are equal to [-20(±2), 77(±1), -5(±15)] MHz). Mims (1)H ENDOR spectra of 1(+) with selectively deuterated pyridine ligands confirm that the amount of unpaired spin on the cobalt-bonding partner is significantly reduced from unity. Multifrequency (14)N ESEEM spectra (acquired at 9.5 and 34.0 GHz) indicate that four nearly equivalent nitrogen nuclei are coupled to the electron spin. Cumulatively, our EPR spectroscopic findings indicate that the unpaired spin is delocalized almost equally across the eight core atoms, a finding corroborated by results from DFT calculations. Each octahedrally coordinated cobalt ion is forced into a low-spin electron configuration by the anionic oxo and carboxylato ligands, and a fractional electron hole is localized on each metal center in a Co 3d(xz,yz)-based molecular orbital for this essentially [Co(+3.125)(4)O(4)] system. Comparing the EPR spectrum of 1(+) with that of the catalyst film allows us to draw conclusions about the electronic structure of this water-oxidation catalyst. PMID:21913664

  18. Disappearance of electron-hole asymmetry in nanoparticles of Nd{sub 1−x}Ca{sub x}MnO{sub 3}(x=0.6,0.4): magnetization and electron paramagnetic resonance evidence

    SciTech Connect

    Bhagyashree, K. S. Bhat, S. V.

    2015-05-07

    We study and compare magnetic and electron paramagnetic resonance behaviors of bulk and nanoparticles of Nd{sub 1−x}Ca{sub x}MnO{sub 3} in hole doped (x=0.4;NCMOH) and electron doped (x=0.6;NCMOE) samples. NCMOH in bulk form shows a complex temperature dependence of magnetization M(T), with a charge ordering transition at ∼250 K, an antiferromagnetic (AFM) transition at ∼150 K, and a transition to a canted AFM phase/mixed phase at ∼80 K. Bulk NCMOE behaves quite differently with just a charge ordering transition at ∼280 K, thus providing a striking example of the so called electron-hole asymmetry. While our magnetization data on bulk samples are consistent with the earlier reports, the new results on the nanoparticles bring out drastic effects of size reduction. They show that M(T) behaviors of the two nanosamples are essentially similar in addition to the absence of the charge order in them thus providing strong evidence for vanishing of the electron-hole asymmetry in nanomanganites. This conclusion is further corroborated by electron paramagnetic resonance studies which show that the large difference in the “g” values and their temperature dependences found for the two bulk samples disappears as they approach a common behavior in the corresponding nanosamples.

  19. Nuclear magnetic resonance-paramagnetic relaxation enhancements: Influence of spatial quantization of the electron spin when the zero-field splitting energy is larger than the Zeeman energy

    NASA Astrophysics Data System (ADS)

    Abernathy, S. M.; Miller, J. C.; Lohr, L. L.; Sharp, R. R.

    1998-09-01

    Dissolved paramagnetic ions generally provide an efficient mechanism for the relaxation of nuclear spins in solution, a phenomenon called the nuclear magnetic resonance-paramagnetic relaxation enhancement (NMR-PRE). Metal ions with electron spins S⩾1 exhibit rich NMR relaxation phenomena originating in the properties of the zero-field splitting (zfs) interaction, which vanishes for spin-1/2 ions but which is nonzero for S⩾1 ions in site symmetry lower than cubic. For S⩾1 ions in the vicinity of the zfs-limit, i.e., at magnetic-field strengths low enough that the zfs energy exceeds the Zeeman energy, the NMR-PRE depends strongly on the detailed structure of the electron spin energy levels as well as on the spatial quantization of the spin motion. It is shown theoretically and experimentally that the NMR-PRE produced by integer spins can be influenced strongly by the small intradoublet zero-field splittings, i.e., the splittings between the components of the non-Kramers doublets, which are produced by noncylindrical components of the crystal field potential. These small splittings produce relatively low-frequency oscillations in the dipolar field associated with (the spin component along the molecule-fixed ẑ axis). These motions decouple the nuclear spin from the electron spin, thereby depressing, in some cases very strongly, the NMR-PRE. The presence of a relatively small Zeeman field, comparable in magnitude to the intradoublet spacing but small compared to the larger interdoublet zfs splittings, causes a major change in the spin wave functions which has profound effects on the motions of the electron spin. When the Zeeman energy exceeds the small zfs splitting, the oscillatory motion of damps out, with the result that the electron spin couples more effectively to the nuclear spin, providing a more efficient NMR relaxation pathway. NMR-PRE data are presented for the S=1 complex Ni(II)(o-pda)2Cl2 (o-pda=ortho-phenylenediamine) which confirm the

  20. Light-induced electron paramagnetic resonance evidence of charge transfer in electrospun fibers containing conjugated polymer/fullerene and conjugated polymer/fullerene/carbon nanotube blends

    NASA Astrophysics Data System (ADS)

    Shames, Alexander I.; Bounioux, Céline; Katz, Eugene A.; Yerushalmi-Rozen, Rachel; Zussman, Eyal

    2012-03-01

    Electrospun sub-micron fibers containing conjugated polymer (poly(3-hexylthiophene), P3HT) with a fullerene derivative, phenyl-C61-butyric acid methylester (PCBM) or a mixture of PCBM and single-walled carbon nanotubes (SWCNTs) were studied by light-induced electron paramagnetic resonance spectroscopy. The results provide experimental evidence of electron transfer between PCBM and P3HT components in both fiber systems and suggest that the presence of a dispersing block-copolymer, which acts via physical adsorption onto the PCBM and SWCNT moieties, does not prevent electron transfer at the P3HT-PCBM interface. These findings suggest a research perspective towards utilization of fibers of functional nanocomposites in fiber-based organic optoelectronic and photovoltaic devices. The latter can be developed in the textile-type large area photovoltaics or individual fiber-based solar cells that will broaden energy applications from macro-power tools to micro-nanoscale power conversion devices and smart textiles.

  1. Light-induced electron paramagnetic resonance evidence of charge transfer in electrospun fibers containing conjugated polymer/fullerene and conjugated polymer/fullerene/carbon nanotube blends

    SciTech Connect

    Shames, Alexander I.; Bounioux, Celine; Katz, Eugene A.; Yerushalmi-Rozen, Rachel; Zussman, Eyal

    2012-03-12

    Electrospun sub-micron fibers containing conjugated polymer (poly(3-hexylthiophene), P3HT) with a fullerene derivative, phenyl-C61-butyric acid methylester (PCBM) or a mixture of PCBM and single-walled carbon nanotubes (SWCNTs) were studied by light-induced electron paramagnetic resonance spectroscopy. The results provide experimental evidence of electron transfer between PCBM and P3HT components in both fiber systems and suggest that the presence of a dispersing block-copolymer, which acts via physical adsorption onto the PCBM and SWCNT moieties, does not prevent electron transfer at the P3HT-PCBM interface. These findings suggest a research perspective towards utilization of fibers of functional nanocomposites in fiber-based organic optoelectronic and photovoltaic devices. The latter can be developed in the textile-type large area photovoltaics or individual fiber-based solar cells that will broaden energy applications from macro-power tools to micro-nanoscale power conversion devices and smart textiles.

  2. Study of a DNA Duplex by Nuclear Magnetic Resonance and Molecular Dynamics Simulations. Validation of Pulsed Dipolar Electron Paramagnetic Resonance Distance Measurements Using Triarylmethyl-Based Spin Labels.

    PubMed

    Lomzov, Alexander A; Sviridov, Eugeniy A; Shernuykov, Andrey V; Shevelev, Georgiy Yu; Pyshnyi, Dmitrii V; Bagryanskaya, Elena G

    2016-06-16

    Pulse dipole-dipole electron paramagnetic resonance (EPR) spectroscopy (double electron-electron resonance [DEER] or pulse electron-electron double resonance [PELDOR] and double quantum coherence [DQC]) allows for measurement of distances in biomolecules and can be used at low temperatures in a frozen solution. Recently, the possibility of distance measurement in a nucleic acid at a physiological temperature using pulse EPR was demonstrated. In these experiments, triarylmethyl (TAM) radicals with long memory time of the electron spin served as a spin label. In addition, the duplex was immobilized on modified silica gel particles (Nucleosil DMA); this approach enables measurement of interspin distances close to 4.5 nm. Nevertheless, the possible influence of TAM on the structure of a biopolymer under study and validity of the data obtained by DQC are debated. In this paper, a combination of molecular dynamics (MD) and nuclear magnetic resonance (NMR) methods was used for verification of interspin distances measured by the X-band DQC method. NMR is widely used for structural analysis of biomolecules under natural conditions (room temperature and an aqueous solution). The ultraviolet (UV) melting method and thermal series (1)H NMR in the range 5-95 °C revealed the presence of only the DNA duplex in solution at oligonucleotide concentrations 1 μM to 1.1 mM at temperatures below 40 °C. The duplex structures and conformation flexibility of native and TAM-labeled DNA complexes obtained by MD simulation were the same as the structure obtained by NMR refinement. Thus, we showed that distance measurements at physiological temperatures by the X-band DQC method allow researchers to obtain valid structural information on an unperturbed DNA duplex using terminal TAM spin labels. PMID:27195671

  3. Electron Paramagnetic Resonance Spectroscopic Study on Nonequilibrium Reaction Pathways in the Photolysis of Solid Nitromethane (CH3NO2) and D3-Nitromethane (CD3NO2).

    PubMed

    Tsegaw, Yetsedaw Andargie; Sander, Wolfram; Kaiser, Ralf I

    2016-03-10

    Thin films of nitromethane (CH3NO2) along with its isotopically labeled counterpart D3-nitromethane (CD3NO2) were photolyzed at discrete wavelength between 266 nm (4.7 eV) and 121 nm (10.2 eV) to explore the underlying mechanisms involved in the decomposition of model compounds of energetic materials in the condensed phase at 5 K. The chemical modifications of the ices were traced in situ via electron paramagnetic resonance, thus focusing on the detection of (hitherto elusive) reaction intermediates and products with unpaired electrons. These studies revealed the formation of two carbon-centered radicals [methyl (CH3), nitromethyl (CH2NO2)], one oxygen-centered radical [methoxy (CH3O)], two nitrogen-centered radicals [nitrogen monoxide (NO), nitrogen dioxide (NO2)], as well as atomic hydrogen (H). The decomposition products of these channels and the carbon-centered nitromethyl (CH2NO2) radical in particular represent crucial reaction intermediates leading via sequential molecular mass growth processes in the exposed nitromethane samples to complex organic molecules as predicted previously by dynamics calculations. The detection of the nitromethyl (CH2NO2) radical along with atomic hydrogen (H) demonstrated the existence of a high-energy decomposition pathway, which is closed under collisionless conditions in the gas phase. PMID:26863093

  4. The g-tensor of the flavin cofactor in (6-4) photolyase: a 360 GHz/12.8 T electron paramagnetic resonance study

    NASA Astrophysics Data System (ADS)

    Schnegg, A.; Kay, C. W. M.; Schleicher, E.; Hitomi, K.; Todo, T.; Möbius, K.; Weber, S.

    2006-05-01

    The g-tensor of the neutral radical form of the flavin adenine dinucleotide cofactor FADH• of (6-4) photolyase from Xenopus laevis has been determined by very high-magnetic-field/high-microwave-frequency electron-paramagnetic resonance (EPR) performed at 360 GHz/12.8 T. Due to the high spectral resolution the anisotropy of the g-tensor could be fully resolved in the frozen-solution continuous-wave EPR spectrum. By least square fittings of spectral simulations to experimental data, the principal values of the g-tensor have been established: gX = 2.00433(5), gY = 2.00368(5), gZ = 2.00218(7). A comparison of very high-field EPR data and proton and deuteron electron-nuclear double resonance measurements yielded precise information concerning the orientation of the g-tensor with respect to the molecular frame. This data allowed a comparison to be made between the principal values of the g-tensors of the FADH• cofactors of photolyases involved in the repair of two different DNA lesions: the cyclobutane pyrimidine dimer (CPD) and the (6-4) photoproduct. It was found that gX and gZ are similar in both enzymes, whereas the gY component is slightly larger in (6-4) photolyase. This result clearly shows the sensitivity of the g-tensor to subtle differences in the protein environment experienced by the flavin.

  5. Electron density compression and oscillating effects on laser energy absorption in overdense plasma targets.

    PubMed

    Ge, Z Y; Zhuo, H B; Yu, W; Yang, X H; Yu, T P; Li, X H; Zou, D B; Ma, Y Y; Yin, Y; Shao, F Q; Peng, X J

    2014-03-01

    An analytical model for energy absorption during the interaction of an ultrashort, ultraintense laser with an overdense plasma is proposed. Both the compression effect of the electron density profile and the oscillation of the electron plasma surface are self-consistently included, which exhibit significant influences on the laser energy absorption. Based on our model, the general scaling law of the compression effect depending on laser strength and initial density is derived, and the temporal variation of the laser absorption due to the boundary oscillating effect is presented. It is found that due to the oscillation of the electron plasma surface, the laser absorption rate will vibrate periodically at ω or 2ω frequency for the p-polarized and s-polarized laser, respectively. The effect of plasma collision on the laser absorption has also been investigated, which shows a considerable rise in absorption with increasing electron-ion collision frequency for both polarizations. PMID:24730955

  6. Electron and proton absorption calculations for a graphite/epoxy composite model. [large space structures

    NASA Technical Reports Server (NTRS)

    Long, E. R., Jr.

    1979-01-01

    The Bethe-Bloch stopping power relations for inelastic collisions were used to determine the absorption of electron and proton energy in cured neat epoxy resin and the absorption of electron energy in a graphite/epoxy composite. Absorption of electron energy due to bremsstrahlung was determined. Electron energies from 0.2 to 4.0 MeV and proton energies from 0.3 to 1.75 MeV were used. Monoenergetic electron energy absorption profiles for models of pure graphite, cured neat epoxy resin, and graphite/epoxy composites are reported. A relation is determined for depth of uniform energy absorption in a composite as a function of fiber volume fraction and initial electron energy. Monoenergetic proton energy absorption profiles are reported for the neat resin model. A relation for total proton penetration in the epoxy resin as a function of initial proton energy is determined. Electron energy absorption in the composite due to bremsstrahlung is reported. Electron and proton energy absorption profiles in cured neat epoxy resin are reported for environments approximating geosynchronous earth orbit.

  7. Electron paramagnetic resonance and fluorescence in situ hybridization-based investigations of individual doses for persons living at Metlino in the upper reaches of the Techa River.

    PubMed

    Degteva, Marina O; Anspaugh, Lynn R; Akleyev, Alexander V; Jacob, Peter; Ivanov, Denis V; Wieser, Albrecht; Vorobiova, Marina I; Shishkina, Elena A; Shved, Valentina A; Vozilova, Alexandra; Bayankin, Sergey N; Napier, Bruce A

    2005-02-01

    Waterborne releases to the Techa River from the Mayak Production Association in Russia during 1949-1956 resulted in significant doses to persons living downstream; the most contaminated village was Metlino, about 7 km from the site of release. Internal and external doses have been estimated for these residents using the Techa River Dosimetry System-2000 (TRDS-2000); the primary purpose is to support epidemiological studies of the members of the Extended Techa River Cohort. Efforts to validate the calculations of external and internal dose are considered essential. One validation study of the TRDS-2000 system has been performed by the comparison of calculated doses to quartz from bricks in old buildings at Metlino with those measured by luminescence dosimetry. Two additional methods of validation considered here are electron paramagnetic resonance (EPR) measurements of teeth and fluorescence in situ hybridization (FISH) measurements of chromosome translocations in circulating lymphocytes. For electron paramagnetic resonance, 36 measurements on 26 teeth from 16 donors from Metlino were made at the GSF-National Research Center for Environment and Health (16 measurements) and the Institute of Metal Physics (20 measurements); the correlation among measurements made at the two laboratories has been found to be 0.99. Background measurements were also made on 218 teeth (63 molars, 128 premolars, and 27 incisors). Fluorescence in situ hybridization measurements were made for 31 residents of Metlino. These measurements were handicapped by the analysis of a limited number of cells; for several individuals no stable translocations were observed. Fluorescence in situ hybridization measurements were also made for 39 individuals believed to be unexposed. The EPR- and FISH-based estimates agreed well for permanent residents of Metlino: 0.67 +/- 0.21 Gy and 0.48 +/- 0.18 Gy (mean +/- standard error of the mean), respectively. Results of the two experimental methods also agreed well

  8. Electron Paramagnetic Resonance and Fluorescence In Situ Hybridization-Based Investigations of Individual Doses for Persons Living at Metlino in the Upper Reaches of the Techa River

    SciTech Connect

    Degteva, M. O.; Anspaugh, L. R.; Akleyev, A V.; Jacob, Peter; Ivanov, Denis V.; Wieser, Albrecht; Vorobiova, M I.; Shishkina, Elena A.; Shved, Valentina A.; Vozilova, Alexandra; Bayankin, Sergey N.; Napier, Bruce A.

    2005-02-01

    Waterborne releases to the Techa River from the Mayak Production Association in Russia during 1949-1956 resulted in significant doses to persons living downstream; the most contaminated village was Metlino, about 7 km from the site of release. Internal and external doses have been estimated for these residents using the Techa River Dosimetry System-2000 (TRDS-2000); the primary purpose is to support epidemiological studies of the members of the Extended Techa River Cohort. Efforts to validate the calculations of external and internal dose are considered essential. One validation study of the TRDS-2000 system has been performed by the comparison of calculated doses to quartz from bricks in old buildings at Metlino with those measured by luminescence dosimetry. Two additional methods of validation considered here are electron paramagnetic resonance (EPR) measurements of teeth and fluorescence in situ hybridization (FISH) measurements of chromosome translocations in circulating lymphocytes. For electron paramagnetic resonance, 36 measurements on 26 teeth from 16 donors from Metlino were made at the GSF-National Research Center for Environment and Health (16 measurements) and the Institute of Metal Physics (20 measurements); the correlation among measurements made at the two laboratories has been found to be 0.99. Background measurements were also made on 218 teeth (63 molars, 128 premolars, and 27 incisors). Fluorescence in situ hybridization measurements were made for 31 residents of Metlino. These measurements were handicapped by the analysis of a limited number of cells; for several individuals no stable translocations were observed. Fluorescence in situ hybridization measurements were also made for 39 individuals believed to be unexposed. The EPR- and FISH-based estimates agreed well for permanent residents of Metlino: 0.67 +/- 0.21 Gy and 0.48 +/- 0.18 Gy (mean +/- standard error of the mean), respectively. Results of the two experimental methods also agreed well

  9. Inter-spin distance determination using L-band (1-2 GHz) non-adiabatic rapid sweep electron paramagnetic resonance (NARS EPR)

    PubMed Central

    Kittell, Aaron W.; Hustedt, Eric J.; Hyde, James S.

    2014-01-01

    Site-directed spin-labeling electron paramagnetic resonance (SDSL EPR) provides insight into the local structure and motion of a spin probe strategically attached to a molecule. When a second spin is introduced to the system, macromolecular information can be obtained through measurement of inter-spin distances either by continuous wave (CW) or pulsed electron double resonance (ELDOR) techniques. If both methodologies are considered, inter-spin distances of 8 to 80 Å can be experimentally determined. However, there exists a region at the upper limit of the conventional X-band (9.5 GHz) CW technique and the lower limit of the four-pulse double electron-electron resonance (DEER) experiment where neither method is particularly reliable. The work presented here utilizes L-band (1.9 GHz) in combination with non-adiabatic rapid sweep (NARS) EPR to address this opportunity by increasing the upper limit of the CW technique. Because L-band linewidths are three to seven times narrower than those at X-band, dipolar broadenings that are small relative to the X-band inhomogeneous linewidth become observable, but the signal loss due to the frequency dependence of the Boltzmann factor, has made L-band especially challenging. NARS has been shown to increase sensitivity by a factor of five, and overcomes much of this loss, making L-band distance determination more feasible [1]. Two different systems are presented and distances of 18–30 Å have been experimentally determined at physiologically relevant temperatures. Measurements are in excellent agreement with a helical model and values determined by DEER. PMID:22750251

  10. Higher-order Zeeman and spin terms in the electron paramagnetic resonance spin Hamiltonian; their description in irreducible form using Cartesian, tesseral spherical tensor and Stevens' operator expressions.

    PubMed

    McGavin, Dennis G; Tennant, W Craighead

    2009-06-17

    In setting up a spin Hamiltonian (SH) to study high-spin Zeeman and high-spin nuclear and/or electronic interactions in electron paramagnetic resonance (EPR) experiments, it is argued that a maximally reduced SH (MRSH) framed in tesseral combinations of spherical tensor operators is necessary. Then, the SH contains only those terms that are necessary and sufficient to describe the particular spin system. The paper proceeds then to obtain interrelationships between the parameters of the MRSH and those of alternative SHs expressed in Cartesian tensor and Stevens operator-equivalent forms. The examples taken, initially, are those of Cartesian and Stevens' expressions for high-spin Zeeman terms of dimension BS(3) and BS(5). Starting from the well-known decomposition of the general Cartesian tensor of second rank to three irreducible tensors of ranks 0, 1 and 2, the decomposition of Cartesian tensors of ranks 4 and 6 are treated similarly. Next, following a generalization of the tesseral spherical tensor equations, the interrelationships amongst the parameters of the three kinds of expressions, as derived from equivalent SHs, are determined and detailed tables, including all redundancy equations, set out. In each of these cases the lowest symmetry, [Formula: see text] Laue class, is assumed and then examples of relationships for specific higher symmetries derived therefrom. The validity of a spin Hamiltonian containing mixtures of terms from the three expressions is considered in some detail for several specific symmetries, including again the lowest symmetry. Finally, we address the application of some of the relationships derived here to seldom-observed low-symmetry effects in EPR spectra, when high-spin electronic and nuclear interactions are present. PMID:21693947

  11. Synthesis of water-soluble 2,2'-diphenyl-1-picrylhydrazyl nanoparticles: a new standard for electron paramagnetic resonance spectroscopy.

    PubMed

    Chen, Ou; Zhuang, Jiaqi; Guzzetta, Fabrizio; Lynch, Jared; Angerhofer, Alexander; Cao, Y Charles

    2009-09-01

    This communication reports a size-controlled synthesis of water-soluble 2,2'-diphenyl-1-picrylhydrazyl (DPPH) nanoparticles (NPs). These nanoparticles exhibit size-dependent absorption spectra and fast spin exchange-narrowed single-line EPR spectra. The linewidths of the EPR spectra of these water-soluble nanoparticles are approximately 1.5-1.8 G, which are equal or close to the narrowest line width (1.5 G) of the common DPPH standard in the form of water-insoluble microcrystals. In addition, these NPs are stable over a wide pH range of 3.0 to 10.0. These properties make these water-soluble DPPH NPs suitable for use as a new type of EPR standard, which is important for fundamental research and practical applications in fields such as the food industry and the life sciences. Furthermore, the DPPH NPs can potentially be used as a spin probe in biomedical studies. PMID:19673526

  12. Investigation of Cu-doped Li2B4O7 single crystals by electron paramagnetic resonance and time-resolved optical spectroscopy

    NASA Astrophysics Data System (ADS)

    Corradi, G.; Nagirnyi, V.; Kotlov, A.; Watterich, A.; Kirm, M.; Polgár, K.; Hofstaetter, A.; Meyer, M.

    2008-01-01

    A low-temperature study of the thermoluminescent dosimeter material, lithium tetraborate (Li2B4O7) doped by Cu, has been carried out by the methods of electron paramagnetic resonance (EPR) and time-resolved polarization spectroscopy using 4-20 eV synchrotron radiation and 1 µs Xe flash lamp pulses in the region 3-6 eV. The observed EPR spectra of an unpaired hole with strong d-character and characteristic hyperfine splittings can be ascribed to Cu2+ substituted at a Li lattice site and displaced due to relaxation. The results on the Cu+-related luminescence strongly support the conclusion about a low-symmetry position of copper impurity ions in the lithium tetraborate lattice. The temperature dependence of the decay kinetics of the Cu+-related 3.35 eV emission indicates a triplet nature for the relaxed excited state of the Cu+ centres. An off-centre position of the Cu+ ion in the relaxed excited state is suggested.

  13. Temperature-Dependent Electron Paramagnetic Resonance Studies of Docosahexaenoic Acid and Gamma Linolenic Acid Effects on Phospholipid Membranes With and Without Cholesterol

    NASA Astrophysics Data System (ADS)

    Yonar, D.; Horasanb, N.; Sünnetçioğlu, M. Maral

    2016-07-01

    Free docosahexaenoic acid (DHAn-3) and gamma linolenic acid (GLAn-6) effects on dimyristoyl phosphatidylcholine (DMPC) membranes were studied as a function of temperature by electron paramagnetic resonance (EPR) spectroscopy. 5- and 16-doxyl stearic acid (5-, 16-DS) spin labels were utilized to obtain information from the interfacial and alkyl chain region, respectively. In the studied temperature range, the presence of DHAn-3 or GLAn-6 caused decreases in maximum hyperfi ne splitting values and correlation times of DMPC membranes. Both in the interfacial region and depths of membrane, changes were more pronounced for DHAn-3 in pure DMPC. In the presence of cholesterol (CH), DHAn-3 and GLAn-6 effects were similar and more pronounced in the depths of the membrane. The changes in the structure and dynamics of samples were obtained from simulations of spectra, which indicated some changes in the number of spectral components by incorporation of DHAn-3 and GLAn-6. In the interfacial region and below the main phase transition temperature of DMPC, there was an increase in heterogeneity. For temperatures above the phase transition, a more homogeneous environment for spin label was obtained in the presence of fatty acids.

  14. Using nitroxide spin labels. How to obtain T1e from continuous wave electron paramagnetic resonance spectra at all rotational rates.

    PubMed Central

    Haas, D A; Mailer, C; Robinson, B H

    1993-01-01

    Historically, the continuous wave electron paramagnetic resonance (CW-EPR) progressive saturation method has been used to obtain information on the spin-lattice relaxation time (T1e) and those processes, such as motion and spin exchange, that occur on a competitive timescale. For example, qualitative information on local dynamics and solvent accessibility of proteins and nucleic acids has been obtained by this method. However, making quantitative estimates of T1e from CW-EPR spectra have been frustrated by a lack of understanding of the role of T1e (and T2e) in the slow-motion regime. Theoretical simulation of the CW-EPR lineshapes in the slow-motion region under increasing power levels has been used in this work to test whether the saturation technique can produce quantitative estimates of the spin-lattice relaxation rates. A method is presented by which the correct T1e may be extracted from an analysis of the power-saturation rollover curve, regardless of the amount of inhomogeneous broadening or the rates of molecular reorientation. The range of motional correlation times from 10 to 200 ns should be optimal for extracting quantitative estimates of T1e values in spin-labeled biomolecules. The progressive-saturation rollover curve method should find wide application in those areas of biophysics where information on molecular interactions and solvent exposure as well as molecular reorientation rates are desired. PMID:8386009

  15. Cytotoxic evaluation of 3-aminopyridine-2-carboxaldehyde thiosemicarbazone in peripheral blood lymphocytes of patients with refractory solid tumors using electron paramagnetic resonance

    PubMed Central

    KOLESAR, JILL M.; SACHIDANANDAM, KAMAKSHI; SCHELMAN, WILLIAM R.; EICKHOFF, JENS; HOLEN, KYLE D.; TRAYNOR, ANNE M.; ALBERTI, DONA B.; THOMAS, JAMES P.; CHITAMBAR, CHRISTOPHER R.; WILDING, GEORGE; ANTHOLINE, WILLIAM E.

    2011-01-01

    3-Aminopyridine-2-carboxaldehyde thiosemicarbazone (3-AP) is a metal chelator that potently inhibits the enzyme ribonucleotide reductase (RR), which plays a key role in cell division and tumor progression. A subunit of RR has a non-heme iron and a tyrosine-free radical, which are required for the enzymatic reduction of ribonucleotides to deoxyribonucleotides. The objective of the present study was to determine whether 3-AP affects its targeted action by measuring electron paramagnetic resonance (EPR) signals formed either directly or indirectly from low molecular weight ferric-3-AP chelates. Peripheral blood lymphocytes were collected from patients with refractory solid tumors at baseline and at 2, 4.5 and 22 h after 3-AP administration. Using EPR spectra, our study identified signals from high-spin Fe-transferrin, high-spin heme and low-spin iron or copper ions. An increase in the Fe-transferrin signal was observed, suggesting blockage of Fe uptake. It is hypothesized that formation of reactive oxygen species by FeT2 or CuT damages the transferrin or the transferrin receptor. An increase in the heme signal was also observed, which was a probable source of cytochrome c release from the mitochondria and potential apoptosis. In addition, increased levels of Fe and Cu were identified. These results, which were consistent with our previous study validating 3-AP-mediated signals by EPR, provide valuable insights into the in vivo mechanism of action of 3-AP. PMID:21373381

  16. Determination of the metallic/semiconducting ratio in bulk single-wall carbon nanotube samples by cobalt porphyrin probe electron paramagnetic resonance spectroscopy.

    PubMed

    Cambré, Sofie; Wenseleers, Wim; Goovaerts, Etienne; Resasco, Daniel E

    2010-11-23

    A simple and quantitative, self-calibrating spectroscopic technique for the determination of the ratio of metallic to semiconducting single-wall carbon nanotubes (SWCNTs) in a bulk sample is presented. The technique is based on the measurement of the electron paramagnetic resonance (EPR) spectrum of the SWCNT sample to which cobalt(II)octaethylporphyrin (CoOEP) probe molecules have been added. This yields signals from both CoOEP molecules on metallic and on semiconducting tubes, which are easily distinguished and accurately characterized in this work. By applying this technique to a variety of SWCNT samples produced by different synthesis methods, it is shown that these signals for metallic and semiconducting tubes are independent of other factors such as tube length, defect density, and diameter, allowing the intensities of both signals for arbitrary samples to be retrieved by a straightforward least-squares regression. The technique is self-calibrating in that the EPR intensity can be directly related to the number of spins (number of CoOEP probe molecules), and as the adsorption of the CoOEP molecules is itself found to be unbiased toward metallic or semiconducting tubes, the measured intensities can be directly related to the mass percentage of metallic and semiconducting tubes in the bulk SWCNT sample. With the use of this method it was found that for some samples the metallic/semiconducting ratios strongly differed from the usual 1:2 ratio. PMID:20958073

  17. Electron paramagnetic resonance study of hydrogen peroxide/ascorbic acid ratio as initiator redox pair in the inulin-gallic acid molecular grafting reaction.

