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Sample records for advanced paramagnetic resonance

  1. 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

  2. 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.

  3. Responses of Mn2+ speciation in Deinococcus radiodurans and Escherichia coli to γ-radiation by advanced paramagnetic resonance methods.

    PubMed

    Sharma, Ajay; Gaidamakova, Elena K; Matrosova, Vera Y; Bennett, Brian; Daly, Michael J; Hoffman, Brian M

    2013-04-09

    The remarkable ability of bacterium Deinococcus radiodurans to survive extreme doses of γ-rays (12,000 Gy), 20 times greater than Escherichia coli, is undiminished by loss of Mn-dependent superoxide dismutase (SodA). D. radiodurans radiation resistance is attributed to the accumulation of low-molecular-weight (LMW) "antioxidant" Mn(2+)-metabolite complexes that protect essential enzymes from oxidative damage. However, in vivo information about such complexes within D. radiodurans cells is lacking, and the idea that they can supplant reactive-oxygen-species (ROS)-scavenging enzymes remains controversial. In this report, measurements by advanced paramagnetic resonance techniques [electron-spin-echo (ESE)-EPR/electron nuclear double resonance/ESE envelope modulation (ESEEM)] reveal differential details of the in vivo Mn(2+) speciation in D. radiodurans and E. coli cells and their responses to 10 kGy γ-irradiation. The Mn(2+) of D. radiodurans exists predominantly as LMW complexes with nitrogenous metabolites and orthophosphate, with negligible EPR signal from Mn(2+) of SodA. Thus, the extreme radiation resistance of D. radiodurans cells cannot be attributed to SodA. Correspondingly, 10 kGy irradiation causes no change in D. radiodurans Mn(2+) speciation, despite the paucity of holo-SodA. In contrast, the EPR signal of E. coli is dominated by signals from low-symmetry enzyme sites such as that of SodA, with a minority pool of LMW Mn(2+) complexes that show negligible coordination by nitrogenous metabolites. Nonetheless, irradiation of E. coli majorly changes LMW Mn(2+) speciation, with extensive binding of nitrogenous ligands created by irradiation. We infer that E. coli is highly susceptible to radiation-induced ROS because it lacks an adequate supply of LMW Mn antioxidants.

  4. In-situ electron paramagnetic resonance studies of paramagnetic point defects in superconducting microwave resonators

    NASA Astrophysics Data System (ADS)

    Zhang, Shengke; Kopas, Cameron; Wagner, Brian; Queen, Daniel; Newman, N.

    2016-09-01

    The physical nature and concentration of paramagnetic point defects in the dielectrics of superconducting planar microwave resonators have been determined using in-situ electron paramagnetic resonance spectroscopy. To perform this work, the quality factor of parallel plate and stripline resonators was measured as a function of the magnitude of a magnetic-field applied parallel to the electrode surfaces. YBa2Cu3O7-δ thin film electrodes proved to be a preferred choice over Nb and MgB2 because they are readily available and have a small surface resistance (Rs) up to high temperatures (˜77 K) and magnetic fields (i.e., <1 T). Stripline resonators with a widely used high performance microwave dielectric, Co2+-doped Ba(Zn1/3Nb2/3)O3, are shown to have losses dominated by d-electron spin-excitations in exchange-coupled Co2+ point-defect clusters, even in the absence of an applied magnetic field. A significant enhanced microwave loss in stripline and parallel plate resonators is found to correlate with the presence of paramagnetic Mn2+ dopants in Ba(Zn1/3Ta2/3)O3 ceramics and dangling bond states in amorphous Si thin films, although the identification of the dominant loss mechanism(s) in these dielectrics requires further investigation.

  5. 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.

  6. 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.

  7. Application of Electron Paramagnetic Resonance to Study of Gallstones

    NASA Astrophysics Data System (ADS)

    Kiselev, S. A.; Tsyro, L. V.; Afanasiev, D. A.; Unger, F. G.; Soloviev, M. M.

    2014-03-01

    We present the results of an electron paramagnetic resonance (EPR) study of mixed cholesterol gallstones. We have established that free radicals are distributed nonuniformly within the interior of the stone. The type and number of paramagnetic centers depend on the pigment content in the selected layer. We show that the parameters of the sextet lines in the EPR spectrum of the pigment are close to the parameters of lines in the spectrum of a brown pigment stone.

  8. Electron paramagnetic resonance studies in neutron-irradiated silicon

    NASA Astrophysics Data System (ADS)

    Corbett, James W.; Kleinhenz, Richard L.; En, Wu; Zhi-pu, You

    1982-08-01

    Electron paramagnetic resonance studies of neutron-irradiated silicon are surveyed, both as being of interest per se and as related to transmutation doping. The emerging panorama progressing from vacancy- and interstitial-related point defects to agglomerates visible in the electron microscope is described. Intrinsic and impurity-driven partial dissociation of defect complexes is discussed.

  9. 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…

  10. 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.

  11. A point about electron paramagnetic resonance detection of irradiated foodstuffs

    NASA Astrophysics Data System (ADS)

    Douifi, Leila; Raffi, Jacques; Stocker, Pierre; Dole, François

    1998-12-01

    This paper makes a point about the identification of irradiated foodstuffs by means of electron paramagnetic resonance (EPR) or electron spin resonance (ESR). EPR is the most accurate method for such routine applications since radicals are stabilised for a long time in all (or part of) foods that are in solid and dry states; consequently, EPR can be applied to meat and fish bones, fruit and relative products (from vegetal origin). More details are given for mollusc shells, such as oysters and mussels.

  12. 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

    2015-03-04

    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.

  13. Magnetic resonance force microscopy with a paramagnetic probe

    NASA Astrophysics Data System (ADS)

    Berman, G. P.; Gorshkov, V. N.; Tsifrinovich, V. I.

    2017-04-01

    We consider theoretically extension of magnetic resonance force microscopy (MRFM) replacing a ferromagnetic probe on a cantilever tip (CT) with a paramagnetic one (PMRFM). The dynamics of the interaction between the paramagnetic probe and a local magnetic moment in a sample is analyzed, using a quasi-classical approach. We show that the application of a proper sequence of electromagnetic pulses provides a significant deflection of the CT from the initial equilibrium position. Periodic application of these sequences of pulses results in quasi-periodic CT deflections from the equilibrium, which can be used for detection of the magnetic moment in a sample.

  14. Magnetic resonance force microscopy with a paramagnetic probe

    DOE PAGES

    Berman, G. P.; Gorshkov, V. N.; Tsifrinovich, V. I.

    2017-04-01

    Here, we consider theoretically extension of magnetic resonance force microscopy (MRFM) replacing a ferromagnetic probe on a cantilever tip (CT) with a paramagnetic one (PMRFM). The dynamics of the interaction between the paramagnetic probe and a local magnetic moment in a sample is analyzed, using a quasi-classical approach. We show that the application of a proper sequence of electromagnetic pulses provides a significant deflection of the CT from the initial equilibrium position. Periodic application of these sequences of pulses results in quasi-periodic CT deflections from the equilibrium, which can be used for detection of the magnetic moment in a sample.

  15. Cut and paste RNA for nuclear magnetic resonance, paramagnetic resonance enhancement, and electron paramagnetic resonance structural studies.

    PubMed

    Duss, Olivier; Diarra Dit Konté, Nana; Allain, Frédéric H-T

    2015-01-01

    RNA is a crucial regulator involved in most molecular processes of life. Understanding its function at the molecular level requires high-resolution structural information. However, the dynamic nature of RNA complicates structure determination because crystallization is often not possible or can result in crystal-packing artifacts resulting in nonnative structures. To study RNA and its complexes in solution, we described an approach in which large multi-domain RNA or protein-RNA complex structures can be determined at high resolution from isolated domains determined by nuclear magnetic resonance (NMR) spectroscopy, and then constructing the entire macromolecular structure using electron paramagnetic resonance (EPR) long-range distance constraints. Every step in this structure determination approach requires different types of isotope or spin-labeled RNAs. Here, we present a simple modular RNA cut and paste approach including protocols to generate (1) small isotopically labeled RNAs (<10 nucleotides) for NMR structural studies, which cannot be obtained by standard protocols, (2) large segmentally isotope and/or spin-labeled RNAs for diamagnetic NMR and paramagnetic relaxation enhancement NMR, and (3) large spin-labeled RNAs for pulse EPR spectroscopy.

  16. Detection of nitric oxide by electron paramagnetic resonance spectroscopy.

    PubMed

    Hogg, Neil

    2010-07-15

    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 of detecting this species by EPR are somewhat different from those of 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.

  17. Luminescence, electron paramagnetic resonance, and optical properties of lunar material.

    PubMed

    Geake, J E; Dollfus, A; Garlick, G F; Lamb, W; Walker, C; Steigmann, G A; Titulaer, C

    1970-01-30

    Dust samples have been found to luminesce weakly under proton excitation, but not under ultraviolet. Damage, recovery, and heating effects have been investigated. Chips of breccia show luminescence, from white inclusions only, under ultraviolet and protons. Some rock chips show general luminescence, mainly from plagioclase. No natural or excited thermoluminescence has been found for dust or chips. The electron paramagnetic resonance spectrum shows the same broad Fe(3+) dipole resonance for dust and for some chips; other chips show no response. The polarization characteristics of dust are found to be identical to those of the Sea of Tranquillity, independently of proton damage. Chips show characteristics unlike any part of the lunar surface.

  18. 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

  19. Electron Paramagnetic Resonance Imaging and Spectroscopy of Polydopamine Radicals.

    PubMed

    Mrówczyński, Radosław; Coy, L Emerson; Scheibe, Błażej; Czechowski, Tomasz; Augustyniak-Jabłokow, Maria; Jurga, Stefan; Tadyszak, Krzysztof

    2015-08-13

    A thorough investigation of biomimetic polydopamine (PDA) by Electron Paramagnetic Resonance (EPR) is shown. In addition, temperature dependent spectroscopic EPR data are presented in the range 3.8-300 K. Small discrepancies in magnetic susceptibility behavior are observed between previously reported melanin samples. These variations were attributed to thermally acitivated processes. More importantly, EPR spatial-spatial 2D imaging of polydopamine radicals on a phantom is presented for the first time. In consequence, a new possible application of polydopamine as EPR imagining marker is addressed.

  20. Multifrequency electron paramagnetic resonance study on deproteinized human bone

    NASA Astrophysics Data System (ADS)

    Strzelczak, Grażyna; Sadło, Jarosław; Danilczuk, Marek; Stachowicz, Wacław; Callens, Freddy; Vanhaelewyn, Gauthier; Goovaerts, Etienne; Michalik, Jacek

    2007-08-01

    Irradiated samples of deproteinized powdered human bone ( femur) have been examined by electron paramagnetic resonance (EPR) spectroscopy in X, Q and W bands. In the bone powder sample only one type of CO 2- radical ion is stabilized in the hydroxyapatite structure in contrast to powdered human tooth enamel, a material also containing hydroxyapatite, widely used for EPR dosimetry and in which a few radicals are stable at room temperature. It is suggested that the use of deproteinized bone for EPR dosimetry could improve the accuracy of dose determination.

  1. 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.

  2. 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.

  3. Electron paramagnetic resonance calculations for hydrogenated Si surfaces

    NASA Astrophysics Data System (ADS)

    Rohrmüller, M.; Schmidt, W. G.; Gerstmann, U.

    2017-03-01

    Electron paramagnetic resonance (EPR) signatures, more specifically the elements of the electronic g tensor, are calculated within density functional theory for hydrogenated Si(111), Si(001), Si(113), Si(114), Si (11 2 ¯) , and Si(110) surfaces. Thereby both perturbation theory and a more sophisticated Berry phase technique are applied. Specific defects on different surface orientations are shown to reproduce the resonances at g ¯=2.0043 and g ¯=2.0052 measured for hydrogenated microcrystalline silicon: The latter value is argued here to originate from regions with low hydrogen coverage; the resonance at g ¯=2.0043 is shown to appear in positions with dihydride environment, where an H atom is directly bound to the silicon dangling-bond atoms. A third group of EPR signals with considerably larger g ¯ values between 2.006 and 2.009 is predicted for highly symmetric dangling bonds resembling single dangling-bond defects in silicon bulk material. As the exact value depends strongly on local strain, this type of defect can explain a less intense signal with large g strain observed in microcrystalline as well as in amorphous material.

  4. 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.

  5. 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.

  6. Effects of water on fingernail electron paramagnetic resonance dosimetry

    PubMed Central

    Zhang, Tengda; Zhao, Zhixin; Zhang, Haiying; Zhai, Hezheng; Ruan, Shuzhou; Jiao, Ling; Zhang, Wenyi

    2016-01-01

    Electron paramagnetic resonance (EPR) is a promising biodosimetric method, and fingernails are sensitive biomaterials to ionizing radiation. Therefore, kinetic energy released per unit mass (kerma) can be estimated by measuring the level of free radicals within fingernails, using EPR. However, to date this dosimetry has been deficient and insufficiently accurate. In the sampling processes and measurements, water plays a significant role. This paper discusses many effects of water on fingernail EPR dosimetry, including disturbance to EPR measurements and two different effects on the production of free radicals. Water that is unable to contact free radicals can promote the production of free radicals due to indirect ionizing effects. Therefore, varying water content within fingernails can lead to varying growth rates in the free radical concentration after irradiation—these two variables have a linear relationship, with a slope of 1.8143. Thus, EPR dosimetry needs to be adjusted according to the water content of the fingernails of an individual. When the free radicals are exposed to water, the eliminating effect will appear. Therefore, soaking fingernail pieces in water before irradiation, as many researchers have previously done, can cause estimation errors. In addition, nails need to be dehydrated before making accurately quantitative EPR measurements. PMID:27342838

  7. 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

  8. Identification of irradiated cashew nut by electron paramagnetic resonance spectroscopy.

    PubMed

    Sanyal, Bhaskar; Sajilata, M G; Chatterjee, Suchandra; Singhal, Rekha S; Variyar, Prasad S; Kamat, M Y; Sharma, Arun

    2008-10-08

    Cashew nut samples were irradiated at gamma-radiation doses of 0.25, 0.5, 0.75, and 1 kGy, the permissible dose range for insect disinfestation of food commodities. A weak and short-lived triplet (g = 2.004 and hfcc = 30 G) along with an anisotropic signal (g perpendicular = 2.0069 and g parallel = 2.000) were produced immediately after irradiation. These signals were assigned to that of cellulose and CO 2 (-) radicals. However, the irradiated samples showed a dose-dependent increase of the central line (g = 2.0045 +/- 0.0002). The nature of the free radicals formed during conventional processing such as thermal treatment was investigated and showed an increase in intensity of the central line (g = 2.0045) similar to that of irradiation. Characteristics of the free radicals were studied by their relaxation and thermal behaviors. The present work explores the possibility to identify irradiated cashew nuts from nonirradiated ones by the thermal behaviors of the radicals beyond the period, when the characteristic electron paramagnetic resonance spectral lines of the cellulose free radicals have essentially disappeared. In addition, this study for the first time reports that relaxation behavior of the radicals could be a useful tool to distinguish between roasted and irradiated cashew nuts.

  9. Electron Paramagnetic Resonance in II-Vi Semiconductor Heterostructures

    NASA Astrophysics Data System (ADS)

    Yang, Gui-Lin

    This dissertation is devoted to investigation of the electron paramagnetic resonance (EPR) of Mn ^{++} ions in II-VI semiconductor heterostructures, in order to determine how EPR is affected by this layered environment and what new information can be extracted by this technique. We first introduce the concept of the effective spin, and we review the theoretical background of the spin Hamiltonian, for describing the ground state of a paramagnetic ion in a solid. The physical origin of the constituent terms in the spin Hamiltonion are discussed, and their characteristics described, for use at later stages in the thesis. We then analyze the effect on EPR of the potential exchange interaction between the localized d-electrons of the Mn^{++} ions and the band electrons. We predict that such exchange interaction can lead to significant changes in the g-factors of Mn ^{++} ions due to the spin polarization of band electrons, resulting in line shifts of EPR spectra. Although such shifts would be too small to be observed for Mn^{++} ions introduced into bulk semiconductors, we show that the shifts can be significantly larger for Mn^ {++} ions in quantum wells, superlattices, and similar heterostructures, due to the electron confinement effect. This effect of the potential exchange interaction on the EPR spectra of Mn^{++} ions leads us to propose to use the Mn ^{++} ions as built-in localized probes for mapping the wave functions of electronic states in II-VI semiconductor quantum wells and superlattices. We then consider the influence of internal strain on the EPR transitions of Mn^{++} in II-VI semiconductor heterostructures. Our analysis of the changes of the Mn^{++} fine structure indicates that EPR can be used to detect even minute amounts of strain (e.g., strain resulting from as little as 0.01% lattice mismatch can readily be measured). Accordingly, we demonstrate EPR to be an ultrasensitive and probably unique tool for small strain measurements in II

  10. 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:...

  11. Retrospective Reconstruction of Radiation Doses of Chernobyl Liquidators by Electron Paramagnetic Resonance

    DTIC Science & Technology

    1997-12-01

    Armed Forces Rad I Research Institute Retrospective Reconstruction of Radiation Doses of Chernobyl Liquidators by Electron Paramagnetic Resonance A...of Radiation Doses of Chernobyl Liquidators by Electron Paramagnetic Resonance Authored by Scientific Center of Radiation Medicine Academy of Medical...libraries associated with the U.S. Government’s Depository Library System. Preface On April 26, 1986, Reactor #4 at the Chernobyl Nuclear Power Plant near

  12. Electronic paramagnetic resonance power saturation of wooden samples

    NASA Astrophysics Data System (ADS)

    Brai, Maria; Longo, Anna; Maccotta, Antonella; Marrale, Maurizio

    2009-05-01

    The deterioration of wood used for artifacts of artistic interest involves the production of different free radicals from the macromolecules of the wooden matrix (cellulose, lignin, and hemicellulose). Among the techniques able to provide information about these free radicals, the contribution of electronic paramagnetic resonance (EPR) can be very valuable. In this paper, the study of EPR signals (with g ≈2) of both modern and ancient wooden taxa was undertaken in order to analyze some features of the free radicals in natural wood. In particular, we have studied the microwave power saturation behaviors of seasoned wooden samples from ten species, and we have found remarkable differences between softwoods and hardwoods. These differences can be correlated to dissimilarities in the relaxation times T1 and T2 attributable to the different microscopic structures of the two trees' categories. The method has been also applied to ancient woods belonging to works of art in order to assess the conservation state of these artifacts. The analysis of the saturation curves has been found to be sensitive to the wood decay state. Indeed the deterioration process of the wooden matrix involves a variation of the relaxation times; this could be ascribed to both possible structure modifications and to concentration increments of the free radicals inside ancient woods due to decay induced by natural (biological, chemical, and physical) agents. This analysis method seems to be promising for the characterization of the wooden decay state and, therefore, it could provide valuable diagnostic indications which are necessary for the restoration and conservation of many artifact of historical-artistic-archaeological interest.

  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. 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).

  15. Paramagnetic resonance studies of defects in titanium dioxide crystals

    NASA Astrophysics Data System (ADS)

    Yang, Shan

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to identify and characterize point defects in TiO2 crystals having the rutile structure. Defect production occurs at low temperature during illumination with 442 nm laser light. Spectra with S = 1/2 and S = 1 are assigned to singly ionized and neutral oxygen vacancies, respectively. These oxygen vacancies have their unpaired spins localized on the two neighboring titanium ions aligned along the [001] axis. A Ti3+ ion next to a substitutional Si4+ ion, a Ti3+ self-trapped electron, and a self-trapped hole on the oxygen sublattice are also observed. Fluorine ions substitute for oxygen and are present as unintentional impurities in TiO2 crystals. Isolated singly ionized fluorine donors in an as-grown (fully oxidized) crystal convert to their neutral charge state during exposure to 442 nm laser light at 6 K. These donors return to the singly ionized charge state within a few seconds when the light is removed. In contrast, the neutral fluorine donors are observed at 6 K without photoexcitation after a crystal is reduced at 600 ºC in flowing nitrogen gas. The angular dependences of the EPR and ENDOR spectra provide a complete set of spin-Hamiltonian parameters (principal values are 1.9746, 1.9782, and 1.9430 for the g matrix and -0.23, 0.47, and 5.15 MHz for the 19F hyperfine matrix). These matrices suggest that the unpaired electron is localized primarily on one of the two equivalent neighboring substitutional titanium ions, i.e., the ground state of the neutral fluorine donor in rutile-structured TiO2 is a Ti 3+ ion adjacent to a F- ion. Hydrogen, in the form of an OH- ion, is a shallow donor in TiO2. In the neutral charge state, the unpaired electron forms an adjacent Ti3+ ion. The hydrogen EPR signal cannot be produced in oxidized crystals containing fluorine donors, which suggest that hydrogen is a shallower donor than fluorine in TiO2 (rutile) crystals. The hydrogen EPR

  16. High-frequency microstrip cross resonators for circular polarization electron paramagnetic resonance spectroscopy.

    PubMed

    Henderson, J J; Ramsey, C M; Quddusi, H M; del Barco, E

    2008-07-01

    In this article we discuss the design and implementation of a novel microstrip resonator which allows absolute control of the microwaves polarization degree for frequencies up to 30 GHz. The sensor is composed of two half-wavelength microstrip line resonators, designed to match the 50 Omega impedance of the lines on a high dielectric constant GaAs substrate. The line resonators cross each other perpendicularly through their centers, forming a cross. Microstrip feed lines are coupled through small gaps to three arms of the cross to connect the resonator to the excitation ports. The control of the relative magnitude and phase between the two microwave stimuli at the input ports of each line allows for tuning the degree and type of polarization of the microwave excitation at the center of the cross resonator. The third (output) port is used to measure the transmitted signal, which is crucial to work at low temperatures, where reflections along lengthy coaxial lines mask the signal reflected by the resonator. Electron paramagnetic resonance spectra recorded at low temperature in an S=5/2 molecular magnet system show that 82% fidelity circular polarization of the microwaves is achieved over the central area of the resonator.

  17. Connecting lipoxygenase function to structure by electron paramagnetic resonance.

    PubMed

    Gaffney, Betty J

    2014-12-16

    CONSPECTUS: Lipoxygenase enzymes insert oxygen in a polyunsaturated lipid, yielding a hydroperoxide product. When the acyl chain is arachidonate, with three cis-pentadiene units, 12 positionally and stereochemically different products might result. The plant lipids, linoleate and linolenate, have, respectively, four and eight potential oxygen insertion sites. The puzzle of how specificity is achieved in these reactions grows as more and more protein structures confirm the conservation of a lipoxygenase protein fold in plants, animals, and bacteria. Lipoxygenases are large enough (60-100 kDa) that they provide a protein shell completely surrounding an active site cavity that has the shape of a long acyl chain and contains a catalytic metal (usually iron). This Account summarizes electron paramagnetic resonance (EPR) spectroscopic, and other, experiments designed to bridge the gap between lipid-lipoxygenase interactions in solution and crystal structures. Experiments with spin-labeled lipids give a picture of bound lipids tethered to protein by an acyl chain, but with a polar end emerging from the cavity to solvent exposure, where the headgroup is highly flexible. The location of a spin on the polar end of a lysolecithin was determined by pulsed, dipolar EPR measurements, by representing the protein structure as a five-point grid of spin-labels with coordinates derived from 10 distance determinations between spin pairs. Distances from the lipid spin to each grid site completed a six-point representation of the enzyme with a bound lipid. Insight into the dynamics that allow substrate/product to enter/exit the cavity was obtained with a different set of spin-labeled protein mutants. Once substrate enters the cavity, the rate-limiting step of catalysis involves redox cycling at the metal center. Here, a mononuclear iron cycles between ferric and ferrous (high-spin) forms. Two helices provide pairs of side-chain ligands to the iron, resulting in characteristic EPR

  18. 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

  19. 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.

  20. Electron paramagnetic resonance study of new paramagnetic centers in microcline-perthites from pegmatites

    NASA Astrophysics Data System (ADS)

    Matyash, I. V.; Bagmut, N. N.; Litovchenko, A. S.; Proshko, V. Ya.

    1982-08-01

    Four new types of paramagnetic centers — NH+ 3, N2-, Al-O-, E 1 — have been detected in microcline perthites from pegmatites in the Ukrainian Shield. Values are tabulated for their g and A tensors and limits of thermal stability determined. The NH+ 3 center substitutes the K+ ion. It occurs naturally in potash feldspars but is intensified by gamma or X-ray irradiation. It is regarded as a radiational development of the more general NH+ 4 ⇄ K+ isomorphism. It disappears after heating to temperatures higher than 470 K. The N2- center is an uncommon example of isomorphous substitution of a bridging oxygen, being located on a O D( m) site between T 2( o) and T 1( m) silicon sites. It is stable to 820 K. The hole center, Al-O-, has been detected on an O A(l) oxygen shared by T 1( o) and T 1( m) tetrahedra. It is stable to 590 K. The E 1 center in these alkali feldspars is similar to the E 1 center in quartz, being an electron trapped in an oxygen vacancy in the O B ( o) position. It is stable to 420 K. The NH+ 3, Al-O- and E 1 centers can be restored from temperatures above their stability limits by gamma radiation. Concentration of centers varies from sample to sample depending on conditions of formation and subsequent history of the minerals.

  1. Magnetic resonance studies of isotopically labeled paramagnetic proteins: (2FE-2S) ferredoxins

    SciTech Connect

    Cheng, H.; Xia, B.; Chae, Y.K.; Westler, W.M.; Markley, J.L.

    1994-12-01

    Recent developments in NMR spectroscopy, especially multidimensional, multinuclear NMR techniques, have made NMR the most versatile tool available for studying protein structure and function in solution. Unlike diamagnetic proteins, paramagnetic proteins contain centers with unpaired electrons. These unpaired electrons interact with magnetic nuclei either through chemical bonds by a contact mechanism or through space by a pseudocontact mechanism. Such interactions make the acquisition and analysis of NMR spectra of paramagnetic proteins more challenging than those of diamagnetic proteins. Some NMR signals from paramagnetic proteins are shifted outside the chemical shift region characteristic of diamagnetic proteins; these {open_quotes}hyperfine-shifted{close_quotes} resonances originate from nuclei that interact with unpaired electrons from the paramagnetic center. The large chemical shift dispersion in spectra of paramagnetic proteins makes it difficult to excite the entire spectral window and leads to distortions in the baseline. Interactions with paramagnetic centers shorten T{sub 1} and T{sub 2} relaxation times of nuclei; the consequences are line broadening and lower spectral sensitivity. Scalar (through bond) and dipolar (through space) interactions between pairs of nuclei are what give rise to crosspeak signals in multi-dimensional NMR spectra of small diamagnetic proteins. When such interactions involve a nucleus that is strongly relaxed by interaction with a paramagnetic center, specialized methods may be needed for its detection or it may be completely undetectable by present nD NMR methods.

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

    PubMed Central

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

    2008-01-01

    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. PMID:19044441

  3. Tuner and radiation shield for planar electron paramagnetic resonance microresonators

    SciTech Connect

    Narkowicz, Ryszard; Suter, Dieter

    2015-02-15

    Planar microresonators provide a large boost of sensitivity for small samples. They can be manufactured lithographically to a wide range of target parameters. The coupler between the resonator and the microwave feedline can be integrated into this design. To optimize the coupling and to compensate manufacturing tolerances, it is sometimes desirable to have a tuning element available that can be adjusted when the resonator is connected to the spectrometer. This paper presents a simple design that allows one to bring undercoupled resonators into the condition for critical coupling. In addition, it also reduces radiation losses and thereby increases the quality factor and the sensitivity of the resonator.

  4. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging

    NASA Astrophysics Data System (ADS)

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-11-01

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the 7Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating.

  5. 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.

  6. 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.

  7. 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.

  8. 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

  9. 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.

  10. Gamma-irradiated ExtraVit M nutritive supplement studied by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Petrişor, Dina; Damian, Grigore; Simon, Simion

    2008-04-01

    An unirradiated and γ-irradiated nutritive supplement named ExtraVit M was studied by electron paramagnetic resonance (EPR) spectroscopy in order to detect stable paramagnetic species following improvement of hygienic quality by γ-radiation. Free radicals were induced by γ-radiation in the studied samples from low absorbed doses, showing a certain sensibility of these samples to the radiation treatment. The EPR spectrum of irradiated ExtraVit M is typical for drugs or nutritive supplements containing high levels of sugars, vitamin C and cellulose.

  11. 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

  12. 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.

  13. 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.

  14. Characterization of humic acids from tundra soils of northern Western Siberia by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Chukov, S. N.; Ejarque, E.; Abakumov, E. V.

    2017-01-01

    Humic acids from polar soils—cryozems (Cryosols), gleyezems (Gleysols), and peat soils (Histosols)—have been studied by electron paramagnetic resonance spectroscopy. First information was acquired on the content of free radicals in humic acids from polar soils for the northern regions of Western Siberia (Gydan Peninsula, Belyi Island). It was found that polar soils are characterized by higher contents of free radicals than other zonal soils. This is related to the lower degree of humification of organic matter and the enhanced hydromorphism under continuous permafrost conditions. The low degree of organic matter humification in the cryolithozone was confirmed by the increased content of free radicals as determined by electron paramagnetic resonance, which indicates a low biothermodynamic stability of organic matter.

  15. Electron paramagnetic resonance study of the nuclear spin dynamics in an AlAs quantum well

    NASA Astrophysics Data System (ADS)

    Shchepetilnikov, A. V.; Frolov, D. D.; Nefyodov, Yu. A.; Kukushkin, I. V.; Tiemann, L.; Reichl, C.; Dietsche, W.; Wegscheider, W.

    2016-12-01

    The nuclear spin dynamics in an asymmetrically doped 16-nm AlAs quantum well grown along the [001] direction has been studied experimentally using the time decay of the Overhauser shift of paramagnetic resonance of conduction electrons. The nonzero spin polarization of nuclei causing the initial observed Overhauser shift is due the relaxation of the nonequilibrium spin polarization of electrons into the nuclear subsystem near electron paramagnetic resonance owing to the hyperfine interaction. The measured relaxation time of nuclear spins near the unity filling factor is (530 ± 30) min at the temperature T = 0.5 K. This value exceeds the characteristic spin relaxation times of nuclei in GaAs/AlGaAs heterostructures by more than an order of magnitude. This fact indicates the decrease in the strength of the hyperfine interaction in the AlAs quantum well in comparison with GaAs/AlGaAs heterostructures.

  16. Determining residual impurities in sapphire by means of electron paramagnetic resonance and nuclear activation analysis

    NASA Astrophysics Data System (ADS)

    Bletskan, D. I.; Bratus', V. Ya.; Luk'yanchuk, A. R.; Maslyuk, V. T.; Parlag, O. A.

    2008-07-01

    Sapphire (α-Al2O3) single crystals grown using the Verneuil and Kyropoulos methods have been analyzed using electron paramagnetic resonance and γ-ray spectroscopy with 12-MeV bremsstrahlung excitation. It is established that uncontrolled impurities in the final sapphire single crystals grown by the Kyropoulos method in molybdenum-tungsten crucibles are supplied both from the initial materials and from the furnace and crucible materials

  17. Field-stepped direct detection electron paramagnetic resonance.

    PubMed

    Yu, Zhelin; Liu, Tengzhi; Elajaili, Hanan; Rinard, George A; Eaton, Sandra S; Eaton, Gareth R

    2015-09-01

    The widest scan that had been demonstrated previously for rapid scan EPR was a 155G sinusoidal scan. As the scan width increases, the voltage requirement across the resonating capacitor and scan coils increases dramatically and the background signal induced by the rapidly changing field increases. An alternate approach is needed to achieve wider scans. A field-stepped direct detection EPR method that is based on rapid-scan technology is now reported, and scan widths up to 6200G have been demonstrated. A linear scan frequency of 5.12kHz was generated with the scan driver described previously. The field was stepped at intervals of 0.01 to 1G, depending on the linewidths in the spectra. At each field data for triangular scans with widths up to 11.5G were acquired. Data from the triangular scans were combined by matching DC offsets for overlapping regions of successive scans. This approach has the following advantages relative to CW, several of which are similar to the advantages of rapid scan. (i) In CW if the modulation amplitude is too large, the signal is broadened. In direct detection field modulation is not used. (ii) In CW the small modulation amplitude detects only a small fraction of the signal amplitude. In direct detection each scan detects a larger fraction of the signal, which improves the signal-to-noise ratio. (iii) If the scan rate is fast enough to cause rapid scan oscillations, the slow scan spectrum can be recovered by deconvolution after the combination of segments. (iv) The data are acquired with quadrature detection, which permits phase correction in the post processing. (v) In the direct detection method the signal typically is oversampled in the field direction. The number of points to be averaged, thereby improving the signal-to-noise ratio, is determined in post processing based on the desired field resolution. A degased lithium phthalocyanine sample was used to demonstrate that the linear deconvolution procedure can be employed with field

  18. 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

  19. 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

  20. Low temperature electron paramagnetic resonance anomalies in Fe-based nanoparticles

    NASA Astrophysics Data System (ADS)

    Koksharov, Yu. A.; Gubin, S. P.; Kosobudsky, I. D.; Beltran, M.; Khodorkovsky, Y.; Tishin, A. M.

    2000-08-01

    A study of the electron paramagnetic resonance of Fe-based nanoparticles embedded in polyethylene matrix was performed as a function of temperature ranging from 3.5 to 500 K. Nanoparticles with a narrow size distribution were prepared by the high-velocity thermodestruction of iron-containing compounds. A temperature-driven transition from superparamagnetic to ferromagnetic resonance was observed for samples with different Fe content. The unusual behavior of the spectra at about 25 K is considered evidence of a spin-glass state in iron oxide nanoparticles.

  1. 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

  2. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging.

    PubMed

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-11-03

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the (7)Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating.

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

    PubMed

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

    2015-02-09

    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 Ru(5+) 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 Ru(5+)/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.

  4. Following lithiation fronts in paramagnetic electrodes with in situ magnetic resonance spectroscopic imaging

    PubMed Central

    Tang, Mingxue; Sarou-Kanian, Vincent; Melin, Philippe; Leriche, Jean-Bernard; Ménétrier, Michel; Tarascon, Jean-Marie; Deschamps, Michaël; Salager, Elodie

    2016-01-01

    Li-ion batteries are invaluable for portable electronics and vehicle electrification. A better knowledge of compositional variations within the electrodes during battery operation is, however, still needed to keep improving their performance. Although essential in the medical field, magnetic resonance imaging of solid paramagnetic battery materials is challenging due to the short lifetime of their signals. Here we develop the scanning image-selected in situ spectroscopy approach, using the strongest commercially available magnetic field gradient. We demonstrate the 7Li magnetic resonance spectroscopic image of a 5 mm-diameter operating battery with a resolution of 100 μm. The time-resolved image-spectra enable the visualization in situ of the displacement of lithiation fronts inside thick paramagnetic electrodes during battery operation. Such observations are critical to identify the key limiting parameters for high-capacity and fast-cycling batteries. This non-invasive technique also offers opportunities to study devices containing paramagnetic materials while operating. PMID:27808094

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

    PubMed

    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.

  6. 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.

  7. 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.

  8. Lithium naphthalocyanine as a new molecular radical probe for electron paramagnetic resonance oximetry

    NASA Astrophysics Data System (ADS)

    Manivannan, Ayyakkannu; Yanagi, Hisao; Ilangovan, Govindasamy; Kuppusamy, Periannan

    2001-08-01

    A new lithium naphthalocyanine dye aggregate [Li 2Nc][LiNc] is reported as a potential electron paramagnetic resonance (EPR) oximetry probe for accurate measurement of oxygen concentration in biological systems. The Li 2Nc is diamagnetic; however, the LiNc molecule has an unpaired electron and hence is paramagnetic. The aggregate shows a strong and single line EPR signal that is non-saturating at normal EPR power levels. An oxygen-dependent peak-to-peak EPR spectral width ranging from 0.51 G (at pO 2: 0 mmHg) to 26.2 G (at pO 2: 760 mmHg) has been observed. The application of this probe has been demonstrated in the measurement of arterial and venous oxygen tensions in a rat.

  9. Electron paramagnetic resonance study of doped synthetic crystals of struvite and its zinc analogue

    NASA Astrophysics Data System (ADS)

    Chand, Prem; Agarwal, O. P.

    The electron paramagnetic resonance (EPR) technique has been used to study the Mn 2+ paramagnetic impurity complexes in synthetic struvite (MgNH 4PO 4β6H 2O) and the zinc isomorph (ZnNH 4PO 4β6H 2O). EPR of VO 2+ ion complexes in vanadyl doped crystals of the zinc isomorph of struvite has also been studied. Two differently oriented, but otherwise identical complexes of both Mn 2+ ion and VO 2+ ion are found in these crystals. The spin Hamiltonian parameters indicate a large orthorhombic distortion of the [Mn 2+(H 2O) 6] octahedra and an axial symmetry of the vanadyl complexes. The results indicate that in both manganese and vanadyl complexes, the metal ions have covalent bonding with the ligands.

  10. 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).

  11. 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

  12. 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.

    2016-12-01

    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.

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

    NASA Astrophysics Data System (ADS)

    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

    2016-05-01

    A key limitation of electron paramagnetic resonance (EPR), an established and powerful tool for studying atomic-scale biomolecular structure and dynamics is its poor sensitivity, samples containing in excess of 10^12 labeled biomolecules are required in typical experiments. In contrast, single molecule measurements provide improved insights into heterogeneous behaviors that can be masked by ensemble measurements and are often essential for illuminating the molecular mechanisms behind the function of a biomolecule. We report EPR measurements of a single labeled biomolecule that merge these two powerful techniques. We selectively label an individual double-stranded DNA molecule with a single nanodiamond containing nitrogen-vacancy (NV) centers, and optically detect the paramagnetic resonance of NV spins in the nanodiamond probe. Analysis of the spectrum reveals that the nanodiamond probe has complete rotational freedom and that the characteristic time scale for reorientation of the nanodiamond probe is slow compared to 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.

  14. 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.

  15. Environmentally sensitive paramagnetic and diamagnetic contrast agents for nuclear magnetic resonance imaging and spectroscopy.

    PubMed

    Pacheco-Torres, Jesus; Calle, Daniel; Lizarbe, Blanca; Negri, Viviana; Ubide, Carmen; Fayos, Rosa; Larrubia, Pilar López; Ballesteros, Paloma; Cerdan, Sebastian

    2011-01-01

    Even though alterations in the microenvironmental properties of tissues underlie the development of the most prevalent and morbid pathologies, they are not directly observable in vivo by Magnetic Resonance Imaging (MRI) or Spectroscopy (MRS) methods. This circumstance has lead to the development of a wide variety of exogenous paramagnetic and diamagnetic MRI and MRS probes able to inform non invasively on microenvironmental variables such as pH, pO(2), ion concentration o even temperature. This review covers the fundamentals of environmental contrast and the current arsenal of endogenous and exogenous MRI and MRS contrast enhancing agents available to visualize it. We begin describing the physicochemical background necessary to understand paramagnetic and diamagnetic contrast enhancement with a special reference to novel magnetization transfer and (13)C hyperpolarization strategies. We describe then the main macrocyclic structures used to support the environmentally sensitive paramagnetic sensors, including CEST and PARACEST pH sensitive probes, temperature probes and enzyme activity or gene expression activatable probes. Finally we address the most commonly used diamagnetic contrast agents including imidazolic derivatives to reveal extracellular pH and tissue pO(2) values by MRS. The potential applications of these agents in multimodal and molecular imaging approaches are discussed.

  16. 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.

  17. 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.

  18. Ordering of PCDTBT revealed by time-resolved electron paramagnetic resonance spectroscopy of its triplet excitons.

    PubMed

    Biskup, Till; Sommer, Michael; Rein, Stephan; Meyer, Deborah L; Kohlstädt, Markus; Würfel, Uli; Weber, Stefan

    2015-06-22

    Time-resolved electron paramagnetic resonance (TREPR) spectroscopy is shown to be a powerful tool to characterize triplet excitons of conjugated polymers. The resulting spectra are highly sensitive to the orientation of the molecule. In thin films cast on PET film, the molecules' orientation with respect to the surface plane can be determined, providing access to sample morphology on a microscopic scale. Surprisingly, the conjugated polymer investigated here, a promising material for organic photovoltaics, exhibits ordering even in bulk samples. Orientation effects may significantly influence the efficiency of solar cells, thus rendering proper control of sample morphology highly important.

  19. Saturation-recovery electron paramagnetic resonance discrimination by oxygen transport (DOT) method for characterizing membrane domains.

    PubMed

    Subczynski, Witold K; Widomska, Justyna; Wisniewska, Anna; Kusumi, Akihiro

    2007-01-01

    The discrimination by oxygen transport (DOT) method is a dual-probe saturation-recovery electron paramagnetic resonance approach in which the observable parameter is the spin-lattice relaxation time (T1) of lipid spin labels, and the measured value is the bimolecular collision rate between molecular oxygen and the nitroxide moiety of spin labels. This method has proven to be extremely sensitive to changes in the local oxygen diffusion-concentration product (around the nitroxide moiety) because of the long T1 of lipid spin labels (1-10 micros) and also because molecular oxygen is a unique probe molecule. Molecular oxygen is paramagnetic, small, and has the appropriate level of hydrophobicity that allows it to partition into various supramolecular structures such as different membrane domains. When located in two different membrane domains, the spin label alone most often cannot differentiate between these domains, giving very similar (indistinguishable) conventional electron paramagnetic resonance spectra and similar T1 values. However, even small differences in lipid packing in these domains will affect oxygen partitioning and oxygen diffusion, which can be easily detected by observing the different T1s from spin labels in these two locations in the presence of molecular oxygen. The DOT method allows one not only to distinguish between the different domains, but also to obtain the value of the oxygen diffusion-concentration product in these domains, which is a useful physical characteristic of the organization of lipids in domains. Profiles of the oxygen diffusion-concentration product (the oxygen transport parameter) in coexisting domains can be obtained in situ without the need for the physical separation of the two domains. Furthermore, under optimal conditions, the exchange rate of spin-labeled molecules between the two domains could be measured.

  20. 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.

  1. Magnetic resonance force microscopy of paramagnetic electron spins at millikelvin temperatures.

    PubMed

    Vinante, A; Wijts, G; Usenko, O; Schinkelshoek, L; Oosterkamp, T H

    2011-12-06

    Magnetic resonance force microscopy (MRFM) is a powerful technique to detect a small number of spins that relies on force detection by an ultrasoft magnetically tipped cantilever and selective magnetic resonance manipulation of the spins. MRFM would greatly benefit from ultralow temperature operation, because of lower thermomechanical noise and increased thermal spin polarization. Here we demonstrate MRFM operation at temperatures as low as 30 mK, thanks to a recently developed superconducting quantum interference device (SQUID)-based cantilever detection technique, which avoids cantilever overheating. In our experiment, we detect dangling bond paramagnetic centres on a silicon surface down to millikelvin temperatures. Fluctuations of such defects are supposedly linked to 1/f magnetic noise and decoherence in SQUIDs, as well as in several superconducting and single spin qubits. We find evidence that spin diffusion has a key role in the low-temperature spin dynamics.

  2. 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

  3. Imaging of nitroxides at 250MHz using rapid-scan electron paramagnetic resonance.

    PubMed

    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

    2014-05-01

    Projections for 2D spectral-spatial images were obtained by continuous wave and rapid-scan electron paramagnetic resonance using a bimodal cross-loop resonator at 251MHz. The phantom consisted of three 4mm tubes containing different (15)N,(2)H-substituted nitroxides. Rapid-scan and continuous wave images were obtained with 5min total acquisition times. For comparison, images also were obtained with 29s acquisition time for rapid scan and 15min 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.

  4. Electron paramagnetic resonance study of ZnAl(2)S(4) spinel.

    PubMed

    Güner, S; Yıldız, F; Rameev, B; Aktaş, B

    2005-06-29

    Single crystals of ZnAl(2)S(4) spinel doped by paramagnetic Cr(3+) and Mn(2+) ions have been studied by the electron paramagnetic resonance (EPR) technique. The crystal field symmetry around the impurity ions has been determined from the angular behaviour of X-band EPR spectra. The anisotropic EPR signal of the Cr(3+) ions shows splitting into 31 narrow lines due to the super-hyperfine interaction between unpaired electron spins of the chromium centres and nuclear spins of six neighbouring Al(27) (I = 5/2) ions. It has been established that the Cr(3+) ions are located at the octahedral sites in the spinel structure, and the super-hyperfine interaction results from a weak covalent bounding with the Al atoms. The EPR signals of the Cr(3+) paramagnetic centres show no fine-structure splitting due to a perfectly cubic symmetry of the local crystal field in the octahedral sites of the ZnAl(2)S(4) spinel structure. A weak EPR signal consisting of six components has been ascribed to the transitions between hyperfine levels of the Mn(2+) (I = 5/2,S = 5/2) ions located at tetrahedral sites, while the fine-structure splitting of each component could be resolved only for special orientations of the sample in the external magnetic field. The parameters of the EPR signal of both chromium and manganese centres indicate that there is an essential covalence in the ZnAl(2)S(4) spinel crystal. Very narrow linewidths (∼2 Oe) of the Cr(3+) EPR signal components point to very high homogeneity and quality of the ZnAl(2)S(4) crystals.

  5. Thin chitosan films containing super-paramagnetic nanoparticles with contrasting capability in magnetic resonance imaging.

    PubMed

    Farjadian, Fatemeh; Moradi, Sahar; Hosseini, Majid

    2017-03-01

    Magnetic nanoparticles have found application as MRI contrasting agents. Herein, chitosan thin films containing super-paramagnetic iron oxide nanoparticles (SPIONs) are evaluated in magnetic resonance imaging (MRI). To determine their contrasting capability, super-paramagnetic nanoparticles coated with citrate (SPIONs-cit) were synthesized. Then, chitosan thin films with different concentrations of SPIONs-cit were prepared and their MRI data (i.e., r 2 and r 2*) was evaluated in an aqueous medium. The synthesized SPIONs-cit and chitosan/SPIONs-cit films were characterized by FTIR, EDX, XRD as well as VSM with the morphology evaluated by SEM and AFM. The nanoparticle sizes and distribution confirmed well-defined nanoparticles and thin films formation along with high contrasting capability in MRI. Images revealed well-dispersed uniform nanoparticles, averaging 10 nm in size. SPIONs-cit's hydrodynamic size averaged 23 nm in diameter. The crystallinity obeyed a chitosan and SPIONs pattern. The in vitro cellular assay of thin films with a novel route was performed within Hek293 cell lines showing that thin films can be biocompatible.

  6. Characterisation of β-tricalcium phosphate-based bone substitute materials by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Matković, Ivo; Maltar-Strmečki, Nadica; Babić-Ivančić, Vesna; Dutour Sikirić, Maja; Noethig-Laslo, Vesna

    2012-10-01

    β-TCP based materials are frequently used as dental implants. Due to their resorption in the body and direct contact with tissues, in order to inactivate bacteria, fungal spores and viruses, they are usually sterilized by γ-irradiation. However, the current literature provides little information about effects of the γ-irradiation on the formation and stability of the free radicals in the bone graft materials during and after sterilization procedure. In this work five different bone graft substitution materials, composed of synthetic beta tricalcium phosphate (β-TCP) and hydroxyapatite (HAP) present in the market were characterized by electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and thermogravimetric analysis (TGA). Paramagnetic species Mn2+, Fe3+, trapped H-atoms and CO2- radicals were detected in the biphasic material (60% HAP, 40% β-TCP), while in β-TCP materials only Mn2+ andor trapped hydrogen atoms were detected. EPR analysis revealed the details of the structure of these materials at the atomic level. The results have shown that EPR spectroscopy is a method which can be used to improve the quality control of bone graft materials after syntering, processing and sterilization procedure.

  7. Electron paramagnetic resonance studies of copper ion-exchanged ZSM-5

    SciTech Connect

    Larsen, S.C.; Aylor, A.; Bell, A.T.; Reimer, J.A. )

    1994-11-03

    Electron paramagnetic resonance (EPR) spectroscopy was utilized to probe the oxidation state and coordination environment of copper in ion-exchanged CuZSM-5. EPR spectra of hydrated samples were consistent with octahedral coordination. Square pyramidal and square-planar sites were identified in pretreated CuZSM-5 samples, and the relative concentration of square-pyramidal sites in these samples was linearly correlated with the copper-exchange level. The extent of autoreduction was monitored by EPR and it was determined that a substantial fraction (approximately 40-60%) of the copper was reduced and the reduction process was reversible in the presence of water. A mechanism for the autoreduction of copper is proposed that is consistent with the EPR results. Further, the reactivity of the proposed copper species was probed in reducing and oxidizing environments and in the presence of nitric oxide. The increase in EPR signal intensity that was observed after room-temperature NO exposure of pretreated and oxidized CuZSM-5 is attributed to the formation of copper nitrite and nitrate species. High-temperature in situ EPR experiments revealed that on the time scale of the EPR experiment, the paramagnetic copper environment did not change at elevated temperatures in the presence of nitric oxide. 39 refs., 13 figs., 3 tabs.

  8. Magnetometry and electron paramagnetic resonance studies of phosphine- and thiol-capped gold nanoparticles

    NASA Astrophysics Data System (ADS)

    Guerrero, E.; Muñoz-Márquez, M. A.; Fernández, A.; Crespo, P.; Hernando, A.; Lucena, R.; Conesa, J. C.

    2010-03-01

    In the last years, the number of studies performed by wholly independent research groups that confirm the permanent magnetism, first observed in our research lab, for thiol-capped Au nanoparticles (NPs) has rapidly increased. Throughout the years, the initial magnetometry studies have been completed with element-specific magnetization measurements based on, for example, the x-ray magnetic circular dichroism technique that have allowed the identification of gold as the magnetic moment carrier. In the research work here presented, we have focused our efforts in the evaluation of the magnetic behavior and iron impurities content in the synthesized samples by means of superconducting quantum interference device magnetometry and electron paramagnetic resonance spectrometry, respectively. As a result, hysteresis cycles typical of a ferromagnetic material have been measured from nominally iron-free gold NPs protected with thiol, phosphine, and chlorine ligands. It is also observed that for samples containing both, capped gold NPs and highly diluted iron concentrations, the magnetic behavior of the NPs is not affected by the presence of paramagnetic iron impurities. The hysteresis cycles reported for phosphine-chlorine-capped gold NPs confirm that the magnetic behavior is not exclusively for the metal-thiol system.

  9. Studying metal ion-protein interactions: electronic absorption, circular dichroism, and electron paramagnetic resonance.

    PubMed

    Quintanar, Liliana; Rivillas-Acevedo, Lina

    2013-01-01

    Metal ions play a wide range of important functional roles in biology, and they often serve as cofactors in enzymes. Some of the metal ions that are essential for life are strongly associated with proteins, forming obligate metalloproteins, while others may bind to proteins with relatively low affinity. The spectroscopic tools presented in this chapter are suitable to study metal ion-protein interactions. Metal sites in proteins are usually low symmetry centers that differentially absorb left and right circularly polarized light. The combination of electronic absorption and circular dichroism (CD) in the UV-visible region allows the characterization of electronic transitions associated with the metal-protein complex, yielding information on the geometry and nature of the metal-ligand interactions. For paramagnetic metal centers in proteins, electron paramagnetic resonance (EPR) is a powerful tool that provides information on the chemical environment around the unpaired electron(s), as it relates to the electronic structure and geometry of the metal-protein complex. EPR can also probe interactions between the electron spin and nuclear spins in the vicinity, yielding valuable information on some metal-ligand interactions. This chapter describes each spectroscopic technique and it provides the necessary information to design and implement the study of metal ion-protein interactions by electronic absorption, CD, and EPR.

  10. Electron Paramagnetic Resonance of Rhyolite and γ-Irradiated Trona Minerals

    NASA Astrophysics Data System (ADS)

    Köksal, F.; Köseoğlu, R.; Bașaran, E.

    2003-06-01

    Rhyolite from the "Yellow Stone of Nevșehir" and γ-irradiated trona from the Ankara Mine have been investigated by electron paramagnetic resonance at ambient temperature and at 113 K. Rhyolite was examined by X-ray powder diffraction and found to consist mainly of SiO2. Before γ-irradiation, the existing paramagnetic species in rhyolite were identified as ṖO42-, ĊH2OH, ĊO3-, ṠO2-, ĊO33-, and ĊO2- free radicals and Fe3+ at ambient temperature. At 113 K ṠO2- , ĊO33- , and ĊO2- radicals and Fe3+ were observed. The γ-irradiation produced neither new species nor detectable effects on these free radicals. The disappearance of some of the radicals at 113 K is attributed to the freezing of their motions. Before γ-irradiation, the trona mineral shows only Mn2+ lines, but after γ-irradiation it indicated the inducement of ĊO33- and ĊO2- radicals at ambient temperature, 113 K, in addition to the Mn2+ lines. The g and a values of the species were determined.

  11. Ion exchange in alginate gels--dynamic behaviour revealed by electron paramagnetic resonance.

    PubMed

    Ionita, Gabriela; Ariciu, Ana Maria; Smith, David K; Chechik, Victor

    2015-12-14

    The formation of alginate gel from low molecular weight alginate and very low molecular weight alginate in the presence of divalent cations was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. The transition from sol to gel in the presence of divalent cations was monitored by the changes in the dynamics of spin labelled alginate. The immobilisation of the spin labelled alginate in the gel reflects the strength of interaction between the cation and alginate chain. Diffusion experiments showed that both the cation and alginate polyanion in the gel fibres can exchange with molecules in solution. In particular, we showed that dissolved alginate polyanions can replace alginates in the gel fibres, which can hence diffuse through the bulk of the gel. This illustrates the surprisingly highly dynamic nature of these gels and opens up the possibility of preparing multicomponent alginate gels via polyanion exchange process.

  12. 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.

  13. 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.

  14. Pulse-electron paramagnetic resonance of Cr3+ centers in SrTiO3

    NASA Astrophysics Data System (ADS)

    Azamat, D. V.; Dejneka, A.; Lančok, J.; Trepakov, V. A.; Jastrabik, L.; Badalyan, A. G.

    2013-05-01

    Electron paramagnetic resonance on chromium doped SrTiO3 samples grown using the Verneuil technique shows the presence of charge-compensated Cr3+-VO as one of the dominant chromium centers. The spin-lattice relaxation processes have been investigated in samples with both isotropic Cr3+ and Cr3+-VO centers in heavily doped SrTiO3. The relaxation of longitudinal magnetization was dominated by the sum of two exponentials with two time constants (i.e., a slow and a fast constant) at liquid-helium temperatures. The results of fitting the temperature variation of T1 suggest that the dominant exponential contribution is related to the spin-phonon relaxation time arising from the local phonon mode.

  15. Imaging thiol redox status in murine tumors in vivo with rapid-scan electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Epel, Boris; Sundramoorthy, Subramanian V.; Krzykawska-Serda, Martyna; Maggio, Matthew C.; Tseytlin, Mark; Eaton, Gareth R.; Eaton, Sandra S.; Rosen, Gerald M.; Kao, Joseph P. Y.; Halpern, Howard J.

