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Sample records for paramagnetic resonance technique

  1. A new pulse width reduction technique for pulsed electron paramagnetic resonance spectroscopy.

    PubMed

    Ohba, Yasunori; Nakazawa, Shigeaki; Kazama, Shunji; Mizuta, Yukio

    2008-03-01

    We present a new technique for a microwave pulse modulator that generates a short microwave pulse of approximately 1ns for use in an electron paramagnetic resonance (EPR) spectrometer. A quadruple-frequency multiplier that generates a signal of 16-20GHz from an input of 4-5GHz was employed to reduce the rise and fall times of the pulse prepared by a PIN diode switch. We examined the transient response characteristics of a commercial frequency multiplier and found that the device can function as a multiplier for pulsed signal even though it was designed for continuous wave operation. We applied the technique to a Ku band pulsed EPR spectrometer and successfully observed a spin echo signal with a broad excitation bandwidth of approximately 1.6mT using 80 degrees pulses of 1.5ns. PMID:18248828

  2. 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.

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

    PubMed Central

    2015-01-01

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

  4. 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.

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

    PubMed

    Khalil, Ahmed A I; Morsy, Mohamed A

    2016-07-01

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

  6. Electron paramagnetic resonance of several lunar rock samples

    NASA Technical Reports Server (NTRS)

    Marov, P. N.; Dubrov, Y. N.; Yermakov, A. N.

    1974-01-01

    The results are presented of investigating lunar rock samples returned by the Luna 16 automatic station, using electron paramagnetic resonance (EPR). The EPR technique makes it possible to detect paramagnetic centers and investigate their nature, with high sensitivity. Regolith (finely dispersed material) and five particles from it, 0.3 mm in size, consisting mostly of olivine, were investigated with EPR.

  7. Novel multisample dielectric resonators for electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Golovina, Iryna S.; Kolesnik, Sergiy P.; Geifman, Ilia N.; Belous, Anatoliy G.

    2010-04-01

    We have developed and tested two types of novel dielectric resonators for simultaneous recording of electron paramagnetic resonance (EPR) spectra from two to four samples. The resonator of the first type contains two holes, and the other resonator contains four holes for introduction of the samples. Also, the resonator structure includes a pair of gradient coils. Dielectric resonators made of materials with high dielectric constant with low losses can be inserted into the standard EPR cavity or waveguide in the maximum microwave magnetic field. Gradient coils are located outside the cavity (or waveguide) so that their axes are parallel to the static magnetic field. Computer simulations were made to obtain microwave characteristics of the resonators such as resonant frequency, sizes, and distribution of the fields. Spacing of the point samples and optimum value of the magnetic-field gradient have been chosen correctly. The designed resonators can be applied in express analysis using EPR technique, for instance.

  8. Multifrequency pulsed electron paramagnetic resonance on metalloproteins.

    PubMed

    Lyubenova, Sevdalina; Maly, Thorsten; Zwicker, Klaus; Brandt, Ulrich; Ludwig, Bernd; Prisner, Thomas

    2010-02-16

    Metalloproteins often contain metal centers that are paramagnetic in some functional state of the protein; hence electron paramagnetic resonance (EPR) spectroscopy can be a powerful tool for studying protein structure and function. Dipolar spectroscopy allows the determination of the dipole-dipole interactions between metal centers in protein complexes, revealing the structural arrangement of different paramagnetic centers at distances of up to 8 nm. Hyperfine spectroscopy can be used to measure the interaction between an unpaired electron spin and nuclear spins within a distance of 0.8 nm; it therefore permits the characterization of the local structure of the paramagnetic center's ligand sphere with very high precision. In this Account, we review our laboratory's recent applications of both dipolar and hyperfine pulsed EPR methods to metalloproteins. We used pulsed dipolar relaxation methods to investigate the complex of cytochrome c and cytochrome c oxidase, a noncovalent protein-protein complex involved in mitochondrial electron-transfer reactions. Hyperfine sublevel correlation spectroscopy (HYSCORE) was used to study the ligand sphere of iron-sulfur clusters in complex I of the mitochondrial respiratory chain and substrate binding to the molybdenum enzyme polysulfide reductase. These examples demonstrate the potential of the two techniques; however, they also highlight the difficulties of data interpretation when several paramagnetic species with overlapping spectra are present in the protein. In such cases, further approaches and data are very useful to enhance the information content. Relaxation filtered hyperfine spectroscopy (REFINE) can be used to separate the individual components of overlapping paramagnetic species on the basis of differences in their longitudinal relaxation rates; it is applicable to any kind of pulsed hyperfine or dipolar spectroscopy. Here, we show that the spectra of the iron-sulfur clusters in complex I can be separated by this

  9. Study of metalloproteins using continuous wave electron paramagnetic resonance (EPR).

    PubMed

    Gambarelli, Serge; Maurel, Vincent

    2014-01-01

    Electron paramagnetic resonance (EPR) is an invaluable tool when studying systems with paramagnetic centers. It is a sensitive spectroscopic method, which can be used with dilute samples in aqueous buffer solutions. Here, we describe the basic procedure for recording an X-band EPR spectrum of a metalloprotein sample at low temperature. We also discuss basic optimization techniques to provide spectra with a high signal to noise ratio and minimum distortion.

  10. 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

    NASA Astrophysics Data System (ADS)

    Zweier, Jay L.; Kuppusamy, Periannan

    1988-08-01

    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 μ M 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.

  11. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-06-01

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

  13. Electron paramagnetic resonance at dislocations in germanium

    SciTech Connect

    Pakulis, E.J.

    1982-06-01

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

  14. Electron Paramagnetic Resonance Study of Pr

    SciTech Connect

    Tezuka, Keitaro; Hinatsu, Yukio

    2001-01-01

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

  15. 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.

  16. Using Electron Paramagnetic Resonance Spectroscopy To Facilitate Problem Solving in Pharmaceutical Research and Development.

    PubMed

    Mangion, Ian; Liu, Yizhou; Reibarkh, Mikhail; Williamson, R Thomas; Welch, Christopher J

    2016-08-19

    As new chemical methodologies driven by single-electron chemistry emerge, process and analytical chemists must develop approaches to rapidly solve problems in this nontraditional arena. Electron paramagnetic resonance spectroscopy has been long known as a preferred technique for the study of paramagnetic species. However, it is only recently finding application in contemporary pharmaceutical development, both to study reactions and to track the presence of undesired impurities. Several case studies are presented here to illustrate its utility in modern pharmaceutical development efforts.

  17. Phosphonated Trityl Probes for Concurrent in Vivo Tissue Oxygen and pH Monitoring Using Electron Paramagnetic Resonance-Based Techniques

    PubMed Central

    Dhimitruka, Ilirian; Bobko, Andrey A.; Eubank, Timothy D.; Komarov, Denis A.; Khramtsov, Valery V.