    PubMed

    Arizmendi-Cotero, Daniel; Gómez-Espinosa, Rosa María; Dublán García, Octavio; Gómez-Vidales, Virginia; Dominguez-Lopez, Aurelio

    2016-01-20

    Gallic acid (GA) was grafted onto inulin using the free radicals method, generated by the hydrogen peroxide/ascorbic acid (H2O2/AA) redox pair. Molar ratios of H2O2/AA at 9, 20, 39 and 49 were evaluated by Electron Paramagnetic Resonance in order to find the effect of the oxidation of the inulin and the efficiency in the inulin-gallic acid grafting (IGA). The highest concentration of the inulin macro-radical was obtained with H2O2/AA molar ratios of 20 and 49 with the removal of a hydrogen atom from a methyl group of the inulin fructose monomers. The highest grafting ratio (30.4 mg GA eq/g IGA) was obtained at 9 M of H2O2/AA. UV-Vis, FT-IR-ATR and XDR results confirmed a successful IGA grafting. The efficiency of the grafting reaction depends on the concentration of the macro-radical, it depends on the molar ratio of H2O2/AA, being affected by simultaneous reactions between components of the mixture (H2O2, AA, inulin, GA and eventually atmospheric oxygen) as well. PMID:26572365

  18. 13C Nuclear Magnetic Resonance and Electron Paramagnetic Spectroscopic Comparison of Hydrophobic Acid, Transphilic Acid, and Reverse Osmosis May 2012 Isolates of Organic Matter from the Suwannee River

    PubMed Central

    Nwosu, Ugwumsinachi G.; Cook, Robert L.

    2015-01-01

    Abstract Dissolved organic matter (DOM) is found in most natural waters at concentrations low enough to make DOM isolation methodologies critical to full analytical characterization and preservation. During the last few decades, two major protocols have been developed for the extraction of DOM isolates from natural waters. These methods utilize XAD resins and reverse osmosis (RO). In this work, the hydrophobic acid (May 2012 HPOA) and transphilic acid (May 2012 TPIA) isolates from XAD-8 and XAD-4 resins, respectively, were compared with the RO (May 2012 RO) natural organic matter isolate of the Suwannee River water using 13C nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies. 13C NMR analysis showed that the May 2012 RO isolate could be viewed as a hybrid of the more hydrophobic May 2012 HPOA isolate and more hydrophilic May 2012 TPIA isolate. The May 2012 HPOA isolate is shown to be higher in alkyl and aromatic moieties, while the May 2012 TPIA isolate is higher in O-alkyl moieties. EPR analysis revealed that the May 2012 TPIA and, in particular, May 2012 HPOA isolates had higher radical concentrations than the May 2012 RO isolate. It is postulated that some of the radical concentrations came from the use of base during the isolation procedures, especially in the XAD method. PMID:25565761

  19. Doubly resonant Raman electron paramagnetic transitions of Cr{sup 3+} in ruby (Al{sub 2}O{sub 3}:Cr{sup 3+}).

    SciTech Connect

    Lu, X.; Venugopalan, S.; Kim, H.; Grimsditch, M.; Rodriguez, S.; Ramdas, A. K.; Materials Science Division; Purdue Univ.; State Univ. of New York at Binghamton; Sogang Univ.

    2009-06-01

    We report the Raman electron paramagnetic resonance (EPR) of Cr{sup 3+} in ruby (Al{sub 2}O{sub 3}:Cr{sup 3+}) in the {sup 4}A{sub 2} (ground) and E{sup -} (excited) states of its well-known R{sub 1} emission line. Using tunable dye laser excitation within the range of the Zeeman components of R{sub 1}, we observe highly selective doubly resonant enhancements of the Raman EPR lines. The double resonances confirm the assignments of the Raman EPR lines, and they underscore the simultaneous occurrence of both 'in resonance' and 'out resonance' as visualized in the Kramers-Heisenberg quantum-mechanical picture of inelastic light scattering. The g factors of the {sup 4}A{sub 2} and E{sup -} states are consistent with the observed magnetic field dependence of the Raman EPR shifts. Through the interplay of Raman effect and the sharp Zeeman components of R{sub 1}, the results provide clear insights into the underlying microscopic mechanism of these resonant Raman EPR spectra of ruby.

  20. Analysis of gamma-irradiated melon, pumpkin, and sunflower seeds by electron paramagnetic resonance spectroscopy and gas chromatography-mass spectrometry.

    PubMed

    Sin, Della W M; Wong, Yiu Chung; Yao, Wai Yin

    2006-09-20

    Seeds of melon (Citrullus lanatus var. sp.), pumpkin (Cucurbita moschata), and sunflower (Heliantus annus) were gamma-irradiated at 1, 3, 5, and 10 kGy and analyzed by electron paramagnetic resonance (EPR) and gas chromatography-mass spectrometry (GC-MS) according to EN1787:2000 and EN1785:2003, respectively. Distinguishable triplet signals due to the presence of induced cellulose radicals were found at 2.0010-2.0047 g in the EPR spectra. The gamma-irradiated radiolytic markers of 2-dodecylcyclobutanone (2-DCB) and 2-tetradecylcyclobutanone (2-TCB) were identified in all irradiated seed samples. Both the free radicals and the alkylcyclobutanones were found to increase with irradiation dose. In general, linear relationships between the amount of radicals and irradiation dosage could be established. Studies at an ambient temperature (20-25 degrees C) in a humidity-controlled environment showed a complete disappearance of the cellulosic peaks for irradiated samples upon 60 days of storage. Such instability behavior was considered to render the usefulness of using EPR alone in the determination of irradiated seed samples. On the other hand, 2-DCB and 2-TCB were also found to decompose rapidly (>85% loss after 120 days of storage), but the radiolytic markers remained quantifiable after 120 days of postirradiation storage. These results suggest that GC-MS is a versatile and complimentary technique for the confirmation of irradiation treatment to seeds. PMID:16968077

  1. The “Beta-Clasp” model of apolipoprotein A-I - a lipid-free solution structure determined by electron paramagnetic resonance spectroscopy

    PubMed Central

    Lagerstedt, Jens O.; Budamagunta, Madhu S.; Liu, Grace S.; DeValle, Nicole C.; Voss, John C.; Oda, Michael N.

    2012-01-01

    Apolipoprotein A-I (apoA-I) is the major protein component of high density lipoproteins (HDL) and plays a central role in cholesterol metabolism. The lipid-free / lipid-poor form of apoA-I is the preferred substrate for the ATP-binding cassette transporter A1 (ABCA1). The interaction of apoA-I with ABCA1 leads to the formation of cholesterol laden high density lipoprotein (HDL) particles, a key step in reverse cholesterol transport and the maintenance of cholesterol homeostasis. Knowledge of the structure of lipid-free apoA-I is essential to understanding its critical interaction with ABCA1 and the molecular mechanisms underlying HDL biogenesis. We therefore examined the structure of lipid-free apoA-I by electron paramagnetic resonance spectroscopy (EPR). Through site directed spin label EPR, we mapped the secondary structure of apoA-I and identified sites of spin coupling as residues 26, 44, 64, 167, 217 and 226. We capitalize on the fact that lipid-free apoA-I self-associates in an anti-parallel manner in solution. We employed these sites of spin coupling to define the central plane in the dimeric apoA-I complex. Applying both the constraints of dipolar coupling with the EPR-derived pattern of solvent accessibility, we assembled the secondary structure into a tertiary context, providing a solution structure for lipid-free apoA-I. PMID:22245143

  2. Tissue oxygen is reduced in white matter of spontaneously hypertensive-stroke prone rats: a longitudinal study with electron paramagnetic resonance.

    PubMed

    Weaver, John; Jalal, Fakhreya Y; Yang, Yi; Thompson, Jeffrey; Rosenberg, Gary A; Liu, Ke J

    2014-05-01

    Small vessel disease is associated with white-matter (WM) magnetic resonance imaging (MRI) hyperintensities (WMHs) in patients with vascular cognitive impairment (VCI) and subsequent damage to the WM. Although WM is vulnerable to hypoxic-ischemic injury and O₂ is critical in brain physiology, tissue O₂ level in the WM has not been measured and explored in vivo. We hypothesized that spontaneously hypertensive stroke-prone rat (SHR/SP) fed a Japanese permissive diet (JPD) and subjected to unilateral carotid artery occlusion (UCAO), a model to study VCI, would lead to reduced tissue oxygen (pO₂) in the deep WM. We tested this hypothesis by monitoring WM tissue pO₂ using in vivo electron paramagnetic resonance (EPR) oximetry in SHR/SP rats over weeks before and after JPD/UCAO. The SHR/SP rats experienced an increase in WM pO₂ from 9 to 12 weeks with a maximal 32% increase at week 12, followed by a dramatic decrease in WM pO₂ to near hypoxic conditions during weeks 13 to 16 after JPD/UCAO. The decreased WM pO₂ was accompanied with WM damage and hemorrhages surrounding microvessels. Our findings suggest that changes in WM pO₂ may contribute to WM damage in SHR/SP rat model, and that EPR oximetry can monitor brain pO₂ in the WM of small animals. PMID:24549186

  3. New opportunities of the application of natural herb and spice extracts in plant oils: application of electron paramagnetic resonance in examining the oxidative stability.

    PubMed

    Kozłowska, Mariola; Szterk, Arkadiusz; Zawada, Katarzyna; Ząbkowski, Tomasz

    2012-09-01

    The aim of this study was to establish the applicability of natural water-ethanol extracts of herbs and spices in increasing the oxidative stability of plant oils and in the production of novel food. Different concentrations (0, 100, 300, 500, and 700 ppm) of spice extracts and butylated hydroxyanisole (BHA) (100 ppm) were added to the studied oils. The antioxidant activity of spice extracts was determined with electron paramagnetic resonance (EPR) spectroscopy using 2,2-diphenyl-1-picrylhydrazyl (DPPH) radical assay. The study showed that the extracts significantly increased the oxidative stability of the examined oils when compared to one of the strongest synthetic antioxidants--BHA. The applied simple production technology and addition of herb and spice extracts to plant oils enabled enhancement of their oxidative stability. The extracts are an alternative to the oils aromatized with an addition of fresh herbs, spices, and vegetables because it did not generate additional flavors thus enabling the maintenance of the characteristic ones. Moreover, it will increase the intake of natural substances in human diet, which are known to possess anticarcinogenic properties. PMID:22900972

  4. Uptake of Cu{sup 2+} by the calcium carbonates vaterite and calcite as studied by continuous wave (CW) and pulse electron paramagnetic resonance

    SciTech Connect

    Schosseler, P.M.; Schweiger, A.; Wehrli, B.

    1999-07-01

    The investigation of the Cu{sup 2+} uptake by the calcium carbonate minerals vaterite and calcite with continuous wave and pulse electron paramagnetic resonance (EPR) yields information on a molecular scale about the relevant complexation reactions at the mineral-water interface. The structural assignment is based on changes in the coordination geometry of the copper complexes. Magnetic interactions of the unpaired Cu{sup 2+} electron with nuclei of {sup 13}C-labeled carbonate ligands and protons from water or hydroxyl ligands in the first and second coordination spheres of the cation are detected by pulse EPR techniques. Results show that the Cu{sup 2+} ions are rapidly dehydrated upon adsorption on the mineral surface. The strong surface binding is due to monodentate coordination to three or four carbonate surface ions, comparable to chelate complexation in solution. The formation of square-planar or square-pyramidal copper complexes at exposed surface sites like kinks and steps yields a convincing explanation for the inhibition of calcium carbonate growth and dissolution. Upon recrystallization the Cu{sup 2+} ions are integrated into the calcite lattice where they exhibit a dynamic Jahn-Teller effect. The resulting local lattice distortions are expected to destabilize the Cu{sub x}-Ca{sub (1{minus}x)}CO{sub 3}(s) solid solution. Results support the concept of a dynamic calcium carbonate surface, covered by a thin, structured surface layer. The detailed structural information obtained for Cu{sup 2+} provides a better understanding of the interaction of other metal ions with calcium carbonate minerals.

  5. Optical absorption properties of electron bubbles and experiments on monitoring individual electron bubbles in liquid helium

    NASA Astrophysics Data System (ADS)

    Guo, Wei

    When a free electron is injected into liquid helium, it forms a microscopic bubble essentially free of helium atoms, which is referred to as an electron bubble. It represents a fine example of a quantum-mechanical particle confined in a potential well. In this dissertation, we describe our studies on bubble properties, especially the optical absorption properties of ground state electron bubbles and experiments on imaging individual electron bubbles in liquid helium. We studied the effect of zero-point and thermal fluctuations on the shape of ground state electron bubbles in liquid helium. The results are used to determine the line shape for the 1S to 1P optical transition. The calculated line shape is in very good agreement with the experimental measurements of Grimes and Adams. For 1S to 2P transition, the obtained transition line width agrees well with the measured data of Zipfel over a range of pressure up to 15 bars. Fluctuations in the bubble shape also make other "unallowed" transitions possible. The transition cross-sections from the 1S state to the 1D and 2D states are calculated with magnitude approximately two orders smaller than that of the 1S to 1P and 2P transitions. In our electron bubble imaging experiments, a planar ultrasonic transducer was used to generate strong sound wave pulse in liquid helium. The sound pulse passed through the liquid so as to produce a transient negative pressure over a large volume (˜ 1 cm3). An electron bubble that was passed by the sound pulse exploded for a fraction of a microsecond and grew to have a radius of around 10 microns. While the bubble had this large size it was illuminated with a flash lamp and its position was recorded. In this way, we can determine its position. Through the application of a series of sound pulses, we can then take images along the track of individual electrons. The motion of individual electron bubbles has been successfully monitored. Interesting bubble tracks that may relate to electrons

  6. Perpendicular electron heating by absorption of auroral kilometric radiation

    NASA Technical Reports Server (NTRS)

    Morgan, D. D.; Menietti, J. D.; Winglee, R. M.; Wong, H. K.

    1994-01-01

    We investigate the possibility of perpendicular heating of electrons and the generation of '90 deg -electron conics' by particle diffusion in velocity space due to wave-particle interaction with intense auroral kilometric radiation. This interaction is made possible by the downward shift in the R-X cutoff below the electron cyclotron frequency that occurs in the presence of warm plasma. We stimulate this condition and solve the diffusion equation using a finite difference algorithm. The results show strong perpendicular electron heating and indicate that the main characteristics of an electron conic distribution can be reproduced under these conditions.

  7. Experimental determination of the radial dose distribution in high gradient regions around {sup 192}Ir wires: Comparison of electron paramagnetic resonance imaging, films, and Monte Carlo simulations

    SciTech Connect

    Kolbun, N.; Leveque, Ph.; Abboud, F.; Bol, A.; Vynckier, S.; Gallez, B.

    2010-10-15

    Purpose: The experimental determination of doses at proximal distances from radioactive sources is difficult because of the steepness of the dose gradient. The goal of this study was to determine the relative radial dose distribution for a low dose rate {sup 192}Ir wire source using electron paramagnetic resonance imaging (EPRI) and to compare the results to those obtained using Gafchromic EBT film dosimetry and Monte Carlo (MC) simulations. Methods: Lithium formate and ammonium formate were chosen as the EPR dosimetric materials and were used to form cylindrical phantoms. The dose distribution of the stable radiation-induced free radicals in the lithium formate and ammonium formate phantoms was assessed by EPRI. EBT films were also inserted inside in ammonium formate phantoms for comparison. MC simulation was performed using the MCNP4C2 software code. Results: The radical signal in irradiated ammonium formate is contained in a single narrow EPR line, with an EPR peak-to-peak linewidth narrower than that of lithium formate ({approx}0.64 and 1.4 mT, respectively). The spatial resolution of EPR images was enhanced by a factor of 2.3 using ammonium formate compared to lithium formate because its linewidth is about 0.75 mT narrower than that of lithium formate. The EPRI results were consistent to within 1% with those of Gafchromic EBT films and MC simulations at distances from 1.0 to 2.9 mm. The radial dose values obtained by EPRI were about 4% lower at distances from 2.9 to 4.0 mm than those determined by MC simulation and EBT film dosimetry. Conclusions: Ammonium formate is a suitable material under certain conditions for use in brachytherapy dosimetry using EPRI. In this study, the authors demonstrated that the EPRI technique allows the estimation of the relative radial dose distribution at short distances for a {sup 192}Ir wire source.

  8. Brain redox imaging in the pentylenetetrazole (PTZ)-induced kindling model of epilepsy by using in vivo electron paramagnetic resonance and a nitroxide imaging probe.

    PubMed

    Emoto, Miho C; Yamato, Mayumi; Sato-Akaba, Hideo; Yamada, Ken-ichi; Fujii, Hirotada G

    2015-11-01

    Much evidence supports the idea that oxidative stress is involved in the pathogenesis of epilepsy, and therapeutic interventions with antioxidants are expected as adjunct antiepileptic therapy. The aims of this study were to non-invasively obtain spatially resolved redox data from control and pentylenetetrazole (PTZ)-induced kindled mouse brains by electron paramagnetic resonance (EPR) imaging and to visualize the brain regions that are sensitive to oxidative damage. After infusion of the redox-sensitive imaging probe 3-methoxycarbonyl-2,2,5,5-tetramethyl-piperidine-1-oxyl (MCP), a series of EPR images of PTZ-induced mouse heads were measured. Based on the pharmacokinetics of the reduction reaction of MCP in the mouse heads, the pixel-based rate constant of its reduction reaction was calculated as an index of redox status in vivo and mapped as a redox map. The obtained redox map showed heterogeneity in the redox status in PTZ-induced mouse brains compared with control. The co-registered image of the redox map and magnetic resonance imaging (MRI) for both control and PTZ-induced mice showed a clear change in the redox status around the hippocampus after PTZ. To examine the role of antioxidants on the brain redox status, the levels of antioxidants were measured in brain tissues of control and PTZ-induced mice. Significantly lower concentrations of glutathione in the hippocampus of PTZ-kindled mice were detected compared with control. From the results of both EPR imaging and the biochemical assay, the hippocampus was found to be susceptible to oxidative damage in the PTZ-induced animal model of epilepsy. PMID:26453762

  9. Analytical description of spin-Rabi oscillation controlled electronic transitions rates between weakly coupled pairs of paramagnetic states with S=(1)/(2)

    NASA Astrophysics Data System (ADS)

    Glenn, R.; Baker, W. J.; Boehme, C.; Raikh, M. E.

    2013-04-01

    We report on the theoretical and experimental study of spin-dependent electronic transition rates which are controlled by a radiation-induced spin-Rabi oscillation of weakly spin-exchange and spin-dipolar coupled paramagnetic states (S=(1)/(2)). The oscillation components [the Fourier content, F(s)] of the net transition rates within spin-pair ensembles are derived for randomly distributed spin resonances, with an account of a possible correlation between the two distributions corresponding to individual pair partners. Our study shows that when electrically detected Rabi spectroscopy is conducted under an increasing driving field B1, the Rabi spectrum, F(s), evolves from a single peak at s=ΩR, where ΩR=γB1 is the Rabi frequency (γ is the gyromagnetic ratio), to three peaks at s=ΩR, s=2ΩR, and low s≪ΩR. The crossover between the two regimes takes place when ΩR exceeds the expectation value δ0 of the difference in the Zeeman energies within the pairs, which corresponds to the broadening of the magnetic resonance by disorder caused by a hyperfine field or distributions of Landé g factors. We capture this crossover by analytically calculating the shapes of all three peaks at an arbitrary relation between ΩR and δ0. When the peaks are well developed their widths are Δs˜δ02/ΩR. We find a good quantitative agreement between the theory and experiment.

  10. Copper doping of ZnO crystals by transmutation of {sup 64}Zn to {sup 65}Cu: An electron paramagnetic resonance and gamma spectroscopy study

    SciTech Connect

    Recker, M. C.; McClory, J. W. Holston, M. S.; Golden, E. M.; Giles, N. C.; Halliburton, L. E.

    2014-06-28

    Transmutation of {sup 64}Zn to {sup 65}Cu has been observed in a ZnO crystal irradiated with neutrons. The crystal was characterized with electron paramagnetic resonance (EPR) before and after the irradiation and with gamma spectroscopy after the irradiation. Major features in the gamma spectrum of the neutron-irradiated crystal included the primary 1115.5 keV gamma ray from the {sup 65}Zn decay and the positron annihilation peak at 511 keV. Their presence confirmed the successful transmutation of {sup 64}Zn nuclei to {sup 65}Cu. Additional direct evidence for transmutation was obtained from the EPR of Cu{sup 2+} ions (where {sup 63}Cu and {sup 65}Cu hyperfine lines are easily resolved). A spectrum from isolated Cu{sup 2+} (3d{sup 9}) ions acquired after the neutron irradiation showed only hyperfine lines from {sup 65}Cu nuclei. The absence of {sup 63}Cu lines in this Cu{sup 2+} spectrum left no doubt that the observed {sup 65}Cu signals were due to transmuted {sup 65}Cu nuclei created as a result of the neutron irradiation. Small concentrations of copper, in the form of Cu{sup +}-H complexes, were inadvertently present in our as-grown ZnO crystal. These Cu{sup +}-H complexes are not affected by the neutron irradiation, but they dissociate when a crystal is heated to 900 °C. This behavior allowed EPR to distinguish between the copper initially in the crystal and the copper subsequently produced by the neutron irradiation. In addition to transmutation, a second major effect of the neutron irradiation was the formation of zinc and oxygen vacancies by displacement. These vacancies were observed with EPR.

  11. An electron paramagnetic resonance spectroscopy investigation of the retention mechanisms of Mn and Cu in the nanopore channels of three zeolite minerals

    SciTech Connect

    Ferreira, Daniel R.; Schulthess, Cristian P.; Amonette, James E.; Walter, Eric D.

    2012-12-01

    The adsorption mechanisms of divalent cations in zeolite nanopore channels can vary as a function of their pore dimensions. The nanopore inner-sphere enhancement (NISE) theory predicts that ions may dehydrate inside small nanopore channels in order to adsorb more closely to the mineral surface if the nanopore channel is sufficiently small. The results of an electron paramagnetic resonance (EPR) spectroscopy study of Mn and Cu adsorption on the zeolite minerals zeolite Y (large nanopores), ZSM-5 (intermediate nanopores), and mordenite (small nanopores) are presented. The Cu and Mn cations both adsorbed via an outer-sphere mechanism on zeolite Y based on the similarity between the adsorbed spectra and the aqueous spectra. Conversely, Mn and Cu adsorbed via an inner-sphere mechanism on mordenite based on spectrum asymmetry and peak broadening of the adsorbed spectra. However, Mn adsorbed via an outer-sphere mechanism on ZSM-5, whereas Cu adsorbed on ZSM-5 shows a high degree of surface interaction that indicates that it is adsorbed closer to the mineral surface. Evidence of dehydration and immobility was more readily evident in the spectrum of mordenite than ZSM-5, indicating that Cu was not as close to the surface on ZSM-5 as it was when adsorbed on mordenite. Divalent Mn cations are strongly hydrated and are held strongly only in zeolites with small nanopore channels. Divalent Cu cations are also strongly hydrated, but can dehydrate more easily, presumably due to the Jahn-Teller effect, and are held strongly in zeolites with medium sized nanopore channels or smaller.

  12. Hyperbolic-cosine waveguide tapers and oversize rectangular waveguide for reduced broadband insertion loss in W-band electron paramagnetic resonance spectroscopy

    PubMed Central

    Mett, R. R.; Sidabras, J. W.; Anderson, J. R.; Hyde, J. S.

    2011-01-01

    The two-way insertion loss of a 1 m length of waveguide was reduced by nearly 5 dB over a 4% bandwidth at W-band (94 GHz) for an electron paramagnetic resonance (EPR) spectrometer relative to WR10 waveguide. The waveguide has an oversize section of commercially available rectangular WR28 and a novel pair of tapers that vary in cross section with axial position according to a hyperbolic-cosine (HC) function. The tapers connect conventional rectangular WR10 waveguide to the WR28. For minimum loss, the main mode electric field is parallel to the long side of the WR28. Using mode coupling theory, the position of maximum flare (inflection point) in the taper was optimized with respect to the coupling to higher order modes and the reflection of the main mode. The optimum inflection point position is about one-tenth of the taper length from the small end of the taper. Reflection and coupling were reduced by about 20 dB relative to a pyramidal (linear) taper of the same length. Comb-like dips in the transmission coefficient produced by resonances of the higher order modes in the oversize section were about 0.03 dB. Specially designed high-precision, adjustable WR28 flanges with alignment to about 5 μm were required to keep higher order mode amplitudes arising from the flanges comparable to those from the HC tapers. Minimum return loss was about 30 dB. This paper provides a foundation for further optimization, if needed. Methods are not specific to EPR or the microwave frequency band. PMID:21806211

  13. Diclofenac-Choline Antioxidant Activity Investigated by means of Luminol Amplified Chemiluminescence of Human Neutrophil Bursts and Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Braga, P C; Lattuada, N; Greco, V; Sibilia, V; Falchi, M; Bianchi, T; Dal Sasso, M

    2015-05-01

    A new diclofenac salt called diclofenac-choline (DC) has recently been proposed for the symptomatic treatment of oropharyngeal inflammatory processes and pain because its greater water solubility allows the use of high concentrations, which are useful when the contact time between the drug and the oropharyngeal mucosa is brief, as in the case of mouthwashes or spray formulations. The antioxidant activity of DC has not yet been investigated, and so the aim was to use luminol-amplified-chemiluminescence (LACL) to verify whether various concentrations of DC (1.48, 0.74 and 0.37 mg/mL for incubation times of 2, 4 and 8 min) interfere with oxygen and nitrogen radicals during the course of human neutrophils respiratory bursts; electron paramagnetic resonance (EPR) spectroscopy was used to investigate its direct antiradical (scavenger) activity. The EPR findings showed that DC has concentration-dependent scavenging activity against the ABTS, the DPPH, and the hydroxyl radicals, but no activity on superoxide anion, as has been previously reported in the case of other NSAIDs. LACL revealed an inhibitory effect that was statistically significant after only 2 min of incubation, and similar after 4 and 8 min. The effects on the peroxynitrite radical paralleled those observed in the previous test. High concentrations and short incubation times showed that there is no interference on PMN viability, and so the inhibitory findings must be attributed to the effect of the drug. The anti-inflammatory effects of DC cannot be attributed solely to the inhibition of prostaglandin synthesis, but its effects on free radicals and neutrophil bursts suggest that they may contribute to its final therapeutic effect. PMID:24918344

  14. Hydrogen interstitial in H-ion implanted ZnO bulk single crystals: Evaluation by elastic recoil detection analysis and electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Kaida, T.; Kamioka, K.; Nishimura, T.; Kuriyama, K.; Kushida, K.; Kinomura, A.

    2015-12-01

    The origins of low resistivity in H ion-implanted ZnO bulk single crystals are evaluated by elastic recoil detection analysis (ERDA), electron paramagnetic resonance (EPR), and Van der Pauw methods. The H-ion implantation (peak concentration: 5.0 × 1015 cm-2) into ZnO is performed using a 500 keV implanter. The maximum of the concentration of the implanted H estimated by a TRIM simulation is at 3600 nm in depth. The resistivity decreases from ∼103 Ω cm for un implanted ZnO to 6.5 Ω cm for as-implanted, 2.3 × 10-1 Ω cm for 200 °C annealed, and 3.2 × 10-1 Ω cm for 400 °C annealed samples. The ERDA measurements can evaluate the concentration of hydrogens which move to the vicinity of the surface (surface to 300 nm or 100 nm) because of the diffusion by the annealing at 200 °C and 400 °C. The hydrogen concentration near the surface estimated using the 2.0 MeV helium beam is ∼3.8 × 1013 cm-2 for annealed samples. From EPR measurements, the oxygen vacancy of +charge state (Vo+) is observed in as-implanted samples. The Vo+ related signal (g = 1.96) observed under no illumination disappears after successive illumination with a red LED and appears again with a blue light illumination. The activation energy of as-implanted, 200 °C annealed, and 400 °C annealed samples estimated from the temperature dependence of carrier concentration lies between 29 meV and 23 meV, suggesting the existence of H interstitial as a shallow donor level.

  15. Manganese binding properties of human calprotectin under conditions of high and low calcium: X-ray crystallographic and advanced electron paramagnetic resonance spectroscopic analysis.

    PubMed

    Gagnon, Derek M; Brophy, Megan Brunjes; Bowman, Sarah E J; Stich, Troy A; Drennan, Catherine L; Britt, R David; Nolan, Elizabeth M

    2015-03-01

    The antimicrobial protein calprotectin (CP), a hetero-oligomer of the S100 family members S100A8 and S100A9, is the only identified mammalian Mn(II)-sequestering protein. Human CP uses Ca(II) ions to tune its Mn(II) affinity at a biologically unprecedented hexahistidine site that forms at the S100A8/S100A9 interface, and the molecular basis for this phenomenon requires elucidation. Herein, we investigate the remarkable Mn(II) coordination chemistry of human CP using X-ray crystallography as well as continuous-wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopies. An X-ray crystallographic structure of Mn(II)-CP containing one Mn(II), two Ca(II), and two Na(I) ions per CP heterodimer is reported. The CW EPR spectrum of Ca(II)- and Mn(II)-bound CP prepared with a 10:0.9:1 Ca(II):Mn(II):CP ratio is characterized by an unusually low zero-field splitting of 485 MHz (E/D = 0.30) for the S = 5/2 Mn(II) ion, consistent with the high symmetry of the His6 binding site observed crystallographically. Results from electron spin-echo envelope modulation and electron-nuclear double resonance experiments reveal that the six Mn(II)-coordinating histidine residues of Ca(II)- and Mn(II)-bound CP are spectroscopically equivalent. The observed (15)N (I = 1/2) hyperfine couplings (A) arise from two distinct classes of nitrogen atoms: the coordinating ε-nitrogen of the imidazole ring of each histidine ligand (A = [3.45, 3.71, 5.91] MHz) and the distal δ-nitrogen (A = [0.11, 0.18, 0.42] MHz). In the absence of Ca(II), the binding affinity of CP for Mn(II) drops by two to three orders of magnitude and coincides with Mn(II) binding at the His6 site as well as other sites. This study demonstrates the role of Ca(II) in enabling high-affinity and specific binding of Mn(II) to the His6 site of human calprotectin. PMID:25597447

  16. Absorption of infrared radiation by electrons in the field of a neutral hydrogen atom

    NASA Technical Reports Server (NTRS)

    Stallcop, J. R.