    2017-03-01

    Thiol redox status is an important physiologic parameter that affects the success or failure of cancer treatment. Rapid scan electron paramagnetic resonance (RS EPR) is a novel technique that has shown higher signal-to-noise ratio than conventional continuous-wave EPR in in vitro studies. Here we used RS EPR to acquire rapid three-dimensional images of the thiol redox status of tumors in living mice. This work presents, for the first time, in vivo RS EPR images of the kinetics of the reaction of 2H,15N-substituted disulfide-linked dinitroxide (PxSSPx) spin probe with intracellular glutathione. The cleavage rate is proportional to the intracellular glutathione concentration. Feasibility was demonstrated in a FSa fibrosarcoma tumor model in C3H mice. Similar to other in vivo and cell model studies, decreasing intracellular glutathione concentration by treating mice with L-buthionine sulfoximine (BSO) markedly altered the kinetic images.

  16. 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.

  17. Electron paramagnetic resonance (EPR) investigations of lichens - 1: effects of air pollution

    NASA Astrophysics Data System (ADS)

    Jezierski, Adam; Bylinska, Ewa; Seaward, Mark R. D.

    Electron paramagnetic resonance (EPR) investigations were carried out on more than 800 samples of lichens from Lower Silesia, southwest Poland. A statistically confirmed correlation between annual average concentration of sulphur dioxide in the atmosphere and concentration of semiquinone radicals in Hypogymnia physodes thalli was found. Similar results were obtained for Umbilicaria species from the Karkonosze Mountains. Distribution of semiquinone radicals in lichen thalli was also investigated. The action of nitrogen dioxide on Umbilicaria species resulted in the synthesis of iminoxy radicals in the thalli. The intensification of the semiquinone free radical production in lichen thalli from atmospherically polluted environments and the degradation of lichen acids to β-diketone compounds would appear to be parallel processes. The properties of the iminoxyls derived from β-diketones in the lichen matrix (anisotropic spectra at room temperature) and in organic solutions after extraction procedure were also examined by EPR.

  18. 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

  19. High-Frequency Electron Paramagnetic Resonance Spectroscopy of Nitroxide-Functionalized Nanodiamonds in Aqueous Solution.

    PubMed

    Akiel, R D; Stepanov, V; Takahashi, S

    2016-06-21

    Nanodiamond (ND) is an attractive class of nanomaterial for fluorescent labeling, magnetic sensing of biological molecules, and targeted drug delivery. Many of those applications require tethering of target biological molecules on the ND surface. Even though many approaches have been developed to attach macromolecules to the ND surface, it remains challenging to characterize dynamics of tethered molecule. Here, we show high-frequency electron paramagnetic resonance (HF EPR) spectroscopy of nitroxide-functionalized NDs. Nitroxide radical is a commonly used spin label to investigate dynamics of biological molecules. In the investigation, we developed a sample holder to overcome water absorption of HF microwave. Then, we demonstrated HF EPR spectroscopy of nitroxide-functionalized NDs in aqueous solution and showed clear spectral distinction of ND and nitroxide EPR signals. Moreover, through EPR spectral analysis, we investigate dynamics of nitroxide radicals on the ND surface. The demonstration sheds light on the use of HF EPR spectroscopy to investigate biological molecule-functionalized nanoparticles.

  20. 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.

  1. Searching for biosignatures using electron paramagnetic resonance (EPR) analysis of manganese oxides.

    PubMed

    Kim, Soon Sam; Bargar, John R; Nealson, Kenneth H; Flood, Beverly E; Kirschvink, Joseph L; Raub, Timothy D; Tebo, Bradley M; Villalobos, Mario

    2011-10-01

    Manganese oxide (Mn oxide) minerals from bacterial sources produce electron paramagnetic resonance (EPR) spectral signatures that are mostly distinct from those of synthetic simulants and abiogenic mineral Mn oxides. Biogenic Mn oxides exhibit only narrow EPR spectral linewidths (∼500 G), whereas abiogenic Mn oxides produce spectral linewidths that are 2-6 times broader and range from 1200 to 3000 G. This distinction is consistent with X-ray structural observations that biogenic Mn oxides have abundant layer site vacancies and edge terminations and are mostly of single ionic species [i.e., Mn(IV)], all of which favor narrow EPR linewidths. In contrast, abiogenic Mn oxides have fewer lattice vacancies, larger particle sizes, and mixed ionic species [Mn(III) and Mn(IV)], which lead to the broader linewidths. These properties could be utilized in the search for extraterrestrial physicochemical biosignatures, for example, on Mars missions that include a miniature version of an EPR spectrometer.

  2. Fluorescence properties and electron paramagnetic resonance studies of γ-irradiated Sm3+-doped oxyfluoroborate glasses

    NASA Astrophysics Data System (ADS)

    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 γ-ray irradiation has been investigated using a steady-state fluorescence and electron paramagnetic resonance techniques. An increase in SrF2 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 Sm3+ to Sm2+ ion. The energy transfer mechanism of induced permanent photoreduction of Sm3+ to Sm2+ 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 SrF2 content in the glass and also with the irradiation dose.

  3. Effects of genistein and daidzein on erythrocyte membrane fluidity: an electron paramagnetic resonance study.

    PubMed

    Ajdzanović, Vladimir; Spasojević, Ivan; Filipović, Branko; Sosić-Jurjević, Branka; Sekulić, Milka; Milosević, Verica

    2010-04-01

    The maintenance of erythrocyte membrane fluidity at the physiological level is an important factor affecting the ability of erythrocytes to pass through blood vessels of small luminal diameter. Genistein and daidzein, which are used as alternative therapeutics in cardiovascular conditions, can be incorporated into the cell membrane and change its fluidity. The aim of this study was to examine the effects of genistein and daidzein on erythrocyte membrane fluidity at graded depths. We used electron paramagnetic resonance (EPR) spectroscopy and fatty acid spin probes (5-DS and 12-DS) where EPR spectra were dependent on fluidity. The results showed that genistein significantly (p < 0.05) decreased erythrocyte membrane fluidity near the hydrophilic surface, while daidzein significantly (p < 0.05) increased the same parameter in deeper regions of the membrane. These data suggest that the deep fluidizing effects of daidzein on erythrocyte membranes make it a better therapeutic choice than genistein in some cardiovascular conditions.

  4. Theoretical calculations of Electron Paramagnetic Resonance parameters of liquid phase Orotic acid radical

    NASA Astrophysics Data System (ADS)

    Sarikaya, Ebru Karakaş; Dereli, Ömer

    2017-02-01

    To obtain liquid phase molecular structure, conformational analysis of Orotic acid was performed and six conformers were determined. For these conformations, eight possible radicals were modelled by using Density Functional Theory computations with respect to molecular structure. Electron Paramagnetic Resonance parameters of these model radicals were calculated and then they were compared with the experimental ones. Geometry optimizations of the molecule and modeled radicals were performed using Becke's three-parameter hybrid-exchange functional combined with the Lee-Yang-Parr correlation functional of Density Functional Theory and 6-311++G(d,p) basis sets in p-dioxane solution. Because Orotic acid can be mutagenic in mammalian somatic cells and it is also mutagenic for bacteria and yeast, it has been studied.

  5. Free radical scavenging activity of erdosteine metabolite I investigated by electron paramagnetic resonance spectroscopy.

    PubMed

    Braga, Pier Carlo; Culici, Maria; Dal Sasso, Monica; Falchi, Mario; Spallino, Alessandra

    2010-01-01

    The aim of this study was to explore the antiradical activity of Met I (an active metabolite of erdosteine) containing a pharmacologically active sulphydryl group, by means of electron paramagnetic resonance (EPR) spectroscopy which has not previously been used to characterize the antiradical activity of Met I. The effects of concentrations of 20, 10, 5, 2.5, 1.25 and 0.625 microg/ml of Met I were tested against: (a) the Fenton reaction model system with EPR detection of HO.; (b) the KO2-crown ether system with EPR detection of O2-.; (c) the EPR assay based on the reduction of the Tempol radical, and (d) the EPR assay based on the reduction of Fremy's salt radical. Our findings show that the intensity of 4 different free radicals was significantly reduced in the presence of Met I, thus indicating the presence of a termination reaction between the free radicals and Met I.

  6. 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

  7. 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.

  8. 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

  9. 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.

  10. Electron paramagnetic resonance, magnetic and electrical properties of CoFe2O4 nanoparticles

    NASA Astrophysics Data System (ADS)

    Jnaneshwara, D. M.; Avadhani, D. N.; Daruka Prasad, B.; Nagabhushana, B. M.; Nagabhushana, H.; Sharma, S. C.; Shivakumara, C.; Rao, J. L.; Gopal, N. O.; Ke, Shyue-Chu; Chakradhar, R. P. S.

    2013-08-01

    CoFe2O4 nanoparticles were prepared by solution combustion method. The nanoparticle are characterized by powder X-ray diffraction (PXRD), Fourier transform infrared spectroscopy and scanning electron microscopy (SEM). PXRD reveals single phase, cubic spinel structure with Fd3¯m (227) space group. SEM micrograph shows the particles are agglomerated and porous in nature. Electron paramagnetic resonance spectrum exhibits a broad resonance signal g=2.150 and is attributed to super exchange between Fe3+ and Co2+. Magnetization values of CoFe2O4 nanoparticle are lower when compared to the literature values of bulk samples. This can be attributed to the surface spin canting due to large surface-to-volume ratio for a nanoscale system. The variation of dielectric constant, dielectric loss, loss tangent and AC conductivity of as-synthesized nano CoFe2O4 particles at room temperature as a function of frequency has been studied. The magnetic and dielectric properties of the samples show that they are suitable for electronic and biomedical applications.

  11. Pulsed Orotron - A new microwave source for submillimeter pulse high-field electron paramagnetic resonance spectroscopy

    SciTech Connect

    Grishin, Yu.A.; Fuchs, M.R.; Schnegg, A.; Dubinskii, A.A.; Dumesh, B.S.; Rusin, F.S.; Bratman, V.L.; Moebius, K.

    2004-09-01

    A vacuum-tube device for the generation of pulsed microwave radiation in the submillimeter range (up to 380 GHz) is presented, designed for use as a source in a 360 GHz high-field/high-frequency electron paramagnetic resonance (EPR) spectrometer - the pulsed Orotron. Analogous to the known continuous wave (cw) version, in the pulsed Orotron microwave radiation is generated by the interaction of a nonrelativistic electron beam with a diffraction grating (stimulated Smith-Purcell radiation) in feedback with an open Fabry-Perot resonator construction. The presented design extends the cw Orotron by a gate electrode and a high-voltage pulsing unit to control the electron beam current. The generated pulses at 360 GHz have pulse lengths from 100 ns-10 {mu}s and a pulse power of (22{+-}5) mW. The output in a broader frequency band between 320 and 380 GHz ranges from 20 up to 60 mW. Within a 10 {mu}s time slot, incoherent pulse trains of arbitrary duration can be generated. The pulsed Orotron has been incorporated in the quasioptical microwave bridge of a heterodyne induction mode EPR spectrometer. The first free induction decay measurements at a microwave frequency of 360 GHz and a magnetic field of 12.8 T on a polycrystalline perylenyl-ion sample are presented and future applications and extensions of Orotron-EPR spectroscopy are discussed.

  12. Rapid Scan Electron Paramagnetic Resonance Opens New Avenues for Imaging Physiologically Important Parameters In Vivo.

    PubMed

    Biller, Joshua R; Mitchell, Deborah G; Tseytlin, Mark; Elajaili, Hanan; Rinard, George A; Quine, Richard W; Eaton, Sandra S; Eaton, Gareth R

    2016-09-26

    We demonstrate a superior method of 2D spectral-spatial imaging of stable radical reporter molecules at 250 MHz using rapid-scan electron-paramagnetic-resonance (RS-EPR), which can provide quantitative information under in vivo conditions on oxygen concentration, pH, redox status and concentration of signaling molecules (i.e., OH(•), NO(•)). The RS-EPR technique has a higher sensitivity, improved spatial resolution (1 mm), and shorter acquisition time in comparison to the standard continuous wave (CW) technique. A variety of phantom configurations have been tested, with spatial resolution varying from 1 to 6 mm, and spectral width of the reporter molecules ranging from 16 µT (160 mG) to 5 mT (50 G). A cross-loop bimodal resonator decouples excitation and detection, reducing the noise, while the rapid scan effect allows more power to be input to the spin system before saturation, increasing the EPR signal. This leads to a substantially higher signal-to-noise ratio than in conventional CW EPR experiments.

  13. 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.

  14. Rapid scan electron paramagnetic resonance at 1.0 GHz of defect centers in γ-irradiated organic solids.

    PubMed

    Shi, Yilin; Rinard, George A; Quine, Richard W; Eaton, Sandra S; Eaton, Gareth R

    2016-02-01

    The radicals in six (60)Co γ-irradiated solids: malonic acid, glycylglycine, 2,6 di-t-butyl 4-methyl phenol, L-alanine, dimethyl malonic acid, and 2-amino isobutyric acid, were studied by rapid scan electron paramagnetic resonance at L-band (1.04 GHz) using a customized Bruker Elexsys spectrometer and a locally-designed dielectric resonator. Sinusoidal scans with widths up to 18.2 mT were generated with the recently described coil driver and Litz wire coils. Power saturation curves showed that the rapid scan signals saturated at higher powers than did conventional continuous wave signals. The rapid scan data were deconvolved and background subtracted to obtain absorption spectra. For the same data acquisition time the signal-to-noise for the absorption spectra obtained in rapid scans were 23 to 37 times higher than for first-derivative spectra obtained by conventional continuous wave electron paramagnetic resonance.

  15. Rapid scan electron paramagnetic resonance at 1.0 GHz of defect centers in γ-irradiated organic solids

    PubMed Central

    Shi, Yilin; Rinard, George A.; Quine, Richard W.; Eaton, Sandra S.; Eaton, Gareth R.

    2016-01-01

    The radicals in six 60Co γ-irradiated solids: malonic acid, glycylglycine, 2,6 di-t-butyl 4-methyl phenol, L-alanine, dimethyl malonic acid, and 2-amino isobutyric acid, were studied by rapid scan electron paramagnetic resonance at L-band (1.04 GHz) using a customized Bruker Elexsys spectrometer and a locally-designed dielectric resonator. Sinusoidal scans with widths up to 18.2 mT were generated with the recently described coil driver and Litz wire coils. Power saturation curves showed that the rapid scan signals saturated at higher powers than did conventional continuous wave signals. The rapid scan data were deconvolved and background subtracted to obtain absorption spectra. For the same data acquisition time the signal-to-noise for the absorption spectra obtained in rapid scans were 23 to 37 times higher than for first-derivative spectra obtained by conventional continuous wave electron paramagnetic resonance. PMID:26834505

  16. PARAMAGNETIC RELAXATION IN CRYSTALS.

    DTIC Science & Technology

    CRYSTALS, PARAMAGNETIC RESONANCE, RELAXATION TIME , CRYSTAL DEFECTS, QUARTZ, GLASS, STRAIN(MECHANICS), TEMPERATURE, NUCLEAR SPINS, HYDROGEN, CALCIUM COMPOUNDS, FLUORIDES, COLOR CENTERS, PHONONS, OXYGEN.

  17. 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.

  18. Electron Paramagnetic Resonance and Mössbauer Spectra of Iron Ions in Bizen Pottery

    NASA Astrophysics Data System (ADS)

    Matsuoka, Yuki; Ikeya, Motoji

    1995-11-01

    Electron paramagnetic resonance (EPR) and Mössbauer spectra of Japanese traditional Bizen pottery and its constituent clays have been measured to study the relationship between the color of pottery surface and the relevant states of iron ions ( Fe3+ and Fe2+). Hyperfine signals of Mn2+, presumably in carbonates, and a broad signal at g=2.0 similar to that of hematite ( Fe2O3) were observed for good-quality clay, while a signal at g>9 similar to that of magnetite ( Fe3O4) was observed for poor-quality clay. In pottery, the apparent g-factor of g=4.3 due to a large orthorhombic distortion E(Sx2-Sy2) and g=6 due to a large axial field DSz2 were observed in addition to the broad signal around g=2 due to oxidation of iron into Fe2O3. Subtle change of colors resulted in the change of EPR spectra. Mössbauer spectra indicatcd that almost all of the iron ions at the surface of pottery are strongly oxidized into Fe3+ when the pottery is fired in oxidizing atmosphere, while those inside the pottery and at the surface fired at reducing atmosphere are not strongly oxidized into Fe3+.

  19. 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.

  20. 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.

  1. 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.

  2. Multi-frequency electron paramagnetic resonance study of irradiated human finger phalanxes

    NASA Astrophysics Data System (ADS)

    Zdravkova, M.; Vanhaelewyn, G.; Callens, F.; Gallez, B.; Debuyst, R.

    2005-10-01

    Electron paramagnetic resonance (EPR) is often used in dosimetry using biological samples such as teeth and bones. It is generally assumed that the radicals, formed after irradiation, are similar in both tissues as the mineral part of bone and tooth is carbonated hydroxyapatite. However, there is a lack of experimental evidence to support this assumption. The aim of the present study was to contribute to that field by studying powder and block samples of human finger phalanxes that were irradiated and analyzed by multi-frequency EPR. The results obtained from bones are different from the ones obtained in enamel by several respects: the ordering of the apatite crystallites is much smaller in bone, complicating the assignment of the observed CO 2- radicals to a specific location, and one type of CO 33- radical was only found in enamel. Moreover, a major difference was found in the non-CO 2- and non-CO 33- signals. The elucidation of the nature of these native signals (in bone and tooth enamel) still represents a big challenge.

  3. Copper Environment in Artificial Metalloproteins Probed by Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Flores, Marco; Olson, Tien L; Wang, Dong; Edwardraja, Selvakumar; Shinde, Sandip; Williams, JoAnn C; Ghirlanda, Giovanna; Allen, James P

    2015-10-29

    The design of binding sites for divalent metals in artificial proteins is a productive platform for examining the characteristics of metal-ligand interactions. In this report, we investigate the spectroscopic properties of small peptides and four-helix bundles that bind Cu(II). Three small peptides, consisting of 15 amino acid residues, were designed to have two arms, each containing a metal-binding site comprised of different combinations of imidazole and carboxylate side chains. Two four-helix bundles each had a binding site for a central dinuclear metal cofactor, with one design incorporating additional potential metal ligands at two identical sites. The small peptides displayed pH-dependent, metal-induced changes in the circular dichroism spectra, consistent with large changes in the secondary structure upon metal binding, while the spectra of the four-helix bundles showed a predominant α-helix content but only small structural changes upon metal binding. Electron paramagnetic resonance spectra were measured at X-band revealing classic Cu(II) axial patterns with hyperfine coupling peaks for the small peptides and four-helix bundles exhibiting a range of values that were related to the specific chemical natures of the ligands. The variety of electronic structures allow us to define the distinctive environment of each metal-binding site in these artificial systems, including the designed additional binding sites in one of the four-helix bundles.

  4. Characterization of molecular mobility in seed tissues: an electron paramagnetic resonance spin probe study.

    PubMed

    Buitink, J; Hemminga, M A; Hoekstra, F A

    1999-06-01

    The relationship between molecular mobility (tauR) of the polar spin probe 3-carboxy-proxyl and water content and temperature was established in pea axes by electron paramagnetic resonance (EPR) and saturation transfer EPR. At room temperature, tauR increased during drying from 10(-11) s at 2.0 g water/g dry weight to 10(-4) s in the dry state. At water contents below 0.07 g water/g dry weight, tauR remained constant upon further drying. At the glass transition temperature, tauR was constant at approximately 10(-4) s for all water contents studied. Above Tg, isomobility lines were found that were approximately parallel to the Tg curve. The temperature dependence of tauR at all water contents studied followed Arrhenius behavior, with a break at Tg. Above Tg the activation energy for rotational motion was approximately 25 kJ/mol compared to 10 kJ/mol below Tg. The temperature dependence of tauR could also be described by the WLF equation, using constants deviating considerably from the universal constants. The temperature effect on tauR above Tg was much smaller in pea axes, as found previously for sugar and polymer glasses. Thus, although glasses are present in seeds, the melting of the glass by raising the temperature will cause only a moderate increase in molecular mobility in the cytoplasm as compared to a huge increase in amorphous sugars.

  5. Membrane-Sugar Interactions Probed by Pulsed Electron Paramagnetic Resonance of Spin Labels.

    PubMed

    Konov, Konstantin B; Leonov, Dmitry V; Isaev, Nikolay P; Fedotov, Kirill Yu; Voronkova, Violeta K; Dzuba, Sergei A

    2015-08-13

    Sugars can stabilize biological systems under extreme desiccation and freezing conditions. Hypothetical molecular mechanisms suggest that the stabilization effect may be determined either by specific interactions of sugars with biological molecules or by the influence of sugars on the solvating shell of the biomolecule. To explore membrane-sugar interactions, we applied electron spin echo envelope modulation (ESEEM) spectroscopy, a pulsed version of electron paramagnetic resonance (EPR), to phospholipid bilayers with spin-labeled lipids added and solvated by aqueous deuterated sucrose and trehalose solutions. The phospholipids were 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC). The spin-labeled lipids were 1,2-dipalmitoyl-sn-glycero-3-phospho(TEMPO)choline (T-PCSL), with spin-label TEMPO at the lipid polar headgroup. The deuterium ESEEM amplitude was calibrated using known concentrations of glassy deuterated sugar solvents. The data obtained indicated that the sugar concentration near the membrane surface obeyed a simple Langmuir model of monolayer adsorption, which assumes direct sugar-molecule bonding to the bilayer surface.

  6. Innovative magnetic resonance imaging diagnostic agents based on paramagnetic Gd(III) complexes.

    PubMed

    Aime, Silvio; Dastrù, Walter; Crich, Simonetta Geninatti; Gianolio, Eliana; Mainero, Valentina

    2002-01-01

    Gd(III) complexes are under intense scrutiny as contrast agents for magnetic resonance imaging (MRI). They act by enhancing tissutal proton relaxation rates. Much has already been done in order to get an in-depth understanding of the relationships between structure, dynamics, and contrastographic ability of these paramagnetic complexes. Their potential in the assessment of flow, perfusion, and capillary permeability has already been established. The next challenges are in the field of molecular imaging applications, which would allow the attainment of early diagnosis based on the recognition of specific reporters of the onset of the pathological state. To this end, Gd(III) complexes have to be endowed with improved targeting capabilities by conjugating suitable recognition synthons on their surfaces. Small peptides are candidates of choice for the attainment of this goal. Moreover, the intrinsic low sensitivity of the NMR techniques implies the need to deliver large amounts of contrast agents to the target in order to get its visualization in the resulting images. Highly efficient delivery systems have been identified, which bring a great promise for the development of innovative diagnostic agents based on Gd(III) complexes.

  7. 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.

  8. 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.

  9. Detection and structural characterization of oxo-chromium(V)-sugar complexes by electron paramagnetic resonance.

    PubMed

    Sala, Luis F; González, Juan C; García, Silvia I; Frascaroli, María I; Van Doorslaer, Sabine

    2011-01-01

    This article describes the detection and characterization of oxo-Cr(V)-saccharide coordination compounds, produced during chromic oxidation of carbohydrates by Cr(VI) and Cr(V), using electron paramagnetic resonance (EPR) spectroscopy. After an introduction into the main importance of chromium (bio)chemistry, and more specifically the oxo-chromium(V)-sugar complexes, a general overview is given of the current state-of-the-art EPR techniques. The next step reviews which types of EPR spectroscopy are currently applied to oxo-Cr(V) complexes, and what information about these systems can be gained from such experiments. The advantages and pitfalls of the different approaches are discussed, and it is shown that the potential of high-field and pulsed EPR techniques is as yet still largely unexploited in the field of oxo-Cr(V) complexes. Subsequently, the discussion focuses on the analysis of oxo-Cr(V) complexes of different types of sugars and the implications of the results in terms of understanding chromium (bio)chemistry.

  10. 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

  11. Characterization of molecular mobility in seed tissues: an electron paramagnetic resonance spin probe study.

    PubMed Central

    Buitink, J; Hemminga, M A; Hoekstra, F A

    1999-01-01

    The relationship between molecular mobility (tauR) of the polar spin probe 3-carboxy-proxyl and water content and temperature was established in pea axes by electron paramagnetic resonance (EPR) and saturation transfer EPR. At room temperature, tauR increased during drying from 10(-11) s at 2.0 g water/g dry weight to 10(-4) s in the dry state. At water contents below 0.07 g water/g dry weight, tauR remained constant upon further drying. At the glass transition temperature, tauR was constant at approximately 10(-4) s for all water contents studied. Above Tg, isomobility lines were found that were approximately parallel to the Tg curve. The temperature dependence of tauR at all water contents studied followed Arrhenius behavior, with a break at Tg. Above Tg the activation energy for rotational motion was approximately 25 kJ/mol compared to 10 kJ/mol below Tg. The temperature dependence of tauR could also be described by the WLF equation, using constants deviating considerably from the universal constants. The temperature effect on tauR above Tg was much smaller in pea axes, as found previously for sugar and polymer glasses. Thus, although glasses are present in seeds, the melting of the glass by raising the temperature will cause only a moderate increase in molecular mobility in the cytoplasm as compared to a huge increase in amorphous sugars. PMID:10354457

  12. 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.

  13. Cysteine-Specific Cu2+ Chelating Tags Used as Paramagnetic Probes in Double Electron Electron Resonance

    PubMed Central

    Cunningham, Timothy F.; Shannon, Matthew D.; Putterman, Miriam R.; Arachchige, Rajith J.; Sengupta, Ishita; Gao, Min; Jaroniec, Christopher P.; Saxena, Sunil

    2015-01-01

    Double electron electron resonance (DEER) is an attractive technique that is utilized for gaining insight into protein structure and dynamics via nanometer-scale distance measurements. The most commonly used paramagnetic tag in these measurements is a nitroxide spin label, R1. Here, we present the application of two types of high-affinity Cu2+ chelating tags, based on the EDTA and cyclen metal-binding motifs as alternative X-band DEER probes, using the B1 immunoglobulin-binding domain of protein G (GB1) as a model system. Both types of tags have been incorporated into a variety of protein secondary structure environments and exhibit high spectral sensitivity. In particular, the cyclen-based tag displays distance distributions with comparable distribution widths and most probable distances within 1–3 Å when compared to homologous R1 distributions. The results display the viability of the cyclen tag as an alternative to the R1 side chain for X-band DEER distance measurements in proteins. PMID:25608028

  14. Menadione-induced cytotoxicity effects on human erythrocyte membranes studied by electron paramagnetic resonance.

    PubMed

    Trad, C H; Butterfield, D A

    1994-08-01

    Menadione (2-methyl-1,4-naphthoquinone) is cytotoxic to hepatocytes. In order to begin to investigate the changes in the physical state of membranes induced by this cytotoxic substance, electron paramagnetic resonance (EPR) spin-labeling techniques were used in conjunction with spin labels specific for cytoskeletal proteins, bilayer lipids, or cell-surface sialic acid or galactose to investigate erythrocyte membranes. We studied the molecular effects of oxidation of 200 microM menadione on the different membrane domains. The major findings are: (1) menadione increases protein-protein interactions (P < 0.001) of cytoskeletal proteins, (2) there is a slightly significant increase in the rotational motion of spin-labeled sialic acid (P < 0.05), while (3) the physical state of galactose residues was unaffected by menadione. Since glycophorin is coupled to the major cytoskeletal protein, spectrin, by protein 4.1, we suggest that menadione-induced oxidation could alter the conformation of protein 4.1. As a consequence, single or multiple sites of weakness could be induced leading to the alteration of the interactions of the cytoskeletal network and its anchoring domains in the membrane. These results are discussed with reference to possible mechanisms involved in the cytotoxic action of menadione.

  15. 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.

  16. Sensor fusion of electron paramagnetic resonance and magnetorelaxometry data for quantitative magnetic nanoparticle imaging

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    Magnetorelaxometry (MRX) imaging and electron paramagnetic resonance (EPR) are two non-invasive techniques capable of recovering the magnetic nanoparticle (MNP) distribution. Both techniques solve an ill-posed inverse problem in order to find the spatial MNP distribution. A lot of research has been done on increasing the stability of these inverse problems with the main objective to improve the quality of MNP imaging. In this paper a proof of concept is presented in which the sensor data of both techniques is fused into EPR–MRX, with the intention to stabilize the inverse problem. First, both techniques are compared by reconstructing several phantoms with different sizes for various noise levels and calculating stability, sensitivity and reconstruction quality parameters for these cases. This study reveals that both techniques are sensitive to different information from the MNP distributions and generate complementary measurement data. As such, their merging might stabilize the inverse problem. In a next step we investigated how both techniques need to be combined to reduce their respective drawbacks, such as a high number of required measurements and reduced stability, and to improve MNP reconstructions. We were able to stabilize both techniques, increase reconstruction quality by an average of 5% and reduce measurement times by 88%. These improvements could make EPR–MRX a valuable and accurate technique in a clinical environment.

  17. 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.

  18. 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.

  19. 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.

  20. Pulsed electron paramagnetic resonance spectroscopy powered by a free-electron laser.

    PubMed

    Takahashi, S; Brunel, L-C; Edwards, D T; van Tol, J; Ramian, G; Han, S; Sherwin, M S

    2012-09-20

    Electron paramagnetic resonance (EPR) spectroscopy interrogates unpaired electron spins in solids and liquids to reveal local structure and dynamics; for example, EPR has elucidated parts of the structure of protein complexes that other techniques in structural biology have not been able to reveal. EPR can also probe the interplay of light and electricity in organic solar cells and light-emitting diodes, and the origin of decoherence in condensed matter, which is of fundamental importance to the development of quantum information processors. Like nuclear magnetic resonance, EPR spectroscopy becomes more powerful at high magnetic fields and frequencies, and with excitation by coherent pulses rather than continuous waves. However, the difficulty of generating sequences of powerful pulses at frequencies above 100 gigahertz has, until now, confined high-power pulsed EPR to magnetic fields of 3.5 teslas and below. Here we demonstrate that one-kilowatt pulses from a free-electron laser can power a pulsed EPR spectrometer at 240 gigahertz (8.5 teslas), providing transformative enhancements over the alternative, a state-of-the-art ∼30-milliwatt solid-state source. Our spectrometer can rotate spin-1/2 electrons through π/2 in only 6 nanoseconds (compared to 300 nanoseconds with the solid-state source). Fourier-transform EPR on nitrogen impurities in diamond demonstrates excitation and detection of EPR lines separated by about 200 megahertz. We measured decoherence times as short as 63 nanoseconds, in a frozen solution of nitroxide free-radicals at temperatures as high as 190 kelvin. Both free-electron lasers and the quasi-optical technology developed for the spectrometer are scalable to frequencies well in excess of one terahertz, opening the way to high-power pulsed EPR spectroscopy up to the highest static magnetic fields currently available.

  1. 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.

  2. Radiation Dosimetry Study in Dental Enamel of Human Tooth Using Electron Paramagnetic Resonance

    NASA Astrophysics Data System (ADS)

    De, Tania; Romanyukha, Alex; Pass, Barry; Misra, Prabhakar

    2009-07-01

    Electron paramagnetic resonance (EPR) dosimetry of tooth enamel is used for individual dose reconstruction following radiation accidents. The purpose of this study is to develop a rapid, minimally invasive technique of obtaining a sample of dental enamel small enough to not disturb the structure and functionality of a tooth and to improve the sensitivity of the spectral signals using X-band (9.4 GHz) and Q-band (34 GHz) EPR technique. In this study EPR measurements in X-band were performed on 100 mg isotropic powdered enamel samples and Q-band was performed on 4 mg, 1×1×3 mm enamel biopsy samples. All samples were obtained from discarded teeth collected during normal dental treatment. To study the variation of the Radiation-Induced Signal (RIS) at different orientations in the applied magnetic field, samples were placed in the resonance cavity for Q-band EPR. X-band EPR measurements were performed on 100 mg isotropic powdered enamel samples. In X-band spectra, the RIS is distinct from the "native" radiation-independent signal only for doses >0.5 Gy. Q-band, however, resolves the RIS and "native" signals and improves sensitivity by a factor of 20, enabling measurements in 2-4 mg tooth enamel samples, as compared to 100 mg for X-band. The estimated lower limit of Q-band dose measurement is 0.5 Gy. Q-band EPR enamel dosimetry results in greater sensitivity and smaller sample size through enhanced spectral resolution. Thus, this can be a valuable technique for population triage in the event of detonation of a radiation dispersal device ("dirty" bomb) or other radiation event with massive casualties. Further, the small 4 mg samples can be obtained by a minimally-invasive biopsy technique.

  3. Electron Paramagnetic Resonance and Electron-Nuclear Double Resonance Characterization of Point Defects in Titanium dioxide Crystals

    NASA Astrophysics Data System (ADS)

    Brant, Adam

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) are used to characterize several point defects in titanium dioxide (TiO2) single crystals in the rutile phase. A defect reported in 1961 by P. F. Chester called the “A Center” is assigned to a neutral hydrogen donor. Many researchers believe that the model for this S = 1/2 defect is an interstitial titanium ion (Ti3+) and that Ti3+ interstitials are the most dominant shallow donor in TiO 2. I show that the model for the A center is a neutral hydrogen donor and suggest that the Ti3+ interstitial model is not the most prevalent shallow donor defect in TiO2. Substitutional Cu2+ defects that are unintentionally introduced to TiO2 (rutile) during growth are characterized and assigned to a Cu2+ ion with an adjacent oxygen vacancy. Exact matrix diagonalization is used here to compute accurate values for the nuclear quadrupole parameter. The reduced intensity of the Cu2+ EPR signal when the sample is illuminated with 442 nm laser light as well as the appearance of photoinduced EPR signals due to singly and doubly ionized oxygen vacancies provide evidence that the Cu2+ defect has an adjacent oxygen vacancy. Interstitial lithium ions (Li+) adjacent to Ti 3+ ions and substitutional Fe3+ defects (Fe 3+ - Li+) are also characterized. These defects were introduced to the rutile crystal by heating at 450 °C in LiOH powder for times on the order of several hours. Principal values and principal axis directions of the g matrix are calculated for the interstitial Li+ ion adjacent to a Ti3+ ion and photoinduced effects of the Fe 3+ - Li+ defect are examined.

  4. 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

  5. Mapping RNA-protein interactions in ribonuclease P from Escherichia coli using electron paramagnetic resonance spectroscopy.

    PubMed

    Gopalan, V; Kühne, H; Biswas, R; Li, H; Brudvig, G W; Altman, S

    1999-02-09

    Ribonuclease P (RNase P) is a catalytic ribonucleoprotein (RNP) essential for tRNA biosynthesis. In Escherichia coli, this RNP complex is composed of a catalytic RNA subunit, M1 RNA, and a protein cofactor, C5 protein. Using the sulfhydryl-specific reagent (1-oxyl-2,2,5, 5-tetramethyl-Delta3-pyrroline-3-methyl)methanethiosulfonate (MTSL), we have introduced a nitroxide spin label individually at six genetically engineered cysteine residues (i.e., positions 16, 21, 44, 54, 66, and 106) and the native cysteine residue (i.e., position 113) in C5 protein. The spin label covalently attached to any protein is sensitive to structural changes in its microenvironment. Therefore, we expected that if the spin label introduced at a particular position in C5 protein was present at the RNA-protein interface, the electron paramagnetic resonance (EPR) spectrum of the spin label would be altered upon binding of the spin-labeled C5 protein to M1 RNA. The EPR spectra observed with the various MTSL-modified mutant derivatives of C5 protein indicate that the spin label attached to the protein at positions 16, 44, 54, 66, and 113 is immobilized to varying degrees upon addition of M1 RNA but not in the presence of a catalytically inactive, deletion derivative of M1 RNA. In contrast, the spin label attached to position 21 displays an increased mobility upon binding to M1 RNA. The results from this EPR spectroscopy-based approach together with those from earlier studies identify residues in C5 protein which are proximal to M1 RNA in the RNase P holoenzyme complex.

  6. Electron paramagnetic resonance method for the quantitative assay of ketoconazole in pharmaceutical preparations.

    PubMed

    Morsy, Mohamed A; Sultan, Salah M; Dafalla, Hatim

    2009-08-15

    In this study, electron paramagnetic resonance (EPR) is used, for the first time, as an analytical tool for the quantitative assay of ketoconazole (KTZ) in drug formulations. The drug was successfully characterized by the prominent signals by two radical species produced as a result of its oxidation with 400 microg/mL cerium(IV) in 0.10 mol dm(-3) sulfuric acid. The EPR signal of the reaction mixture was measured in eight capillary tubes housed in a 4 mm EPR sample tube. The radical stability was investigated by obtaining multi-EPR scans of each KTZ sample solution at time intervals of 2.5 min of the reaction mixing time. The plot of the disappearance of the radical species show that the disappearance is apparently of zero order. The zero-time intercept of the EPR signal amplitude, which should be proportional to the initial radical concentration, is linear in the sample concentration in the range between 100 and 400 microg/mL, with a correlation coefficient, r, of 0.999. The detection limit was determined to be 11.7 +/- 2.5 microg/mL. The method newly adopted was fully validated following the United States Pharmacopeia (USP) monograph protocol in both the generic and the proprietary forms. The method is very accurate, such that we were able to measure the concentration at confidence levels of 99.9%. The method was also found to be suitable for the assay of KTZ in its tablet and cream pharmaceutical preparations, as no interferences were encountered from excipients of the proprietary drugs. High specificity, simplicity, and rapidity are the merits of the present method compared to the previously reported methods.

  7. 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

  8. Pulse radiolysis of alkanes: A time-resolved electron paramagnetic resonance study

    SciTech Connect

    Shkrob, I.A.; Trifunac, A.D.

    1994-02-14

    Time-resolved spin-echo-detected electron paramagnetic resonance (EPR) was applied to examine short-lived alkyl radicals formed in pulse radiolysis of liquid alkanes. It was found that the ratio of yields of penultimate and interior radicals in n-alkanes at the instant of their generation is temperature-independent and is ca. 1.25 times greater than the statistical quantity. This higher-than-statistical production of penultimate radicals indicates that the fast ion molecule reactions involving radical cations are a significant route of radical generation. The analysis of spin-echo kinetics in n-alkanes suggests that the alkyl radicals are emissively polarized in spur reactions. this initial polarization rapidly increases with shortening of the aliphatic chain. Another finding is that a long-chain structure of these radicals results in much higher rate of Heisenberg spin exchange relative to the recombination rate. The relative yields of hydrogen abstraction and fragmentation for various branched alkanes are estimated. It is concluded that the fragmentation occurs prior to the formation of radicals in an excited precursor species. Effects of phenolic and alkene additives in radiolysis of n-alkanes are examined. It is demonstrated that phenoxy radicals are produced in dissociative capture of electrons and alkane holes. Another route is a reaction of phenols with free hydrogen atoms. A rapid transfer of singlet correlation from the geminate radical ion pairs is responsible for unusual polarization patterns in the phenoxy and cyclohexadienyl radicals. The significance of these results in the context of cross-linking in polyethylene and higher paraffins is discussed. 56 refs.

  9. Motion of subfragment-1 in myosin and its supramolecular complexes: saturation transfer electron paramagnetic resonance.

    PubMed Central

    Thomas, D D; Seidel, J C; Hyde, J S; Gergely, J

    1975-01-01

    Molecular dynamics in spin-labeled muscle proteins was studied with a recently developed electron paramagnetic resonance (EPR) technique, saturation transfer spectroscopy, which is uniquely sensitive to rotational motion in the range of 10(-7)-10(-3) sec. Rotational correlation time (tau2) were determined for a spin label analog of iodoacetamide bound to the subfragment-1 (S-1) region of myosin under a variety of conditions likely to shed light on the molecular mechanism of muscle contraction. Results show that (a) the spin labels are rigidly bound to the isolated S-1 (tau2 = 2 x 10(-7) sec) and can be used to estimate values of tau2 for the S-1 region of the myosin molecule; (b) in solutions of intact myosin, S-1 has considerable mobility relative to the rest of the myosin molecule, the value of tau2 for the S-1 segment of myosin being less than twice that for isolated S-1, while the molecular weights differ by a factor of 4 to 5; (c) in myosin filaments, tau2 increases by a factor of only about 10, suggesting motion of the S-1 regions independent of the backbone of the myosin filament, but slower than that in a single molecule; (d) addition of F-actin to solutions of myosin or S-1 increases tau2 by a factor of nearly 10(3), indicating strong immobilization of S-1 upon binding to actin. Saturation transfer spectroscopy promises to provide an extremely useful tool for the study of the motions of the crossbridges and thin filaments in reconstituted systems and in glycerinated muscle fibers. PMID:168572

  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. The sensitivity of saturation transfer electron paramagnetic resonance spectra to restricted amplitude uniaxial rotational diffusion.

    PubMed

    Hustedt, E J; Beth, A H

    2001-12-01

    Computational methods have been developed to model the effects of constrained or restricted amplitude uniaxial rotational diffusion (URD) on saturation transfer electron paramagnetic resonance (ST-EPR) signals observed from nitroxide spin labels. These methods, which have been developed to model the global rotational motion of intrinsic membrane proteins that can interact with the cytoskeleton or other peripheral proteins, are an extension of previous work that described computationally efficient algorithms for calculating ST-EPR spectra for unconstrained URD (Hustedt and Beth, 1995, Biophys. J. 69:1409-1423). Calculations are presented that demonstrate the dependence of the ST-EPR signal (V'(2)) on the width (Delta) of a square-well potential as a function of the microwave frequency, the correlation time for URD, and the orientation of the spin-label with respect to the URD axis. At a correlation time of 10 micros, the V'(2) signal is very sensitive to Delta in the range from 0 to 60 degrees, marginally sensitive from 60 degrees to 90 degrees, and insensitive beyond 90 degrees. Sensitivity to Delta depends on the correlation time for URD with higher sensitivity to large values of Delta at the shorter correlation times, on the microwave frequency, and on the orientation of the spin-label relative to the URD axis. The computational algorithm has been incorporated into a global nonlinear least-squares analysis approach, based upon the Marquardt-Levenberg method (Blackman et al., 2001, Biophys. J. 81:3363-3376). This has permitted determination of the correlation time for URD and the width of the square-well potential by automated fitting of experimental ST-EPR data sets obtained from a spin-labeled membrane protein and provided a new automated method for analysis of data obtained from any system that exhibits restricted amplitude URD.

  12. In vivo nuclear magnetic resonance imaging of myocardial perfusion using the paramagnetic contrast agent manganese gluconate.

    PubMed

    Schaefer, S; Lange, R A; Kulkarni, P V; Katz, J; Parkey, R W; Willerson, J T; Peshock, R M

    1989-08-01

    Previous nuclear magnetic resonance (NMR) imaging studies have indicated that coronary occlusion does not produce sufficient changes in standard tissue relaxation times to allow the detection of acute ischemia. To identify acute myocardial perfusion abnormalities, the use of the paramagnetic agent manganese gluconate combined with calcium gluconate (MnGlu/CaGlu) was investigated in canine models of acute coronary artery occlusion. In vitro studies showed that MnGlu/CaGlu was a more efficient relaxing agent than gadolinium-DTPA (relaxivity of 7.8 versus 5.1 s-1 mM-1) and demonstrated affinity for normal myocardium. The distribution of MnGlu/CaGlu as measured by manganese-54 tracer studies was proportional to myocardial blood flow in both normal and ischemic tissue. Hearts excised from dogs after coronary artery occlusion and administration of 0.035 mM/kg MnGlu/CaGlu were imaged ex vivo using a relatively spin-lattice relaxation time (T1)-weighted gradient reversal technique (repetition time [TR] 50 ms and echo time [TE] 9 ms). These images showed increased signal intensity in the normally perfused myocardium with a mean signal intensity ratio of hypoperfused to normal myocardium of 0.55 +/- 0.12 (mean +/- SD). In vivo images obtained in nine dogs after coronary artery occlusion and administration of the same dose of MnGlu/CaGlu demonstrated the region of hypoperfused myocardium in six dogs with a signal intensity ratio of hypoperfused to normal myocardium of 0.64 +/- 0.23 (p less than 0.05 versus control). When a higher dose of 0.1 mM/kg MnGlu/CaGlu was utilized and in vivo imaging was performed using a relatively spin-spin relaxation time (T2)-weighted (TR gated, TE 60 ms) spin-echo sequence in six dogs, the signal intensity of normal myocardium was decreased.(ABSTRACT TRUNCATED AT 250 WORDS)

  13. Synthesis and characterization of a combined fluorescence, phosphorescence, and electron paramagnetic resonance probe

    NASA Astrophysics Data System (ADS)

    Beth, Albert H.; Cobb, Charles E.; Beechem, Joseph M.

    1992-04-01

    A spin-labeled derivative of eosin was chemically synthesized from 5-aminoeosin and the nitroxide spin label 2,2,5,5-tetramethylpyrrolin-1-oxyl-3-carboxylic acid. Following determination of the chemical identity of the spin-labeled eosin (5-SLE) by FAB mass spectroscopy, its optical and magnetic resonance spectroscopic properties were characterized in aqueous solution and compared to a diamagnetic eosin derivative, 5-acetamido eosin (5- AcE). The visible light absorption maximum of 5-SLE was 518 nm, the same as for 5-AcE. The fluorescence quantum yield of 5-SLE was only reduced by approximately 10% relative to 5-AcE, and the fluorescence lifetime was marginally reduced relative to 5-AcE. The phosphorescence lifetime and yield for 5-SLE were very similar to those for 5-AcE. The phosphorescence yield of 5-SLE bound noncovalently to BSA was reduced by approximately 60% relative to 5-AcE, and the phosphorescence lifetime reduced from approximately 2.4 msec (5-AcE) to 1.6 msec (5-SLE). Reduction of the nitroxide moiety of the 5-SLE with sodium ascorbate resulted in minimal changes in the fluorescence and phosphorescence quantum yields and lifetimes. This indicated that the unpaired electron of the nitroxide spin label did not seriously affect the optical spectroscopic characteristics of the spin-labeled eosin molecule. The quantum yields and lifetimes of 5-SLE were still quite acceptable for time- resolved fluorescence and phosphorescence studies. The electron paramagnetic resonance (EPR) spectrum of 5-SLE in aqueous solution has a lineshape consistent with a molecule the size of 5-SLE undergoing rapid rotational reorientation. When bound to BSA, the EPR spectrum of 5-SLE was broadened to a near slow motion limit for EPR, as expected for the relatively slowly rotating protein-5-SLE complex. Time-resolved phosphorescence anisotropy and saturation transfer EPR (ST-EPR) experiments with samples of 5-SLE bound to BSA in solutions of varying glycerol concentrations at 2

  14. 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

  15. 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.

  16. 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

  17. 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

  18. Sources of signals in electron paramagnetic resonance radiation biodosimetry in bone

    NASA Astrophysics Data System (ADS)

    Melanson, Mark Allen

    1999-10-01

    Electron paramagnetic resonance dosimetry, or EPR, is a useful biomarker of radiation absorbed dose in bone and teeth because the tissue itself serves as the dosimeter, with each sample being self-calibrated in terms of its response. In actual cases of retrospective dose assessment, comparisons between EPR and traditional dosimetric methods have revealed both significant underestimations and overestimations of dose on the part of EPR. While radiation induced EPR signals in bone crystal eventually stabilize, the composite signal initially fades after dosing (IK85). Irradiation of the crystal structure of bone produces multiple signals, some stable and some transient. It is hypothesized that one of these unstable signals is responsible for the immediate fading of the radiation induced crystalline signal, thereby causing the widely observed deviations in dose estimations between EPR and other, well established dosimetric methods. To test this hypothesis, both untreated bone and bone treated with diethylenetriamine, a solvent used to deproteinate bone, were studied. Repeated measurements of the radiation induced signal in both untreated and deproteinated bone showed a partial fading of the primary signal used in EPR bone dosimetry. Spectral algebra identified the source of this instability to be the decay of an interfering signal in the bone crystal, also radiation induced, that overlaps the signal of interest. This work has produced four major results: (1)Sample preparation and treatment can generate extraneous signals that interfere with the proper measurement of the radiation induced EPR signal. (2)The interfering signal from another transient, radiogenic radical in hydroxyapatite, CO 33-, affects accurate measurement of the primary signal used in dosimetry, CO2-, causing underestimations at low doses and overestimations at high doses. A model devised to explain how this interfering signal actually distorts the dose estimation process was consistent with data

  19. 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

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

    PubMed Central

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

    2016-01-01

    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 – 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

  1. 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

  2. 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

  3. Electron paramagnetic resonance study of 14N and 19F superhyperfine interaction in VO 2+ doped propylenediammonium hexafluorozirconate

    NASA Astrophysics Data System (ADS)

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

    1998-05-01

    Electron paramagnetic resonance spectra have been recorded at X-band frequencies at room temperature on VO 2+ molecular ion in propylenediammonium hexafluorozirconate, [H 3N(CH 2) 3NH 3]ZrF 6, single crystals. The superhyperfine structure caused by 14N and 19F has been clearly observed in the spectra. The two sets of spectra observed are related to each other by the symmetry operations of the host crystals and represent vanadyl ion at two magnetically distinguishable interstitial sites in the unit cell.

  4. Influence of zeolite water on paramagnetic and ferromagnetic resonances in the Co2[Nb(CN)8] · 8H2O molecular magnet

    NASA Astrophysics Data System (ADS)

    Dmitriev, A. I.; Koplak, O. V.; Kirman, M. V.; Tokoro, H.; Ohkoshi, S.; Morgunov, R. B.

    2013-08-01

    The contributions of Co2+ and Nb4+ ions to the high-frequency dynamic magnetic susceptibility of the Co2[Nb(CN)8] · 8H2O molecular magnet in the paramagnetic state at T > 12 K are separated. It is found that the ferromagnetic ordering, which leads to the reconstruction of the electron paramagnetic resonance spectrum into the ferromagnetic resonance spectrum, occurs at T < 12 K. The influence of zeolite water on the spectra of the paramagnetic and ferromagnetic resonances is found. Dehydration leads to a decrease in the time of the spin relaxation of the ferromagnetic system from 50 ps to 17 ps at T = 4 K and to the variation in the temperature dependences of the widths of the lines and g factors in the electron spin resonance spectra.

  5. 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 (Qresonance while enabling measurement of the transmitted signal. The large filling factor of the resonator permits sensitivities comparable to that of high-quality factor resonant cavities. The integrated sensor enables measurement of the magnetization response of micron scale samples upon application of microwave fields. In particular, the combined measurement of the magnetization change and the microwave power under cw microwave irradiation of single crystal of molecular magnets is used to determine of the energy relaxation time of the molecular spin states. In addition, real-time measurements of the magnetization dynamics upon application of fast microwave pulses are demonstrated.

  6. 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

  7. Development and validation of an ex vivo electron paramagnetic resonance fingernail biodosimetric method.

    PubMed

    He, Xiaoming; Swarts, Steven G; Demidenko, Eugene; Flood, Ann B; Grinberg, Oleg; Gui, Jiang; Mariani, Michael; Marsh, Stephen D; Ruuge, Andres E; Sidabras, Jason W; Tipikin, Dmitry; Wilcox, Dean E; Swartz, Harold M

    2014-06-01

    There is an imperative need to develop methods that can rapidly and accurately determine individual exposure to radiation for screening (triage) populations and guiding medical treatment in an emergency response to a large-scale radiological/nuclear event. To this end, a number of methods that rely on dose-dependent chemical and/or physical alterations in biomaterials or biological responses are in various stages of development. One such method, ex vivo electron paramagnetic resonance (EPR) nail dosimetry using human nail clippings, is a physical biodosimetry technique that takes advantage of a stable radiation-induced signal (RIS) in the keratin matrix of fingernails and toenails. This dosimetry method has the advantages of ubiquitous availability of the dosimetric material, easy and non-invasive sampling, and the potential for immediate and rapid dose assessment. The major challenge for ex vivo EPR nail dosimetry is the overlap of mechanically induced signals and the RIS. The difficulties of analysing the mixed EPR spectra of a clipped irradiated nail were addressed in the work described here. The following key factors lead to successful spectral analysis and dose assessment in ex vivo EPR nail dosimetry: (1) obtaining a thorough understanding of the chemical nature, the decay behaviour, and the microwave power dependence of the EPR signals, as well as the influence of variation in temperature, humidity, water content, and O₂ level; (2) control of the variability among individual samples to achieve consistent shape and kinetics of the EPR spectra; (3) use of correlations between the multiple spectral components; and (4) use of optimised modelling and fitting of the EPR spectra to improve the accuracy and precision of the dose estimates derived from the nail spectra. In the work described here, two large clipped nail datasets were used to test the procedures and the spectral fitting model of the results obtained with it. A 15-donor nail set with 90 nail samples

  8. Domain structure in biphenyl incommensurate phase II observed by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Véron, A.; Emery, J.; Spiesser, M.

    1994-11-01

    The domain structure in incommensurate phase II of single biphenyl crystal has been observed by investigations of the optically excited states of the Electronic Paramagnetic Resonance (E.P.R.) deuterated naphthalene molecular probes which substitute biphenyl molecules. Our results confirm that this phase is a 1q bi-domain one. The analysis of the spectra obtained in X band (9.5 GHz) experiments, in relation with the spin Hamiltonian parameter properties permits us to show that the E.P.R. probe rotates around a direction perpendicular to its long axis while the biphenyl molecule undergoes a twist movement around this axis. They also account for a regime which is like a “ multi-soliton " regime while the modulation is a plane wave one in the pure single crystal. The two molecules of the high temperature cell do not exactly experience the saure displacement field in the incommensurate phase and consequently the two domains can be distinguished. The spin Hamiltonian parameters which characterize the E.P.R. probes have been determined in the incommensurate phase II of biphenyl. La structure en domaines de la phase II du biphényle est mise en évidence par les investigations dans les états photo-excités des molécules de naphtalène deutéré, utilisées comme sondes de Résonance Paramagnétique Electronique, se substituant de manière diluée dans le mono-cristal de biphényle. Ceci confirme que cette phase est 1q bi-domaine. L'analyse des spectres obtenus dans des expériences en bande X (9.5 GHz) en relation avec les propriétés de l'hamiltonien de spin permet de montrer que la sonde moléculaire tourne autour d'une direction perpendiculaire à son grand axe alors que la molécule de biphényle subit un mouvement de twist autour de cet axe. Les résultats montrent que ces sondes rendent compte d'un régime qui est comme un régime “ multi-solitons " alors que la modulation est plane dans le cristal pur. Les deux molécules sondes de la cellule

  9. Electron Paramagnetic Resonance Characterization of Tetrahydrobiopterin Radical Formation in Bacterial Nitric Oxide Synthase Compared to Mammalian Nitric Oxide Synthase

    PubMed Central

    Brunel, Albane; Santolini, Jérôme; Dorlet, Pierre

    2012-01-01

    H4B is an essential catalytic cofactor of the mNOSs. It acts as an electron donor and activates the ferrous heme-oxygen complex intermediate during Arg oxidation (first step) and NOHA oxidation (second step) leading to nitric oxide and citrulline as final products. However, its role as a proton donor is still debated. Furthermore, its exact involvement has never been explored for other NOSs such as NOS-like proteins from bacteria. This article proposes a comparative study of the role of H4B between iNOS and bsNOS. In this work, we have used freeze-quench to stop the arginine and NOHA oxidation reactions and trap reaction intermediates. We have characterized these intermediates using multifrequency electron paramagnetic resonance. For the first time, to our knowledge, we report a radical formation for a nonmammalian NOS. The results indicate that bsNOS, like iNOS, has the capacity to generate a pterin radical during Arg oxidation. Our current electron paramagnetic resonance data suggest that this radical is protonated indicating that H4B may not transfer any proton. In the 2nd step, the radical trapped for iNOS is also suggested to be protonated as in the 1st step, whereas it was not possible to trap a radical for the bsNOS 2nd step. Our data highlight potential differences for the catalytic mechanism of NOHA oxidation between mammalian and bacterial NOSs. PMID:22828337

  10. Comparison of electron paramagnetic resonance methods to determine distances between spin labels on human carbonic anhydrase II.