    2014-01-01

    Previously we proposed the concept of dual function pH and oxygen paramagnetic probes based on the incorporation of ionizable groups into the structure of persistent triarylmethyl radicals, TAMs (J. Am. Chem. Soc. 2007, 129, 7240–7241). In this paper, we synthesized an asymmetric monophosphonated TAM probe with the simplest doublet hfs pattern ideally suited for dual function electron paramagnetic resonance (EPR)-based applications. An extraordinary low line width of the synthesized deuterated derivative, p1TAM-D (ΔHpp ≤ 50 mG, Lorentz line width, ≤20 mG) results in high sensitivity to pO2 due to oxygen-induced line broadening (ΔLW/ΔpO2 ≈ 0.5 mG/mmHg or ≈400 mG/mM); accuracy of pO2 measurement, ≈1 mmHg). The presence of a phosphono group in the p1TAM-D structure provides pH sensitivity to its EPR spectra in the physiological range of pH from 5.9 to 8.2 with the ratio of signal intensities of protonated and deprotonated states being a reliable pH marker (accuracy of pH measurements, ± 0.05). The independent character of pH and [O2] effects on the EPR spectra of p1TAM-D provides dual functionality to this probe. The L-band EPR studies performed in breast tumor-bearing mice show a significant difference in extracellular pH and pO2 between tumor and normal mammary gland tissues, as well as the effect of animal breathing with 100% O2 on tissue oxygenation. The developed dual function phosphonated p1TAM-D probe provides a unique tool for in vivo concurrent tissue oxygen and pH monitoring. PMID:23517077

  18. Phosphonated trityl probes for concurrent in vivo tissue oxygen and pH monitoring using electron paramagnetic resonance-based techniques.

    PubMed

    Dhimitruka, Ilirian; Bobko, Andrey A; Eubank, Timothy D; Komarov, Denis A; Khramtsov, Valery V

    2013-04-17

    Previously we proposed the concept of dual function pH and oxygen paramagnetic probes based on the incorporation of ionizable groups into the structure of persistent triarylmethyl radicals, TAMs (J. Am. Chem. Soc.2007, 129, 7240-7241). In this paper, we synthesized an asymmetric monophosphonated TAM probe with the simplest doublet hfs pattern ideally suited for dual function electron paramagnetic resonance (EPR)-based applications. An extraordinary low line width of the synthesized deuterated derivative, p1TAM-D (ΔHpp ≤ 50 mG, Lorentz line width, ≤20 mG) results in high sensitivity to pO2 due to oxygen-induced line broadening (ΔLW/ΔpO2 ≈ 0.5 mG/mmHg or ≈400 mG/mM); accuracy of pO2 measurement, ≈1 mmHg). The presence of a phosphono group in the p1TAM-D structure provides pH sensitivity to its EPR spectra in the physiological range of pH from 5.9 to 8.2 with the ratio of signal intensities of protonated and deprotonated states being a reliable pH marker (accuracy of pH measurements, ± 0.05). The independent character of pH and [O2] effects on the EPR spectra of p1TAM-D provides dual functionality to this probe. The L-band EPR studies performed in breast tumor-bearing mice show a significant difference in extracellular pH and pO2 between tumor and normal mammary gland tissues, as well as the effect of animal breathing with 100% O2 on tissue oxygenation. The developed dual function phosphonated p1TAM-D probe provides a unique tool for in vivo concurrent tissue oxygen and pH monitoring.

  19. 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.

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

    ERIC Educational Resources Information Center

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

    2013-01-01

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

  1. 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.

  2. Reconstruction of images from radiofrequency electron paramagnetic resonance spectra.

    PubMed

    Smith, C M; Stevens, A D

    1994-12-01

    This paper discusses methods for obtaining image reconstructions from electron paramagnetic resonance (EPR) spectra which constitute object projections. An automatic baselining technique is described which treats each spectrum consistently; rotating the non-horizontal baselines which are caused by stray magnetic effects onto the horizontal axis. The convolved backprojection method is described for both two- and three-dimensional reconstruction and the effect of cut-off frequency on the reconstruction is illustrated. A slower, indirect, iterative method, which does a non-linear fit to the projection data, is shown to give a far smoother reconstructed image when the method of maximum entropy is used to determine the value of the final residual sum of squares. Although this requires more computing time than the convolved backprojection method, it is more flexible and overcomes the problem of numerical instability encountered in deconvolution. Images from phantom samples in vitro are discussed. The spectral data for these have been accumulated quickly and have a low signal-to-noise ratio. The results show that as few as 16 spectra can still be processed to give an image. Artifacts in the image due to a small number of projections using the convolved backprojection reconstruction method can be removed by applying a threshold, i.e. only plotting contours higher than a given value. These artifacts are not present in an image which has been reconstructed by the maximum entropy technique. At present these techniques are being applied directly to in vivo studies.

  3. 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.

  4. 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.

  5. Single Acquisition Quantitative Single Point Electron Paramagnetic Resonance Imaging

    PubMed Central

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

    2013-01-01

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

  6. Electron paramagnetic resonance of nitroxide-doped magnetic fluids

    NASA Astrophysics Data System (ADS)

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

    2002-11-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2007-11-01

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

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

    PubMed

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

    2007-11-01

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

  9. A new electron paramagnetic resonance method to identify irradiated soybean.

    PubMed

    Sanyal, Bhaskar; Sharma, Arun

    2009-10-01

    Low-dose gamma irradiation causes minimal changes in food matrix making identification of radiation-processed foods a challenging task. In the present study, soybean samples were irradiated with commercially permitted gamma radiation dose in the 0.25 to 1.0 kGy range for insect disinfestations of food. Immediately after irradiation electron paramagnetic resonance (EPR) spectrum of the skin part of soybean showed a triplet signal (g = 2.0046, hyperfine coupling constant hfcc = 3.0 mT) superimposed on naturally present singlet. These signals were characterized as cellulose and phenoxyl radicals using EPR spectrum simulation technique. Kernel part of the samples exhibited a short-lived, radiation-induced singlet of carbon-centered radical superimposed on naturally present sextet signal of Mn2+. A detailed study on relaxation and thermal behavior of induced radicals in skin part was carried out using EPR spectroscopy. These findings revealed that progressive saturation and thermal characteristics of the induced radicals may be the most suitable parameters to distinguish soybean subjected to radiation dose as low as 0.25 kGy from thermally treated and nonirradiated samples, even after a prolonged period of storage.

  10. 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

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

    PubMed

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

    2015-10-23

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

  12. 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

  13. 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

  14. The continuous wave electron paramagnetic resonance experiment revisited

    NASA Astrophysics Data System (ADS)

    Kälin, Moritz; Gromov, Igor; Schweiger, Arthur

    2003-02-01

    When the modulation frequency used in continuous wave electron paramagnetic resonance (cw EPR) spectroscopy exceeds the linewidth, modulation sidebands appear in the spectrum. It is shown theoretically and experimentally that these sidebands are actually multiple photon transitions, σ ++ k×π, where one microwave (mw) σ + photon is absorbed from the mw radiation field and an arbitrary number k of radio frequency (rf) π photons are absorbed from or emitted to the modulation rf field. Furthermore, it is demonstrated that both the derivative shape of the lines in standard cw EPR spectra and the distortions due to overmodulation are caused by the unresolved sideband pattern of these lines. The single-photon transition does not even give a contribution to the first-harmonic cw EPR signal. Multiple photon transitions are described semiclassically in a toggling frame and their existence is proven using second quantization. With the toggling frame approach and perturbation theory an effective Hamiltonian for an arbitrary sideband transition is derived. Based on the effective Hamiltonians an expression for the steady-state density operator in the singly rotating frame is derived, completely describing all sidebands in all modulation frequency harmonics of the cw EPR signal. The relative intensities of the sidebands are found to depend in a very sensitive way on the actual rf amplitude and the saturation of single sidebands is shown to depend strongly on the effective field amplitude of the multiple photon transitions. By comparison with the analogous solutions for frequency-modulation EPR it is shown that the field-modulation and the frequency-modulation technique are not equivalent. The experimental data fully verify the theoretical predictions with respect to intensities and lineshapes.