    1974-01-01

    An analytical expression for the absorption coefficient is developed from a relationship between the cross-section for inverse bremsstrahlung absorption and the cross-section for electron-atom momentum transfer; it is accurate for those photon frequencies v and temperatures such that hv/kT is small. The determination of the absorption of infrared radiation by free-free transitions of the negative hydrogen ion has been extended to higher temperatures. A simple analytical expression for the absorption coefficient has been derived.

  17. Twin-peaks absorption spectra of excess electron in ionic liquids

    NASA Astrophysics Data System (ADS)

    Musat, Raluca M.; Kondoh, Takafumi; Yoshida, Yoichi; Takahashi, Kenji

    2014-07-01

    The solvated electron in room temperature ionic liquids (RTILs) has been the subject of several investigations and several reports exist on its nature and absorption spectrum. These studies concluded that the solvated electron exhibits an absorption spectrum peaking in the 1000-1400 nm region; a second absorption band peaking in the UV region has been assigned to the hole or dication radicals simultaneously formed in the system. Here we report on the fate of the excess electron in the ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide, P14+/NTf2- using nanosecond pulse radiolysis. Scavenging experiments allowed us to record and disentangle the complex spectrum measured in P14+/NTf2-. We identified a bi-component absorption spectrum, due to the solvated electron, the absorption maxima located at 1080 nm and around 300 nm, as predicted by previous ab-initio molecular dynamics simulations for the dry excess electron. We also measured the spectra using different ionic liquids and confirmed the same feature of two absorption peaks. The present results have important implications for the characterization of solvated electrons in ionic liquids and better understanding of their structure and reactivity.

  18. Determination of g-tensors of low-symmetry Nd{sup 3+} centers in LiNbO{sub 3} by rectification of angular dependence of electron paramagnetic resonance spectra

    SciTech Connect

    Grachev, V. Malovichko, G.; Munro, M.; Kokanyan, E.

    2015-07-28

    Two procedures for facilitation of line tracing and deciphering of complicated spectra of electron paramagnetic resonance (EPR) were developed: a correction of microwave frequencies for every orientation of external magnetic field on the base of known values of g-tensor components for a reference paramagnetic center and followed rectification of measured angular dependences using plots of effective deviation of g{sup 2}-factors of observed lines from effective g{sup 2}-factors of the reference center versus angles or squared cosines of angles describing magnetic field orientations. Their application to EPR spectra of nearly stoichiometric lithium niobate crystals doped with neodymium allowed identifying two axial and six different low-symmetry Nd{sup 3+} centers, to determine all components of their g-tensors, and to propose common divacancy models for a whole family of Nd{sup 3+} centers.

  19. Electronic absorption by Ti3+ ions and electron delocalization in synthetic blue rutile

    NASA Astrophysics Data System (ADS)

    Khomenko, V. M.; Langer, K.; Rager, H.; Fett, A.

    Polarized absorption spectra, σ and π, in the spectral range 30000-400 cm-1 (3.71-0.05 eV) were obtained on crystal slabs // [001] of deep blue rutile at various temperatures from 88 to 773 K. The rutile crystals were grown in Pt-capsules from carefully dried 99.999% TiO2 rutile powder at 50 kbar/1500 °C using graphite heating cells in a belt-type apparatus. Impurities were below the detection limits of the electron microprobe (about 0.005 wt% for elements with Z>=13). The spectra are characterized by an unpolarized absorption edge at 24300 cm-1, two weak and relatively narrow (Δν1/2 3500-4000 cm-1), slightly σ-polarized bands ν1 at 23500 cm-1 and ν2 at 18500 cm-1, and a complex, strong band system in the NIR (near infra red) with sharp weak peaks in the region of the OH stretching fundamentals superimposed on the NIR system in the σ-spectra. The NIR band system and the UV edge produce an absorption minimum in both spectra, σ and π, at 21000 cm-1, i.e. in the blue, which explains the colour of the crystals. Bands ν1 and ν2 are assigned to dd transitions to the Jahn-Teller split upper Eg state of octahedral Ti3+. The NIR band system can be fitted as a sum of three components. Two of them are partly π-polarized, nearly Gaussian bands, both with large half widths 6000-7000 cm-1, ν3 at 12000 cm-1 and the most intense ν4 at 6500 cm-1. The third NIR band ν5 of a mixed Lorentz-Gaussian shape with a maximum at 3000 cm-1 forms a shoulder on the low-energy wing of ν4. Energy positions, half band widths and temperature behaviour of these bands are consistent with a small polaron type of Ti3+Ti4+ charge transfer (CT). Polarization dependence of CT bands can be explained on the basis of the structural model of defect rutile by Bursill and Blanchin (1983) involving interstitial titanium. Two OH bands at 3322 and 3279 cm-1 in σ-spectra show different stability during annealing, indicating two different positions of proton in the rutile structure, one of them

  20. Effect of MoO3 on electron paramagnetic resonance spectra, optical spectra and dc conductivity of vanadyl ion doped alkali molybdo-borate glasses

    NASA Astrophysics Data System (ADS)

    Agarwal, A.; Khasa, S.; Seth, V. P.; Sanghi, S.; Arora, M.

    2014-02-01

    Alkali molybdo-borate glasses having composition xMoO3·(30 - x)M2O·70B2O3 and xMoO3·(70 - x)B2O3·30M2O (M = Li, Na, K) with 0 ⩽ x ⩽ 15 (mol%) doped with 2.0 mol% of V2O5 have been prepared in order to study the influence of MoO3 on electrical conductivity, electron paramagnetic resonance (EPR) and optical spectra. From EPR studies it is observed that V4+ ions in these samples exist as VO2+ ions in octahedral coordination with a tetragonal compression and belong to C4V symmetry. The tetragonal nature and octahedral symmetry of V4+O6 complex increase as well as decrease depending upon the composition of glasses with increase in MoO3 but 3dxy orbit of unpaired electron in the VO2+ ion expands in all the glasses. The decrease in optical band gap suggests that there is an increase in the concentration of non-bridging oxygen's. From the study of optical transmission spectra it is observed that for all the glasses the degree of covalency of the σ-bonding decreases with increase in MoO3 content and the degree of covalency of the π-bonding also varies. These results based on optical spectroscopy are in agreement with EPR findings. It is found that dc conductivity decreases and activation energy increases with increase in MoO3:M2O (M = Li, Na, K) ratio in MoO3·M2O·B2O3 glasses, whereas the conductivity increases and activation energy decreases with increase in MoO3:B2O3 ratio in xMoO3·B2O3·M2O glasses, which is governed by the increase in nonbridging oxygen's. The variation in theoretical optical basicity, Λth is also studied.

  1. Effect of methanobactin on the activity and electron paramagnetic resonance spectra of the membrane-associated methane monooxygenase in Methylococcus capsulatus Bath.

    PubMed

    Choi, Dong W; Antholine, William E; Do, Young S; Semrau, Jeremy D; Kisting, Clint J; Kunz, Ryan C; Campbell, Damon; Rao, Vinay; Hartsel, Scott C; DiSpirito, Alan A

    2005-10-01

    Improvements in the purification of methanobactin (mb) from either Methylosinus trichosporium OB3b(T) or Methylococcus capsulatus Bath resulted in preparations that stimulated methane-oxidation activity in both whole-cell and cell-free fractions of Methylococcus capsulatus Bath expressing the membrane-associated methane monooxygenase (pMMO). By using washed membrane factions with pMMO activities in the 290 nmol propylene oxidized min(-1) (mg protein)(-1) range, activities approaching 400 nmol propylene oxidized min(-1) (mg protein)(-1) were commonly observed following addition of copper-containing mb (Cu-mb), which represented 50-75 % of the total whole-cell activity. The stimulation of methane-oxidation activity by Cu-mb was similar to or greater than that observed with equimolar concentrations of Cu(II), without the inhibitory effects observed with high copper concentrations. Stimulation of pMMO activity was not observed with copper-free mb, nor was it observed when the copper-to-mb ratio was <0.5 Cu atoms per mb. The electron paramagnetic resonance (EPR) spectra of mb differed depending on the copper-to-mb ratio. At copper-to-mb ratios of <0.4 Cu(II) per mb, Cu(II) addition to mb showed an initial coordination by both sulfur and nitrogen, followed by reduction to Cu(I) in <2 min. At Cu(II)-to-mb ratios between 0.4 and 0.9 Cu(II) per mb, the intensity of the Cu(II) signal in EPR spectra was more representative of the Cu(II) added and indicated more nitrogen coordination. The EPR spectral properties of mb and pMMO were also examined in the washed membrane fraction following the addition of Cu(II), mb and Cu-mb in the presence or absence of reductants (NADH or duroquinol) and substrates (CH4 and/or O2). The results indicated that Cu-mb increased electron flow to the pMMO, increased the free radical formed following the addition of O2 and decreased the residual free radical following the addition of O2 plus CH4. The increase in pMMO activity and EPR spectral changes

  2. Paramagnetic spin pumping.

    PubMed

    Shiomi, Y; Saitoh, E

    2014-12-31

    We have demonstrated spin pumping from a paramagnetic state of an insulator La2NiMnO6 into a Pt film. Single-crystalline films of La2NiMnO6 which exhibit a ferromagnetic order at TC≈270  K were grown by pulsed laser deposition. The inverse spin Hall voltage induced by spin-current injection has been observed in the Pt layer not only in the ferromagnetic phase of La2NiMnO6, but also in a wide temperature range above TC. The efficient spin pumping in the paramagnetic phase is ascribable to ferromagnetic correlation, not to ferromagnetic order. PMID:25615367

  3. Electronic absorption spectra of some arylidene pyrazolone derivatives

    NASA Astrophysics Data System (ADS)

    Mahmoud, M. R.; El-Kashef, H. S.; El-Hamide, R. Abd

    The u.v. and visible spectra of some 1 - phenyl - 3 - methyl - 4 - arylidene - 2 - pyrazolin - 5 - one derivatives are investigated in pure and mixed organic solvents as well as in aqueous buffer solutions. Electronic transitions have been identified as either locally excited or predominantly charge transfer states. Moreover, the spectra of the hydroxy derivatives in proton acceptor solvents (DMF, DMSO, ethanol) are characterized by an extra band located at longer wavelengths, which is ascribed to an intermolecular CT transition. This involves an electron transfer from the lone pair of electrons of the oxygen atom of the solvent molecules (ψ ol) to the antibonding orbital of the substituent OH group. The spectral shifts are discussed in terms of medium effects and in relation to molecular structure. The variation of absorbance with pH is utilized for the determination of p K a for the dimethylamino and hydroxy derivatives.

  4. Profile modification and hot electron temperature from resonant absorption at modest intensity

    SciTech Connect

    Albritton, J.R.; Langdon, A.B.

    1980-10-13

    Resonant absorption is investigated in expanding plasmas. The momentum deposition associated with the ejection of hot electrons toward low density via wavebreaking readily exceeds that of the incident laser radiation and results in significant modification of the density profile at critical. New scaling of hot electron temperature with laser and plasma parameters is presented.

  5. Multi-photon absorption in the channeling of electrons in an external field

    NASA Astrophysics Data System (ADS)

    Yaralov, V.

    2016-07-01

    Following the methods developed for atom ionization by alternating electric field the probability of multi-photon absorption of photons of the strong external laser field by channeled electron (extraction of electron from the channel) have been calculated for different strengths of the monochromatic external field. The emission spectra of 54 MeV electron channeled in diamond crystal planes (110) are shown for different values of the resonant laser field of a frequency close to the transition frequency in the channel taking into account multi-photon absorption. It is shown that the multi-photon phenomena give some contribution to the total level width.

  6. Electron paramagnetic resonance analyses of surface radical chemistries of gamma-sterilized orthopedic materials: implications pointing to cytotoxicity via wear debris-induced inflammation.

    PubMed

    DiCicco, Michael; Compton, Ryan; Duong, Thanh; Jansen-Varnum, Susan A

    2005-10-01

    In this research, electron paramagnetic resonance (EPR) spin-trapping was utilized to determine if surface radical chemistries occur for gamma (gamma)-sterilized orthopedic materials-ultra-high molecular weight polyethylene (UHMWPE) and the novel, hybrid, diurethane dimethacrylate (DUDMA)-based RHAKOSS. The materials' ability to competitively chelate catalytic ferrous ions (Fe(2+)) or readily reduce ferric ions (Fe(3+)), and hydrogen peroxide (H(2)O(2)) directly, in facilitating the Fenton reaction (FR), is indicative of cytotoxicity. Validations with a radical scavenger aids to confirm a radical mechanism. In conjunction, materials were thermally annealed and characterized by attenuated total reflectance-Fourier-transform infrared (ATR-FTIR) spectroscopy in order to explore accelerated oxidative degradation induced by residual radicals evolving from gamma-sterilization. Particularly, there was a significant decrease in spin-adduct peak areas obtained from the reduction of H(2)O(2) in the presence of RHAKOSS or UHMWPE, evaluated against their respective controls. Additionally, chelated Fe(2+) accelerated the rate of FR. This phenomenon suggests that the materials are not better chelators than the Fe-activating chelator, edta. Neither material had the propensity to readily reduce Fe(3+) to the relevant Fe(2+), as certified by a nonradical mechanism. Alternatively, the false spin-adduct signal acquired when chelated Fe(3+) is employed arises via the nucleophilic addition of water onto the DMPO spin trap. Residual radicals in UHMWPE did not recombine/terminate following thermal annealing in an inert atmosphere. The radicals in RHAKOSS, however, did recombine under mild heating in an oxidizing or inert atmosphere. Both materials displayed quenching of ( )OH; however, for UHMWPE, this mechanism was jointly accountable for its accelerated degradation, evidenced by ATR-FTIR. Quenching of ( )OH by the silica found in RHAKOSS manifested in a competing effect that

  7. Hyperbolic-cosine waveguide tapers and oversize rectangular waveguide for reduced broadband insertion loss in W-band electron paramagnetic resonance spectroscopy. II. Broadband characterization.

    PubMed

    Sidabras, Jason W; Strangeway, Robert A; Mett, Richard R; Anderson, James R; Mainali, Laxman; Hyde, James S

    2016-03-01

    Experimental results have been reported on an oversize rectangular waveguide assembly operating nominally at 94 GHz. It was formed using commercially available WR28 waveguide as well as a pair of specially designed tapers with a hyperbolic-cosine shape from WR28 to WR10 waveguide [R. R. Mett et al., Rev. Sci. Instrum. 82, 074704 (2011)]. The oversize section reduces broadband insertion loss for an Electron Paramagnetic Resonance (EPR) probe placed in a 3.36 T magnet. Hyperbolic-cosine tapers minimize reflection of the main mode and the excitation of unwanted propagating waveguide modes. Oversize waveguide is distinguished from corrugated waveguide, overmoded waveguide, or quasi-optic techniques by minimal coupling to higher-order modes. Only the TE10 mode of the parent WR10 waveguide is propagated. In the present work, a new oversize assembly with a gradual 90° twist was implemented. Microwave power measurements show that the twisted oversize waveguide assembly reduces the power loss in the observe and pump arms of a W-band bridge by an average of 2.35 dB and 2.41 dB, respectively, over a measured 1.25 GHz bandwidth relative to a straight length of WR10 waveguide. Network analyzer measurements confirm a decrease in insertion loss of 2.37 dB over a 4 GHz bandwidth and show minimal amplitude distortion of approximately 0.15 dB. Continuous wave EPR experiments confirm these results. The measured phase variations of the twisted oversize waveguide assembly, relative to an ideal distortionless transmission line, are reduced by a factor of two compared to a straight length of WR10 waveguide. Oversize waveguide with proper transitions is demonstrated as an effective way to increase incident power and the return signal for broadband EPR experiments. Detailed performance characteristics, including continuous wave experiment using 1 μM 2,2,6,6-tetramethylpiperidine-1-oxyl in aqueous solution, provided here serve as a benchmark for other broadband low-loss probes in

  8. Hyperbolic-cosine waveguide tapers and oversize rectangular waveguide for reduced broadband insertion loss in W-band electron paramagnetic resonance spectroscopy. II. Broadband characterization

    NASA Astrophysics Data System (ADS)

    Sidabras, Jason W.; Strangeway, Robert A.; Mett, Richard R.; Anderson, James R.; Mainali, Laxman; Hyde, James S.

    2016-03-01

    Experimental results have been reported on an oversize rectangular waveguide assembly operating nominally at 94 GHz. It was formed using commercially available WR28 waveguide as well as a pair of specially designed tapers with a hyperbolic-cosine shape from WR28 to WR10 waveguide [R. R. Mett et al., Rev. Sci. Instrum. 82, 074704 (2011)]. The oversize section reduces broadband insertion loss for an Electron Paramagnetic Resonance (EPR) probe placed in a 3.36 T magnet. Hyperbolic-cosine tapers minimize reflection of the main mode and the excitation of unwanted propagating waveguide modes. Oversize waveguide is distinguished from corrugated waveguide, overmoded waveguide, or quasi-optic techniques by minimal coupling to higher-order modes. Only the TE10 mode of the parent WR10 waveguide is propagated. In the present work, a new oversize assembly with a gradual 90° twist was implemented. Microwave power measurements show that the twisted oversize waveguide assembly reduces the power loss in the observe and pump arms of a W-band bridge by an average of 2.35 dB and 2.41 dB, respectively, over a measured 1.25 GHz bandwidth relative to a straight length of WR10 waveguide. Network analyzer measurements confirm a decrease in insertion loss of 2.37 dB over a 4 GHz bandwidth and show minimal amplitude distortion of approximately 0.15 dB. Continuous wave EPR experiments confirm these results. The measured phase variations of the twisted oversize waveguide assembly, relative to an ideal distortionless transmission line, are reduced by a factor of two compared to a straight length of WR10 waveguide. Oversize waveguide with proper transitions is demonstrated as an effective way to increase incident power and the return signal for broadband EPR experiments. Detailed performance characteristics, including continuous wave experiment using 1 μM 2,2,6,6-tetramethylpiperidine-1-oxyl in aqueous solution, provided here serve as a benchmark for other broadband low-loss probes in

  9. The active site of the [FeFe]-hydrogenase from Desulfovibrio desulfuricans. I. Light sensitivity and magnetic hyperfine interactions as observed by electron paramagnetic resonance.

    PubMed

    Albracht, Simon P J; Roseboom, Winfried; Hatchikian, E Claude

    2006-01-01

    The hydrogen-activating cluster (H cluster) in [FeFe]-hydrogenases consists of two moieties. The [2Fe]H subcluster is a (L)(CO)(CN)Fe(mu-RS2)(mu-CO)Fe(CysS)(CO)(CN) centre. The Cys-bound Fe is called Fe1, the other iron Fe2. The Cys-thiol forms a bridge to a [4Fe-4S] cluster, the [4Fe-4S]H subcluster. We report that electron paramagnetic resonance (EPR) spectra of the 57Fe-enriched enzyme from Desulfovibrio desulfuricans in the H(ox)-CO state are consistent with a magnetic hyperfine interaction of the unpaired spin with all six Fe atoms of the H cluster. In contrast to the inactive aerobic enzyme, the active enzyme is easily destroyed by light. The [2Fe]H subcluster in some enzyme molecules loses CO by photolysis, whereupon other molecules firmly bind the released CO to form the H(ox)-CO state giving rise to the so-called axial 2.06 EPR signal. Though not destroyed by light, the H(ox)-CO state is affected by it. As demonstrated in the accompanying paper [49] two of the intrinsic COs, both bound to Fe2, can be exchanged by extrinsic 13CO during illumination at 2 degrees C. We found that only one of the three 13COs, the one at the extrinsic position, gives an EPR-detectable isotropic superhyperfine interaction of 0.6 mT. At 30 K both the inhibiting extrinsic CO bound to Fe2 and one more CO can be photolysed. EPR spectra of the photolysed products are consistent with a 3d7 system of Fe with the formal oxidation state +1. The damaged enzyme shows a light-sensitive g = 5 signal which is ascribed to an S = 3/2 form of the [2Fe](H) subcluster. The light sensitivity of the enzyme explains the occurrence of the g = 5 signal and the axial 2.06 signal in published EPR spectra of nearly all preparations studied thus far. PMID:16323020

  10. Electron Paramagnetic Resonance and Fluorescence In Situ Hybridization-Based Investigations of Individual Doses for Persons Living at Metlino in the Upper Reaches of the Techa River

    SciTech Connect

    Degteva, M. O.; Anspaugh, L. R.; Akleyev, A. V.; Jacob, Peter; Ivanov, Denis V.; Wieser, Albrecht; Vorobiova, M. I.; Shishkina, Elena A.; Shved, Valentina A.; Vozilova, Alexandra; Bayankin, Sergey N.; Napier, Bruce A.

    2005-02-01

    Waterborne releases from the Mayak Production Association in Russia during 1949–1956 resulted in significant doses to persons living downstream; the most contaminated village was Metlino about 7 km downstream. Internal and external doses have been estimated for these residents using the Techa River Dosimetry System–2000; the primary purpose is to support epidemiological studies of the members of the Extended Techa River Cohort (ETRC). Efforts to validate the calculations of external and internal dose are considered essential. Two methods used for the validation of external dose are electron paramagnetic resonance (EPR) measurements of teeth and fluorescence in situ hybridization (FISH) measurements of chromosome translocations in circulating lymphocytes. For EPR, 36 measurements on 26 teeth from 16 donors from Metlino were made at the GSF (16 measurements) and the IMP (20 measurements); the correlation between measurements made at the two laboratories has been found to be 0.99. Background measurements were also made on 218 teeth (63 molars, 128 premolars, and 27 incisors). FISH measurements were made for 31 residents of Metlino at the GSF. These measurements were handicapped by the analysis of a limited number of cells; for several individuals no stable translocations were observed. FISH measurements were also made for 39 individuals believed to be unexposed. The majority of EPR-measurement results fell within the range of 70 to 2700 mGy (including background). The results of FISH-based measurements fell within the range of nondetectable to 2 Gy (background subtracted). The results of individual measurements using EPR and FISH methods were generally consistent with each other and with results of other assays, including thermoluminescent measurements of quartz extracted from bricks taken from old buildings. Results were also consistent with those estimated with the TRDS-2000. Thus, the limited sets of data currently available tend to validate the present

  11. Electron paramagnetic resonance study of the generation of reactive oxygen species catalysed by transition metals and quinoid redox cycling by inhalable ambient particulate matter.

    PubMed

    Valavanidis, A; Fiotakis, K; Bakeas, E; Vlahogianni, T

    2005-01-01

    A range of epidemiological studies in the 1990s showed that exposure to ambient particulate matter (PM) is associated with adverse health effects in the respiratory system and increased morbidity and mortality rates. Oxidative stress has emerged as a pivotal mechanism that underlies the toxic pulmonary effects of PM. A key question from a variety of studies was whether the adverse health effects of PM are mediated by the carbonaceous particles of their reactive chemical compounds adsorbed into the particles. Experimental evidence showed that PM contains redox-active transition metals, redox cycling quinoids and polycyclic aromatic hydrocarbons (PAHs) which act synergistically to produce reactive oxygen species (ROS). Fine PM has the ability to penetrate deep into the respiratory tree where it overcomes the antioxidant defences in the fluid lining of the lungs by the oxidative action of ROS. From a previous study [Valavanidis A, Salika A, Theodoropoulou A. Generation of hydroxyl radicals by urban suspended particulate air matter. The role of iron ions. Atmospher Environ 2000; 34 : 2379-2386], we established that ferrous ions in PM play an important role in the generation of hydroxyl radicals in the presence of hydrogen peroxide (H2O2). In the present study, we investigated the synergistic effect of transition metals and persistent quinoid and semiquinone radicals for the generation of ROS without the presence of H2O2. We experimented with airborne particulate matter, such as TSPs (total suspended particulates), fresh automobile exhaust particles (diesel, DEP and gasoline, GEP) and fresh wood smoke soot. Using electron paramagnetic resonance (EPR), we examined the quantities of persistent free radicals, characteristic of a mixture of quinoid radicals with different structures and a carbonaceous core of carbon-centred radicals. We extracted, separated and analysed the quinoid compounds by EPR at alkaline solution (pH 9.5) and by TLC. Also, we studied the direct

  12. Paramagnetic and Diamagnetic Materials

    ERIC Educational Resources Information Center

    Thompson, Frank

    2011-01-01

    Paramagnetic and diamagnetic materials are now generally known as the "Cinderella" materials of the magnetic world. However, susceptibility measurements made on these materials in the past have revealed many details about the molecular bonding and the atomic structure of the so-called "transition" elements. Indeed, the magnetic moment of neodymium…

  13. Unitized paramagnetic salt thermometer

    SciTech Connect

    Abraham, B.M.

    1982-06-01

    The details of construction and assembly of a cerous magnesium nitrate (CMN) paramagnetic thermometer are presented. The thermometer is a small unit consisting of a primary, two secondaries, the salt pill, and thermal links. The thermometer calibration changes very little on successive coolings and is reliable to 35 mK. A typical calibration curve is also presented.

  14. Demonstrating Paramagnetism Using Liquid Nitrogen.

    ERIC Educational Resources Information Center

    Simmonds, Ray; And Others

    1994-01-01

    Describes how liquid nitrogen is attracted to the poles of neodymium magnets. Nitrogen is not paramagnetic, so the attraction suggests that the liquid nitrogen contains a small amount of oxygen, which causes the paramagnetism. (MVL)

  15. Collective modes in cold paramagnetic gases

    SciTech Connect

    Andreeva, T L; Rubin, P L

    2014-02-28

    We have obtained a condition for the emergence of spin waves in paramagnetic gases Re >> ImÂ, which is fulfilled only at temperatures of the order of 1 μK. (laser applications and other topics in quantum electronics)

  16. Theoretical analysis of electronic absorption spectra of vitamin B12 models

    NASA Astrophysics Data System (ADS)

    Andruniow, Tadeusz; Kozlowski, Pawel M.; Zgierski, Marek Z.

    2001-10-01

    Time-dependent density-functional theory (TD-DFT) is applied to analyze the electronic absorption spectra of vitamin B12. To accomplish this two model systems were considered: CN-[CoIII-corrin]-CN (dicyanocobinamide, DCC) and imidazole-[CoIII-corrin]-CN (cyanocobalamin, ImCC). For both models 30 lowest excited states were calculated together with transition dipole moments. When the results of TD-DFT calculations were directly compared with experiment it was found that the theoretical values systematically overestimate experimental data by approximately 0.5 eV. The uniform adjustment of the calculated transition energies allowed detailed analysis of electronic absorption spectra of vitamin B12 models. All absorption bands in spectral range 2.0-5.0 eV were readily assigned. In particular, TD-DFT calculations were able to explain the origin of the shift of the lowest absorption band caused by replacement of the-CN axial ligand by imidazole.

  17. A Guide to Electronic Multipoles in Photon Scattering and Absorption

    NASA Astrophysics Data System (ADS)

    Lovesey, Stephen William; Balcar, Ewald

    2013-02-01

    The practice of replacing matrix elements in atomic calculations by those of convenient operators with strong physical appeal has a long history, and in condensed matter physics it is perhaps best known through use of operator equivalents in electron resonance by Elliott and Stevens. Likewise, electronic multipoles, created with irreducible spherical-tensors, to represent charge-like and magnetic-like quantities are widespread in modern physics. Examples in recent headlines include a magnetic charge (a monopole), an anapole (a dipole) and a triakontadipole (a magnetic-like atomic multipole of rank 5). In this communication, we aim to guide the reader through use of atomic, spherical multipoles in photon scattering, and resonant Bragg diffraction and dichroic signals in particular. Applications to copper oxide CuO and neptunium dioxide (NpO2) are described. In keeping with it being a simple guide, there is sparse use in the communication of algebra and expressions are gathered from the published literature and not derived, even when central to the exposition. An exception is a thorough grounding, contained in an Appendix, for an appropriate version of the photon scattering length based on quantum electrodynamics. A theme of the guide is application of symmetry in scattering, in particular constraints imposed on results by symmetry in crystals. To this end, a second Appendix catalogues constraints on multipoles imposed by symmetry in crystal point-groups.

  18. Unified theory of electron-phonon renormalization and phonon-assisted optical absorption

    NASA Astrophysics Data System (ADS)

    Patrick, Christopher E.; Giustino, Feliciano

    2014-09-01

    We present a theory of electronic excitation energies and optical absorption spectra which incorporates energy-level renormalization and phonon-assisted optical absorption within a unified framework. Using time-independent perturbation theory we show how the standard approaches for studying vibronic effects in molecules and those for addressing electron-phonon interactions in solids correspond to slightly different choices for the non-interacting Hamiltonian. Our present approach naturally leads to the Allen-Heine theory of temperature-dependent energy levels, the Franck-Condon principle, the Herzberg-Teller effect and to phonon-assisted optical absorption in indirect band gap materials. In addition, our theory predicts sub-gap phonon-assisted optical absorption in direct gap materials, as well as an exponential edge which we tentatively assign to the Urbach tail. We also consider a semiclassical approach to the calculation of optical absorption spectra which simultaneously captures energy-level renormalization and phonon-assisted transitions and is especially suited to first-principles electronic structure calculations. We demonstrate this approach by calculating the phonon-assisted optical absorption spectrum of bulk silicon.

  19. Relativistic effects on cyclotron wave absorption by an energetic electron tail in the PLT tokamak

    SciTech Connect

    Mazzucato, E.; Efthimion, P.; Fidone, I.

    1984-07-01

    Electron cyclotron wave absorption by mildly relativistic electrons in the low density regime of the PLT tokamak is investigated. Appreciable wave damping is found for vertical propagation at frequencies of 50, 60, and 70 GHz when the spatially constant cyclotron frequency is 89 GHz. The perpendicular temperature T/sub perpendicular/(v/sub parallel/) of the fast tail is also measured from emission of radiation in the same direction. The results obtained are in satisfactory agreement with the theory of wave emission and absorption.

  20. Polarization and absorption effects in electron-helium scattering at 30--400 eV

    SciTech Connect

    Thirumalai, D.; Truhlar, D.G.; Brandt, M.A.; Eades, R.A.; Dixon, D.A.