    PubMed Central

    Persson, M; Harbridge, J R; Hammarström, P; Mitri, R; Mårtensson, L G; Carlsson, U; Eaton, G R; Eaton, S S

    2001-01-01

    Four doubly spin-labeled variants of human carbonic anhydrase II and corresponding singly labeled variants were prepared by site-directed spin labeling. The distances between the spin labels were obtained from continuous-wave electron paramagnetic resonance spectra by analysis of the relative intensity of the half-field transition, Fourier deconvolution of line-shape broadening, and computer simulation of line-shape changes. Distances also were determined by four-pulse double electron-electron resonance. For each variant, at least two methods were applicable and reasonable agreement between methods was obtained. Distances ranged from 7 to 24 A. The doubly spin-labeled samples contained some singly labeled protein due to incomplete labeling. The sensitivity of each of the distance determination methods to the non-interacting component was compared. PMID:11371461

  11. 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.

  12. 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.

  13. 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

  14. In vitro neurotoxicity of magnetic resonance imaging (MRI) contrast agents: influence of the molecular structure and paramagnetic ion.

    PubMed

    Bertin, Annabelle; Michou-Gallani, Anne-Isabelle; Gallani, Jean-Louis; Felder-Flesch, Delphine

    2010-08-01

    Interest in contrast agent's (CA) neurotoxicity has greatly increased due to the growing need of new compounds dedicated to brain imaging. Magnetic resonance imaging (MRI) CA have been evaluated by means of different toxicological assays with cultured rat primary neurons (evaluation of neurite specific parameters via immunostaining of the cells and LDH leakage). To determine the potential neurotoxicity of a precise paramagnetic ion in a defined structure (architecture and molecular weight), novel hydrosoluble dendritic Manganese (II) and Gadolinium (III) complexes derived from diethylenetriamine pentaacetic acid (DTPA) have been studied and compared to a linear homologue (same molecular weight) and commercially available low molecular weight MRI CA like Mn-DPDP (Teslascan, GE Healthcare) and Gd-DTPA (Magnevist, Schering). The range of CA concentrations studied was 0.1-10mM, suitable for MRI examinations. This set of experiments allows a toxicity ranking of these reagents as a function of molecular structure and nature of the paramagnetic ion. We could determine that the architecture (linear vs. dendritic) does not play an important role in the in vitro neurotoxicity, whereas the structure of the chelating cage is of greater importance.

  15. Exploring the Radical Nature of a Carbon Surface by Electron Paramagnetic Resonance and a Calibrated Gas Flow

    PubMed Central

    Green, Uri; Shenberger, Yulia; Aizenshtat, Zeev; Cohen, Haim; Ruthstein, Sharon

    2014-01-01

    While the first Electron Paramagnetic Resonance (EPR) studies regarding the effects of oxidation on the structure and stability of carbon radicals date back to the early 1980s the focus of these early papers primarily characterized the changes to the structures under extremely harsh conditions (pH or temperature)1-3. It is also known that paramagnetic molecular oxygen undergoes a Heisenberg spin exchange interaction with stable radicals that extremely broadens the EPR signal4-6. Recently, we reported interesting results where this interaction of molecular oxygen with a certain part of the existing stable radical structure can be reversibly affected simply by flowing a diamagnetic gas through the carbon samples at STP7. As flows of He, CO2, and N2 had a similar effect these interactions occur at the surface area of the macropore system. This manuscript highlights the experimental techniques, work-up, and analysis towards affecting the existing stable radical nature in the carbon structures. It is hoped that it will help towards further development and understanding of these interactions in the community at large. PMID:24796382

  16. 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.

  17. 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

  18. 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.

  19. 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

  20. 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.

  1. Superoxide Anion Radical Production in the Tardigrade Paramacrobiotus richtersi, the First Electron Paramagnetic Resonance Spin-Trapping Study.

    PubMed

    Savic, Aleksandar G; Guidetti, Roberto; Turi, Ana; Pavicevic, Aleksandra; Giovannini, Ilaria; Rebecchi, Lorena; Mojovic, Milos

    2015-01-01

    Anhydrobiosis is an adaptive strategy that allows withstanding almost complete body water loss. It has been developed independently by many organisms belonging to different evolutionary lines, including tardigrades. The loss of water during anhydrobiotic processes leads to oxidative stress. To date, the metabolism of free radicals in tardigrades remained unclear. We present a method for in vivo monitoring of free radical production in tardigrades, based on electron paramagnetic resonance and spin-trap DEPMPO, which provides simultaneous identification of various spin adducts (i.e., different types of free radicals). The spin trap can be easily absorbed in animals, and tardigrades stay alive during the measurements and during 24-h monitoring after the treatment. The results show that hydrated specimens of the tardigrade Paramacrobiotus richtersi produce the pure superoxide anion radical ((•)O2(-)). This is an unexpected result, as all previously examined animals and plants produce both superoxide anion radical and hydroxyl radical ((•)OH) or exclusively hydroxyl radical.

  2. 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.

  3. Characterization of calcium-binding sites in the kidney stone inhibitor glycoprotein nephrocalcin with vanadyl ions: electron paramagnetic resonance and electron nuclear double resonance spectroscopy.

    PubMed Central

    Mustafi, D; Nakagawa, Y

    1994-01-01

    Nephrocalcin (NC) is a calcium-binding glycoprotein of 14,000 molecular weight. It inhibits the growth of calcium oxalate monohydrate crystals in renal tubules. The NC used in this study was isolated from bovine kidney tissue and purified with the use of DEAE-cellulose chromatography into four isoforms, designated as fractions A-D. They differ primarily according to the content of phosphate and gamma-carboxy-glutamic acid. Fractions A and B are strong inhibitors of the growth of calcium oxalate monohydrate crystal, whereas fractions C and D inhibit crystal growth weakly. Fraction A, with the highest Ca(2+)-binding affinity, was characterized with respect to its metal-binding sites by using the vanadyl ion (VO2+) as a paramagnetic probe in electron paramagnetic resonance (EPR) and electron nuclear double resonance (ENDOR) spectroscopic studies. By EPR spectrometric titration, it was shown that fraction A of NC bound VO2+ with a stoichiometry of metal:protein binding of 4:1. Also, the binding of VO2+ to NC was shown to be competitive with Ca2+. Only protein residues were detected by proton ENDOR as ligands, and these ligands bound with complete exclusion of solvent from the inner coordination sphere of the metal ion. This type of metal-binding environment, as derived from VO(2+)-reconstituted NC, differs significantly from the binding sites in other Ca(2+)-binding proteins. PMID:7972057

  4. Structure of radical cations of saturated heterocyclic compounds with two heteroatoms as studied by electron paramagnetic resonance, electron-nuclear double resonance, and density functional theory calculations.

    PubMed

    Nuzhdin, Kirill B; Nesterov, Sergej V; Tyurin, Daniil A; Feldman, Vladimir I; Wei, Liu; Lund, Anders

    2005-07-21

    The radical cations of piperazine, morpholine, thiomorpholine, and thioxane were investigated by electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) spectroscopy in a solid Freon matrix. Optimized geometry and magnetic parameters of the radical cations were calculated using a density functional theory (DFT)/Perdew-Burke-Ernzerhof (PBE) method. Both experimental and theoretical results suggest that all the studied species adopt chair (or distorted chair) conformations. No evidence for the boat conformers with intramolecular sigma-bonding between heteroatoms were obtained. In the cases of morpholine and thioxane, the oxygen atoms are characterized by relatively small spin populations, whereas a major part of spin density is located at N and S atoms, respectively. The thiomorpholine radical cation exhibits nearly equal spin population of N and S atoms. In most cases (except for thioxane), the calculated magnetic parameters agree with the experimental data reasonably well.

  5. Double electron-electron resonance measurements of diamond to determine T2 dependence on concentration of paramagnetic impurities

    NASA Astrophysics Data System (ADS)

    Stepanov, Viktor; Takahashi, Susumu

    A nitrogen-vacancy (NV) center in diamond is a promising candidate for investigation of fundamental sciences and applications to a nanoscale magnetic field sensing device because of unique properties of a NV center in diamond including capability to detect optically detected magnetic resonance (ODMR) signals from a single NV and initialize its spin state. Fundamental studies and applications of NV centers relay on coherent control of the NV centers that is limited by decoherence time (T2) and, as often observed, T2 is limited by paramagnetic impurity contents in diamond crystals. In this work, we will investigate T2 dependence on concentration of nitrogen impurities in type-Ib and type-IIa diamond crystals. For precise determination of the nitrogen concentration, we employ a home-built high-frequency electron spin resonance spectrometer which enables broadband double electron-electron resonance spectroscopy with high spectral resolution. This work is supported by the National Science Foundation (DMR-1508661) and the Searle scholars program.

  6. Exploring intrinsically disordered proteins using site-directed spin labeling electron paramagnetic resonance spectroscopy

    PubMed Central

    Le Breton, Nolwenn; Martinho, Marlène; Mileo, Elisabetta; Etienne, Emilien; Gerbaud, Guillaume; Guigliarelli, Bruno; Belle, Valérie

    2015-01-01

    Proteins are highly variable biological systems, not only in their structures but also in their dynamics. The most extreme example of dynamics is encountered within the family of Intrinsically Disordered Proteins (IDPs), which are proteins lacking a well-defined 3D structure under physiological conditions. Among the biophysical techniques well-suited to study such highly flexible proteins, Site-Directed Spin Labeling combined with EPR spectroscopy (SDSL-EPR) is one of the most powerful, being able to reveal, at the residue level, structural transitions such as folding events. SDSL-EPR is based on selective grafting of a paramagnetic label on the protein under study and is limited neither by the size nor by the complexity of the system. The objective of this mini-review is to describe the basic strategy of SDSL-EPR and to illustrate how it can be successfully applied to characterize the structural behavior of IDPs. Recent developments aimed at enlarging the panoply of SDSL-EPR approaches are presented in particular newly synthesized spin labels that allow the limitations of the classical ones to be overcome. The potentialities of these new spin labels will be demonstrated on different examples of IDPs. PMID:26042221

  7. 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.

  8. Magnetic field distribution in the presence of paramagnetic plates in magnetic resonance imaging: a combined numerical and experimental study.

    PubMed

    Mertens, Philipp; Machann, Juergen; Mueller-Bierl, Bernd; Steidle, Guenter; Bellemann, Matthias E; Schick, Fritz

    2008-05-01

    The amount and geometric distribution of paramagnetic components in tissue is considered as the basis of T2*-weighted magnetic resonance imaging (MRI). Such techniques are routinely applied for assessment of iron in parenchymal organs such as the liver (hemosiderosis). Furthermore, susceptibility sensitive MRI is discussed as an alternative method to x-ray techniques for quantitative assessment of paramagnetic spongy bone components in patients with osteoporosis. The presented work is dedicated to systematically examining the possible influences of macroscopic arrangements of paramagnetic plates on the magnetic field. In a theoretical approach magnetic field distribution was simulated applying decomposition of the plates in single dipoles. Plate size and distances between parallel plates, as well as plate orientation with respect to the static field, were varied for these numerical simulations. Experiments on corresponding plate arrangements were carried out on a 3 T whole body MR scanner using the field-sensitive MR sequence technique for B0 field mapping. Further examinations were carried out on a bone preparation of the femur, where T2* maps were measured and analyzed on a pixel-by-pixel basis at two orientations with respect to the static field. A series of experiments were performed using isotropic and anisotropic volume elements in three-dimensional gradient echo sequences. Resulting magnetic field distributions in the experimentally recorded B0 field maps were in good agreement with the numerical simulations. Field distortions dominated in areas close to the plates and especially near the edges. Those areas showed strong local field gradients, leading to pronounced signal dephasing effects. The examination of the bone preparations revealed different T2* values for identical regions in the bone when the orientation of the bone or the pixel geometry was changed with respect to the magnetic field. Those effects amounted to nearly 70% (22.9 ms versus 13.6 ms in

  9. Characterisation and evaluation of paramagnetic fluorine labelled glycol chitosan conjugates for (19)F and (1)H magnetic resonance imaging.

    PubMed

    De Luca, Elena; Harvey, Peter; Chalmers, Kirsten H; Mishra, Anurag; Senanayake, P Kanthi; Wilson, J Ian; Botta, Mauro; Fekete, Marianna; Blamire, Andrew M; Parker, David

    2014-02-01

    Medium molecular weight glycol chitosan conjugates have been prepared, linked by an amide bond to paramagnetic Gd(III), Ho(III) and Dy(III) macrocyclic complexes in which a trifluoromethyl reporter group is located 6.5 Å from the paramagnetic centre. The faster relaxation of the observed nucleus allows modified pulse sequences to be used with shorter acquisition times. The polydisperse materials have been characterised by gel permeation chromatography, revealing an average molecular weight on the order of 13,800 (Gd), 14,600 (Dy) and 16,200 (Ho), consistent with the presence of 8.5, 9.5 and 13 complexes, respectively. The gadolinium conjugate was prepared for both a q = 1 monoamide tricarboxylate conjugate (r1p 11.2 mM(-1) s(-1), 310 K, 1.4 T) and a q = 0 triphosphinate system, and conventional contrast-enhanced proton MRI studies at 7 T were undertaken in mice bearing an HT-29 or an HCT-116 colorectal tumour xenograft (17 μmol/kg). Enhanced contrast was observed following injection in the tail vein in tumour tissue, with uptake also evident in the liver and kidney with a tumour-to-liver ratio of 2:1 at 13 min, and large amounts in the kidney and bladder consistent with predominant renal clearance. Parallel experiments observing the (19)F resonance in the holmium conjugate complex using a surface coil did not succeed owing to its high R2 value (750 Hz, 7 T). However, the fluorine signal in the dysprosium triphosphinate chitosan conjugate [R1/R2 = 0.6 and R1 = 145 Hz (7 T)] was sharper and could be observed in vivo at -65.7 ppm, following intravenous tail vein injection of a dose of 34 μmol/kg.

  10. Electron paramagnetic resonance of Nb-doped BaTiO3 ceramics with positive temperature coefficient of resistivity

    NASA Astrophysics Data System (ADS)

    Jida, Shin'suke; Miki, Toshikatsu

    1996-11-01

    Paramagnetic centers in Nb-doped BaTiO3 ceramics are measured at 77-500 K by electron paramagnetic resonance (EPR) for investigating the role of the centers on the well-known positive temperature coefficient of resistivity (PTCR) effect (PTCR at the Curie temperature). EPR detects four signals; an anisotropically broad singlet signal at g=2.005, a sextet signal due to Mn2+, a Cr3+ signal, and a Ti3+ signal. The former two signals arise in the rhombohedral and cubic phases, but disappear in the tetragonal and orthorhombic phases. The Cr3+ signal appears in all of the phases, while the Ti3+ signal is detected only at low temperatures. The singlet signal also arises in undoped, barium-deficient BaTiO3 ceramics, therefore the signal is attributable to barium-vacancy-associated centers rather than Nb4+ ions or Fe3+ ions proposed by several authors. In this article, we propose that the singlet signal is due to vacancy-pairs of VBa-F+ type, i.e., the vacancy pair of VBa-VO capturing one electron. The electrical resistivity data show a polaronic character of low-temperature conduction and a high resistivity jump around the Curie temperature. The low-temperature polaronic conduction is explained in terms of electron-hopping between Ti4+ and Ti3+ ions. The resistivity jump at the Curie temperature occurs along with the EPR intensity increase of the singlet signal, the Mn2+ signal and the Cr3+ signal. We conclude that the PTCR of Nb-doped BaTiO3 ceramics is strongly associated with the trap activation of the VBa-VO vacancy-pairs and manganese centers at the tetragonal-to-cubic transition.

  11. Electron spin resonance spectroscopy of small ensemble paramagnetic spins using a single nitrogen-vacancy center in diamond

    NASA Astrophysics Data System (ADS)

    Abeywardana, Chathuranga; Stepanov, Viktor; Cho, Franklin H.; Takahashi, Susumu

    2016-09-01

    A nitrogen-vacancy (NV) center in diamond is a promising sensor for nanoscale magnetic sensing. Here, we report on electron spin resonance (ESR) spectroscopy using a single NV center in diamond. First, using a 230 GHz ESR spectrometer, we performed ensemble ESR of a type-Ib sample crystal and identified a substitutional single nitrogen impurity as a major paramagnetic center in the sample crystal. Then, we carried out free-induction decay and spin echo measurements of the single NV center to study static and dynamic properties of nanoscale bath spins surrounding the NV center. We also measured ESR spectrum of the bath spins using double electron-electron resonance spectroscopy with the single NV center. The spectrum analysis of the NV-based ESR measurement identified that the detected spins are the nitrogen impurity spins. The experiment was also performed with several other single NV centers in the diamond sample and demonstrated that the properties of the bath spins are unique to the NV centers indicating the probe of spins in the microscopic volume using NV-based ESR. Finally, we discussed the number of spins detected by the NV-based ESR spectroscopy. By comparing the experimental result with simulation, we estimated the number of the detected spins to be ≤50 spins.

  12. High-frequency and high-field electron paramagnetic resonance (HFEPR): a new spectroscopic tool for bioinorganic chemistry.

    PubMed

    Telser, Joshua; Krzystek, J; Ozarowski, Andrew

    2014-03-01

    This minireview describes high-frequency and high-field electron paramagnetic resonance (HFEPR) spectroscopy in the context of its application to bioinorganic chemistry, specifically to metalloproteins and model compounds. HFEPR is defined as frequencies above ~100 GHz (i.e., above W-band) and a resonant field reaching 25 T and above. The ability of HFEPR to provide high-resolution determination of g values of S = 1/2 is shown; however, the main aim of the minireview is to demonstrate how HFEPR can extract spin Hamiltonian parameters [zero-field splitting (zfs) and g values] for species with S > 1/2 with an accuracy and precision unrivalled by other physical methods. Background theory on the nature of zfs in S = 1, 3/2, 2, and 5/2 systems is presented, along with selected examples of HFEPR spectroscopy of each that are relevant to bioinorganic chemistry. The minireview also provides some suggestions of specific systems in bioinorganic chemistry where HFEPR could be rewardingly applied, in the hope of inspiring workers in this area.

  13. 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.

  14. Two-dimensional electron paramagnetic resonance spectroscopy of nitroxides: Elucidation of restricted molecular motions in glassy solids

    NASA Astrophysics Data System (ADS)

    Dubinskii, Alexander A.; Maresch, Günter G.; Spiess, Hans-Wolfgang

    1994-02-01

    The combination of concepts of two-dimensional (2D) spectroscopy with the well-known field step electron-electron double resonance (ELDOR) method offers a practical route to recording 2D ELDOR spectra covering the full spectral range needed for electron paramagnetic resonance (EPR) of nitroxide spin labels in the solid state. The 2D ELDOR pattern provides information about molecular reorientation measured in real time, the anisotropies of electron phase, and electron spin-lattice relaxation as well as nuclear spin-lattice relaxation all of which are connected with the detailed geometry of the molecular reorientation. Thus, in 2D ELDOR the same electron spin probes the motional behavior over a wide range of correlation times from 10-4 to 10-12 s. An efficient algorithm for simulating 2D ELDOR spectra is derived, based on analytical solutions of the spin relaxation behavior for small-angle fluctuations and offers a means of quantitatively analyzing experimental data. As an example, the motion of nitroxide spin labels in a liquid-crystalline side-group polymer well below its glass transition is determined as a β-relaxation process with a mean angular amplitude of 5° and a distribution of correlation times with a mean correlation time of 0.9×10-10 s and a width of 2.5 decades.

  15. Pulse saturation recovery, pulse ELDOR, and free induction decay electron paramagnetic resonance detection using time-locked subsampling

    NASA Astrophysics Data System (ADS)

    Froncisz, W.; Camenisch, Theodore G.; Ratke, Joseph J.; Hyde, James S.

    2001-03-01

    Time locked subsampling (TLSS) in electron paramagnetic resonance (EPR) involves the steps of (i) translation of the signal from a microwave carrier to an intermediate frequency (IF) carrier where the (IF) offset between the signal oscillator and local oscillator frequencies is synthesized, (ii) sampling the IF carrier four times in an odd number of cycles, say 4 in 3, where the analog-to-digital (A/D) converter is driven by a frequency synthesizer that has the same clock input as the IF synthesizer, (iii) signal averaging as required for adequate signal to noise, (iv) separating the even and odd digitized words into two separate signal channels, which correspond to signals in phase and in quadrature with respect to the IF carrier, i.e., I and Q, and (v) detecting the envelope of I and also of Q by changing the signs of alternate words in each of the two channels. TLSS detection has been demonstrated in three forms of pulse EPR spectroscopy at X band: saturation recovery, pulse electron-electron double resonance, and free induction decay. The IF was 187.5 MHz, the A/D converter frequency was 250 MHz, the overall bandwidth was 125 MHz, and the bandwidths for the separate I and Q channels were each 62.5 MHz. Experiments were conducted on nitroxide radical spin labels. The work was directed towards development of methodology to monitor bimolecular collisions of oxygen with spin labels in a context of site-directed spin labeling.

  16. 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.

  17. 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

  18. An in vitro L-band electron paramagnetic resonance study of highly irradiated whole teeth.

    PubMed

    Zdravkova, M; Wieser, A; El-Faramawy, N; Gallez, B; Debuyst, R

    2002-01-01

    Regarding in vivo L-band dosimetry with human teeth, a number of preliminary experiments were carried out that were linked to the resonators response and the relative contribution of enamel to the EPR signal intensity of irradiated whole teeth. The sensitivity of the extended loop resonator varies in the antenna plane, but this variation tends to vanish when the sample is moved away from this plane. When the loop antenna is placed just above the highly irradiated molar, around 88% of the dosimetric signal is due to the crown enamel. The sensitivity inside a birdcage cavity is approximately equal over the volume of a molar; only 30% of the molar's total dosimetric signal results from enamel. Some decrease in the intensity of the dosimetric signal from enamel is observed after irradiation. At room temperature, the signal is reduced by about 20% within 90 days and approaches a plateau with a time constant of about 35 days.

  19. 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

  20. Two-state transition between molten globule and unfolded states of acetylcholinesterase as monitored by electron paramagnetic resonance spectroscopy.

    PubMed Central

    Kreimer, D I; Szosenfogel, R; Goldfarb, D; Silman, I; Weiner, L

    1994-01-01

    Cys-231 of Torpedo californica acetylcholinesterase (EC 3.1.1.7) was selectively labeled with the mercury derivative of a stable nitroxyl radical. In 1.5 M guanidinium chloride, this conjugate exists in a molten globule state (MG), whereas in 5 M denaturant, it is in an unfolded state (U). The transition between the two states is reversible. In the MG, the label is highly immobilized, whereas in the U, it is almost freely rotating. The clearly distinct electron paramagnetic resonance (EPR) spectra of the two states permits the study of this transition. Upon elevating the guanidinium chloride concentration, a decrease in the EPR signal of the MG occurs concomitantly with an increase in the U signal, the total intensity of the EPR spectra remaining constant. This behavior is characteristic of a two-state transition. The thermodynamic characteristics of this transition (delta G0 and m), whether estimated directly from the EPR data or from both CD and fluorescence data analyzed by assuming a two-state scheme, are in good agreement. PMID:7991597

  1. 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).

  2. Increased Electron Paramagnetic Resonance Signal Correlates with Mitochondrial Dysfunction and Oxidative Stress in an Alzheimer’s Disease Mouse Brain

    PubMed Central

    Fang, Du; Zhang, Zhihua; Li, Hang; Yu, Qing; Douglas, Justin T.; Bratasz, Anna; Kuppusamy, Periannan; Yan, Shirley ShiDu

    2016-01-01

    Alzheimer’s disease (AD) is a progressive neurodegenerative disease characterized clinically by cognitive decline and memory loss. The pathological features are amyloid-β peptide (Aβ) plaques and intracellular neurofibrillary tangles. Many studies have suggested that oxidative damage induced by reactive oxygen species (ROS) is an important mechanism for AD progression. Our recent study demonstrated that oxidative stress could further impair mitochondrial function. In the present study, we adopted a transgenic mouse model of AD (mAPP, overexpressing AβPP/Aβ in neurons) and performed redox measurements using in vivo electron paramagnetic resonance (EPR) imaging with methoxycarbamyl-proxyl (MCP) as a redox-sensitive probe for studying oxidative stress in an early stage of pathology in a transgenic AD mouse model. Through assessing oxidative stress, mitochondrial function and cognitive behaviors of mAPP mice at the age of 8–9 months, we found that oxidative stress and mitochondrial dysfunction appeared in the early onset of AD. Increased ROS levels were associated with defects of mitochondrial and cognitive dysfunction. Notably, the in vivo EPR method offers a unique way of assessing tissue oxidative stress in living animals under noninvasive conditions, and thus holds a potential for early diagnosis and monitoring the progression of AD. PMID:26890765

  3. One and Two Dimensional Pulsed Electron Paramagnetic Resonance Studies of in vivo Vanadyl Coordination in Rat Kidney

    PubMed Central

    Liboiron, Barry D.; Thompson, Katherine H.; Vera, Erika; Yuen, Violet G.; McNeill, John H.

    2003-01-01

    The biological fate of a chelated vanadium source is investigated by/n vivo spectroscopic methods to elucidate the chemical form in which the metal ion is accumulated. A pulsed electron paramagnetic resonance study of vanadyl ions in kidney tissue, taken from rats previously treated with bis(ethylmaltolato)oxovanadium(IV) (BEOV) in drinking water, is presented. A combined approach using stimulated echo (3-pulse) electron spin echo envelope modulation (ESEEM) and the two dimensional 4-pulse hyperfine sublevel correlation (HYSCORE) spectroscopies has shown that at least some of the VO2+ ions are involved in the coordination with nitrogen-containing ligands. From the experimental spectra, a 4N hyperfine coupling constant of 4.9 MHz and a quadrupole coupling constant of 0.6 + 0.04 MHz were determined, consistent with amine coordination of the vanadyl ions. Study of VO-histidine model complexes allowed for a determination of the percentage of nitrogen-coordinated VO2+ ions in the tissue sample that is found nitrogen-coordinated. By taking into account the bidentate nature of histidine coordination to VO2+ ions, a more accurate determination of this value is reported. The biological fate of chelated versus free (i.e. salts) vanadyl ion sources has been deduced by comparison to earlier reports. In contrast to its superior pharmacological efficacy over VOSO4, BEOV shares a remarkably similar biological fate after uptake into kidney tissue. PMID:18365044

  4. 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.

  5. Mn(II) Binding and Subsequent Oxidation by the Multicopper Oxidase MnxG Investigated by Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Tao, Lizhi; Stich, Troy A; Butterfield, Cristina N; Romano, Christine A; Spiro, Thomas G; Tebo, Bradley M; Casey, William H; Britt, R David

    2015-08-26

    The dynamics of manganese solid formation (as MnOx) by the multicopper oxidase (MCO)-containing Mnx protein complex were examined by electron paramagnetic resonance (EPR) spectroscopy. Continuous-wave (CW) EPR spectra of samples of Mnx, prepared in atmosphere and then reacted with Mn(II) for times ranging from 7 to 600 s, indicate rapid oxidation of the substrate manganese (with two-phase pseudo-first-order kinetics modeled using rate coefficients of: k(1obs) = 0.205 ± 0.001 s(-1) and k(2obs) = 0.019 ± 0.001 s(-1)). This process occurs on approximately the same time scale as in vitro solid MnOx formation when there is a large excess of Mn(II). We also found CW and pulse EPR spectroscopic evidence for at least three classes of Mn(II)-containing species in the reaction mixtures: (i) aqueous Mn(II), (ii) a specifically bound mononuclear Mn(II) ion coordinated to the Mnx complex by one nitrogenous ligand, and (iii) a weakly exchange-coupled dimeric Mn(II) species. These findings provide new insights into the molecular mechanism of manganese mineralization.

  6. Retrospective assessment of radiation exposure using biological dosimetry: chromosome painting, electron paramagnetic resonance and the glycophorin a mutation assay.

    PubMed

    Kleinerman, R A; Romanyukha, A A; Schauer, D A; Tucker, J D

    2006-07-01

    Biological monitoring of dose can contribute important, independent estimates of cumulative radiation exposure in epidemiological studies, especially in studies in which the physical dosimetry is lacking. Three biodosimeters that have been used in epidemiological studies to estimate past radiation exposure from external sources will be highlighted: chromosome painting or FISH (fluorescence in situ hybridization), the glycophorin A somatic mutation assay (GPA), and electron paramagnetic resonance (EPR) with teeth. All three biodosimeters have been applied to A-bomb survivors, Chernobyl clean-up workers, and radiation workers. Each biodosimeter has unique advantages and limitations depending upon the level and type of radiation exposure. Chromosome painting has been the most widely applied biodosimeter in epidemiological studies of past radiation exposure, and results of these studies provide evidence that dose-related translocations persist for decades. EPR tooth dosimetry has been used to validate dose models of acute and chronic radiation exposure, although the present requirement of extracted teeth has been a disadvantage. GPA has been correlated with physically based radiation dose after high-dose, acute exposures but not after low-dose, chronic exposures. Interindividual variability appears to be a limitation for both chromosome painting and GPA. Both of these techniques can be used to estimate the level of past radiation exposure to a population, whereas EPR can provide individual dose estimates of past exposure. This paper will review each of these three biodosimeters and compare their application in selected epidemiological studies.

  7. Use of Fe(3+) ion probe to study the stability of urea-intercalated kaolinite by electron paramagnetic resonance.

    PubMed

    Budziak Fukamachi, Cristiane Regina; Wypych, Fernando; Mangrich, Antonio Salvio

    2007-09-15

    The effect of mechanical and chemical activation in processes of urea intercalation in the interlayer spacing of kaolinite and the effect of varying the temperature of the intercalation product between 100 and 200 degrees C were studied using Fe(3+) ions as a probe in electron paramagnetic resonance (EPR) spectroscopy. Other techniques were also used to characterize the samples. Monitoring the heating of urea-intercalated kaolinite, FTIR, and XRD revealed that the product obtained was stable up to a temperature of 150-160 degrees C. The EPR data indicated that the intercalation process promoted an approximation and increase of the magnetic interactions among the Fe(3+) ions. The DRUV-vis analysis of the product before heating showed an absorption band at 680 nm that was absent in the raw kaolinite. This band was attributed to the transition A(1)6-->T(2)4(G4) in the adjacent Fe(3+) ions, intensified by magnetic coupling among these ions. We suggest that intercalated urea forms hydrogen bonds between the carbonyl's oxygen and the hydroxyls bound to the Fe(3+) ions of the kaolinite structure. This would cause the approximation of the Fe(3+) ions, maximizing magnetic couplings and intensifying concentrated centers of Fe(3+), as was visible by EPR spectroscopy.

  8. 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.

  9. 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.

  10. Axially uniform magnetic field-modulation excitation for electron paramagnetic resonance in rectangular and cylindrical cavities by slot cutting

    NASA Astrophysics Data System (ADS)

    Sidabras, Jason W.; Richie, James E.; Hyde, James S.

    2017-01-01

    In continuous-wave (CW) Electron Paramagnetic Resonance (EPR) a low-frequency time-harmonic magnetic field, called field modulation, is applied parallel to the static magnetic field and incident on the sample. Varying amplitude of the field modulation incident on the sample has consequences on spectral line-shape and line-height over the axis of the sample. Here we present a method of coupling magnetic field into the cavity using slots perpendicular to the sample axis where the slot depths are designed in such a way to produce an axially uniform magnetic field along the sample. Previous literature typically assumes a uniform cross-section and axial excitation due to the wavelength of the field modulation being much larger than the cavity. Through numerical analysis and insights obtained from the eigenfunction expansion of dyadic Green's functions, it is shown that evanescent standing-wave modes with complex cross-sections are formed within the cavity. From this analysis, a W-band (94 GHz) cylindrical cavity is designed where modulation slots are optimized to present a uniform 100 kHz field modulation over the length of the sample.

  11. Mechanism for formation of the lightstruck flavor in beer revealed by time-resolved electron paramagnetic resonance.

    PubMed

    Burns, C S; Heyerick, A; De Keukeleire, D; Forbes, M D

    2001-11-05

    Time-resolved electron paramagnetic resonance (TREPR) data collected during the photodegradation of iso-a-acids (isohumulones), the principal bittering agents from hops in beer, are presented and discussed, and, from the data, the photophysics leading to free-radical production as the primary step in the photodecomposition of iso-alpha-acids towards the development of "skunky" beer are explained. During laser flash photolysis of iso-alpha-acids at 308 nm in toluene/methylcyclohexane (1:1), TREPR spectra exhibit net emissive signals that are strongly spin polarized by the triplet mechanism of chemically induced electron spin polarization. From two potential photochemically active sites, the TREPR data show that although the first site, an enolized beta-triketone, is the primary light-absorbing chromophore, an uphill intramolecular triplet energy transfer process leads to Norrish type I alpha-cleavage at a second site, an alpha-hydroxycarbonyl. The energy transfer mechanism is supported by additional TREPR experiments with chemically modified hop compounds. Structural parameters (hyperfine coupling constants, g factors, line widths) for the observed free radicals, obtained from computer simulations, are presented and discussed.

  12. 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.

  13. 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.

  14. Electron paramagnetic resonance investigation on modulatory effect of benidipine on membrane fluidity of erythrocytes in essential hypertension.

    PubMed

    Tsuda, Kazushi

    2008-03-01

    It has been shown that benidipine, a long-lasting calcium (Ca) channel blocker, may exert its protective effect against vascular disorders by increasing nitric oxide (NO) production. The purpose of the present study was to investigate whether orally administered benidipine might influence the membrane function in patients with essential hypertension. We measured the membrane fluidity of erythrocytes by using an electron paramagnetic resonance (EPR) and spin-labeling method. In the preliminary study using erythrocytes obtained from healthy volunteers, benidipine decreased the order parameter (S) for 5-nitroxide stearate (5-NS) and the peak height ratio (ho/h-1) for 16-NS in the EPR spectra in vitro. The finding indicated that benidipine increased the membrane fluidity and improved the microviscosity of erythrocytes. In addition, it was demonstrated that the effect of benidipine on membrane fluidity of erythrocytes was significantly potentiated by the NO-substrate, L-arginine. In the separate series of the study, we observed that orally administered benidipine for 4 weeks significantly increased the membrane fluidity of erythrocytes with a concomitant increase in plasma NO metabolite levels in hypertensive subjects. The results of the present study demonstrated that benidipine might increase the membrane fluidity and improve the microviscosity of erythrocytes both in vitro and in vivo, to some extent, by the NO-dependent mechanism. Furthermore, it is strongly suggested that orally administered benidipine might have a beneficial effect on the rheologic behavior of erythrocytes and the improvement of the microcirculation in hypertensive subjects.

  15. An electron paramagnetic resonance method for measuring the affinity of a spin-labeled analog of cholesterol for phospholipids.

    PubMed

    Williams, Justin A; Wassall, Cynthia D; Kemple, Marvin D; Wassall, Stephen R

    2013-09-01

    Cholesterol (chol)-lipid interactions are thought to play an intrinsic role in determining lateral organization within cellular membranes. Steric compatibility of the rigid steroid moiety for ordered saturated chains contributes to the high affinity that holds chol and sphingomyelin together in lipid rafts whereas, conversely, poor affinity of the sterol for highly disordered polyunsaturated fatty acids (PUFAs) is hypothesized to drive the formation of PUFA-containing phospholipid domains depleted in chol. Here, we describe a novel method using electron paramagnetic resonance (EPR) to measure the relative affinity of chol for different phospholipids. We monitor the partitioning of 3β-doxyl-5α-cholestane (chlstn), a spin-labeled analog of chol, between large unilamellar vesicles (LUVs) and cyclodextrin (mβCD) through analysis of EPR spectra. Because the shape of the EPR spectrum for chlstn is sensitive to the very different tumbling rates of the two environments, the ratio of the population of chlstn in LUVs and mβCD can be determined directly from spectra. Partition coefficients (K(B)(A)) between lipids derived from our results for chlstn agree with values obtained for chol and confirm that decreased affinity for the sterol accompanies increasing acyl chain unsaturation. The virtue of this EPR method is that it provides a measure of chol binding that is quick, employs a commercially available probe and avoids the necessity for physical separation of LUVs and mβCD.

  16. Electron Energy Structure and Electron Paramagnetic Resonance of Binuclear Niobium Molecules in Li-Nb Phosphate Glass Dielectrics

    NASA Astrophysics Data System (ADS)

    Arrington-Peet, Sabrina

    2005-03-01

    Electron paramagnetic resonance (EPR) spectra of Nb4+ ions in lithium-niobium phosphate glass insulators with different composition of oxide components have been studied. The EPR data reveal formation of triplet Nb binuclear complex in Li-Nb glass dielectric. Equilibrium atomic geometries of a model molecule (OH)3-Nb-O-Nb-(OH)3 embedded into Li-Nb phosphate glass are determined by molecular dynamics. The total energy and electron energy structure of the system have been studied by first principles generalized gradient approximation (GGA) method within density functional theory (DFT). Molecular geometry in substantially distorted as a result of external potential of the glass. Total energy analysis of the (OH)3-Nb-O-Nb-(OH)3 molecule embedded into Li-Nb phosphate glass indicates appearance of two non-equivalent atomic geometries with the oxygen atom in --Nb-O-Nb- fragment shifted from its undisturbed symmetrical position. Predicted modifications of electron energy structure of the system are discussed in comparison with measured EPR data.

  17. Electron paramagnetic resonance studies of electron and hole traps related to optical damage in KTiOPO(4)

    NASA Astrophysics Data System (ADS)

    Setzler, Scott Douglas

    Electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR) studies have been performed on flux-grown and hydrothermal-grown potassium titanyl phosphate (KTiOPOsb4, or KTP) crystals. Four radiation-induced tapped-electron centers have been identified and a complete angular dependence analysis has provided spin-Hamiltonian parameters for each center. Either near-band-edge laser light (355-nm third-harmonic output from a Nd:YAG laser) or 60-kV x-rays can be used to produce the defects. These electron traps are perturbed Tisp{3+} ions, where the perturbation acts to stabilize the electron. Hyperfine parameters have been used to deduce that protons (in the form of OH-ions) act to stabilize the electron in hydrothermal material, while the stabilization in flux material probably comes from divalent impurities and oxygen vacancies. The thermal stability of the centers varies from 150 K to 300 K. The principal g values have been used to confirm that the titanium centers have related optical absorption bands in the visible region. Preliminary transient absorption experiments have been developed to measure the lifetime of the induced absorption. It is postulated that these centers can be formed during normal device operation and are closely related to the "gray-track" effect. Additional analysis has also been performed on the previously identified radiation-induced trapped-hole center (Edwards et. al., Phys. Rev. B 48, 6884 (1993)). The g values and hyperfine parameters are revised though the defect model remains unchanged.

  18. Paramagnetic fluorinated nanoemulsions for sensitive cellular fluorine-19 magnetic resonance imaging

    PubMed Central

    Kislukhin, Alexander A.; Xu, Hongyan; Adams, Stephen R.; Narsinh, Kazim H.; Tsien, Roger Y.; Ahrens, Eric T.

    2016-01-01

    Fluorine-19 magnetic resonance imaging (19F MRI) probes enable quantitative in vivo detection of cell therapies and inflammatory cells. Here, we describe the formulation of perfluorocarbon-based nanoemulsions with improved sensitivity for cellular MRI. Reduction of the 19F spin-lattice relaxation time (T1) enables rapid imaging and an improved signal-to-noise ratio, thereby improving cell detection sensitivity. We synthesized metal-binding β-diketones conjugated to linear perfluoropolyether (PFPE), formulated these fluorinated ligands as aqueous nanoemulsions, and then metalated them with various transition and lanthanide ions in the fluorous phase. Iron(III) tris-β-diketonate ('FETRIS') nanoemulsions with PFPE have low cytotoxicity (<20%) and superior MRI properties. Moreover, the 19F T1 can readily be reduced by an order of magnitude and tuned by stoichiometric modulation of the iron concentration. The resulting 19F MRI detection sensitivity is enhanced by 3-to-5 fold over previously used tracers at 11.7 T, and is predicted to increase by at least 8-fold at clinical field strength of 3 T. PMID:26974409

  19. Electron paramagnetic resonance method for the determination of orientation in the amorphous regions of polymers

    SciTech Connect

    Shimada, S.; Williams, F.

    1980-11-01

    An elongated film of polyethylene was cut into narrow strips which were stacked together and placed in sample tubes. Samples were prepared with the stretching of the film stack being either parallel or perpendicular to the axis of the sample tube. Tetrafluoroethylene (C/sub 2/F/sub 4/) was condensed into the tube at -196/sup 0/C from a storage bulb. The amount of C/sub 2/F/sub 4/ transferred into the tube was ca 10 mol% of the ethylene units in the polyethylene sample, generating a pressure of ca 5 atm in the sealed tube at room temperature. The samples were stored for 1 week at ambient temperature, then irradiated at -196/sup 0/C with /sup 60/Co gamma rays for a total dose of 1 Mrd. Electron spin resonance measurements were conducted on the irradiated samples at 80K and higher temperatures. The spectra indicate that the preferred orientation of the C-C symmetry axis of C/sub 2/F/sub 4//sup -/ is perpendicular to the stretching direction in the polymer and, therefore, perpendicular to the polymer main chain. The anisotropy shown can be considered to reflect the degree of order in the amorphous regions. Results for computer simulated spectra show correlation with experimental values. 10 references, 3 figures.

  20. Effect of Rabi splitting on the low-temperature electron paramagnetic resonance signal of anthracite

    NASA Astrophysics Data System (ADS)

    Fedaruk, Ryhor; Strzelczyk, Roman; Tadyszak, Krzysztof; Markevich, Siarhei A.; Augustyniak-Jabłokow, Maria Aldona

    2017-01-01

    Specific distortions of the EPR signal of bulk anthracite are observed at low temperatures. They are accompanied by variations in the microwave oscillator frequency and are explained by the manifestation of the Rabi splitting due to the strong coupling between electron spins and the cavity, combined with the use of an automatic frequency-control (AFC) system. EPR signals are recorded at negligible saturation in the temperature range of 4-300 K with use of the AFC system to keep the oscillator frequency locked to the resonant frequency of the TM110 cylinder cavity loaded with the sample. For the sample with a mass of 3.6 mg the line distortions are observed below 50 K and increase with temperature lowering. The oscillator frequency variations are used to estimate the coupling strength as well as the number of spins in the sample. It is shown that the spin-cavity coupling strength is inversely proportional to temperature and can be used for the absolute determination of the number of spins in a sample. Our results indicate that at low temperatures even 1016 spins of the anthracite sample, with a mass of about 0.5 mg, can distort the EPR line.

  1. 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

    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.

  2. Antioxidant activity of Calendula officinalis extract: inhibitory effects on chemiluminescence of human neutrophil bursts and electron paramagnetic resonance spectroscopy.

    PubMed

    Braga, Pier Carlo; Dal Sasso, Monica; Culici, Maria; Spallino, Alessandra; Falchi, Mario; Bertelli, Aldo; Morelli, Roberto; Lo Scalzo, Roberto

    2009-01-01

    There is growing interest in natural chemical compounds from aromatic, spicy, medicinal and other plants with antioxidant properties in order to find new sources of compounds inactivating free radicals generated by metabolic pathways within body tissue and cells, mainly polymorphonuclear leukocytes (PMNs) whose overregulated recruitment and activation generate a large amount of reactive oxygen species (ROS) and reactive nitrogen species (RNS), leading to an imbalance of redox homeostasis and oxidative stress. The aim of this study was to examine whether a propylene glycol extract of Calendula officinalis interferes with ROS and RNS during the PMN respiratory bursts, and to establish the lowest concentration at which it still exerts antioxidant activity by means of luminol-amplified chemiluminescence. Electron paramagnetic resonance (EPR) spectroscopy was also used in order to confirm the activity of the C. officinalis extract. The C. officinalis extract exerted its anti-ROS and anti-RNS activity in a concentration-dependent manner, with significant effects being observed at even very low concentrations: 0.20 microg/ml without L-arginine, 0.10 microg/ml when L-arginine was added to the test with phorbol 12-myristate 13-acetate and 0.05 microg/ml when it was added to the test with N-formyl-methionyl-leucyl-phenylalanine. The EPR study confirmed these findings, 0.20 microg/ml being the lowest concentration of C. officinalis extract that significantly reduced 2,2-diphenyl-1-picrylhydrazyl. These findings are interesting for improving the antioxidant network and restoring the redox balance in human cells with plant-derived molecules as well as extending the possibility of antagonizing the oxidative stress generated in living organisms when the balance is in favor of free radicals as a result of the depletion of cell antioxidants.

  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. A new structural model of Alzheimer's Aβ42 fibrils based on electron paramagnetic resonance data and Rosetta modeling

    PubMed Central

    Gu, Lei; Tran, Joyce; Jiang, Lin; Guo, Zhefeng

    2016-01-01

    Brain deposition of Aβ in the form of amyloid plaques is a pathological hallmark of Alzheimer's disease. There are two major species of Aβ in the brain: Aβ42 and Aβ40. Although Aβ40 is several-fold more abundant than Aβ42 in soluble form, Aβ42 is the major component of amyloid plaques. Structural knowledge of Aβ42 fibrils is important both for understanding the process of Aβ aggregation and for designing fibril-targeting drugs. Here we report site-specific structural information of Aβ42 fibrils at 22 residue positions based on electron paramagnetic resonance data. In combination with structure prediction program Rosetta, we modeled Aβ42 fibril structure at atomic resolution. Our Aβ42 fibril model consists of four parallel in-register β-sheets: βN (residues ~7-13), β1 (residues ~17-20), β2 (residues ~32-36), and βC (residues 39-41). The region of β1-loop-β2 in Aβ42 fibrils adopts similar structure as that in Aβ40 fibrils. This is consistent with our cross seeding data that Aβ42 fibril seeds shortened the lag phase of Aβ40 fibrillization. On the other hand, Aβ42 fibrils contain a C-terminal β-arc-β motif with a special turn, termed “arc”, at residues 37-38, which is absent in Aβ40 fibrils. Our results can explain both the higher aggregation propensity of Aβ42 and the importance of Aβ42 to Aβ40 ratio in the pathogenesis of Alzheimer's disease. PMID:26827680

  5. 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.

  6. Pulsed Electron Paramagnetic Resonance Study of Domain Docking in Neuronal Nitric Oxide Synthase: The Calmodulin and Output State Perspective

    PubMed Central

    2015-01-01

    The binding of calmodulin (CaM) to neuronal nitric oxide synthase (nNOS) enables formation of the output state of nNOS for nitric oxide production. Essential to NOS function is the geometry and dynamics of CaM docking to the NOS oxygenase domain, but little is known about these details. In the present work, the domain docking in a CaM-bound oxygenase/FMN (oxyFMN) construct of nNOS was investigated using the relaxation-induced dipolar modulation enhancement (RIDME) technique, which is a pulsed electron paramagnetic resonance technique sensitive to the magnetic dipole interaction between the electron spins. A cysteine was introduced at position 110 of CaM, after which a nitroxide spin label was attached at the position. The RIDME study of the magnetic dipole interaction between the spin label and the ferric heme centers in the oxygenase domain of nNOS revealed that, with increasing [Ca2+], the concentration of nNOS·CaM complexes increases and reaches a maximum at [Ca2+]/[CaM] ≥ 4. The RIDME kinetics of CaM-bound nNOS represented monotonous decays without well-defined oscillations. The analysis of these kinetics based on the structural models for the open and docked states has shown that only about 15 ± 3% of the CaM-bound nNOS is in the docked state at any given time, while the remaining 85 ± 3% of the protein is in the open conformations characterized by a wide distribution of distances between the bound CaM and the oxygenase domain. The results of this investigation are consistent with a model that the Ca2+–CaM interaction causes CaM docking with the oxygenase domain. The low population of the docked state indicates that the CaM-controlled docking between the FMN and heme domains is highly dynamic. PMID:25046446

  7. 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

  8. Electron paramagnetic resonance and quantum-mechanical analysis of binuclear niobium clusters in lithium-niobium phosphate glasses

    NASA Astrophysics Data System (ADS)

    Rakhimov, R. R.; Turney, V. J.; Jones, D. E.; Dobryakov, S. N.; Borisov, Yu. A.; Prokof'ev, A. I.; Aleksandrov, A. I.

    2003-04-01

    Electron paramagnetic resonance (EPR) spectra of Nb4+ ions in Li2O-Nb2O5-P2O5 glasses with different composition of oxide components have been investigated. The EPR spectrum shape analysis of Nb4+ (electron configuration 4d1, electron spin S=1/2) reveals the formation of triplet niobium binuclear complex (total electron spin S=1) in glasses. The amount of Nb4+ ions in glasses reversibly changes with temperature and is explained via the mechanism of electron hopping between niobium ions in clusters. The dependence of the amount of Nb4+ ions upon Li2O content has a maximal character, which implies that small amounts of Li+ ions stabilize the Nb4+ pairs, but cause their disproportionation at higher concentrations of Li+ ions in the glass. Quantum mechanical analysis of electronic and spin states of binuclear niobium clusters has been performed on model binuclear complexes, (HO)3Nb-O-Nb(OH)3, [(HO)3Nb-O-Nb(OH)3]Li+, and [(HO)3Nb-O-Nb(OH)3](Li+)2 that exhibit the reversible disproportionation reaction Nb4+-O-Nb4+⇔Nb3+-O-Nb5+. Triplet states of these complexes (total electron spin S=1) have lower energies than singlet states (S=0), and Li+ ions stabilize the binuclear niobium complex. We have found that electron spin densities on niobium ions change depending upon the shift of the bridging oxygen atom. Application of this theoretical modeling to the analysis of the experimental EPR spectrum in Li2O-Nb2O5-P2O5 glass concludes noncentrosymmetric structure of binuclear niobium complex with ˜0.1 Å offset of the bridging oxygen atom towards one Nb atom.

  9. Advanced magnetic resonance imaging of neurodegenerative diseases.

    PubMed

    Agosta, Federica; Galantucci, Sebastiano; Filippi, Massimo

    2017-01-01

    Magnetic resonance imaging (MRI) is playing an increasingly important role in the study of neurodegenerative diseases, delineating the structural and functional alterations determined by these conditions. Advanced MRI techniques are of special interest for their potential to characterize the signature of each neurodegenerative condition and aid both the diagnostic process and the monitoring of disease progression. This aspect will become crucial when disease-modifying (personalized) therapies will be established. MRI techniques are very diverse and go from the visual inspection of MRI scans to more complex approaches, such as manual and automatic volume measurements, diffusion tensor MRI, and functional MRI. All these techniques allow us to investigate the different features of neurodegeneration. In this review, we summarize the most recent advances concerning the use of MRI in some of the most important neurodegenerative conditions, putting an emphasis on the advanced techniques.

  10. 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.

  11. Synthesis of Ba1-xKxBiO3 ceramic specimens: Electron paramagnetic resonance and microwave absorption

    NASA Astrophysics Data System (ADS)

    Misra, Sushil K.; Andronenko, Serguei I.; Andronenko, Rosa R.; Mezentseva, Larisa P.

    1996-04-01

    Ba1-xKxBiO3 ceramic samples were synthesized with many initial relative amounts of reagents. Chemical analysis was used to determine the final concentration x¯ in the synthesized samples. It was found that only four values of x¯=0.13, 0.25, 0.4, 0.5 with Δx¯=+/-0.03 were possible. Electron-paramagnetic resonance (EPR) and microwave-absorption investigations of the synthesized ceramic specimens were carried out in the temperature range 4-100 K. In the two nonsuperconducting specimens characterized by the smaller concentrations x¯=0.13, 0.25 the same two EPR lines at g=2.09 and g=4.25 were observed, whose intensities increased sharply below 40 K with decreasing temperature, likely due to the phase Ba0.875K0.125BiO3. A least-squares fitting of the intensity of the line at g=4.25 for the sample with x¯=0.13 with (1/T)exp(-Jp/T), yielded the value of the exchange constant Jp=2.3+/-0.5 K, confirming that this line is indeed due to a transition within the energy levels belonging to the excited triplet state of hole pairs localized on the oxygen ions. Low-field microwave absorption and x-ray diffraction by the superconducting specimens characterized by the higher concentrations x¯=0.4, 0.5 indicate that these samples consist of two different superconducting phases: one, with x=0.375, possessing Tc=28 K, and the other with x=0.5, possessing Tc=16 K. Four possible configurations of the solid solutions Ba1-xKxBiO3 wherein one, two, three, and four K+ ions substitute for the same number of Ba2+ ions, with well-defined positions of K+ ions in the unit cell, have been presently proposed.

  12. 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

  13. 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.

  14. Electron paramagnetic resonance crystallography of 17O-enriched oxycobaltomyoglobin: Stereoelectronic structure of the cobalt dioxygen system

    PubMed Central

    Dickinson, L. Charles; Chien, James C. W.

    1980-01-01

    An electron paramagnetic resonance crystallographic study was made on oxycobaltomyoglobin with the dioxygen ligand enriched to 19.1% in 17O. There are two spectroscopically distinct cobalt dioxygen species. The less abundant species, II (40%), has nonequivalent oxygen atoms with superhyperfine tensors OAα = (5, -67.5, 22.4)G and OAβ = (5.4, -83.3, 30.3)G. Together with the previously reported 59Co hyperfine tensor [Chien, J. C. W. & Dickinson, L. C. (1972) Proc. Natl. Acad. Sci. USA 69, 2783-2787], the orbital spin densities are found to be Oα(pη) = 0.48, Oα(pζ) = -0.11, Oβ(pη) = 0.74, Oβ(pζ) = -0.16, Co(dxz) = -0.01, Co(dyz) = 0.06 for a total electron density of 1.01. The O—O axis is directed toward His-E7, suggesting a possible hydrogen bonding interaction which may contribute to the nonequivalency of the oxygen atoms; its projection approximately bisects N1—Fe—N2. The z axis of the CoA tensor is tilted at an angle of 28° from the heme normal, resulting in a Co—O—O angle of 120°. The more abundant species, I (60%), has equivalent oxygen atoms with OAγ = (12, -72.5, 20)G and orbital spin densities of Oγ(pη) = 0.54, Oγ(pζ) = -0.05, Co(dxz) = -0.02, Co(dyz) = 0.09 for a total spin density of 1.10. Although the direction cosines for this molecule cannot be precisely determined, the projection of its O—O axis approximately bisects N2—Fe—N3 and is parallel to the imidazole ring of His-F8. Increase of temperature changes g, CoA, and OA values, with the largest effect seen with OA. This temperature dependence indicates averaging of the two bond structures which are stabilized at 77 K. PMID:6246485

  15. 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

  16. 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.