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

    PubMed

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

    2015-01-01

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

  16. Anomaly of the rotational nonergodicity parameter of glass formers probed by high field electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Bercu, V.; Martinelli, M.; Massa, C. A.; Pardi, L. A.; Rössler, E. A.; Leporini, D.

    2008-08-01

    Exploiting the high angular resolution of high field electron paramagnetic resonance measured at 95, 190, and 285 GHz we determine the rotational nonergodicity parameter of different probe molecules in the glass former o-terphenyl and polybutadiene in a model-independent way. Our results clearly show a characteristic change in the temperature of the nonergodicity parameter proving a rather sharp dynamic crossover in both systems, in contrast to previous results from other techniques.

  17. 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.

  18. 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.

  19. 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.

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

    NASA Astrophysics Data System (ADS)

    Redler, Gage

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

  1. Free-electron laser-based pulsed electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Takahashi, Susumu; Sherwin, Mark S.; Ramian, Gerald; Brunel, Louis-Claude; van Tol, Johan

    2008-03-01

    High-power pulsed electron paramagnetic resonance (EPR) is extremely useful to study the ultrafast dynamics of spins. At present, most high-power pulsed EPR spectrometers operate near the X-band frequency of 9.5 GHz with kW-level power. A trend in the evolution of next generation pulsed EPR is for higher magnetic field and frequency, both for finer spectral and time resolution and because motional averaging becomes negligible. Since the linewidth of resonances studied by pulsed EPR tends to be extremely narrow, the source radiation also has to be stable and have narrow bandwidth. High-power pulsed EPR, using few-ns pulses to rapidly manipulate spins for spin-echo and related experiments, has been demonstrated at 95 GHz using kW- power Klystron-based sources. A bottleneck for higher frequency pulsed EPR spectroscopy is a lack of sources with high power and narrow bandwidth. The University of California Santa Barbara (UCSB) free-electron lasers (FEL) are potential sources for high-power pulsed EPR because they generate kW of power tunable from 120 GHz to 4.7 THz. We present the current status of the UCSB FEL-based 240 GHz pulsed EPR spectrometer.

  2. 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

  3. 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

  4. 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

    2008-10-01

    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.

  5. 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

  6. 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.

  7. 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:...

  8. 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).

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

    PubMed Central

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

    2013-01-01

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

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

    PubMed

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

    2013-02-01

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

  11. Electron paramagnetic resonance: a powerful tool to support magnetic resonance imaging research.

    PubMed

    Danhier, Pierre; Gallez, Bernard

    2015-01-01

    The purpose of this paper is to describe some of the areas where electron paramagnetic resonance (EPR) has provided unique information to MRI developments. The field of application mainly encompasses the EPR characterization of MRI paramagnetic contrast agents (gadolinium and manganese chelates, nitroxides) and superparamagnetic agents (iron oxide particles). The combined use of MRI and EPR has also been used to qualify or disqualify sources of contrast in MRI. Illustrative examples are presented with attempts to qualify oxygen sensitive contrast (i.e. T1 - and T2 *-based methods), redox status or melanin content in tissues. Other areas are likely to benefit from the combined EPR/MRI approach, namely cell tracking studies. Finally, the combination of EPR and MRI studies on the same models provides invaluable data regarding tissue oxygenation, hemodynamics and energetics. Our description will be illustrative rather than exhaustive to give to the readers a flavour of 'what EPR can do for MRI'.

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

    PubMed

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

    2015-09-28

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

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

    PubMed

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

    2015-09-28

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

  14. Towards Human Oxygen Images with Electron Paramagnetic Resonance Imaging.

    PubMed

    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 (~1 mm) and in pO2 (1-3 mmHg). 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 20 dB 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, and require 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 spin

  15. 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

  16. Electron paramagnetic resonance in human fingernails: the sponge model implication.

    PubMed

    Reyes, R A; Romanyukha, A; Trompier, F; Mitchell, C A; Clairand, I; De, T; Benevides, L A; Swartz, H M

    2008-11-01

    The most significant problem of electron paramagnetic resonance (EPR) fingernail dosimetry is the presence of two signals of non-radiation origin that overlap the radiation-induced signal (RIS), making it almost impossible to perform dose measurements below 5 Gy. Historically, these two non-radiation components were named mechanically induced signal (MIS) and background signal (BKS). In order to investigate them in detail, three different methods of MIS and BKS mutual isolation have been developed and implemented. After applying these methods, it is shown here that fingernail tissue, after cut, can be modeled as a deformed sponge, where the MIS and BKS are associated with the stress from elastic and plastic deformations, respectively. A sponge has a unique mechanism of mechanical stress absorption, which is necessary for fingernails in order to perform its everyday function of protecting the fingertips from hits and trauma. Like a sponge, fingernails are also known to be an effective water absorber. When a sponge is saturated with water, it tends to restore to its original shape, and when it loses water, it becomes deformed again. The same happens to fingernail tissue. It is proposed that the MIS and BKS signals of mechanical origin be named MIS1 and MIS2 for MISs 1 and 2, respectively. Our suggested interpretation of the mechanical deformation in fingernails gives also a way to distinguish between the MIS and RIS. The results obtained show that the MIS in irradiated fingernails can be almost completely eliminated without a significant change to the RIS by soaking the sample for 10 min in water. The proposed method to measure porosity (the fraction of void space in spongy material) of the fingernails gave values of 0.46-0.48 for three of the studied samples. Existing results of fingernail dosimetry have been obtained on mechanically stressed samples and are not related to the "real" in vivo dosimetric properties of fingernails. A preliminary study of these

  17. Assessment of tumor oxygenation by electron paramagnetic resonance: principles and applications.

    PubMed

    Gallez, Bernard; Baudelet, Christine; Jordan, Bénédicte F

    2004-08-01

    This review paper attempts to provide an overview of the principles and techniques that are often termed electron paramagnetic resonance (EPR) oximetry. The paper discusses the potential of such methods and illustrates they have been successfully applied to measure oxygen tension, an essential parameter of the tumor microenvironment. To help the reader understand the motivation for carrying out these measurements, the importance of tumor hypoxia is first discussed: the basic issues of why a tumor is hypoxic, why these hypoxic microenvironments promote processes driving malignant progression and why hypoxia dramatically influences the response of tumors to cytotoxic treatments will be explained. The different methods that have been used to estimate the oxygenation in tumors will be reviewed. To introduce the basics of EPR oximetry, the specificity of in vivo EPR will be discussed by comparing this technique with NMR and MRI. The different types of paramagnetic oxygen sensors will be presented, as well as the methods for recording the information (EPR spectroscopy, EPR imaging, dynamic nuclear polarization). Several applications of EPR for characterizing tumor oxygenation will be illustrated, with a special emphasis on pharmacological interventions that modulate the tumor microenvironment. Finally, the challenges for transposing the method into the clinic will also be discussed. PMID:15366026

  18. 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.