    1982-06-01

    We report several calculations of the differential, integral, and momentum-transfer cross sections for elastic scattering, and of the absorption cross sections (for the sum of all electronically inelastic and ionization processes) for electron-He collisions at 30--400 eV. We consider two basically different approaches to include the effect of absorption, i.e., loss of flux from the initial channel. The first is the matrix effective potential (MEP) based on a variational calculation of the polarization potential; this models absorption by including a pseudochannel whose properties are based on a variational adiabatic polarization potential. This method predicts both the absorption and elastic cross sections. The second method involves phenomenological absorption (A) potentials, calibrated against experimental absorption cross sections. These potentials, when combined with static (S), exchange (E), and real polarization (P) potentials form an SEPA optical model potential that is used to predict the elastic cross sections. The MEP model based on the variational polarization potential predicts the absorption cross sections with an average absolute error of 28% at 30 and 50 eV and 5% at 100--400 eV. It predicts the elastic integral cross sections with an average absolute error of 8% over the whole energy range. The SEPA models, including a nonadiabatic polarization potential, predict the elastic integral cross sections with average absolute errors of 12 or 6%, depending on the shape function (i.e., r dependence) of the absorption potential. The adiabatic approximation for polarization is less accurate than the nonadiabatic one, even when absorption effects are included. Five new calculations of the differential cross sections at each of five impact energies are compared to experimental results in detail.

  1. Polarization and absorption effects in electron-helium scattering at 30-400 eV

    NASA Astrophysics Data System (ADS)

    Thirumalai, Devarajan; Truhlar, Donald G.; Brandt, Maynard A.; Eades, Robert A.; Dixon, David A.

    1982-06-01

    We report several calculations of the differential, integral, and momentum-transfer cross sections for elastic scattering, and of the absorption cross sections (for the sum of all electronically inelastic and ionization processes) for electron-He collisions at 30-400 eV. We consider two basically different approaches to include the effect of absorption, i.e., loss of flux from the initial channel. The first is the matrix effective potential (MEP) based on a variational calculation of the polarization potential; this models absorption by including a pseudochannel whose properties are based on a variational adiabatic polarization potential. This method predicts both the absorption and elastic cross sections. The second method involves phenomenological absorption (A) potentials, calibrated against experimental absorption cross sections. These potentials, when combined with static (S), exchange (E), and real polarization (P) potentials form an SEPA optical model potential that is used to predict the elastic cross sections. The MEP model based on the variational polarization potential predicts the absorption cross sections with an average absolute error of 28% at 30 and 50 eV, and 5% at 100-400 eV. It predicts the elastic integral cross sections with an average absolute error of 8% over the whole energy range. The SEPA models, including a nonadiabatic polarization potential, predict the elastic integral cross sections with average absolute errors of 12 or 6%, depending on the shape function (i.e., r dependence) of the absorption potential. The adiabatic approximation for polarization is less accurate than the nonadiabatic one, even when absorption effects are included. Five new calculations of the differential cross sections at each of five impact energies are compared to experimental results in detail.

  2. Theoretical calculations on the electron absorption spectra of selected Polycyclic Aromatic Hydrocarbons (PAH) and derivatives

    NASA Technical Reports Server (NTRS)

    Du, Ping

    1993-01-01

    As a theoretical component of the joint effort with the laboratory of Dr. Lou Allamandola to search for potential candidates for interstellar organic carbon compound that are responsible for the visible diffuse interstellar absorption bands (DIB's), quantum mechanical calculations were performed on the electron absorption spectra of selected polycyclic aromatic hydrocarbons (PAH) and derivatives. In the completed project, 15 different species of naphthalene, its hydrogen abstraction and addition derivatives, and corresponding cations and anions were studied. Using semiempirical quantum mechanical method INDO/S, the ground electronic state of each species was evaluated with restricted Hartree-Fock scheme and limited configuration interaction. The lowest energy spin state for each species was used for electron absorption calculations. Results indicate that these calculations are accurate enough to reproduce the spectra of naphthalene cation and anion observed in neon matrix. The spectral pattern of the hydrogen abstraction and addition derivatives predicted based on these results indicate that the electron configuration of the pi orbitals of these species is the dominant determinant. A combined list of 19 absorptions calculated from 4500 A to 10,400 A were compiled and suggested as potential candidates that are relevant for the DIB's absorptions. Continued studies on pyrene and derivatives revealed the ground state symmetries and multiplicities of its neutral, anionic, and cationic species. Spectral calculations show that the cation (B(sub 3g)-2) and the anion (A(sub u)-2) are more likely to have low energy absorptions in the regions between 10 kK and 20 kK, similar to naphthalene. These absorptions, together with those to be determined from the hydrogen abstraction and addition derivatives of pyrene, can be used to provide additional candidates and suggest experimental work in the search for interstellar compounds that are responsible for DIB's.

  3. Sources of hot electrons in laser-plasma interaction with emphasis on Raman and turbulence absorption

    SciTech Connect

    Estabrook, K.; Kruer, W.L.; Phillion, D.W.; Turner, R.E.; Campbell, E.M.

    1982-04-06

    Heating targets with high power lasers results in a sizable fraction of the absorbed energy going into electrons of temperature much greater than thermal which can pre-heat the pellet core and accelerate fast ion blowoff which results in poor momentum transfer and hence poor compression efficiency. The present emphasis is to build lasers of higher frequency, ..omega../sub 0/, which at the same W/cm/sup 2/ results in more absorption into cooler electrons. Two physical reasons are that the laser can propagate to a higher electron density, n, infinity..omega../sub 0//sup 2/ resulting in more collisional inverse bremsstrahlung absorption proportional to n, and because the hot temperatures from some plasma absorption processes increase as the oscillatory velocity of an electron in the laser electric field v/sub 0//c = eE/(m/sub e/..omega../sub 0/). The heated electron temperatures from other plasma processes (Raman for example approx.(m/sub e//2)v/sup 2//sub phase/ and the higher laser frequency helps by increasing the competing collisional absorption and decreasing the Raman gain.

  4. Ab initio calculation of the electronic absorption spectrum of liquid water

    NASA Astrophysics Data System (ADS)

    Martiniano, Hugo F. M. C.; Galamba, Nuno; Cabral, Benedito J. Costa

    2014-04-01

    The electronic absorption spectrum of liquid water was investigated by coupling a one-body energy decomposition scheme to configurations generated by classical and Born-Oppenheimer Molecular Dynamics (BOMD). A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies in the liquid phase were calculated with the equation of motion coupled cluster with single and double excitations method. Molecular dynamics configurations were generated by different approaches. Classical MD were carried out with the TIP4P-Ew and AMOEBA force fields. The BLYP and BLYP-D3 exchange-correlation functionals were used in BOMD. Theoretical and experimental results for the electronic absorption spectrum of liquid water are in good agreement. Emphasis is placed on the relationship between the structure of liquid water predicted by the different models and the electronic absorption spectrum. The theoretical gas to liquid phase blue-shift of the peak positions of the electronic absorption spectrum is in good agreement with experiment. The overall shift is determined by a competition between the O-H stretching of the water monomer in liquid water that leads to a red-shift and polarization effects that induce a blue-shift. The results illustrate the importance of coupling many-body energy decomposition schemes to molecular dynamics configurations to carry out ab initio calculations of the electronic properties in liquid phase.

  5. Ab initio calculation of the electronic absorption spectrum of liquid water

    SciTech Connect

    Martiniano, Hugo F. M. C.; Galamba, Nuno; Cabral, Benedito J. Costa

    2014-04-28

    The electronic absorption spectrum of liquid water was investigated by coupling a one-body energy decomposition scheme to configurations generated by classical and Born-Oppenheimer Molecular Dynamics (BOMD). A Frenkel exciton Hamiltonian formalism was adopted and the excitation energies in the liquid phase were calculated with the equation of motion coupled cluster with single and double excitations method. Molecular dynamics configurations were generated by different approaches. Classical MD were carried out with the TIP4P-Ew and AMOEBA force fields. The BLYP and BLYP-D3 exchange-correlation functionals were used in BOMD. Theoretical and experimental results for the electronic absorption spectrum of liquid water are in good agreement. Emphasis is placed on the relationship between the structure of liquid water predicted by the different models and the electronic absorption spectrum. The theoretical gas to liquid phase blue-shift of the peak positions of the electronic absorption spectrum is in good agreement with experiment. The overall shift is determined by a competition between the O–H stretching of the water monomer in liquid water that leads to a red-shift and polarization effects that induce a blue-shift. The results illustrate the importance of coupling many-body energy decomposition schemes to molecular dynamics configurations to carry out ab initio calculations of the electronic properties in liquid phase.

  6. Acoustic paramagnetic logging tool

    DOEpatents

    Vail, III, William B.

    1988-01-01

    New methods and apparatus are disclosed which allow measurement of the presence of oil and water in geological formations using a new physical effect called the Acoustic Paramagnetic Logging Effect (APLE). The presence of petroleum in formation causes a slight increase in the earth's magnetic field in the vicinity of the reservoir. This is the phenomena of paramagnetism. Application of an acoustic source to a geological formation at the Larmor frequency of the nucleons present causes the paramagnetism of the formation to disappear. This results in a decrease in the earth3 s magnetic field in the vicinity of the oil bearing formation. Repetitively frequency sweeping the acoustic source through the Larmor frequency of the nucleons present (approx. 2 kHz) causes an amplitude modulation of the earth's magnetic field which is a consequence of the APLE. The amplitude modulation of the earth's magnetic field is measured with an induction coil gradiometer and provides a direct measure of the amount of oil and water in the excitation zone of the formation . The phase of the signal is used to infer the longitudinal relaxation times of the fluids present, which results in the ability in general to separate oil and water and to measure the viscosity of the oil present. Such measurements may be preformed in open boreholes and in cased well bores.

  7. Electron spin-echo studies of the composition of the paramagnetic intermediate formed during the deamination of propanolamine by ethanolamine ammonia-lyase, and AdoCbl-dependent enzyme.

    PubMed

    Tan, S L; Kopczynski, M G; Bachovchin, W W; Orme-Johnson, W H; Babior, B M

    1986-03-15

    During the deamination of S-2-aminopropanol by the AdoCbl-dependent ethanolamine ammonia-lyase of Clostridia sp., a catalytic intermediate accumulates whose active site contains two paramagnetic species: cob(II)alamin and a free radical derived from the substrate molecule. Spin-echo spectroscopy has revealed that the unpaired electron on the substrate-derived radical is delocalized over a nitrogen atom that from its quadrupole splittings is probably a component of a secondary amide group. Experiments with 15N- and deuterium-labeled propanolamine gave no evidence of an interaction between this unpaired electron and the nitrogen originally attached to the substrate molecule. These results strongly suggest that the substrate-derived radical in this intermediate has already lost its nitrogen, and that this radical is stabilized by delocalization of the unpaired electron onto a nitrogen most likely situated in one of the peptide bonds of the enzyme backbone. PMID:3949775

  8. X-ray absorption study of the electronic structure of Mn-doped amorphous Si

    SciTech Connect

    Arenholz, Elke; Zeng, Li; Huegel, A.; Helgren, E.; Hellman, F.; Piamonteze, C.; Arenholz, E.

    2008-03-08

    The electronic structure of Mn in amorphous Si (a-Mn{sub x}Si{sub 1?x}) is studied by X-ray absorption spectroscopy at the Mn L{sub 3,2} edges for x = 0.005-0.18. Except the x = 0.005 sample, which shows a slight signature of Mn{sup 2+} atomic multiplets associated with a local Mn moment, all samples have broad and featureless L{sub 3,2} absorption peaks, corresponding to an itinerant state for all 3d electrons. The broad X-ray absorption spectra exclude the possibility of a localized 3d moment and explain the unexpectedly quenched Mn moment in this magnetically-doped amorphous semiconductor. Such a fully delocalized d state of Mn dopant in Si has not been previously suggested.

  9. Electrically Driven Spin Dynamics of Paramagnetic Impurities

    NASA Astrophysics Data System (ADS)

    Saha, D.; Siddiqui, L.; Bhattacharya, P.; Datta, S.; Basu, D.; Holub, M.

    2008-05-01

    The spin dynamics of dilute paramagnetic impurities embedded in a semiconductor GaAs channel of a conventional lateral spin valve has been investigated. It is observed that the electron spin of paramagnetic Mn atoms can be polarized electrically when driven by a spin valve in the antiparallel configuration. The transient current through the MnAs/GaAs/MnAs spin valve bears the signature of the underlying spin dynamics driven by the exchange interaction between the conduction band electrons in GaAs and the localized Mn electron spins. The time constant for this interaction is observed to be dependent on temperature and is estimated to be 80 ns at 15 K.

  10. Electrically driven spin dynamics of paramagnetic impurities.

    PubMed

    Saha, D; Siddiqui, L; Bhattacharya, P; Datta, S; Basu, D; Holub, M

    2008-05-16

    The spin dynamics of dilute paramagnetic impurities embedded in a semiconductor GaAs channel of a conventional lateral spin valve has been investigated. It is observed that the electron spin of paramagnetic Mn atoms can be polarized electrically when driven by a spin valve in the antiparallel configuration. The transient current through the MnAs/GaAs/MnAs spin valve bears the signature of the underlying spin dynamics driven by the exchange interaction between the conduction band electrons in GaAs and the localized Mn electron spins. The time constant for this interaction is observed to be dependent on temperature and is estimated to be 80 ns at 15 K. PMID:18518470

  11. Paramagnetic Meissner effect and related dynamical phenomena

    NASA Astrophysics Data System (ADS)

    Li, Mai Suan

    2003-03-01

    The hallmark of superconductivity is the diamagnetic response to external magnetic field. In striking contrast to this behavior, a paramagnetic response or paramagnetic Meissner effect was observed in ceramic high- Tc and in conventional superconductors. The present review is given on this interesting effect and related phenomena. We begin with a detailed discussion of experimental results on the paramagnetic Meissner effect in both granular and conventional superconductors. There are two main mechanisms leading to the paramagnetic response: the so-called d-wave and the flux compression. In the first scenario, the Josephson critical current between two d-wave superconductors becomes negative or equivalently one has a π junction. The paramagnetic signal occurs due to the nonzero spontaneous supercurrent circulating in a loop consisting of odd number of π junctions. In addition to the d-wave mechanism we present the flux compression mechanism for the paramagnetic Meissner effect. The compression may be due to either an inhomogeneous superconducting transition or flux trap inside the giant vortex state. The flux trapping which acts like a total nonzero spontaneous magnetic moment causes the paramagnetic signal. The anisotropic pairing scenario is believed to be valid for granular materials while the flux trap one can be applied to both conventional and high- Tc superconductors. The study of different phenomena by a three-dimensional lattice model of randomly distributed π Josephson junctions with finite self-inductance occupies the main part of our review. By simulations one can show that the chiral glass phase in which chiralities are frozen in time and in space may occur in granular superconductors possessing d-wave pairing symmetry. Experimental attempts on the search for the chiral glass phase are analysed. Experiments on dynamical phenomena such as AC susceptibility, compensation effect, anomalous microwave absorption, aging effect, AC resistivity and

  12. Paramagnetic Molecular Grippers: The Elements of Six-State Redox Switches.

    PubMed

    Milić, Jovana; Zalibera, Michal; Pochorovski, Igor; Trapp, Nils; Nomrowski, Julia; Neshchadin, Dmytro; Ruhlmann, Laurent; Boudon, Corinne; Wenger, Oliver S; Savitsky, Anton; Lubitz, Wolfgang; Gescheidt, Georg; Diederich, François

    2016-07-01

    The development of semiquinone-based resorcin[4]arene cavitands expands the toolbox of switchable molecular grippers by introducing the first paramagnetic representatives. The semiquinone (SQ) states were generated electrochemically, chemically, and photochemically. We analyzed their electronic, conformational, and binding properties by cyclic voltammetry, ultraviolet/visible (UV/vis) spectroelectrochemistry, electron paramagnetic resonance (EPR) and transient absorption spectroscopy, in conjunction with density functional theory (DFT) calculations. The utility of UV/vis spectroelectrochemistry and EPR spectroscopy in evaluating the conformational features of resorcin[4]arene cavitands is demonstrated. Guest binding properties were found to be enhanced in the SQ state as compared to the quinone (Q) or the hydroquinone (HQ) states of the cavitands. Thus, these paramagnetic SQ intermediates open the way to six-state redox switches provided by two conformations (open and closed) in three redox states (Q, SQ, and HQ) possessing distinct binding ability. The switchable magnetic properties of these molecular grippers and their responsiveness to electrical stimuli has the potential for development of efficient molecular devices. PMID:27300355

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

    PubMed

    Ji, Ming; Ruthstein, Sharon; Saxena, Sunil

    2014-02-18

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

  14. Potential benefits of triethylamine as n-electron donor in the estimation of forskolin by electronic absorption and emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Raju, Gajula; Ram Reddy, A.

    2016-02-01

    Diterpenoid forskolin was isolated from Coleus forskolii. The electronic absorption and emission studies of forskolin were investigated in various solvents with an aim to improve its detection limits. The two chromophores present in the diterpenoid are not conjugated leading to the poor absorption and emission of UV light. The absorption and fluorescence spectra were solvent specific. In the presence of a monodentate ligand, triethylamine the detection of forskolin is improved by 3.63 times in ethanol with the fluorescence method and 3.36 times in DMSO by the absorption spectral method. The longer wavelength absorption maximum is blue shifted while the lower energy fluorescence maximum is red shifted in the presence of triethylamine. From the wavelength of fluorescence maxima of the exciplex formed between excited forskolin and triethylamine it is concluded that the order of reactivity of hydroxyl groups in the excited state forskolin is in the reverse order to that of the order of the reactivity of hydroxyl groups in its ground state.

  15. Non-uniform absorption of terahertz radiation on superconducting hot electron bolometer microbridges

    SciTech Connect

    Miao, W.; Zhang, W.; Zhong, J. Q.; Shi, S. C.; Delorme, Y.; Lefevre, R.; Feret, A.; Vacelet, T.

    2014-02-03

    We interpret the experimental observation of a frequency-dependence of superconducting hot electron bolometer (HEB) mixers by taking into account the non-uniform absorption of the terahertz radiation on the superconducting HEB microbridge. The radiation absorption is assumed to be proportional to the local surface resistance of the HEB microbridge, which is computed using the Mattis-Bardeen theory. With this assumption the dc and mixing characteristics of a superconducting niobium-nitride (NbN) HEB device have been modeled at frequencies below and above the equilibrium gap frequency of the NbN film.

  16. Production and EPR characterization of exohedrally perfluoroalkylated paramagnetic lanthanum metallofullerenes: (La@C 82)-(C 8F 17) 2

    NASA Astrophysics Data System (ADS)

    Tagmatarchis, Nikos; Taninaka, Atsushi; Shinohara, Hisanori

    2002-04-01

    A strategy to chemically derivatize the outer sphere of endohedral metallofullerenes by using a fluorous synthesis-partitioning approach has been developed. The newly synthesized materials were found to be paramagnetic species and were characterized by electron paramagnetic resonance spectroscopy (EPR), laser desorption time-of-flight spectrometry (LD-TOF) and electronic absorption spectroscopy (UV-VIS-NIR). The fluorous-phase partitioning method (or liquid-liquid extraction), successfully applied for the first time in fullerene chemistry, aided by multi-stage recycling high performance liquid chromatography (HPLC) resulted in their isolation in isomer-free form. The present study opens the way to organic transformations of fullerene-based materials as a powerful separation technique.

  17. Electronic Band Structure and Sub-band-gap Absorption of Nitrogen Hyperdoped Silicon

    PubMed Central

    Zhu, Zhen; Shao, Hezhu; Dong, Xiao; Li, Ning; Ning, Bo-Yuan; Ning, Xi-Jing; Zhao, Li; Zhuang, Jun

    2015-01-01

    We investigated the atomic geometry, electronic band structure, and optical absorption of nitrogen hyperdoped silicon based on first-principles calculations. The results show that all the paired nitrogen defects we studied do not introduce intermediate band, while most of single nitrogen defects can introduce intermediate band in the gap. Considering the stability of the single defects and the rapid resolidification following the laser melting process in our sample preparation method, we conclude that the substitutional nitrogen defect, whose fraction was tiny and could be neglected before, should have considerable fraction in the hyperdoped silicon and results in the visible sub-band-gap absorption as observed in the experiment. Furthermore, our calculations show that the substitutional nitrogen defect has good stability, which could be one of the reasons why the sub-band-gap absorptance remains almost unchanged after annealing. PMID:26012369

  18. Electron paramagnetic resonance study of alinement induced by magnetic fields in two smectic-A liquid crystals not exhibiting nematic phases

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Gelerinter, E.

    1972-01-01

    Using vanadyl acetylacetonate (VAAC) as a paramagnetic probe, the molecular ordering in two smectic-A liquid crystals that do not display nematic phases were studied. Reproducible alinement was attained by slow cooling throughout the isotropic smectic-A transition in dc magnetic fields of 1.1 and 2.15 teslas. The degree of order attained is small for a smectic-A liquid crystal. Measurements were made of the variation of the average hyperfine splitting of the alined samples as a function of orientation relative to the dc magnetic field of the spectrometer. This functional dependence is in agreement with the theoretical prediction except where the viscosity of the liquid crystal becomes large enough to slow the tumbling of the VAAC, as indicated by asymmetry in the end lines of the spectrum.

  19. Proton nuclear magnetic resonance and electron paramagnetic resonance studies on skeletal muscle actin indicate that the metal and nucleotide binding sites are separate.

    PubMed

    Barden, J A; Cooke, R; Wright, P E; dos Remedios, C G

    1980-12-01

    The distance separating the high-affinity binding sites of actin for a divalent metal ion and nucleotide was evaluated by using high-resolution proton NMR and EPR spectroscopy. Replacement of the Ca2+ or Mg2+ bound to the high-affinity divalent cation site of G-actin by trivalent lanthanide ions such as La3+, EU3+, or Gd3+ results in an increase in the mobility of the bound ATP as observed in the NMR spectra of G-actin monomers. Little difference was observed between the spectra obtained in the presence of the diamagnetic La3+ control and the paramagnetic ions Eu3+ and Gd3+ which respectively shift and broaden the proton resonances of amino acids in the vicinity of the binding site. Analysis of the NMR spectra indicates that the metal and nucleotide binding sites are separated by a distance of at least 16 A. In the past, the metal and ATP have been widely assumed to bind as a complex. Further verification that the two sites on actin are physically separated was obtained by using an ATP analogue with a nitroxide spin-label bound at the 6' position of the purine ring. An estimate of the distance was made between the site containing the ATP analogue and the paramagnetic ion, Mn2+, bound to the cation binding site. These EPR experiments were not affected by the state of polymerization of the actin. The data obtained by using this technique support the conclusion stated above, namely, that the cation and nucleotide sites on either G- or F-actin are well separated. PMID:6257295

  20. Collisionless absorption, hot electron generation, and energy scaling in intense laser-target interaction

    SciTech Connect

    Liseykina, T.; Mulser, P.; Murakami, M.

    2015-03-15

    Among the various attempts to understand collisionless absorption of intense and superintense ultrashort laser pulses, a whole variety of models and hypotheses has been invented to describe the laser beam target interaction. In terms of basic physics, collisionless absorption is understood now as the interplay of the oscillating laser field with the space charge field produced by it in the plasma. A first approach to this idea is realized in Brunel's model the essence of which consists in the formation of an oscillating charge cloud in the vacuum in front of the target, therefore frequently addressed by the vague term “vacuum heating.” The investigation of statistical ensembles of orbits shows that the absorption process is localized at the ion-vacuum interface and in the skin layer: Single electrons enter into resonance with the laser field thereby undergoing a phase shift which causes orbit crossing and braking of Brunel's laminar flow. This anharmonic resonance acts like an attractor for the electrons and leads to the formation of a Maxwellian tail in the electron energy spectrum. Most remarkable results of our investigations are the Brunel like spectral hot electron distribution at the relativistic threshold, the minimum of absorption at Iλ{sup 2}≅(0.3−1.2)×10{sup 21} Wcm{sup −2}μm{sup 2} in the plasma target with the electron density of n{sub e}λ{sup 2}∼10{sup 23}cm{sup −3}μm{sup 2}, the drastic reduction of the number of hot electrons in this domain and their reappearance in the highly relativistic domain, and strong coupling, beyond expectation, of the fast electron jets with the return current through Cherenkov emission of plasmons. The hot electron energy scaling shows a strong dependence on intensity in the moderately relativistic domain Iλ{sup 2}≅(10{sup 18}−10{sup 20}) Wcm{sup −2}μm{sup 2}, a scaling in vague accordance with current published estimates in the range Iλ{sup 2}≅(0.14−3.5)×10{sup 21} Wcm{sup −2}

  1. Collisionless absorption, hot electron generation, and energy scaling in intense laser-target interaction

    NASA Astrophysics Data System (ADS)

    Liseykina, T.; Mulser, P.; Murakami, M.

    2015-03-01

    Among the various attempts to understand collisionless absorption of intense and superintense ultrashort laser pulses, a whole variety of models and hypotheses has been invented to describe the laser beam target interaction. In terms of basic physics, collisionless absorption is understood now as the interplay of the oscillating laser field with the space charge field produced by it in the plasma. A first approach to this idea is realized in Brunel's model the essence of which consists in the formation of an oscillating charge cloud in the vacuum in front of the target, therefore frequently addressed by the vague term "vacuum heating." The investigation of statistical ensembles of orbits shows that the absorption process is localized at the ion-vacuum interface and in the skin layer: Single electrons enter into resonance with the laser field thereby undergoing a phase shift which causes orbit crossing and braking of Brunel's laminar flow. This anharmonic resonance acts like an attractor for the electrons and leads to the formation of a Maxwellian tail in the electron energy spectrum. Most remarkable results of our investigations are the Brunel like spectral hot electron distribution at the relativistic threshold, the minimum of absorption at I λ 2 ≅ ( 0.3 - 1.2 ) × 10 21 Wcm - 2 μ m 2 in the plasma target with the electron density of n e λ 2 ˜ 10 23 cm - 3 μ m 2 , the drastic reduction of the number of hot electrons in this domain and their reappearance in the highly relativistic domain, and strong coupling, beyond expectation, of the fast electron jets with the return current through Cherenkov emission of plasmons. The hot electron energy scaling shows a strong dependence on intensity in the moderately relativistic domain I λ 2 ≅ ( 10 18 - 10 20 ) Wcm - 2 μ m 2 , a scaling in vague accordance with current published estimates in the range I λ 2 ≅ ( 0.14 - 3.5 ) × 10 21 Wcm - 2 μ m 2 , and again a distinct power increase beyond I = 3.5 × 10 21 Wcm

  2. Depth-selective X-ray absorption spectroscopy by detection of energy-loss Auger electrons

    NASA Astrophysics Data System (ADS)

    Isomura, Noritake; Soejima, Narumasa; Iwasaki, Shiro; Nomoto, Toyokazu; Murai, Takaaki; Kimoto, Yasuji

    2015-11-01

    A unique X-ray absorption spectroscopy (XAS) method is proposed for depth profiling of chemical states in material surfaces. Partial electron yield mode detecting energy-loss Auger electrons, called the inelastic electron yield (IEY) mode, enables a variation in the probe depth. As an example, Si K-edge XAS spectra for a well-defined multilayer sample (Si3N4/SiO2/Si) have been investigated using this method at various kinetic energies. We found that the peaks assigned to the layers from the top layer to the substrate appeared in the spectra in the order of increasing energy loss relative to the Auger electrons. Thus, the probe depth can be changed by the selection of the kinetic energy of the energy loss electrons in IEY-XAS.

  3. Support Effects on Electronic Behaviors of Gold Nanoparticles Studied by X-Ray Absorption Fine Structure

    SciTech Connect

    Li Zhongrui; Yan Wensheng; Wei Shiqiang

    2007-02-02

    The electronic properties of gold nanoparticles supported on different supports were studied with X-ray absorption fine structure (XAFS). It was found that the tunability of the d-electron distribution in the nano-sized Au clusters can be realized by selective supporting. The Au atoms in the clusters gain 5d electrons when supported on SiO2, and lose 5d electrons when loaded over MgO, Al2O3, and TiO2. Contractions in bond lengths of between 0.5 and 1.6% from bulk metal values were observed from EXAFS data. This work demonstrates that the important role of the different supports in the 5d-charge distribution of Au nanoparticles and usefulness of XAFS in probing the electronic behavior of noble metal nanoparticles.

  4. Analysis of paramagnetic centers for threevalent iron in aluminosilicates

    NASA Astrophysics Data System (ADS)

    Apushkinskaya, D.; Apushkinskiy, E.; Popov, B.; Romanov, V. N.; Saveliev, V.; Sobolevskiy, V.

    2015-09-01

    We present the results of investigation of the defects in fluorine aluminosilicates from the Volyn-field Al2 [SiO4][F,OH]2 by the Electron Paramagnetic Resonance (EPR) method. The studies were carried out on the spectrometer Bruker ER 220D. Three types of EPR spectra of single centers were obtained. Their angular dependence was also investigated. The obtained EPR spectra correspond to the paramagnetic ion Fe3+ in the high-spin state S = 5/2. Three types of paramagnetic centers were found: one with cubic-symmetry and two with orthorhombic- symmetries.

  5. Imaging electronic trap states in perovskite thin films with combined fluorescence and femtosecond transient absorption microscopy

    DOE PAGESBeta

    Xiao, Kai; Ma, Ying -Zhong; Simpson, Mary Jane; Doughty, Benjamin; Yang, Bin

    2016-04-22

    Charge carrier trapping degrades the performance of organometallic halide perovskite solar cells. To characterize the locations of electronic trap states in a heterogeneous photoactive layer, a spatially resolved approach is essential. Here, we report a comparative study on methylammonium lead tri-iodide perovskite thin films subject to different thermal annealing times using a combined photoluminescence (PL) and femtosecond transient absorption microscopy (TAM) approach to spatially map trap states. This approach coregisters the initially populated electronic excited states with the regions that recombine radiatively. Although the TAM images are relatively homogeneous for both samples, the corresponding PL images are highly structured. Themore » remarkable variation in the PL intensities as compared to transient absorption signal amplitude suggests spatially dependent PL quantum efficiency, indicative of trapping events. Furthermore, detailed analysis enables identification of two trapping regimes: a densely packed trapping region and a sparse trapping area that appear as unique spatial features in scaled PL maps.« less

  6. Imaging Electronic Trap States in Perovskite Thin Films with Combined Fluorescence and Femtosecond Transient Absorption Microscopy.