  17. Electron-paramagnetic-resonance study of the isolated arsenic antisite in electron irradiated GaAs and its relation to the EL2 center

    SciTech Connect

    Rong, F.C.; Buchwald, W.R.; Harmatz, M.; Poindexter, E.H. ); Warren, W.L. )

    1991-10-28

    Arsenic antisites produced in GaAs by room-temperature electron irradiation (RTEI) are examined by electron paramagnetic resonance (EPR). For the first time, this RTEI antisite, which has been believed to be the isolated antisite, is found to be metastable. The most efficient photon energy for photoquenching is found to be approximately 1.15 eV, which is very close to that observed for the well-known EL2 center in undoped semi-insulating GaAs. However, the thermal recovery temperature is about 200--250 K, much higher than that for the EL2 center.

  18. Science Drivers and Technical Challenges for Advanced Magnetic Resonance

    SciTech Connect

    Mueller, Karl T.; Pruski, Marek; Washton, Nancy M.; Lipton, Andrew S.

    2013-03-07

    This report recaps the "Science Drivers and Technical Challenges for Advanced Magnetic Resonance" workshop, held in late 2011. This exploratory workshop's goal was to discuss and address challenges for the next generation of magnetic resonance experimentation. During the workshop, participants from throughout the world outlined the science drivers and instrumentation demands for high-field dynamic nuclear polarization (DNP) and associated magnetic resonance techniques, discussed barriers to their advancement, and deliberated the path forward for significant and impactful advances in the field.

  19. Surface plasmon resonance biosensors: advances and applications

    NASA Astrophysics Data System (ADS)

    Homola, Jirí

    2009-10-01

    Surface plasmon resonance (SPR) biosensors represent the most advanced label-free optical affinity biosensor technology. In the last decade numerous SPR sensor platforms have been developed and applied in the life sciences and bioanalytics. This contribution reviews the state of the art in the development of SPR (bio)sensor technology and presents selected results of research into SPR biosensors at the Institute of Photonics and Electronics, Prague. The developments discussed in detail include a miniature fiber optic SPR sensor for localized measurements, a compact SPR sensor for field use and a multichannel SPR sensor for high-throughput screening. Examples of applications for the detection of analytes related to medical diagnostics (biomarkers, hormones, antibodies), environmental monitoring (endocrine disrupting compounds), and food safety (pathogens and toxins) are given.

  20. 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.

  1. Formation of carbon nanodots with different spin states in mechanically processed mixtures of ZnO with carbon nanoparticles: an electron paramagnetic resonance study.

    PubMed

    Kakazey, M; Vlasova, M; Gómez-Vidales, V; Ángeles-Pascual, A; Basiuk, V A

    2017-02-01

    Mixtures of zinc oxide with carbon nanoparticles, ZnO + xC (x = 0.1%, 1% and 3% by weight), were subjected to mechanical processing (MP) in a hermetically sealed grinding chamber. Using electron paramagnetic resonance (EPR) spectroscopy, we monitored the evolution of spin centers in CNPs. While the initial CNPs were EPR silent, their short-duration MP (tMP) gave rise to emergence of low-intensity carbon signal. Increasing the sample temperature at tMP > 9 min induced CNP oxidation, which lead to a dramatic increase in the intensity of C signal. The oxidation process also manifested itself in the appearance of a photoluminescence (PL) band at ∼2.8 eV, which is characteristic for carbon nanodots with an average size of ∼2.7 nm. A limited amount of oxygen in the grinding chamber lead to different ways of carbon nanodot oxidation, depending on carbon content in the samples, which in turn influenced the characteristics of C EPR signals observed. The number of spins calculated per one CNP (NSOP) was found to depend on carbon content in ZnO + xC samples. Based on a detailed analysis of EPR spectral lines, we suggest the existence of a broad variety of relaxation mechanisms for forming C paramagnetic centers.

  2. Fusinite: A coal-derived EPR probe for O[sub 2]. Mechanism and application in vivo and in vitro. [EPR (electron paramagnetic resonance)

    SciTech Connect

    Vahidi, N.

    1993-01-01

    Fusinite, an inertinite coal maceral, exhibits a symmetric and exchange-narrowed electron paramagnetic resonance (EPR) line (g = 2.00276), with a first derivative peak-to-peak linewidth ([Delta]B) which is reversibly broaded by molecular O[sub 2]. To explain the mechanism of this type of broadening, pulse and multifrequency EPR measurements (0.25-250 GHz) were carried out in conjunction with O[sub 2] adsorption isotherm studies. The data suggest that, at ambient temperatures, homogeneous broadening of the EPR line of fusinite probably occurs by the exchange modulation of a group of delocalized unpaired electrons at the surface of fusinite by physical adsorbed O[sub 2]. At temperatures below 260[degrees] K, dipole-dipole mechanism begin to contribute more to the broadening of this component. The possibility of two different classes of sites for interaction with O[sub 2] is discussed. The extent of broadening per unit concentration of molecular oxygen is unusually large. This paramagnetic property of fusinite, combined with its very table physiochemical properties and low toxicity, is of utility for the measurement of the concentration of oxygen or [O[sub 2

  3. Advances in mechanical detection of magnetic resonance

    PubMed Central

    Kuehn, Seppe; Hickman, Steven A.; Marohn, John A.

    2008-01-01

    The invention and initial demonstration of magnetic resonance force microscopy (MRFM) in the early 1990s launched a renaissance of mechanical approaches to detecting magnetic resonance. This article reviews progress made in MRFM in the last decade, including the demonstration of scanned probe detection of magnetic resonance (electron spin resonance, ferromagnetic resonance, and nuclear magnetic resonance) and the mechanical detection of electron spin resonance from a single spin. Force and force-gradient approaches to mechanical detection are reviewed and recent related work using attonewton sensitivity cantilevers to probe minute fluctuating electric fields near surfaces is discussed. Given recent progress, pushing MRFM to single proton sensitivity remains an exciting possibility. We will survey some practical and fundamental issues that must be resolved to meet this challenge. PMID:18266413

  4. Optical and electron paramagnetic resonance studies of hydrogenated amorphous carbon (a-C:H) thin films formed by direct ion beam deposition method

    NASA Astrophysics Data System (ADS)

    Silinskas, M.; Grigonis, A.; Dikcius, G.; Manikowski, H.

    2001-04-01

    The diamond-like carbon films, deposited by direct ion beam deposition method using mixture of C6H14 and H2 with and without silicon presence, have been investigated by Raman spectroscopy, X-ray photoelectron spectroscopy, ellipsometry, IR-visible-UV transmission, and electron paramagnetic resonance techniques. The D and G line widths and peak positions, integrated intensity ratio (ID/IG) in Raman spectra indicate these films being amorphous, mixture of sp2 and sp3 bonds. It has been found that a-C:H films formed while increasing substrate temperature and deposition ion energy tend to be graphite-like. Increasing of hydrogen content in gas mixture made these films more polymer-like with low content of dangling bonds. Traces of silicon increase sp3/sp2 ratio. The DLC films on silicon are able to greatly reduce IR reflection.

  5. Hyperbolic decay of photo-created Sb2+ ions in Sn2P2S6:Sb crystals detected with electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Basun, S. A.; Halliburton, L. E.; Evans, D. R.

    2017-01-01

    In this paper, we employed a method that overcomes the known limitations of electron paramagnetic resonance (EPR) to monitor charge trap dynamics over a broad temperature range not normally accessible due to the lifetime broadening of the EPR lines at higher temperatures. This was achieved by measuring the decay of the EPR intensity after thermal annealing by rapid cycling back to low temperatures for the EPR measurement. This technique was used to experimentally demonstrate interesting physics in the form of a direct measurement of the hyperbolic decay 1/(1+t) of a charge trap population, which previously was only considered theoretically. The nontrivial effects of bimolecular recombination are demonstrated in the Sn2S2P6:Sb crystals, providing an explanation of the optical sensitization process observed in photorefractive Sn2P2S6:Sb used for dynamic holography.

  6. Differential effects of cholesterol on acyl chain order in erythrocyte membranes as a function of depth from the surface. An electron paramagnetic resonance (EPR) spin label study.

    PubMed

    Cassera, M B; Silber, A M; Gennaro, A M

    2002-10-16

    The purpose of this work is to analyze the effects of cholesterol modulation on acyl chain ordering in the membrane of human erythrocytes as a function of depth from the surface. Partial cholesterol depletion was achieved by incubation of erythrocytes with liposomes containing saturated phospholipids, or with methyl-beta-cyclodextrin (MbetaCD). Cholesterol enrichment was achieved by incubation with liposomes formed by phospholipids/cholesterol, or with the complex MbetaCD/cholesterol. Acyl chain order was studied with electron paramagnetic resonance spectroscopy (EPR) using spin labels that sense the lipid bilayer at different depths. It is shown that the increase in cholesterol stiffens acyl chains but decreases the interaction among lipid headgroups, while cholesterol depletion causes the opposite behavior. It is likely that the observed cholesterol effects are related to those stabilizing the cholesterol-rich detergent-insoluble membrane domains (rafts), recently shown to exist in erythrocytes.

  7. Electron paramagnetic resonance and ultraviolet/visible study of compounds I and II in the horseradish peroxidase-H 2O 2-silk fiber reaction system

    NASA Astrophysics Data System (ADS)

    Oliva, C.; Freddi, G.; Repetto, S.; D'Ambrosio, A.

    2003-06-01

    The enzymatic oxidation of silk with H2O2 in the presence of horseradish peroxidase (HRP) has been investigated. Two intermediate complexes have been observed during this reaction. Both can be attributed to Fe4+ ions axially bonded to an oxygen atom and to a porphyrin radical (Prad ). In the most unstable of them, indicated as compound II, the chemical bond between [FeIVO]2+ and Prad was weaker than in the other, indicated as compound I. The former compound disappeared within 1 h of the reaction, at difference with the latter, traces of which were observed even after 3 weeks with dried samples. However, the chemical bond between [FeIVO]2+ and Prad in compound I weakened during the sample ageing. All these phenomena have been enlightened by electron paramagnetic resonance (EPR) and spectrophotometric ultraviolet/visible (UV/Vis) measurements.

  8. 31P MAS-NMR study of flux-grown rare-earth element orthophosphate (monazite/xenotime) solid solutions: Evidence of random cation distribution from paramagnetically shifted NMR resonances

    SciTech Connect

    Palke, A. C.; Stebbins, J. F.; Boatner, Lynn A

    2013-01-01

    We present 31P magic angle spinning nuclear magnetic resonance (MAS-NMR) spectra of flux-grown solid solutions of La1-xCexPO4 ( x between 0.027 and 0.32) having the monoclinic monazite structure, and of Y1-xMxPO4 (M = Vn+, Ce3+, Nd3+, x between 0.001 and 0.014) having the tetragonal zircon structure. Paramagnetically shifted NMR resonances are observed in all samples due to the presence of paramagnetic Vn+, Ce3+, and Nd3+ in the diamagnetic LaPO4 or YPO4. As a first-order observation, the number and relative intensity of these peaks is related to the symmetry and structure of the diamagnetic host phase. The presence of paramagnetic shifts allows for increased resolution between NMR resonances for distinct atomic species which leads to the observation of low intensity peaks related to PO4 species having more than one paramagnetic neighbor two or four atomic bonds away. Through careful analysis of peak areas and comparison with predictions for simple models, it was determined that solid solutions in the systems examined here are characterized by complete disorder (random distribution) of diamagnetic La3+ or Y3+ with the paramagnetic substitutional species Ce3+ and Nd3+. The increased resolution given by the paramagnetic interactions also leads to the observation of splitting of specific resonances in the 31P NMR spectra that may be caused by local, small-scale distortions from the substitution of ions having dissimilar ionic radii.

  9. Electron paramagnetic resonance measurements of free radicals in the intact beating heart: a technique for detection and characterization of free radicals in whole biological tissues.

    PubMed Central

    Zweier, J L; Kuppusamy, P

    1988-01-01

    Free radicals have been hypothesized to be important mediators of disease in a variety of organs and tissues. Electron paramagnetic resonance (EPR) spectroscopy can be applied to directly measure free radicals; however, it has not been possible to measure important biological radicals in situ because conventional spectrometer designs are not suitable for the performance of measurements on whole organs or tissues. We report the development of an EPR spectrometer designed for optimum performance in measuring free radicals in intact biological organs or tissues. This spectrometer consists of a 1- to 2-GHz microwave bridge with the source locked to the resonant frequency of a recessed gap loop-gap resonator. With this spectrometer, radical concentrations as low as 0.4 microM can be measured. Isolated beating hearts were studied in which simultaneous real time measurements of free radicals and cardiac contractile function were performed. This in vivo EPR technique was applied to study the kinetics of free radical uptake and metabolism in normally perfused and globally ischemic hearts. In addition, we show that this technique can be used to noninvasively measure tissue oxygen consumption. Thus, it is demonstrated that EPR spectroscopy can be applied to directly measure in vivo free radical metabolism and tissue oxygen consumption. This technique offers great promise in the study of in vivo free radical generation and the effects of this radical generation on whole biological tissues. PMID:2840672

  10. Advances in resonance based NDT for ceramic components

    NASA Astrophysics Data System (ADS)

    Hunter, L. J.; Jauriqui, L. M.; Gatewood, G. D.; Sisneros, R.

    2012-05-01

    The application of resonance based non-destructive testing methods has been providing benefit to manufacturers of metal components in the automotive and aerospace industries for many years. Recent developments in resonance based technologies are now allowing the application of resonance NDT to ceramic components including turbine engine components, armor, and hybrid bearing rolling elements. Application of higher frequencies and advanced signal interpretation are now allowing Process Compensated Resonance Testing to detect both internal material defects and surface breaking cracks in a variety of ceramic components. Resonance techniques can also be applied to determine material properties of coupons and to evaluate process capability for new manufacturing methods.

  11. 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.

  12. Magnetic interactions between a [4Fe-4S]1+ cluster and a flavin mononucleotide radical in the enzyme trimethylamine dehydrogenase: A high-field electron paramagnetic resonance study

    NASA Astrophysics Data System (ADS)

    Fournel, Andre; Gambarelli, Serge; Guigliarelli, Bruno; More, Claude; Asso, Marcel; Chouteau, Gerard; Hille, Russ; Bertrand, Patrick

    1998-12-01

    Trimethylamine dehydrogenase is a bacterial enzyme which contains two redox centers: a flavin mononucleotide (FMN) group which constitutes the active site and a [4Fe-4S]1+,2+ cluster which transfers the electrons provided by the FMN to an electron-transferring flavoprotein. According to the x-ray crystal structure, the center-to-center distance is equal to 12 Å and the nearest atoms of the two centers are separated by a 4 Å gap. Although this arrangement does not appear especially favorable for mediating strong magnetic interactions, a triplet state electron paramagnetic resonance (EPR) spectrum arising from the intercenter magnetic coupling is observed at X band (9 GHz) when the enzyme is reduced by its substrate. In earlier work, the temperature dependence of this spectrum and its analysis based on a triplet state spin Hamiltonian were used to propose the range (0.8-100 cm-1) for the parameter J0 of the isotropic interaction J0SA.SB, but neither the magnitude of J0 nor its sign could be further specified [R. C. Stevenson, W. R. Dunham, R. H. Sands, T. P. Singer, and H. Beinert, Biochim. Biophys. Acta 869, 81 (1986)]. In the present work, we have studied the interaction EPR spectrum in the range 9-340 GHz. Numerical simulations based on a spin Hamiltonian describing a system of two S=1/2 interacting spins allowed us to determine the full set of parameters describing the magnetic interactions between the FMN radical and the [4Fe-4S]1+ cluster. In particular, our study demonstrates that the coupling is antiferromagnetic with J0=+0.72 cm-1. Although this value corresponds to the lower limit of the range proposed previously, it still appears markedly larger than those measured in biological systems in which a similar arrangement of two paramagnetic centers is found.

  13. Upconverting rare-earth nanoparticles with a paramagnetic lanthanide complex shell for upconversion fluorescent and magnetic resonance dual-modality imaging

    NASA Astrophysics Data System (ADS)

    Wang, Yan; Ji, Lei; Zhang, Bingbo; Yin, Peihao; Qiu, Yanyan; Song, Daqian; Zhou, Juying; Li, Qi

    2013-05-01

    Multi-modal imaging based on multifunctional nanoparticles is a promising alternative approach to improve the sensitivity of early cancer diagnosis. In this study, highly upconverting fluorescence and strong relaxivity rare-earth nanoparticles coated with paramagnetic lanthanide complex shells and polyethylene glycol (PEGylated UCNPs@DTPA-Gd3+) are synthesized as dual-modality imaging contrast agents (CAs) for upconverting fluorescent and magnetic resonance dual-modality imaging. PEGylated UCNPs@DTPA-Gd3+ with sizes in the range of 32-86 nm are colloidally stable. They exhibit higher longitudinal relaxivity and transverse relaxivity in water (r1 and r2 values are 7.4 and 27.8 s-1 per mM Gd3+, respectively) than does commercial Gd-DTPA (r1 and r2 values of 3.7 and 4.6 s-1 per mM Gd3+, respectively). They are found to be biocompatible. In vitro cancer cell imaging shows good imaging contrast of PEGylated UCNPs@DTPA-Gd3+. In vivo upconversion fluorescent imaging and T1-weighted MRI show excellent enhancement of both fluorescent and MR signals in the livers of mice administered PEGylated UCNPs@DTPA-Gd3+. All the experimental results indicate that the synthesized PEGylated UCNPs@DTPA-Gd3+ present great potential for biomedical upconversion of fluorescent and magnetic resonance dual-modality imaging applications.

  14. 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

  15. 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.

  16. The Involvement of Respiration in Free Radical Processes during Loss of Desiccation Tolerance in Germinating Zea mays L. (An Electron Paramagnetic Resonance Study).

    PubMed

    Leprince, O.; Atherton, N. M.; Deltour, R.; Hendry, GAF.

    1994-04-01

    When germinating Zea mays L. seeds are rapidly desiccated, free radical-mediated lipid peroxidation and phospholipid de-esterification is accompanied by a desiccation-induced buildup of a stable free radical associated with rapid loss of desiccation tolerance. Comparison of the electron paramagnetic resonance and electron nuclear double resonance properties of this radical with those of the radical in dried, desiccation-intolerant moss showed that the two were identical. At the subcellular level, the radical was associated with the hydrophilic fraction resulting from lipid extraction. Isolated mitochondria subjected to drying were also found to accumulate an identical radical in vitro. When increasing concentrations of cyanide were used, a significant positive correlation was shown between rates of respiration and the accumulation of the radical in desiccation-intolerant tissues. Another positive correlation was found when rates of O2 uptake by radicles at different stages of germination were plotted against free radical content following desiccation. This indicates that free radical production is closely linked to respiration in a process likely to involve the desiccation-induced impairment of the mitochondrial electron transport chain to form thermodynamically favorable conditions to induce accumulation of a stable free radical and peroxidized lipids. Modulation of respiration using a range of inhibitors resulted in broadly similar modulation of the buildup of the stable free radical. One site of radical generation was likely to be the NADH dehydrogenase of complex I and probably as a direct consequence of desiccation-impaired electron flow at or close to the ubiquinone pool.

  17. 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

  18. Inter-spin distance determination using L-band (1-2 GHz) non-adiabatic rapid sweep electron paramagnetic resonance (NARS EPR)

    NASA Astrophysics Data System (ADS)

    Kittell, Aaron W.; Hustedt, Eric J.; Hyde, James S.

    2012-08-01

    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 8-80 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.

  19. Experimental assessment of absorbed dose to mineralized bone tissue from internal emitters: An electron paramagnetic resonance study

    SciTech Connect

    Desrosiers, M.F.

    1994-12-31

    EPR resonances attributable to radiation-induced centers in hydroxyapatite were not detectable in bone samples supplied by the USTUR. These centers are the basis for imaging and dose assessment. Presumable, the short range of the alpha particles emitted precluded the formation of appreciable amounts of hydroxyapatite centers. However, one bone sample did offer a suggestion of hydroxyapatite centers and newly-developed methods to extract this information will be pursued.

  20. 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

  1. 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

  2. Physical, Optical and Electron paramagnetic resonance studies of PbBr2-PbO-B2O3 glasses containing Cu2+ ions

    NASA Astrophysics Data System (ADS)

    Sekhar, K. Chandra; Hameed, Abdul; Chary, M. Narasimha; Shareefuddin, Md

    2016-09-01

    The glasses with the composition PbBr2-PbO-B2O3 glasses containing Cu2+ ions were prepared by melt quenching technique. X-ray diffractograms revealed the amorphous nature of the glasses. Density and molar volume were determined. Density is found to decrease while the molar volume increases with increase of PbBr2 content. The optical absorption spectra exhibited a broad band corresponding to the d- d transition of Cu2+ ion. From optical absorption spectra Eopt and Urbach energies were determined. Electron Paramagnetic Resonance (EPR) studies were carried out by introducing Cu2+ as the spin probe. Glasses containing transition metal(TM) ions such as Cu2+ give the information about the structure and the site symmetry around the TM ions. EPR spectra of all the glass samples were recorded at X-band frequencies. From the EPR spectra spin-Hamiltonian parameters were evaluated. It was observed that g∥ >g±>ge (2.0023) and A∥>A±. From this values it is concluded that the ground state of Cu2+ is dx2-y2 (2B1g) and the site symmetry around Cu2+ ion is tetragonally distorted octahedral. From the EPR and Optical data bonding coefficients were evaluated. The in plane o-bonding(α2) is moderately ionic while out of plane 7t-bonding(β2) and in plane 7t-bonding(β1 2) are ionic nature

  3. Integrated Paramagnetic Resonance of High-Spin Co(II) in Axial Symmetry: Chemical Separation of Dipolar and Contact Electron-Nuclear Couplings

    PubMed Central

    Myers, William K.; Duesler, Eileen N.; Tierney, David L.

    2015-01-01

    Integrated paramagnetic resonance, utilizing EPR, NMR and ENDOR, of a series of cobalt bis-trispyrazolylborates, Co(Tpx)2, are reported. Systematic substitutions at the ring carbons and on the apical boron provide a unique opportunity to separate through-bond and through-space contributions to the NMR hyperfine shifts for the parent, unsubstituted Tp complex. A simple relationship between the chemical shift difference (δH − δMe) and the contact shift of the proton in that position is developed. This approach allows independent extraction of the isotropic hyperfine coupling, Aiso, for each proton in the molecule. The Co··H contact coupling energies derived from the NMR, together with the known metrics of the compounds, were used to predict the ENDOR couplings at gζ. Proton ENDOR data is presented that shows good agreement with the NMR-derived model. ENDOR signals from all other magnetic nuclei in the complex (14N, coordinating and non-coordinating, 11B and 13C) are also reported. PMID:18605690

  4. Localization of dexamethasone within dendritic core-multishell (CMS) nanoparticles and skin penetration properties studied by multi-frequency electron paramagnetic resonance (EPR) spectroscopy.

    PubMed

    Saeidpour, S; Lohan, S B; Anske, M; Unbehauen, M; Fleige, E; Haag, R; Meinke, M C; Bittl, R; Teutloff, C

    2016-10-15

    The skin and especially the stratum corneum (SC) act as a barrier and protect epidermal cells and thus the whole body against xenobiotica of the external environment. Topical skin treatment requires an efficient drug delivery system (DDS). Polymer-based nanocarriers represent novel transport vehicles for dermal application of drugs. In this study dendritic core-multishell (CMS) nanoparticles were investigated as promising candidates. CMS nanoparticles were loaded with a drug (analogue) and were applied to penetration studies of skin. We determined by dual-frequency electron paramagnetic resonance (EPR) how dexamethasone (Dx) labelled with 3-carboxy-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (PCA) is associated with the CMS. The micro-environment of the drug loaded to CMS nanoparticles was investigated by pulsed high-field EPR at cryogenic temperature, making use of the fact that magnetic parameters (g-, A-matrices, and spin-lattice relaxation time) represent specific probes for the micro-environment. Additionally, the rotational correlation time of spin-labelled Dx was probed by continuous wave EPR at ambient temperature, which provides independent information on the drug environment. Furthermore, the penetration depth of Dx into the stratum corneum of porcine skin after different topical applications was investigated. The location of Dx in the CMS nanoparticles is revealed and the function of CMS as penetration enhancers for topical application is shown.

  5. Substitution mechanisms and location of Co2+ ions in congruent and stoichiometric lithium niobate crystals derived from electron paramagnetic resonance data

    NASA Astrophysics Data System (ADS)

    Grachev, V. G.; Hansen, K.; Meyer, M.; Kokanyan, E. P.; Malovichko, G. I.

    2017-03-01

    Electron paramagnetic resonance (EPR) spectra and their angular dependencies were measured for Co2+ trace impurities in stoichiometric samples of lithium niobate doped with rhodium. It was found that Co2+ substitutes for Li+ in the dominant axial center (CoLi) and that the principal substitution mechanism in stoichiometric lithium niobate is 4Co2+ ↔ 3Li+  +  Nb5+. The four Co2+ ions can occupy the nearest possible cation sites by occupying a Nb site and its three nearest-neighbor Li sites, creating a trigonal pyramid with C3 symmetry, as well as non-neighboring sites (e.g. a CoNb–CoLi pair at the nearest sites on the C3 axis with two nearby isolated single Co2+ ions substituted for Li+). In congruent crystals and samples with Li content enriched by vapor transport equilibrium treatment the excess charge of the Co2+ centers is compensated by lithium vacancies located rather far from the Co2+ ions for the dominant axial center or in the nearest neighborhood for low-symmetry satellite centers (the Co2+ ↔ 2Li+ substitution mechanism). The use of exact numerical diagonalization of the spin-Hamiltonian matrices explains all the details of the EPR spectra and gives a value for hyperfine interaction A || that is several times smaller than that obtained using perturbation formulae. The refined values of A and g-tensor components can be used as reliable cornerstones for ab initio and cluster calculations.

  6. 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.

  7. 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.

  8. Role of chloride ion in hydroxyl radical production in photosystem II under heat stress: electron paramagnetic resonance spin-trapping study.

    PubMed

    Yadav, Deepak Kumar; Pospíšil, Pavel

    2012-06-01

    Hydroxyl radical (HO•) production in photosystem II (PSII) was studied by electron paramagnetic resonance (EPR) spin-trapping technique. It is demonstrated here that the exposure of PSII membranes to heat stress (40 °C) results in HO• formation, as monitored by the formation of EMPO-OH adduct EPR signal. The presence of different exogenous halides significantly suppressed the EMPO-OH adduct EPR signal in PSII membranes under heat stress. The addition of exogenous acetate and blocker of chloride channel suppressed the EMPO-OH adduct EPR signal, whereas the blocker of calcium channel did not affect the EMPO-OH adduct EPR signal. Heat-induced hydrogen peroxide (H₂O₂) production was studied by amplex red fluorescent assay. The presence of exogenous halides, acetate and chloride blocker showed the suppression of H₂O₂ production in PSII membranes under heat stress. Based on our results, it is proposed that the formation of HO• under heat stress is linked to uncontrolled accessibility of water to the water-splitting manganese complex caused by the release of chloride ion on the electron donor side of PSII. Uncontrolled water accessibility to the water-splitting manganese complex causes the formation of H₂O₂ due to improper water oxidation, which leads to the formation of HO• via the Fenton reaction under heat stress.

  9. Electron paramagnetic resonance, scanning electron microscopy with energy dispersion X-ray spectrometry, X-ray powder diffraction, and NMR characterization of iron-rich fired clays.

    PubMed

    Presciutti, Federica; Capitani, Donatella; Sgamellotti, Antonio; Brunetti, Brunetto Giovanni; Costantino, Ferdinando; Viel, Stéphane; Segre, Annalaura

    2005-12-01

    The aim of this study is to clarify the structure of an iron-rich clay and the structural changes involved in the firing process as a preliminary step to get information on ancient ceramic technology. To this purpose, illite-rich clay samples fired at different temperatures were characterized using a multitechnique approach, i.e., by electron paramagnetic resonance, scanning electron microscopy with electron dispersion X-ray spectrometry, X-ray powder diffraction, magic angle spinning and multiple quantum magic angle spinning NMR. During firing, four main reaction processes occur: dehydration, dehydroxylation, structural breakdown, and recrystallization. When the results are combined from all characterization methods, the following conclusions could be obtained. Interlayer H2O is located close to aluminum in octahedral sites and is driven off at temperatures lower than 600 degrees C. Between 600 and 700 degrees C dehydroxylation occurs whereas, between 800 and 900 degrees C, the aluminum in octahedral sites disappears, due to the breakdown of the illite structure, and all iron present is oxidized to Fe3+. In samples fired at 1000 and 1100 degrees C iron clustering was observed as well as large single crystals of iron with the occurrence of ferro- or ferrimagnetic effects. Below 900 degrees C the aluminum in octahedral sites presents a continuous distribution of chemical shift, suggesting the presence of slightly distorted sites. Finally, over the whole temperature range, the presence of at least two tetrahedral aluminum sites was revealed, characterized by different values of the quadrupolar coupling constant.

  10. Sn vacancies in photorefractive Sn2P2S6 crystals: An electron paramagnetic resonance study of an optically active hole trap

    NASA Astrophysics Data System (ADS)

    Golden, E. M.; Basun, S. A.; Evans, D. R.; Grabar, A. A.; Stoika, I. M.; Giles, N. C.; Halliburton, L. E.

    2016-10-01

    Electron paramagnetic resonance (EPR) is used to identify the singly ionized charge state of the Sn vacancy ( VSn - ) in single crystals of Sn2P2S6 (often referred to as SPS). These vacancies, acting as a hole trap, are expected to be important participants in the photorefractive effect observed in undoped SPS crystals. In as-grown crystals, the Sn vacancies are doubly ionized ( VSn 2 - ) with no unpaired spins. They are then converted to a stable EPR-active state when an electron is removed (i.e., a hole is trapped) during an illumination below 100 K with 633 nm laser light. The resulting EPR spectrum has g-matrix principal values of 2.0079, 2.0231, and 1.9717. There are resolved hyperfine interactions with two P neighbors and one Sn neighbor. The isotropic portions of these hyperfine matrices are 167 and 79 MHz for the two 31P neighbors and 8504 MHz for the one Sn neighbor (this latter value is the average for 117Sn and 119Sn). These VSn - vacancies are shallow acceptors with the hole occupying a diffuse wave function that overlaps the neighboring Sn2+ ion and (P2S6)4- anionic unit. Using a general-order kinetics approach, an analysis of isothermal decay curves of the VSn - EPR spectrum in the 107-115 K region gives an activation energy of 283 meV.

  11. 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.

  12. Ferrimagnetism and magnetic phase separation in Nd1-xYxMnO3 studied by magnetization and high frequency electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Nair, Harikrishnan S.; Yadav, Ruchika; Adiga, Shilpa; Rao, S. S.; van Tol, Johan; Elizabeth, Suja

    2015-01-01

    Ferrimagnetism and metamagnetic features tunable by composition are observed in the magnetic response of Nd1-xYxMnO3, for x=0.1-0.5. For all values of x in the series, the compound crystallizes in orthorhombic Pbnm space group similar to NdMnO3. Magnetization studies reveal a phase transition of the Mn-sublattice below T N Mn ≈ 80 K for all compositions, which, decreases up on diluting the Nd-site with Yttrium. For x=0.35, ferrimagnetism is observed. At 5 K, metamagnetic transition is observed for all compositions x < 0.4. The evolution of magnetic ground states and appearance of ferrimagnetism in Nd1-xYxMnO3 can be accounted for by invoking the scenario of magnetic phase separation. The high frequency electron paramagnetic resonance measurements on x=0.4 sample, which is close to the critical composition for phase separation, revealed complex temperature dependent lineshapes clearly supporting the assumption of magnetic phase separation.

  13. 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.

  14. 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.

  15. 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.

  16. Characterization of structural changes in vimentin bearing an epidermolysis bullosa simplex-like mutation using site-directed spin labeling and electron paramagnetic resonance.

    PubMed

    Hess, John F; Budamagunta, Madhu S; FitzGerald, Paul G; Voss, John C

    2005-01-21

    Mutations in intermediate filament protein genes are responsible for a number of inherited genetic diseases including skin blistering diseases, corneal opacities, and neurological degenerations. Mutation of the arginine (Arg) residue of the highly conserved LNDR motif has been shown to be causative in inherited disorders in at least four different intermediate filament (IF) proteins found in skin, cornea, and the central nervous system. Thus this residue appears to be broadly important to IF assembly and/or function. While the genetic basis for these diseases has been clearly defined, the inability to determine crystal structure for IFs has precluded a determination of how these mutations affect assembly/structure/function of IFs. To investigate the impact of mutation at this site in IFs, we have mutated the LNDR to LNDS in vimentin, a Type III intermediate filament protein, and have examined the impact of this change on assembly using electron paramagnetic resonance. Compared with wild type vimentin, the mutant shows normal formation of the coiled coil dimer, with a slight reduction in the stability of the dimer in rod domain 1. Probing the dimer-dimer interactions shows the formation of normal dimer centered on residue 191 but a failure of dimerization at residue 348 in rod domain 2. These data point toward a specific stage of assembly at which a common disease-causing mutation in IF proteins interrupts assembly.

  17. Association of resistin with impaired membrane fluidity of red blood cells in hypertensive and normotensive men: an electron paramagnetic resonance study.

    PubMed

    Tsuda, Kazushi

    2016-10-01

    Abnormalities in physical properties of the cell membranes may strongly be linked to hypertension. Recent evidence indicates that resistin may actively participate in the pathophysiology of insulin resistance, diabetes mellitus, hypertension and other circulatory disorders. The present study was undertaken to investigate the possible relationships among plasma resistin, oxidative stress and membrane fluidity (a reciprocal value of membrane microviscosity) in hypertension. We measured the membrane fluidity of red blood cells (RBCs) in hypertensive and normotensive men using an electron paramagnetic resonance (EPR) and spin-labeling method. The order parameter (S) for the spin-label agents (5-nitroxide stearate) in EPR spectra of red blood cell (RBC) membranes was significantly higher in hypertensive men than in normotensive men, indicating that membrane fluidity was decreased in hypertension. Plasma resistin levels were correlated with systolic blood pressure and 8-iso-prostaglandin F2α levels (an index of oxidative stress). Furthermore, the order parameter (S) of RBCs significantly correlated with plasma resistin and plasma 8-isoPG F2α, suggesting that reduced membrane fluidity of RBCs might be associated with hyperresistinemia and increased oxidative stress. Multivariate regression analysis showed that, after adjustment for confounding factors, plasma resistin might be an independent determinant of membrane fluidity of RBCs. The EPR study suggests that resistin might have a close correlation with impaired rheologic behavior of RBCs and microcirculatory dysfunction in hypertension, at least in part, via an oxidative stress-dependent mechanism.

  18. A calcium channel blocker, benidipine, improves cell membrane fluidity in human subjects via a nitric oxide-dependent mechanism. An electron paramagnetic resonance investigation.

    PubMed

    Tsuda, Kazushi; Nishio, Ichiro

    2004-12-01

    Recent studies have revealed that benidipine, a long-acting dihydropyridine-type of calcium (Ca) channel blocker, may exert its protective effect against vascular disorders by increasing nitric oxide (NO) production. The purpose of the present study was to investigate the effects of benidipine and NO on the membrane function in human subjects. We measured the membrane fluidity of erythrocytes by using an electron paramagnetic resonance (EPR) and spin-labeling method. Benidipine decreased the order parameter (S) for 5-nitroxide stearate (5-NS) and the peak height ratio (h(o)/h(-1)) for 16-NS obtained from EPR spectra of erythrocyte membranes in a dose-dependent manner in normotensive volunteers. The finding indicated that benidipine increased the membrane fluidity and improved the microviscosity of erythrocytes. The effect of benidipine was significantly potentiated by the NO donor, S-nitroso-n-acetylpenicillamine, and by the cyclic guanosine 3', 5'-monophosphate (cGMP) analog, 8-bromo-cGMP. In contrast, the change evoked by benidipine was counteracted by the NO synthase inhibitors, N(G)-nitro-L-arginine-methyl-ester and asymmetric dimethyl-L-arginine. These results demonstrated that benidipine increased the membrane fluidity of erythrocytes, at least in part, via the NO- and cGMP-dependent mechanism. Furthermore, the data strongly suggest that benidipine might have a beneficial effect on the rheologic behavior of erythrocytes and the improvement of the microcirculation in humans.

  19. Ab initioelectron paramagnetic resonance study of 3C-SiC/SiO2 interfaces in SiC-nanofiber based solar cells

    NASA Astrophysics Data System (ADS)

    Nugraha, Taufik Adi; Gerstmann, Uwe; Schmidt, Wolfgang Gero; Wippermann, Stefan

    Semiconducting nanocomposites, e. g. hybrid materials based on inorganic semiconducting 3C-SiC nanofibers and organic surfactants, provide genuinely novel pathways to exceed the Shockley-Queisser limit for solar energy conversion. The synthesis of such functionalized fibers can be performed completely using only inexpensive wet chemical solution processing. During synthesis a thin passivation layer is introduced between the SiC-fiber and surfactants, e. g. the native oxide, whose atomistic details are poorly understood. In this study, we utilize unpaired spins in interfacial defects to probe the local chemical environment with ab initio EPR (Electron Paramagnetic Resonance) calculations, which can be directly compared to experiment. Considering a wide variety of possible interfacial structures, a grand canonical approach is used to generate a phase diagram of the 3C-SiC/SiO2 interface as a function of the chemical potentials of Si, O and H, to provide favorable interfacial structures for g-tensor calculations. This study provides directions about specific types of interfacial defects and their impact on the electronic properties of the interface. The authors wish to thank S. Greulich-Weber for helpful discussions. S. W. acknowledges BMBF NanoMatFutur Grant No. 13N12972.

  20. Dose-dependent vitamin C uptake and radical scavenging activity in human skin measured with in vivo electron paramagnetic resonance spectroscopy.

    PubMed

    Lauer, Anna-Christina; Groth, Norbert; Haag, Stefan F; Darvin, Maxim E; Lademann, Jürgen; Meinke, Martina C

    2013-01-01

    Vitamin C is a potent radical scavenger and a physiological part of the antioxidant system in human skin. The aim of this study was to measure changes in the radical-scavenging activity of human skin in vivo due to supplementation with different doses of vitamin C and at different time points. Therefore, 33 volunteers were supplemented with vitamin C or placebo for 4 weeks. The skin radical-scavenging activity was measured with electron paramagnetic resonance spectroscopy. After 4 weeks, the intake of 100 mg vitamin C/day resulted in a significant increase in the radical-scavenging activity by 22%. Intake of 180 mg/day even resulted in a significant increase of 37%. No changes were found in the placebo group. A part of the study population was additionally measured after 2 weeks: in this group radical scavenging had already reached maximal activity after 2 weeks. In conclusion, orally administered vitamin C increases the radical-scavenging activity of the skin. The effect occurs fast and is enhanced with higher doses of vitamin C.

  1. Investigation of the local structure of Cu2+ ions doped in alkali lead tetraborate glasses by their electron paramagnetic resonance and optical spectra

    NASA Astrophysics Data System (ADS)

    Wu, Ying; Chen, Zhi

    2014-06-01

    The local structure of the Cu2+ centers in alkali lead tetraborate glasses was theoretically studied based on the optical spectra data and high-order perturbation formulas of the spin Hamiltonian parameters (electron paramagnetic resonance g factors g∥, g⊥ and hyperfine structure constants A∥, A⊥) for a 3d9 ion in a tetragonally elongated octahedron. In these formulas, the relative axial elongation of the ligand O2- octahedron around the Cu2+ due to the Jahn-Teller effect is taken into account by considering the contributions to the g factors from the tetragonal distortion which is characterized by the tetragonal crystal-field parameters Ds and Dt. From the calculations, the ligand O2- octahedral around Cu2+ is determined to suffer about 19.2% relative elongation along the C4 axis of the alkali lead tetraborate glass system, and a negative sign for A∥ and a positive sign for A⊥ for these Cu2+ centers are suggested in the discussion.

  2. 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.

  3. Strong reduction of V4+ amount in vanadium oxide/hexadecylamine nanotubes by doping with Co2+ and Ni2+ ions: Electron paramagnetic resonance and magnetic studies

    NASA Astrophysics Data System (ADS)

    Saleta, M. E.; Troiani, H. E.; Ribeiro Guevara, S.; Ruano, G.; Sánchez, 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 (VOx/Hexa NT's) doped with Co2+ and Ni2+ 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 (Co2+, S = 3/2 and Ni2+, S = 1) decreases notably the amount of V4+ 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 V4+ in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes.

  4. A Study of Mechanochemical Doping of Fluoride Crystals with a Fluorite Structure by Er3+ Ions via Electron Paramagnetic Resonance Spectra

    NASA Astrophysics Data System (ADS)

    Irisova, I. A.; Rodionov, A. A.; Tayurskii, D. A.; Yusupov, R. V.

    2014-05-01

    Using electron paramagnetic resonance (EPR) spectroscopy, we have shown that, upon mecha- noactivated doping of powders of compounds CaF2, SrF2, and BaF2 with Er3+ ions, impurity centers of single erbium ions with cubic symmetry are formed. Investigations of dependences of EPR spectra intensities on the particle size show that the process of mechanochemical doping with Er3+ ions proceeds differently for CaF2, SrF2, and BaF2 host matrices. In the case of CaF2, impurity centers are localized in a very thin near-surface layer of CaF2 particles, in SrF2, the impurity is distributed over the volume of particles, while, in BaF2, there is a layer of a finite thickness for which the probability of doping in the course of mechanosynthesis is very small and the impurity of the rare-earth element is localized in the core of large particles. These data can be explained assuming that the result of mechanosynthesis of particles of fluorides with a fluorite structure doped with Er3+ ions at room temperature is governed by two processes—mechanoactivated diffusion of rare-earth ions into particles and segregation of impurity ions at grain boundaries. In this case, the typical scales for compounds CaF2, SrF2, and BaF2 considerably differ from each other.

  5. The lead acceptor in p-type natural 2H-polytype MoS2 crystals evidenced by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

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

    2017-03-01

    A low-temperature (T  =  1.5-8 K) electron paramagnetic resonance study of p-type 2H-polytype natural MoS2 crystals reveals a previously unreported anisotropic signal of corresponding defect density (spin S  =  ½) ~5  ×  1014 cm-3. For the applied magnetic field B//c-axis, the response is comprised of a single central asymmetric Zeeman peak at zero-crossing g  =  2.102(1), amid a symmetrically positioned hyperfine doublet of splitting 6.6(2) G. Field angular observations reveal a two-branch g pattern, indicative of a defect of lower than axial symmetry, likely orthorhombic (C 2v). Based on the signal specifics, it is ascribed to a system of decoupled Pb impurities substituting for Mo, the defect operating as an acceptor, with estimated thermal activation energy  >10 meV. Supporting theoretical anticipation, the results pinpoint the conduct of the Pb impurity in layered MoS2.

  6. Evaluation of oxidative stress in the brain of a transgenic mouse model of Alzheimer disease by in vivo electron paramagnetic resonance imaging.

    PubMed

    Matsumura, Akihiro; Emoto, Miho C; Suzuki, Syuuichirou; Iwahara, Naotoshi; Hisahara, Shin; Kawamata, Jun; Suzuki, Hiromi; Yamauchi, Ayano; Sato-Akaba, Hideo; Fujii, Hirotada G; Shimohama, Shun

    2015-08-01

    Alzheimer disease (AD) is a neurodegenerative disease clinically characterized by progressive cognitive dysfunction. Deposition of amyloid-β (Aβ) peptides is the most important pathophysiological hallmark of AD. Oxidative stress induced by reactive oxygen species is prominent in AD, and several reports suggest the relationship between a change in redox status and AD pathology containing progressive Aβ deposition, the activation of glial cells, and mitochondrial dysfunction. Therefore, we performed immunohistochemical analysis using a transgenic mouse model of AD (APdE9) and evaluated the activity of superoxide dismutase in brain tissue homogenates of APdE9 mice in vitro. Together with those analyses, in vivo changes in redox status with age in both wild-type (WT) and APdE9 mouse brains were measured noninvasively by three-dimensional electron paramagnetic resonance (EPR) imaging using nitroxide (3-methoxycarbonyl-2,2,5,5-tetramethylpyrrolidine-1-yloxy) as a redox-sensitive probe. Both methods found similar changes in redox status with age, and in particular a significant change in redox status in the hippocampus was observed noninvasively by EPR imaging between APdE9 mice and age-matched WT mice from 9 to 18 months of age. EPR imaging clearly visualized the accelerated change in redox status of APdE9 mouse brain compared with WT. The evaluation of the redox status in the brain of AD model rodents by EPR imaging should be useful for diagnostic study of AD.

  7. 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

    2015-11-03

    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.

  8. Influence of Ring-Expanded N-Heterocyclic Carbenes on the Structures of Half-Sandwich Ni(I) Complexes: An X-ray, Electron Paramagnetic Resonance (EPR), and Electron Nuclear Double Resonance (ENDOR) Study.

    PubMed

    Pelties, Stefan; Carter, Emma; Folli, Andrea; Mahon, Mary F; Murphy, Damien M; Whittlesey, Michael K; Wolf, Robert

    2016-11-07

    Potassium graphite reduction of the half-sandwich Ni(II) ring-expanded diamino/diamidocarbene complexes CpNi(RE-NHC)Br gave the Ni(I) derivatives CpNi(RE-NHC) (where RE-NHC = 6-Mes (1), 7-Mes (2), 6-MesDAC (3)) in yields of 40%-50%. The electronic structures of paramagnetic 1-3 were investigated by CW X-/Q-band electron paramagnetic resonance (EPR) and Q-band (1)H electron nuclear double resonance (ENDOR) spectroscopy. While small variations in the g-values were observed between the diaminocarbene complexes 1 and 2, pronounced changes in the g-values were detected between the almost isostructural species (1) and diamidocarbene species (3). These results highlight the sensitivity of the EPR g-tensor to changes in the electronic structure of the Ni(I) centers generated by incorporation of heteroatom substituents onto the backbone ring positions. Variable-temperature EPR analysis also revealed the presence of a second Ni(I) site in 3. The experimental g-values for these two Ni(I) sites detected by EPR in frozen solutions of 3 are consistent with resolution on the EPR time scale of the disordered components evident in the X-ray crystallographically determined structure and the corresponding density functional theory (DFT)-calculated g-tensor. Q-band (1)H ENDOR measurements revealed a small amount of unpaired electron spin density on the Cp rings, consistent with the calculated SOMO of complexes 1-3. The magnitude of the (1)H A values for 3 were also notably larger, compared to 1 and 2, again highlighting the influence of the diamidocarbene on the electronic properties of 3.

  9. L-band electron paramagnetic resonance spectrometer for use in vivo and in studies of aqueous biological samples

    NASA Astrophysics Data System (ADS)

    Walczak, T.; Leśniewski, P.; Salikhov, I.; Sucheta, A.; Szybiński, K.; Swartz, H. M.

    2005-01-01

    The development of L-band (˜1.2GHz) frequency EPR spectrometers has made feasible many in vivo studies in laboratory animals and, recently, in human volunteers. The lower dielectric and eddy current losses that occur at L-band balance the lower Zeeman splitting so useful measurements can be made in conductive aqueous samples. We describe typical resonators used in such studies and provide details on the construction of the spectrometer, including the bridge, the automatic frequency control subsystem, the low-noise high-stability tunable L-band frequency source, as well as the low-frequency components—the signal receiver and the modulation unit. The application of EPR spectroscopy to larger subjects requires special care in the design of an appropriate magnet with sufficient homogeneity and stability, yet with dimensions that allow operation with a wide range of subject sizes. We describe our solution, which involves a permanent magnet, air-core scan coils to provide the field sweep and offset, and field stabilization by means of a field-frequency lock. We also describe the magnetic field modulation system, which operates at 25 kHz to avoid distortion in spectra from materials with narrow lines (such as lithium phthalocyanine). We refer to recent reviews to illustrate the range of in vivo studies and the clinical applications of the type of spectrometer described here.

  10. Applications of in vivo electron paramagnetic resonance (EPR) spectroscopy: measurements of pO2 and NO in endotoxin shock.

    PubMed

    Jackson, S K; Madhani, M; Thomas, M; Timmins, G S; James, P E

    2001-03-31

    Recent developments of EPR instrumentation that allow the use of large tissue samples or whole animals and the ability to image spatially resolved EPR signals has led to novel applications of EPR spectroscopy in vivo. Utilising a 1 GHz EPR spectrometer with a 3.4-cm birdcage resonator, it was possible to detect and measure nitric oxide and oxygen in the livers of mice with lipopolysaccharide (LPS)-induced septic shock. Nitric oxide was detected as the nitric oxide (NO) complex of Fe-diethyldithiocarbamic acid (Fe-DETC) while pO2 was measured from the EPR linewidth of the oxygen-sensitive coal material 'gloxy'. LPS treatment stimulated the production of nitric oxide in the liver and the general circulation and the oxygenation of liver tissue was decreased. Selective placement of the EPR probes allowed images of nitric oxide and oxygen to be obtained in the liver. The spectral and spatial information obtained with this technique will allow improved understanding of the pathophysiology of such diseases.

  11. An advanced EPR stopped-flow apparatus based on a dielectric ring resonator

    NASA Astrophysics Data System (ADS)

    Lassmann, Günter; Schmidt, Peter Paul; Lubitz, Wolfgang

    2005-02-01

    A novel EPR stopped-flow accessory is described which allows time-dependent cw-EPR measurements of rate constants of reactions involving paramagnetic species after rapid mixing of two liquid reagents. The EPR stopped-flow design represents a state-of-the-art, computer controlled fluid driving system, a miniresonant EPR structure with an integrated small ball mixer, and a stopping valve. The X-band EPR detection system is an improved version of that reported by Sienkiewicz et al. [Rev. Sci. Instr. 65 (1994) 68], and utilizes a resonator with two stacked ceramic dielectric rings separated by a variable spacer. The resonator with the mode TE( H) 011 is tailored particularly for conditions of fast flowing and rapidly stopped aqueous solutions, and for a high time resolution. The short distance between the ball mixer and the small EPR active volume (1.8 μl) yields a measured dead time of 330 μs. A compact assembly of all parts results in minimization of disturbing microphonics. The computer controlled driving system from BioLogic with two independent stepping motors was optimized for EPR stopped-flow with a hard-stop valve. Performance tests on the EPR spectrometer ESP 300E from BRUKER using redox reactions of nitroxide radicals revealed the EPR stopped-flow accessory as an advanced, versatile, and reliable instrument with high reproducibility.

  12. Advanced and Conventional Magnetic Resonance Imaging in Neuropsychiatric Lupus

    PubMed Central

    Sarbu, Nicolae; Bargalló, Núria; Cervera, Ricard

    2015-01-01

    Neuropsychiatric lupus is a major diagnostic challenge, and a main cause of morbidity and mortality in patients with systemic lupus erythematosus (SLE). Magnetic resonance imaging (MRI) is, by far, the main tool for assessing the brain in this disease. Conventional and advanced MRI techniques are used to help establishing the diagnosis, to rule out alternative diagnoses, and recently, to monitor the evolution of the disease. This review explores the neuroimaging findings in SLE, including the recent advances in new MRI methods. PMID:26236469

  13. Probing the Hydrogen Bonding of the Ferrous–NO Heme Center of nNOS by Pulsed Electron Paramagnetic Resonance

    PubMed Central

    Astashkin, Andrei V.; Chen, Li; Elmore, Bradley O.; Kunwar, Deepak; Miao, Yubin; Li, Huiying; Poulos, Thomas L.; Roman, Linda J.; Feng, Changjian

    2015-01-01

    Oxidation of L-arginine (L-Arg) to nitric oxide (NO) by NO synthase (NOS) takes place at the heme active site. It is of current interest to study structures of the heme species that activates O2 and transforms the substrate. The NOS ferrous–NO complex is a close mimic of the obligatory ferric (hydro)peroxo intermediate in NOS catalysis. In this work, pulsed electron–nuclear double resonance (ENDOR) spectroscopy was used to probe the hydrogen bonding of the NO ligand in the ferrous–NO heme center of neuronal NOS (nNOS) without a substrate and with L-Arg or N-hydroxy-L-arginine (NOHA) substrates. Unexpectedly, no H-bonding interaction connecting the NO ligand to the active site water molecule or the Arg substrate was detected, in contrast to the results obtained by X-ray crystallography for the Arg-bound nNOS heme domain [Li et al. J. Biol. Inorg. Chem. 2006, 11, 753–768]. The nearby exchangeable proton in both the no-substrate and Arg-containing nNOS samples is located outside the H-bonding range and, on the basis of the obtained structural constraints, can belong to the active site water (or OH). On the contrary, in the NOHA-bound sample, the nearby exchangeable hydrogen forms an H-bond with the NO ligand (on the basis of its distance from the NO ligand and a nonzero isotropic hfi constant), but it does not belong to the active site water molecule because the water oxygen atom (detected by 17O ENDOR) is too far. This hydrogen should therefore come from the NOHA substrate, which is in agreement with the X-ray crystallography work [Li et al. Biochemistry 2009, 48, 10246–10254]. The nearby nonexchangeable hydrogen atom assigned as Hɛ of Phe584 was detected in all three samples. This hydrogen atom may have a stabilizing effect on the NO ligand and probably determines its position. PMID:26035438

  14. Acoustic resonance spectroscopy for the advanced undergraduate laboratory

    NASA Astrophysics Data System (ADS)

    Franco-Villafañe, J. A.; Flores-Olmedo, E.; Báez, G.; Gandarilla-Carrillo, O.; Méndez-Sánchez, R. A.

    2012-11-01

    We present a simple experiment that allows advanced undergraduates to learn the principles and applications of spectroscopy. The technique, known as acoustic resonance spectroscopy, is applied to study a vibrating rod. The setup includes electromagnetic-acoustic transducers, an audio amplifier and a vector network analyzer. Typical results of compressional, torsional and bending waves are analyzed and compared with analytical results.

  15. Nuclear resonant scattering beamline at the Advanced Photon Source

    SciTech Connect

    Alp, E.E.; Mooney, T.M.; Toellner, T.; Sturhahn, W.