  19. Stationary and high-frequency pulsed electron paramagnetic resonance of a calcified atherosclerotic plaque

    NASA Astrophysics Data System (ADS)

    Abdul'Yanov, V. A.; Galiullina, L. F.; Galyavich, A. S.; Izotov, V. G.; Mamin, G. V.; Orlinskii, S. B.; Rodionov, A. A.; Salakhov, M. Kh.; Silkin, N. I.; Sitdikova, L. M.; Khairullin, R. N.; Chelyshev, Yu. A.

    2008-09-01

    New possibilities of applying high-frequency electron paramagnetic resonance in medicine are demonstrated on an example of the investigation of a calcified atherosclerotic plaque. After the irradiation of the atherosclerotic plaque by x rays, a new type of paramagnetic centers—organomineral radicals—is detected. The spectral and relaxation characteristics of these radicals depend on the calcification degree of the atherosclerotic plaque and can be used for diagnostics.

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

    NASA Astrophysics Data System (ADS)

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

    2008-09-01

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

  1. Fe(3+) ions in alkali lead tetraborate glasses--an electron paramagnetic resonance and optical study.

    PubMed

    Chakradhar, R P Sreekanth; Sivaramaiah, G; Rao, J Lakshmana; Gopal, N O

    2005-11-01

    Glass systems of composition 90R(2)B(4)O(7)+9PbO+1Fe(2)O(3) (R=Li, Na and K) and 90Li(2)B(4)O(7)+(10-x)PbO+xFe(2)O(3) (x=0.5, 1, 3, 4, 5, 7 and 9 mol %) have been investigated by means of electron paramagnetic resonance (EPR) and optical absorption techniques. The EPR spectra exhibit three resonance signals at g approximately 6.0, 4.2 and 2.0. The resonances at g approximately 6.0 and 4.2 are attributed to Fe(3+) ions in rhombic and axial symmetry sites, respectively. The g approximately 2.0 resonance signal is due to two or more Fe(3+) ions coupled together with dipolar interaction. The EPR spectra of 1 mol % of Fe(2)O(3) doped in lithium lead tetraborate glass samples have been studied at different temperatures (123-433 K). The intensity of g approximately 4.2 resonance signal decreases and the intensity of g approximately 2.0 resonance signal increases with the increase of temperature. The line widths are found to be independent of temperature. The EPR spectra exhibit a marked concentration dependence on iron content. A decrease in intensity for the resonance signal at g approximately 4.2 with increase in iron content for more than 4 mol % has been observed in lithium lead tetraborate glass samples and this has been attributed to the formation of Fe(3+) ion clusters in the glass samples. The paramagnetic susceptibility (chi) is calculated from the EPR data at various temperatures and the Curie constant (C) has been evaluated from 1/chi versus T graph. The optical absorption spectrum of Fe(3+) ions in lithium lead tetraborate glasses exhibits three bands characteristic of Fe(3+) ions in an octahedral symmetry. The crystal field parameter D(q) and the Racah interelectronic repulsion parameters B and C have also been evaluated. The value of interelectronic repulsion parameter B (825 cm(-1)) obtained in the present work suggests that the bonding is moderately covalent.

  2. 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

  3. Application of electron paramagnetic resonance (EPR) spectroscopy and imaging in drug delivery research - chances and challenges.

    PubMed

    Kempe, Sabine; Metz, Hendrik; Mäder, Karsten

    2010-01-01

    Electron Paramagnetic Resonance (EPR) spectroscopy is a powerful technique to study chemical species with unpaired electrons. Since its discovery in 1944, it has been widely used in a number of research fields such as physics, chemistry, biology and material and food science. This review is focused on its application in drug delivery research. EPR permits the direct measurement of microviscosity and micropolarity inside drug delivery systems (DDS), the detection of microacidity, phase transitions and the characterization of colloidal drug carriers. Additional information about the spatial distribution can be obtained by EPR imaging. The chances and also the challenges of in vitro and in vivo EPR spectroscopy and imaging in the field of drug delivery are discussed.

  4. 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.

  5. Reduction of artifact of metallic implant in magnetic resonance imaging by combining paramagnetic and diamagnetic materials

    NASA Astrophysics Data System (ADS)

    Gao, Yanhui; Muramatsu, Kazuhiro; Kushibe, Atsumichi; Yamazaki, Keita; Chiba, Akihiko; Yamamoto, Toru

    2010-05-01

    The method of coating the metallic implant made of paramagnetic materials with diamagnetic materials has been proposed to reduce the magnetic disturbance of metallic implants which causes artifact in magnetic resonance imaging. The optimal thicknesses of the diamagnetic coatings have been obtained for a straight cylindrical hip joint and an aneurysm clip by using the magnetic field analysis of the finite element method (FEM). Whereas in the manufacturing, with respect to the mechanical force of the diamagnetic material, etc., the new structure of dual-material model with diamagnetic material inside and paramagnetic material outside is considered better. In this paper, first the effectiveness of the structure of the dual-material model with actual diamagnetic material inside and paramagnetic material outside is investigated by using the FEM. Then optimal thicknesses of paramagnetic coating of two models are obtained. Finally the effectiveness of the dual-material model is verified by the experiment.

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

    PubMed

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

    2015-06-01

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

  7. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2014-10-01

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

  9. 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.

  10. 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

  11. 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.

  12. 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.

  13. 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.

  14. Electron paramagnetic resonance oxygen mapping (EPROM): direct visualization of oxygen concentration in tissue.

    PubMed

    Velan, S S; Spencer, R G; Zweier, J L; Kuppusamy, P

    2000-06-01

    Tissue oxygen content is a central parameter in physiology but is difficult to measure. We report a novel procedure for spatial mapping of oxygen by electron paramagnetic resonance (EPR) utilizing a spectral-spatial imaging data set, in which an EPR spectrum is obtained from each image volume element. From this data set, spatial maps corresponding to local spin density and maximum EPR spectral line amplitude are generated. A map of local EPR spectral linewidth is then computed. Because linewidth directly correlates with oxygen concentration, the linewidth image provides a map of oxygenation. This method avoids a difficulty inherent in other oxygen content mapping techniques using EPR, that is, the unwanted influence of local spin probe density on the image. We provide simulation results and data from phantom studies demonstrating the validity of this method. We then apply the method to map oxygen content in rat tail tissue and vasculature. This method provides a new, widely applicable, approach to direct visualization of oxygen concentration in living tissue. Magn Reson Med 43:804-809, 2000.

  15. Robustness assessment of 1-d electron paramagnetic resonance for improved magnetic nanoparticle reconstructions.

    PubMed

    Coene, Annelies; Crevecoeur, Guillaume; Dupre, Luc

    2015-06-01

    Electron paramagnetic resonance (EPR) is a sensitive measurement technique which can be used to recover the 1-D spatial distribution of magnetic nanoparticles (MNP) noninvasively. This can be achieved by solving an inverse problem that requires a numerical model for interpreting the EPR measurement data. This paper assesses the robustness of this technique by including different types of errors such as setup errors, measurement errors, and sample positioning errors in the numerical model. The impact of each error is estimated for different spatial MNP distributions. Additionally, our error models are validated by comparing the simulated impact of errors to the impact on lab EPR measurements. Furthermore, we improve the solution of the inverse problem by introducing a combination of truncated singular value decomposition and nonnegative least squares. This combination enables to recover both smooth and discontinuous MNP distributions. From this analysis, conclusions are drawn to improve MNP reconstructions with EPR and to state requirements for using EPR as a 2-D and 3-D imaging technique for MNP. PMID:25667347

  16. 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.