    PubMed

    Simpson, Mary Jane; Doughty, Benjamin; Yang, Bin; Xiao, Kai; Ma, Ying-Zhong

    2016-05-01

    Charge carrier trapping degrades the performance of organometallic halide perovskite solar cells. To characterize the locations of electronic trap states in a heterogeneous photoactive layer, a spatially resolved approach is essential. Here, we report a comparative study on methylammonium lead tri-iodide perovskite thin films subject to different thermal annealing times using a combined photoluminescence (PL) and femtosecond transient absorption microscopy (TAM) approach to spatially map trap states. This approach coregisters the initially populated electronic excited states with the regions that recombine radiatively. Although the TAM images are relatively homogeneous for both samples, the corresponding PL images are highly structured. The remarkable variation in the PL intensities as compared to transient absorption signal amplitude suggests spatially dependent PL quantum efficiency, indicative of trapping events. Detailed analysis enables identification of two trapping regimes: a densely packed trapping region and a sparse trapping area that appear as unique spatial features in scaled PL maps. PMID:27103096

  7. Electron Paramagnetic Resonance Studies of Single Crystals of Manganese Ion-Doped Ammonium Sulfate, Gadolinium Ion-Doped Ammonium Praseodymium SULFATE.WATER, Vanadium Oxide Ion-Doped M Ammonium SULFATE.WATER

    NASA Astrophysics Data System (ADS)

    Sun, Jiansheng

    Detailed X-band electron paramagnetic resonance (EPR) measurements on single crystals of Mn^ {2+}-doped (NH_4)_2 SO_4, Gd^ {3+}-doped NH_4Pr(SO _4)_2cdot4H _2O, VO^{2+} -doped M(NH_4)_2(SO _4)_2cdot6H_2 O (M = Cd, Co, Mg, Fe, Zn) and Mg(ND_4) _2(SO_4)_2cdot 6D_2O, and Cu^ {2+}-doped MNa_2(SO _4)_2cdot4H _2O (M = Mg, Co) are made at variable temperatures. The spin-Hamiltonian parameters for Mn^{2+ }, Gd^{3+}, VO^{2+} and Cu ^{2+} ions are evaluated using a least-squares-fitting procedure. The positions and local symmetries of the impurity ions in these hosts have been well deduced. The ferroelectric transition in (NH_4) _2SO_4 has been extensively studied via the splittings of Mn^{2+ } EPR lines, leading to the determination of the critical exponent beta. The existence of two inequivalent sublattices in the (NH _4)_2SO_4 crystal is confirmed. Temperature variation of Gd^{3+ } EPR spectra reveal two first-order phase transitions in the NH_4Pr(SO _4)_2cdot4H_2 O crystal. The host-ion spin-lattice relaxation (SLR) times (tau) of Pr^ {3+} have been estimated via the EPR linewidths of Gd^{3+} impurity ions using an appropriate expression. The predominant processes of SLR of Pr^{3+} host -ions have been deduced. The superhyperfine structures of VO^ {2+} EPR spectra in the hydrated Tutton -salt hosts M(NH_4)_2(SO _4)_2cdot6H_2 O have been well explained by comparison with the VO^{2+} EPR spectra in the deuterated host crystal Mg(ND_4)_2 (SO_4)_2cdot6D _2O. Using the VO^ {2+} EPR and optical-absorption spectra, the bonding coefficients of the (VO(H_2 O)_5]^{2+ } complex have been estimated. The systematics of EPR of the VO^{2+} ion in this series of Tutton salts is analyzed. The impurity-host exchange-interaction constant of VO^{2+}-Fe ^{2+} pair is determined in the Fe(NH_4)_2(SO_4) _2cdot6H_2O host, using the g-shift due to the exchange interaction and the shape of the crystal at liquid-helium temperature. The tau values of Fe^ {2+} and Co^{2+} in the Fe(NH_4)_2(SO _4

  8. Electronic states of DNA and M-DNA studied by optical absorption

    NASA Astrophysics Data System (ADS)

    Tsuburaya, Makoto; Sakamoto, Hirokazu; Mizoguchi, Kenji

    2014-02-01

    To unveil the electronic states of divalent metal ion incorporated M-DNAs, where M is Mg, Mn, Ni, Co, or Fe, optical absorption spectra have been studied in aqueous solutions of single-stranded (SS) 30mer DNA of poly(dA) (adenine), poly(dG) (guanine), poly(dT) (thymine), poly(dC) (cytosine), salmon-sperm DNA (B-DNA), and M-DNA. The absorption spectrum of the double-stranded (DS) B-DNA can be reproduced with the sum of the four absorption spectra of the SS oligo-DNAs in the ratio corresponding to the composition of B-DNA. This observation suggests that the interactions between complementary strands of DS DNA are negligibly weaker than the bandwidths of the optical spectra. In the metal-incorporated M-DNAs, except for Fe-DNA, the absorption spectra show no significant qualitative change from that of B-DNA. Quantitatively, however, the absorption intensity decreases by ≈15% uniquely in a DS poly(dA)-poly(dT) solution with adding MCl2, while nothing happens quantitatively and qualitatively in any SS oligo-DNA and DS poly(dG)-poly(dC) solutions, suggesting some suppression of the electronic excitation only in the Adenine-M-Thymine complex. In contrast, remarkable differences have been observed in Fe-DNA, prepared with FeCl2 and B-DNA. New absorption bands appear in the intragap energy of Fe-DNA, in addition to the suppression of the interband absorption peak of DNA at 4.8 eV. The intragap absorption is attributed to the appearance of Fe3+ species with the same spectral feature as that of FeCl3, that is, purely ionic Fe3+ species. This observation suggests that FeCl2+B-DNA forms Fe-DNA with hydrated Fe3+ ions with ionic bonds. Thus, it is concluded that the charge transfer from Fe2+ to DNA has occurred in Fe-DNA and that the transferred charges are expected to be located in the nearby bases.

  9. Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes

    DOE PAGESBeta

    Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; Gray, Harry B.; Fujita, Etsuko; Muckerman, James T.; Fontecave, Marc; Artero, Vincent; Arantes, Guilherme M.; Field, Martin J.

    2014-08-11

    Here, we report that the reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task.

  10. Theoretical modeling of low-energy electronic absorption bands in reduced cobaloximes

    SciTech Connect

    Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; Gray, Harry B.; Fujita, Etsuko; Muckerman, James T.; Fontecave, Marc; Artero, Vincent; Arantes, Guilherme M.; Field, Martin J.

    2014-08-11

    Here, we report that the reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task.

  11. Theoretical Modeling of Low Energy Electronic Absorption Bands in Reduced Cobaloximes

    PubMed Central

    Bhattacharjee, Anirban; Chavarot-Kerlidou, Murielle; Dempsey, Jillian L.; Gray, Harry B.; Fujita, Etsuko; Muckerman, James T.; Fontecave, Marc; Artero, Vincent; Arantes, Guilherme M.; Field, Martin J.

    2015-01-01

    The reduced Co(I) states of cobaloximes are powerful nucleophiles that play an important role in the hydrogen-evolving catalytic activity of these species. In this work we have analyzed the low energy electronic absorption bands of two cobaloxime systems experimentally and using a variety of density functional theory and molecular orbital ab initio quantum chemical approaches. Overall we find a reasonable qualitative understanding of the electronic excitation spectra of these compounds but show that obtaining quantitative results remains a challenging task. PMID:25113847

  12. Ozone absorption spectroscopy in search of low-lying electronic states

    NASA Technical Reports Server (NTRS)

    Anderson, S. M.; Mauersberger, K.

    1995-01-01

    A spectrometer capable of detecting ozone absorption features 9 orders of magnitude weaker than the Hartley band has been employed to investigate the molecule's near-infrared absorption spectrum. At this sensitivity a wealth of information on the low-lying electronically excited states often believed to play a role in atmospheric chemistry is available in the form of vibrational and rotational structure. We have analyzed these spectra using a combination of digital filtering and isotope substitution and find evidence for three electronically excited states below 1.5 eV. The lowest of these states is metastable, bound by approximately 0.1 eV and probably the (3)A2 rather than the (3)B2 state. Its adiabatic electronic energy is 1.24 +/- 0.01 eV, slightly above the dissociation energy of the ground state. Two higher states, at 1.29 +/- 0.03 and 1.48 +/- 0.03 eV are identified as the (3)B2 and the (3)B1, respectively. Combined with other recent theoretical and experimental data on the low-lying electronic states of ozone, these results imply that these are, in fact, the lowest three excited states; that is, there are no electronically excited states of ozone lying below the energy of O(3P) + O2((3)Sigma(-), v = 0). Some of the implications for atmospheric chemistry are considered.

  13. Elastic and absorption cross sections for electron-nitrous oxide collisions

    NASA Astrophysics Data System (ADS)

    Lee, M.-T.; Iga, I.; Homem, M. G.; Machado, L. E.; Brescansin, L. M.

    2002-06-01

    In this work, we present a joint theoretical-experimental study on electron-N2O collisions in the intermediate energy range. More specifically, calculated and measured elastic differential, integral, and momentum-transfer cross sections, as well as calculated total and absorption cross sections are reported. The measurements were performed using a crossed electron-beam-molecular-beam geometry. The angular distribution of the scattered electrons was converted to absolute cross sections using the relative-flow technique. Theoretically, a complex optical potential is used to represent the electron-molecule interaction dynamics in the present calculation. The Schwinger variational iterative method combined with the distorted-wave approximation is used to solve the scattering equations. The comparison of the present calculated results with the measured results as well as with the existing experimental and theoretical data shows good agreement.

  14. Understanding the electronic properties of the CuA site from the soluble domain of cytochrome c oxidase through paramagnetic 1H NMR.

    PubMed

    Salgado, J; Warmerdam, G; Bubacco, L; Canters, G W

    1998-05-19

    The soluble domain of the subunit II of cytochrome c oxidase from Paracoccus versutus was cloned, expressed, and studied by 1H NMR at 600 MHz. The properties of the redox-active dinuclear CuA site in the paramagnetic mixed-valence Cu(I)-Cu(II) state were investigated in detail. A group of relatively sharp signals found between 30 and 15 ppm in the 1H NMR spectrum correspond to the imidazole protons of the coordinated histidines (H181 and H224). A second group of broader and farther shifted signals between 50 and 300 ppm are assigned to Hbeta protons of the bridging cysteines (C216 and C220); the protons from the weak M227 and E218 ligands do not shift outside of the diamagnetic envelope. About 40% of the total spin density appears delocalized over the cysteine-bridging ligands while a much smaller amount is delocalized on the two ligand histidines. The latter have similar spin density distributions. Analysis of the pattern of the hyperfine shifts of the Cys H beta protons shows that the ground state bears 2B3u character, in which the sulfur lobes in the singly occupied molecular orbital are aligned with the Cu-Cu axis. Analysis of the temperature dependence of the shifts of the Cys H beta signals leads to the conclusion that the 2B2u excited state is thermally accessible at room temperature (Delta E approximately kT). PMID:9585552

  15. Stoner-enhanced paramagnetism in tungsten tetraboride.

    PubMed

    Shen, Jiaoyan; Zhou, Jingming; Zhao, Meng; Liu, Guozhen; Gao, Ju; Yao, Jinlei

    2016-01-20

    We demonstrate that tungsten tetraboride (WB4), a heavy transition metallic compound without magnetic atoms, is an exchange-enhanced paramagnet revealed by the magnetization and specific heat measurements. WB4 has a small effective magnetic moment of 0.53 μB/fu. The high magnetic susceptibility in the magnitude of 1 memu (mol·Oe)(-1) below 10 K obeys quadratic temperature dependence. The upturn behavior of C(P)/T versus T(2) at low temperatures is attributed to the electron-paramagnon interactions. A high Stoner enhancement parameter, Z  =  0.93, was derived to explain the enhanced paramagnetism based on the Stoner model. PMID:26683343

  16. Suppression of infrared absorption in nanostructured metals by controlling Faraday inductance and electron path length.

    PubMed

    Han, Sang Eon

    2016-02-01

    Nanostructured metals have been intensively studied for optical applications over the past few decades. However, the intrinsic loss of metals has limited the optical performance of the metal nanostructures in diverse applications. In particular, light concentration in metals by surface plasmons or other resonances causes substantial absorption in metals. Here, we avoid plasmonic excitations for low loss and investigate methods to further suppress loss in nanostructured metals. We demonstrate that parasitic absorption in metal nanostructures can be significantly reduced over a broad band by increasing the Faraday inductance and the electron path length. For an example structure, the loss is reduced in comparison to flat films by more than an order of magnitude over most of the very broad spectrum between short and long wavelength infrared. For a photodetector structure, the fraction of absorption in the photoactive material increases by two orders of magnitude and the photoresponsivity increases by 15 times because of the selective suppression of metal absorption. These findings could benefit many metal-based applications that require low loss such as photovoltaics, photoconductive detectors, solar selective surfaces, infrared-transparent defrosting windows, and other metamaterials. PMID:26906830

  17. Femtosecond X-ray absorption study of electron localization in photoexcited anatase TiO2

    NASA Astrophysics Data System (ADS)

    Santomauro, F. G.; Lübcke, A.; Rittmann, J.; Baldini, E.; Ferrer, A.; Silatani, M.; Zimmermann, P.; Grübel, S.; Johnson, J. A.; Mariager, S. O.; Beaud, P.; Grolimund, D.; Borca, C.; Ingold, G.; Johnson, S. L.; Chergui, M.

    2015-10-01

    Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter’s dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti3+ centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides.

  18. Femtosecond X-ray absorption study of electron localization in photoexcited anatase TiO2.

    PubMed

    Santomauro, F G; Lübcke, A; Rittmann, J; Baldini, E; Ferrer, A; Silatani, M; Zimmermann, P; Grübel, S; Johnson, J A; Mariager, S O; Beaud, P; Grolimund, D; Borca, C; Ingold, G; Johnson, S L; Chergui, M

    2015-01-01

    Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter's dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti(3+) centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides. PMID:26437873

  19. Femtosecond X-ray absorption study of electron localization in photoexcited anatase TiO2

    PubMed Central

    Santomauro, F. G.; Lübcke, A.; Rittmann, J.; Baldini, E.; Ferrer, A.; Silatani, M.; Zimmermann, P.; Grübel, S.; Johnson, J. A.; Mariager, S. O.; Beaud, P.; Grolimund, D.; Borca, C.; Ingold, G.; Johnson, S.L.; Chergui, M.

    2015-01-01

    Transition metal oxides are among the most promising solar materials, whose properties rely on the generation, transport and trapping of charge carriers (electrons and holes). Identifying the latter’s dynamics at room temperature requires tools that combine elemental and structural sensitivity, with the atomic scale resolution of time (femtoseconds, fs). Here, we use fs Ti K-edge X-ray absorption spectroscopy (XAS) upon 3.49 eV (355 nm) excitation of aqueous colloidal anatase titanium dioxide nanoparticles to probe the trapping dynamics of photogenerated electrons. We find that their localization at Titanium atoms occurs in <300 fs, forming Ti3+ centres, in or near the unit cell where the electron is created. We conclude that electron localization is due to its trapping at pentacoordinated sites, mostly present in the surface shell region. The present demonstration of fs hard X-ray absorption capabilities opens the way to a detailed description of the charge carrier dynamics in transition metal oxides. PMID:26437873

  20. First-principles calculation of electronic structure and optical absorption of BN ZnO

    NASA Astrophysics Data System (ADS)

    Zhang, Xiao; Schleife, Andre

    2015-03-01

    The α-BN structure of ZnO, a nonequilibrium phase with a transition pressure of 25 GPa, has been found in nano structures of ZnO. The structural difference between the BN structure and the equilibrium wurtzite structure can play an important role for applications of nanostructured ZnO. In order to understand the difference, first principles calculations have been performed on both phases. The electronic structure is computed using the GW method based on Density Functional Theory and HSE hybrid functional calculations. The GW method includes the quasiparticle effects due to the screened electron-electron interaction which gives an accurate description of the electronic band structure and density of states. After that, by solving the Bethe-Salpeter Equation for the optical polarization function, which take excitonic effects into account, we have achieved an accurate description of optical absorption spectra for both structures. We find a good agreement with experimental and previous computational results for WZ structure, and predict the absorption for the BN structure. The BN structure shows a larger band gap and we found a very large optical anisotropy: The gap for extraordinary light polarization is almost 0.7eV larger than that for ordinary light polarization.

  1. Solvent effects on the resonance Raman and electronic absorption spectra of bacteriochlorophyll a cation radical

    SciTech Connect

    Misono, Yasuhito; Itoh, Koichi; Limanatara, Leenawaty; Koyama, Yasushi

    1996-02-08

    Resonance Raman and electronic absorption spectra of bacteriocholrophyll a cation radical (BChl a{sup .+}) were recorded in 14 different kinds of solvents. The frequency of the ring-breathing Raman band of BChl a{sup .+} was in the region of 1596-1599 cm{sup -1} in solvents forming the pentacoordinated state in neutral bacteriochlorophyll a (BChl a), while it was in the region of 1584-1588 cm{sup -1} in solvents forming the hexacoordinated state. BChl a{sup .+} exhibited a key absorption band in the regions 546-554 and 557-563 nm in the above penta- and hexa-coordinating solvents. Therefore, it has been concluded that the penta- and hexa-coordinated states are retained even after conversion of BChl a into BChl a{sup .+} (one-electron oxidization). Application of this rule to the case of 2-propanol solution showed transformation from the penta- to the hexa-coordinated state upon one-electron oxidation in this particular solution. The coordination states of BChl a{sup .+} could be correlated with the donor number(DN) and the Taft parameters, {Beta} and {pi}{sup *}, of the solvent: The hexacoordinated state was formed in solvents with DN >= 18 or {Beta} > 0.5 showing higher electron donating power, while the pentacoordinated state was formed in solvents with {pi}{sup *} > 0.65 showing higher dielectric stabilization. 27 refs., 8 figs., 3 tabs.

  2. Interplay between structural and electronic properties of various fullerene derivatives, and their absorption spectra

    NASA Astrophysics Data System (ADS)

    Park, Sora; Ahn, Jeung Sun; Kwon, Young-Kyun

    2011-03-01

    Using density functional theory (DFT), we investigate the geometrical structures and electronic properties of various fullerene derivatives formed by attaching several kinds of addends on C60 through [2+2] cycloaddition. Various forms of such derivatives are modeled by considering different kinds, different positions and different numbers of addends to study how structural configurations will affect their electronic structures. Our results reveal that some derivatives with certain symmetries determined by the configuration of addends may have wider energy gap than that of pristine C60 . This suggests that absorption properties could be adjusted by controlling the addends configurations. To describe the excited state properties, such as absorption spectra, of various C60 derivatives more accurately, we performed time-dependent (TD) DFT calculations. We find the position and the intensity of the peak of absorption spectra of derivatives are affected by the specific symmetry of the derivatives defined by the configurations of the addends. To explore such peculiar effects, we analyze the charge distribution and orbital mixing characters.

  3. Electronic relaxation dynamics of PCDA-PDA studied by transient absorption spectroscopy.

    PubMed

    Joung, Joonyoung F; Baek, Junwoo; Kim, Youngseo; Lee, Songyi; Kim, Myung Hwa; Yoon, Juyoung; Park, Sungnam

    2016-08-17

    Photo-curable polymers originating from 10,12-pentacosadiynoic acid (PCDA-PDA) are commonly used polydiacetylenes (PDAs). PCDA-PDA exhibits thermochromic properties undergoing a unique colorimetric transition from blue to red as the temperature is increased from low to high. In this work, we have carefully studied the temperature-dependent optical properties of PCDA-PDA by using UV-visible absorption, FTIR, Raman, and transient absorption (TA) spectroscopy in combination with quantum chemical calculations. Temperature-dependent UV-visible absorption spectra indicate that PCDA-PDA exhibits reversible thermochromic properties up to 60 °C and its thermochromic properties become irreversible above 60 °C. Such distinct thermochromic properties are also manifested in TA signals so that the electronically excited PCDA-PDA relaxes to the ground state via an intermediate state at 20 °C (blue form) but it relaxes directly back to the ground state at 80 °C (red form). The electronic relaxation dynamics of PCDA-PDA are comprehensively analyzed based on different kinetic models by using the global fitting analysis method. The intermediate state in the blue form of PCDA-PDA is clearly found to be responsible for fluorescence quenching. FTIR and Raman spectroscopy and quantum chemical calculations confirm that the H-bonds between the carboxylic acid groups in PCDA-PDA are broken at high temperatures leading to an irreversible structural change of PCDA-PDA. PMID:27492212

  4. The electronic absorption study of imide anion radicals in terms of time dependent density functional theory

    NASA Astrophysics Data System (ADS)

    Andrzejak, Marcin; Sterzel, Mariusz; Pawlikowski, Marek T.

    2005-07-01

    The absorption spectra of the N-(2,5-di- tert-butylphenyl) phthalimide ( 1-), N-(2,5-di- tert-butylphenyl)-1,8-naphthalimide ( 2-) and N-(2,5-di- tert-butylphenyl)-perylene-3,4-dicarboximide ( 3-) anion radicals are studied in terms of time dependent density functional theory (TDDFT). For these anion radicals a large number electronic states (from 30 to 60) was found in the visible and near-IR regions (5000-45000 cm -1). In these regions the TD/B3LYP treatment at the 6-1+G* level is shown to reproduce satisfactorily the empirical absorption spectra of all three anion radicals studied. The most apparent discrepancies between purely electronic theory and the experiment could be found in the excitation region corresponding to D0→ D1 transitions in the 2- and 3- molecules. For these species we argue that the structures seen in the lowest energy part of the absorptions of the 2- and 3- species are very likely due to Franck-Condon (FC) activity of the totally symmetric vibrations not studied in this Letter.

  5. Temperature dependent electronic structure of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film probed by X-ray absorption near edge structure

    SciTech Connect

    Zhang, Bangmin; Sun, Cheng-Jun E-mail: msecgm@nus.edu.sg; Heald, Steve M.; Chen, Jing-Sheng; Moog Chow, Gan E-mail: msecgm@nus.edu.sg; Venkatesan, T.

    2014-05-07

    The Mn K edge X-ray absorption near edge structures (XANES) of Pr{sub 0.67}Sr{sub 0.33}MnO{sub 3} film (100 nm) on (001) LaAlO{sub 3} substrate was measured at different temperatures to probe the MnO{sub 6} octahedron distortion and corresponding electronic structure. The absorption of high temperature paramagnetic-insulator phase differed from that of the low temperature ferromagnetic-metal phase. The temperature-dependent absorption intensity of Mn K edge XANES was correlated with the relaxation of distorted MnO{sub 6} octahedron, which changed the crystal field acting on the Mn site and the related electronic structure and properties. At low temperature, the splitting of Mn majority e{sub g} orbitals decreased and the density of states above the Fermi level increased in the relaxed MnO{sub 6} octahedron, as reflected by a wider separation between two sub-peaks in the pre-edge XANES spectra.

  6. Resonant two-photon absorption of extreme-ultraviolet free-electron-laser radiation in helium

    SciTech Connect

    Nagasono, Mitsuru; Suljoti, Edlira; Pietzsch, Annette; Hennies, Franz; Wellhoefer, Michael; Hoeft, Jon-Tobias; Martins, Michael; Wurth, Wilfried; Foehlisch, Alexander; Treusch, Rolf; Feldhaus, Josef; Schneider, Jochen R.

    2007-05-15

    We have investigated the nonlinear response of helium to intense extreme-ultraviolet radiation from the free-electron laser in Hamburg (FLASH). We observe a spectral feature between 24 and 26 eV electron kinetic energy in photoemission which shows a quadratic fluence dependence. The feature is explained as a result of subsequent processes involving a resonant two-photon absorption process into doubly excited levels of even parity (N=5 and 6), radiative decay to the doubly excited states in the vicinity of the He{sup +} (N=2) ionization threshold and finally the photoionization of the inner electron by the radiation of the next microbunches. This observation suggests that even-parity states, which have been elusive to be measured with the low pulse energy of synchrotron radiation sources, can be investigated with the intense radiation of FLASH. This also demonstrates a first step to bring nonlinear spectroscopy into the xuv and soft-x-ray regime.

  7. Two-dimensional stanane: strain-tunable electronic structure, high carrier mobility, and pronounced light absorption.

    PubMed

    Liu, Xiuhong; Wang, Yu; Li, Feng; Li, Yafei

    2016-06-01

    By means of state-of-the-art density functional theory (DFT) computations, we systematically studied the structural, electronic, and optical properties of a novel two dimensional material, namely stanane (SnH). According to our computational results, stanane is semiconducting with a direct band gap of 1.00 eV, which can be flexibly tuned by applying an external strain. Remarkably, stanane has much higher electron and hole mobilities than those of a MoS2 monolayer at room temperature. Moreover, stanane has rather strong optical absorption in the visible as well as infrared regions of the solar spectrum. These results provide many useful insights for the wide application of stanane in electronics and optoelectronics. PMID:27181028

  8. Pressure dependence of Hexanitrostilbene Raman/ electronic absorption spectra to validate DFT EOS

    NASA Astrophysics Data System (ADS)

    Farrow, Darcie; Alam, Kathleen; Martin, Laura; Fan, Hongyou; Kay, Jeffrey; Wixom, Ryan

    2015-06-01

    Due to its thermal stability and low vapor pressure, Hexanitrostilbene (HNS) is often used in high-temperature or vacuum applications as a detonator explosive or in mild detonating fuse. Toward improving the accuracy of the equation of state used in hydrodynamic simulations of the performance of HNS, we have measured the Raman and electronic absorption spectra of this material under static pressure in a diamond anvil cell. Density functional theory calculations were used to simulate the pressure dependence of the Raman/Electronic spectra along the Hugoniot and 300K isotherm for comparison and to aid in interpreting the data. We will discuss changes in the electronic structure of HNS under pressure, validation of a DFT predicted equation of state (EOS), and using this data as a basis for understanding future pulsed Raman measurements on dynamically compressed HNS samples.

  9. Electronic absorption spectra of H₂C₆O⁺ isomers: produced by ion-molecule reactions.

    PubMed

    Chakraborty, Arghya; Fulara, Jan; Maier, John P

    2015-01-01

    Three absorption systems with origins at 354, 497, and 528 nm were detected after mass-selected deposition of H2C6O(+) in a 6 K neon matrix. The ions were formed by the reaction of C2O with HC4H(+) in a mixture of C3O2 and diacetylene in a hot cathode source, or by dissociative ionization of tetrabromocyclohexadienone. The 497 and 354 nm systems are assigned to the 1(2)A″ ← X(2)A″ and 2(2)A″ ← X(2)A″ electronic transitions of B(+), (2-ethynylcycloallyl)methanone cation, and the 528 nm absorption to the 1(2)A2 ← X(2)B1 transition of F(+), 2-ethynylbut-3-yn-1-enone-1-ylide, on the basis of calculated excitation energies with CASPT2. PMID:25495044

  10. Electronic structure investigation of highly compressed aluminum with K edge absorption spectroscopy.

    PubMed

    Benuzzi-Mounaix, A; Dorchies, F; Recoules, V; Festa, F; Peyrusse, O; Levy, A; Ravasio, A; Hall, T; Koenig, M; Amadou, N; Brambrink, E; Mazevet, S

    2011-10-14

    The electronic structure evolution of highly compressed aluminum has been investigated using time resolved K edge x-ray absorption spectroscopy. A long laser pulse (500 ps, I(L)≈8×10(13) W/cm(2)) was used to create a uniform shock. A second ps pulse (I(L)≈10(17)  W/cm(2)) generated an ultrashort broadband x-ray source near the Al K edge. The main target was designed to probe aluminum at reshocked conditions up to now unexplored (3 times the solid density and temperatures around 8 eV). The hydrodynamical conditions were obtained using rear side visible diagnostics. Data were compared to ab initio and dense plasma calculations, indicating potential improvements in either description. This comparison shows that x-ray-absorption near-edge structure measurements provide a unique capability to probe matter at these extreme conditions and severally constrains theoretical approaches currently used. PMID:22107398

  11. Electronic structure and absorption spectrum of biexciton obtained by using exciton basis

    SciTech Connect

    Shiau, Shiue-Yuan; Combescot, Monique; Chang, Yia-Chung

    2013-09-15

    We approach the biexciton Schrödinger equation not through the free-carrier basis as usually done, but through the free-exciton basis, exciton–exciton interactions being treated according to the recently developed composite boson many-body formalism which allows an exact handling of carrier exchange between excitons, as induced by the Pauli exclusion principle. We numerically solve the resulting biexciton Schrödinger equation with the exciton levels restricted to the ground state and we derive the biexciton ground state as well as the bound and unbound excited states as a function of hole-to-electron mass ratio. The biexciton ground-state energy we find, agrees reasonably well with variational results. Next, we use the obtained biexciton wave functions to calculate optical absorption in the presence of a dilute exciton gas in quantum well. We find an asymmetric peak with a characteristic low-energy tail, identified with the biexciton ground state, and a set of Lorentzian-like peaks associated with biexciton unbound states, i.e., exciton–exciton scattering states. Last, we propose a pump–probe experiment to probe the momentum distribution of the exciton condensate. -- Highlights: •New composite boson many-body theory is used to derive exactly the biexciton Schrödinger equation using the exciton basis. •We solved the 2D and 3D biexciton ground- and excited-state binding energies for various electron-to-hole mass ratios. •The absorption spectrum shows an asymmetric low-energy peak identified with the biexciton ground state. •High-energy Lorentzian-like peaks in the absorption spectrum are associated with the exciton–exciton scattering states. •The exciton gas momentum distribution can be determined by the absorption spectrum via the biexciton wave functions.

  12. Electronic structure of some adenosine receptor antagonists. III. Quantitative investigation of the electronic absorption spectra of alkyl xanthines

    NASA Astrophysics Data System (ADS)

    Moustafa, H.; Shalaby, Samia H.; El-sawy, K. M.; Hilal, Rifaat

    2002-07-01

    Quantitative and comparative investigation of the electronic absorption spectra of theophylline, caffeine and their derivatives is reported. The spectra of theophylline, caffeine and theobromine were compared to establish the predominant tautomeric species in solution. This comparison, analysis of solvent effects and assignments of the observed transitions via MO computations indicate the exits of only one tautomeric species in solution that is the N7 form. A low-lying triplet state was identified which corresponds to a HOMO-LUMO transition. This relatively long-lived T 1 state is always less polar than the ground state and may very well underlie the photochemical reactivity of alkyl xanthines. Substituents of different electron donating or withdrawing strengths and solvent effects are investigated and analyzed. The present analysis is facilitated via computer deconvolution of the observed spectra and MO computation.