    1993-09-01

    The principal and engineering aspects of a dedicated synchrotron radiation beamline under construction at the Advanced Photon Source for nuclear resonant scattering purposes are explained. The expected performance in terms of isotopes to be studied, flux, and timing properties is discussed.

  16. 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

  17. Recent advances in cardiac magnetic resonance

    PubMed Central

    Greulich, Simon; Arai, Andrew E.; Sechtem, Udo; Mahrholdt, Heiko

    2016-01-01

    Cardiac magnetic resonance (CMR) is a non-invasive imaging modality that has rapidly emerged during the last few years and has become a valuable, well-established clinical tool. Beside the evaluation of anatomy and function, CMR has its strengths in providing detailed non-invasive myocardial tissue characterization, for which it is considered the current diagnostic gold standard. Late gadolinium enhancement (LGE), with its capability to detect necrosis and to separate ischemic from non-ischemic cardiomyopathies by distinct LGE patterns, offers unique clinical possibilities. The presence of LGE has also proven to be a good predictor of an adverse outcome in various studies. T2-weighted (T2w) images, which are supposed to identify areas of edema and inflammation, are another CMR approach to tissue characterization. However, T2w images have not held their promise owing to several technical limitations and potential physiological concerns. Newer mapping techniques may overcome some of these limitations: they assess quantitatively myocardial tissue properties in absolute terms and show promising results in studies for characterization of diffuse fibrosis (T1 mapping) and/or inflammatory processes (T2 mapping). However, these techniques are still research tools and are not part of the clinical routine yet. T2* CMR has had significant impact in the management of thalassemia because it is possible to image the amount of iron in the heart and the liver, improving both diagnostic imaging and the management of patients with thalassemia. CMR findings frequently have clinical impact on further patient management, and CMR seems to be cost effective in the clinical routine. PMID:27635240

  18. Effect of TiO2 on electron paramagnetic resonance, optical transmission and dc conductivity of vanadyl doped sodium borate glasses.

    PubMed

    Agarwal, A; Seth, V P; Gahlot, P; Goyal, D R; Arora, M; Gupta, S K

    2004-11-01

    Glass systems with composition xTiO2.(30 - x)Na2O.70B2O3 (series I) and xTiO2.(70 - x)B2O3.30Na2O (series II) containing 2 mol% V2O5 have been prepared (0 < or = x < or = 7, mol%) by normal melt-quenching. The electron paramagnetic resonance (EPR) spectra of VO2+ ions have been recorded in the X-band (approximately 9.13 GHz) at room temperature. Spin Hamiltonian parameters, gparallel, gperpendicular, Aparallel, Aperpendicular, the dipolar hyperfine coupling parameter (P) and the Fermi contact interaction parameter (K) have been calculated. The increase in Deltagparallel/Deltagperpendicular with increase in TiO2 content in series I shows that the octahedral symmetry of V4+O6 complex is reduced, whereas in series II the octahedral symmetry is improved with increase in x. The decrease in P, in both the series, indicates that the 3dxy orbit expands with increase in mol% of TiO2. The molecular orbital coefficients, alpha2 and gamma2 have been calculated by recording the optical transmission spectra in the range 500-850 nm. alpha2 and gamma2 increase with increase in x in both the series, which indicates that, the covalency of the vanadium oxygen bonds decreases. The dc conductivity sigma, decreases and activation energy, W increases with increase in TiO2:Na2O ratio whereas with increase in TiO2:B2O3 ratio the variation in sigma and W is within experimental error.

  19. 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.

  20. 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.

  1. The internal dynamics of mini c TAR DNA probed by electron paramagnetic resonance of nitroxide spin-labels at the lower stem, the loop, and the bulge.

    PubMed

    Sun, Yan; Zhang, Ziwei; Grigoryants, Vladimir M; Myers, William K; Liu, Fei; Earle, Keith A; Freed, Jack H; Scholes, Charles P

    2012-10-30

    Electron paramagnetic resonance (EPR) at 236.6 and 9.5 GHz probed the tumbling of nitroxide spin probes in the lower stem, in the upper loop, and near the bulge of mini c TAR DNA. High-frequency 236.6 GHz EPR, not previously applied to spin-labeled oligonucleotides, was notably sensitive to fast, anisotropic, hindered local rotational motion of the spin probe, occurring approximately about the NO nitroxide axis. Labels attached to the 2'-aminocytidine sugar in the mini c TAR DNA showed such anisotropic motion, which was faster in the lower stem, a region previously thought to be partially melted. More flexible labels attached to phosphorothioates at the end of the lower stem tumbled isotropically in mini c TAR DNA, mini TAR RNA, and ψ(3) RNA, but at 5 °C, the motion became more anisotropic for the labeled RNAs, implying more order within the RNA lower stems. As observed by 9.5 GHz EPR, the slowing of nanosecond motions of large segments of the oligonucleotide was enhanced by increasing the ratio of the nucleocapsid protein NCp7 to mini c TAR DNA from 0 to 2. The slowing was most significant at labels in the loop and near the bulge. At a 4:1 ratio of NCp7 to mini c TAR DNA, all labels reported tumbling times of >5 ns, indicating a condensation of NCp7 and TAR DNA. At the 4:1 ratio, pulse dipolar EPR spectroscopy of bilabels attached near the 3' and 5' termini showed evidence of an NCp7-induced increase in the 3'-5' end-to-end distance distribution and a partially melted stem.

  2. Thermally activated spin fluctuations in stoichiometric LiCoO2 clarified by electron paramagnetic resonance and muon-spin rotation and relaxation measurements

    NASA Astrophysics Data System (ADS)

    Mukai, Kazuhiko; Aoki, Yoshifumi; Andreica, Daniel; Amato, Alex; Watanabe, Isao; Giblin, Sean R.; Sugiyama, Jun

    2014-03-01

    Lithium cobalt dioxide (LiCoO2) belongs to a family of layered CoO2-based materials and has considerable interests in both fundamental physics and technological applications in lithium-ion batteries. We report the results of structural, electrochemical, magnetic susceptibility (χ), electron paramagnetic resonance (EPR), and muon-spin rotation and relaxation (μSR) measurements on powder Lix0CoO2 samples, where the nominal Li/Co ratios (x0) were 0.95, 1.00, 1.02, 1.05, and 1.10, respectively. Structural, electrochemical, and χ measurements suggested that the sample with x0 = 1.02 is very close to single stoichiometric LiCoO2 (ST-LCO) phase and that the Co ions in the x0 = 1.02 sample are in a nonmagnetic low-spin state with S = 0 (t2g6). However, both EPR and μSR revealed that the x0 = 1.02 (ST-LCO) sample includes a large amount of nonordered magnetic phase in the temperature (T) range between 100 and 500 K. The volume fraction of such magnetic phase was found to be ˜45 vol% at 300 K by μSR, indicating an intrinsic bulk feature for ST-LCO. In fact, structural and photoelectron spectroscopic analyses clearly excluded the possibility that the nonordered magnetism is caused by impurities, defects, or surfaces. Because EPR and μSR sense static and dynamic nature of local magnetic environments, we concluded that Co spins in ST-LCO are fluctuating in the EPR and μSR time-windows. We also proposed possible origins of such nonordered magnetism, that is, a spin-state transition and charge disproportionation.

  3. Head and rod 1 interactions in vimentin: identification of contact sites, structure, and changes with phosphorylation using site-directed spin labeling and electron paramagnetic resonance.

    PubMed

    Aziz, Atya; Hess, John F; Budamagunta, Madhu S; FitzGerald, Paul G; Voss, John C

    2009-03-13

    We have used site-directed spin labeling (SDSL) and electron paramagnetic resonance (EPR) to identify residues 17 and 137 as sites of interaction between the head domain and rod domain 1A of the intermediate filament protein vimentin. This interaction was maximal when compared with the spin labels placed at up- and downstream positions in both head and rod regions, indicating that residues 17 and 137 were the closest point of interaction in this region. SDSL EPR characterization of residues 120-145, which includes the site of head contact with rod 1A, reveals that this region exhibits the heptad repeat pattern indicative of alpha-helical coiled-coil structure, but that this heptad repeat pattern begins to decay near residue 139, suggesting a transition out of coiled-coil structure. By monitoring the spectra of spin labels placed at the 17 and 137 residues during in vitro assembly, we show that 17-137 interaction occurs early in the assembly process. We also explored the effect of phosphorylation on the 17-137 interaction and found that phosphorylation-induced changes affected the head-head interaction (17-17) in the dimer, without significantly influencing the rod-rod (137-137) and head-rod (17-137) interactions in the dimer. These data provide the first direct evidence for, and location of, head-rod interactions in assembled intermediate filaments, as well as direct evidence of coiled-coil structure in rod 1A. Finally, the data identify changes in the structure in this region following in vitro phosphorylation.

  4. Structural and dynamic study of the tetramerization region of non-erythroid alpha-spectrin: a frayed helix revealed by site-directed spin labeling electron paramagnetic resonance.

    PubMed

    Li, Qufei; Fung, L W-M

    2009-01-13

    The N-terminal region of alpha-spectrin is responsible for its association with beta-spectrin in a heterodimer, forming functional tetramers. Non-erythroid alpha-spectrin (alphaII-spectrin) has a significantly higher association affinity for beta-spectrin than the homologous erythroid alpha-spectrin (alphaI-spectrin). We have previously determined the solution structure of the N-terminal region of alphaI-spectrin by NMR methods, but currently no structural information is available for alphaII-spectrin. We have used cysteine scanning, spin labeling electron paramagnetic resonance (EPR), and isothermal titration calorimetry (ITC) methods to study the tetramerization region of alphaII-spectrin. EPR data clearly show that, in alphaII-spectrin, the first nine N-terminal residues were unstructured, followed by an irregular helix (helix C'), frayed at the N-terminal end, but rigid at the C-terminal end, which merges into the putative triple-helical structural domain. The region corresponding to the important unstructured junction region linking helix C' to the first structural domain in alphaI-spectrin was clearly structured. On the basis of the published model for aligning helices A', B', and C', important interactions among residues in helix C' of alphaI- and alphaII-spectrin and helices A' and B' of betaI- and betaII-spectrin are identified, suggesting similar coiled coil helical bundling for spectrin I and II in forming tetramers. The differences in affinity are likely due to the differences in the conformation of the junction regions. Equilibrium dissociation constants of spin-labeled alphaII and betaI complexes from ITC measurements indicate that residues 15, 19, 37, and 40 are functionally important residues in alphaII-spectrin. Interestingly, all four corresponding homologous residues in alphaI-spectrin (residues 24, 28, 46, and 49) have been reported to be clinically significant residues involved in hematological diseases.

  5. Rapid kinetics of insertion and accessibility of spin-labeled phospholipid analogs in lipid membranes: a stopped-flow electron paramagnetic resonance approach.

    PubMed Central

    Marx, U; Lassmann, G; Wimalasena, K; Müller, P; Herrmann, A

    1997-01-01

    Spin-labeled phospholipid analogs have been employed to probe the transbilayer distribution of endogenous phospholipids in various membrane systems. To determine the transmembrane distribution of the spin-labeled analogs, the analogs are usually inserted into the membrane of interest and subsequently the amount of analog in the outer membrane leaflet is determined either by chemical reduction with ascorbate or by back-exchange to bovine serum albumin (BSA). For accurate determination of the transbilayer distribution of analogs, both the kinetics of incorporation and those of accessibility of analogs to ascorbate or BSA have to be fast in comparison to their transbilayer movement. By means of stopped-flow electron paramagnetic resonance (EPR) spectroscopy, we have studied the kinetics of incorporation of the spin-labeled phosphatidylcholine (PC) analog 1-palmitoyl-2-(4-doxylpentanoyl)-sn-glycero-3-phosphocholine (SL-PC) and of its accessibility to chemical reduction and to back-exchange at room temperature. Incorporation of SL-PC into the outer leaflet of egg phosphatidylcholine (EPC) and red cell ghost membranes was essentially completed within 5 s. Ninety percent of the SL-PC molecules located in the outer membrane leaflet of those membranes were extracted by BSA within 15 s. All exterior-facing SL-PC molecules were reduced by ascorbate in a pseudo-first-order reaction within 60 s in EPC membranes and within 90 s in red cell ghost membranes. The rate of the reduction process could be enhanced by approximately 30-fold when 6-O-phenyl-ascorbic acid was used instead of ascorbate as the reducing agent. The results are discussed in light of assaying rapid transbilayer movement of spin-labeled analogs in biological membranes. PMID:9284331

  6. Modulation of the ligand-field anisotropy in a series of ferric low-spin cytochrome c mutants derived from Pseudomonas aeruginosa cytochrome c-551 and Nitrosomonas europaea cytochrome c-552: a nuclear magnetic resonance and electron paramagnetic resonance study.

    PubMed

    Zoppellaro, Giorgio; Harbitz, Espen; Kaur, Ravinder; Ensign, Amy A; Bren, Kara L; Andersson, K Kristoffer

    2008-11-19

    Cytochromes of the c type with histidine-methionine (His-Met) heme axial ligation play important roles in electron-transfer reactions and in enzymes. In this work, two series of cytochrome c mutants derived from Pseudomonas aeruginosa (Pa c-551) and from the ammonia-oxidizing bacterium Nitrosomonas europaea (Ne c-552) were engineered and overexpressed. In these proteins, point mutations were induced in a key residue (Asn64) near the Met axial ligand; these mutations have a considerable impact both on heme ligand-field strength and on the Met orientation and dynamics (fluxionality), as judged by low-temperature electron paramagnetic resonance (EPR) and nuclear magnetic resonance (NMR) spectra. Ne c-552 has a ferric low-spin (S = 1/2) EPR signal characterized by large g anisotropy with g(max) resonance at 3.34; a similar large g(max) value EPR signal is found in the mitochondrial complex III cytochrome c1. In Ne c-552, deletion of Asn64 (NeN64Delta) changes the heme ligand field from more axial to rhombic (small g anisotropy and g(max) at 3.13) and furthermore hinders the Met fluxionality present in the wild-type protein. In Pa c-551 (g(max) at 3.20), replacement of Asn64 with valine (PaN64V) induces a decrease in the axial strain (g(max) at 3.05) and changes the Met configuration. Another set of mutants prepared by insertion (ins) and/or deletion (Delta) of a valine residue adjacent to Asn64, resulting in modifications in the length of the axial Met-donating loop (NeV65Delta, NeG50N/V65Delta, PaN50G/V65ins), did not result in appreciable alterations of the originally weak (Ne c-552) or very weak (Pa c-551) axial field but had an impact on Met orientation, fluxionality, and relaxation dynamics. Comparison of the electronic fingerprints in the overexpressed proteins and their mutants reveals a linear relationship between axial strain and average paramagnetic heme methyl shifts, irrespective of Met orientation or dynamics. Thus, for these His-Met axially coordinated Fe

  7. 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.

  8. A copper(II) complex with a Cu-S₈ bond. Attenuated total reflectance, electron paramagnetic resonance, resonance Raman and atoms-in-molecule calculations.

    PubMed

    Shee, Nirmal K; Adekunle, Florence A O; Verma, Ravi; Kumar, Devesh; Datta, Dipankar

    2015-12-05

    Green [Cu(1,10-phenanthroline)2OH2](ClO4)2 (1) reacts with yellow elemental sulfur at room temperature in methanol to yield turquoise blue [Cu(1,10-phenanthro-line)2(S8)](ClO4)2 (2). A comparative study of the EPR spectra of 1 and 2 in solid state and in methanol glass indicates that the S8 unit in 2 is bound to the metal. High level DFT calculations show that the cation in 2 is five coordinate, distorted square pyramidal with S8 occupying the apical position. The crucial Cu(II)-S bond is around 2.9Å. Such long Cu(II)-S bonds occur in oxidized plastocyanin where it is considered to be bonding. Presence of a weak Cu-S8 bond is revealed in the resonance Raman spectra of 2. Satisfactory matching of the calculated and experimental IR spectra vindicates the theoretically derived structure of the cation in 2.

  9. A comparative study by electron paramagnetic resonance of free radical species in the mainstream and sidestream smoke of cigarettes with conventional acetate filters and 'bio-filters'.

    PubMed

    Valavanidis, A; Haralambous, E

    2001-01-01

    Tobacco smoking is the most important extrinsic cause, after the diet, for increasing morbidity and mortality in humans. Unless current tobacco smoking patterns in industrialised and non-industrialised countries change, cigarettes will kill prematurely 10 million people a year by 2025. Greece is at the top of the list of European countries in cigarette consumption. In 1997, a Greek tobacco company introduced a new 'bio-filter' (BF) claiming that it reduces substantially the risks of smoking. In a recent publication [Deliconstantinos G, Villiotou V, Stavrides J. Scavenging effects of hemoglobin and related heme containing compounds on nitric oxide, reactive oxidants and carcinogenic volatile nitrosocompounds of cigarette smoke. A new method for protection against the dangerous cigarette constituents. Anticancer Res 1994; 14: 2717-2726] it was claimed that the new 'bio-filter' (activated carbon impregnated with dry hemoglobin) reduces certain toxic substances and oxidants (like NO, CO, NOx, H2O2, aldehydes, trace elements and nitroso-compounds) in the gas-phase of the mainstream smoke. We have investigated by electron paramagnetic resonance (EPR) the mainstream and sidestream smoke of the BF cigarette, in comparison with three other cigarettes with similar tar and nicotine contents, that have conventional acetate filters. We found that BF cigarette smoke has similar tar radical species with the same intensity EPR signals to those of the other cigarettes. The ability of the aqueous cigarette tar extracts to produce hydroxyl radicals (HO*), which were spin trapped by DMPO, was very similar to, or even higher than, the other 3 brands. The gas-phase of the mainstream smoke of the BF cigarette showed a 30-35% reduction in the production of oxygen-centered radicals (spin trapped with PBN). In the case of the sidestream smoke, BF cigarettes produced substantially higher concentrations of gas-phase radicals, compared to the other brands. These results suggest that BF is

  10. I. Impact Spallation Experiments: Fracture Patterns and Spall Velocities. I. Craters in Carbonate Rocks: AN Electron Paramagnetic Resonance Analysis of Shock Damage.

    NASA Astrophysics Data System (ADS)

    Polanskey, Carol Ann

    This work is divided into two independent papers. Paper 1. Spall velocities were measured for nine experimental impacts into San Marcos gabbro targets. Impact velocities ranged from 1 to 6.5 km/sec. Projectiles were iron, aluminum, lead, and basalt of varying sizes. The projectile masses ranged from a 4 g lead bullet to a 0.04 g aluminum sphere. The velocities of fragments were measured from high-speed films taken of the events. The maximum spall velocity observed was 30 m/sec, or 0.56 percent of the 5.4 km/sec impact velocity. The measured velocities were compared to the spall velocities predicted by the spallation model of Melosh (1984). The compatibility between the spallation model for large planetary impacts and the results of these small scale experiments are considered in detail. The targets were also bisected to observe the pattern of internal fractures. A series of fractures were observed, whose location coincided with the boundary between rock subjected to the peak shock compression and a theoretical "near surface zone" predicted by the spallation model. Thus, between this boundary and the free surface, the target material should receive reduced levels of compressive stress as compared to the more highly shocked region below. Paper 2. Carbonate samples from the nuclear explosion crater, OAK, and a terrestrial impact crater, Meteor Crater, were analyzed for shock damage using electron paramagnetic resonance, EPR. The first series of samples for OAK Crater were obtained from six boreholes within the crater, and the second series were ejecta samples recovered from the crater floor. The degree of shock damage in the carbonate material was assessed by comparing the sample spectra to spectra of Solenhofen limestone, which had been shocked to known pressures. The results of the OAK borehole analysis have identified a thin zone of highly shocked carbonate material underneath the crater floor. This zone has a maximum depth of approximately 200 ft below sea floor

  11. 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

  12. Hyperbolic-cosine waveguide tapers and oversize rectangular waveguide for reduced broadband insertion loss in W-band electron paramagnetic resonance spectroscopy. II. Broadband characterization

    PubMed Central

    Strangeway, Robert A.; Mett, Richard R.; Anderson, James R.; Mainali, Laxman; Hyde, James S.

    2016-01-01

    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

  13. In vivo visualization and ex vivo quantification of murine breast cancer cells in the mouse brain using MRI cell tracking and electron paramagnetic resonance.

    PubMed

    Danhier, Pierre; Magat, Julie; Levêque, Philippe; De Preter, Géraldine; Porporato, Paolo E; Bouzin, Caroline; Jordan, Bénédicte F; Demeur, Gladys; Haufroid, Vincent; Feron, Olivier; Sonveaux, Pierre; Gallez, Bernard

    2015-03-01

    Cell tracking could be useful to elucidate fundamental processes of cancer biology such as metastasis. The aim of this study was to visualize, using MRI, and to quantify, using electron paramagnetic resonance (EPR), the entrapment of murine breast cancer cells labeled with superparamagnetic iron oxide particles (SPIOs) in the mouse brain after intracardiac injection. For this purpose, luciferase-expressing murine 4 T1-luc breast cancer cells were labeled with fluorescent Molday ION Rhodamine B SPIOs. Following intracardiac injection, SPIO-labeled 4 T1-luc cells were imaged using multiple gradient-echo sequences. Ex vivo iron oxide quantification in the mouse brain was performed using EPR (9 GHz). The long-term fate of 4 T1-luc cells after injection was characterized using bioluminescence imaging (BLI), brain MRI and immunofluorescence. We observed hypointense spots due to SPIO-labeled cells in the mouse brain 4 h after injection on T2 *-weighted images. Histology studies showed that SPIO-labeled cancer cells were localized within blood vessels shortly after delivery. Ex vivo quantification of SPIOs showed that less than 1% of the injected cells were taken up by the mouse brain after injection. MRI experiments did not reveal the development of macrometastases in the mouse brain several days after injection, but immunofluorescence studies demonstrated that these cells found in the brain established micrometastases. Concerning the metastatic patterns of 4 T1-luc cells, an EPR biodistribution study demonstrated that SPIO-labeled 4 T1-luc cells were also entrapped in the lungs of mice after intracardiac injection. BLI performed 6 days after injection of 4 T1-luc cells showed that this cell line formed macrometastases in the lungs and in the bones. Conclusively, EPR and MRI were found to be complementary for cell tracking applications. MRI cell tracking at 11.7 T allowed sensitive detection of isolated SPIO-labeled cells in the mouse brain, whereas EPR

  14. 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

  15. Electron paramagnetic resonance and Mössbauer spectroscopy and density functional theory analysis of a high-spin Fe(IV)-oxo complex.

    PubMed

    Gupta, Rupal; Lacy, David C; Bominaar, Emile L; Borovik, A S; Hendrich, Michael P

    2012-06-13

    High-spin Fe(IV)-oxo species are known to be kinetically competent oxidants in non-heme iron enzymes. The properties of these oxidants are not as well understood as the corresponding intermediate-spin oxidants of heme complexes. The present work gives a detailed characterization of the structurally similar complexes [Fe(IV)H(3)buea(O)](-), [Fe(III)H(3)buea(O)](2-), and [Fe(III)H(3)buea(OH)](-) (H(3)buea = tris[(N'-tert-butylureaylato)-N-ethylene]aminato) using Mössbauer and dual-frequency/dual-mode electron paramagnetic resonance (EPR) spectroscopies. The [Fe(IV)H(3)buea(O)](-) complex has a high-spin (S = 2) configuration imposed by the C(3)-symmetric ligand. The EPR spectra of the [Fe(IV)H(3)buea(O)](-) complex presented here represent the first documented examples of an EPR signal from an Fe(IV)-oxo complex, demonstrating the ability to detect and quantify Fe(IV) species with EPR spectroscopy. Quantitative simulations allowed the determination of the zero-field parameter, D = +4.7 cm(-1), and the species concentration. Density functional theory (DFT) calculations of the zero-field parameter were found to be in agreement with the experimental value and indicated that the major contribution to the D value is from spin-orbit coupling of the ground state with an excited S = 1 electronic configuration at 1.2 eV. (17)O isotope enrichment experiments allowed the determination of the hyperfine constants ((17)O)A(z) = 10 MHz for [Fe(IV)H(3)buea(O)](-) and ((17)O)A(y) = 8 MHz, ((17)O)A(z) = 12 MHz for [Fe(III)H(3)buea(OH)](-). The isotropic hyperfine constant (((17)O)A(iso) = -16.8 MHz) was derived from the experimental value to allow a quantitative determination of the spin polarization (ρ(p) = 0.56) of the oxo p orbitals of the Fe-oxo bond in [Fe(IV)H(3)buea(O)](-). This is the first experimental determination for non-heme complexes and indicates significant covalency in the Fe-oxo bond. High-field Mössbauer spectroscopy gave an (57)Fe A(dip) tensor of (+5.6, +5

  16. Mechanism-based inhibition reveals transitions between two conformational states in the action of lysine 5,6-aminomutase: a combination of electron paramagnetic resonance spectroscopy, electron nuclear double resonance spectroscopy, and density functional theory study.

    PubMed

    Chen, Yung-Han; Maity, Amarendra N; Frey, Perry A; Ke, Shyue-Chu

    2013-01-16

    An "open"-state crystal structure of lysine 5,6-aminomutase suggests that transition to a hypothetical "closed"-state is required to bring the cofactors adenosylcobalamin (AdoCbl) and pyridoxal-5'-phosphate (PLP) and the substrate into proximity for the radical-mediated 1,2-amino group migration. This process is achieved by transaldimination of the PLP-Lys144β internal aldimine with the PLP-substrate external aldimine. A closed-state crystal structure is not available. UV-vis and electron paramagnetic resonance studies show that homologues of substrate D-lysine, 2,5-DAPn, 2,4-DAB, and 2,3-DAPr bind to PLP as an external aldimine and elicit the AdoCbl Co-C bond homolysis and the accumulations of cob(II)alamin and analogue-based radicals, demonstrating the existence of a closed state. (2)H- and (31)P-electron nuclear double resonance studies, supported by computations, show that the position for hydrogen atom abstraction from 2,5-DAPn and 2,4-DAB by the 5'-deoxyadenosyl radical occurs at the carbon adjacent to the imine, resulting in overstabilized radicals by spin delocalization through the imine into the pyridine ring of PLP. These radicals block the active site, inhibit the enzyme, and poise the enzyme into two distinct conformations: for even-numbered analogues, the cob(II)alamin remains proximal to and spin-coupled with the analogue-based radical in the closed state while odd-numbered analogues could trigger the transition to the open state of the enzyme. We provide here direct spectroscopic evidence that strongly support the existence of a closed state and its analogue-dependent transition to the open state, which is one step that was proposed to complete the catalytic turnover of the substrate lysine.

  17. Investigation of 60Co γ-irradiated L-(-) malic acid, N-methyl- DL-valine and L-glutamic acid γ-ethyl ester by electron paramagnetic resonance technique

    NASA Astrophysics Data System (ADS)

    Başkan, M. Halim; Aydın, Murat; Osmanoğlu, Şemsettin

    The electron paramagnetic resonance spectra of γ-irradiated L-(-) malic acid, N-methyl- DL-valine and L-glutamic acid γ-ethyl ester powders have been investigation at room temperature. Radiation damage centres are attributed to HOOCCH 2ĊHCOOH, (CH 3) 2ĊCH(NHCH 3)COOH and C 2H 5OCOCH 2CH 2Ċ(NH 2)COOH radicals, respectively. The spectra have been computer simulated. The EPR parameters of the observed radicals have been determined and discussed.

  18. Structural characterization of human vimentin rod 1 and the sequencing of assembly steps in intermediate filament formation in vitro using site-directed spin labeling and electron paramagnetic resonance.

    PubMed

    Hess, John F; Budamagunta, Madhu S; Voss, John C; FitzGerald, Paul G

    2004-10-22

    We have previously established the utility of site-directed spin labeling and electron paramagnetic resonance to determine structural relationships among proteins in intact intermediate filaments. Using this same approach we have introduced spin labels at 21 residues between amino acids 169 and 193 in rod domain 1 of human vimentin. The electron paramagnetic resonance spectra provide direct evidence for the coiled coil nature of the vimentin dimer in this region. This finding is consistent with predictions but has never been demonstrated previously. In a previous study we identified residue 348 in the rod domain 2 as one point of overlap between adjacent dimers in intact filaments. In the present study we defined residue 191 in the rod domain 1 as a second point of overlap and established that the dimers are arranged in an anti-parallel and staggered orientation at this site. Finally, by isolating spin-labeled samples at successive stages during the dialysis that lead to filament assembly in vitro, we have been able to establish a sequence of interactions that occurs during in vitro assembly, starting with the alpha helix and loose coiled coil dimer formation, then the formation of tetrameric species centered on residue 191, followed by interactions centered on residue 348 suggestive of octamer or higher order multimer formation. A continuation of this strategy revealed that both 191-191 and 348-348 interactions are present in low ionic strength Tris buffers when vimentin is maintained at the "protofilament" stage of assembly.

  19. Advances in Magnetic Resonance Imaging of the Skull Base

    PubMed Central

    Kirsch, Claudia F.E.

    2014-01-01

    Introduction Over the past 20 years, magnetic resonance imaging (MRI) has advanced due to new techniques involving increased magnetic field strength and developments in coils and pulse sequences. These advances allow increased opportunity to delineate the complex skull base anatomy and may guide the diagnosis and treatment of the myriad of pathologies that can affect the skull base. Objectives The objective of this article is to provide a brief background of the development of MRI and illustrate advances in skull base imaging, including techniques that allow improved conspicuity, characterization, and correlative physiologic assessment of skull base pathologies. Data Synthesis Specific radiographic illustrations of increased skull base conspicuity including the lower cranial nerves, vessels, foramina, cerebrospinal fluid (CSF) leaks, and effacement of endolymph are provided. In addition, MRIs demonstrating characterization of skull base lesions, such as recurrent cholesteatoma versus granulation tissue or abscess versus tumor, are also provided as well as correlative clinical findings in CSF flow studies in a patient pre- and post-suboccipital decompression for a Chiari I malformation. Conclusions This article illustrates MRI radiographic advances over the past 20 years, which have improved clinicians' ability to diagnose, define, and hopefully improve the treatment and outcomes of patients with underlying skull base pathologies. PMID:25992137

  20. Advances in Nuclear Magnetic Resonance for Drug Discovery

    PubMed Central

    Powers, Robert

    2010-01-01

    Background Drug discovery is a complex and unpredictable endeavor with a high failure rate. Current trends in the pharmaceutical industry have exasperated these challenges and are contributing to the dramatic decline in productivity observed over the last decade. The industrialization of science by forcing the drug discovery process to adhere to assembly-line protocols is imposing unnecessary restrictions, such as short project time-lines. Recent advances in nuclear magnetic resonance are responding to these self-imposed limitations and are providing opportunities to increase the success rate of drug discovery. Objective/Method A review of recent advancements in NMR technology that have the potential of significantly impacting and benefiting the drug discovery process will be presented. These include fast NMR data collection protocols and high-throughput protein structure determination, rapid protein-ligand co-structure determination, lead discovery using fragment-based NMR affinity screens, NMR metabolomics to monitor in vivo efficacy and toxicity for lead compounds, and the identification of new therapeutic targets through the functional annotation of proteins by FAST-NMR. Conclusion NMR is a critical component of the drug discovery process, where the versatility of the technique enables it to continually expand and evolve its role. NMR is expected to maintain this growth over the next decade with advancements in automation, speed of structure calculation, in-cell imaging techniques, and the expansion of NMR amenable targets. PMID:20333269

  1. 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.

  2. Advances in Magnetic Resonance Imaging Contrast Agents for Biomarker Detection

    NASA Astrophysics Data System (ADS)

    Sinharay, Sanhita; Pagel, Mark D.

    2016-06-01

    Recent advances in magnetic resonance imaging (MRI) contrast agents have provided new capabilities for biomarker detection through molecular imaging. MRI contrast agents based on the T2 exchange mechanism have more recently expanded the armamentarium of agents for molecular imaging. Compared with T1 and T2* agents, T2 exchange agents have a slower chemical exchange rate, which improves the ability to design these MRI contrast agents with greater specificity for detecting the intended biomarker. MRI contrast agents that are detected through chemical exchange saturation transfer (CEST) have even slower chemical exchange rates. Another emerging class of MRI contrast agents uses hyperpolarized 13C to detect the agent with outstanding sensitivity. These hyperpolarized 13C agents can be used to track metabolism and monitor characteristics of the tissue microenvironment. Together, these various MRI contrast agents provide excellent opportunities to develop molecular imaging for biomarker detection.

  3. Advances in Magnetic Resonance Imaging Contrast Agents for Biomarker Detection

    PubMed Central

    Sinharay, Sanhita; Pagel, Mark D.

    2016-01-01

    Recent advances in magnetic resonance imaging (MRI) contrast agents have provided new capabilities for biomarker detection through molecular imaging. MRI contrast agents based on the T2 exchange mechanism have more recently expanded the armamentarium of agents for molecular imaging. Compared with T1 and T2* agents, T2 exchange agents have a slower chemical exchange rate, which improves the ability to design these MRI contrast agents with greater specificity for detecting the intended biomarker. MRI contrast agents that are detected through chemical exchange saturation transfer (CEST) have even slower chemical exchange rates. Another emerging class of MRI contrast agents uses hyperpolarized 13C to detect the agent with outstanding sensitivity. These hyperpolarized 13C agents can be used to track metabolism and monitor characteristics of the tissue microenvironment. Together, these various MRI contrast agents provide excellent opportunities to develop molecular imaging for biomarker detection. PMID:27049630

  4. The Local Structural State of Aluminosilicate Garnet Solid Solutions: An Investigation of Grospydite Garnet from the Roberts Victor Kimberlite Using Paramagnetically Shifted 27Al and 29Si MAS NMR Resonances

    NASA Astrophysics Data System (ADS)

    Geiger, C. A.; Palke, A. C.; Stebbins, J. F.

    2014-12-01

    Most rock-forming silicates are substitutional solid solutions. Over the years extensive research has been done to determine their structural and crystal chemical properties. Here, the distribution of cations, or order-disorder behavior, is of central importance. In the case of aluminosilicate garnet solid solutions (X3Al2Si3O12 with X = Mg, Fe2+, Mn2+ and Ca) it has been shown that both synthetic and natural crystals have random long-range X-cation disorder in space group Ia-3d, as given by X-ray single-crystal diffraction measurements. However, the structural state of natural garnets at the local scale is not known. Garnet from a grospydite xenolith from the Roberts Victor kimberlite, South Africa, was studied by 27Al and 29Si MAS NMR spectroscopy. The research thrust was placed on measuring and analyzing paramagnetically shifted resonances to determine the local (short range) structural state of the X-cations in a grossular-rich ternary aluminosilicate garnet solid solution. The garnet crystals are compositionally homogeneous based on microprobe analysis, showing no measurable zoning, and have the formula Grs46.7Prp30.0Alm23.3. The garnet is cubic with the standard garnet space group Ia-3d. The 27Al MAS NMR spectrum shows a very broad asymmetric resonance located between about 100 and -50 ppm. It consists of a number of individual overlapping paramagnetically shifted resonances, which are difficult to analyze quantitatively. The 29Si MAS NMR spectrum, showing better resolution, has two observable resonances termed S0 and S4. S0 is located between about -60 ppm and -160 ppm and S4 is centered at roughly 95 ppm. Both S0 and S4 are composite resonances in nature containing many overlapping individual peaks. S0 contains information on local cation configurations whereby an isolated SiO4 group in the garnet structure does not have an edge-shared Fe2+-containing dodecahedron. S4 involves local configurations where there is one edge-shared dodecahedron containing Fe2

  5. 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

  6. 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.

  7. Paramagnetic spin seebeck effect.

    PubMed

    Wu, Stephen M; Pearson, John E; Bhattacharya, Anand

    2015-05-08

    We report the observation of the longitudinal spin Seebeck effect in paramagnetic insulators. By using a microscale on-chip local heater, we generate a large thermal gradient confined to the chip surface without a large increase in the total sample temperature. Using this technique at low temperatures (<20  K), we resolve the paramagnetic spin Seebeck effect in the insulating paramagnets Gd3Ga5O12 (gadolinium gallium garnet) and DyScO3 (DSO), using either W or Pt as the spin detector layer. By taking advantage of the strong magnetocrystalline anisotropy of DSO, we eliminate contributions from the Nernst effect in W or Pt, which produces a phenomenologically similar signal.

  8. Paramagnetic Spin Seebeck Effect

    NASA Astrophysics Data System (ADS)

    Wu, Stephen M.; Pearson, John E.; Bhattacharya, Anand

    2015-05-01

    We report the observation of the longitudinal spin Seebeck effect in paramagnetic insulators. By using a microscale on-chip local heater, we generate a large thermal gradient confined to the chip surface without a large increase in the total sample temperature. Using this technique at low temperatures (<20 K ), we resolve the paramagnetic spin Seebeck effect in the insulating paramagnets Gd3Ga5O12 (gadolinium gallium garnet) and DyScO3 (DSO), using either W or Pt as the spin detector layer. By taking advantage of the strong magnetocrystalline anisotropy of DSO, we eliminate contributions from the Nernst effect in W or Pt, which produces a phenomenologically similar signal.

  9. Labeling adipose derived stem cell sheet by ultrasmall super-paramagnetic Fe3O4 nanoparticles and magnetic resonance tracking in vivo.

    PubMed

    Zhou, Shukui; Yin, Ting; Zou, Qingsong; Zhang, Kaile; Gao, Guo; Shapter, Joseph G; Huang, Peng; Fu, Qiang

    2017-02-21

    Cell sheet therapy has emerged as a potential therapeutic option for reparation and reconstruction of damaged tissues and organs. However, an effective means to assess the fate and distribution of transplanted cell sheets in a serial and noninvasive manner is still lacking. To investigate the feasibility of tracking Adipose derived stem cells (ADSCs) sheet in vivo using ultrasmall super-paramagnetic Fe3O4 nanoparticles (USPIO), canine ADSCs were cultured and incubated with USPIO and 0.75 μg/ml Poly-L-Lysine (PLL) for 12 h. Labeling efficiency, cell viability, apoptotic cell rate were assessed to screen the optimum concentrations of USPIO for best labeling ADSCs. The results showed ADSCs were labeled by USPIO at an iron dose of 50 μg/ml for a 12 h incubation time, which can most efficiently mark cells and did not impair the cell survival, self-renewal, and proliferation capacity. USPIO-labeled ADSCs sheets can be easily and clearly detected in vivo and have persisted for at least 12 weeks. Our experiment confirmed USPIO was feasible for in vivo labeling of the ADSCs sheets with the optimal concentration of 50 μg Fe/ml and the tracing time is no less than 12 weeks.

  10. Labeling adipose derived stem cell sheet by ultrasmall super-paramagnetic Fe3O4 nanoparticles and magnetic resonance tracking in vivo

    PubMed Central

    Zhou, Shukui; Yin, Ting; Zou, Qingsong; Zhang, Kaile; Gao, Guo; Shapter, Joseph G.; Huang, Peng; Fu, Qiang

    2017-01-01

    Cell sheet therapy has emerged as a potential therapeutic option for reparation and reconstruction of damaged tissues and organs. However, an effective means to assess the fate and distribution of transplanted cell sheets in a serial and noninvasive manner is still lacking. To investigate the feasibility of tracking Adipose derived stem cells (ADSCs) sheet in vivo using ultrasmall super-paramagnetic Fe3O4 nanoparticles (USPIO), canine ADSCs were cultured and incubated with USPIO and 0.75 μg/ml Poly-L-Lysine (PLL) for 12 h. Labeling efficiency, cell viability, apoptotic cell rate were assessed to screen the optimum concentrations of USPIO for best labeling ADSCs. The results showed ADSCs were labeled by USPIO at an iron dose of 50 μg/ml for a 12 h incubation time, which can most efficiently mark cells and did not impair the cell survival, self-renewal, and proliferation capacity. USPIO-labeled ADSCs sheets can be easily and clearly detected in vivo and have persisted for at least 12 weeks. Our experiment confirmed USPIO was feasible for in vivo labeling of the ADSCs sheets with the optimal concentration of 50 μg Fe/ml and the tracing time is no less than 12 weeks. PMID:28220818

  11. Electron paramagnetic resonance reveals a large-scale conformational change in the cytoplasmic domain of phospholamban upon binding to the sarcoplasmic reticulum Ca-ATPase.

    PubMed

    Kirby, Tara L; Karim, Christine B; Thomas, David D

    2004-05-18

    We used EPR spectroscopy to probe directly the interaction between phospholamban (PLB) and its regulatory target, the sarcoplasmic reticulum Ca-ATPase (SERCA). Synthetic monomeric PLB was prepared with a single cytoplasmic cysteine at residue 11, which was then spin labeled. PLB was reconstituted into membranes in the presence or absence of SERCA, and spin label mobility and accessibility were measured. The spin label was quite rotationally mobile in the absence of SERCA, but became more restricted in the presence of SERCA. SERCA also decreased the dependence of spin label mobility on PLB concentration in the membrane, indicating that SERCA reduces PLB-PLB interactions. The spin label MTSSL, attached to Cys11 on PLB by a disulfide bond, was stable at position 11 in the absence of SERCA. In the presence of SERCA, the spin label was released and a covalent bond was formed between PLB and SERCA, indicating direct interaction of one or more SERCA cysteine residues with Cys11 on PLB. The accessibility of the PLB-bound spin label IPSL to paramagnetic agents, localized in different phases of the membrane, indicates that SERCA greatly reduces the level of interaction of the spin label with the membrane surface. We propose that the cytoplasmic domain of PLB associates with the lipid surface, and that association with SERCA induces a major conformational change in PLB in which the cytoplasmic domain is drawn away from the lipid surface by SERCA.

  12. Phosphorus-31 and carbon-13 nuclear magnetic resonance studies of divalent cation binding to phosphatidylserine membranes. Use of cobalt as a paramagnetic probe

    SciTech Connect

    McLaughlin, A.C.

    1982-01-01

    The paramagnetic divalent cation cobalt has large and well-understood effects on NMR signals from ligands bound in the first coordination sphere, i.e., inner-sphere ligands, and the authors have used these effects to identify divalent cation binding sites at the surface of phosphatidylserine membranes. /sup 31/P NMR results show that 13% of the bound cobalt ions are involved in inner-sphere complexes with the phosphodiester group, while /sup 13/C NMR results show that 54% of the bound cobalt ions are involved in unidentate inner sphere complexes with the carboxyl group. No evidence is found for cobalt binding to the carbonyl groups, but proton release studies suggest that 32% of the bound cobalt ions are involved in chelate complexes that contain both the carboxyl and the amine groups. All of the bound cobalt ions can thus be accounted for in terms of inner sphere complexes with the phosphodiester group or the carboxyl group. They suggest that the unidentate inner-sphere complex between cobalt and the carboxyl group of phosphatidylserine and the inner-sphere complex between cobalt and the phosphodiester group of phosphatidylserine provide reasonable models for complexes between alkaline earth cations and phosphatidylserine membranes.

  13. Phosphorus-31 and carbon-13 nuclear magnetic resonance studies of divalent cation binding to phosphatidylserine membranes: use of cobalt as a paramagnetic probe

    SciTech Connect

    McLaughlin, A.C.

    1982-09-28

    The paramagnetic divalent cation cobalt has large and well-understood effects on NMR signals from ligands bound in the first coordination sphere, i.e., inner-sphere ligands, and we have used these effects to identify divalent cation binding sites at the surface of phosphatidylserine membranes. /sup 31/P NMR results show that 13% of the bound cobalt ions are involved in inner-sphere complexes with the phosphodiester group, while /sup 13/C NMR results show that 54% of the bound cobalt ions are involved in unidentate inner sphere complexes with the carboxyl group. No evidence is found for cobalt binding to the carbonyl groups, but proton release studies suggest that 32% of the bound cobalt ions are involved in chelate complexes that contain both the carboxyl and the amine groups. All (i.e., 13% + 54% + 32% = 99%) of the bound cobalt ions can thus be accounted for in terms of inner sphere complexes with the phosphodiester group or the carboxyl group. We suggest that the unidentate inner-sphere complex between cobalt and the carboxyl group of phosphatidylserine and the inner-sphere complex between cobalt and the phosphodiester group of phosphatidylserine provide reasonable models for complexes between alkaline earth cations and phosphatidylserine membranes.

  14. In vivo proton-electron double-resonance imaging of extracellular tumor pH using an advanced nitroxide probe.

    PubMed

    Samouilov, Alexandre; Efimova, Olga V; Bobko, Andrey A; Sun, Ziqi; Petryakov, Sergey; Eubank, Timothy D; Trofimov, Dmitrii G; Kirilyuk, Igor A; Grigor'ev, Igor A; Takahashi, Wataru; Zweier, Jay L; Khramtsov, Valery V

    2014-01-21

    A variable radio frequency proton-electron double-resonance imaging (VRF PEDRI) approach for pH mapping of aqueous samples has been recently developed (Efimova et al. J. Magn. Reson. 2011, 209, 227-232). A pH map is extracted from two PEDRI acquisitions performed at electron paramagnetic resonance (EPR) frequencies of protonated and unprotonated forms of a pH-sensitive probe. To translate VRF PEDRI to an in vivo setting, an advanced pH probe was synthesized. Probe deuteration resulted in a narrow spectral line of 1.2 G compared to a nondeuterated analogue line width of 2.1 G allowing for an increase of Overhauser enhancements and reduction in rf power deposition. Binding of the probe to the cell-impermeable tripeptide, glutathione (GSH), allows for targeting to extracellular tissue space for monitoring extracellular tumor acidosis, a prognostic factor in tumor pathophysiology. The probe demonstrated pH sensitivity in the 5.8-7.8 range, optimum for measurement of acidic extracellular tumor pH (pH(e)). In vivo VRF PEDRI was performed on Met-1 tumor-bearing mice. Compared to normal mammary glands with a neutral mean pH(e) (7.1 ± 0.1), we observed broader pH distribution with acidic mean pH(e) (6.8 ± 0.1) in tumor tissue. In summary, VRF PEDRI in combination with a newly developed pH probe provides an analytical approach for spatially resolved noninvasive pHe monitoring, in vivo.

  15. Protein structure determination with paramagnetic solid-state NMR spectroscopy.

    PubMed

    Sengupta, Ishita; Nadaud, Philippe S; Jaroniec, Christopher P

    2013-09-17

    Many structures of the proteins and protein assemblies that play central roles in fundamental biological processes and disease pathogenesis are not readily accessible via the conventional techniques of single-crystal X-ray diffraction and solution-state nuclear magnetic resonance (NMR). On the other hand, many of these challenging biological systems are suitable targets for atomic-level structural and dynamic analysis by magic-angle spinning (MAS) solid-state NMR spectroscopy, a technique that has far less stringent limitations on the molecular size and crystalline state. Over the past decade, major advances in instrumentation and methodology have prompted rapid growth in the field of biological solid-state NMR. However, despite this progress, one challenge for the elucidation of three-dimensional (3D) protein structures via conventional MAS NMR methods is the relative lack of long-distance data. Specifically, extracting unambiguous interatomic distance restraints larger than ∼5 Å from through-space magnetic dipole-dipole couplings among the protein (1)H, (13)C, and (15)N nuclei has proven to be a considerable challenge for researchers. It is possible to circumvent this problem by extending the structural studies to include several analogs of the protein of interest, intentionally modified to contain covalently attached paramagnetic tags at selected sites. In these paramagnetic proteins, the hyperfine couplings between the nuclei and unpaired electrons can manifest themselves in NMR spectra in the form of relaxation enhancements of the nuclear spins that depend on the electron-nucleus distance. These effects can be significant for nuclei located up to ∼20 Å away from the paramagnetic center. In this Account, we discuss MAS NMR structural studies of nitroxide and EDTA-Cu(2+) labeled variants of a model 56 amino acid globular protein, B1 immunoglobulin-binding domain of protein G (GB1), in the microcrystalline solid phase. We used a set of six EDTA-Cu(2

  16. 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…

  17. 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.

  18. Advances in Theory of Solid-State Nuclear Magnetic Resonance.

    PubMed

    Mananga, Eugene S; Moghaddasi, Jalil; Sana, Ajaz; Akinmoladun, Andrew; Sadoqi, Mostafa

    Recent advances in theory of solid state nuclear magnetic resonance (NMR) such as Floquet-Magnus expansion and Fer expansion, address alternative methods for solving a time-dependent linear differential equation which is a central problem in quantum physics in general and solid-state NMR in particular. The power and the salient features of these theoretical approaches that are helpful to describe the time evolution of the spin system at all times are presented. This review article presents a broad view of manipulations of spin systems in solid-state NMR, based on milestones theories including the average Hamiltonian theory and the Floquet theory, and the approaches currently developing such as the Floquet-Magnus expansion and the Fer expansion. All these approaches provide procedures to control and describe the spin dynamics in solid-state NMR. Applications of these theoretical methods to stroboscopic and synchronized manipulations, non-synchronized experiments, multiple incommensurated frequencies, magic-angle spinning samples, are illustrated. We also reviewed the propagators of these theories and discussed their convergences. Note that the FME is an extension of the popular Magnus Expansion and Average Hamiltonian Theory. It aims is to bridge the AHT to the Floquet Theorem but in a more concise and efficient formalism. Calculations can then be performed in a finite-dimensional Hilbert space instead of an infinite dimensional space within the so-called Floquet theory. We expected that the FME will provide means for more accurate and efficient spin dynamics simulation and for devising new RF pulse sequence.

  19. Advances in Theory of Solid-State Nuclear Magnetic Resonance

    PubMed Central

    Mananga, Eugene S.; Moghaddasi, Jalil; Sana, Ajaz; Akinmoladun, Andrew; Sadoqi, Mostafa

    2015-01-01

    Recent advances in theory of solid state nuclear magnetic resonance (NMR) such as Floquet-Magnus expansion and Fer expansion, address alternative methods for solving a time-dependent linear differential equation which is a central problem in quantum physics in general and solid-state NMR in particular. The power and the salient features of these theoretical approaches that are helpful to describe the time evolution of the spin system at all times are presented. This review article presents a broad view of manipulations of spin systems in solid-state NMR, based on milestones theories including the average Hamiltonian theory and the Floquet theory, and the approaches currently developing such as the Floquet-Magnus expansion and the Fer expansion. All these approaches provide procedures to control and describe the spin dynamics in solid-state NMR. Applications of these theoretical methods to stroboscopic and synchronized manipulations, non-synchronized experiments, multiple incommensurated frequencies, magic-angle spinning samples, are illustrated. We also reviewed the propagators of these theories and discussed their convergences. Note that the FME is an extension of the popular Magnus Expansion and Average Hamiltonian Theory. It aims is to bridge the AHT to the Floquet Theorem but in a more concise and efficient formalism. Calculations can then be performed in a finite-dimensional Hilbert space instead of an infinite dimensional space within the so-called Floquet theory. We expected that the FME will provide means for more accurate and efficient spin dynamics simulation and for devising new RF pulse sequence. PMID:26878063

  20. 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)

  1. Effective optical Faraday rotations of semiconductor EuS nanocrystals with paramagnetic transition-metal ions.

    PubMed

    Hasegawa, Yasuchika; Maeda, Masashi; Nakanishi, Takayuki; Doi, Yoshihiro; Hinatsu, Yukio; Fujita, Koji; Tanaka, Katsuhisa; Koizumi, Hitoshi; Fushimi, Koji

    2013-02-20

    Novel EuS nanocrystals containing paramagnetic Mn(II), Co(II), or Fe(II) ions have been reported as advanced semiconductor materials with effective optical rotation under a magnetic field, Faraday rotation. EuS nanocrystals with transition-metal ions, EuS:M nanocrystals, were prepared by the reduction of the Eu(III) dithiocarbamate complex tetraphenylphosphonium tetrakis(diethyldithiocarbamate)europium(III) with transition-metal complexes at 300 °C. The EuS:M nanocrystals thus prepared were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), inductively coupled plasma atomic emission spectroanalysis (ICP-AES), and a superconducting quantum interference device (SQUID) magnetometer. Enhanced Faraday rotations of the EuS:M nanocrystals were observed around 550 nm, and their enhanced spin polarization was estimated using electron paramagnetic resonance (EPR) measurements. In this report, the magneto-optical relationship between the Faraday rotation efficiency and spin polarization is discussed.

  2. Advanced Undergraduate-Laboratory Experiment on Electron Spin Resonance in Single-Crystal Ruby

    ERIC Educational Resources Information Center

    Collins, Lee A.; And Others

    1974-01-01

    An electron-spin-resonance experiment which has been successfully performed in an advanced undergraduate physics laboratory is described. A discussion of that part of the theory of magnetic resonance necessary for the understanding of the experiment is also provided in this article. (DT)

  3. 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.

  4. Rubber particles from four different species, examined by transmission electron microscopy and electron-paramagnetic-resonance spin labeling, are found to consist of a homogeneous rubber core enclosed by a contiguous, monolayer biomembrane

    PubMed

    Cornish; Wood; Windle

    1999-11-01

    The physical characteristics of rubber particles from the four rubber (cis-1,4-polyisoprene) producing species Euphorbia lactiflua Phil., Ficus elastica Roxb., Hevea brasiliensis Mull. Arg., and Parthenium argentatum Gray, were investigated using transmission electron microscopy (TEM) and electron-paramagnetic-resonance (EPR) spin labeling spectroscopy. Transmission electron microscopy showed the rubber particles to be composed of a spherical, homogeneous, core of rubber enclosed by a contiguous, electron-dense, single-track surface layer. The biochemical composition of the surface layer and its single-track TEM suggested that a monolayer biomembrane was the surface structure most compatible with the hydrophobic rubber core. The EPR spectra for a series of positional isomers of doxyl stearic acid, used to label the surface layer of the rubber particles, exhibited flexibility gradients and evidence for lipid-protein interactions for all four rubber particle types that is consistent with a biomembrane-like surface. The EPR spectra confirmed that the surface biomembrane is a monolayer. Thus, rubber particles appear similar to oil bodies in their basic architecture. The EPR spectra also provided information on protein location and degree of biomembrane penetration that correlated with the known properties of the rubber-particle-bound proteins. The monolayer biomembrane serves as an interface between the hydrophobic rubber interior and the aqueous cytosol and prevents aggregation of the particles. An unexpected observation for the probes in pure polyisoprene was evidence of an intrinsic flexibility gradient associated with the stearic acid molecule itself.

  5. 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

  6. Formation of a Manganese Tricarbonyl on the MgO Surface from Mn[subscript 2](CO)[subscript 10]: Characterization by Infrared, Electron Paramagnetic Resonance, and X-ray Absorption Spectroscopies

    SciTech Connect

    Khabuanchalad, Supattra; Wittayakun, Jatuporn; Lobo-Lapidus, Rodrigo J.; Stoll, Stefan; Britt, R. David; Gates, Bruce C.