  17. 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

  18. [Electron paramagnetic resonance study of blood of anemic patients with urological cancer].

    PubMed

    Ibragimova, M I; Chushnikov, V N; Moiseev, V N; Petukhov, V Iu; Zheglov, E P; Cherepnev, G V

    2013-01-01

    Changes in Fe(3+)-transferrin (Fe(3+)-Tf) and Cu(2+)-ceruloplasmin (Cu(2+)-Cp) concentrations in venous blood sampled from anemic patients with urinary bladder and kidney cancer in I-IV stages were investigated using electron paramagnetic resonance spectroscopy. It was established that at malignancy-associated anemia the paramagnetic Fe3+ ion concentration in transferrin is below a norm, while in anemic non-oncology patients the Tf iron saturation is normal. Moreover, in patients with malignancy-associated anemia the Cu(2+)-Cp average value is nearly twice as large as that for healthy volunteers (confidence probability P). It was shown that simultaneous EPR measuring of paramagnetic centers (such as Fe(3+)-Tf and Cu(2+)-Cp) in blood of anemic patients can be used as a biomarker for urological cancer diagnosis even at early stages of the growth of a malignant tumor.

  19. 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

  20. Site directed spin labelling and pulsed dipolar electron paramagnetic resonance (double electron electron resonance) of force activation in muscle

    NASA Astrophysics Data System (ADS)

    Fajer, Piotr G.

    2005-05-01

    The recent development of site specific spin labelling and advances in pulsed electron paramagnetic resonance (EPR) have established spin labelling as a viable structural biology technique. Specific protein sites or whole domains can be selectively targeted for spin labelling by cysteine mutagenesis. The secondary structure of the proteins is determined from the trends in EPR signals of labels attached to consecutive residues. Solvent accessibility or label mobility display periodicities along the labelled polypeptide chain that are characteristic of β-strands (periodicity of 2 residues) or α-helices (3.6 residues). Low-resolution 3D structure of proteins is determined from the distance restraints. Two spin labels placed within 60-70 Å of each other create a local dipolar field experienced by the other spin labels. The strength of this field is related to the interspin distance, {\\propto } r^{-3 } . The dipolar field can be measured by the broadening of the EPR lines for the short distances (8-20 Å) or for the longer distances (17-70 Å) by the pulsed EPR methods, double electron-electron resonance (DEER) and double quantum coherence (DQC). A brief review of the methodology and its applications to the multisubunit muscle protein troponin is presented below.

  1. A novel probe head for high-field, high-frequency electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Annino, G.; Cassettari, M.; Longo, I.; Martinelli, M.; Van Bentum, P. J. M.; Van der Horst, E.

    1999-03-01

    A probe head especially useful for electron paramagnetic resonance (EPR) spectrometers working at high field—high frequency is presented. The probe head is based on the whispering gallery mode dielectric resonators that proved very effective in the ultrahigh frequency range. The excitation network uses a properly shaped dielectric waveguide sharing its external field pattern with the field of the resonators. Very simple resonators made with polyethylene in both single and doubly stacked disk configurations are used. The experimental characterization by a submillimeter network analyzer shows for the resonances studied in a wide range of frequencies up to ≈400 GHz high loaded merit factor QL values and good coupling factors. Resonators also maintain their general characteristics when large quantities of low loss samples for EPR measurements are properly inserted. Preliminary EPR spectra of diphenylpicrylhyldrazyl at 7 and 10 T obtained with the novel apparatus are finally presented.

  2. Biodosimetry: chromosome aberration in lymphocytes and electron paramagnetic resonance in tooth enamel from atomic bomb survivors.

    PubMed

    Nakamura, N; Miyazawa, C; Akiyama, M; Sawada, S; Awa, A A

    1996-01-01

    One hundred enamel samples isolated from extracted teeth donated by atomic bomb survivors were subjected to free radical measurement by means of electron paramagnetic resonance (ESR). Results comparing ESR with the chromosome aberration frequency in lymphocytes of the tooth donors, and with the physically estimated DS86 dose suggested that ESR data correlated more closely with chromosome data than with the estimated DS86 doses, probably because DS86 may depend on erroneous memory in some cases.

  3. Electron Paramagnetic Resonance Resolves Effects of Oxidative Stress on Muscle Proteins

    PubMed Central

    Moen, Rebecca J.; Klein, Jennifer C.; Thomas, David D.

    2014-01-01

    We have used site-directed spin labeling and electron paramagnetic resonance (EPR) to explore the effects of oxidation on muscle function, with particular focus on the actin-myosin interaction. EPR measurements show that aging or oxidative modification cause a decrease in the fraction of myosins in the strong-binding state, which can be traced to the actin-binding cleft of the myosin catalytic domain. PMID:24188980

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

    PubMed Central

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

    2009-01-01

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

  5. Absolute Oxygen R1e Imaging In Vivo with Pulse Electron Paramagnetic Resonance

    PubMed Central

    Epel, Boris; Bowman, Michael K.; Mailer, Colin; Halpern, Howard J.

    2015-01-01

    Purpose Tissue oxygen (O2) levels are among the most important and most quantifiable stimuli to which cells and tissues respond through inducible signaling pathways. Tumor O2 levels are major determinants of the response to cancer therapy. Developing more accurate measurements and images of tissue O2 partial pressure (pO2), assumes enormous practical, biological, and medical importance. Methods We present a fundamentally new technique to image pO2 in tumors and tissues with pulse electron paramagnetic resonance (EPR) imaging enabled by an injected, nontoxic, triaryl methyl (trityl) spin probe whose unpaired electron’s slow relaxation rates report the tissue pO2. Heretofore, virtually all in vivo EPR O2 imaging measures pO2 with the transverse electron spin relaxation rate, R2e, which is susceptible to the self-relaxation confounding O2 sensitivity. Results We found that the trityl electron longitudinal relaxation rate, R1e, is an order of magnitude less sensitive to confounding self-relaxation. R1e imaging has greater accuracy and brings EPR O2 images to an absolute pO2 image, within uncertainties. Conclusion R1e imaging more accurately determines oxygenation of cancer and normal tissue in animal models than has been available. It will enable enhanced, rapid, noninvasive O2 images for understanding oxygen biology and the relationship of oxygenation patterns to therapy outcome in living animal systems. PMID:24006331

  6. 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.

  7. 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.

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

    PubMed

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

    2015-12-01

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

  9. Analyzing Xanthine Dehydrogenase Iron-Sulfur Clusters Using Electron Paramagnetic Resonance Spectroscopy

    SciTech Connect

    Hodson, R.

    2004-02-05

    Xanthine dehydrogenase is a metalloenzyme that is present in a variety of eukaryotic and prokaryotic organisms. The oxidation of the xanthine occurs at the molybdenum site, and the catalytic cycle is completed by electron transfer to the iron-sulfur (Fe/S) clusters and finally the flavin, where they are accepted by nicotinamide adenine dinucleotide (NAD). Since the site giving rise to the Fe/S I electron paramagnetic resonance (EPR) signal is thought to be the initial recipient of the electrons from the Mo, we wish to understand which EPR signal is associated with which Fe/S cluster in the structure in order to develop an understanding of the electron flow within the molecule. Samples of xanthine dehydrogenase wild-type and mutant forms were analyzed with EPR spectroscopy techniques at low and high temperatures. The results showed an altered Fe/S I signal along with an unaltered Fe/S II signal. The converted Cysteine, in the mutant, did affect the Fe/S cluster immediately adjacent to it. Therefore, the Fe/S I signal arises from the Fe/S cluster closest to the Mo and immediately adjacent to the mutated amino acid, and the Fe/S II signal must arise from the more distant Fe/S cluster.