  13. A cyanide-bridged heterometallic coordination polymer constructed from square-planar [Ni(CN)4](2-): synthesis, crystal structure, thermal decomposition, electron paramagnetic resonance (EPR) spectrum and magnetic properties.

    PubMed

    Qin, Ying Lian; Yang, Bin Wu; Wang, Gao Feng; Sun, Hong

    2016-07-01

    Square-planar complexes are commonly formed by transition metal ions having a d(8) electron configuration. Planar cyanometallate anions have been used extensively as design elements in supramolecular coordination systems. In particular, square-planar tetracyanometallate(II) ions, i.e. [M(CN)4](2-) (M(II) = Ni, Pd or Pt), are used as good building blocks for bimetallic Hofmann-type assemblies and their analogues. Square-planar tetracyanonickellate(II) complexes have been extensively developed with N-donor groups as additional co-ligands, but studies of these systems using O-donor ligands are scarce. A new cyanide-bridged Cu(II)-Ni(II) heterometallic compound, poly[[diaquatetra-μ2-cyanido-κ(8)C:N-nickel(II)copper(II)] monohydrate], {[Cu(II)Ni(II)(CN)4(H2O)2]·H2O}n, has been synthesized and characterized by X-ray single-crystal diffraction analyses, vibrational spectroscopy (FT-IR), thermal analysis, electron paramagnetic resonance (EPR) and magnetic moment measurements. The structural analysis revealed that it has a two-dimensional grid-like structure built up of cationic [Cu(H2O)2](2+) and anionic [Ni(CN)4](2-) units connected through bridging cyanide ligands. The overall three-dimensional supramolecular network is expanded by a combination of interlayer O-H...N and intralayer O-H...O hydrogen-bond interactions. The first decomposition reactions take place at 335 K under a static air atmosphere, which illustrates the existence of guest water molecules in the interlayer spaces. The electron paramagnetic resonance (EPR) spectrum confirms that the Cu(II) cation has an axial coordination symmetry and that the unpaired electrons occupy the d(x(2)-y(2)) orbital. In addition, magnetic investigations showed that antiferromagnetic interactions exist in the Cu(II) atoms through the diamagnetic [Ni(CN)4](2-) ion. PMID:27377277

  14. Electronic structure of barium strontium titanate by soft-x-ray absorption spectroscopy

    SciTech Connect

    Uehara, Y.; Underwood, J.H.; Gullikson, E.M.; Perera, R.C.C.

    1997-04-01

    Perovskite-type titanates, such as Strontium Titanate (STO), Barium Titanate (BTO), and Lead Titanate (PTO) have been widely studied because they show good electric and optical properties. In recent years, thin films of Barium Strontium Titanate (BST) have been paid much attention as dielectrics of dynamic random access memory (DRAM) capacitors. BST is a better insulator with a higher dielectric constant than STO and can be controlled in a paraelectric phase with an appropriate ratio of Ba/Sr composition, however, few studies have been done on the electronic structure of the material. Studies of the electronic structure of such materials can be beneficial, both for fundamental physics research and for improving technological applications. BTO is a famous ferroelectric material with a tetragonal structure, in which Ti and Ba atoms are slightly displaced from the lattice points. On the other hand, BST keeps a paraelectric phase, which means that the atoms are still at the cubic lattice points. It should be of great interest to see how this difference of the local structure around Ti atoms between BTO and BST effects the electronic structure of these two materials. In this report, the authors present the Ti L{sub 2,3} absorption spectra of STO, BTO, and BST measured with very high accuracy in energy of the absorption features.

  15. Paramagnetic copper centers in ferroelectric lead germanate with halogens

    NASA Astrophysics Data System (ADS)

    Vazhenin, V. A.; Potapov, A. P.; Artyomov, M. Yu.; Vylkov, A. I.

    2014-08-01

    The electron paramagnetic resonance spectrum of triclinic bivalent copper centers in copper-doped Pb5Ge3O11 single crystals has been investigated. The spectrum intensity increases after thermal treatment in a chlorine- or fluorine-containing atmosphere. The parameters of the electron Zeeman, hyperfine, and nuclear quadrupole interactions have been determined. The model of the observed centers has been proposed.

  16. Electronic absorption band broadening and surface roughening of phthalocyanine double layers by saturated solvent vapor treatment

    SciTech Connect

    Kim, Jinhyun; Yim, Sanggyu

    2012-10-15

    Variations in the electronic absorption (EA) and surface morphology of three types of phthalocyanine (Pc) thin film systems, i.e. copper phthalocyanine (CuPc) single layer, zinc phthalocyanine (ZnPc) single layer, and ZnPc on CuPc (CuPc/ZnPc) double layer film, treated with saturated acetone vapor were investigated. For the treated CuPc single layer film, the surface roughness slightly increased and bundles of nanorods were formed, while the EA varied little. In contrast, for the ZnPc single layer film, the relatively high solubility of ZnPc led to a considerable shift in the absorption bands as well as a large increase in the surface roughness and formation of long and wide nano-beams, indicating a part of the ZnPc molecules dissolved in acetone, which altered their molecular stacking. For the CuPc/ZnPc film, the saturated acetone vapor treatment resulted in morphological changes in mainly the upper ZnPc layer due to the significantly low solubility of the underlying CuPc layer. The treatment also broadened the EA band, which involved a combination of unchanged CuPc and changed ZnPc absorption.

  17. Femtosecond x-ray absorption spectroscopy with hard x-ray free electron laser

    SciTech Connect

    Katayama, Tetsuo; Togashi, Tadashi; Tono, Kensuke; Kameshima, Takashi; Inubushi, Yuichi; Sato, Takahiro; Hatsui, Takaki; Yabashi, Makina; Obara, Yuki; Misawa, Kazuhiko; Bhattacharya, Atanu; Kurahashi, Naoya; Ogi, Yoshihiro; Suzuki, Toshinori

    2013-09-23

    We have developed a method of dispersive x-ray absorption spectroscopy with a hard x-ray free electron laser (XFEL), generated by a self-amplified spontaneous emission (SASE) mechanism. A transmission grating was utilized for splitting SASE-XFEL light, which has a relatively large bandwidth (ΔE/E ∼ 5 × 10{sup −3}), into several branches. Two primary split beams were introduced into a dispersive spectrometer for measuring signal and reference spectra simultaneously. After normalization, we obtained a Zn K-edge absorption spectrum with a photon-energy range of 210 eV, which is in excellent agreement with that measured by a conventional wavelength-scanning method. From the analysis of the difference spectra, the noise ratio was evaluated to be ∼3 × 10{sup −3}, which is sufficiently small to trace minute changes in transient spectra induced by an ultrafast optical laser. This scheme enables us to perform single-shot, high-accuracy x-ray absorption spectroscopy with femtosecond time resolution.

  18. First principle studies on the electronic structures and absorption spectra in KMgF 3 crystal with fluorine vacancy

    NASA Astrophysics Data System (ADS)

    Cheng, Fang; Liu, Tingyu; Zhang, Qiren; Qiao, Hailin; Zhou, Xiuwen

    2010-08-01

    The experiments indicate that the perfect KMgF 3 crystal has no absorption in the visible range, however the electron irradiation induces a complex absorption spectrum. The absorption spectra can be decomposed by five Gaussian bands peaking at 2.5 eV (488 nm), 3.4 eV (359 nm), 4.2 eV (295 nm), 4.6 eV (270 nm) and 5.2 eV (239 nm), respectively. The purpose of this paper is to seek the origins of the absorption bands. The electronic structures and absorption spectra either for the perfect KMgF 3 or for KMgF 3: VF+ with electrical neutrality have been studied by using density functional theory code CASTEP with the lattice structure optimized. The calculation results predicate that KMgF 3: VF+ also exhibits five absorption bands caused by the existence of the fluorine ion vacancy VF+ and the five absorption bands well coincide with the experimental results. It is believable that the five absorption bands are related to VF+ in KMgF 3 crystal produced by the electron irradiation.

  19. Bound states in optical absorption of semiconductor quantum wells containing a two-dimensional electron Gas

    PubMed

    Huard; Cox; Saminadayar; Arnoult; Tatarenko

    2000-01-01

    The dependence of the optical absorption spectrum of a semiconductor quantum well on two-dimensional electron concentration n(e) is studied using CdTe samples. The trion peak (X-) seen at low n(e) evolves smoothly into the Fermi edge singularity at high n(e). The exciton peak (X) moves off to high energy, weakens, and disappears. The X,X- splitting is linear in n(e) and closely equal to the Fermi energy plus the trion binding energy. For Cd0.998Mn0.002Te quantum wells in a magnetic field, the X,X- splitting reflects unequal Fermi energies for M = +/-1/2 electrons. The data are explained by Hawrylak's theory of the many-body optical response including spin effects. PMID:11015866

  20. Electron bubbles in liquid helium: Density functional calculations of infrared absorption spectra

    SciTech Connect

    Grau, Victor; Barranco, Manuel; Mayol, Ricardo; Pi, Marti

    2006-02-01

    Within density functional theory, we have calculated the energy of the transitions from the ground state to the first two excited states in the electron bubbles in liquid helium at pressures from zero to about the solidification pressure. For {sup 4}He at low temperatures, our results are in very good agreement with infrared absorption experiments. Above a temperature of {approx}2 K, we overestimate the energy of the 1s-1p transition. We attribute this to the break down of the Franck-Condon principle due to the presence of helium vapor inside the bubble. Our results indicate that the 1s-2p transition energies are sensitive not only to the size of the electron bubble, but also to its surface thickness. We also present results for the infrared transitions in the case of liquid {sup 3}He, for which we lack experimental data.

  1. The power of using continuous-wave and pulsed electron paramagnetic resonance methods for the structure analysis of ferric forms and nitric oxide-ligated ferrous forms of globins.

    PubMed

    Van Doorslaer, Sabine; Desmet, Filip

    2008-01-01

    For several decades now, electron paramagnetic resonance (EPR) has been a valuable spectroscopic tool for the characterization of globin proteins. In the early years, the majority of EPR studies were performed using standard continuous-wave EPR techniques at conventional microwave frequencies. In the last years, the field of EPR has known tremendous technological developments, including the introduction of advanced pulsed EPR and high-frequency EPR techniques. After a short overview of the basics of EPR and recent advances in the field, we will illustrate how these different EPR methods can provide information about the dynamics and geometric and electronic structures of heme proteins. Although the main focus of this chapter lies on the EPR analysis of nitric oxide-ligated ferrous heme proteins and ferric heme systems, we also briefly outline the possibility of site-directed spin labeling of heme proteins. The last section highlights the future potential and challenges in using this magnetic resonance technique in globin research. PMID:18433634

  2. Strong reduction of V{sup 4+} amount in vanadium oxide/hexadecylamine nanotubes by doping with Co{sup 2+} and Ni{sup 2+} ions: Electron paramagnetic resonance and magnetic studies

    SciTech Connect

    Saleta, M. E.; Troiani, H. E.; Ribeiro Guevara, S.; Ruano, G.; Sanchez, R. D.; Malta, M.; Torresi, R. M.

    2011-05-01

    In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO{sub x}/Hexa NT's) doped with Co{sup 2+} and Ni{sup 2+} ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co{sup 2+}, S = 3/2 and Ni{sup 2+}, S = 1) decreases notably the amount of V{sup 4+} ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V{sup 4+} in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes.

  3. Time-resolved X-ray Absorption Spectroscopy for Electron Transport Study in Warm Dense Gold

    NASA Astrophysics Data System (ADS)

    Lee, Jong-Won; Bae, Leejin; Engelhorn, Kyle; Heimann, Philip; Ping, Yuan; Barbrel, Ben; Fernandez, Amalia; Beckwith, Martha Anne; Cho, Byoung-Ick; GIST Team; IBS Team; LBNL Collaboration; SLAC Collaboration; LLNL Collaboration

    2015-11-01

    The warm dense Matter represents states of which the temperature is comparable to Fermi energy and ions are strongly coupled. One of the experimental techniques to create such state in the laboratory condition is the isochoric heating of thin metal foil with femtosecond laser pulses. This concept largely relies on the ballistic transport of electrons near the Fermi-level, which were mainly studied for the metals in ambient conditions. However, they were barely investigated in warm dense conditions. We present a time-resolved x-ray absorption spectroscopy measured for the Au/Cu dual layered sample. The front Au layer was isochorically heated with a femtosecond laser pulse, and the x-ray absorption changes around L-edge of Cu, which was attached on the backside of Au, was measured with a picosecond resolution. Time delays between the heating of the `front surface' of Au layer and the alternation of x-ray spectrum of Cu attached on the `rear surface' of Au indicate the energetic electron transport mechanism through Au in the warm dense conditions. IBS (IBS-R012-D1) and the NRF (No. 2013R1A1A1007084) of Korea.

  4. Free-free absorption of infrared radiation in collisions of electrons with neutral rare-gas atoms

    NASA Technical Reports Server (NTRS)

    Stallcop, J. R.

    1974-01-01

    A relationship between the inverse bremsstrahlung absorption cross section and the electron neutral momentum transfer cross section has been utilized to determine the infrared free-free continuum absorption coefficient for the negative ions of helium, neon, argon, krypton, and xenon. The values of the momentum transfer cross section for this calculation have been obtained from experimental measurements. Analytical expressions for the absorption coefficient have also been developed. From the results of this calculation, it is possible to determine the absorption coefficient per unit electron density per neutral atom for temperatures in the range from 2500 to 25,000 K. The results are compared with those from tabulations of previous calculations and those computed from theoretical values of the phase shifts for the elastic scattering of electrons by neutral atoms.

  5. Effective light absorption and absolute electron transport rates in the coral Pocillopora damicornis.

    PubMed

    Szabó, Milán; Wangpraseurt, Daniel; Tamburic, Bojan; Larkum, Anthony W D; Schreiber, Ulrich; Suggett, David J; Kühl, Michael; Ralph, Peter J

    2014-10-01

    Pulse Amplitude Modulation (PAM) fluorometry has been widely used to estimate the relative photosynthetic efficiency of corals. However, both the optical properties of intact corals as well as past technical constrains to PAM fluorometers have prevented calculations of the electron turnover rate of PSII. We used a new Multi-colour PAM (MC-PAM) in parallel with light microsensors to determine for the first time the wavelength-specific effective absorption cross-section of PSII photochemistry, σII(λ), and thus PAM-based absolute electron transport rates of the coral photosymbiont Symbiodinium both in culture and in hospite in the coral Pocillopora damicornis. In both cases, σII of Symbiodinium was highest in the blue spectral region and showed a progressive decrease towards red wavelengths. Absolute values for σII at 440 nm were up to 1.5-times higher in culture than in hospite. Scalar irradiance within the living coral tissue was reduced by 20% in the blue when compared to the incident downwelling irradiance. Absolute electron transport rates of P. damicornis at 440 nm revealed a maximum PSII turnover rate of ca. 250 electrons PSII(-1) s(-1), consistent with one PSII turnover for every 4 photons absorbed by PSII; this likely reflects the limiting steps in electron transfer between PSII and PSI. Our results show that optical properties of the coral host strongly affect light use efficiency of Symbiodinium. Therefore, relative electron transport rates do not reflect the productivity rates (or indeed how the photosynthesis-light response is parameterised). Here we provide a non-invasive approach to estimate absolute electron transport rates in corals. PMID:25146689

  6. Predicting X-ray absorption spectra of semiconducting polymers for electronic structure and morphology characterization

    NASA Astrophysics Data System (ADS)

    Su, Gregory; Patel, Shrayesh; Pemmaraju, C. Das; Kramer, Edward; Prendergast, David; Chabinyc, Michael

    2015-03-01

    Core-level X-ray absorption spectroscopy (XAS) reveals important information on the electronic structure of materials and plays a key role in morphology characterization. Semiconducting polymers are the active component in many organic electronics. Their electronic properties are critically linked to device performance, and a proper understanding of semiconducting polymer XAS is crucial. Techniques such as resonant X-ray scattering rely on core-level transitions to gain materials contrast and probe orientational order. However, it is difficult to identify these transitions based on experiments alone, and complementary simulations are required. We show that first-principles calculations can capture the essential features of experimental XAS of semiconducting polymers, and provide insight into which molecular model, such as oligomers or periodic boundary conditions, are best suited for XAS calculations. Simulated XAS can reveal contributions from individual atoms and be used to visualize molecular orbitals. This allows for improved characterization of molecular orientation and scattering analysis. These predictions lay the groundwork for understanding how chemical makeup is linked to electronic structure, and to properly utilize experiments to characterize semiconducting polymers.

  7. Electronic transitions and fermi edge singularity in polar heterostructures studied by absorption and emission spectroscopy

    NASA Astrophysics Data System (ADS)

    Pandey, S.; Cavalcoli, D.; Minj, A.; Fraboni, B.; Cavallini, A.; Gamarra, P.; Poisson, M. A.

    2012-12-01

    Optically induced electronic transitions in nitride based polar heterostructures have been investigated by absorption and emission spectroscopy. Surface photovoltage (SPV), photocurrent (PC), and photo luminescence spectroscopy have been applied to high quality InAlN/AlN/GaN structures to study the optical properties of two dimensional electron gas. Energy levels within the two dimensional electron gas (2DEG) well at the interface between the GaN and AlN have been directly observed by SPV and PC. Moreover, a strong enhancement of the photoluminescence intensity due to holes recombining with electrons at the Fermi Energy, known as fermi energy singularity, has been observed. These analyses have been carried out on InAlN/AlN/GaN heterojunctions with the InAlN barrier layer having different In content, a parameter which affects the energy levels within the 2DEG well as well as the optical signal intensity. The measured energy values are in a very good agreement with the ones obtained by Schrödinger-Poisson simulations.

  8. Hot-Electron Temperature and Laser-Light Absorption in Fast Ignition

    SciTech Connect

    Haines, M. G.; Wei, M. S.; Beg, F. N.; Stephens, R. B.

    2009-01-30

    Experimental data [F. N. Beg et al., Phys. Plasmas 4, 447 (1997)] indicate that for intense short-pulse laser-solid interactions at intensities up to 5x10{sup 18} W cm{sup -2} the hot-electron temperature {proportional_to}(I{lambda}{sup 2}){sup 1/3}. A fully relativistic analytic model based on energy and momentum conservation laws for the laser interaction with an overdense plasma is presented here. A general formula for the hot-electron temperature is found that closely agrees with the experimental scaling over the relevant intensity range. This scaling is much lower than ponderomotive scaling. Examination of the electron forward displacement compared to the collisionless skin depth shows that electrons experience only a fraction of a laser-light period before being accelerated forward beyond the laser light's penetration region. Inclusion of backscattered light in a modified model indicates that light absorption approaches 80%-90% for intensity >10{sup 19} W cm{sup -2}.

  9. Low-lying singlet states of carotenoids having 8-13 conjugated double bonds as determined by electronic absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Peng; Nakamura, Ryosuke; Kanematsu, Yasuo; Koyama, Yasushi; Nagae, Hiroyoshi; Nishio, Tomohiro; Hashimoto, Hideki; Zhang, Jian-Ping

    2005-07-01

    Electronic absorption spectra were recorded at room temperature in solutions of carotenoids having different numbers of conjugated double bonds, n = 8-13, including a spheroidene derivatives, neurosporene, spheroidene, lycopene, anhydrorhodovibrin and spirilloxanthin. The vibronic states of 1Bu+(v=0-4), 2Ag-(v=0-3), 3Ag- (0) and 1Bu- (0) were clearly identified. The arrangement of the four electronic states determined by electronic absorption spectroscopy was identical to that determined by measurement of resonance Raman excitation profiles [K. Furuichi et al., Chem. Phys. Lett. 356 (2002) 547] for carotenoids in crystals.

  10. Special aspects of the temperature dependence of EPR absorption of chemically carbonized polyvinylidene fluoride derivatives

    NASA Astrophysics Data System (ADS)

    Zhivulin, V. E.; Pesin, L. A.; Ivanov, D. V.

    2016-01-01

    The temperature dependences of electron paramagnetic resonance (EPR) absorption of two samples of chemically carbonized derivatives of polyvinylidene fluoride (PVDF) synthesized under different conditions have been measured in the range of 100-300 K. It has been found that the temperature dependence of the integrated intensity of the EPR signal of both samples is nonmonotonic and does not obey the classical Curie dependence characteristic of free radicals. An analytical expression that is consistent with experimental data and suggests the presence of an activation component of paramagnetism in the test samples has been obtained. The presence of a term independent of temperature in this equation also indicates the paramagnetic contribution of free electrons. The magnitude of the activation energy of the singlet-triplet transitions has been evaluated: δ = 0.067 eV. The HYSCORE spectra of chemically carbonized PVDF derivatives have been obtained for the first time.

  11. Paramagnetic squeezing of QCD matter.

    PubMed

    Bali, G S; Bruckmann, F; Endrődi, G; Schäfer, A

    2014-01-31

    We determine the magnetization of quantum chromodynamics for several temperatures around and above the transition between the hadronic and the quark-gluon phases of strongly interacting matter. We obtain a paramagnetic response that increases in strength with the temperature. We argue that due to this paramagnetism, chunks of quark-gluon plasma produced in noncentral heavy ion collisions should become squeezed perpendicular to the magnetic field. This anisotropy will then contribute to the elliptic flow v2 observed in such collisions, in addition to the pressure gradient that is usually taken into account. We present a simple estimate for the magnitude of this new effect and a rough comparison to the effect due to the initial collision geometry. We conclude that the paramagnetic effect might have a significant impact on the value of v2. PMID:24580441

  12. Neutron diffraction, Mössbauer effect and electron paramagnetic resonance studies on multiferroic Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3}

    SciTech Connect

    Matteppanavar, Shidaling; Angadi, Basavaraj; Rayaprol, Sudhindra; AV, Anupama; Sahoo, Balaram

    2015-06-24

    Multiferroic Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3} ceramics were synthesized via a modified two-stage Columbite method. Single phase formation was confirmed from the analysis of x-ray and neutron diffraction patterns recorded at room temperature. Structural analysis of the diffraction data reveals cubic phase (space group Pm-3m) for the title compound. Magnetic structure of the title compound at room temperature exhibits G-type antiferromagnetic structure. The Mössbauer spectroscopy and Electron Paramagnetic Resonance (EPR) studies were carried out at 300 K. The isomer shift and quadrupole splitting of the Mössbauer spectra confirms the trivalent state of iron (Fe{sup 3+}). The Mössbauer spectra also suggest that the iron and tungsten are randomly distributed at the octahedral, B site. EPR spectra show a single broad line associated with Fe{sup 3+} ions. Both spectra clearly exhibit weak ferromagnetic behaviour of Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3} ceramic at 300 K. Considering neutron diffraction, Mössbauer and EPR results together, it may be stated here that Pb(Fe{sub 2/3}W{sub 1/3})O{sub 3} exhibits antiferromagnetic behavior along with weak ferromagnetism at room temperature.

  13. The relationship between partial pressure of oxygen and perfusion in two murine tumors after X-ray irradiation: a combined gadopentetate dimeglumine dynamic magnetic resonance imaging and in vivo electron paramagnetic resonance oximetry study.

    PubMed

    Goda, F; Bacic, G; O'Hara, J A; Gallez, B; Swartz, H M; Dunn, J F

    1996-07-15

    Changes of partial pressure of oxygen (pO2) and blood perfusion were studied in MTG-B and RIF-1 tumors (n = 5 each) before and after a single 20-Gy dose of X-ray irradiation. Using electron paramagnetic resonance oximetry, we have observed an initial fast decrease of pO2 after irradiation, followed by a slow increase. The time course of these changes was faster in the MTG-B tumors than in the RIF-1 tumors. Gadopentetate dimeglumine (Gd-DTPA) dynamic magnetic resonance imaging studies showed a reduction in uptake of Gd-DTPA at the time of minimum pO2 and a recovery at the time of maximum pO2 in each tumor. Previous work indicates that there is microscopic heterogeneity in tumors, with well-vascularized "capillary regions" being closer to capillaries than poorly vascularized "noncapillary regions." We propose a two-component (slow and fast) model of Gd-DTPA uptake that is designed to quantify the kinetics of these two compartments by analyzing the total tumor uptake kinetics without having to identify specific regions of interest. Total perfusion in the tumors was greatly reduced at the time of minimum oxygenation, and the volume of the slow component increased after irradiation. We conclude that a decrease in blood perfusion is one of the main causes of the decline in pO2 observed after irradiation. PMID:8764132

  14. Very high frequency electron paramagnetic resonance of 2,2,6,6-tetramethyl-1-piperidinyloxy in 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine liposomes: partitioning and molecular dynamics.

    PubMed Central

    Smirnov, A I; Smirnova, T I; Morse, P D

    1995-01-01

    Partitioning and molecular dynamics of 2,2,6,6,-tetramethylpiperedine-1-oxyl (TEMPO) nitroxide radicals in large unilamellar liposomes (LUV) composed from 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine were investigated by using very high frequency electron paramagnetic resonance (EPR) spectroscopy. Experiments carried out at a microwave frequency of 94.3 GHz completely resolved the TEMPO EPR spectrum in the aqueous and hydrocarbon phases. An accurate computer simulation method combined with Levenberg-Marquardt optimization was used to analyze the TEMPO EPR spectra in both phases. Spectral parameters extracted from the simulations gave the actual partitioning of the TEMPO probe between the LUV hydrocarbon and aqueous phases and allowed analysis of picosecond rotational dynamics of the probe in the LUV hydrocarbon phase. In very high frequency EPR experiments, phase transitions in the LUV-TEMPO system were observed as sharp changes in both partitioning and rotational correlation times of the TEMPO probe. The phase transition temperatures (40.5 +/- 0.2 and 32.7 +/- 0.5 degrees C) are in agreement with previously reported differential scanning microcalorimetry data. Spectral line widths were analyzed by using existing theoretical expressions for motionally narrowed nitroxide spectra. It was found that the motion of the small, nearly spherical, TEMPO probe can be well described by anisotropic Brownian diffusion in isotropic media and is not restricted by the much larger hydrocarbon chains existing in ripple structure (P beta') or fluid bilayer structure (L alpha) phases. PMID:7647239

  15. The Structure of Vimentin Linker 1 and Rod 1B Domains Characterized by Site-directed Spin-labeling Electron Paramagnetic Resonance (SDSL-EPR) and X-ray Crystallography*

    PubMed Central

    Aziz, Atya; Hess, John F.; Budamagunta, Madhu S.; Voss, John C.; Kuzin, Alexandre P.; Huang, Yuanpeng J.; Xiao, Rong; Montelione, Gaetano T.; FitzGerald, Paul G.; Hunt, John F.

    2012-01-01

    Despite the passage of ∼30 years since the complete primary sequence of the intermediate filament (IF) protein vimentin was reported, the structure remains unknown for both an individual protomer and the assembled filament. In this report, we present data describing the structure of vimentin linker 1 (L1) and rod 1B. Electron paramagnetic resonance spectra collected from samples bearing site-directed spin labels demonstrate that L1 is not a flexible segment between coiled-coils (CCs) but instead forms a rigid, tightly packed structure. An x-ray crystal structure of a construct containing L1 and rod 1B shows that it forms a tetramer comprising two equivalent parallel CC dimers that interact with one another in the form of a symmetrical anti-parallel dimer. Remarkably, the parallel CC dimers are themselves asymmetrical, which enables them to tetramerize rather than undergoing higher order oligomerization. This functionally vital asymmetry in the CC structure, encoded in the primary sequence of rod 1B, provides a striking example of evolutionary exploitation of the structural plasticity of proteins. EPR and crystallographic data consistently suggest that a very short region within L1 represents a minor local distortion in what is likely to be a continuous CC from the end of rod 1A through the entirety of rod 1B. The concordance of this structural model with previously published cross-linking and spectral data supports the conclusion that the crystallographic oligomer represents a native biological structure. PMID:22740688

  16. {sup 13}C, {sup 1}H, {sup 6}Li magic-angle spinning nuclear magnetic resonance, electron paramagnetic resonance, and Fourier transform infrared study of intercalation electrodes based in ultrasoft carbons obtained below 3100 K

    SciTech Connect

    Alcantara, R.; Madrigal, F.J.F.; Lavela, P.; Tirado, J.L.; Mateos, J.M.J.; Stoyanova, R.; Zhecheva, E.

    1999-01-01

    The past decade has seen an important development of materials for high-performance energy storage systems. Particularly, the field of electrode materials for advanced lithium batteries has attracted the interest of numerous researchers. Petroleum coke samples of different origins and heat treated at different temperatures below 3100 K have been studied by spectroscopic and electrochemical procedures. According to {sup 13}C and {sup 1}H magic-angle spinning (MAS) nuclear magnetic resonance (NMR), infrared (IR), and electron paramagnetic resonance (EPR) data, aromatic compounds and surface OH groups are present in green coke samples. The preparation of CMB (combustible) sample from 1673 K leads to a low-temperature graphitization process, as shown by the occurrence of multiphase products containing both turbostatic and graphitized solid. This process is accompanied by the loss of aromatic compounds and surface hydroxyls. The optimization of the lithium intercalation electrodes based in the green coke materials was carried out by thermal treatment at 1023 K under dynamic vacuum conditions. Such pretreatment of the electrode material leads to marked enhancement of reversible capacities without the higher temperatures usually required for other soft carbon materials. Finally, the results of {sup 6}Li MAS NMR and EPR have been correlated with the experimental determination of lithium diffusion coefficients and surface properties. On the basis of these results, spin resonance spectroscopies are found to be a powerful tool to discern between the different petroleum coke samples to select the active electrode material with best performance.

  17. Understanding the magnetic behavior of heat treated CaO-P2O5-Na2O-Fe2O3-SiO2 bioactive glass using electron paramagnetic resonance studies

    NASA Astrophysics Data System (ADS)

    Shankhwar, Nisha; Kothiyal, G. P.; Srinivasan, A.

    2014-09-01

    Bioactive glass of composition 41CaO-44SiO2-4P2O5-8Fe2O3-3Na2O has been heat treated in the temperature (TA) range of 750-1150 °C for time periods (tA) ranging from 1 h to 3 h to yield magnetic bioactive glass ceramics (MBCs). X-ray diffraction studies indicate the presence of bone mineral (hydroxyapatite and wollastonite) and magnetic (magnetite and α-hematite) phases in nanocrystalline form in the MBCs. Electron paramagnetic resonance (EPR) study was carried out to understand the variation in saturation magnetization and coercivity of the MBCs with TA and tA. These studies reveal the nature and amount of iron ions present in the MBCs and their interaction in the glassy oxide matrix as a function of annealing parameters. The deterioration in the magnetic properties of the glass heat treated above 1050 °C is attributed to the crystallization of the non-magnetic α-hematite phase. These results are expected to be useful in the application of these MBCs as thermoseeds in hyperthermia treatment of cancer.