    2010-12-07

    The goal of this work was to prepare structurally well-defined manganese complexes on high-area MgO powder by vapor deposition of Mn{sub 2}(CO){sub 10}. The supported species were characterized by infrared (IR), electron paramagnetic resonance (EPR), and X-ray absorption spectroscopies. The results show that when the manganese loading of the sample was 3.0 wt %, most of the Mn{sub 2}(CO){sub 10} was physisorbed, but when the loadings were less, chemisorbed species predominated, being formed by adsorption of Mn{sub 2}(CO){sub 10} on hydroxyl groups on the MgO surface. Treatment of samples containing 1.0 wt % Mn with O{sub 2} at room temperature resulted in oxidation of the manganese and the formation of surface species that are well represented as the d{sup 4} complex Mn(CO){sub 3}(Os){sub 3} (where O{sub s} is surface oxygen of MgO), as indicated by IR and extended X-ray absorption fine structure (EXAFS) spectra. The EXAFS data show Mn-C, C{triple_bond}O, and Mn-O{sub s} bond lengths as 1.90, 1.43, and 1.98 {angstrom}, respectively.

  7. A combined electron paramagnetic resonance and fourier transform infrared study of the co(c(6)h(6))(1,2) complexes isolated in neat benzene or in cryogenic matrixes.

    PubMed

    Béchamp, Kevin; Levesque, Michelle; Joly, Helen; Manceron, Laurent

    2006-05-11

    The products obtained in the reaction of cobalt atoms in neat benzene or in a benzene/argon mixture at low temperature have been reinvestigated. At least three cobalt-containing species were detected by IR, namely, Co(C(6)H(6)), Co(C(6)H(6))(2), and Co(x)(C(6)H(6)), x>1. The IR bands were assigned to these complexes by monitoring their behavior as a function of (a) Co and C(6)H(6) concentration, (b) isotopic substitution, and (c) photoirradiation. We were able to analyze the sample in neat benzene by both electron paramagnetic resonance (EPR) and IR spectroscopy and to determine the magnetic parameters (g tensor and Co hyperfine interaction) for the Co(C(6)H(6))(2) sandwich compound. The large number of fundamental bands observed in the IR spectrum of Co(C(6)H(6))(2), the absorption pattern observed in the Co-ring stretching region of the IR spectrum of the mixed complex, Co(C(6)H(6))(C(6)D(6)) and the orthorhombic g-values extracted from the EPR spectrum are most consistent with nonequivalent benzene ligands in Co(C(6)H(6))(2), i.e., C(s) symmetry. A bonding scheme consistent with both the EPR and IR data for Co(C(6)H(6))(2) is discussed.

  8. 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.

  9. 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.

  10. 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 LiNi(0.5)Mn(1.5)O4 (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.

  11. Advanced Silicon Microring Resonator Devices for Optical Signal Processing

    NASA Astrophysics Data System (ADS)

    Masilamani, Ashok Prabhu

    Chip level optical interconnects has gained momentum with recent demonstrations of silicon-on-insulator (SOI) based photonic modules such as lasers, modulators, wavelength division multiplexing (WDM) filters, etc. A fundamental building block that has enabled many of these silicon photonic modules is the compact, high Q factor microring resonator cavity. However, most of these demonstrations have WDM processing components based on simple add-drop filters that cannot realize the dense WDM systems required for the chip level interconnects. Dense WDM filters have stringent spectral shape requirements such as flat-top filter passband, steep band transition etc. Optical filters that can meet these specifications involve precise placement of the poles and zeros of the filter transfer function. Realization of such filters requires the use of multiple coupled microring resonators arranged in complex coupling topologies. In this thesis we have proposed and demonstrated new multiple coupled resonator topologies based on compact microring resonators in SOI material system. First we explored novel microring architectures which resulted in the proposal of two new coupled microring architectures, namely, the general 2D microring array topology and the general cascaded microring network topology. We also developed the synthesis procedures for these two microring architectures. The second part of this thesis focussed on the demonstration of the proposed architectures in the SOI material system. To accomplish this, a fabrication process for SOI was developed at the UofA Nanofab facility. Using this process, ultra-compact single microring filters with microring radii as small as 1mum were demonstrated. Higher order filter demonstration with multiple microrings necessitated post-fabrication microring resonance tuning. We developed additional fabrication steps to install micro heaters on top of the microrings to thermally tune its resonance. Subsequently, a thermally tuned fourth

  12. Viability, differentiation capacity, and detectability of super-paramagnetic iron oxide-labeled muscle precursor cells for magnetic-resonance imaging.

    PubMed

    Azzabi, Fahd; Rottmar, Markus; Jovaisaite, Virginija; Rudin, Markus; Sulser, Tullio; Boss, Andreas; Eberli, Daniel

    2015-02-01

    Cell therapies are a promising approach for the treatment of a variety of human conditions including stress urinary incontinence, but their success greatly depends on the biodistribution, migration, survival, and differentiation of the transplanted cells. Noninvasive in vivo cell tracking therefore presents an important aspect for translation of such a procedure into the clinics. Upon labeling with superparamagnetic iron oxide (SPIO) nanoparticles, cells can be tracked by magnetic resonance imaging (MRI), but possible adverse effect of the labeling have to be considered when labeling stem cells with SPIOs. In this study, human muscle precursor cells (hMPC) were labeled with increasing concentrations of SPIO nanoparticles (100-1600 μg/mL) and cell viability and differentiation capacity upon labeling was assessed in vitro. While a linear dependence between cell viability and nanoparticle concentration could be observed, differentiation capacity was not affected by the presence of SPIOs. Using a nude mouse model, a concentration (400 μg/mL) could be defined that allows reliable detection of hMPCs by MRI but does not influence myogenic in vivo differentiation to mature and functional muscle tissue. This suggests that such an approach can be safely used in a clinical setting to track muscle regeneration in patients undergoing cell therapy without negative effects on the functionality of the bioengineered muscle.

  13. Viability, Differentiation Capacity, and Detectability of Super-Paramagnetic Iron Oxide-Labeled Muscle Precursor Cells for Magnetic-Resonance Imaging

    PubMed Central

    Azzabi, Fahd; Rottmar, Markus; Jovaisaite, Virginija; Rudin, Markus; Sulser, Tullio; Boss, Andreas

    2015-01-01

    Cell therapies are a promising approach for the treatment of a variety of human conditions including stress urinary incontinence, but their success greatly depends on the biodistribution, migration, survival, and differentiation of the transplanted cells. Noninvasive in vivo cell tracking therefore presents an important aspect for translation of such a procedure into the clinics. Upon labeling with superparamagnetic iron oxide (SPIO) nanoparticles, cells can be tracked by magnetic resonance imaging (MRI), but possible adverse effect of the labeling have to be considered when labeling stem cells with SPIOs. In this study, human muscle precursor cells (hMPC) were labeled with increasing concentrations of SPIO nanoparticles (100–1600 μg/mL) and cell viability and differentiation capacity upon labeling was assessed in vitro. While a linear dependence between cell viability and nanoparticle concentration could be observed, differentiation capacity was not affected by the presence of SPIOs. Using a nude mouse model, a concentration (400 μg/mL) could be defined that allows reliable detection of hMPCs by MRI but does not influence myogenic in vivo differentiation to mature and functional muscle tissue. This suggests that such an approach can be safely used in a clinical setting to track muscle regeneration in patients undergoing cell therapy without negative effects on the functionality of the bioengineered muscle. PMID:24988198

  14. Paramagnetic nuclear magnetic resonance relaxation and molecular mechanics studies of the chloroperoxidase-indole complex: insights into the mechanism of chloroperoxidase-catalyzed regioselective oxidation of indole.

    PubMed

    Zhang, Rui; He, Qinghao; Chatfield, David; Wang, Xiaotang

    2013-05-28

    To unravel the mechanism of chloroperoxidase (CPO)-catalyzed regioselective oxidation of indole, we studied the structure of the CPO-indole complex using nuclear magnetic resonance (NMR) relaxation measurements and computational techniques. The dissociation constant (KD) of the CPO-indole complex was calculated to be approximately 21 mM. The distances (r) between protons of indole and the heme iron calculated via NMR relaxation measurements and molecular docking revealed that the pyrrole ring of indole is oriented toward the heme with its 2-H pointing directly at the heme iron. Both KD and r values are independent of pH in the range of 3.0-6.5. The stability and structure of the CPO-indole complex are also independent of the concentration of chloride or iodide ion. Molecular docking suggests the formation of a hydrogen bond between the NH group of indole and the carboxyl O of Glu 183 in the binding of indole to CPO. Simulated annealing of the CPO-indole complex using r values from NMR experiments as distance restraints reveals that the van der Waals interactions were much stronger than the Coulomb interactions in the binding of indole to CPO, indicating that the association of indole with CPO is primarily governed by hydrophobic rather than electrostatic interactions. This work provides the first experimental and theoretical evidence of the long-sought mechanism that leads to the "unexpected" regioselectivity of the CPO-catalyzed oxidation of indole. The structure of the CPO-indole complex will serve as a lighthouse in guiding the design of CPO mutants with tailor-made activities for biotechnological applications.

  15. Pulse electron paramagnetic resonance studies of the interaction of methanol with the S2 state of the Mn4O5Ca cluster of photosystem II.

    PubMed

    Oyala, Paul H; Stich, Troy A; Stull, Jamie A; Yu, Fangting; Pecoraro, Vincent L; Britt, R David

    2014-12-23

    The binding of the substrate analogue methanol to the catalytic Mn4CaO5 cluster of the water-oxidizing enzyme photosystem II is known to alter the electronic structure properties of the oxygen-evolving complex without retarding O2-evolution under steady-state illumination conditions. We report the binding mode of (13)C-labeled methanol determined using 9.4 GHz (X-band) hyperfine sublevel-correlation (HYSCORE) and 34 GHz (Q-band) electron spin-echo electron nuclear double resonance (ESE-ENDOR) spectroscopies. These results are compared to analogous experiments on a mixed-valence Mn(III)Mn(IV) complex (2-OH-3,5-Cl2-salpn)2Mn(III)Mn(IV) (salpn = N,N'-bis(3,5-dichlorosalicylidene)-1,3-diamino-2-hydroxypropane) in which methanol ligates to the Mn(III) ion ( Larson et al. (1992) J. Am. Chem. Soc. , 114 , 6263 ). In the mixed-valence Mn(III,IV) complex, the hyperfine coupling to the (13)C of the bound methanol (Aiso = 0.65 MHz, T = 1.25 MHz) is appreciably larger than that observed for (13)C methanol associated with the Mn4CaO5 cluster poised in the S2 state, where only a weak dipolar hyperfine interaction (Aiso = 0.05 MHz, T = 0.27 MHz) is observed. An evaluation of the (13)C hyperfine interaction using the X-ray structure coordinates of the Mn4CaO5 cluster indicates that methanol does not bind as a terminal ligand to any of the manganese ions in the oxygen-evolving complex. We favor methanol binding in place of a water ligand to the Ca(2+) in the Mn4CaO5 cluster or in place of one of the waters that form hydrogen bonds with the oxygen bridges of the cluster.

  16. Nuclear magnetic resonance and optical absorption spectroscopic studies on paramagnetic praseodymium(III) complexes with beta-diketone and heterocyclic amines.

    PubMed

    Ansari, A A; Ahmed, Zubair; Iftikhar, K

    2007-09-01

    The optical absorption spectra of [Pr(acac)(3)(H(2)O)(2)].H(2)O, [Pr(acac)(3)phen.H(2)O] and [Pr(acac)(3)bpy] (where acac is the anion of acetylacetone, phen is 1,10-phenanthroline and bpy is 2,2'-bipyridyl) have been analyzed in the visible region in a series of non-aqueous solvents (methanol, ethanol, isopropanol, chloroform, acetonitrile and pyridine). The complexes display four non-hypersensitive 4f-4f transitions ((3)P(2), (3)P(1)+(1)I(6), (3)P(0) and (1)D(2)) from the (3)H(4) ground state. The band shape of the transitions shows remarkable changes upon dissolving in different solvents. Distinctively different band shapes have been observed for phen and bpy complexes. The phen is more effective in producing changes and the splitting of the bands is more pronounced in phen complex since it is a stronger ligand and leads to stronger Pr-N(phen) bond. The splitting of the bands is indicative of partaking of f-orbitals in bonding. The NMR signals of heterocyclic amines have been shifted to high fields while the resonances due to acetylacetone moiety have moved to low fields which is the consequence of change in geometry of the complexes upon coordination of the heterocyclic amines and reflects the importance of geometric factor (3cos(2)theta-1) in changing sign of the shift and to a good approximation the shifts arise predominantly from the dipolar mechanism. The phen complexes have narrower line width than bpy complexes. The line broadening in the case of bpy complexes is suggestive of exchange between inter-converting forms. The bpy possesses some degree of rotational freedom about C(6)-C(6') bond and the two pyridine rings undergo scissoring motion with respect to each other.

  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.

  18. Effect of Bi2O3 addition on electron paramagnetic resonance, optical absorption, and conductivity in vanadyl-doped Li2O-K2O-Bi2O3-B2O3 glasses.

    PubMed

    Subhadra, M; Kistaiah, P

    2011-02-17

    Glasses with composition 15Li(2)O-15K(2)O-xBi(2)O(3)-(65 - x)-B(2)O(3)/5V(2)O(5) (3 ≤ x ≤ 15) have been prepared by the conventional melt quench technique. The electron paramagnetic resonance spectra of VO(2+) in these glasses have been recorded in the X-band frequency (≈9.3 GHz) at room temperature. The spin Hamiltonian parameters and covalency rates were evaluated. It was found that the V(4+) ions exist as vanadyl (VO(2+)) ions and are in an octahedral coordination with a tetragonal compression. The covalency rates (1 - α(2)) and (1 - γ(2)) indicate moderate covalency for the σ- and π-bonds. It was observed that the spin-Hamiltonian parameters depend slightly on the relative concentration of Bi(2)O(3). The optical properties of this glass system are studied from the optical absorption spectra recorded in the wavelength range 200-800 nm. The fundamental absorption edge has been identified from the optical absorption spectra. The values of optical band gap for indirect allowed transitions have been determined using available theories. The direct current electrical conductivity, σ, has been measured in the temperature range 373-573 K. The conductivity decreases with the increase in Bi(2)O(3) concentration. This has been discussed in terms of the decrease in the number of mobile ions and their mobility. An attempt is made to correlate the EPR, optical, and electrical results and to find the effect of Bi(2)O(3) content on these parameters.

  19. Nuclear magnetic resonance structure of the III-IV-V three-way junction from the Varkud satellite ribozyme and identification of magnesium-binding sites using paramagnetic relaxation enhancement.

    PubMed

    Bonneau, Eric; Legault, Pascale

    2014-10-07

    The VS ribozyme is a catalytic RNA found within some natural isolates of Neurospora that is being used as a model system to improve our understanding of RNA structure, catalysis, and engineering. The catalytic domain contains five helical domains (SLII-SLVI) that are organized by two three-way junctions. The III-IV-V junction is required for high-affinity binding of the substrate domain (SLI) through formation of a kissing loop interaction with SLV. Here, we determine the high-resolution nuclear magnetic resonance (NMR) structure of a 47-nucleotide RNA containing the III-IV-V junction (J345). The J345 RNA adopts a Y-shaped fold typical of the family C three-way junctions, with coaxial stacking between stems III and IV and an acute angle between stems III and V. The NMR structure reveals that the core of the III-IV-V junction contains four stacked base triples, a U-turn motif, a cross-strand stacking interaction, an A-minor interaction, and a ribose zipper. In addition, the NMR structure shows that the cCUUGg tetraloop used to stabilize stem IV adopts a novel RNA tetraloop fold, different from the known gCUUGc tetraloop structure. Using Mn(2+)-induced paramagnetic relaxation enhancement, we identify six Mg(2+)-binding sites within J345, including one associated with the cCUUGg tetraloop and two with the junction core. The NMR structure of J345 likely represents the conformation of the III-IV-V junction in the context of the active VS ribozyme and suggests that this junction functions as a dynamic hinge that contributes to substrate recognition and catalysis. Moreover, this study highlights a new role for family C three-way junctions in long-range tertiary interactions.

  20. A Long-Lived FeIII-(Hydroperoxo) Intermediate in the Active H200C Variant of Homoprotocatechuate 2,3-Dioxygenase: Characterization by Mössbauer, Electron Paramagnetic Resonance, and Density Functional Theory Methods

    PubMed Central

    Meier, Katlyn K.; Rogers, Melanie S.; Kovaleva, Elena G.; Mbughuni, Michael M.; Bominaar, Emile L.; Lipscomb, John D.; Münck, Eckard

    2015-01-01

    The extradiol-cleaving dioxygenase homoprotocatechuate 2,3-dioxygenase (HPCD) binds substrate homoprotocatechuate (HPCA) and O2 sequentially in adjacent ligand sites of the active site FeII. Kinetic and spectroscopic studies of HPCD have elucidated catalytic roles of several active site residues, including the crucial acid base chemistry of His200. In the present study, reaction of the His200Cys (H200C) variant with native substrate HPCA resulted in a decrease in both kcat and the rate constants for the activation steps following O2 binding by > 400 fold. The reaction proceeds to form the correct extradiol product. This slow reaction allowed a long-lived (t1/2 = 1.5 min) intermediate, H200C-HPCAInt1 (Int1), to be trapped. Mössbauer and parallel mode electron paramagnetic resonance (EPR) studies show that Int1 contains an S1 = 5/2 FeIII center coupled to an SR = 1/2 radical to give a ground state with total spin S = 2 (J > 40 cm−1) in Hexch=JS^1⋅S^R. Density functional theory (DFT) property calculations for structural models Int1 is a (HPCA semiquinone•)FeIII(OOH) complex, in which OOH is protonated at the distal O and the substrate hydroxyls are deprotonated. By combining Mössbauer and EPR data of Int1 with DFT calculations, the orientations of the principal axes of the 57Fe electric field gradient and the zero-field splitting (ZFS) tensors (D = 1.6 cm−1, E/D = 0.05) were determined. This information was used to predict hyperfine splittings from bound 17OOH. DFT reactivity analysis suggests that Int1 can evolve from a ferromagnetically coupled FeIII-superoxo precursor by an inner-sphere proton-coupled-electron-transfer process. Our spectroscopic and DFT results suggest that a ferric hydroperoxo species is capable of extradiol catalysis. PMID:26485328

  1. Upcycling: converting waste plastics into paramagnetic, conducting, solid, pure carbon microspheres.

    PubMed

    Pol, Vilas Ganpat

    2010-06-15

    The recent tremendous increase in the volume of waste plastics (WP) will have a harmful environmental impact on the health of living beings. Hundreds of years are required to degrade WP in atmospheric conditions. Hence, in coming years, in addition to traditional recycling services, innovative "upcycling" processes are necessary. This article presents an environmentally benign, solvent-free autogenic process that converts various WP [low density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene terephthalate (PET), polystyrene (PS), or their mixtures] into carbon microspheres (CMSs), an industrially significant, value-added product. The thermal dissociation of these individual or mixed WP in a closed reactor under autogenic pressure ( approximately 1000 psi) produced dry, pure powder of CMSs. In this paper, the optimization of process parameters such as the effect of mixing of WP with other materials, and the role of reaction temperature and time are reported. Employing advanced analytical techniques, the atomic structure, composition, and morphology of as-obtained CMSs were analyzed. The room-temperature paramagnetism in CMSs prepared from waste LDPE, HDPE, and PS was further studied by electron paramagnetic resonance (EPR). The conducting and paramagnetic nature of CMSs holds promise for their potential applications in toners, printers, paints, batteries, lubricants, and tires.

  2. Upcycling : converting waste plastics into paramagnetic, conducting, solid, pure carbon microspheres.

    SciTech Connect

    Pol, V.

    2010-06-15

    The recent tremendous increase in the volume of waste plastics (WP) will have a harmful environmental impact on the health of living beings. Hundreds of years are required to degrade WP in atmospheric conditions. Hence, in coming years, in addition to traditional recycling services, innovative 'upcycling' processes are necessary. This article presents an environmentally benign, solvent-free autogenic process that converts various WP [low density polyethylene (LDPE), high density polyethylene (HDPE), polyethylene terephthalate (PET), polystyrene (PS), or their mixtures] into carbon microspheres (CMSs), an industrially significant, value-added product. The thermal dissociation of these individual or mixed WP in a closed reactor under autogenic pressure (1000 psi) produced dry, pure powder of CMSs. In this paper, the optimization of process parameters such as the effect of mixing of WP with other materials, and the role of reaction temperature and time are reported. Employing advanced analytical techniques, the atomic structure, composition, and morphology of as-obtained CMSs were analyzed. The room-temperature paramagnetism in CMSs prepared from waste LDPE, HDPE, and PS was further studied by electron paramagnetic resonance (EPR). The conducting and paramagnetic nature of CMSs holds promise for their potential applications in toners, printers, paints, batteries, lubricants, and tires.

  3. The electron paramagnetic resonance of polyradicals

    NASA Astrophysics Data System (ADS)

    Catala, L.; Turek, P.

    1999-10-01

    The chemical synthesis and the characterisation of the organic polyradicals build up a representative part of the research in the field of magnetic molecular materials. For such single molecule units bearing two or more radical spins submitted to magnetic exchange interaction, the knowledge of the spin multiplicity of the magnetic ground state is of crucial interest. The various ways for the EPR techniques, e.g. CW-EPR, FT-EPR (Transient Spin Nutation), and ENDOR, to answer this question and others are reviewed. The basic contributions to the EPR response of an organic polyradical are summarised. Some results have been selected in the literature as illustrating examples, from the primary example of the biradical up to the (semi)infinite systems (dendrimers, polymers) through the oligoradical molecules (triradicals, tetraradicals,...). La synthèse et la caractérisation de polyradicaux organiques constituent une part importante de l'activité de recherche menée dans le domaine des matériaux magnétiques moléculaires. Parmi les problèmes posés par la caractérisation de tels systèmes constitués de plusieurs spins en échange magnétique sur une seule unité moléculaire, la détermination de la multiplicité de spin de l'état fondamental ainsi que la détection d'éventuels amas de spins sont considérées en particulier avec les réponses apportées par les techniques de RPE en onde continue, en onde pulsée (nutation transitoire de spin), et d'ENDOR. Les contributions à la réponse de RPE de polyradicaux organiques en solution fluide et en solution gelée sont rappelées. Une sélection de résultats d'études exposés dans la littérature est présentée : du biradical comme exemple de base étendu aux oligoradicaux (triradicaux, tétraradicaux,...) et aux systèmes multi-spins polyradicalaires d'extension infinie en théorie tels que des polymères ou des dendrimères.

  4. Electron Paramagnetic Resonance on Asphaltic Materials

    DTIC Science & Technology

    1987-01-01

    They studied a Venezuela asphaltene in solutions 4 found one type of vanadium to be "bound’ and the other "free.’ With increasing temperature or... asphaltene fractions 19 m, ,•-,••-..• : ,v-,• ".•.-.-,•• >• •--.,e-v•?.• • •.• •,:.*..- .-....- contained concentrations of organic free radicals and...vanadium is found in the asphaltene fraction, with a small amount in the polar compounds. This particular observAtion is significant because other studies

  5. Advanced theory of driven birdcage resonator with losses for biomedical magnetic resonance imaging and spectroscopy.

    PubMed

    Novikov, Alexander

    2011-02-01

    A complete time-dependent physics theory of symmetric unperturbed driven hybrid birdcage resonator was developed for general application. In particular, the theory can be applied for radiofrequency (RF) coil engineering, computer simulations of coil-sample interaction, etc. Explicit time dependence is evaluated for different forms of driving voltage. The major steps of the solution development are shown and appropriate explanations are given. Green's functions and spectral density formula were developed for any form of periodic driving voltage. The concept of distributed power losses based on transmission line theory is developed for evaluation of local losses of a coil. Three major types of power losses are estimated as equivalent series resistances in the circuit of the birdcage resonator. Values of generated resistances in legs and end-rings are estimated. An application of the theory is shown for many practical cases. Experimental curve of B(1) field polarization dependence is measured for eight-sections birdcage coil. It was shown that the steady-state driven resonance frequencies do not depend on damping factor unlike the free oscillation (transient) frequencies. An equivalent active resistance is generated due to interaction of RF electromagnetic field with a sample. Resistance of the conductor (enhanced by skin effect), Eddy currents and dielectric losses are the major types of losses which contribute to the values of generated resistances. A biomedical sample for magnetic resonance imaging and spectroscopy is the source of the both Eddy current and dielectric losses of a coil. As demonstrated by the theory, Eddy current loss is the major effect of coil shielding.

  6. ADVANCED MAGNETIC RESONANCE IMAGING OF CEREBRAL CAVERNOUS MALFORMATIONS

    PubMed Central

    Shenkar, Robert; Venkatasubramanian, Palamadai N.; Wyrwicz, Alice M.; Zhao, Jin-cheng; Shi, Changbin; Akers, Amy; Marchuk, Douglas A.; Awad, Issam A.

    2008-01-01

    Objective We sought to assess the appearance of cerebral cavernous malformations (CCMs) on magnetic resonance (MR) imaging in murine Ccm1 and Ccm2 gene knockout models, and to develop a technique of lesion localization for correlative pathobiologic studies Methods Brains from eighteen CCM mutant mice (Ccm1+/-Trp53-/- and Ccm2+/-Trp53-/-) and 28 controls were imaged by gradient recalled echo (T2*)-weighted MR at 4.7 T and 14.1 T in vivo and/or ex vivo. After MR imaging, the brains were removed and stained with hematoxylin and eosin and cells were laser microdissected for molecular biologic studies. Results T2*-weighted MR imaging of brains in vivo and ex vivo revealed lesions similar to human CCMs in mutant mice, but not in control animals. Stereotactic localization and hematoxylin and eosin-staining of correlative tissue sections confirmed lesion histology, and revealed other areas of dilated capillaries in the same brains. Some lesions were identified by MR imaging at 14.1 T, but not at 4.7 T. PCR amplification from Ccm1 and β-actin genes was demonstrated from nucleic acids extracted from laser microdissected lesional and perilesional cells. Conclusions The high field MR imaging techniques offer new opportunities for further investigation of disease pathogenesis in vivo, and the localization, staging and histobiologic dissection of lesions, including the presumed earliest stages of CCM lesion development. PMID:18981891

  7. Site-directed spin labeling electron paramagnetic resonance study of the calcium-induced structural transition in the N-domain of human cardiac troponin C complexed with troponin I.

    PubMed

    Ueki, Shoji; Nakamura, Motoyoshi; Komori, Tomotaka; Arata, Toshiaki

    2005-01-11

    Calcium-induced structural transition in the amino-terminal domain of troponin C (TnC) triggers skeletal and cardiac muscle contraction. The salient feature of this structural transition is the movement of the B and C helices, which is termed the "opening" of the N-domain. This movement exposes a hydrophobic region, allowing interaction with the regulatory domain of troponin I (TnI) as can be seen in the crystal structure of the troponin ternary complex [Takeda, S., Yamashita, A., Maeda, K., and Maeda, Y. (2003) Nature 424, 35-41]. In contrast to skeletal TnC, Ca(2+)-binding site I (an EF-hand motif that consists of an A helix-loop-B helix motif) is inactive in cardiac TnC. The question arising from comparisons with skeletal TnC is how both helices move according to Ca(2+) binding or interact with TnI in cardiac TnC. In this study, we examined the Ca(2+)-induced movement of the B and C helices relative to the D helix in a cardiac TnC monomer state and TnC-TnI binary complex by means of site-directed spin labeling electron paramagnetic resonance (EPR). Doubly spin-labeled TnC mutants were prepared, and the spin-spin distances were estimated by analyzing dipolar interactions with the Fourier deconvolution method. An interspin distance of 18.4 A was estimated for mutants spin labeled at G42C on the B helix and C84 on the D helix in a Mg(2+)-saturated monomer state. The interspin distance between Q58C on the C helix and C84 on the D helix was estimated to be 18.3 A under the same conditions. Distance changes were observed by the addition of Ca(2+) ions and the formation of a complex with TnI. Our data indicated that the C helix moved away from the D helix in a distinct Ca(2+)-dependent manner, while the B helix did not. A movement of the B helix by interaction with TnI was observed. Both Ca(2+) and TnI were also shown to be essential for the full opening of the N-domain in cardiac TnC.

  8. 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

    2016-04-04

    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

  9. Advanced coupled-micro-resonator architectures for dispersion and spectral engineering applications

    NASA Astrophysics Data System (ADS)

    Van, Vien

    2009-02-01

    We report recent progress in the design and fabrication of coupled optical micro-resonators and their applications in realizing compact OEIC devices for optical spectral engineering. By leveraging synthesis techniques for analog and digital electrical circuits, advanced coupled-microring device architectures can be realized with the complexity and functionality approaching that of state-of-the-art microwave filters. In addition, the traveling wave nature of microring resonators can be exploited to realize novel devices not possible with standing wave resonators. Applications of coupledmicro- resonator devices in realizing complex optical transfer functions for amplitude, phase and group delay engineering will be presented. Progress in the practical implementation of these devices in the Silicon-on-Insulator OEIC platform will be highlighted along with the challenges and potential for constructing very high order optical filters using coupledmicroring architectures.

  10. Advances in functional magnetic resonance imaging: technology and clinical applications.

    PubMed

    Dickerson, Bradford C

    2007-07-01

    Functional MRI (fMRI) is a valuable method for use by clinical investigators to study task-related brain activation in patients with neurological or neuropsychiatric illness. Despite the relative infancy of the field, the rapid adoption of this functional neuroimaging technology has resulted from, among other factors, its ready availability, its relatively high spatial and temporal resolution, and its safety as a noninvasive imaging tool that enables multiple repeated scans over the course of a longitudinal study, and thus may lend itself well as a measure in clinical drug trials. Investigators have used fMRI to identify abnormal functional brain activity during task performance in a variety of patient populations, including those with neurodegenerative, demyelinating, cerebrovascular, and other neurological disorders that highlight the potential utility of fMRI in both basic and clinical spheres of research. In addition, fMRI studies reveal processes related to neuroplasticity, including compensatory hyperactivation, which may be a universally-occurring, adaptive neural response to insult. Functional MRI is being used to study the modulatory effects of genetic risk factors for neurological disease on brain activation; it is being applied to differential diagnosis, as a predictive biomarker of disease course, and as a means to identify neural correlates of neurotherapeutic interventions. Technological advances are rapidly occurring that should provide new applications for fMRI, including improved spatial resolution, which promises to reveal novel insights into the function of fine-scale neural circuitry of the human brain in health and disease.

  11. Solid state nuclear magnetic resonance investigations of advanced energy materials

    NASA Astrophysics Data System (ADS)

    Bennett, George D.

    In order to better understand the physical electrochemical changes that take place in lithium ion batteries and asymmetric hybrid supercapacitors solid state nuclear magnetic resonance (NMR) spectroscopy has been useful to probe and identify changes on the atomic and molecular level. NMR is used to characterize the local environment and investigate the dynamical properties of materials used in electrochemical storage devices (ESD). NMR investigations was used to better understand the chemical composition of the solid electrolyte interphase which form on the negative and positive electrodes of lithium batteries as well as identify the breakdown products that occur in the operation of the asymmetric hybrid supercapacitors. The use of nano-structured particles in the development of new materials causes changes in the electrical, structural and other material properties. NMR was used to investigate the affects of fluorinated and non fluorinated single wall nanotubes (SWNT). In this thesis three experiments were performed using solid state NMR samples to better characterize them. The electrochemical reactions of a lithium ion battery determine its operational profile. Numerous means have been employed to enhance battery cycle life and operating temperature range. One primary means is the choice and makeup of the electrolyte. This study focuses on the characteristics of the solid electrolyte interphase (SEI) that is formed on the electrodes surface during the charge discharge cycle. The electrolyte in this study was altered with several additives in order to determine the influence of the additives on SEI formation as well as the intercalation and de-intercalation of lithium ions in the electrodes. 7Li NMR studies where used to characterize the SEI and its composition. Solid state NMR studies of the carbon enriched acetonitrile electrolyte in a nonaqueous asymmetric hybrid supercapacitor were performed. Magic angle spinning (MAS) coupled with cross polarization NMR

  12. Removal of magnetic resonance imaging contrast agents through advanced water treatment plants.

    PubMed

    Lawrence, Michael G; Keller, Jurg; Poussade, Yvan

    2010-01-01

    Stable gadolinium (Gd) complexes have been used as paramagnetic contrast agents for magnetic resonance imaging (MRI) for over 20 years, and have recently been identified as environmental contaminants. As the rare earth elements (REE), which include Gd, are able to be measured accurately at very low concentrations (e.g. Tb is measured at 7 fmol/kg in this study) using inductively coupled plasma mass spectrometry (ICP-MS), it is possible to determine the fate of this class of compounds during the production of purified recycled water from effluent. Coagulation and microfiltration have negligible removal, with the major removal step occurring across the reverse osmosis membrane where anthropogenic Gd (the amount of Gd attributable to MRI contrast agents) is reduced from 0.39 nmol/kg to 0.59 pmol/kg, a reduction of 99.85%. The RO concentrate has anthropogenic Gd concentrations of 2.6 nmol/kg, an increase in concentration in line with the design characteristics of the plant. The increased concentration in the RO concentrate may allow further development of anthropogenic Gd as a tracer of the fate of the RO concentrate in the environment.

  13. 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

  14. Recent advances in computational methods for nuclear magnetic resonance data processing.

    PubMed

    Gao, Xin

    2013-02-01

    Although three-dimensional protein structure determination using nuclear magnetic resonance (NMR) spectroscopy is a computationally costly and tedious process that would benefit from advanced computational techniques, it has not garnered much research attention from specialists in bioinformatics and computational biology. In this paper, we review recent advances in computational methods for NMR protein structure determination. We summarize the advantages of and bottlenecks in the existing methods and outline some open problems in the field. We also discuss current trends in NMR technology development and suggest directions for research on future computational methods for NMR.

  15. A new paramagnetically shifted imaging probe for MRI

    PubMed Central

    Senanayake, P. Kanthi; Rogers, Nicola J.; Finney, Katie‐Louise N.A.; Harvey, Peter; Funk, Alexander M.; Wilson, J. Ian; O'Hogain, Dara; Maxwell, Ross; Parker, David

    2016-01-01

    Purpose To develop and characterize a new paramagnetic contrast agent for molecular imaging by MRI. Methods A contrast agent was developed for direct MRI detection through the paramagnetically shifted proton magnetic resonances of two chemically equivalent tert‐butyl reporter groups within a dysprosium(III) complex. The complex was characterized in phantoms and imaged in physiologically intact mice at 7 Tesla (T) using three‐dimensional (3D) gradient echo and spectroscopic imaging (MRSI) sequences to measure spatial distribution and signal frequency. Results The reporter protons reside ∼6.5 Å from the paramagnetic center, resulting in fast T 1 relaxation (T 1 = 8 ms) and a large paramagnetic frequency shift exceeding 60 ppm. Fast relaxation allowed short scan repetition times with high excitation flip angle, resulting in high sensitivity. The large dipolar shift allowed direct frequency selective excitation and acquisition of the dysprosium(III) complex, independent of the tissue water signal. The biokinetics of the complex were followed in vivo with a temporal resolution of 62 s following a single, low‐dose intravenous injection. The lower concentration limit for detection was ∼23 μM. Through MRSI, the temperature dependence of the paramagnetic shift (0.28 ppm.K−1) was exploited to examine tissue temperature variation. Conclusions These data demonstrate a new MRI agent with the potential for physiological monitoring by MRI. Magn Reson Med 77:1307–1317, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:26922918

  16. Application of Advanced Magnetic Resonance Imaging Techniques in Evaluation of the Lower Extremity

    PubMed Central

    Braun, Hillary J.; Dragoo, Jason L.; Hargreaves, Brian A.; Levenston, Marc E.; Gold, Garry E.

    2012-01-01

    Synopsis This article reviews current magnetic resonance imaging techniques for imaging the lower extremity, focusing on imaging of the knee, ankle, and hip joints. Recent advancements in MRI include imaging at 7 Tesla, using multiple receiver channels, T2* imaging, and metal suppression techniques, allowing more detailed visualization of complex anatomy, evaluation of morphological changes within articular cartilage, and imaging around orthopedic hardware. PMID:23622097

  17. Perspective on Advances in Resonance-Region Nuclear Modeling and Opportunities for Future Research

    SciTech Connect

    Dunn, Michael E; Larson, Nancy M; Derrien, Herve; Leal, Luiz C

    2007-01-01

    The advent of high-fidelity radiation-transport modeling capabilities, coupled with the need to analyze complex nuclear systems, has served to emphasize the importance of high-precision cross section data, including the associated covariance information. Due to the complex nature of resonance-region interactions, cross section data cannot be calculated directly from theory; rather, high-precision resonance-region cross section measurements must be made at facilities such as the Oak Ridge Electron Linear Accelerator (ORELA) at Oak Ridge National Laboratory (ORNL), Geel Electron Linear Accelerator (GELINA), Rensselaer Polytechnic Institute (RPI). To extract accurate cross section data from these measurements, detailed nuclear modeling of the measured data is performed to parameterize the cross section behavior in the resonance range. The objective of this paper is to highlight recent advances in resonance-region nuclear modeling with particular emphasis on the covariance analysis capabilities. Opportunities for future research are identified in an effort to stimulate further advances in the state of the art nuclear modeling capabilities.

  18. Characterization of the manganese O2-evolving complex and the iron-quinone acceptor complex in photosystem II from a thermophilic cyanobacterium by electron paramagnetic resonance and X-ray absorption spectroscopy.

    PubMed

    McDermott, A E; Yachandra, V K; Guiles, R D; Cole, J L; Dexheimer, S L; Britt, R D; Sauer, K; Klein, M P

    1988-05-31

    The Mn donor complex in the S1 and S2 states and the iron-quinone acceptor complex (Fe2+-Q) in O2-evolving photosystem II (PS II) preparations from a thermophilic cyanobacterium, Synechococcus sp., have been studied with X-ray absorption spectroscopy and electron paramagnetic resonance (EPR). Illumination of these preparations at 220-240 K results in formation of a multiline EPR signal very similar to that assigned to a Mn S2 species observed in spinach PS II, together with g = 1.8 and 1.9 EPR signals similar to the Fe2+-QA- acceptor signals seen in spinach PS II. Illumination at 110-160 K does not produce the g = 1.8 or 1.9 EPR signals, nor the multiline or g = 4.1 EPR signals associated with the S2 state of PS II in spinach; however, a signal which peaks at g = 1.6 appears. The most probable assignment of this signal is an altered configuration of the Fe2+-QA- complex. In addition, no donor signal was seen upon warming the 140 K illuminated sample to 215 K. Following continuous illumination at temperatures between 140 and 215 K, the average X-ray absorption Mn K-edge inflection energy changes from 6550 eV for a dark-adapted (S1) sample to 6551 eV for the illuminated (S2) sample. The shift in edge inflection energy indicates an oxidation of Mn, and the absolute edge inflection energies indicate an average Mn oxidation state higher than Mn(II). Upon illumination a significant change was observed in the shape of the features associated with 1s to 3d transitions. The S1 spectrum resembles those of Mn(III) complexes, and the S2 spectrum resembles those of Mn(IV) complexes. The extended X-ray absorption fine structure (EXAFS) spectrum of the Mn complex is similar in the S1 and S2 states. Simulations indicate O or N ligands at 1.75 +/- 0.05 A, transition metal neighbor(s) at 2.73 +/- 0.05 A, which are assumed to be Mn, and terminal ligands which are probably N and O at a range of distances around 2.2 A. The Mn-O bond length of 1.75 A and the transition metal at 2.7 A

  19. Towards An Advanced Graphene-Based Magnetic Resonance Imaging Contrast Agent: Sub-acute Toxicity and Efficacy Studies in Small Animals

    PubMed Central

    Kanakia, Shruti; Toussaint, Jimmy; Hoang, Dung Minh; Mullick Chowdhury, Sayan; Lee, Stephen; Shroyer, Kenneth R.; Moore, William; Wadghiri, Youssef Z.; Sitharaman, Balaji

    2015-01-01

    Current clinical Gd3+-based T1 magnetic resonance imaging (MRI) contrast agents (CAs) are suboptimal or unsuitable, especially at higher magnetic fields (>1.5 Tesla) for advanced MRI applications such as blood pool, cellular and molecular imaging. Herein, towards the goal of developing a safe and more efficacious high field T1 MRI CA for these applications, we report the sub-acute toxicity and contrast enhancing capabilities of a novel nanoparticle MRI CA comprising of manganese (Mn2+) intercalated graphene nanoparticles functionalized with dextran (hereafter, Mangradex) in rodents. Sub-acute toxicology performed on rats intravenously injected with Mangradex at 1, 50 or 100 mg/kg dosages 3 times per week for three weeks indicated that dosages ≤50 mg/kg could serve as potential diagnostic doses. Whole body 7 Tesla MRI performed on mice injected with Mangradex at a potential diagnostic dose (25 mg/kg or 455 nanomoles Mn2+/kg; ~2 orders of magnitude lower than the paramagnetic ion concentration in a typical clinical dose) showed persistent (up to at least 2 hours) contrast enhancement in the vascular branches (Mn2+ concentration in blood at steady state = 300 ppb, per voxel = 45 femtomoles). The results lay the foundations for further development of Mangradex as a vascular and cellular/ molecular MRI probe. PMID:26625867

  20. Force-detected nuclear magnetic resonance: recent advances and future challenges.

    PubMed

    Poggio, M; Degen, C L

    2010-08-27

    We review recent efforts to detect small numbers of nuclear spins using magnetic resonance force microscopy. Magnetic resonance force microscopy (MRFM) is a scanning probe technique that relies on the mechanical measurement of the weak magnetic force between a microscopic magnet and the magnetic moments in a sample. Spurred by the recent progress in fabricating ultrasensitive force detectors, MRFM has rapidly improved its capability over the last decade. Today it boasts a spin sensitivity that surpasses conventional, inductive nuclear magnetic resonance detectors by about eight orders of magnitude. In this review we touch on the origins of this technique and focus on its recent application to nanoscale nuclear spin ensembles, in particular on the imaging of nanoscale objects with a three-dimensional (3D) spatial resolution better than 10 nm. We consider the experimental advances driving this work and highlight the underlying physical principles and limitations of the method. Finally, we discuss the challenges that must be met in order to advance the technique towards single nuclear spin sensitivity-and perhaps-to 3D microscopy of molecules with atomic resolution.

  1. Paramagnetic Precipitates May Raise Supercurrent

    NASA Technical Reports Server (NTRS)

    Collings, E. W.

    1985-01-01

    Addition of Mn to Ti/Nb superconducting alloy increases critical current. Adding Mn to Ti/Nb alloy has little effect on major superconducting phase, but confers strong paramagnetic susceptibility on alpha-phase particles. beta-phase particles become stronger flux pinners, resulting in increase in critical current.

  2. Resonance Region Nuclear Data Analysis to Support Advanced Fuel Cycle Development

    SciTech Connect

    Dunn, Michael E; Derrien, Herve; Leal, Luiz C; Gil, Choong-Sup; Kim, D.

    2011-01-01

    The Oak Ridge National Laboratory (ORNL) and the Korean Atomic Energy Research Institute (KAERI) are performing collaborative research as part of a three-year United States (U.S.) / Republic of Korea (ROK) International Nuclear Energy Research Initiative (I-NERI) project to provide improved neutron cross-section data with uncertainty or covariance data important for advanced fuel cycle and nuclear safeguards applications. ORNL and KAERI have initiated efforts to prepare new cross-section evaluations for 240Pu, 237Np, and the stable Cm isotopes. At the current stage of the I-NERI project, ORNL has recently completed a preliminary resonance-region cross-section evaluation with covariance data for 240Pu and initiated resonance evaluation efforts for 237Np and 244Cm. Likewise, KAERI is performing corresponding high-energy cross-section analyses (i.e., above the resonance region) for the noted isotopes. The paper provides results pertaining to the new resonance region evaluation efforts with emphasis on the new 240Pu evaluation.

  3. Development of advanced magnetic resonance sensor for industrial applications. Final report

    SciTech Connect

    De Los Santos, A.

    1997-06-01

    Southwest Research Institute (SwRI) and various subcontractors, in a cooperative agreement with the DOE, have developed and tested an advanced magnetic resonance (MR) sensor for several industrial applications and made various market surveys. The original goal of the program was to develop an advanced moisture sensor to allow more precise and rapid control of drying processes so that energy and/or product would not be wasted. Over the course of the program, it was shown that energy savings were achievable but in many processes the return in investment did not justify the cost of a magnetic resonance sensor. However, in many processes, particularly chemical, petrochemical, paper and others, the return in investment can be very high as to easily justify the cost of a magnetic resonance sensor. In these industries, substantial improvements in product yield, quality, and efficiency in production can cause substantial energy savings and reductions in product wastage with substantial environmental effects. The initial applications selected for this program included measurement of corn gluten at three different points and corn germ at one point in an American Maize corn processing plant. During the initial phases (I and II) of this program, SwRI developed a prototype advanced moisture sensor utilizing NMR technology capable of accurately and reliably measuring moisture in industrial applications and tested the sensor in the laboratory under conditions simulating on-line products in the corn wet milling industry. The objective of Phase III was to test the prototype sensor in the plant environment to determine robustness, reliability and long term stability. Meeting these objectives would permit extended field testing to improve the statistical database used to calibrate the sensor and subject the sensor to true variations in operating conditions encountered in the process rather than those which could only be simulated in the laboratory.

  4. Advanced Imaging of Athletes: Added Value of Coronary Computed Tomography and Cardiac Magnetic Resonance Imaging.

    PubMed

    Martinez, Matthew W

    2015-07-01

    Cardiac magnetic resonance imaging and cardiac computed tomographic angiography have become important parts of the armamentarium for noninvasive diagnosis of cardiovascular disease. Emerging technologies have produced faster imaging, lower radiation dose, improved spatial and temporal resolution, as well as a wealth of prognostic data to support usage. Investigating true pathologic disease as well as distinguishing normal from potentially dangerous is now increasingly more routine for the cardiologist in practice. This article investigates how advanced imaging technologies can assist the clinician when evaluating all athletes for pathologic disease that may put them at risk.

  5. Fiber Optic Surface Plasmon Resonance-Based Biosensor Technique: Fabrication, Advancement, and Application.

    PubMed

    Liang, Gaoling; Luo, Zewei; Liu, Kunping; Wang, Yimin; Dai, Jianxiong; Duan, Yixiang

    2016-05-03

    Fiber optic-based biosensors with surface plasmon resonance (SPR) technology are advanced label-free optical biosensing methods. They have brought tremendous progress in the sensing of various chemical and biological species. This review summarizes four sensing configurations (prism, grating, waveguide, and fiber optic) with two ways, attenuated total reflection (ATR) and diffraction, to excite the surface plasmons. Meanwhile, the designs of different probes (U-bent, tapered, and other probes) are also described. Finally, four major types of biosensors, immunosensor, DNA biosensor, enzyme biosensor, and living cell biosensor, are discussed in detail for their sensing principles and applications. Future prospects of fiber optic-based SPR sensor technology are discussed.

  6. Basic principles and concepts underlying recent advances in magnetic resonance imaging of the developing brain.

    PubMed

    Panigrahy, Ashok; Borzage, Matthew; Blüml, Stefan

    2010-02-01

    Over the last decade, magnetic resonance (MR) imaging has become an essential tool in the evaluation of both in vivo human brain development and perinatal brain injury. Recent technology including MR-compatible neonatal incubators, neonatal head coils, advanced MR pulse sequences, and 3-T field strength magnets allow high-quality MR imaging studies to be performed on sick neonates. This article will review basic principles and concepts underlying recent advances in MR spectroscopy, diffusion, perfusion, and volumetric MR imaging. These techniques provide quantitative assessment and novel insight of both brain development and brain injury in the immature brain. Knowledge of normal developmental changes in quantitative MR values is also essential to interpret pathologic cases.

  7. Imaging of skull base pathologies: Role of advanced magnetic resonance imaging techniques

    PubMed Central

    Mathur, Ankit; Kesavadas, C; Thomas, Bejoy; Kapilamoorthy, TR

    2015-01-01

    Imaging plays a vital role in evaluation of skull base pathologies as this region is not directly accessible for clinical evaluation. Computerized tomography (CT) and magnetic resonance imaging (MRI) have played complementary roles in the diagnosis of the various neoplastic and non-neoplastic lesions of the skull base. However, CT and conventional MRI may at times be insufficient to correctly pinpoint the accurate diagnosis. Advanced MRI techniques, though difficult to apply in the skull base region, in conjunction with CT and conventional MRI can however help in improving the diagnostic accuracy. This article aims to highlight the importance of advanced MRI techniques like diffusion-weighted imaging, susceptibility-weighted imaging, perfusion-weighted imaging, and MR spectroscopy in differentiation of various lesions involving the skull base. PMID:26427895

  8. Enhanced Wireless Power Transmission Using Strong Paramagnetic Response.

    PubMed

    Ahn, Dukju; Kiani, Mehdi; Ghovanloo, Maysam

    2014-03-01

    A method of quasi-static magnetic resonant coupling has been presented for improving the power transmission efficiency (PTE) in near-field wireless power transmission, which improves upon the state of the art. The traditional source resonator on the transmitter side is equipped with an additional resonator with a resonance frequency that is tuned substantially higher than the magnetic field excitation frequency. This additional resonator enhances the magnetic dipole moment and the effective permeability of the power transmitter, owing to a phenomenon known as the strong paramagnetic response. Both theoretical calculations and experimental results show increased PTE due to amplification of the effective permeability. In measurements, the PTE was improved from 57.8% to 64.2% at the nominal distance of 15 cm when the effective permeability was 2.6. The power delivered to load was also improved significantly, with the same 10 V excitation voltage, from 0.38 to 5.26 W.

  9. Advanced Magnetic Resonance Techniques for the Structural Characterization of Aminoxyl Radicals and Their Inorganic-Organic Nanocomposite Systems.

    PubMed

    Eckert, Hellmut

    2016-11-15

    Electron and nuclear spins are extremely sensitive probes of their local structural and dynamic surroundings. Their Zeeman energy levels are modified by different types of local magnetic and electric fields created by their structural environment, which influence their magnetic resonance condition. For this reason, electron spin resonance (ESR) and nuclear magnetic resonance (NMR) spectroscopies have become extremely powerful tools of structural analysis, which are being widely used for the structural characterization of complex solids. Following a brief introduction into the basic theoretical foundations the most commonly used techniques and their application towards the structural characterization of paramagnetic solids based on aminoxyl radicals and their inorganic-organic nanocomposites will be described. Both ESR and NMR observables are useful for monitoring intermolecular interactions between unpaired electron spins, which are particularly important for the design of organically based ferromagnetic systems. ESR and NMR methods based on this effect can be used for monitoring the synthesis of polynitroxides and for evaluating the catalytic function of aminoxyl intercalation compounds. Finally, the sensitivity of ESR signals to motional dynamics can be exploited for characterizing molecule-surface interactions in nanocomposite systems. In the context of the latter work recently developed signal enhancement strategies are described, using polarization transfer from electron spins to nuclear spins for NMR spectroscopic detection.

  10. Biologically-compatible gadolinium(at)(carbon nanostructures) as advanced contrast agents for magnetic resonance imaging

    NASA Astrophysics Data System (ADS)

    Sitharaman, Balaji

    2005-11-01

    Paramagnetic gadolinium-based carbon nanostructures are introduced as a new paradigm in high-performance magnetic resonance imaging (MRI) contrast agent (CA) design. Two Gd C60-based nanomaterials, Gd C60 [C(COOH)2]10 and Gd C60(OH)x are shown to have MRI efficacies (relaxivities) 5 to 20 times larger than any current Gd3+-based CA in clinical use. The first detailed and systematic physicochemical characterization was performed on these materials using the same experimental techniques usually applied to traditional Gd 3+-based CAs. Water-proton relaxivities were measured for the first time on these materials, as a function of magnetic field (5 x 10-4--9.4 T) to elucidate the different interaction mechanisms and dynamic processes influencing the relaxation behavior. These studies attribute the observed enhanced relaxivities completely to the "outer sphere" proton relaxation mechanism. These "outer sphere" relaxation effects are the largest reported for any Gd3+-based agent without inner-sphere water molecules. The proton relaxivities displayed a remarkable pH-dependency, increasing dramatically with decreasing pH (pH: 3--12). The increase in relaxivity resulted mainly from aggregation and subsequent three-order-of-magnitude increase in tauR, the rotational correlation time. Water-soluble fullerene materials (such as the neuroprotective fullerene drug, C3) readily cross cell membranes, suggesting an application for these gadofullerenes as the first intracellular, as well as pH-responsive MRI CAs. Studies performed at 60 MHz in the presence of phosphate-buffered saline (PBS, mice serum pH: 7.4) to mimic physiological conditions demonstrated that the aggregates can be disrupted by addition of salts, leading to a decrease in relaxivity. Biological fluids present a high salt concentration and should strongly modify the behavior of any fullerenes/metallofullerene-based drug in vivo. Gd C60[C(COOH)2]10 also showed enhanced relaxivity (23% increase) in the presence of the

  11. The Paramagnetic Pillared Bentonites as Digestive Tract MRI Contrast Agents

    NASA Astrophysics Data System (ADS)

    Mojović, Miloš; Daković, Marko; Omerašević, Mia; Mojović, Zorica; Banković, Predrag; Milutinović-Nikolić, Aleksandra; Jovanović, Dušan

    The increased use of imaging techniques in diagnostic studies, such as MRI, has contributed to the development of the wide range of new materials which could be successfully used as image improving agents. However, there is a lack of such substances in the area of gastrointestinal tract MRI. Many of the traditionally popular relaxation altering agents show poor results and disadvantages provoking black bowel, side effects of diarrhea and the presence of artifacts arising from clumping. Paramagnetic species seem to be potentially suitable agents for these studies, but contrast opacification has been reported and less than 60% of the gastrointestinal tract magnetic resonance scans showed improved delineation of abdominal pathologies. The new solution has been proposed as zeolites or smectite clays (hectorite and montmorillonite) enclosing of paramagnetic metal ions obtained by ion-exchange methods. However, such materials have problems of leakage of paramagnetic ions causing the appearance of the various side-effects. In this study we show that Co+2 and Dy+3 paramagnetic-pillared bentonites could be successfully used as MRI digestive tract non-leaching contrast agents, altering the longitudinal and transverse relaxation times of fluids in contact with the clay minerals.