  10. Electron paramagnetic resonance of natural and gamma-irradiated alunite and kaolin mineral powders

    NASA Astrophysics Data System (ADS)

    Koksal, F.; Koseoglu, R.; Saka, I.; Basaran, E.; Sener, F.

    2004-06-01

    Natural alunite and kaolin minerals obtained from West Anatolia were investigated by electron paramagnetic resonance (EPR) in natural and gamma-irradiated states at room temperature and at 113 K. The paramagnetic centres at ambient temperature in natural alunite were attributed to the (C) over dot H 2OH, (C) over dot O-3(-), (S) over dot O-2(-), (C) over dot O-2(-) and [AlO4 ](0) radicals. In natural kaolin, the paramagnetic centres were attributed to the (C) over dot O-3(-), (S) over dot O-2(-) (C) over dot O-2(-) and [AlO4](0) radicals. The gamma-irradiation does not produce any detectable effects on these radicals. At 113 K, the lines for (C) over dot H2OH could not be observed well, probably due to the anisotropic behaviour of the hyperfine interaction of the methylene protons, but the lines for [AlO4](0) centres were found to be perfectly observable at above 20 mW microwave power in both alunite and kaolin powders before and after gamma-irradiation. The EPR parameters of the observed paramagnetic centres were reported.

  11. 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. PMID:22996555

  12. 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.

  13. Field-stepped direct detection electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    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 155 G 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 6200 G have been demonstrated. A linear scan frequency of 5.12 kHz was generated with the scan driver described previously. The field was stepped at intervals of 0.01 to 1 G, depending on the linewidths in the spectra. At each field data for triangular scans with widths up to 11.5 G 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

  14. 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

  15. 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

  16. Lithium phthalocyanine: a probe for electron paramagnetic resonance oximetry in viable biological systems.

    PubMed Central

    Liu, K J; Gast, P; Moussavi, M; Norby, S W; Vahidi, N; Walczak, T; Wu, M; Swartz, H M

    1993-01-01

    Lithium phthalocyanine (LiPc) is a prototype of another generation of synthetic, metallic-organic, paramagnetic crystallites that appear very useful for in vitro and in vivo electron paramagnetic resonance oximetry. The peak-to-peak line width of the electron paramagnetic resonance spectrum of LiPc is a linear function of the partial pressure of oxygen (pO2); this linear relation is independent of the medium surrounding the LiPc. It has an extremely exchange-narrowed spectrum (peak-to-peak line width = 14 mG in the absence of O2). Physicochemically LiPc is very stable; its response to pO2 does not change with conditions and environments (e.g., pH, temperature, redox conditions) likely to occur in viable biological systems. These characteristics provide the sensitivity, accuracy, and range to measure physiologically and pathologically pertinent O2 tensions (0.1-50 mmHg; 1 mmHg = 133 Pa). The application of LiPc in biological systems is demonstrated in measurements of pO2 in vivo in the heart, brain, and kidney of rats. PMID:8390665

  17. 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

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

    PubMed

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

    2015-01-01

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

  19. 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).

  20. Temperature dependence of Q-band electron paramagnetic resonance spectra of nitrosyl heme proteins.

    PubMed Central

    Flores, M; Wajnberg, E; Bemski, G

    1997-01-01

    The Q-band (35 GHz) electron paramagnetic resonance (EPR) spectra of nitrosyl hemoglobin (HbNO) and nitrosyl myoglobin (MbNO) were studied as a function of temperature between 19 K and 200 K. The spectra of both heme proteins show two classes of variations as a function of temperature. The first one has previously been associated with the existence of two paramagnetic species, one with rhombic and the other with axial symmetry. The second one manifests itself in changes in the g-factors and linewidths of each species. These changes are correlated with the conformational substates model and associate the variations of g-values with changes in the angle of the N(his)-Fe-N(NO) bond in the rhombic species and with changes in the distance between Fe and N of the proximal (F8) histidine in the axial species. PMID:9414233

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

    NASA Astrophysics Data System (ADS)

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

    2014-08-01

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

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

    SciTech Connect

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

    2014-08-01

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

  3. Lipid chain dynamics in stratum corneum studied by spin label electron paramagnetic resonance.

    PubMed

    Alonso, A; Meirelles, N C; Tabak, M

    2000-02-01

    The lipid chain motions in stratum corneum (SC) membranes have been studied through electron paramagnetic resonance (EPR) spectroscopy of stearic acid spin-labeled at the 5th, 12th and 16th carbon atom positions of the acyl chain. Lipids have been extracted from SC with a series of chloroform/methanol mixtures, in order to compare the molecular dynamics and the thermotropic behavior in intact SC, lipid-depleted SC (containing covalently bound lipids of the corneocyte envelope) and dispersion of extracted SC lipids. The segmental motion of 5- and 12-doxylstearic acid (5- and 12-DSA) and the rotational correlation time of 16-doxylstearic acid (16-DSA) showed that the envelope lipids are more rigid and the extracted lipids are more fluid than the lipids of the intact SC over the range of temperature measured. The lower fluidity observed for the corneocyte envelope, that may be caused mainly due to lipid-protein interactions, suggests a major contribution of this lipid domain to the barrier function of SC. Changes in the activation energy for reorientational diffusion of the 16-DSA spin label showed apparent phase transitions around 54 degrees C, for the three SC samples. Some lipid reorganization may occur in SC above 54 degrees C, in agreement with results reported from studies with several other techniques. This reorganization is sensitive to the presence of the extractable intercellular lipids, being different in the lipid-depleted sample as compared to native SC and lipid dispersion. The results contribute to the understanding of alkyl chain packing and mobility in the SC membranes, which are involved in the mechanisms that control the permeability of different compounds through skin, suggesting an important involvement of the envelope in the skin barrier.

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

    PubMed

    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 24 h 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. 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

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

    PubMed Central

    Squier, T C; Thomas, D D

    1986-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  8. Electron paramagnetic resonance and low-field microwave absorption in the manganese-gallium oxide

    NASA Astrophysics Data System (ADS)

    Montiel, H.; Alvarez, G.; Conde-Gallardo, A.; Zamorano, R.

    2015-07-01

    Microwave absorption measurements in MnGa2O4 powders are carried out at X-band (8.8-9.8 GHz) in 92-296 K temperature range. For all temperatures, the electron paramagnetic resonance (EPR) spectra show a single broad line due to Mn2+ ions. Temperature dependence of the EPR parameters: the peak-to-peak linewidth (ΔHpp), the integrated intensity (IEPR) and the g-factor, suggests the presence of magnetic fluctuations that precede to antiferromagnetic ordering at low temperature. Additionally, the low-field microwave absorption (LFMA) is used to give further information on this material, giving also evidence of these magnetic fluctuations.