  18. Characterization of the electronic structure of silicon nanoparticles using x-ray absorption and emission

    NASA Astrophysics Data System (ADS)

    Montoya Vaverka, April Susan

    Resolving open questions regarding transport in nanostructures can have a huge impact on a broad range of future technologies such as light harvesting for energy. Silicon has potential to be used in many of these applications. Understanding how the band edges of nanostructures move as a function of size, surface termination and assembly is of fundamental importance in understanding the transport properties of these materials. In this thesis work I have investigated the change in the electronic structure of silicon nanoparticle assemblies as the surface termination is changed. Nanoparticles are synthesized using a thermal evaporation technique and sizes are determined using atomic force microscopy (AFM). By passivating the particles with molecules containing alcohol groups we are able to modify the size dependent band edge shifts. Both the valence and conduction bands are measured using synchrotron based x-ray absorption spectroscopy (XAS) and soft x-ray fluorescence (SXF) techniques. Particles synthesized via recrystallization of amorphous silicon/SiO2 multilayers of thicknesses below 10 rim are also investigated using the synchrotron techniques. These samples also show quantum confinement effects but the electronic structure is different from those synthesized via evaporation methods. The total bandgap is determined for all samples measured. The origins of these differences in the electronic structures are discussed.

  19. Characterization of the Electronic Structure of Silicon Nanoparticles Using X-ray Absorption and Emission

    SciTech Connect

    Vaverka, April Susan Montoya

    2008-01-01

    Resolving open questions regarding transport in nanostructures can have a huge impact on a broad range of future technologies such as light harvesting for energy. Silicon has potential to be used in many of these applications. Understanding how the band edges of nanostructures move as a function of size, surface termination and assembly is of fundamental importance in understanding the transport properties of these materials. In this thesis work I have investigated the change in the electronic structure of silicon nanoparticle assemblies as the surface termination is changed. Nanoparticles are synthesized using a thermal evaporation technique and sizes are determined using atomic force microscopy (AFM). By passivating the particles with molecules containing alcohol groups we are able to modify the size dependent band edge shifts. Both the valence and conduction bands are measured using synchrotron based x-ray absorption spectroscopy (XAS) and soft x-ray fluorescence (SXF) techniques. Particles synthesized via recrystallization of amorphous silicon/SiO2 multilayers of thicknesses below 10 nm are also investigated using the synchrotron techniques. These samples also show quantum confinement effects but the electronic structure is different from those synthesized via evaporation methods. The total bandgap is determined for all samples measured. The origins of these differences in the electronic structures are discussed.

  20. Electronic absorption spectroscopy probed side-chain movement in chromic transitions of polydiacetylene vesicles.

    PubMed

    Potisatityuenyong, Anupat; Rojanathanes, Rojrit; Tumcharern, Gamolwan; Sukwattanasinitt, Mongkol

    2008-05-01

    Thermochromism, solvatochromism, and alkalinochromism of a poly-10,12-pentacosadiynoic acid (poly(PCDA)) vesicle solution are studied by electronic absorption spectroscopy. The spectroscopic profiles reveal different sequences of side-chain movement during the chromic transitions. The gradual hypsochromic shift and reversibility of the purple solution at low temperature in the thermochromic transition indicates that the transition starts with reversible conformational alteration of methylene side chains leading to metastable purple vesicles. Further heating to 80 degrees C or higher eventually causes the hydrogen bonds at the carboxylic head groups to break and turns the vesicle solution to red. The irreversibility of the red vesicles indicates that it is the most thermodynamically stable form. In the ethanolochromism and alkalinochromism, the processes are however induced at the vesicle-media interface, directly bringing about the hydrogen bond breaking. The purple solutions observed in the ethanolochromism and alkalinochromism cannot reverse back to the blue one. The absorption spectra clearly demonstrate that they are mixtures of the blue and red vesicles. PMID:18366237

  1. Broadband Transient Absorption and Two-Dimensional Electronic Spectroscopy of Methylene Blue.

    PubMed

    Dean, Jacob C; Rafiq, Shahnawaz; Oblinsky, Daniel G; Cassette, Elsa; Jumper, Chanelle C; Scholes, Gregory D

    2015-08-27

    Broadband transient absorption and two-dimensional electronic spectroscopy (2DES) studies of methylene blue in aqueous solution are reported. By isolating the coherent oscillations of the nonlinear signal amplitude and Fourier transforming with respect to the population time, we analyzed a significant number of coherences in the frequency domain and compared them with predictions of the vibronic spectrum from density function theory (DFT) calculations. We show here that such a comparison enables reliable assignments of vibrational coherences to particular vibrational modes, with their constituent combination bands and overtones also being identified via Franck–Condon analysis aided by DFT. Evaluation of the Fourier transform (FT) spectrum of transient absorption recorded to picosecond population times, in coincidence with 2D oscillation maps that disperse the FT spectrum into the additional excitation axis, is shown to be a complementary approach toward detailed coherence determination. Using the Franck–Condon overlap integrals determined from DFT calculations, we modeled 2D oscillation maps up to two vibrational quanta in the ground and excited state (six-level model), showing agreement with experiment. This semiquantitative analysis is used to interpret the geometry change upon photoexcitation as an expansion of the central sulfur/nitrogen containing ring due to the increased antibonding character in the excited state. PMID:26274093

  2. Attosecond transient absorption probing of electronic superpositions of bound states in neon. Detection of quantum beats

    SciTech Connect

    Beck, Annelise R; Bernhardt, Birgitta; Warrick, Erika R.; Wu, Mengxi; Chen, Shaohao; Gaarde, Mette B.; Schafer, Kenneth J.; Neumark, Daniel M.; Leone, Stephen R.

    2014-11-07

    Electronic wavepackets composed of multiple bound excited states of atomic neon lying between 19.6 and 21.5 eV are launched using an isolated attosecond pulse. Individual quantum beats of the wavepacket are detected by perturbing the induced polarization of the medium with a time-delayed few-femtosecond near-infrared (NIR) pulse via coupling the individual states to multiple neighboring levels. All of the initially excited states are monitored simultaneously in the attosecond transient absorption spectrum, revealing Lorentzian to Fano lineshape spectral changes as well as quantum beats. The most prominent beating of the several that were observed was in the spin–orbit split 3d absorption features, which has a 40 femtosecond period that corresponds to the spin–orbit splitting of 0.1 eV. The few-level models and multilevel calculations confirm that the observed magnitude of oscillation depends strongly on the spectral bandwidth and tuning of the NIR pulse and on the location of possible coupling states.

  3. Change In The Electronic Structure And Optical Absorption Of Cuprate Delafossites Via B-site Alloying

    NASA Astrophysics Data System (ADS)

    Beesley, Ramon; Panapitiya, Gihan; Lewis, James; Lewis Group Team

    Delafossite oxides are a family of materials with the form ABO2 , where the A-site is a monovalent cation (Cu , Ag , Au) and the B-site is a trivalent cation (Ga , Al , In). Delafossites typically have a wide optical band gap, this band gap may be tuned by adding a second B-site element forming an AB(1- x) 1B(x)2O2 alloy. We investigate changes in the electronic structure of CuAlO2 , CuGaO2 , and CuInO2 when alloyed with CuFeO2 . Using the FIREBALL program to optimize the atomic structure, calculate the total and partial density of states, calculate the valence band edge for each alloy level, and investigate the clustering factor of the second B-site atom, it is found that alloying with Fe creates midgap states caused by Fe - O interactions. From the partial density of state, each type of atoms contribution to the change in the valence band edge can be seen. Observed changes to the materials include increased optical absorption in the visible range, and symmetry breaking because of the deformation in the crystal structure. The CuFeO2 alloying percentages range from 0-5%. We are synthesizing these alloys to experimentally verify the changes in the optical absorption spectra.

  4. Electron-cyclotron wave propagation, absorption and current drive in the presence of neoclassical tearing modes

    NASA Astrophysics Data System (ADS)

    Isliker, Heinz; Chatziantonaki, Ioanna; Tsironis, Christos; Vlahos, Loukas

    2012-09-01

    We analyze the propagation of electron-cyclotron waves, their absorption and current drive when neoclassical tearing modes (NTMs), in the form of magnetic islands, are present in a tokamak plasma. So far, the analysis of the wave propagation and power deposition in the presence of NTMs has been performed mainly in the frame of an axisymmetric magnetic field, ignoring any effects from the island topology. Our analysis starts from an axisymmetric magnetic equilibrium, which is perturbed such as to exhibit magnetic islands. In this geometry, we compute the wave evolution with a ray-tracing code, focusing on the effect of the island topology on the efficiency of the absorption and current drive. To increase the precision in the calculation of the power deposition, the standard analytical flux-surface labeling for the island region has been adjusted from the usual cylindrical to toroidal geometry. The propagation up to the O-point is found to be little affected by the island topology, whereas the power absorbed and the driven current are significantly enhanced, because the resonant particles are bound to the small volumes in between the flux surfaces of the island. The consequences of these effects on the NTM evolution are investigated in terms of the modified Rutherford equation.

  5. Electronic Structure and Absorption Properties of Strongly Coupled Porphyrin-Perylene Arrays.

    PubMed

    High, Judah S; Virgil, Kyle A; Jakubikova, Elena

    2015-09-24

    Porphyrin-perylene arrays are ideal candidates for light-harvesting systems capable of panchromatic absorption. In this work, we employ density functional theory (DFT) and time-dependent DFT to investigate the unique UV-vis absorption properties exhibited by a series of ethynyl-linked porphyrin-perylene arrays that were previously synthesized and characterized spectroscopically [Chem. Commun. 2014, 50, 14512-5]. We find that the ethynyl linker is responsible for strong electronic coupling of porphyrin and perylene subunits in these systems. Additionally, these arrays exhibit a low barrier to rotation around the ethynyl linker (<1.4 kcal/mol per one perylene substituent), which results in a wide range of molecular conformations characterized by different porphyrin-perylene dihedral angles being accessible at room temperature. The best match between the calculated and experimental UV-vis spectra is obtained by averaging the calculated UV-vis spectra over the range of conformations defined by the porphyrin-perylene dihedral angles. Finally, our calculations suggest that the transitions in the lower energy region (550-750 nm) can be assigned to the excitations originating from the porphyrin subunit; the mid-energy region transitions (450-550 nm) are assigned to the perylene-centered excitations, while the high-energy transitions (350-450 nm) involve contributions from both porphyrin and perylene subunits. PMID:26322743

  6. Electron cyclotron ray tracing and absorption predictions for Compact Toroidal Hybrid plasmas using TRAVIS

    NASA Astrophysics Data System (ADS)

    Knowlton, S. F.; Hartwell, G. J.; Maurer, D. A.; Marushchenko, N. B.; Turkin, Y.; Bigelow, T.

    2015-11-01

    Plasmas in the Compact Toroidal Hybrid (CTH), a five field period, l = 2 torsatron (B0 = 0 . 5 T R0 = 0 . 75 m, ap ~ 0 . 2 m) will be heated by second harmonic X-mode electron cyclotron heating with power provided by a 28 GHz gyrotron capable of producing up to 200 kW. Ray-tracing calculations that will guide the selection of the launching position, antenna focal length, and beam-steering characteristics are performed with the TRAVIS code. Non-axisymmetric vacuum and current-carrying CTH equilibria for the ray tracing are modeled with the V3FIT code. The calculated absorption is highest for vertically propagating rays that traverse the region where a saddle of resonant field strength exists. However, the absorption for top-launched waves is more sensitive to variations in the magnetic equilibria than for a radial side launch where the magnetic field profile is tokamak-like. This work is supported by U.S. Department of Energy Grant No. DE-FG02-00ER54610.

  7. Electronic absorption spectroscopy of polycyclic aromatic hydrocarbons (PAHs) radical cations generated in oleum: A superacid medium

    NASA Astrophysics Data System (ADS)

    Cataldo, Franco; Iglesias-Groth, Susana; Manchado, Arturo

    2010-12-01

    Oleum (fuming sulphuric acid), a well known superacid, was used as medium for the generation of the radical cation of a series of selected PAHs. The resulting radical cation spectra were studied by electronic absorption spectroscopy. Not only common PAHs like naphthalene, anthracene, tetracene, pentacene, perylene, pyrene, benzo[ a]pyrene, phenanthrene and picene were studied but also the less common and very large PAHs relevant also for the astrochemical research, like coronene, hexabenzocoronene, quaterrylene, dicoronylene and a coronene oligomer. A correlation between the first ionization potential ( IP1) of the PAHs studied and the energy to the so-called A-type band of the radical cations observed in oleum has led to the equation IP1 = 1.30 EA + 4.39 (in eV) which permits to estimate the energy of the PAHs radical cation transition ( EA) in the VIS-NIR knowing the relative ionization potential or vice versa.

  8. The Electronic Absorption Spectrum of Molecular Iodine: A New Fitting Procedure for the Physical Chemistry Laboratory

    NASA Astrophysics Data System (ADS)

    Pursell, Christopher J.; Doezema, Lambert

    1999-06-01

    This paper presents a different approach to the data treatment for the electronic absorption spectrum of molecular iodine, a standard experiment in the undergraduate physical chemistry laboratory. Traditionally, students analyze the transitions originating from the u'' = 0 level using a Birge-Sponer plot and thereby determine the various molecular constants and energies. Our treatment involves simply fitting the transition frequencies to a second-order polynomial. This fit then yields a direct determination of the important molecular constants along with the various energy terms. With the availability of common graphing programs such as Excel, Kaleidagraph, and SigmaPlot, students can take advantage of more advanced fitting techniques and no longer have to rely on simple linear plots. Additionally, students find this new approach more satisfying and we believe it has pedagogical advantages over the Birge-Sponer treatment.

  9. Electronic absorption spectra of protonated pyrene and coronene in neon matrixes.

    PubMed

    Garkusha, Iryna; Fulara, Jan; Sarre, Peter J; Maier, John P

    2011-10-13

    Protonated pyrene and coronene have been isolated in 6 K neon matrixes. The cations were produced in the reaction of the parent aromatics with protonated ethanol in a hot-cathode discharge source, mass selected, and co-deposited with neon. Three electronic transitions of the most stable isomer of protonated pyrene and four of protonated coronene were recorded. The strongest, S(1) ← S(0) transitions, are in the visible region, with onset at 487.5 nm for protonated pyrene and 695.6 nm for protonated coronene. The corresponding neutrals were also observed. The absorptions were assigned on the basis of ab initio coupled-cluster and time-dependent density functional theory calculations. The astrophysical relevance of protonated polycyclic aromatic hydrocarbons is discussed. PMID:21861507

  10. Selective two-photon absorptive resonance femtosecond-laser electronic-excitation tagging velocimetry.

    PubMed

    Jiang, Naibo; Halls, Benjamin R; Stauffer, Hans U; Danehy, Paul M; Gord, James R; Roy, Sukesh

    2016-05-15

    Selective two-photon absorptive resonance femtosecond-laser electronic-excitation tagging (STARFLEET), a nonseeded ultrafast-laser-based velocimetry technique, is demonstrated in reactive and nonreactive flows. STARFLEET is pumped via a two-photon resonance in N2 using 202.25 nm 100 fs light. STARFLEET greatly reduces the per-pulse energy required (30 μJ/pulse) to generate the signature FLEET emission compared to the conventional FLEET technique (1.1 mJ/pulse). This reduction in laser energy results in less energy deposited in the flow, which allows for reduced flow perturbations (reactive and nonreactive), increased thermometric accuracy, and less severe damage to materials. Velocity measurements conducted in a free jet of N2 and in a premixed flame show good agreement with theoretical velocities, and further demonstrate the significantly less intrusive nature of STARFLEET. PMID:27176968

  11. Electronic Structure of Transition Metal-Cysteine Complexes From X-Ray Absorption Spectroscopy

    SciTech Connect

    Leung, B.O.; Jalilehvand, F.; Szilagyi, R.K.

    2009-05-19

    The electronic structures of Hg{sup II}, Ni{sup II}, Cr{sup III}, and Mo{sup V} complexes with cysteine were investigated by sulfur K-edge X-ray absorption near-edge structure (XANES) spectroscopy and density functional theory. The covalency in the metal-sulfur bond was determined by analyzing the intensities of the electric-dipole allowed pre-edge features appearing in the XANES spectra below the ionization threshold. Because of the well-defined structures of the selected cysteine complexes, the current work provides a reference set for further sulfur K-edge XAS studies of bioinorganic active sites with transition metal-sulfur bonds from cysteine residues as well as more complex coordination compounds with thiolate ligands.

  12. A study of coal extraction with electron paramagnetic resonance (EPR) and proton nuclear magnetic resonance relaxation techniques. Quarterly technical progress report, April 1, 1993--June 30, 1993

    SciTech Connect

    Doetschman, D.C.; Mehlenbacher, R.C.; Ito, O.

    1993-09-01

    An electron spin and proton magnetic relaxation study is presented on the effects of the solvent extraction of coal on the macromoleculer network of the coal and on the mobile molecular species that are initially within the coal. The eight Argonne Premium coals were extracted at room temperature with a 1:1 (v/v) N-methylpyrrolidinone (NMP)-CS2 solvent mixture under an inert atmosphere. As much solvent as possible was removed from extract and residue by treatment in a vacuum. The mobilization of molecular free radicals by the solvent and the exposure of free radicals in the macromoleculer matrix to solvent or to species dissolved in the solvent, results in a preferential survival of residue radicals of types that depend on the particular coal and results in the apparently fairly uniform loss of all types of radicals in bituminous coal extracts. The surviving extract and residue free radicals are more predominantly of the odd- alternate hydrocarbon free radical type. The spin-lattice relaxation (SLR) of these coal free radicals has previously been inferred (Doetschman and Dwyer, Energy Fuels, 1992, 6, 783) to be from the modulation of the intramolecular electron-nuclear dipole-interactions of the CH groups in a magnetic field by rocldng motions of the radical in the coal matrix. Such a modulation would depend not only on the rocking amplitude and frequency but also upon the electron spin density at the CH groups in the radical. The observed SLR rates decrease with coal rank in agreement with the smaller spin densities and the lower rocidng amplitudes that are expected for the larger polycondensed ring systems in coals of higher rank. The SLR rates are found to be generally faster in the extracts (than residues) where the molecular species would be expected to have a smaller polycondensed ring system than in the macromoleculer matrix of the residue.

  13. Studies of fullerene absorption and production using an infrared free-electron laser

    SciTech Connect

    Affatigato, M.; Haglund, R.F.; Ying, Z.C.; Compton, R.N.

    1995-12-31

    Tunable photon sources such as free-electron lasers are potentially valuable tools in spectroscopic studies of fullerenes, a new class of carbon materials with unique cage structures. We have used the infrared free-electron-laser facility at Vanderbilt University to study the infrared absorption of gas-phase fullerene molecules and also to investigate the effects of an infrared laser in the synthesis and crystallization of fullerene materials. In one experiment, fullerene vapor was created in a heat pipe through which the FEL beam was passed; the transmission of the FEL beam relative to a reference detector was measured as a function of wavelength. A large (>10%) absorption of the IR laser was observed when it passed through C{sub 60} vapor at {approximately}800{degrees}C. Due to the broad spectral width of the FEL as well as spectral congestion, no spectral peaks were seen when the laser wavelength was tuned across a T{sub 1u}C{sub 60} IR mode near 7.0 {mu}. However, it is expected that the vibrational features can be resolved experimentally by passing the transmitted beam through a monochromator. In a separate experiment, the FEL beam was focused onto a surface of graphite or graphite/metal mixture target. Various fullerene molecules, including endohedral types, were produced when the soot was recovered from the ablation chamber. The yield of the products was measured to be {approximately}0.4 g/J of the incident laser energy. However, both the yield and the product distribution are virtually, the same as those in experiments using a nanosecond Nd:YAG laser. This suggests that the laser wavelength is not a crucial parameter in making fullerenes by laser ablation. Even when the laser is at resonance with one of the vibrational modes of C{sub 60}, the fullerene production is neither substantially enhanced nor suppressed.

  14. Shallow electron traps in alkali halide crystals: Mollwo-Ivey relations of the optical absorption bands

    NASA Astrophysics Data System (ADS)

    Ziraps, Valters

    2001-03-01

    Evidences are given that two classes of the transient IR- absorption bands: (a) with max. at 0.27-0.36 eV in NaCl, KCl, KBr, KI and RbCl (due to shallow electron traps according G. Jacobs or due to bound polarons according E.V. Korovkin and T.A. Lebedkina) and (b) with max. at 0.15-0.36 eV in NaI, NaBr, NaCl:I, KCl:I, RbCl:I and RbBr:I (due to on-center STE localized at iodine dimer according M. Hirai and collaborators) are caused by the same defect- atomic alkali impurity center [M+]c0e- (electron e- trapped by a substitutional smaller size alkali cation impurity [M+]c0). The Mollwo-Ivey plots (for the transient IR-absorption bands) of the zero-phonon line energy E0 (for NaCl, KCl, KBr, RbCl and NaBr, KCl:I) and/or the low-energy edge valued E0 (for NaI, RbCl:I, RbBr:I) versus anion-cation distance (d) evidence that two types of the [M+]c0e- centers are predominant: (a) [Na+]c0e- in the KX and RbX host crystals with the relation E0approximately equals 6.15/d2.74, (b) [Li+]c03- in the NaX host crystals - E0approximately equals 29.4/d4.72. The Mollwo-Ivey relation E0approximately equals 18.36/d(superscript 2.70 is fulfilled as well for the F' band in NaCl, KCl, KBr, KI, RbCl, RbI if we use the F' center optical binding energy values E0.

  15. Spin paramagnetic deformation of a neutron star

    NASA Astrophysics Data System (ADS)

    Suvorov, A. G.; Mastrano, A.; Melatos, A.

    2016-02-01

    Quantum mechanical corrections to the hydromagnetic force balance equation, derived from the microscopic Schrödinger-Pauli theory of quantum plasmas, modify the equilibrium structure and hence the mass quadrupole moment of a neutron star. It is shown here that the dominant effect - spin paramagnetism - is most significant in a magnetar, where one typically has μ _B|B|≳ k_B T_e, where μB is the Bohr magneton, B is the magnetic field, and Te is the electron temperature. The spin paramagnetic deformation of a non-barotropic magnetar with a linked poloidal-toroidal magnetic field is calculated to be up to ˜10 times greater than the deformation caused solely by the Lorentz force. It depends on the degree of Pauli blocking by conduction electrons and the propensity to form magnetic domains, processes which are incompletely modelled at magnetar field strengths. The star becomes more oblate, as the toroidal field component strengthens. The result implies that existing classical predictions underestimate the maximum strength of the gravitational wave signal from rapidly spinning magnetars at birth. Turning the argument around, future gravitational-wave upper limits of increasing sensitivity will place ever-stricter constraints on the physics of Pauli blocking and magnetic domain formation under magnetar conditions.

  16. Study of radical pairs generated by photoreduction of anthraquinone-2,6-disulfonic acid with thymine by Fourier transform electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Geimer, J.; Beckert, D.

    1998-05-01

    Using laser photolysis at 308 nm and FT-EPR, the triplet sensitized electron transfer from thymine to 9,10-anthraquinone-2,6-disulfonate in aqueous solution was studied. The anthraquinone radical anion and the deprotonated thymine-1-yl radical are spin-polarized by the CIDEP triplet mechanism and radical pair mechanism. The structure of the anthraquinone radical anion is strongly influenced by the pH of the solution. In weak acidic solution the radical anion dominates whereas the p K of the radical protonation was determined to be 3.2. The deprotonated thymine-1-yl radical shows two different radical pair polarization patterns which are distinguished by the phase of the polarization. This unusual behavior can be attributed to two different states in the primary radical pair.

  17. Visible light induction of an electron paramagnetic resonance split signal in Photosystem II in the S(2) state reveals the importance of charges in the oxygen-evolving center during catalysis: a unifying model.

    PubMed

    Sjöholm, Johannes; Styring, Stenbjörn; Havelius, Kajsa G V; Ho, Felix M

    2012-03-13

    Cryogenic illumination of Photosystem II (PSII) can lead to the trapping of the metastable radical Y(Z)(•), the radical form of the redox-active tyrosine residue D1-Tyr161 (known as Y(Z)). Magnetic interaction between this radical and the CaMn(4) cluster of PSII gives rise to so-called split electron paramagnetic resonance (EPR) signals with characteristics that are dependent on the S state. We report here the observation and characterization of a split EPR signal that can be directly induced from PSII centers in the S(2) state through visible light illumination at 10 K. We further show that the induction of this split signal takes place via a Mn-centered mechanism, in the same way as when using near-infrared light illumination [Koulougliotis, D., et al. (2003) Biochemistry 42, 3045-3053]. On the basis of interpretations of these results, and in combination with literature data for other split signals induced under a variety of conditions (temperature and light quality), we propose a unified model for the mechanisms of split signal induction across the four S states (S(0), S(1), S(2), and S(3)). At the heart of this model is the stability or instability of the Y(Z)(•)(D1-His190)(+) pair that would be formed during cryogenic oxidation of Y(Z). Furthermore, the model is closely related to the sequence of transfers of protons and electrons from the CaMn(4) cluster during the S cycle and further demonstrates the utility of the split signals in probing the immediate environment of the oxygen-evolving center in PSII. PMID:22352968

  18. Nuclear magnetic resonance characterization of a paramagnetic DNA-drug complex with high spin cobalt; assignment of the 1H and 31P NMR spectra, and determination of electronic, spectroscopic and molecular properties.

    PubMed

    Gochin, M

    1998-08-01

    The proton NMR spectrum of the ternary complex between the octamer duplex d(TTGGCCAA)2, two molecules of the drug chromomycin-A3, and a divalent cobalt ion has been assigned. Assignment procedures used standard two-dimensional techniques and relied upon the expected NOE contacts observed in the equivalent diamagnetic complex containing zinc. The magnetic susceptibility tensor for the cobalt was determined and used to calculate shifts for all nuclei, aiding in the assignment process and verification. Relaxation, susceptibility, temperature and field dependence studies of the paramagnetic spectrum enabled determination of electronic properties of the octahedral cobalt complex. The electronic relaxation tau(s) was determined to be 2.5 +/- 1.5 ps; the effective isotropic g value was found to be 2.6 +/- 0.2, indicating strong spin-orbit coupling. The magnetic susceptibility tensor was determined to be chi(xx) = 8.9 x 10(-3) cm3/mol, chi(yy) = 9.5 x 10(-3) cm3/mol, chi(zz) = 12.8 * 10(-3) cm3/mol. A tentative rotational correlation time of 8 ns was obtained for the complex. Both macroscopic and microscopic susceptibility measurements revealed deviations from Curie behavior over the temperature range accessible in the study. Non-selective relaxation rates were found to be inaccurate for defining distances from the metal center. However, pseudocontact shifts could be calculated with high accuracy using the dipolar shift equation. Isotropic hyperfine shifts were factored into contact and dipolar terms, revealing that the dipolar shift predominates and that contact shifts are relatively small. PMID:9751997

  19. Mössbauer, electron paramagnetic resonance, and magnetic susceptibility studies on members of a new family of cyano-bridged 3d-4f complexes. Demonstration of anisotropic exchange in a Fe-Gd complex.

    PubMed

    Stoian, Sebastian A; Paraschiv, Carmen; Kiritsakas, Nathalie; Lloret, Francesc; Münck, Eckard; Bominaar, Emile L; Andruh, Marius

    2010-04-01

    The synthesis and crystallographic characterization of a new family of M(mu-CN)Ln complexes are reported. Two structural series have been prepared by reacting in water rare earth nitrates (Ln(III) = La, Pr, Nd, Sm, Eu, Gd, Dy, Ho) with K(3)[M(CN)(6)] (M(III) = Fe, Co) in the presence of hexamethylenetetramine (hmt). The first series consists of six isomorphous heterobinuclear complexes, [(CN)(5)M-CN-Ln(H(2)O)(8)].2hmt ([FeLa] 1, [FePr] 2, [FeNd] 3, [FeSm] 4, [FeEu] 5, [FeGd] 6), while the second series consists of four isostructural ionic complexes, [M(CN)(6)][Ln(H(2)O)(8)].hmt ([FeDy] 7, [FeHo] 8, [CoEu] 9, [CoGd] 10). The hexamethylenetetramine molecules contribute to the stabilization of the crystals by participating in an extended network of hydrogen bond interactions. In both series the aqua ligands are hydrogen bonded to the nitrogen atoms from both the terminal CN(-) groups and the hmt molecules. The [FeGd] complex has been analyzed with (57)Fe Mossbauer spectroscopy and magnetic susceptibility measurements. We have also analyzed the [FeLa] complex, in which the paramagnetic Gd(III) is replaced by diamagnetic La(III), with (57)Fe Mossbauer spectroscopy, electron paramagnetic resonance (EPR), and magnetic susceptibility measurements, to obtain information about the low-spin Fe(III) site that is not accessible in the presence of a paramagnetic ion at the complementary site. For the same reason, the [CoGd] complex, containing diamagnetic Co(III), was studied with EPR and magnetic susceptibility measurements, which confirmed the S = 7/2 spin of Gd(III). Prior knowledge about the paramagnetic sites in [FeGd] allows a detailed analysis of the exchange interactions between them. In particular, the question of whether the exchange interaction in [FeGd] is isotropic or anisotropic has been addressed. Standard variable-temperature magnetic susceptibility measurements provide only the value for a linear combination of J(x), J(y), and J(z) but contain no information

  20. Ultra reliable infrared absorption water vapor detection through the all-electronic feedback stabilization

    NASA Astrophysics Data System (ADS)

    Zhu, C. G.; Chang, J.; Wang, P. P.; Wang, Q.; Wei, W.; Tian, J. Q.; Chang, H. T.; Liu, X. Z.; Zhang, S. S.

    2014-03-01

    Single-beam balanced radiometric detection (BRD) system with all-electronic feedback stabilization has been proposed for high reliability water vapor detection under rough environmental conditions, which is insensitive to the fluctuation of transmission loss of light. The majority of photocurrent attenuation caused by the optical loss can be effectively compensated by automatically adjusting the splitting ratio of probe photocurrent. Based on the Ebers-Moll model, we present a theoretical analysis which can be suppressed the photocurrent attenuation caused by optical loss from 0.5552 dB to 0.0004 dB by using the all-electronic feedback stabilization. The deviation of the single-beam BRD system is below 0.29% with the bending loss of 0.31 dB in fiber, which is obviously lower than the dual-beam BRD system (5.96%) and subtraction system (11.3%). After averaging and filtering, the absorption sensitivity of water vapor at 1368.597 nm has been demonstrated, which is 7.368×10-6.