  12. Advanced magnetic resonance neuroimaging of language function recovery after aphasic stroke: a technical review.

    PubMed

    Smits, Marion; Visch-Brink, Evy G; van de Sandt-Koenderman, Mieke E; van der Lugt, Aad

    2012-01-01

    Two advanced magnetic resonance neuroimaging techniques, functional magnetic resonance imaging (fMRI) and diffusion tensor imaging (DTI), have recently made their way into clinically oriented research and hold great promise to study the brain's adaptive changes of function and structure after aphasic stroke, respectively. Such functional and structural neuroplasticity is thought to underlie the recovery of language function, occurring spontaneously and/or in the context of therapeutic intervention. With fMRI, brain activity can be visualized. Spontaneous brain activity, present in multiple brain networks, is measured with resting-state fMRI and language-related brain activity by having the subject perform a language task during scanning (task-based fMRI). With DTI the major white matter tracts, such as the dorsal and ventral language pathways and the commissural fibers, can be visualized and quantified. Both techniques are entirely noninvasive and thus offer the unique opportunity to perform multiple assessments within the same subject. To gain more insight in functional and structural neuroplasticity after aphasic stroke, advanced magnetic resonance neuroimaging studies in specific patient populations, at several stages after stroke and in the course of language recovery, are needed. Such studies will help to clarify the influence of the many factors that play a role in the recovery of language function and are thus vital to further the development of aphasia therapy. Application of these techniques in aphasic stroke patients, however, is not without challenge. The purpose of this article is to discuss the methodologic challenges of fMRI and DTI in the assessment of language recovery after aphasic stroke.

  13. Magnetic resonance elastography is accurate in detecting advanced fibrosis in autoimmune hepatitis

    PubMed Central

    Wang, Jin; Malik, Neera; Yin, Meng; Smyrk, Thomas C; Czaja, Albert J; Ehman, Richard L; Venkatesh, Sudhakar K

    2017-01-01

    AIM To assess the value of magnetic resonance elastography (MRE) in detecting advanced fibrosis/cirrhosis in autoimmune hepatitis (AIH). METHODS In this retrospective study, 36 patients (19 treated and 17 untreated) with histologically confirmed AIH and liver biopsy performed within 3 mo of MRE were identified at a tertiary care referral center. Liver stiffness (LS) with MRE was calculated by a radiologist, and inflammation grade and fibrosis stage in liver biopsy was assessed by a pathologist in a blinded fashion. Two radiologists evaluated morphological features of cirrhosis on conventional magnetic resonance imaging (MRI). Accuracy of MRE was compared to laboratory markers and MRI for detection of advanced fibrosis/cirrhosis. RESULTS Liver fibrosis stages of 0, 1, 2, 3 and 4 were present in 4, 6, 7, 6 and 13 patients respectively. There were no significant differences in distribution of fibrosis stage and inflammation grade between treated and untreated patient groups. LS with MRE demonstrated stronger correlation with liver fibrosis stage in comparison to laboratory markers for chronic liver disease (r = 0.88 vs -0.48-0.70). A trend of decreased mean LS in treated patients compared to untreated patients was observed (3.7 kPa vs 3.84 kPa) but was not statistically significant. MRE had an accuracy/sensitivity/specificity/positive predictive value/negative predictive value of 0.97/90%/100%/100%/90% and 0.98/92.3%/96%/92.3%/96% for detection of advanced fibrosis and cirrhosis, respectively. The performance of MRE was significantly better than laboratory tests for detection of advanced fibrosis (0.97 vs 0.53-0.80, P < 0.01), and cirrhosis (0.98 vs 0.58-0.80, P < 0.01) and better than conventional MRI for diagnosis of cirrhosis (0.98 vs 0.78, P = 0.002). CONCLUSION MRE is a promising modality for detection of advanced fibrosis and cirrhosis in patients with AIH with superior diagnostic accuracy compared to laboratory assessment and MRI. PMID:28223730

  14. Laser irradiations of advanced targets promoting absorption resonance for ion acceleration in TNSA regime

    NASA Astrophysics Data System (ADS)

    Torrisi, L.; Calcagno, L.; Giulietti, D.; Cutroneo, M.; Zimbone, M.; Skala, J.

    2015-07-01

    Advanced targets based on Au nanoparticles embedded in polymers films show high absorption coefficient in the UV-visible and infrared region. They can be employed to enhance the proton and ion acceleration from the laser-generated plasma in TNSA regime. In conditions of "p" polarized laser irradiations at 1015 W/cm2 intensity, in these films can be induced resonant absorption due to plasma wave excitation. Plasma on-line diagnostics is based on SiC detectors, Thomson spectrometry and X-ray streak camera imaging. Measurements of kinetic energy of accelerated ions indicate a significant increment using polymer targets containing gold nanoparticles and "p" polarized laser light with respect to pure polymers and unpolarized light irradiation.

  15. Advanced magnetic resonance imaging techniques in the preterm brain: methods and applications.

    PubMed

    Tao, Joshua D; Neil, Jeffrey J

    2014-01-01

    Brain development and brain injury in preterm infants are areas of active research. Magnetic resonance imaging (MRI), a non-invasive tool applicable to both animal models and human infants, provides a wealth of information on this process by bridging the gap between histology (available from animal studies) and developmental outcome (available from clinical studies). Moreover, MRI also offers information regarding diagnosis and prognosis in the clinical setting. Recent advances in MR methods - diffusion tensor imaging, volumetric segmentation, surface based analysis, functional MRI, and quantitative metrics - further increase the sophistication of information available regarding both brain structure and function. In this review, we discuss the basics of these newer methods as well as their application to the study of premature infants.

  16. Magnetic resonance imaging for planning intracavitary brachytherapy for the treatment of locally advanced cervical cancer.

    PubMed

    Oñate Miranda, M; Pinho, D F; Wardak, Z; Albuquerque, K; Pedrosa, I

    2016-01-01

    Cervical cancer is the third most common gynecological cancer. Its treatment depends on tumor staging at the time of diagnosis, and a combination of chemotherapy and radiotherapy is the treatment of choice in locally advanced cervical cancers. The combined use of external beam radiotherapy and brachytherapy increases survival in these patients. Brachytherapy enables a larger dose of radiation to be delivered to the tumor with less toxicity for neighboring tissues with less toxicity for neighboring tissues compared to the use of external beam radiotherapy alone. For years, brachytherapy was planned exclusively using computed tomography (CT). The recent incorporation of magnetic resonance imaging (MRI) provides essential information about the tumor and neighboring structures making possible to better define the target volumes. Nevertheless, MRI has limitations, some of which can be compensated for by fusing CT and MRI. Fusing the images from the two techniques ensures optimal planning by combining the advantages of each technique.

  17. Recent Advances in 19Fluorine Magnetic Resonance Imaging with Perfluorocarbon Emulsions

    PubMed Central

    Schmieder, Anne H.; Caruthers, Shelton D.; Keupp, Jochen; Wickline, Samuel A.; Lanza, Gregory M.

    2016-01-01

    The research roots of 19fluorine (19F) magnetic resonance imaging (MRI) date back over 35 years. Over that time span, 1H imaging flourished and was adopted worldwide with an endless array of applications and imaging approaches, making magnetic resonance an indispensable pillar of biomedical diagnostic imaging. For many years during this timeframe, 19F imaging research continued at a slow pace as the various attributes of the technique were explored. However, over the last decade and particularly the last several years, the pace and clinical relevance of 19F imaging has exploded. In part, this is due to advances in MRI instrumentation, 19F/1H coil designs, and ultrafast pulse sequence development for both preclinical and clinical scanners. These achievements, coupled with interest in the molecular imaging of anatomy and physiology, and combined with a cadre of innovative agents, have brought the concept of 19F into early clinical evaluation. In this review, we attempt to provide a slice of this rich history of research and development, with a particular focus on liquid perfluorocarbon compound-based agents. PMID:27110430

  18. Magic angle spinning NMR of paramagnetic proteins.

    PubMed

    Knight, Michael J; Felli, Isabella C; Pierattelli, Roberta; Emsley, Lyndon; Pintacuda, Guido

    2013-09-17

    Metal ions are ubiquitous in biochemical and cellular processes. Since many metal ions are paramagnetic due to the presence of unpaired electrons, paramagnetic molecules are an important class of targets for research in structural biology and related fields. Today, NMR spectroscopy plays a central role in the investigation of the structure and chemical properties of paramagnetic metalloproteins, linking the observed paramagnetic phenomena directly to electronic and molecular structure. A major step forward in the study of proteins by solid-state NMR came with the advent of ultrafast magic angle spinning (MAS) and the ability to use (1)H detection. Combined, these techniques have allowed investigators to observe nuclei that previously were invisible in highly paramagnetic metalloproteins. In addition, these techniques have enabled quantitative site-specific measurement of a variety of long-range paramagnetic effects. Instead of limiting solid-state NMR studies of biological systems, paramagnetism provides an information-rich phenomenon that can be exploited in these studies. This Account emphasizes state-of-the-art methods and applications of solid-state NMR in paramagnetic systems in biological chemistry. In particular, we discuss the use of ultrafast MAS and (1)H-detection in perdeuterated paramagnetic metalloproteins. Current methodology allows us to determine the structure and dynamics of metalloenzymes, and, as an example, we describe solid-state NMR studies of microcrystalline superoxide dismutase, a 32 kDa dimer. Data were acquired with remarkably short times, and these experiments required only a few milligrams of sample.

  19. Use of Advanced Magnetic Resonance Imaging Techniques in Neuromyelitis Optica Spectrum Disorder.

    PubMed

    Kremer, Stephane; Renard, Felix; Achard, Sophie; Lana-Peixoto, Marco A; Palace, Jacqueline; Asgari, Nasrin; Klawiter, Eric C; Tenembaum, Silvia N; Banwell, Brenda; Greenberg, Benjamin M; Bennett, Jeffrey L; Levy, Michael; Villoslada, Pablo; Saiz, Albert; Fujihara, Kazuo; Chan, Koon Ho; Schippling, Sven; Paul, Friedemann; Kim, Ho Jin; de Seze, Jerome; Wuerfel, Jens T; Cabre, Philippe; Marignier, Romain; Tedder, Thomas; van Pelt, Danielle; Broadley, Simon; Chitnis, Tanuja; Wingerchuk, Dean; Pandit, Lekha; Leite, Maria Isabel; Apiwattanakul, Metha; Kleiter, Ingo; Prayoonwiwat, Naraporn; Han, May; Hellwig, Kerstin; van Herle, Katja; John, Gareth; Hooper, D Craig; Nakashima, Ichiro; Sato, Douglas; Yeaman, Michael R; Waubant, Emmanuelle; Zamvil, Scott; Stüve, Olaf; Aktas, Orhan; Smith, Terry J; Jacob, Anu; O'Connor, Kevin

    2015-07-01

    Brain parenchymal lesions are frequently observed on conventional magnetic resonance imaging (MRI) scans of patients with neuromyelitis optica (NMO) spectrum disorder, but the specific morphological and temporal patterns distinguishing them unequivocally from lesions caused by other disorders have not been identified. This literature review summarizes the literature on advanced quantitative imaging measures reported for patients with NMO spectrum disorder, including proton MR spectroscopy, diffusion tensor imaging, magnetization transfer imaging, quantitative MR volumetry, and ultrahigh-field strength MRI. It was undertaken to consider the advanced MRI techniques used for patients with NMO by different specialists in the field. Although quantitative measures such as proton MR spectroscopy or magnetization transfer imaging have not reproducibly revealed diffuse brain injury, preliminary data from diffusion-weighted imaging and brain tissue volumetry indicate greater white matter than gray matter degradation. These findings could be confirmed by ultrahigh-field MRI. The use of nonconventional MRI techniques may further our understanding of the pathogenic processes in NMO spectrum disorders and may help us identify the distinct radiographic features corresponding to specific phenotypic manifestations of this disease.

  20. Magnetoresistance in paramagnetic heavy fermion metals.

    PubMed

    Parihari, D; Vidhyadhiraja, N S

    2009-10-07

    A theoretical study of magnetic field (h) effects on single-particle spectra and the transport quantities of heavy fermion metals in the paramagnetic phase is carried out. We have employed a non-perturbative local moment approach (LMA) to the asymmetric periodic Anderson model within the dynamical mean field framework. The lattice coherence scale ω(L), which is proportional within the LMA to the spin-flip energy scale, and has been shown in earlier studies to be the energy scale at which crossover to single-impurity physics occurs, increases monotonically with increasing magnetic field. The many body Kondo resonance in the density of states at the Fermi level splits into two, with the splitting being proportional to the field itself. For h≥0, we demonstrate adiabatic continuity from the strongly interacting case to a corresponding non-interacting limit, thus establishing Fermi liquid behaviour for heavy fermion metals in the presence of a magnetic field. In the Kondo lattice regime, the theoretically computed magnetoresistance is found to be negative in the entire temperature range. We argue that such a result could be understood at [Formula: see text] by field-induced suppression of spin-flip scattering and at [Formula: see text] through lattice coherence. The coherence peak in the heavy fermion resistivity diminishes and moves to higher temperatures with increasing field. Direct comparison of the theoretical results to the field dependent resistivity measurements in CeB(6) yields good agreement.

  1. 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)

  2. Tris buffer modulates polydopamine growth, aggregation, and paramagnetic properties.

    PubMed

    Della Vecchia, Nicola Fyodor; Luchini, Alessandra; Napolitano, Alessandra; D'Errico, Gerardino; Vitiello, Giuseppe; Szekely, Noemi; d'Ischia, Marco; Paduano, Luigi

    2014-08-19

    Despite the growing technological interest of polydopamine (dopamine melanin)-based coatings for a broad variety of applications, the factors governing particle size, shape, and electronic properties of this bioinspired multifunctional material have remained little understood. Herein, we report a detailed characterization of polydopamine growth, particle morphology, and paramagnetic properties as a function of dopamine concentration and nature of the buffer (pH 8.5). Dynamic Light Scattering data revealed an increase in the hydrodynamic radii (Rh) of melanin particles with increasing dopamine concentration in all buffers examined, especially in phosphate buffer. Conversely, a marked inhibition of particle growth was apparent in Tris buffer, with Rh remaining as low as <100 nm during polymerization of 0.5 mM dopamine. Small angle neutron scattering data suggested formation of bidimensional structures in phosphate or bicarbonate buffers, while apparently three-dimensional fractal objects prevailed in Tris buffer. Finally, electron paramagnetic resonance spectra revealed a broader signal amplitude with a peculiar power saturation decay profile for polydopamine samples prepared in Tris buffer, denoting more homogeneous paramagnetic centers with respect to similar samples obtained in phosphate and bicarbonate buffers. Overall, these results disclose Tris buffer as an efficient modulator of polydopamine buildup and properties for the rational control and fine-tuning of melanin aggregate size, morphology, and free radical behavior.

  3. Advancing Cardiovascular, Neurovascular, and Renal Magnetic Resonance Imaging in Small Rodents Using Cryogenic Radiofrequency Coil Technology

    PubMed Central

    Niendorf, Thoralf; Pohlmann, Andreas; Reimann, Henning M.; Waiczies, Helmar; Peper, Eva; Huelnhagen, Till; Seeliger, Erdmann; Schreiber, Adrian; Kettritz, Ralph; Strobel, Klaus; Ku, Min-Chi; Waiczies, Sonia

    2015-01-01

    Research in pathologies of the brain, heart and kidney have gained immensely from the plethora of studies that have helped shape new methods in magnetic resonance (MR) for characterizing preclinical disease models. Methodical probing into preclinical animal models by MR is invaluable since it allows a careful interpretation and extrapolation of data derived from these models to human disease. In this review we will focus on the applications of cryogenic radiofrequency (RF) coils in small animal MR as a means of boosting image quality (e.g., by supporting MR microscopy) and making data acquisition more efficient (e.g., by reducing measuring time); both being important constituents for thorough investigational studies on animal models of disease. This review attempts to make the (bio)medical imaging, molecular medicine, and pharmaceutical communities aware of this productive ferment and its outstanding significance for anatomical and functional MR in small rodents. The goal is to inspire a more intense interdisciplinary collaboration across the fields to further advance and progress non-invasive MR methods that ultimately support thorough (patho)physiological characterization of animal disease models. In this review, current and potential future applications for the RF coil technology in cardiovascular, neurovascular, and renal disease will be discussed. PMID:26617515

  4. Advances and applications of dynamic-angle spinning nuclear magnetic resonance

    SciTech Connect

    Baltisberger, Jay Harvey

    1993-06-01

    This dissertation describes nuclear magnetic resonance experiments and theory which have been developed to study quadrupolar nuclei (those nuclei with spin greater than one-half) in the solid state. Primarily, the technique of dynamic-angle spinning (DAS) is extensively reviewed and expanded upon in this thesis. Specifically, the improvement in both the resolution (two-dimensional pure-absorptive phase methods and DAS angle choice) and sensitivity (pulse-sequence development), along with effective spinning speed enhancement (again through choice of DAS conditions or alternative multiple pulse schemes) of dynamic-angle spinning experiment was realized with both theory and experimental examples. The application of DAS to new types of nuclei (specifically the {sup 87}Rb and {sup 85}Rb nuclear spins) and materials (specifically amorphous solids) has also greatly expanded the possibilities of the use of DAS to study a larger range of materials. This dissertation is meant to demonstrate both recent advances and applications of the DAS technique, and by no means represents a comprehensive study of any particular chemical problem.

  5. Advancing Cardiovascular, Neurovascular, and Renal Magnetic Resonance Imaging in Small Rodents Using Cryogenic Radiofrequency Coil Technology.

    PubMed

    Niendorf, Thoralf; Pohlmann, Andreas; Reimann, Henning M; Waiczies, Helmar; Peper, Eva; Huelnhagen, Till; Seeliger, Erdmann; Schreiber, Adrian; Kettritz, Ralph; Strobel, Klaus; Ku, Min-Chi; Waiczies, Sonia

    2015-01-01

    Research in pathologies of the brain, heart and kidney have gained immensely from the plethora of studies that have helped shape new methods in magnetic resonance (MR) for characterizing preclinical disease models. Methodical probing into preclinical animal models by MR is invaluable since it allows a careful interpretation and extrapolation of data derived from these models to human disease. In this review we will focus on the applications of cryogenic radiofrequency (RF) coils in small animal MR as a means of boosting image quality (e.g., by supporting MR microscopy) and making data acquisition more efficient (e.g., by reducing measuring time); both being important constituents for thorough investigational studies on animal models of disease. This review attempts to make the (bio)medical imaging, molecular medicine, and pharmaceutical communities aware of this productive ferment and its outstanding significance for anatomical and functional MR in small rodents. The goal is to inspire a more intense interdisciplinary collaboration across the fields to further advance and progress non-invasive MR methods that ultimately support thorough (patho)physiological characterization of animal disease models. In this review, current and potential future applications for the RF coil technology in cardiovascular, neurovascular, and renal disease will be discussed.

  6. Advances in Surface Plasmon Resonance Imaging enable quantitative measurement of laterally heterogeneous coatings of nanoscale thickness

    NASA Astrophysics Data System (ADS)

    Raegen, Adam; Reiter, Kyle; Clarke, Anthony; Lipkowski, Jacek; Dutcher, John

    2013-03-01

    The Surface Plasmon Resonance (SPR) phenomenon is routinely exploited to qualitatively probe changes to the optical properties of nanoscale coatings on thin metallic surfaces, for use in probes and sensors. Unfortunately, extracting truly quantitative information is usually limited to a select few cases - uniform absorption/desorption of small biomolecules and films, in which a continuous ``slab'' model is a good approximation. We present advancements in the SPR technique that expand the number of cases for which the technique can provide meaningful results. Use of a custom, angle-scanning SPR imaging system, together with a refined data analysis method, allow for quantitative kinetic measurements of laterally heterogeneous systems. We first demonstrate the directionally heterogeneous nature of the SPR phenomenon using a directionally ordered sample, then show how this allows for the calculation of the average coverage of a heterogeneous sample. Finally, the degradation of cellulose microfibrils and bundles of microfibrils due to the action of cellulolytic enzymes will be presented as an excellent example of the capabilities of the SPR imaging system.

  7. Paramagnetic Enhancement of Nuclear Spin-Spin Coupling.

    PubMed

    Cherry, Peter John; Rouf, Syed Awais; Vaara, Juha

    2017-03-14

    We present a derivation and computations of the paramagnetic enhancement of the nuclear magnetic resonance (NMR) spin-spin coupling, which may be expressed in terms of the hyperfine coupling (HFC) and (for systems with multiple unpaired electrons) zero-field splitting (ZFS) tensors. This enhancement is formally analogous to the hyperfine contributions to the NMR shielding tensor as formulated by Kurland and McGarvey. The significance of the spin-spin coupling enhancement is demonstrated by using a combination of density-functional theory and correlated ab initio calculations, to determine the HFC and ZFS tensors, respectively, for two paramagnetic 3d metallocenes, a Cr(II)(acac)2 complex, a Co(II) pyrazolylborate complex, and a lanthanide system, Gd-DOTA. Particular attention is paid to relativistic effects in HFC tensors, which are calculated using two methods: a nonrelativistic method supplemented by perturbational spin-orbit coupling corrections, and a fully relativistic, four-component matrix-Dirac-Kohn-Sham approach. The paramagnetic enhancement lacks a direct dependence on the distance between the coupled nuclei, and represents more the strength and orientation of the individual hyperfine couplings of the two nuclei to the spin density distribution. Therefore, the enhancement gains relative importance as compared to conventional coupling as the distance between the nuclei increases, or generally in the cases where the conventional coupling mechanisms result in a small value. With the development of the experimental techniques of paramagnetic NMR, the more significant enhancements, e.g., of the (13)C(13)C couplings in the Gd-DOTA complex (as large as 9.4 Hz), may eventually become important.

  8. Magnetic resonance imaging of pediatric muscular disorders: recent advances and clinical applications.

    PubMed

    Kim, Hee Kyung; Lindquist, Diana M; Serai, Suraj D; Mariappan, Yogesh K; Wang, Lily L; Merrow, Arnold C; McGee, Kiaran P; Ehman, Richard L; Laor, Tal

    2013-07-01

    This review describes various quantitative magnetic resonance imaging techniques that can be used to objectively analyze the composition (T2 relaxation time mapping, Dixon imaging, and diffusion-weighted imaging), architecture (diffusion tensor imaging), mechanical properties (magnetic resonance elastography), and function (magnetic resonance spectroscopy) of normal and pathologic skeletal muscle in the pediatric population.

  9. DFT investigation of the effect of spin-orbit coupling on the NMR shifts in paramagnetic solids

    NASA Astrophysics Data System (ADS)

    Pigliapochi, Roberta; Pell, Andrew J.; Seymour, Ieuan D.; Grey, Clare P.; Ceresoli, Davide; Kaupp, Martin

    2017-02-01

    Nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for studying the structural and electronic properties of paramagnetic solids. However, the interpretation of paramagnetic NMR spectra is often challenging as a result of the interactions of unpaired electrons with the nuclear spins of interest. In this work, we extend the formalism of the paramagnetic NMR shielding in the presence of spin-orbit coupling towards solid systems with multiple paramagnetic centers. We demonstrate how the single-ion electron paramagnetic resonance g tensor is defined and calculated in periodic paramagnetic solids. We then calculate the hyperfine tensor and the g tensor with density functional theory to show the validity of the presented model and we further demonstrate how these interactions can be combined to give the overall paramagnetic shielding tensor, σs. The method is applied to a series of olivine-type LiTMPO4 materials (with TM=Mn , Fe, Co, and Ni) and the corresponding 7Li and 31P NMR spectra are simulated. We analyze the effects of spin-orbit coupling and of the electron-nuclear magnetic interactions on the calculated NMR parameters. A detailed comparison is presented between contact and dipolar interactions across the LiTMPO4 series, in which the magnitudes and signs of the nonrelativistic and relativistic components of the overall isotropic shift and shift anisotropy are computed and rationalized.

  10. Magnetic Resonance Facility (Fact Sheet)

    SciTech Connect

    Not Available

    2012-03-01

    This fact sheet provides information about Magnetic Resonance Facility capabilities and applications at NREL's National Bioenergy Center. Liquid and solid-state analysis capability for a variety of biomass, photovoltaic, and materials characterization applications across NREL. NREL scientists analyze solid and liquid samples on three nuclear magnetic resonance (NMR) spectrometers as well as an electron paramagnetic resonance (EPR) spectrometer.

  11. Direct determination of the number of electrons needed to reduce coenzyme F430 pentamethyl ester to the Ni(I) species exhibiting the electron paramagnetic resonance and ultraviolet-visible spectra characteristic for the MCR(red1) state of methyl-coenzyme M reductase.

    PubMed

    Piskorski, Rafal; Jaun, Bernhard

    2003-10-29

    The UV-visible and electron paramagnetic resonance (EPR) spectra of MCR(red1), the catalytically active state of methyl-coenzyme M reductase, are almost identical to those observed when free coenzyme F430 or its pentamethyl ester (F430M) are reduced to the Ni(I) valence state. Investigations and proposals concerning the catalytic mechanism of MCR were therefore based on MCR(red1) containing Ni(I)F430 until, in a recent report, Tang et al. (J. Am. Chem. Soc. 2002, 124, 13242) interpreted their resonance Raman data and titration experiments as indicating that, in MCR(red1), coenzyme F430 is not only reduced at the nickel center but at one of the C=N double bonds of the hydrocorphinoid macrocycle as well. To resolve this contradiction, we have investigated the stoichiometry of the reduction of coenzyme F430 pentamethyl ester (F430M) by three independent methods. Spectroelectrochemistry showed clean reduction to a single product that exhibits the UV-vis spectrum typical for MCR(red1). In three bulk electrolysis experiments, 0.96 +/- 0.1 F/mol was required to generate the reduced species. Reduction with decamethylcobaltocene in tetrahydrofuran (THF) consumed 1 mol of (Cp)(2)Co/mol of F430M, and the stoichiometry of the reoxidation of the reduced form with the two-electron oxidant methylene blue was 0.46 +/- 0.05 mol of methylene blue/mol of reduced F430M. These experiments demonstrate that the reduction of coenzyme F430M to the species having almost identical UV-vis and EPR spectra as MCR(red1) is a one-electron process and therefore inconsistent with a reduction of the macrocycle chromophore.

  12. Locally Advanced Prostate Cancer: Three-Dimensional Magnetic Resonance Spectroscopy to Monitor Prostate Response to Therapy

    SciTech Connect

    Valentini, Anna Lia; Gui, Benedetta; D'Agostino, Giuseppe Roberto; Mattiucci, Giancarlo; Clementi, Valeria; Di Molfetta, Ippolita Valentina; Bonomo, Pierluigi; Mantini, Giovanna

    2012-11-01

    Purpose: To correlate results of three-dimensional magnetic resonance spectroscopic imaging (MRSI) with prostate-specific antigen (PSA) levels and time since external beam irradiation (EBRT) in patients treated with long-term hormone therapy (HT) and EBRT for locally advanced disease to verify successful treatment by documenting the achievement of metabolic atrophy (MA). Methods and Materials: Between 2006 and 2008, 109 patients were consecutively enrolled. MA was assessed by choline and citrate peak area-to-noise-ratio <5:1. Cancerous metabolism (CM) was defined by choline-to-creatine ratio >1.5:1 or choline signal-to-noise-ratio >5:1. To test the strength of association between MRSI results and the time elapsed since EBRT (TEFRT), PSA levels, Gleason score (GS), and stage, logistic regression (LR) was performed. p value <0.05 was statistically significant. The patients' outcomes were verified in 2011. Results: MRSI documented MA in 84 of 109 and CM in 25 of 109 cases. LR showed that age, GS, stage, and initial and recent PSA had no significant impact on MRSI results which were significantly related to PSA values at the time of MRSI and to TEFRT. Patients were divided into three groups according to TEFRT: <1 year, 1-2 years, and >2 years. MA was detected in 54.1% of patients of group 1, 88.9% of group 2, and in 94.5% of group 3 (100% when PSA nadir was reached). CM was detected in 50% of patients with reached PSA nadir in group 1. Local relapse was found in 3 patients previously showing CM at long TEFRT. Conclusion: MA detection, indicative of successful treatment because growth of normal or abnormal cells cannot occur without metabolism, increases with decreasing PSA levels and increasing time on HT after EBRT. This supports long-term HT in advanced prostate cancer. Larger study series are needed to assess whether MRSI could predict local relapse by detecting CM at long TEFRT.

  13. Advancement of 31P Magnetic Resonance Spectroscopy Using GRAPPA Reconstruction on a 3D Volume

    NASA Astrophysics Data System (ADS)

    Clevenger, Tony

    The overall objective of this research is to improve currently available metabolic imaging techniques for clinical use in monitoring and predicting treatment response to radiation therapy in liver cancer. Liver metabolism correlates with inflammatory and neoplastic liver diseases, which alter the intracellular concentration of phosphorus- 31 (31P) metabolites [1]. It is assumed that such metabolic changes occur prior to physical changes of the tissue. Therefore, information on regional changes of 31P metabolites in the liver, obtained by Magnetic Resonance Spectroscopic Imaging (MRSI) [1,2], can help in diagnosis and follow-up of various liver diseases. Specifically, there appears to be an immediate need of this technology for both the assessment of tumor response in patients with Hepatocellular Carcinoma (HCC) treated with Stereotactic Body Radiation Therapy (SBRT) [3--5], as well as assessment of radiation toxicity, which can result in worsening liver dysfunction [6]. Pilot data from our lab has shown that 31P MRSI has the potential to identify treatment response five months sooner than conventional methods [7], and to assess the biological response of liver tissue to radiation 24 hours post radiation therapy [8]. While this data is very promising, commonly occurring drawbacks for 31P MRSI are patient discomfort due to long scan times and prone positioning within the scanner, as well as reduced data quality due to patient motion and respiration. To further advance the full potential of 31P MRSI as a clinical diagnostic tool in the management of liver cancer, this PhD research project had the following aims: I) Reduce the long acquisition time of 3D 31P MRS by formulating and imple- menting an appropriate GRAPPA undersampling scheme and reconstruction on a clinical MRI scanner II) Testing and quantitative validation of GRAPPA reconstruction on 3D 31P MRSI on developmental phantoms and healthy volunteers At completion, this work should considerably advance 31P MRSI

  14. Investigation of relativistic runaway electrons in electron cyclotron resonance heating discharges on Korea Superconducting Tokamak Advanced Research

    SciTech Connect

    Kang, C. S.; Lee, S. G.

    2014-07-15

    The behavior of relativistic runaway electrons during Electron Cyclotron Resonance Heating (ECRH) discharges is investigated in the Korea Superconducting Tokamak Advanced Research device. The effect of the ECRH on the runaway electron population is discussed. Observations on the generation of superthermal electrons during ECRH will be reported, which will be shown to be consistent with existing theory for the development of a superthermal electron avalanche during ECRH [A. Lazaros, Phys. Plasmas 8, 1263 (2001)].

  15. Studying microstructure and microstructural changes in plant tissues by advanced diffusion magnetic resonance imaging techniques.

    PubMed

    Morozov, Darya; Tal, Iris; Pisanty, Odelia; Shani, Eilon; Cohen, Yoram

    2017-04-08

    As sessile organisms, plants must respond to the environment by adjusting their growth and development. Most of the plant body is formed post-embryonically by continuous activity of apical and lateral meristems. The development of lateral adventitious roots is a complex process, and therefore the development of methods that can visualize, non-invasively, the plant microstructure and organ initiation that occur during growth and development is of paramount importance. In this study, relaxation-based and advanced diffusion magnetic resonance imaging (MRI) methods including diffusion tensor (DTI), q-space diffusion imaging (QSI), and double-pulsed-field-gradient (d-PFG) MRI, at 14.1 T, were used to characterize the hypocotyl microstructure and the microstructural changes that occurred during the development of lateral adventitious roots in tomato. Better contrast was observed in relaxation-based MRI using higher in-plane resolution but this also resulted in a significant reduction in the signal-to-noise ratio of the T2-weighted MR images. Diffusion MRI revealed that water diffusion is highly anisotropic in the vascular cylinder. QSI and d-PGSE MRI showed that in the vascular cylinder some of the cells have sizes in the range of 6-10 μm. The MR images captured cell reorganization during adventitious root formation in the periphery of the primary vascular bundles, adjacent to the xylem pole that broke through the cortex and epidermis layers. This study demonstrates that MRI and diffusion MRI methods allow the non-invasive study of microstructural features of plants, and enable microstructural changes associated with adventitious root formation to be followed.

  16. Resonances and resonance widths

    SciTech Connect

    Collins, T.

    1986-05-01

    Two-dimensional betatron resonances are much more important than their simple one-dimensional counterparts and exhibit a strong dependence on the betatron phase advance per cell. A practical definition of ''width'' is expanded upon in order to display these relations in tables. A primarily pedagogical introduction is given to explain the tables, and also to encourage a wider capability for deriving resonance behavior and wider use of ''designer'' resonances.

  17. Susceptibility cancellation of a microcoil wound with a paramagnetic-liquid-filled copper capillary

    NASA Astrophysics Data System (ADS)

    Takeda, Kazuyuki; Takasaki, Tomoya; Takegoshi, K.

    2015-09-01

    Even though microcoils improve the sensitivity of NMR measurement of tiny samples, magnetic-field inhomogeneity due to the bulk susceptibility effect of the coil material can cause serious resonance-line broadening. Here, we propose to fabricate the microcoil using a thin, hollow copper capillary instead of a wire and fill paramagnetic liquid inside the capillary, so as to cancel the diamagnetic contribution of the copper. Susceptibility cancellation is demonstrated using aqueous solution of NiSO4. In addition, the paramagnetic liquid serves as coolant when it is circulated through the copper capillary, effectively transferring the heat generated by radiofrequency pulses.

  18. Susceptibility cancellation of a microcoil wound with a paramagnetic-liquid-filled copper capillary.

    PubMed

    Takeda, Kazuyuki; Takasaki, Tomoya; Takegoshi, K

    2015-09-01

    Even though microcoils improve the sensitivity of NMR measurement of tiny samples, magnetic-field inhomogeneity due to the bulk susceptibility effect of the coil material can cause serious resonance-line broadening. Here, we propose to fabricate the microcoil using a thin, hollow copper capillary instead of a wire and fill paramagnetic liquid inside the capillary, so as to cancel the diamagnetic contribution of the copper. Susceptibility cancellation is demonstrated using aqueous solution of NiSO4. In addition, the paramagnetic liquid serves as coolant when it is circulated through the copper capillary, effectively transferring the heat generated by radiofrequency pulses.

  19. A prospective study of the efficacy of magnetic resonance spectroscopy imaging for predicting locally advanced prostate cancer

    PubMed Central

    Razi, Ali; Parizi, Mehdi Kardoust; Kazemeini, Seid Mohammad; Abedi, Akbar

    2015-01-01

    Objective: To evaluate the efficacy of magnetic resonance spectroscopy imaging (MRSI) for predicting locally advanced prostate cancer (PC). Materials and methods: Between April 2009 and July 2012, 80 consecutive patients with clinically localized PC had undergone endorectal MRSI before radical retropubic prostatectomy. Clinicopathological parameters, including age, preoperative prostate-specific antigen (PSA), Gleason score (GS) at biopsy, perinural invasion at biopsy, prostate weight at surgery, GS of surgical specimen, and pathological staging were recorded. The MRSI findings were compared with the histopathological findings of the radical prostatectomy. The diagnostic accuracy measures consisting of sensitivity, specificity, positive predictive value (PPV), negative predictive value (NPV) of MRSI, and other variables in the diagnosis of locally advanced PC (Pathology Stages pT3a, pT3b, or pT4) were evaluated. Results: Sensitivity, specificity, PPV, and NPV of MRSI in detecting locally advanced PC is 42.4%, 93.6%, 82.3%, and 69.8%, respectively [area under the receiver operating characteristic (ROC) curve=0.658, p value <0.0001]. MRSI, cancer-positive core percentage at biopsy, and GS at biopsy are more accurate factors among all the predictive variables in predicting locally advanced PC. Conclusion: MRSI may be considered as a complementary diagnostic modality with high specificity and moderate sensitivity in predicting locally advanced PC. Combination of this modality with other predictive factors helps the surgeon and patient to select an appropriate treatment strategy. PMID:26328204

  20. Advanced simulation methods to detect resonant frequency stack up in focal plane design

    NASA Astrophysics Data System (ADS)

    Adams, Craig; Malone, Neil R.; Torres, Raymond; Fajardo, Armando; Vampola, John; Drechsler, William; Parlato, Russell; Cobb, Christopher; Randolph, Max; Chiourn, Surath; Swinehart, Robert

    2014-09-01

    Wire used to connect focal plane electrical connections to external electrical circuitry can be modeled using the length, diameter and loop height to determine the resonant frequency. The design of the adjacent electric board and mounting platform can also be analyzed. The combined resonant frequency analysis can then be used to decouple the different component resonant frequencies to eliminate the potential for metal fatigue in the wires. It is important to note that the nominal maximum stress values that cause metal fatigue can be much less than the ultimate tensile stress limit or the yield stress limit and are degraded further at resonant frequencies. It is critical that tests be done to qualify designs that are not easily simulated due to material property variation and complex structures. Sine wave vibration testing is a critical component of qualification vibration and provides the highest accuracy in determining the resonant frequencies which can be reduced or uncorrelated improving the structural performance of the focal plane assembly by small changes in design damping or modern space material selection. Vibration flow down from higher levels of assembly needs consideration for intermediary hardware, which may amplify or attenuate the full up system vibration profile. A simple pass through of vibration requirements may result in over test or missing amplified resonant frequencies that can cause system failure. Examples are shown of metal wire fatigue such as discoloration and microscopic cracks which are visible at the submicron level by the use of a scanning electron microscope. While it is important to model and test resonant frequencies the Focal plane must also be constrained such that Coefficient of Thermal expansion mismatches are allowed to move and not overstress the FPA.

  1. Internalization of paramagnetic phosphatidylserine-containing liposomes by macrophages

    PubMed Central

    2012-01-01

    Background Inflammation plays an important role in many pathologies, including cardiovascular diseases, neurological conditions and oncology, and is considered an important predictor for disease progression and outcome. In vivo imaging of inflammatory cells will improve diagnosis and provide a read-out for therapy efficacy. Paramagnetic phosphatidylserine (PS)-containing liposomes were developed for magnetic resonance imaging (MRI) and confocal microscopy imaging of macrophages. These nanoparticles also provide a platform to combine imaging with targeted drug delivery. Results Incorporation of PS into liposomes did not affect liposomal size and morphology up to 12 mol% of PS. Liposomes containing 6 mol% of PS showed the highest uptake by murine macrophages, while only minor uptake was observed in endothelial cells. Uptake of liposomes containing 6 mol% of PS was dependent on the presence of Ca2+ and Mg2+. Furthermore, these 6 mol% PS-containing liposomes were mainly internalized into macrophages, whereas liposomes without PS only bound to the macrophage cell membrane. Conclusions Paramagnetic liposomes containing 6 mol% of PS for MR imaging of macrophages have been developed. In vitro these liposomes showed specific internalization by macrophages. Therefore, these liposomes might be suitable for in vivo visualization of macrophage content and for (visualization of) targeted drug delivery to inflammatory cells. PMID:22929153

  2. Advanced Quantification of Plutonium Ionization Potential to Support Nuclear Forensic Evaluations by Resonance Ionization Mass Spectrometry

    DTIC Science & Technology

    2015-06-01

    decay and induced emission and absorption are almost identical. Their probability distributions are closely related. The electromagnetic radiation ...NAVAL POSTGRADUATE SCHOOL MONTEREY, CALIFORNIA THESIS Approved for public release; distribution is unlimited ADVANCED ...ONLY (Leave blank) 2. REPORT DATE June 2015 3. REPORT TYPE AND DATES COVERED Master’s Thesis 4. TITLE AND SUBTITLE ADVANCED QUANTIFICATION OF

  3. Advances in real-time magnetic resonance imaging of the vocal tract for speech science and technology research.

    PubMed

    Toutios, Asterios; Narayanan, Shrikanth S

    2016-01-01

    Real-time magnetic resonance imaging (rtMRI) of the moving vocal tract during running speech production is an important emerging tool for speech production research providing dynamic information of a speaker's upper airway from the entire mid-sagittal plane or any other scan plane of interest. There have been several advances in the development of speech rtMRI and corresponding analysis tools, and their application to domains such as phonetics and phonological theory, articulatory modeling, and speaker characterization. An important recent development has been the open release of a database that includes speech rtMRI data from five male and five female speakers of American English each producing 460 phonetically balanced sentences. The purpose of the present paper is to give an overview and outlook of the advances in rtMRI as a tool for speech research and technology development.

  4. Pulse advancement and delay in an integrated-optical two-port ring-resonator circuit: direct experimental observations.

    PubMed

    Uranus, H P; Zhuang, L; Roeloffzen, C G H; Hoekstra, H J W M

    2007-09-01

    We report experimental observations of the negative-group-velocity (v(g)) phenomenon in an integrated-optical two-port ring-resonator circuit. We demonstrate that when the v(g) is negative, the (main) peak of output pulse appears earlier than the peak of a reference pulse, while for a positive v(g), the situation is the other way around. We observed that a pulse splitting phenomenon occurs in the neighborhood of the critical-coupling point. This pulse splitting limits the maximum achievable delay and advancement of a single device as well as facilitating a smooth transition from highly advanced to highly delayed pulse, and vice versa, across the critical-coupling point.

  5. Advances in real-time magnetic resonance imaging of the vocal tract for speech science and technology research

    PubMed Central

    TOUTIOS, ASTERIOS; NARAYANAN, SHRIKANTH S.

    2016-01-01

    Real-time magnetic resonance imaging (rtMRI) of the moving vocal tract during running speech production is an important emerging tool for speech production research providing dynamic information of a speaker's upper airway from the entire mid-sagittal plane or any other scan plane of interest. There have been several advances in the development of speech rtMRI and corresponding analysis tools, and their application to domains such as phonetics and phonological theory, articulatory modeling, and speaker characterization. An important recent development has been the open release of a database that includes speech rtMRI data from five male and five female speakers of American English each producing 460 phonetically balanced sentences. The purpose of the present paper is to give an overview and outlook of the advances in rtMRI as a tool for speech research and technology development. PMID:27833745

  6. New paradigms for old problems: some (small) advances in laser resonator research at the CSIR

    NASA Astrophysics Data System (ADS)

    Forbes, Andrew

    2010-02-01

    In this paper we outline new approaches to old problems, namely understanding the transverse modes in Porro prism resonators, and creating methods to select Gaussian beams by phase-only intra-cavity elements. In the process we outline some of the recent research that has taken place within the Mathematical Optics research group.

  7. Tunable plasmonic resonances based on elliptical annular aperture arrays on conducting substrates for advanced biosensing.

    PubMed

    Liang, Yuzhang; Peng, Wei; Li, Lixia; Qian, Siyu; Wang, Qiao

    2015-08-15

    Introducing a conducting metal layer and the structural asymmetry to elliptical annular aperture arrays, multiple plasmonic coupled-resonant modes are generated under normal incidence in the visible light range. The electromagnetic fields can be strongly enhanced at resonant modes in this device, which increases the interaction volume of the detected analyte and optical fields; therefore, multiple plamonic coupled modes exhibit higher refractive index sensitivity than as large as 610 nm/RIU. The distinct Fano-like resonance around a wavelength of 681 nm originates from the interference between bonding dipolar and the quadrupolar modes. Due to the excitation of sharp spectral features as narrow as 7 nm, high figure of merits of 94 at the Fano-like dip is obtained in a wide refractive index range of 1.33-1.40. Furthermore, to generate strong Fano-like resonance, the geometric shape of ellipse is selected, which is a good geometric shape candidate compared to the circle shape. This device is promising for biosensing applications with high sensitivity and low limit of detection.

  8. Paramagnetic Centers in DOPA-Melanin-Dihydrostreptomycin Complexes

    NASA Astrophysics Data System (ADS)

    Buszman, E.; Pilawa, B.; Zdybel, M.; Wrześniok, D.; Grzegorczyk, A.; Wilczok, T.

    2006-08-01

    DOPA-melanin-dihydrostreptomycin complexes with drug concentrations 1×10-4-1×10-2 M were examined by the use of electron paramagnetic resonance spectroscopy at X-band (9.3 GHz). Dihydrostreptomycin was chosen for studies, because this aminoglycoside antibiotic causes strong toxic effects in organism. It was stated that dihydrostreptomycin generates o-semiquinone free radicals with g=2.0038 in melanin. Free radicals formation increases with increase in the antibiotic concentration. Changes of EPR lines with microwave powers pointed out that slow spin-lattice relaxation processes exist in DOPA-melanin and in its complexes with dihydrostreptomycin. The measured EPR lines were homogeneously broadened.

  9. The electron paramagnetic resonance spectrum of Ag2 3

    NASA Astrophysics Data System (ADS)

    van der Pol, A.; Reijersen, E. J.; de Boer, E.; Wasowicz, T.; Michalik, J.

    A highly resolved EPR spectrum of the silver trimer 109Ag2+3, present in 109Ag1-NaA zeolite, has been measured. The spectrum is characterized by an axially symmetric spin Hamiltonian having and for each of the 109Ag nuclei tMPH0037_images.

  10. Low field electron paramagnetic resonance imaging with SQUID detection

    NASA Technical Reports Server (NTRS)

    Hahn, Inseob (Inventor); Day, Peter K. (Inventor); Penanen, Konstantin I. (Inventor); Eom, Byeong H. (Inventor); Cohen, Mark S. (Inventor)

    2012-01-01

    In one embodiment, a flux transformer with a gradiometer pickup coil is magnetically coupled to a SQUID, and a SQUID array amplifier comprising a plurality of SQUIDs, connected in series, is magnetically coupled to the output of the SQUID. Other embodiments are described and claimed.

  11. Electron Paramagnetic Resonance Saturation Characteristics of Pristine and Doped Polyacetylenes.

    DTIC Science & Technology

    1981-11-11

    Polym. Sci., Polym. Lett. Ed. .17, 263 (1979). 34. B. Francois, M. Bernard and J.J. Andre, J. Chem. Phys., in press. 35. J.M. Pochan , H.W. Gibson and F.C...Bailey, J. Polym. Sci., Polym. Lett. Ed. 18, 447 (1980). 36. J.M. Pochan , D.F. Pochan , H. Rommelmann and H.W. Gibson, Macromolecules 14, 110 (1981

  12. Magnetic Resonance Annual, 1985

    SciTech Connect

    Kressel, H.Y.

    1985-01-01

    The inaugural volume of Magnetic Resonance Annual includes reviews of MRI of the posterior fossa, cerebral neoplasms, and the cardiovascular and genitourinary systems. A chapter on contrast materials outlines the mechanisms of paramagnetic contrast enhancement and highlights several promising contrast agents.

  13. Pseudo-spin paramagnetism in graphene

    SciTech Connect

    Koshino, Mikito; Ando, Tsuneya

    2011-12-23

    We calculate the orbital diamagnetic susceptibility of monolayer graphene with an energy gap. The valley pseudo-spin produces paramagnetic susceptibility analogous to contribution from real spin, and explains the origin of a singular orbital magnetism at Dirac point of monolayer graphene.

  14. Paramagnetic ellipsoidal microswimmer in a magnetic field

    NASA Astrophysics Data System (ADS)

    Sandoval, Mario; Fan, Louis; Pak, On Shun

    We study the two-dimensional Brownian dynamics of an ellipsoidal paramagnetic microswimmer moving at low-Reynolds-number and subject to a magnetic field. Its corresponding mean-square displacement tensor showing the effect of particles's shape, activity and magnetic field, on the microswimmer's diffusion is analytically obtained. A comparison among analytical and computational results is also made and we obtain excellent agreement.

  15. Dual excitation acoustic paramagnetic logging tool

    DOEpatents

    Vail, III, William B.

    1989-01-01

    New methods and apparatus are disclosed which allow measurement of the presence of oil and water in gelogical 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 nucleous present causes the paramagnetism of the formation to disappear. This results in a decrease in the earth'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. The Dual Excitation Acoustic Paramagnetic Logging Tool employing two acoustic sources is also described.

  16. Dual excitation acoustic paramagnetic logging tool

    DOEpatents

    Vail, W.B. III.

    1989-02-14

    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 earth'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 performed in open boreholes and in cased well bores. The Dual Excitation Acoustic Paramagnetic Logging Tool employing two acoustic sources is also described. 6 figs.

  17. 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)

  18. Exploratory Development of FMR (Ferromagnetic Resonance) Advanced Surface Flaw Detection Methods.

    DTIC Science & Technology

    1985-04-01

    chip components and a DC magnetic field source consisting of a single miniature samarium cobalt permanent magnet without bulky pole pieces. A...of crystal anisotropy in cubic crystals (like YIG) is "Microwave Resonance Relations in Anisotropic Single Crystal Ferrites ,"( 6) from which Figure...minimizes the size of the samarium cobalt permanent magnet required in probe construction, an important factor in the case of bolt-hole probes. In YIG filter

  19. Exploring the electron transfer pathways in photosystem I by high-time-resolution electron paramagnetic resonance: observation of the B-side radical pair P700(+)A1B(-) in whole cells of the deuterated green alga Chlamydomonas reinhardtii at cryogenic temperatures.

    PubMed

    Berthold, Thomas; von Gromoff, Erika Donner; Santabarbara, Stefano; Stehle, Patricia; Link, Gerhard; Poluektov, Oleg G; Heathcote, Peter; Beck, Christoph F; Thurnauer, Marion C; Kothe, Gerd

    2012-03-28

    Crystallographic models of photosystem I (PS I) highlight a symmetrical arrangement of the electron transfer cofactors which are organized in two parallel branches (A, B) relative to a pseudo-C2 symmetry axis that is perpendicular to the membrane plane. Here, we explore the electron transfer pathways of PS I in whole cells of the deuterated green alga Chlamydomonas reinhardtii using high-time-resolution electron paramagnetic resonance (EPR) at cryogenic temperatures. Particular emphasis is given to quantum oscillations detectable in the tertiary radical pairs P700(+)A1A(-) and P700(+)A1B(-) of the electron transfer chain. Results are presented first for the deuterated site-directed mutant PsaA-M684H in which electron transfer beyond the primary electron acceptor A0A on the PsaA branch of electron transfer is impaired. Analysis of the quantum oscillations, observed in a two-dimensional Q-band (34 GHz) EPR experiment, provides the geometry of the B-side radical pair. The orientation of the g tensor of P700(+) in an external reference system is adapted from a time-resolved multifrequency EPR study of deuterated and 15N-substituted cyanobacteria (Link, G.; Berthold, T.; Bechtold, M.; Weidner, J.-U.; Ohmes, E.; Tang, J.; Poluektov, O.; Utschig, L.; Schlesselman, S. L.; Thurnauer, M. C.; Kothe, G. J. Am. Chem. Soc. 2001, 123, 4211-4222). Thus, we obtain the three-dimensional structure of the B-side radical pair following photoexcitation of PS I in its native membrane. The new structure describes the position and orientation of the reduced B-side quinone A1B(-) on a nanosecond time scale after light-induced charge separation. Furthermore, we present results for deuterated wild-type cells of C. reinhardtii demonstrating that both radical pairs P700(+)A1A(-) and P700(+)A1B(-) participate in the electron transfer process according to a mole ratio of 0.71/0.29 in favor of P700(+)A1A(-). A detailed comparison reveals different orientations of A1A(-) and A1B(-) in their

  20. The impact of mandibular advancement on articulation, resonance and voice characteristics in Flemish speaking adults: a pilot study.

    PubMed

    Van Lierde, K M; Schepers, S; Timmermans, L; Verhoye, I; Van Cauwenberge, P

    2006-02-01

    Bilateral saggital split osteotomy (BSSO) of the mandible is a frequently performed mandibular orthognathic procedure, used to resolve mandibular disharmonies. Literature review showed contradictory findings regarding the effect of the orthognathic surgery on speech characteristics. The purpose of the present study was to determine a detailed analysis of the articulation, resonance and voice characteristics after BSSO with mandibular advancement for the treatment of Class II malocclusions using objective and subjective assessment techniques (perceptual evaluations, Dysphonia Severity Index, nasalance scores) in eight subjects. The findings of the present study indicate that before and after BSSO with mandibular advancement three types of articulation disorders may predominate in the Flemish language: the incorrect production of the trill sound /r/ and the /s/ sound and devoicing of the /z/. After orthognathic surgery most patients showed an identical articulation pattern (normal or disturbed pattern) as in the presurgical condition. In this study the BSSO with mandibular advancement had no significant impact on the nasality characteristics and the nasalance values probably due to the competent velopharyngeal valving in the presurgical condition. And, as expected the vocal quality revealed no significant difference. The maxillofacial surgeon and the speech language pathologist must be aware of the persistency of these preoperative articulation errors in the postsurgical condition.

  1. Advances in series resonant inverter technology and its effect on spacecraft employing electric propulsion

    NASA Technical Reports Server (NTRS)

    Robson, R. R.

    1982-01-01

    The efficiency of transistorized Series Resonant Inverters (SRIs), which is higher than that of silicon-controlled rectifier alternatives, reduces spacecraft radiator requirements by 40% and may eliminate the need for heat pipes on 30-cm ion thruster systems. Recently developed 10- and 25-kW inverters have potential applications in gas thrusters, and represent the first spaceborne SRI designs for such power levels. Attention is given to the design and control system approaches employed in these inverter designs to improve efficiency and reduce weight, along with the impact of such improved parameters on electric propulsion systems.

  2. Recent Advances of MEMS Resonators for Lorentz Force Based Magnetic Field Sensors: Design, Applications and Challenges

    PubMed Central

    Herrera-May, Agustín Leobardo; Soler-Balcazar, Juan Carlos; Vázquez-Leal, Héctor; Martínez-Castillo, Jaime; Vigueras-Zuñiga, Marco Osvaldo; Aguilera-Cortés, Luz Antonio

    2016-01-01

    Microelectromechanical systems (MEMS) resonators have allowed the development of magnetic field sensors with potential applications such as biomedicine, automotive industry, navigation systems, space satellites, telecommunications and non-destructive testing. We present a review of recent magnetic field sensors based on MEMS resonators, which operate with Lorentz force. These sensors have a compact structure, wide measurement range, low energy consumption, high sensitivity and suitable performance. The design methodology, simulation tools, damping sources, sensing techniques and future applications of magnetic field sensors are discussed. The design process is fundamental in achieving correct selection of the operation principle, sensing technique, materials, fabrication process and readout systems of the sensors. In addition, the description of the main sensing systems and challenges of the MEMS sensors are discussed. To develop the best devices, researches of their mechanical reliability, vacuum packaging, design optimization and temperature compensation circuits are needed. Future applications will require multifunctional sensors for monitoring several physical parameters (e.g., magnetic field, acceleration, angular ratio, humidity, temperature and gases). PMID:27563912

  3. Recent Advances of MEMS Resonators for Lorentz Force Based Magnetic Field Sensors: Design, Applications and Challenges.

    PubMed

    Herrera-May, Agustín Leobardo; Soler-Balcazar, Juan Carlos; Vázquez-Leal, Héctor; Martínez-Castillo, Jaime; Vigueras-Zuñiga, Marco Osvaldo; Aguilera-Cortés, Luz Antonio

    2016-08-24

    Microelectromechanical systems (MEMS) resonators have allowed the development of magnetic field sensors with potential applications such as biomedicine, automotive industry, navigation systems, space satellites, telecommunications and non-destructive testing. We present a review of recent magnetic field sensors based on MEMS resonators, which operate with Lorentz force. These sensors have a compact structure, wide measurement range, low energy consumption, high sensitivity and suitable performance. The design methodology, simulation tools, damping sources, sensing techniques and future applications of magnetic field sensors are discussed. The design process is fundamental in achieving correct selection of the operation principle, sensing technique, materials, fabrication process and readout systems of the sensors. In addition, the description of the main sensing systems and challenges of the MEMS sensors are discussed. To develop the best devices, researches of their mechanical reliability, vacuum packaging, design optimization and temperature compensation circuits are needed. Future applications will require multifunctional sensors for monitoring several physical parameters (e.g., magnetic field, acceleration, angular ratio, humidity, temperature and gases).