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

    PubMed

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

    2012-08-01

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

  10. Electron paramagnetic resonance as an effective method for a characterization of functionalized iron oxide

    NASA Astrophysics Data System (ADS)

    Dobosz, Bernadeta; Krzyminiewski, Ryszard; Schroeder, Grzegorz; Kurczewska, Joanna

    2014-05-01

    Iron(II, III) oxide magnetic nanoparticles (NPs) have been coated with (3-Chloropropyl) trimethoxysilane and subsequently functionalized with 4-Amino-2,2,6,6-tetramethylpiperidine-N-oxyl and Amoxicillin. Finally, the functionalized iron oxide NPs have been coated with natural polymer, chitosan, in order to prevent NPs agglomeration in aqueous environment. The product was characterized by Fourier transform infrared (FTIR) spectroscopy and transmission electron microscopy (TEM). It was studied by the electron paramagnetic resonance method and the parameters describing the magnetic properties of the investigated nanoparticles, such as g-factor and line width, were calculated.

  11. Use of alanine-silicone pellets for electron paramagnetic resonance gamma dosimetry

    SciTech Connect

    Flores, J.; Galindo, S. )

    1991-03-01

    Silicone is proposed as an alternative binding substance in the production of D-L alanine pellets used in electron paramagnetic resonance (EPR) dosimetry of gamma rays. The dosimeters are manufactured at room temperature, making the production simple. Examination by EPR silicone-alanine pellets irradiated with 60Co gamma rays in the dose range 10 to 10(6) Gy shows that the proposed silicone binder does not affect typical alanine dose-response curves. Thermal stability of the pellets below 40 degrees C is good, but their pre-dose EPR signal amplitude is slightly higher than for nonirradiated alanine.

  12. 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.

  13. Single-ion anisotropy in the gadolinium pyrochlores studied by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Glazkov, V. N.; Zhitomirsky, M. E.; Smirnov, A. I.; Krug von Nidda, H.-A.; Loidl, A.; Marin, C.; Sanchez, J.-P.

    2005-07-01

    The electron paramagnetic resonance is used to measure the single-ion anisotropy of Gd3+ ions in the pyrochlore structure of (Y1-xGdx)2Ti2O7 . A rather strong easy-plane-type anisotropy is found. The anisotropy constant D is comparable to the exchange integral J in the prototype Gd2Ti2O7 , D≃0.75J , and exceeds the dipolar energy scale. Physical implications of an easy-plane anisotropy for a pyrochlore antiferromagnet are considered. We calculate the magnetization curves at T=0 and discuss phase transitions in a magnetic field.

  14. 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.

  15. Electron paramagnetic resonance and photoluminescence investigation on ultraviolet-emitting gadolinium-ion-doped CaAl₁₂O₁₉ phosphors.

    PubMed

    Singh, Vijay; Borkotoky, S; Murali, A; Rao, J L; Rao, T K Gundu; Dhoble, S J

    2015-03-15

    The gadolinium doped CaAl12O19 phosphor has been prepared by a low temperature solution combustion method in a short time and characterized using powder X-ray diffraction, energy dispersive analysis of X-ray mapping, electron paramagnetic resonance (EPR) and photoluminescence spectroscopic techniques. EPR and optical analysis of the sample confirm the presence of Gd(3+) in the CaAl12O19 matrix. PMID:25546490

  16. 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

  17. Optically detected electron paramagnetic resonance by microwave modulated magnetic circular dichroism

    NASA Astrophysics Data System (ADS)

    Börger, Birgit; Bingham, Stephen J.; Gutschank, Jörg; Schweika, Marc Oliver; Suter, Dieter; Thomson, Andrew J.

    1999-11-01

    Electron paramagnetic resonance (EPR) can be detected optically, with a laser beam propagating perpendicular to the static magnetic field. As in conventional EPR, excitation uses a resonant microwave field. The detection process can be interpreted as coherent Raman scattering or as a modulation of the laser beam by the circular dichroism of the sample oscillating at the microwave frequency. The latter model suggests that the signal should show the same dependence on the optical wavelength as the MCD signal. We check this for two different samples [cytochrome c-551, a metalloprotein, and ruby (Cr3+:Al2O3)]. In both cases, the observed wavelength dependence is almost identical to that of the MCD signal. A quantitative estimate of the amplitude of the optically detected EPR signal from the MCD also shows good agreement with the experimental results.

  18. 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

  19. [Electron paramagnetic resonance determination of ceruloplasmin concentration in the blood of patients for the diagnosis of urological cancer diseases].

    PubMed

    Ibragimova, M I; Chushnikov, A I; Moiseev, V N; Petukhov, V Iu; Zheglov, E P; Pogorel'tsev, V I; Khardina, N B

    2010-04-01

    The electron paramagnetic resonance technique was used to study the venous blood levels of ceruloplasmin (CP) in 93 cancer patients with Stages I-IV malignancies of the urinary bladder and kidneys. Two groups were selected as a control; one of them comprised 44 donors who were considered to be apparently healthy and the other included 32 outpatients, some of whom had noncancer diseases. It has been established that in urological cancer, the level of the paramagnetic phase of Cu2+ -CP may vary in the wide range: from the lower to exceeding upper normal range in noncancer disease. The content of Cu2+ -CP does not virtually depend on the site and differentiation of a tumor. A correlation between the blood concentration of Cu2+ -CP and erythrocyte sedimentation rate (ESR) in urological cancer patients has been considered. Determination of CP levels at the ESR exceeding the normal values may be expedient for the early diagnosis of cancer and also an addition to the biological individual screening of patients in the preoperative period to choose the correct and effective treatment tactics.

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

    PubMed Central

    Steinhoff, H J; Hubbell, W L

    1996-01-01

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

  1. Application of Paramagnetically Tagged Molecules for Magnetic Resonance Imaging of Biofilm Mass Transport Processes▿

    PubMed Central

    Ramanan, B.; Holmes, W. M.; Sloan, W. T.; Phoenix, V. R.

    2010-01-01

    Molecules become readily visible by magnetic resonance imaging (MRI) when labeled with a paramagnetic tag. Consequently, MRI can be used to image their transport through porous media. In this study, we demonstrated that this method could be applied to image mass transport processes in biofilms. The transport of a complex of gadolinium and diethylenetriamine pentaacetic acid (Gd-DTPA), a commercially available paramagnetic molecule, was imaged both in agar (as a homogeneous test system) and in a phototrophic biofilm. The images collected were T1 weighted, where T1 is an MRI property of the biofilm and is dependent on Gd-DTPA concentration. A calibration protocol was applied to convert T1 parameter maps into concentration maps, thus revealing the spatially resolved concentrations of this tracer at different time intervals. Comparing the data obtained from the agar experiment with data from a one-dimensional diffusion model revealed that transport of Gd-DTPA in agar was purely via diffusion, with a diffusion coefficient of 7.2 × 10−10 m2 s−1. In contrast, comparison of data from the phototrophic biofilm experiment with data from a two-dimensional diffusion model revealed that transport of Gd-DTPA inside the biofilm was by both diffusion and advection, equivalent to a diffusion coefficient of 1.04 × 10−9 m2 s−1. This technology can be used to further explore mass transport processes in biofilms, either by using the wide range of commercially available paramagnetically tagged molecules and nanoparticles or by using bespoke tagged molecules. PMID:20435773

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

    NASA Astrophysics Data System (ADS)

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

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

  3. 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

  4. Electron paramagnetic resonance (EPR) spectroscopy characterization of wheat grains from plants of different water stress tolerance.