  1. Enhancement of Paramagnetic Relaxation by Photoexcited Gold Nanorods

    PubMed Central

    Wen, Tao; Wamer, Wayne G.; Subczynski, Witold K.; Hou, Shuai; Wu, Xiaochun; Yin, Jun-Jie

    2016-01-01

    Electron spin resonance (ESR) spectroscopy was used to investigate the switchable, light-dependent effects of gold nanorods (GNRs) on paramagnetic properties of nitroxide spin probes. The photoexcited GNRs enhanced the spin-spin and spin-lattice relaxations of nitroxide spin probes. It was shown that molecular oxygen plays the key role in this process. Our results demonstrate that ESR is a powerful tool for investigating the events following photoexcitation of GNRs. The novel light-controlled effects observed for GNRs on paramagnetic properties and activities of surrounding molecules have a number of significant applications where oxygen sensing and oxygen activity is important. PMID:27071507

  2. A study of C-13-enriched chemical vapor deposited diamond film by means of C-13 nuclear magnetic resonance, electron paramagnetic resonance, and dynamic nuclear polarization

    NASA Astrophysics Data System (ADS)

    Lock, Herman; Wind, Robert A.; Maciel, Gary E.; Johnson, Curtis E.

    1993-09-01

    The results are presented of a study, based on EPR and various NMR techniques, of the effect on the nature of CVD diamond films of the addition of O2 to the methane-hydrogen mixture used to produce the film. The addition of oxygen to the feed gas results in a reduction of the number of unpaired electron spins, roughly from 10 exp 18 spins/g up to 10 exp 17 spins/g. There is a small aromatic signal in the dynamic nuclear polarization (DNP)-cross polarization (CP)-magic angle spinning (MAS) C-13 spectrum and a small peak at 28 ppm in the 14 T DP-MAS C-13 spectrum for only the diamond film sample grown without O2 present in the feed gas. The combination of DNP and CP at 1.4 T enables one to obtain a useful DNP-CP-MAS C-13 spectrum, ostensibly probing only the surface and intergrain boundary regions, in a matter of hours.

  3. Constraint on a Cosmological Variation in the Proton-to-electron Mass Ratio from Electronic CO Absorption

    NASA Astrophysics Data System (ADS)

    Daprà, M.; Niu, M. L.; Salumbides, E. J.; Murphy, M. T.; Ubachs, W.

    2016-08-01

    Carbon monoxide (CO) absorption in the sub-damped Lyα absorber at redshift {z}{abs}≃ 2.69 toward the background quasar SDSS J123714.60+064759.5 (J1237+0647) was investigated for the first time in order to search for a possible variation of the proton-to-electron mass ratio, μ, over a cosmological timescale. The observations were performed with the Very Large Telescope/Ultraviolet and Visual Echelle Spectrograph with a signal-to-noise ratio of 40 per 2.5 km s‑1 per pixel at ˜5000 Å. Thirteen CO vibrational bands in this absorber are detected: the {{{A}}}1{{\\Pi }} ‑ {{{X}}}1{{{Σ }}}+ (ν \\prime , 0) for ν \\prime =0{--}8, {{{B}}}1{{{Σ }}}+ ‑ {{{X}}}1{{{Σ }}}+ (0, 0), {{{C}}}1{{{Σ }}}+ ‑ {{{X}}}1{{{Σ }}}+ (0, 0), and {{{E}}}1{{\\Pi }} ‑ {{{X}}}1{{{Σ }}}+ (0, 0) singlet–singlet bands and the {d}3{{Δ }} ‑ {{{X}}}1{{{Σ }}}+ (5, 0) singlet–triplet band. An updated database including the most precise molecular inputs needed for a μ-variation analysis is presented for rotational levels J = 0–5, consisting of transition wavelengths, oscillator strengths, natural lifetime damping parameters, and sensitivity coefficients to a variation of the proton-to-electron mass ratio. A comprehensive fitting method was used to fit all the CO bands at once and an independent constraint of {{Δ }}μ /μ =(0.7+/- {1.6}{stat}+/- {0.5}{syst})× {10}-5 was derived from CO only. A combined analysis using both molecular hydrogen and CO in the same J1237+0647 absorber returned a final constraint on the relative variation of {{Δ }}μ /μ =(-5.6+/- {5.6}{stat}+/- {3.1}{syst})× {10}-6, which is consistent with no variation over a look-back time of ˜11.4 Gyr.

  4. Constraint on a Cosmological Variation in the Proton-to-electron Mass Ratio from Electronic CO Absorption

    NASA Astrophysics Data System (ADS)

    Daprà, M.; Niu, M. L.; Salumbides, E. J.; Murphy, M. T.; Ubachs, W.

    2016-08-01

    Carbon monoxide (CO) absorption in the sub-damped Lyα absorber at redshift {z}{abs}≃ 2.69 toward the background quasar SDSS J123714.60+064759.5 (J1237+0647) was investigated for the first time in order to search for a possible variation of the proton-to-electron mass ratio, μ, over a cosmological timescale. The observations were performed with the Very Large Telescope/Ultraviolet and Visual Echelle Spectrograph with a signal-to-noise ratio of 40 per 2.5 km s‑1 per pixel at ∼5000 Å. Thirteen CO vibrational bands in this absorber are detected: the {{{A}}}1{{\\Pi }} ‑ {{{X}}}1{{{Σ }}}+ (ν \\prime , 0) for ν \\prime =0{--}8, {{{B}}}1{{{Σ }}}+ ‑ {{{X}}}1{{{Σ }}}+ (0, 0), {{{C}}}1{{{Σ }}}+ ‑ {{{X}}}1{{{Σ }}}+ (0, 0), and {{{E}}}1{{\\Pi }} ‑ {{{X}}}1{{{Σ }}}+ (0, 0) singlet–singlet bands and the {d}3{{Δ }} ‑ {{{X}}}1{{{Σ }}}+ (5, 0) singlet–triplet band. An updated database including the most precise molecular inputs needed for a μ-variation analysis is presented for rotational levels J = 0–5, consisting of transition wavelengths, oscillator strengths, natural lifetime damping parameters, and sensitivity coefficients to a variation of the proton-to-electron mass ratio. A comprehensive fitting method was used to fit all the CO bands at once and an independent constraint of {{Δ }}μ /μ =(0.7+/- {1.6}{stat}+/- {0.5}{syst})× {10}-5 was derived from CO only. A combined analysis using both molecular hydrogen and CO in the same J1237+0647 absorber returned a final constraint on the relative variation of {{Δ }}μ /μ =(-5.6+/- {5.6}{stat}+/- {3.1}{syst})× {10}-6, which is consistent with no variation over a look-back time of ∼11.4 Gyr.

  5. Polarized electronic absorption spectra of Cr2SiO4 single crystals

    NASA Astrophysics Data System (ADS)

    Furche, A.; Langer, K.

    Polarized electronic absorption spectra, E∥a(∥X), E∥b(∥Y) and E∥c(∥Z), in the energy range 3000-5000 cm-1 were obtained for the orthorhombic thenardite-type phase Cr2SiO4, unique in its Cr2+-allocation suggesting some metal-metal bonding in Cr2+Cr2+ pairs with Cr-Cr distance 2.75 Å along [001]. The spectra were scanned at 273 and 120 K on single crystal platelets ∥(100), containing optical Y and Z, and ∥(010), containing optical X and Z, with thicknesses 12.3 and 15.6 μm, respectively. Microscope-spectrometric techniques with a spatial resolution of 20 μm and 1 nm spectral resolution were used. The orientations were obtained by means of X-ray precession photographs. The xenomorphic, strongly pleochroic crystal fragments (X deeply greenish-blue, Y faint blue almost colourless, Z deeply purple almost opaque) were extracted from polycrystalline Cr2SiO4, synthesized at 35 kbar, above 1440 °C from high purity Cr2O3, Cr (10% excess) and SiO2 in chromium capsules. The Cr2SiO4-phase was identified by X-ray diffraction (XRD). Four strongly polarized bands, at about 13500 (I), 15700 (II), 18700 (III) and 19700 (IV) cm-1, in the absorption spectra of Cr2SiO4 single crystals show properties (temperature behaviour of linear and integral absorption coefficients, polarization behaviour, molar absorptivities) which are compatible with an assignment to localized spin-allowed transitions of Cr2+ in a distorted square planar coordination of point symmetry C2. The crystal field parameter of Cr2+ is estimated to be 10 Dq =10700 cm-1. A relatively intense, sharp band at 18400 cm-1 and three other minor features can, from their small half widths, be assigned to spin-forbidden dd-transitions of Cr2+. The intensity of such bands strongly decreases on decreasing temperature. The large half widths, near 5000 cm-1 of band III are indicative of some Cr-Cr interactions, i.e. δ-δ* transitions of Cr24+, whereas the latter alone would be in conflict with the strong

  6. Paramagnetism of the Co sublattice in ferromagnetic Zn1-xCoxO films

    NASA Astrophysics Data System (ADS)

    Barla, A.; Schmerber, G.; Beaurepaire, E.; Dinia, A.; Bieber, H.; Colis, S.; Scheurer, F.; Kappler, J.-P.; Imperia, P.; Nolting, F.; Wilhelm, F.; Rogalev, A.; Müller, D.; Grob, J. J.

    2007-09-01

    Using the spectroscopies based on x-ray absorption, we have studied the structural and magnetic properties of Zn1-xCoxO films ( x=0.1 and 0.25) produced by reactive magnetron sputtering. These films show ferromagnetism with a Curie temperature TC above room temperature in bulk magnetization measurements. Our results show that the Co atoms are in a divalent state and in tetrahedral coordination, thus substituting Zn in the wurtzite-type structure of ZnO. However, x-ray magnetic circular dichroism at the CoL2,3 edges reveals that the Co3d sublattice is paramagnetic at all temperatures down to 2K , both at the surface and in the bulk of the films. The Co3d magnetic moment at room temperature is considerably smaller than that inferred from bulk magnetization measurements, suggesting that the Co3d electrons are not directly at the origin of the observed ferromagnetism.

  7. Near Edge X-Ray Absorption Fine Structure Spectroscopy with X-Ray Free-Electron Lasers

    SciTech Connect

    Bernstein, D.P.; Acremann, Y.; Scherz, A.; Burkhardt, M.; Stohr, J.; Beye, M.; Schlotter, W.F.; Beeck, T.; Sorgenfrei, F.; Pietzsch, A.; Wurth, W.; Fohlisch, A.; /Hamburg U.

    2009-12-11

    We demonstrate the feasibility of Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy on solids by means of femtosecond soft x-ray pulses from a free-electron laser (FEL). Our experiments, carried out at the Free-Electron Laser at Hamburg (FLASH), used a special sample geometry, spectrographic energy dispersion, single shot position-sensitive detection and a data normalization procedure that eliminates the severe fluctuations of the incident intensity in space and photon energy. As an example we recorded the {sup 3}D{sub 1} N{sub 4,5}-edge absorption resonance of La{sup 3+}-ions in LaMnO{sub 3}. Our study opens the door for x-ray absorption measurements on future x-ray FEL facilities.

  8. In vivo high-resolution magic angle spinning magnetic and electron paramagnetic resonance spectroscopic analysis of mitochondria-targeted peptide in Drosophila melanogaster with trauma-induced thoracic injury

    PubMed Central

    CONSTANTINOU, CATERINA; APIDIANAKIS, YIORGOS; PSYCHOGIOS, NIKOLAOS; RIGHI, VALERIA; MINDRINOS, MICHAEL N.; KHAN, NADEEM; SWARTZ, HAROLD M.; SZETO, HAZEL H.; TOMPKINS, RONALD G.; RAHME, LAURENCE G.; TZIKA, A. ARIA

    2016-01-01

    Trauma is the most common cause of mortality among individuals aged between 1 and 44 years and the third leading cause of mortality overall in the US. In this study, we examined the effects of trauma on the expression of genes in Drosophila melanogaster, a useful model for investigating genetics and physiology. After trauma was induced by a non-lethal needle puncture of the thorax, we observed the differential expression of genes encoding for mitochondrial uncoupling proteins, as well as those encoding for apoptosis-related and insulin signaling-related proteins, thus indicating muscle functional dysregulation. These results prompted us to examine the link between insulin signaling and mitochondrial dysfunction using in vivo nuclear magnetic resonance (NMR) with complementary electron paramagnetic resonance (EPR) spectroscopy. Trauma significantly increased insulin resistance biomarkers, and the NMR spectral profile of the aged flies with trauma-induced thoracic injury resembled that of insulin-resistant chico mutant flies. In addition, the mitochondrial redox status, as measured by EPR, was significantly altered following trauma, indicating mitochondrial uncoupling. A mitochondria-targeted compound, Szeto-Schiller (SS)-31 that promotes adenosine triphosphate (ATP) synthesis normalized the NMR spectral profile, as well as the mitochondrial redox status of the flies with trauma-induced thoracic injury, as assessed by EPR. Based on these findings, we propose a molecular mechanism responsible for trauma-related mortality and also propose that trauma sequelae in aging are linked to insulin signaling and mitochondrial dysfunction. Our findings further suggest that SS-31 attenuates trauma-associated pathological changes. PMID:26648055

  9. Structural effects of insulin-loading into HII mesophases monitored by electron paramagnetic resonance (EPR), small angle X-ray spectroscopy (SAXS), and attenuated total reflection Fourier transform spectroscopy (ATR-FTIR).

    PubMed

    Mishraki, Tehila; Ottaviani, Maria Francesca; Shames, Alexander I; Aserin, Abraham; Garti, Nissim

    2011-06-30

    Insulin entrapment within a monoolein-based reverse hexagonal (H(II)) mesophase was investigated under temperature-dependent conditions at acidic (pH 3) and basic (pH 8) conditions. Studying the structure of the host H(II) system and the interactions of insulin under temperature-dependent conditions has great impact on the enhancement of its thermal stabilization and controlled release for the purposes of transdermal delivery. Small angle X-ray spectroscopy (SAXS) measurements show that pH variation and/or insulin entrapment preserve the hexagonal structure and do not influence the lattice parameter. Attenuated total reflection Fourier transform spectroscopy (ATR-FTIR) spectra indicate that, although insulin interacts with hydroxyl groups of GMO in the interface region, it is not affected by pH variations. Hence different microenvironments within the H(II) mesophase were monitored by a computer-aided electron paramagnetic resonance (EPR) analysis using 5-doxylstearic acid (5-DSA) as a pH-dependent probe. The microviscosity, micropolarity, order of systems, and distribution of the probes in different microenvironments were influenced by three factors: temperature, pH, and insulin solubilization. When the temperature is increased, microviscosity and order parameters decreased at both pH 3 and 8, presenting different decrease trends. It was found that, at pH 3, the protein perturbs the lipid structure while "pushing aside" the un-ionized 5-DSA probe to fit into the narrow water cylinders. At the interface region (pH 8), the probe was distributed in two differently structured environments that significantly modifies by increasing temperature. Insulin loading within the H(II) mesophase decreased the order and microviscosity of both the microenvironments and increased their micropolarity. Finally, the EPR analysis also provides information about the unfolding/denaturation of insulin within the channel at high temperatures. PMID:21591776

  10. Revealing electronic structure changes in Chevrel phase cathodes upon Mg insertion using X-ray absorption spectroscopy.

    PubMed

    Wan, Liwen F; Wright, Joshua; Perdue, Brian R; Fister, Timothy T; Kim, Soojeong; Apblett, Christopher A; Prendergast, David

    2016-06-29

    Following previous work predicting the electronic response of the Chevrel phase Mo6S8 upon Mg insertion (Thöle et al., Phys. Chem. Chem. Phys., 2015, 17, 22548), we provide the experimental proof, evident in X-ray absorption spectroscopy, to illustrate the charge compensation mechanism of the Chevrel phase compound during Mg insertion and de-insertion processes. PMID:27314253

  11. Barnett effect in paramagnetic states

    NASA Astrophysics Data System (ADS)

    Ono, Masao; Chudo, Hiroyuki; Harii, Kazuya; Okayasu, Satoru; Matsuo, Mamoru; Ieda, Jun'ichi; Takahashi, Ryo; Maekawa, Sadamichi; Saitoh, Eiji

    2015-11-01

    We report the observation of the Barnett effect in paramagnetic states by mechanically rotating gadolinium (Gd) metal with a rotational frequency of up to 1.5 kHz above the Curie temperature. An in situ magnetic measurement setup comprising a high-speed rotational system and a fluxgate magnetic sensor was developed for the measurement. Temperature dependence of the observed magnetization follows that of paramagnetic susceptibility, indicating that any emergent magnetic field is proportional to the rotational frequency and is independent of temperature. From the proportionality constant of the emergent field, the gyromagnetic ratio of Gd is calculated to be -29 ±5 GHz /T . This study revisits the primordial issue of magnetism with modern technologies to shed new light on the fundamental spin-rotation coupling.

  12. X-Band Electron Paramagnetic Resonance Comparison of Mononuclear Mn(IV)-oxo and Mn(IV)-hydroxo Complexes and Quantum Chemical Investigation of Mn(IV) Zero-Field Splitting.

    PubMed

    Leto, Domenick F; Massie, Allyssa A; Colmer, Hannah E; Jackson, Timothy A

    2016-04-01

    X-band electron paramagnetic resonance (EPR) spectroscopy was used to probe the ground-state electronic structures of mononuclear Mn(IV) complexes [Mn(IV)(OH)2(Me2EBC)](2+) and [Mn(IV)(O)(OH)(Me2EBC)](+). These compounds are known to effect C-H bond oxidation reactions by a hydrogen-atom transfer mechanism. They provide an ideal system for comparing Mn(IV)-hydroxo versus Mn(IV)-oxo motifs, as they differ by only a proton. Simulations of 5 K EPR data, along with analysis of variable-temperature EPR signal intensities, allowed for the estimation of ground-state zero-field splitting (ZFS) and (55)Mn hyperfine parameters for both complexes. From this analysis, it was concluded that the Mn(IV)-oxo complex [Mn(IV)(O)(OH)(Me2EBC)](+) has an axial ZFS parameter D (D = +1.2(0.4) cm(-1)) and rhombicity (E/D = 0.22(1)) perturbed relative to the Mn(IV)-hydroxo analogue [Mn(IV)(OH)2(Me2EBC)](2+) (|D| = 0.75(0.25) cm(-1); E/D = 0.15(2)), although the complexes have similar (55)Mn values (a = 7.7 and 7.5 mT, respectively). The ZFS parameters for [Mn(IV)(OH)2(Me2EBC)](2+) were compared with values obtained previously through variable-temperature, variable-field magnetic circular dichroism (VTVH MCD) experiments. While the VTVH MCD analysis can provide a reasonable estimate of the magnitude of D, the E/D values were poorly defined. Using the ZFS parameters reported for these complexes and five other mononuclear Mn(IV) complexes, we employed coupled-perturbed density functional theory (CP-DFT) and complete active space self-consistent field (CASSCF) calculations with second-order n-electron valence-state perturbation theory (NEVPT2) correction, to compare the ability of these two quantum chemical methods for reproducing experimental ZFS parameters for Mn(IV) centers. The CP-DFT approach was found to provide reasonably acceptable values for D, whereas the CASSCF/NEVPT2 method fared worse, considerably overestimating the magnitude of D in several cases. Both methods were poor in

  13. Molecular dynamics in paramagnetic materials as studied by magic-angle spinning 2H NMR spectra.

    PubMed

    Mizuno, Motohiro; Suzuki, You; Endo, Kazunaka; Murakami, Miwa; Tansho, Masataka; Shimizu, Tadashi

    2007-12-20

    A magic-angle spinning (MAS) 2H NMR experiment was applied to study the molecular motion in paramagnetic compounds. The temperature dependences of 2H MAS NMR spectra were measured for paramagnetic [M(H2O)6][SiF6] (M=Ni2+, Mn2+, Co2+) and diamagnetic [Zn(H2O)6][SiF6]. The paramagnetic compounds exhibited an asymmetric line shape in 2H MAS NMR spectra because of the electron-nuclear dipolar coupling. The drastic changes in the shape of spinning sideband patterns and in the line width of spinning sidebands due to the 180 degrees flip of water molecules and the reorientation of [M(H2O)6]2+ about its C3 axis were observed. In the paramagnetic compounds, paramagnetic spin-spin relaxation and anisotropic g-factor result in additional linebroadening of each of the spinning sidebands. The spectral simulation of MAS 2H NMR, including the effects of paramagnetic shift and anisotropic spin-spin relaxation due to electron-nuclear dipolar coupling and anisotropic g-factor, was performed for several molecular motions. Information about molecular motions in the dynamic range of 10(2) s(-1)paramagnetic compounds from the analysis of 2H MAS NMR spectra when these paramagnetic effects are taken into account. PMID:18027914

  14. Probing Warm Dense Matter electronic structure using X-ray absorption Near Edge Spectroscopy (XANES)

    NASA Astrophysics Data System (ADS)

    Benuzzi Mounaix, Alessandra

    2011-06-01

    The behavior and physical properties of warm dense matter, fundamental for various branches of physics including planetology and Inertial Confinement Fusion, are non trivial to simulate either theoretically, numerically or experimentally. Despite important progress obtained in the last decade on macroscopic characterization (e.g. equations of state), microscopic studies are today necessary to investigate finely the WDM structure changes, the phase transitions and to test physical hypothesis and approximations commonly used in calculations. In this work, highly compressed aluminum has been investigated with the aim of bringing information on the evolution of its electronic structure by using K-edge shift and XANES. The experiment was performed at LULI laboratory where we used one long pulse (500 ps, IL ~ 8 1013 W/cm2) to create a uniform shock and a second ps beam (IL ~ 1017 W/cm2) to generate an ultra-short broadband X-ray source near the Al K-edge. The spectra were registered by using two conical KAP Bragg crystals. The main target was designed to probe the Aluminum in reshocked conditions allowing us to probe and to test theories in an extreme regime up to now unexplored (ρ ~ 3 ρ0 and T ~ 8 eV). The hydrodynamical Al conditions were measured by using VISARs interferometers and self-emission diagnostics. By increasing the delay between the two beams, we have been able to observe the modification of absorption spectra for unloading Al conditions (ρ >= 0.5 g/cc), and to put in evidence the relocalization of the 3p valence electrons occurring in the metal-non metal transition. All data have been compared to ab initio and dense plasma calculations.

  15. Theory of the electronic states and absorption spectrum of the LiCl:Ag+ impurity system

    NASA Astrophysics Data System (ADS)

    Jackson, Koblar A.; Lin, Chun C.

    1990-01-01

    The impurity absorption spectra of Ag+ and Cu+ impurities in alkali halide hosts show characteristically different features, despite the similar nature of the corresponding free ions. We use the self-interaction-corrected local-spin-density (SIC-LSD) theory to calculate the electronic structure of the ground state (4d) and the 5s and 5p excited states of the LiCl:Ag+ impurity ion. The method of linear combinations of atomic orbitals is used to determine the wave functions and energy levels. By comparing with previous calculations for LiCl:Cu+, we are able to attribute the differences in the d-->s and d-->p transitions in the ultraviolet spectra of these systems to the increased bonding between host crystal and impurity orbitals in LiCl:Ag+, due to the more extensive nature of the Ag+ 4d orbitals. A modification of the earlier SIC-LSD impurity-crystal procedure is introduced to treat the strongly mixed impurity states.

  16. Electronic structures of silicon monoxide film probed by X-ray absorption spectroscopy

    NASA Astrophysics Data System (ADS)

    Baba, Yuji; Sekiguchi, Tetsuhiro; Shimoyama, Iwao; Hirao, Norie

    2013-06-01

    Electronic structures of thin films of silicon monoxides (SiO) deposited on a solid surface have been in-situ investigated by X-ray photoelectron spectroscopy (XPS) and X-ray absorption fine structure (XAFS). As a substrate, a highly oriented pyrolytic graphite (HOPG) was used because the hybridization between molecules and substrate can be excluded due to the inertness of the surface. For thin films with less than monolayer, XPS spectrum showed that the binding energy of the Si 1s is located just between those of the elemental silicon (Si0) and SiO2 (Si4 +). The result indicates that the stable divalent silicon surely exists in the deposited SiO layer. For the Si K-edge XAFS spectrum of the SiO thin film, the energy of the core-to-valence resonance peak is also located between those of the elemental silicon (Si0) and SiO2 (Si4 +). The polarization dependence of the Si K-edge XAFS spectra for the SiO film revealed that the SiO molecules are well-ordered and almost perpendicularly oriented on HOPG surface. The XAFS results also support the existence of the silicon divalent states in the deposited SiO films. The obtained well-ordered SiO films with divalent silicon will become an excellent starting material for the synthesis of low-dimensional SiOx films.

  17. Attosecond transient absorption probing of electronic superpositions of bound states in neon. Detection of quantum beats

    DOE PAGESBeta

    Beck, Annelise R; Bernhardt, Birgitta; Warrick, Erika R.; Wu, Mengxi; Chen, Shaohao; Gaarde, Mette B.; Schafer, Kenneth J.; Neumark, Daniel M.; Leone, Stephen R.

    2014-11-07

    Electronic wavepackets composed of multiple bound excited states of atomic neon lying between 19.6 and 21.5 eV are launched using an isolated attosecond pulse. Individual quantum beats of the wavepacket are detected by perturbing the induced polarization of the medium with a time-delayed few-femtosecond near-infrared (NIR) pulse via coupling the individual states to multiple neighboring levels. All of the initially excited states are monitored simultaneously in the attosecond transient absorption spectrum, revealing Lorentzian to Fano lineshape spectral changes as well as quantum beats. The most prominent beating of the several that were observed was in the spin–orbit split 3d absorptionmore » features, which has a 40 femtosecond period that corresponds to the spin–orbit splitting of 0.1 eV. The few-level models and multilevel calculations confirm that the observed magnitude of oscillation depends strongly on the spectral bandwidth and tuning of the NIR pulse and on the location of possible coupling states.« less

  18. Electronic absorption spectra of U3+ and U4+ in molten LiCl-RbCl eutectic

    NASA Astrophysics Data System (ADS)

    Nagai, T.; Uehara, A.; Fujii, T.; Sato, N.; Yamana, H.

    2010-03-01

    In the non-aqueous reprocessing process of spent nuclear fuels by the pyro-electrochemical method, a spent fuel is dissolved into molten LiCl-KCl and NaCl-CsCl eutectics and dissolved uranium and plutonium are collected as either metal or oxide. However, the binary alkali chloride mixture with the lowest melting point is the LiCl-RbCl eutectic. In this study, electronic absorption spectra of U3+ and U4+ in molten LiCl-RbCl eutectic at various temperatures between 673 and 973 K were measured by the UV/Vis/NIR spectrophotometry. We confirmed that these spectra were similar to those in molten LiCl-KCl and NaCl-CsCl eutectics. The sensitive absorption bands of U4+ in LiCl-RbCl eutectic were found at 22000, 16500, 14900, 8600, and 4950 cm-1. The large absorption bands of U4+ over 25000 cm-1 increased with increasing melt temperature, while absorption peaks at 15500-4000 cm-1 decreased. The large absorption bands of U3+ in LiCl-RbCl eutectic were observed over 14000 cm-1. The sensitive absorption bands of U3+ at Vis/NIR region were found at 13300, 11500-11200, 9800-9400, and 8250 cm-1, and these peaks decreased with increasing temperature.

  19. Tunable Microwave Absorption Frequency by Aspect Ratio of Hollow Polydopamine@α-MnO2 Microspindles Studied by Electron Holography.

    PubMed

    She, Wen; Bi, Han; Wen, Zhiwei; Liu, Qinghe; Zhao, Xuebing; Zhang, Jie; Che, Renchao

    2016-04-20

    A tunable response frequency is highly desirable for practical applications of microwave absorption materials but remains a great challenge. Here, hollow lightweight polydopamine@α-MnO2 microspindles were facilely synthesized with the tunable absorption frequency governed by the aspect ratio. The size of the hard template is a key factor to achieve the unique shape; the polymer layer with uniform thickness plays an important role in obtaining spindles with homogeneous size. With the aspect ratio increasing, the maximum reflection loss, as well as the absorption bandwidth (<-10 dB), increases and then decreases; meanwhile, the microwave absorption band shifts to the low frequency. The optimized aspect ratio of the cavity about the hollow polydopamine@α-MnO2 microspindles is ∼2.8. With 3 mm thickness at 9.7 GHz, the strongest reflection reaches -21.8 dB, and the width of the absorbing band (<-10 dB) is as wide as 3.3 GHz. Via electron holography, it is confirmed that strong charge accumulates around the interface between the polydopamine and α-MnO2 layers, which mainly contributes to the dielectric polarization absorption. This study proposes a reliable strategy to tune the absorption frequency via different aspect ratio polymer@α-MnO2 microspindles. PMID:27027922

  20. Evidence for strong electron correlations in graphene molecular fragments: Theory and experiments on two-photon absorptions

    NASA Astrophysics Data System (ADS)

    Aryanpour, Karan; Roberts, Adam; Sandhu, Arvinder; Shukla, Alok; Mazumdar, Sumit

    2013-03-01

    Historically, the occurrence of the lowest two-photon state below the optical one-photon state in linear polyenes, polyacetylenes and polydiacetylenes provided the strongest evidence for strong electron correlations in these linear π-conjugated systems. We demonstrate similar behavior in several molecular fragments of graphene with D6 h symmetry, theoretically and experimentally. Theoretically, we have calculated one versus two-photon absorptions in coronene, two different hexabenzocoronenes and circumcoronene, within the Pariser-Parr-Pople π-electron Hamiltonian using high order configuration interaction. Experimentally, we have performed z-scan measurements using a white light super-continuum source on coronene and hexa-peri-hexabenzocoronene to determine frequency-dependent two-photon absorption coefficients, for comparison to the ground state absorptions. Excellent agreement between experiment and theory in our work gives strong evidence for significant electron correlations between the π-electrons in the graphene molecular fragments. We particularly benchmark high order electron-hole excitations in graphene fragments as a key element behind the agreement between theory and experiment in this work. We acknowledge NSF-CHE-1151475 grant as our funding source.