  4. Observations of compound sawteeth in ion cyclotron resonant heating plasma using ECE imaging on experimental advanced superconducting tokamak

    NASA Astrophysics Data System (ADS)

    Hussain, Azam; Zhao, Zhenling; Xie, Jinlin; Zhu, Ping; Liu, Wandong; Ti, Ang

    2016-04-01

    The spatial and temporal evolutions of compound sawteeth were directly observed using 2D electron cyclotron emission imaging on experimental advanced superconducting tokamak. The compound sawtooth consists of partial and full collapses. After partial collapse, the hot core survives as only a small amount of heat disperses outwards, whereas in the following full collapse a large amount of heat is released and the hot core dissipates. The presence of two q = 1 surfaces was not observed. Instead, the compound sawtooth occurs mainly at the beginning of an ion cyclotron resonant frequency heating pulse and during the L-H transition phase, which may be related to heat transport suppression caused by a decrease in electron heat diffusivity.

  5. Advances in 133Cs Fountains: Control of the Cold Collision Shift and Observation of Feshbach Resonances

    SciTech Connect

    Bize, S.; Marion, H.; Cacciapuoti, L.; Vian, C.; Rosenbusch, P.; Pereira dos Santos, F.; Wolf, P.; Abgrall, M.; Maksimovic, I.; Gruenert, J.; Santarelli, G.; Laurent, P.; Clairon, A.; Luiten, A.; Tobar, M.; Kokkelmans, S.; Salomon, C.

    2005-05-05

    This paper describes the work performed at BNM-SYRTE (Observatoire de Paris) over the past few years toward the improvement and the use of microwave frequency standards using laser-cooled atoms. First, recent improvements of the 133Cs and 87Rb atomic fountains are described. An important advance is the achievement of a fractional frequency instability of 1.6 x 10-14{tau}-1/2 where {tau} is the measurement time in seconds, thanks to the routine use of a cryogenic sapphire oscillator as an ultra-stable local frequency reference. The second advance is a powerful method to control the frequency shift due to cold collisions. These two advances lead to a frequency stability of 2 x 10-16 at 50,000 s for the first time for primary standards. In addition, these clocks realize the SI second with an accuracy of 7 x 10-16, one order of magnitude below that of uncooled devices.

  6. Joseph F. Keithley Award For Advances in Measurement Science: Resonant Ultrasound Spectroscopy: An Odyssey in Measurement Science

    NASA Astrophysics Data System (ADS)

    Migliori, Albert

    Perhaps the speeds of sound, or, equivalently, the elastic moduli are some of the most fundamental attributes of a solid, connecting to fundamental physics, metallurgy, non-destructive testing, and more. Unlike most of the quantities used to characterize condensed matter, the elastic moduli are fourth-rank tensors containing a wealth of detail, directional information, and consistency constraints that provide some of the most revealing probes of solids. We describe here the current state of the art in one method, Resonant Ultrasound Spectroscopy, where the mechanical resonances of a specimen of regular shape (easy to measure) are analyzed (difficult computational problem) to obtain the full elastic tensor. With modern advances in electronics and analysis, fractions of a part per million changes in elastic moduli are detectable providing new and important insight into grand challenges in condensed matter physics. This work was supported as part of the Materials Science of Actinides, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences under Award # DE-SC0001089.

  7. Evidence of surface paramagnetism in niobium and consequences for the superconducting cavity surface impedance.

    SciTech Connect

    Prolier, T.; Kharitonov, M.; Pellin, M.; Zasadzinski, J.; Ciovati, G.

    2011-06-01

    The presence of magnetic impurities in native niobium oxides have been confirmed by Point contact spectroscopy (PCT), SQUID magnetometry and Electron paramagnetic resonance (EPR). All niobium (Nb) samples displayed a small impurity contribution to the magnetic susceptibility at low temperatures which exhibited Curie-Weiss behavior, indicative of weakly coupled localized paramagnetic moments. By examining Nb samples with widely varying surface-to-volume ratios (rods, foils, wires, powders) it was found that the impurity contribution is correlated with surface area. Tunneling measurements which use the native oxide layers as barriers exhibit a zero-bias conductance peak which splits in a magnetic field >; 4T, consistent with the Appelbaum-Anderson model for spin flip tunneling. Viewed together the experiments strongly suggest that the native oxides of Nb are intrinsically defective, and consistently exhibit localized paramagnetic moments caused by oxygen vacancies in Nb{sub 2}O{sub 5}. The computation of the surface impedance (R{sub s}) in presence of magnetic impurities in the Shiba approximation reveals the saturation at low temperature of R{sub s}, suggesting that magnetic impurities are responsible for the so-called residual resistance. These properties may have an impact on Nb based superconducting devices and shine a new light on the origin of the paramagnetic Meissner effect (PME).

  8. An EPR study on tea: Identification of paramagnetic species, effect of heat and sweeteners

    NASA Astrophysics Data System (ADS)

    Bıyık, Recep; Tapramaz, Recep

    2009-10-01

    Tea ( Camellia Sinensis) is the most widely consumed beverage in the world, and is known to be having therapeutic, antioxidant and nutritional effects. Electron paramagnetic resonance (EPR) spectral studies made on the tea cultivated along the shore of Black Sea, Turkey, show Mn 2+ and Fe 3+ centers in green tea leaves and in black tea extract. Dry black tea flakes and dry extract show additional sharp line attributed to semiquinone radical. The origins of the paramagnetic species in black tea are defined and discussed. Effect of humidity and heat are investigated. It is observed that dry extract of black tea melts at 100 °C and the semiquinone radical lives up to 140 °C while Mn 2+ sextet disappears just above 100 °C in tea extract. Natural and synthetics sweeteners have different effects on the paramagnetic centers. White sugar (sucrose) quenches the Mn 2+ and semiquinone lines in black tea EPR spectrum, and glucose, fructose, lactose and maltose quench Fe 3+ line while synthetic sweeteners acesulfam potassium, aspartame and sodium saccharine do not have any effect on paramagnetic species in tea.

  9. Prospects for advanced electron cyclotron resonance and electron beam ion source charge breeding methods for EURISOL

    SciTech Connect

    Delahaye, P.; Jardin, P.; Maunoury, L.; Traykov, E.; Varenne, F.; Angot, J.; Lamy, T.; Sortais, P.; Thuillier, T.; Ban, G.; Celona, L.; Lunney, D.; Choinski, J.; Gmaj, P.; Jakubowski, A.; Steckiewicz, O.; Kalvas, T.; and others

    2012-02-15

    As the most ambitious concept of isotope separation on line (ISOL) facility, EURISOL aims at producing unprecedented intensities of post-accelerated radioactive isotopes. Charge breeding, which transforms the charge state of radioactive beams from 1+ to an n+ charge state prior to post-acceleration, is a key technology which has to overcome the following challenges: high charge states for high energies, efficiency, rapidity and purity. On the roadmap to EURISOL, a dedicated R and D is being undertaken to push forward the frontiers of the present state-of-the-art techniques which use either electron cyclotron resonance or electron beam ion sources. We describe here the guidelines of this R and D.

  10. Magnetic Resonance Imaging of Polymeric Drug Delivery Systems in Breast Cancer Solid Tumors

    DTIC Science & Technology

    2007-07-01

    obtained from Promega (Madison, WI). All other (2) Thorek, D. L.; Chen, A. K.; Czupryna, J.; Tsourkas, A. Super - paramagnetic Iron Oxide Nanoparticle Probes...glutathione (1mM) was evaluated by Electron Paramagnetic Resonance (EPR) spectroscopy (E-109,Varian Associates, CA) at room temperature (Appendix 1...dinitroxide (50 µM) conjugates in the presence of glutathione (1mM) was evaluated by Electron Paramagnetic Resonance (EPR) spectroscopy (E-109,Varian

  11. Paramagnetic atom number and paramagnetic critical pressure of the sc, bcc and fcc Ising nanolattices

    NASA Astrophysics Data System (ADS)

    Şarlı, Numan

    2015-01-01

    The effects of the magnetic atom number in the unit volume on the magnetic properties are investigated by using sc (n=8), bcc (n=9) and fcc (n=14) Ising NLs within the effective field theory with correlations. We find that the magnetic properties expand as the magnetic atom number increases in the unit volume and this expanding constitutes an elliptical path at TC. The effect of the magnetic atom number (n) in the unit volume on the magnetic properties (mp) appear as nscparamagnetic hysteresis curves are directly proportional with the atom number in the unit volume. This proportion is the confirmation that the Curie's constant is directly proportional with the atom number in the unit volume (C α n). Hence, by using the slopes of the paramagnetic hysteresis curves of any nanosystem, it can be predicted that the number of particles in its unit volume. Moreover, the magnetic atoms in the paramagnetic region can be considered as particles in the gas. Because of the absence of an external magnetic field, the spin orientations of these atoms are random and free to rotate. Hence, they act on individually with no mutual interaction between two nearest-neighbor magnetic atoms. Therefore, we use the statistical mechanics form of the ideal gas law in the paramagnetic region and we obtain the critical paramagnetic pressure (PC=npkBTC) of the Ising NLs at TC. We define the paramagnetic magnetic atom number in the unit volume as np=n(1-M(T)).

  12. Advances in Monitoring Cell-Based Therapies with Magnetic Resonance Imaging: Future Perspectives

    PubMed Central

    Ngen, Ethel J.; Artemov, Dmitri

    2017-01-01

    Cell-based therapies are currently being developed for applications in both regenerative medicine and in oncology. Preclinical, translational, and clinical research on cell-based therapies will benefit tremendously from novel imaging approaches that enable the effective monitoring of the delivery, survival, migration, biodistribution, and integration of transplanted cells. Magnetic resonance imaging (MRI) offers several advantages over other imaging modalities for elucidating the fate of transplanted cells both preclinically and clinically. These advantages include the ability to image transplanted cells longitudinally at high spatial resolution without exposure to ionizing radiation, and the possibility to co-register anatomical structures with molecular processes and functional changes. However, since cellular MRI is still in its infancy, it currently faces a number of challenges, which provide avenues for future research and development. In this review, we describe the basic principle of cell-tracking with MRI; explain the different approaches currently used to monitor cell-based therapies; describe currently available MRI contrast generation mechanisms and strategies for monitoring transplanted cells; discuss some of the challenges in tracking transplanted cells; and suggest future research directions. PMID:28106829

  13. Nuclear magnetic resonance based metabolomics and liver diseases: Recent advances and future clinical applications

    PubMed Central

    Amathieu, Roland; Triba, Mohamed Nawfal; Goossens, Corentine; Bouchemal, Nadia; Nahon, Pierre; Savarin, Philippe; Le Moyec, Laurence

    2016-01-01

    Metabolomics is defined as the quantitative measurement of the dynamic multiparametric metabolic response of living systems to pathophysiological stimuli or genetic modification. It is an “omics” technique that is situated downstream of genomics, transcriptomics and proteomics. Metabolomics is recognized as a promising technique in the field of systems biology for the evaluation of global metabolic changes. During the last decade, metabolomics approaches have become widely used in the study of liver diseases for the detection of early biomarkers and altered metabolic pathways. It is a powerful technique to improve our pathophysiological knowledge of various liver diseases. It can be a useful tool to help clinicians in the diagnostic process especially to distinguish malignant and non-malignant liver disease as well as to determine the etiology or severity of the liver disease. It can also assess therapeutic response or predict drug induced liver injury. Nevertheless, the usefulness of metabolomics is often not understood by clinicians, especially the concept of metabolomics profiling or fingerprinting. In the present work, after a concise description of the different techniques and processes used in metabolomics, we will review the main research on this subject by focusing specifically on in vitro proton nuclear magnetic resonance spectroscopy based metabolomics approaches in human studies. We will first consider the clinical point of view enlighten physicians on this new approach and emphasis its future use in clinical “routine”. PMID:26755887

  14. Advanced characterisation of encapsulated lipid powders regarding microstructure by time domain-nuclear magnetic resonance.

    PubMed

    Linke, Annika; Anzmann, Theresa; Weiss, Jochen; Kohlus, Reinhard

    2017-03-15

    Encapsulation is an established technique to protect sensitive materials from environmental stress. In order to understand the physical protection mechanism against oxidation, knowledge about the powder microstructure is required. Time domain-nuclear magnetic resonance (TD-NMR) has the potential to determine the surface oil (SO) and droplet size distribution by relaxation and restricted self-diffusion, respectively. The amount of SO, the retention and encapsulation efficiency are determined based on a lipid balance. The oil load of the initial powder and after SO removal is measured by TD-NMR. The results correlate with gravimetric and photometric references. The oil droplet size obtained by TD-NMR correlates well with static light scattering. The diameter of droplets in emulsions and dried powder both measured by TD-NMR, correlates (r = 0.998), implying that oil droplets embedded in a solid matrix can be measured. Summarising, TD-NMR allows analysis of the microstructure of encapsulated lipid powders, in a rapid, simple and non-destructive way.

  15. Nuclear magnetic resonance based metabolomics and liver diseases: Recent advances and future clinical applications.

    PubMed

    Amathieu, Roland; Triba, Mohamed Nawfal; Goossens, Corentine; Bouchemal, Nadia; Nahon, Pierre; Savarin, Philippe; Le Moyec, Laurence

    2016-01-07

    Metabolomics is defined as the quantitative measurement of the dynamic multiparametric metabolic response of living systems to pathophysiological stimuli or genetic modification. It is an "omics" technique that is situated downstream of genomics, transcriptomics and proteomics. Metabolomics is recognized as a promising technique in the field of systems biology for the evaluation of global metabolic changes. During the last decade, metabolomics approaches have become widely used in the study of liver diseases for the detection of early biomarkers and altered metabolic pathways. It is a powerful technique to improve our pathophysiological knowledge of various liver diseases. It can be a useful tool to help clinicians in the diagnostic process especially to distinguish malignant and non-malignant liver disease as well as to determine the etiology or severity of the liver disease. It can also assess therapeutic response or predict drug induced liver injury. Nevertheless, the usefulness of metabolomics is often not understood by clinicians, especially the concept of metabolomics profiling or fingerprinting. In the present work, after a concise description of the different techniques and processes used in metabolomics, we will review the main research on this subject by focusing specifically on in vitro proton nuclear magnetic resonance spectroscopy based metabolomics approaches in human studies. We will first consider the clinical point of view enlighten physicians on this new approach and emphasis its future use in clinical "routine".

  16. Advanced Magnetic Resonance Imaging of the Physical Processes in Human Glioblastoma

    PubMed Central

    Emblem, Kyrre E.; Andronesi, Ovidiu; Rosen, Bruce

    2014-01-01

    The most common malignant primary brain tumor, glioblastoma (GBM) is a devastating disease with a grim prognosis. Patient survival is typically less than 2 years and fewer than 10% of patients survive more than 5 years. Magnetic Resonance Imaging (MRI) can have great utility in the diagnosis, grading and management of patients with GBM as many of the physical manifestations of the pathological processes in GBM can be visualized and quantified using MRI. Newer MRI techniques such as dynamic contrast enhanced (DCE) and dynamic susceptibility contrast (DSC) MRI provide functional information regarding the tumor hemodynamic status. Diffusion MRI can shed light on tumor cellularity and the disruption of white matter tracts in the proximity of tumors. MR spectroscopy can be used to study new tumor tissue markers such as IDH mutations. MRI is helping to noninvasively explore the link between the molecular basis of gliomas and the imaging characteristics of their physical processes. We will review several approaches to MR-based imaging and discuss the potential for these techniques to quantify the physical processes in glioblastoma including tumor cellularity and vascularity, metabolite expression, and patterns of tumor growth and recurrence. We will conclude with challenges and opportunities for further research in applying physical principles to better understand the biological process in this deadly disease. PMID:25183787

  17. Advanced slow-magic angle spinning probe for magnetic resonance imaging and spectroscopy

    DOEpatents

    Wind, Robert A.; Hu, Jian Zhi; Minard, Kevin R.; Rommereim, Donald N.

    2006-01-24

    The present invention relates to a probe and processes useful for magnetic resonance imaging and spectroscopy instruments. More particularly, the invention relates to a MR probe and processes for obtaining resolution enhancements of fluid objects, including live specimens, using an ultra-slow (magic angle) spinning (MAS) of the specimen combined with a modified phase-corrected magic angle turning (PHORMAT) pulse sequence. Proton NMR spectra were measured of the torso and the top part of the belly of a female BALBc mouse in a 2T field, while spinning the animal at a speed of 1.5 Hz. Results show that even in this relatively low field with PHORMAT, an isotropic spectrum is obtained with line widths that are a factor 4.6 smaller than those obtained in a stationary mouse. Resolution of 1H NMR metabolite spectra are thus significantly enhanced. Results indicate that PHORMAT has the potential to significantly increase the utility of 1H NMR spectroscopy for in vivo biochemical, biomedical and/or medical applications involving large-sized biological objects such as mice, rats and even humans within a hospital setting. For small-sized objects, including biological objects, such as excised tissues, organs, live bacterial cells, and biofilms, use of PASS at a spinning rate of 30 Hz and above is preferred.

  18. Applications of nuclear magnetic resonance to nondestructive evaluation of advanced materials

    SciTech Connect

    Lizak, M.J.

    1991-01-01

    Two applications of nuclear magnetic resonance to nondestructive evaluation are presented. The first application is NMR imaging of gases and liquids imbibed into porous ceramic matrix composites. This inspection technique takes advantages of the porosity of the ceramic composite material. A fluorocarbon liquid or gas is infiltrated into the pores of the material, and NMR imaging is performed on the fluorine nuclei. The gases and liquids have more amenable relaxation times for imaging than the ceramic itself, enabling imaging to be performed on commercially available equipment. The ceramic composite restricts the diffusion rate of the gas and dramatically alters the spin relaxation times. These differences provide good contrast mechanisms for the NMR imaging techniques. The second application is to monitoring curing of epoxies. Relaxation times were measured for several curing-epoxy systems. It was found that the transverse relaxation time, T{sub 2}, and the relaxation time of dipolar order, T{sub 1D}, were good indicators of the epoxy cure state. The relaxation times are easy to measure and are relatively insensitive to instrumental settings.

  19. Audio-band coating thermal noise measurement for Advanced LIGO with a multimode optical resonator

    NASA Astrophysics Data System (ADS)

    Gras, S.; Yu, H.; Yam, W.; Martynov, D.; Evans, M.

    2017-01-01

    In modern high precision optical instruments, such as in gravitational wave detectors or frequency references, thermally induced fluctuations in the reflective coatings can be a limiting noise source. This noise, known as coating thermal noise, can be reduced by choosing materials with low mechanical loss. Examination of new materials becomes a necessity in order to further minimize the coating thermal noise and thus improve sensitivity of next generation instruments. We present a novel approach to directly measure coating thermal noise using a high finesse folded cavity in which multiple Hermite-Gaussian modes coresonate. This method is used to probe surface fluctuations on the order 10-17 m /√{Hz } in the frequency range 30-400 Hz. We applied this technique to measure thermal noise and loss angle of the coating used in Advanced LIGO.

  20. Recent advances in metamaterial split-ring-resonator circuits as biosensors and therapeutic agents.

    PubMed

    RoyChoudhury, Sohini; Rawat, Vaishali; Jalal, Ahmed Hasnain; Kale, S N; Bhansali, Shekhar

    2016-12-15

    Potential applications of thin film metamaterials are diverse and their realization to offer miniaturized waveguides, antennas and shielding patterns are on anvil. These artificially engineered structures can produce astonishing electromagnetic responses because of their constituents being engineered at much smaller dimensions than the wavelength of the incident electromagnetic wave, hence behaving as artificial materials. Such micro-nano dimensions of thin film metamaterial structures can be customized for various applications due to their exclusive responses to not only electromagnetic, but also to acoustic and thermal waves that surpass the natural materials' properties. In this paper, the recent major advancements in the emerging fields of diagnostics (sensors) and therapeutics involving thin film metamaterials have been reviewed and underlined; discussing their edge over conventional counterpart techniques; concentrating on their design considerations and feasible ways of achieving them. Challenges faced in sensitivity, precision, accuracy and factors that interfere with the degree of performance of the sensors are also dealt with, herein.

  1. Chemical structures of swine-manure chars produced under different carbonization conditions investigated by advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Two types of swine manure chars, hydrothermally-produced hydrochar and slow-pyrolysis pyrochar, and their raw swine manure solid were characterized using advanced 13C solid-state nuclear magnetic resonance (NMR) spectroscopy. Compared with the parent raw swine manure, both hydrochars and pyrochar di...

  2. Advances in the physics understanding of ELM suppression using resonant magnetic perturbations in DIII-D

    SciTech Connect

    Wade, M. R.; Nazikian, R.; deGrassie, John S.; Evans, T. E.; Ferraro, N. M.; Moyer, R. A.; Orlov, D. M.; Buttery, R. J.; Fenstermacher, Max E.; Garofalo, Andrea M.; Lanctot, M. A.; McKee, George R.; Osborne, T. H.; Shafer, M. A.; Solomon, W. M.; Snyder, P. B.; Suttrop, Wolfgang; Wingen, Andreas; Unterberg, Ezekial A.; Zeng, L.

    2015-01-14

    Recent experiments on DIII-D have increased confidence in the ability to suppress edge-localized modes (ELMs) using edge-resonant magnetic perturbations (RMPs) in ITER, including an improved physics basis for the edge response to RMPs as well as expansion of RMP ELM suppression to more ITER-like conditions. In this study, complete ELM suppression has been achieved utilizing n = 3 RMPs in the ITER baseline scenario. In addition, RMP ELM suppression has been expanded to include plasmas with helium concentrations near 25% and the use of n = 2 RMPs. Analysis of the kinetic profile response suggests that ELM suppression is correlated with the co-alignment of the ω⊥e = 0 location, an n = 3 rational surface, and the top of the pedestal. Modelling predicts that such a co-alignment could potentially lead to island (or island chain) formation just inside the top of the pedestal, inhibiting the growth of the pedestal and thereby maintaining the ELM-free state. Detailed analysis of data obtained during toroidal phase variations of the applied n = 3 RMPs have provided further evidence of an island-like structure at the top of the pedestal. In addition, nearly matched discharges with co-neutral-beam-injection (co-NBI) and counter-NBI have demonstrated the importance of the presence of the ω⊥e = 0 location for ELM suppression. Finally, in the counter-NBI cases, the toroidal rotation profile is such that there is no ω⊥e = 0 location and ELMs are not suppressed in conditions in which ELM suppression is generally observed with co-NBI.

  3. Advances in the physics understanding of ELM suppression using resonant magnetic perturbations in DIII-D

    DOE PAGES

    Wade, M. R.; Nazikian, R.; deGrassie, John S.; ...

    2015-01-14

    Recent experiments on DIII-D have increased confidence in the ability to suppress edge-localized modes (ELMs) using edge-resonant magnetic perturbations (RMPs) in ITER, including an improved physics basis for the edge response to RMPs as well as expansion of RMP ELM suppression to more ITER-like conditions. In this study, complete ELM suppression has been achieved utilizing n = 3 RMPs in the ITER baseline scenario. In addition, RMP ELM suppression has been expanded to include plasmas with helium concentrations near 25% and the use of n = 2 RMPs. Analysis of the kinetic profile response suggests that ELM suppression is correlatedmore » with the co-alignment of the ω⊥e = 0 location, an n = 3 rational surface, and the top of the pedestal. Modelling predicts that such a co-alignment could potentially lead to island (or island chain) formation just inside the top of the pedestal, inhibiting the growth of the pedestal and thereby maintaining the ELM-free state. Detailed analysis of data obtained during toroidal phase variations of the applied n = 3 RMPs have provided further evidence of an island-like structure at the top of the pedestal. In addition, nearly matched discharges with co-neutral-beam-injection (co-NBI) and counter-NBI have demonstrated the importance of the presence of the ω⊥e = 0 location for ELM suppression. Finally, in the counter-NBI cases, the toroidal rotation profile is such that there is no ω⊥e = 0 location and ELMs are not suppressed in conditions in which ELM suppression is generally observed with co-NBI.« less

  4. ADVANCED MAGNETIC RESONANCE IMAGING OF CEREBRAL CAVERNOUS MALFORMATIONS: I. HIGH FIELD IMAGING OF EXCISED HUMAN LESIONS

    PubMed Central

    Shenkar, Robert; Venkatasubramanian, Palamadai N.; Zhao, Jin-cheng; Batjer, H. Hunt; Wyrwicz, Alice M.; Awad, Issam A.

    2008-01-01

    Objectives We hypothesized that structural details would be revealed in cerebral cavernous malformations (CCMs) through the use of high field magnetic resonance (MR) and confocal microscopy, which have not been described previously. The structural details of CCMs excised from human patients were sought by examination with high field MR imaging, and correlated with confocal microscopy of the same specimens. Novel features of CCM structure are outlined, including methodological limitations, venues for future research and possible clinical implications. Methods CCM lesions excised from four patients were fixed in 2% paraformaldehyde and subjected to high resolution MR imaging at 9.4 or 14.1 Tesla by spin-echo and gradient recalled echo methods. Histological validation of angioarchitecture was conducted on thick sections of CCM lesions using fluorescent probes to endothelium under confocal microscopy. Results Images of excised human CCM lesions were acquired with proton density-weighted, T1-weighted, T2-weighted spin echo and T2*-weighted gradient-recalled echo MR. These images revealed large “bland” regions with thin walled caverns, and “honeycombed” regions with notable capillary proliferation and smaller caverns surrounding larger caverns. Proliferating capillaries and caverns of various sizes were also associated with the wall of apparent larger blood vessels in the lesions. Similar features were confirmed within thick sections of CCMs by confocal microscopy. MR relaxation times in different regions of interest suggested the presence of different states of blood breakdown products in areas with apparent angiogenic proliferative activity. Conclusions The high field MR imaging techniques demonstrate novel features of CCM angioarchitecture, visible at near histological resolution, including regions with apparently different biologic activity. These preliminary observations will motivate future research, correlating lesion biologic and clinical activity with

  5. Paramagnetic and Antiferromagnetic Spin Seebeck Effect

    NASA Astrophysics Data System (ADS)

    Wu, Stephen

    We report on the observation of the longitudinal spin Seebeck effect in both antiferromagnetic and paramagnetic insulators. By using a microscale on-chip local heater, it is possible to generate a large thermal gradient confined to the chip surface without a large increase in the total sample temperature. This technique allows us to easily access low temperatures (200 mK) and high magnetic fields (14 T) through conventional dilution refrigeration and superconducting magnet setups. By exploring this regime, we detect the spin Seebeck effect through the spin-flop transition in antiferromagnetic MnF2 when a large magnetic field (>9 T) is applied along the easy axis direction. Using the same technique, we are also able to resolve a spin Seebeck effect from the paramagnetic phase of geometrically frustrated antiferromagnet Gd3Ga5O12 (gadolinium gallium garnet) and antiferromagnetic DyScO3 (DSO). Since these measurements occur above the ordering temperatures of these two materials, short-range magnetic order is implicated as the cause of the spin Seebeck effect in these systems. The discovery of the spin Seebeck effect in these two materials classes suggest that both antiferromagnetic spin waves and spin excitations from short range magnetic order may be used to generate spin current from insulators and that the spin wave spectra of individual materials are highly important to the specifics of the longitudinal spin Seebeck effect. Since insulating antiferromagnets and paramagnets are far more common than the typical insulating ferrimagnetic materials used in spin Seebeck experiments, this discovery opens up a large new class of materials for use in spin caloritronic devices. All authors acknowledge support of the U.S. Department of Energy (DOE), Office of Science, Basic Energy Sciences (BES), Materials Sciences and Engineering Division. The use of facilities at the Center for Nanoscale Materials, was supported by the U.S. DOE, BES under Contract No. DE-AC02-06CH11357.

  6. Paramagnetic excited vortex states in superconductors

    NASA Astrophysics Data System (ADS)

    Gomes, Rodolpho Ribeiro; Doria, Mauro M.; Romaguera, Antonio R. de C.

    2016-06-01

    We consider excited vortex states, which are vortex states left inside a superconductor once the external applied magnetic field is switched off and whose energy is lower than of the normal state. We show that this state is paramagnetic and develop here a general method to obtain its Gibbs free energy through conformal mapping. The solution for any number of vortices in any cross-section geometry can be read off from the Schwarz-Christoffel mapping. The method is based on the first-order equations used by Abrikosov to discover vortices.

  7. Change in the paramagnetic characteristics of coals during metamorphism

    SciTech Connect

    Bineev, E.A.; Peresun'ko, T.F.

    1983-01-01

    The paper studies the paramagnetic properties of deep-mined coals on samples taken from one seam with a wide spectrum of metamorphism. Changes which take place in the concentration of paramagnetic centres within the various types of coal are related to structural and chemical transformations which occur with progressive coalification. Comparisons of EPR and X-ray structural and elementary analyses produce a picture of those particular paramagnetic centres which are responsible for the wide- and narrow-band EPR signals.

  8. Advanced Magnetic Resonance Imaging techniques to probe muscle structure and function

    NASA Astrophysics Data System (ADS)

    Malis, Vadim

    Structural and functional Magnetic Resonance Imaging (MRI) studies of skeletal muscle allow the elucidation of muscle physiology under normal and pathological conditions. Continuing on the efforts of the Muscle Imaging and Modeling laboratory, the focus of the thesis is to (i) extend and refine two challenging imaging modalities: structural imaging using Diffusion Tensor Imaging (DTI) and functional imaging based on Velocity Encoded Phase Contrast Imaging (VE-PC) and (ii) apply these methods to explore age related structure and functional differences of the gastrocnemius muscle. Diffusion Tensor Imaging allows the study of tissue microstructure as well as muscle fiber architecture. The images, based on an ultrafast single shot Echo Planar Imaging (EPI) sequence, suffer from geometric distortions and low signal to noise ratio. A processing pipeline was developed to correct for distortions and to improve image Signal to Noise Ratio (SNR). DTI acquired on a senior and young cohort of subjects were processed through the pipeline and differences in DTI derived indices and fiber architecture between the two cohorts were explored. The DTI indices indicated that at the microstructural level, fiber atrophy was accompanied with a reduction in fiber volume fraction. At the fiber architecture level, fiber length and pennation angles decreased with age that potentially contribute to the loss of muscle force with age. Velocity Encoded Phase Contrast imaging provides tissue (e.g. muscle) velocity at each voxel which allows the study of strain and Strain Rate (SR) under dynamic conditions. The focus of the thesis was to extract 2D strain rate tensor maps from the velocity images and apply the method to study age related differences. The tensor mapping can potentially provide unique information on the extracellular matrix and lateral transmission the role of these two elements has recently emerged as important determinants of force loss with age. In the cross sectional study on

  9. 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.

  10. Local structure and paramagnetic properties of the nanostructured carbonaceous material shungite.

    PubMed

    Krasnovyd, Serhii Volodymyrovich; Konchits, Andriy Andriyovich; Shanina, Bela Dmytrivna; Valakh, Mykhaylo Yakovych; Yanchuk, Igor Bogdanovich; Yukhymchuk, Volodymyr Olexsandrovych; Yefanov, Andriy Volodymyrovich; Skoryk, Mykola Andriyovich

    2015-01-01

    Using a scanning electron microscopy, elemental analysis, electron paramagnetic resonance, and Raman scattering methods, two types of the shungite materials (Sh-II from Zazhogino deposit and shungite from a commercial filter (ShF)), with different carbon content and porosity, are studied in this work. It was established by scanning electron microscopy data that the structure of the shungite samples is formed by a micron-size agglomeration of carbon and silicon dioxide clusters. It is found from the Raman data that carbon fraction is formed from sp(2)-hybridized clusters, size of which increases from 9 up to 12 nm after annealing of the samples. High conductivity of shungite is found to belong to the carbon nanoclusters of different sizes. Big clusters give the conduction electron spin resonance signal with a Dysonian line shape with variable g-factor and line width. The careful search of the nature of two other narrow electron paramagnetic resonance signals in shungite, which used to be prescribed to fullerene-like molecules, is fulfilled. Here, it is shown that the oxygen-deficient E'γ centers are responsible for these signals. A strong correlation is revealed between the concentration of Е'γ centers and the line width of conduction electron spin resonance signal, which occurs under annealing process of the samples at T = 570 K. The correlation reasons are a spin-spin coupling between two spin subsystems and time dependent of the Е'γ concentration during annealing process.

  11. Evaluation of Neoadjuvant Chemotherapy Response with Dynamic Contrast Enhanced Breast Magnetic Resonance Imaging in Locally Advanced Invasive Breast Cancer

    PubMed Central

    Gezer, Naciye Sinem; Orbay, Özge; Balcı, Pınar; Durak, Merih Guray; Demirkan, Binnaz; Saydam, Serdar

    2014-01-01

    Objective The reliability of traditional methods such as physical examination, ultrasonography (US) and mammography is limited in determining the type of treatment response in patients with neoadjuvant chemotherapy (NAC) application for locally advanced breast cancer (LABC). Dynamic contrast-enhanced magnetic resonance imaging (MRI) is gaining popularity in the evaluation of NAC response. This study aimed to compare NAC response as determined by dynamic contrast-enhanced breast MRI in patients with LABC to histopathology that is the gold standard; and evaluate the compatibility of MRI, mammography and US with response types. Materials and Methods The US, mammography and MRI findings of 38 patients who received NAC with a diagnosis of locally advanced breast cancer and surgical treatment were retrospectively analyzed and compared to histopathology results. Type of response to treatment was determined according to the “Criteria in Solid Tumors Response Evolution 1.1” by mammography, US and MRI criteria. The relationship between response types as defined by all three imaging modalities and histopathology were evaluated, and the correlation of response type as detected by MRI and pathological response and histopathological type of breast cancer was further determined. For statistical analysis, the chi-square, paired t test, correlation and kappa tests were used. Results There is a statistical moderate positive correlation between response type according to pathology and MRI (kappa: 0.63). There was a weak correlation between response type according to mammography or US and according to pathology (kappa: 0.2). When the distribution of treatment response by MRI is stratified according to histopathological types, partial response was higher in all histopathological types similar to the type of pathologic response. When compared with pathology MRI detected treatment response accurately in 84.2% of the patients. Conclusion Dynamic contrast-enhanced breast MRI appears to

  12. High-efficiency in situ resonant inelastic x-ray scattering (iRIXS) endstation at the Advanced Light Source

    NASA Astrophysics Data System (ADS)

    Qiao, Ruimin; Li, Qinghao; Zhuo, Zengqing; Sallis, Shawn; Fuchs, Oliver; Blum, Monika; Weinhardt, Lothar; Heske, Clemens; Pepper, John; Jones, Michael; Brown, Adam; Spucces, Adrian; Chow, Ken; Smith, Brian; Glans, Per-Anders; Chen, Yanxue; Yan, Shishen; Pan, Feng; Piper, Louis F. J.; Denlinger, Jonathan; Guo, Jinghua; Hussain, Zahid; Chuang, Yi-De; Yang, Wanli

    2017-03-01

    An endstation with two high-efficiency soft x-ray spectrographs was developed at Beamline 8.0.1 of the Advanced Light Source, Lawrence Berkeley National Laboratory. The endstation is capable of performing soft x-ray absorption spectroscopy, emission spectroscopy, and, in particular, resonant inelastic soft x-ray scattering (RIXS). Two slit-less variable line-spacing grating spectrographs are installed at different detection geometries. The endstation covers the photon energy range from 80 to 1500 eV. For studying transition-metal oxides, the large detection energy window allows a simultaneous collection of x-ray emission spectra with energies ranging from the O K-edge to the Ni L-edge without moving any mechanical components. The record-high efficiency enables the recording of comprehensive two-dimensional RIXS maps with good statistics within a short acquisition time. By virtue of the large energy window and high throughput of the spectrographs, partial fluorescence yield and inverse partial fluorescence yield signals could be obtained for all transition metal L-edges including Mn. Moreover, the different geometries of these two spectrographs (parallel and perpendicular to the horizontal polarization of the beamline) provide contrasts in RIXS features with two different momentum transfers.

  13. Numerical Study of the Impact of Resonant Magnetic Perturbations on Recycling Sources In Advanced Divertor Configurations of NSTX-U

    NASA Astrophysics Data System (ADS)

    Waters, Ian; Flesch, Kurt; Frerichs, Heinke; Schmitz, Oliver; Ahn, Joon-Wook; Canal, Gustavo; Evans, Todd; Soukhanovskii, Vsevolod

    2016-10-01

    Explorations are under way to optimize the magnetic topology in the plasma edge of NSTX-U with the goal of improving neutral and impurity fueling and exhaust. Advanced divertor configurations combined with resonant magnetic perturbation (RMP) fields are being considered to improve peak heat and particle loads, stabilize edge instabilities, adjust plasma refueling, and control impurity transport. In this study, the EMC3-EIRENE fluid plasma and kinetic neutral transport code is used to investigate snowflake divertor configurations with and without RMP fields. Analysis of the edge recycling sources show that RMP fields induce a transition from a linear recycling regime into a high recycling regime at densities that are lower than in non-perturbed cases. This transition is also accompanied by a shift in the spatial distribution of these recycling sources and neutral atoms, and is impacted by the strength of the perturbations. An overview of results from different standard and snowflake divertor configurations will be presented. This work was funded by the Department of Energy under Grant DE-SC0012315.

  14. Recent advances in biosynthetic modeling of nitric oxide reductases and insights gained from nuclear resonance vibrational and other spectroscopic studies

    SciTech Connect

    Chakraborty, Saumen; Reed, Julian; Sage, Timothy; Branagan, Nicole C.; Petrik, Igor D.; Miner, Kyle D.; Hu, Michael Y.; Zhao, Jiyong; Alp, E. Ercan; Lu, Yi

    2015-10-05

    This Forum Article focuses on recent advances in structural and spectroscopic studies of biosynthetic models of nitric oxide reductases (NORs). NORs are complex metalloenzymes found in the denitrification pathway of Earth's nitrogen cycle where they catalyze the proton-dependent twoelectron reduction of nitric oxide (NO) to nitrous oxide (N2O). While much progress has been made in biochemical and biophysical studies of native NORs and their variants, a. clear mechanistic understanding of this important metalloenzyme related to its function is still elusive. We report herein UV vis and nuclear resonance vibrational spectroscopy (NRVS) studies of mononitrosylated intermediates of the NOR reaction of a biosynthetic model. The ability to selectively substitute metals at either heme or nonheme metal sites allows the introduction of independent 57Fe probe atoms at either site, as well as allowing the preparation of analogues of stable reaction intermediates by replacing either metal with a redox inactive metal. Together with previous structural and spectroscopic results, we summarize insights gained from studying these biosynthetic models toward understanding structural features responsible for the NOR activity and its mechanism. As a result, the outlook on NOR modeling is also discussed, with an emphasis on the design of models capable of catalytic turnovers designed based on close mimics of the secondary coordination sphere of native NORs.

  15. Implementation of advanced feedback control algorithms for controlled resonant magnetic perturbation physics studies on EXTRAP T2R

    NASA Astrophysics Data System (ADS)

    Frassinetti, L.; Olofsson, K. E. J.; Brunsell, P. R.; Drake, J. R.

    2011-06-01

    The EXTRAP T2R feedback system (active coils, sensor coils and controller) is used to study and develop new tools for advanced control of the MHD instabilities in fusion plasmas. New feedback algorithms developed in EXTRAP T2R reversed-field pinch allow flexible and independent control of each magnetic harmonic. Methods developed in control theory and applied to EXTRAP T2R allow a closed-loop identification of the machine plant and of the resistive wall modes growth rates. The plant identification is the starting point for the development of output-tracking algorithms which enable the generation of external magnetic perturbations. These algorithms will then be used to study the effect of a resonant magnetic perturbation (RMP) on the tearing mode (TM) dynamics. It will be shown that the stationary RMP can induce oscillations in the amplitude and jumps in the phase of the rotating TM. It will be shown that the RMP strongly affects the magnetic island position.

  16. Advanced light ion source extraction system for a new electron cyclotron resonance ion source geometry at Saclay.

    PubMed

    Delferrière, O; Gobin, R; Harrault, F; Nyckees, S; Sauce, Y; Tuske, O

    2012-02-01

    One of the main goal of intense light ion injector projects such as IPHI, IFMIF, or SPIRAL2, is to produce high current beams while keeping transverse emittance as low as possible. To prevent emittance growth induced in a dual solenoid low energy transfer line, its length has to be minimized. This can be performed with the advanced light ion source extraction system concept that we are developing: a new ECR 2.45 GHz type ion source based on the use of an additional low energy beam transport (LEBT) short length solenoid close to the extraction aperture to create the resonance in the plasma chamber. The geometry of the source has been considerably modified to allow easy maintenance of each component and to save space in front of the extraction. The source aims to be very flexible and to be able to extract high current ion beams at energy up to 100 kV. A specific experimental setup for this source is under installation on the BETSI test bench, to compare its performances with sources developed up to now in the laboratory, such as SILHI, IFMIF, or SPIRAL2 ECR sources. This original extraction source concept is presented, as well as electromagnetic simulations with OPERA-2D code. Ion beam extraction in space charge compensation regime with AXCEL, and beam dynamics simulation with SOLMAXP codes show the beam quality improvement at the end of the LEBT.

  17. Advanced light ion source extraction system for a new electron cyclotron resonance ion source geometry at Saclaya)

    NASA Astrophysics Data System (ADS)

    Delferrière, O.; Gobin, R.; Harrault, F.; Nyckees, S.; Sauce, Y.; Tuske, O.

    2012-02-01

    One of the main goal of intense light ion injector projects such as IPHI, IFMIF, or SPIRAL2, is to produce high current beams while keeping transverse emittance as low as possible. To prevent emittance growth induced in a dual solenoid low energy transfer line, its length has to be minimized. This can be performed with the advanced light ion source extraction system concept that we are developing: a new ECR 2.45 GHz type ion source based on the use of an additional low energy beam transport (LEBT) short length solenoid close to the extraction aperture to create the resonance in the plasma chamber. The geometry of the source has been considerably modified to allow easy maintenance of each component and to save space in front of the extraction. The source aims to be very flexible and to be able to extract high current ion beams at energy up to 100 kV. A specific experimental setup for this source is under installation on the BETSI test bench, to compare its performances with sources developed up to now in the laboratory, such as SILHI, IFMIF, or SPIRAL2 ECR sources. This original extraction source concept is presented, as well as electromagnetic simulations with OPERA-2D code. Ion beam extraction in space charge compensation regime with AXCEL, and beam dynamics simulation with SOLMAXP codes show the beam quality improvement at the end of the LEBT.

  18. Paramagnetic Manganese in the Atherosclerotic Plaque of Carotid Arteries

    PubMed Central

    Chelyshev, Yury; Ignatyev, Igor; Zanochkin, Alexey; Mamin, Georgy; Sorokin, Boris; Sorokina, Alexandra; Lyapkalo, Natalya; Gizatullina, Nazima; Orlinskii, Sergei

    2016-01-01

    The search for adequate markers of atherosclerotic plaque (AP) instability in the context of assessment of the ischemic stroke risk in patients with atherosclerosis of the carotid arteries as well as for solid physical and chemical factors that are connected with the AP stability is extremely important. We investigate the inner lining of the carotid artery specimens from the male patients with atherosclerosis (27 patients, 42–64 years old) obtained during carotid endarterectomy by using different analytical tools including ultrasound angiography, X-ray analysis, immunological, histochemical analyses, and high-field (3.4 T) pulse electron paramagnetic resonance (EPR) at 94 GHz. No correlation between the stable and unstable APs in the sense of the calcification is revealed. In all of the investigated samples, the EPR spectra of manganese, namely, Mn2+ ions, are registered. Spectral and relaxation characteristics of Mn2+ ions are close to those obtained for the synthetic (nano) hydroxyapatite species but differ from each other for stable and unstable APs. This demonstrates that AP stability could be specified by the molecular organization of their hydroxyapatite components. The origin of the obtained differences and the possibility of using EPR of Mn2+ as an AP stability marker are discussed. PMID:28078287

  19. Density-functional study of paramagnetic iron

    NASA Astrophysics Data System (ADS)

    Zhang, Hualei; Johansson, Börje; Vitos, Levente

    2011-10-01

    By using density-functional theory in combination with the coherent-potential approximation and the disordered local magnetic moment picture, we demonstrate that the competing high-temperature cubic phases of paramagnetic Fe correspond to two distinct total energy minima in the tetragonal (Bain) configurational space. Both the face-centered-cubic (fcc) and the body-centered-cubic (bcc) lattices are dynamically stable, and at static conditions the fcc structure is found to be the thermodynamically stable phase. The theoretical bcc and fcc bulk parameters are in agreement with the experimental data. Due to the shallow energy minimum around the bcc structure, increasing temperature is predicted to stabilize the bcc (δ) phase against the fcc (γ) one.

  20. A prospective study of the value of pre- and post-treatment magnetic resonance imaging examinations for advanced cervical cancer

    PubMed Central

    CSUTAK, CSABA; ORDEANU, CLAUDIA; NAGY, VIORICA MAGDALENA; POP, DIANA CRISTINA; BOLBOACA, SORANA DANIELA; BADEA, RADU; CHIOREAN, LILIANA; DUDEA, SORIN MARIAN

    2016-01-01

    Background and aim Cervical cancer has high incidence and mortality in developing countries. It is the only gynecological malignancy that is clinically staged. Staging at the time of diagnosis is crucial for treatment planning. After radiation therapy, clinical examination is limited because of radiation changes. An imaging method relatively unaffected by radiation changes would be useful for the assessment of therapy results and for management. We sought to demonstrate the value of magnetic resonance imaging (MRI) in the pre- and post-treatment assessment of cervical cancer. Methods This was a prospective study, carried out between November 2012 and October 2014 on 18 subjects with advanced-stage cervical cancer diagnosed by colposcopy. The disease stage was determined clinically according to the International Federation of Gynecology and Obstetrics (FIGO) criteria. Only patients with disease stage ≥ IIB or IIA with one of the tumor dimensions > 4 cm were enrolled in the study. All patients underwent abdominal-pelvic contrast-enhanced MRI as part of the workup. Tumor size, local invasion, involved pelvic lymph nodes, and staging according to MRI criteria were evaluated. Clinical and MRI examinations were also performed after chemoradiotherapy. After chemoradiotherapy, 94% of the patients (17 of 18) were treated surgically. Results Eighteen patients aged 32–67 met the inclusion criteria and were enrolled: 10 stage IIB, 6 stage IIIA, 1 stage IIA and 1 stage IIIB, according to clinical staging. Using histopathological findings as a reference, MRI staging accuracy was 83.3%. The concordance of the clinical stage with MRI stage at the first examination was 56%. Parametrial involvement was assessed on pretreatment and post-treatment MRI, with post-treatment MRI compared with histology. There was no statistically significant difference between the pre- and post-therapy gynecological examinations (GYN) and the corresponding MRI assessments as to tumor size

  1. Paramagnetic Intermediates Generated by Radical S-Adenosylmethionine (SAM) Enzymes

    PubMed Central

    2015-01-01

    Conspectus A [4Fe–4S]+ cluster reduces a bound S-adenosylmethionine (SAM) molecule, cleaving it into methionine and a 5′-deoxyadenosyl radical (5′-dA•). This step initiates the varied chemistry catalyzed by each of the so-called radical SAM enzymes. The strongly oxidizing 5′-dA• is quenched by abstracting a H-atom from a target species. In some cases, this species is an exogenous molecule of substrate, for example, l-tyrosine in the [FeFe] hydrogenase maturase, HydG. In other cases, the target is a proteinaceous residue as in all the glycyl radical forming enzymes. The generation of this initial radical species and the subsequent chemistry involving downstream radical intermediates is meticulously controlled by the enzyme so as to prevent unwanted reactions. But the manner in which this control is exerted is unknown. Electron paramagnetic resonance (EPR) spectroscopy has proven to be a valuable tool used to gain insight into these mechanisms. In this Account, we summarize efforts to trap such radical intermediates in radical SAM enzymes and highlight four examples in which EPR spectroscopic results have shed significant light on the corresponding mechanism. For lysine 2,3-aminomutase, nearly each possible intermediate, from an analogue of the initial 5′-dA• to the product radical l-β-lysine, has been explored. A paramagnetic intermediate observed in biotin synthase is shown to involve an auxiliary [FeS] cluster whose bridging sulfide is a co-substrate for the final step in the biosynthesis of vitamin B7. In HydG, the l-tyrosine substrate is converted in unprecedented fashion to a 4-oxidobenzyl radical on the way to generating CO and CN– ligands for the [FeFe] cluster of hydrogenase. And finally, EPR has confirmed a mechanistic proposal for the antibiotic resistance protein Cfr, which methylates the unactivated sp2-hybridized C8-carbon of an adenosine base of 23S ribosomal RNA. These four systems provide just a brief survey of the ever-growing set

  2. Advances in the Understanding of ELM Suppression by Resonant Magnetic Perturbations (RMPs) in DIII-D and Implications for ITER

    SciTech Connect

    Nazikian, R.

    2014-09-01

    Experiments on DIII-D have expanding the operating window for RMP ELM suppression to higher q95 with dominant electron heating and fully non-inductive current drive relevant to advanced modes of ITER operation. Robust ELM suppression has also been obtained with a reduced coil set, mitigating the risk of coil failure in maintaining ELM suppression in ITER. These results significantly expand the operating space and reduce risk for obtaining RMP ELM suppression in ITER. Efforts have also been made to search for 3D cause of ELM suppression. No internal non-axisymmetric structure is detected at the top of the pedestal, indicating that the dominant effect of the RMP is to produce an n=0 transport modification of the profiles. Linear two fluid MHD simulations using M3D-C1 indicate resonant field penetration and significant magnetic stochasticity at the top of the pedestal, consistent with the absence of detectable 3D structure in that region. A profile database was developed to compare the scaling of the pedestal and global confinement with the applied 3D field strength in ELM suppressed and ELM mitigated plasmas. The EPED pedestal model accurately predicts the measured pedestal pressure at the threshold of ELM suppression, increasing confidence in theoretical projections to ITER pedestal conditions. Both the H-factor (H(sub)98y2) and thermal energy confinement time do not degrade substantially with applied RMP fields near the threshold of ELM suppression, enhancing confidence in the compatibility of ITER high performance operation with RMP ELM suppression.

  3. 3D Computational Modeling of Proteins Using Sparse Paramagnetic NMR Data.

    PubMed

    Pilla, Kala Bharath; Otting, Gottfried; Huber, Thomas

    2017-01-01

    Computational modeling of proteins using evolutionary or de novo approaches offers rapid structural characterization, but often suffers from low success rates in generating high quality models comparable to the accuracy of structures observed in X-ray crystallography or nuclear magnetic resonance (NMR) spectroscopy. A computational/experimental hybrid approach incorporating sparse experimental restraints in computational modeling algorithms drastically improves reliability and accuracy of 3D models. This chapter discusses the use of structural information obtained from various paramagnetic NMR measurements and demonstrates computational algorithms implementing pseudocontact shifts as restraints to determine the structure of proteins at atomic resolution.

  4. Influence of the electron spin resonance saturation on the power sensitivity of cryogenic sapphire resonators

    SciTech Connect

    Giordano, Vincent Grop, Serge; Bourgeois, Pierre-Yves; Kersalé, Yann; Rubiola, Enrico

    2014-08-07

    Here, we study the paramagnetic ions behavior in presence of a strong microwave electromagnetic field sustained inside a cryogenic sapphire whispering gallery mode resonator. The high frequency measurement resolution that can be now achieved by comparing two Cryogenic Sapphire Oscillators (CSOs) permit to observe clearly the non-linearity of the resonator power sensitivity. These observations that, in turn, allow us to optimize the CSO operation are well explained by the electron spin resonance saturation of the paramagnetic impurities contained in the sapphire crystal.

  5. Induced Orbital Paramagnetism and Paratropism in Closed-Shell Molecules

    NASA Astrophysics Data System (ADS)

    Pelloni, Stefano; Lazzeretti, Paolo; Zanasi, Riccardo

    2009-07-01

    Three-dimensional models of the quantum-mechanical current density induced by a uniform magnetic field in the electron cloud have been obtained for closed-shell systems BeH-, BH, and CH+, characterized by induced orbital paramagnetism, and in planar unsaturated hydrocarbons C4H4 and clamped C8H8, exhibiting π paramagnetism. It is shown that, even for these paramagnetic systems, the paramagnetic contributions to magnetic susceptibilities and nuclear magnetic shielding, customarily taken into account in perturbation theory approaches, can formally be eliminated via the procedure of continuous transformation of the origin of the current density-paramagnetic zero. The definition of magnetic response properties can therefore be recast as a sum of two formally "diamagnetic" terms for any molecule, including systems showing strong induced orbital paramagnetism. It is shown that the paramagnetism in the compounds studied arises from the nodal topology of the electronic wave function. In particular, paratropic vortices circulate about stagnation lines at the intersection of nodal surfaces of the highest-occupied zero-order molecular orbital and corresponding first-order orbital.

  6. Induced orbital paramagnetism and paratropism in closed-shell molecules.

    PubMed

    Pelloni, Stefano; Lazzeretti, Paolo; Zanasi, Riccardo

    2009-12-31

    Three-dimensional models of the quantum-mechanical current density induced by a uniform magnetic field in the electron cloud have been obtained for closed-shell systems BeH(-), BH, and CH(+), characterized by induced orbital paramagnetism, and in planar unsaturated hydrocarbons C(4)H(4) and clamped C(8)H(8), exhibiting pi paramagnetism. It is shown that, even for these paramagnetic systems, the paramagnetic contributions to magnetic susceptibilities and nuclear magnetic shielding, customarily taken into account in perturbation theory approaches, can formally be eliminated via the procedure of continuous transformation of the origin of the current density-paramagnetic zero. The definition of magnetic response properties can therefore be recast as a sum of two formally "diamagnetic" terms for any molecule, including systems showing strong induced orbital paramagnetism. It is shown that the paramagnetism in the compounds studied arises from the nodal topology of the electronic wave function. In particular, paratropic vortices circulate about stagnation lines at the intersection of nodal surfaces of the highest-occupied zero-order molecular orbital and corresponding first-order orbital.

  7. Ultrasensitive proteome analysis using paramagnetic bead technology

    PubMed Central

    Hughes, Christopher S; Foehr, Sophia; Garfield, David A; Furlong, Eileen E; Steinmetz, Lars M; Krijgsveld, Jeroen

    2014-01-01

    In order to obtain a systems-level understanding of a complex biological system, detailed proteome information is essential. Despite great progress in proteomics technologies, thorough interrogation of the proteome from quantity-limited biological samples is hampered by inefficiencies