    PubMed

    Łabanowska, Maria; Filek, Maria; Kurdziel, Magdalena; Bednarska, Elżbieta; Dłubacz, Aleksandra; Hartikainen, Helina

    2012-09-01

    Grains of five genotypes of wheat (four Polish and one Finnish), differing in their tolerance to drought stress were chosen for this investigation. Electron paramagnetic resonance spectroscopy allowed observation of transition metal ions (Mn, Fe, Cu) and different types of stable radicals, including semiquinone centers, present in seed coats, as well as several types of carbohydrate radicals found mainly in the inner parts of grains. The content of paramagnetic metal centers was higher in sensitive genotypes (Radunia, Raweta) than in tolerant ones (Parabola, Nawra), whereas the Finnish genotype (Manu) exhibited intermediate amounts. Similarly, the concentrations of both types of radicals, carbohydrates and semiquinone were significantly higher in the grains originating from more sensitive wheat genotypes. The nature of carbohydrate radicals and their concentrations were confronted with the kinds and amounts of sugars found by the biochemical analyses and microscopy observations. It is suggested that some long lived radicals (semiquinone and starch radicals) occurring in grains could be indicators of stress resistance of wheat plants.

  5. Identification of the deep level defects in AlN single crystals by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

    Soltamov, V. A.; Ilyin, I. V.; Soltamova, A. A.; Mokhov, E. N.; Baranov, P. G.

    2010-06-01

    Electron paramagnetic resonance (EPR) at 9.4 and 35 GHz were studied on two types of AlN single crystals, grown by a sublimation sandwich method. These investigations revealed the presence of transition metals impurities in the first sample: Fe2+ (S =2) and some paramagnetic centers with S =3/2, we suggest Cr3+ or Ni3+ as the possible candidates. The EPR spectra of Fe2+ were observed up to the room temperature. After sample illumination at 5 K with light (wavelength shorter 700 nm) strong EPR signal with a g factor of shallow donors (SDs) and slightly anisotropic linewidth appears. This light-induced EPR signal, once excited at low temperature, still persists after switching off the light and is about constant up to 30 K then it drops quickly. SDs show a negative correlation energy U and oxygen in the N position (ON) is the most probable model. EPR spectra of deep-donor center which was assumed to be the nitrogen vacancy VN have been observed in the second sample. The x-ray irradiation leads to considerable enhancement of deep donor's (VN) signals intensity. The annealing resulted in recombination thermoluminescence and the deep donor (VN) energy level was estimated to be about 0.5 eV. The models of shallow (ON) and deep (VN) donor centers were supported by comprehensive hyperfine structure analysis.

  6. Electron paramagnetic resonance study of 3,4,5-trimethoxytetraphenyl porphyrinoxovanadium (IV) complex.

    PubMed

    Sharma, Swati; Kumar, Anil; Chand, Prem; Sharma, B K; Sarkar, Sabyasachi

    2006-03-01

    3,4,5-Trimetoxytetraphenylporphyrinoxovanadium (IV) complex (3,4,5-TMVOTPP) was synthesized by a new one pot synthetic method. The complex was studied in the form of single crystal, powder (polycrystalline state), solution and frozen solution (glassy state) by electron paramagnetic resonance (EPR) between room temperature (RT) and liquid nitrogen temperature (LNT). Interestingly a well-resolved octet in the EPR spectrum at RT is observed in the pure paramagnetic state of the crystal. This observation is attributed to a greatly reduced dipolar interaction between paramagnetic vanadyl ions due to the large size of the molecule and the resultant stacking in the crystalline state. The line width of the EPR signals in single crystal at RT is approximately 3.3 mT which is more than the usual line width in diluted paramagnets ( approximately 1.5 mT) and is attributed to some kind of broadening effect akin to slow motion broadening. The line width in solvents is more than the crystal value but decreases appreciably at low temperatures. The decrease in line width at low temperature is attributed to the increase in spin-lattice-relaxation time and quenching of RT broadening motion. Only one octet is observed in the crystal EPR spectra which suggests only one formula unit per unit cell or a parallel/antiparallel ordering of V=O vectors in case the formula units per unit cell are more than one. This result needs verification by a detailed X-ray investigation. The crystalline field symmetry around the V(4+) metal ion is revealed to be axial by the observed angular dependence of the EPR spectrum and the powder EPR spectrum. No super hyperfine splitting of the hyperfine lines of the vanadyl ion is observed in solid state or diluted glass up to liquid nitrogen temperature. This suggests an expected weak in-plane pi-bonding with ligands. The spin Hamiltonian parameters for vanadyl ion in crystal, powder, diluted solutions and frozen glasses are evaluated and discussed.

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

    NASA Astrophysics Data System (ADS)

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

    1998-05-01

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

  8. Nanostructured lipid carriers as nitroxide depot system measured by electron paramagnetic resonance spectroscopy.

    PubMed

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

    2011-12-15

    Various nanometer scaled transport systems are used in pharmaceutics and cosmetics to increase penetration or storage of actives. Nanostructured lipid carriers (NLCs) are efficient drug delivery systems for dermatological applications. Electron paramagnetic resonance (EPR) spectroscopy was used for the determination of TEMPO (2,2,6,6-tetramethyl-1-piperidinyloxy) distribution within the carrier and to investigate the dynamics of skin penetration. Results of ex vivo penetration of porcine skin and in vivo data - forearm of human volunteers - are compared and discussed to previously obtained results with invasomes under comparable conditions. W-band measurements show 35% of TEMPO associated with the lipid compartments of the NLC. Application of TEMPO loaded NLC to skin ex vivo increases the observation time by 12min showing a stabilisation of the nitroxide radical. Moreover, stabilisation is also seen with data generated in vivo. Thus, same as invasomes NLCs are a suitable slow release depot system. PMID:22001533

  9. Effect of surfactants on human stratum corneum: electron paramagnetic resonance study.

    PubMed

    Mizushima, J; Kawasaki, Y; Tabohashi, T; Kitano, T; Sakamoto, K; Kawashima, M; Cooke, R; Maibach, H I

    2000-03-20

    Electron paramagnetic resonance (EPR) spectra of nitroxide spin probes are useful for studying biological membranes and chemical-membrane interactions. Recently, we established a stripping method to remove stratum corneum (SC) for this purpose. To assess this stripping method with EPR and correlate with standard methods, we quantified the irritant effects of three types of surfactants by measurements of visual score and transepidermal water loss (TEWL), SC hydration and chromametry and studied EPR spectra measurements of surfactant-treated cadaver SC (C-SC) and stripped off SC (S-SC) on patch tested sites. 5-Doxyl stearic acid was the spin label. The order parameter S obtained from the spectra of S-SC correlated with those of C-SC and TEWL values. The results suggest that this method is capable of evaluating the fluidity of SC and correlates with the above bioengineering parameters.

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  11. Radical scavenging of white tea and its flavonoid constituents by electron paramagnetic resonance (EPR) spectroscopy.

    PubMed

    Azman, Nurul A M; Peiró, Sara; Fajarí, Lluís; Julià, Luis; Almajano, Maria Pilar

    2014-06-25

    White tea (WT) presents high levels of catechins, which are known to reduce oxidative stress. WT is the least processed tea, unfermented and prepared only from very young tea leaves. The subject of this paper is the use of the spin trap method and electron paramagnetic resonance (EPR) spectroscopy as the analytical tool to measure, for the first time, the radical scavenging activity of WT and its major catechin components, epicatechin (EC), epicatechin-3-gallate (ECG), epigallocatechin (EGC), and epigallocatechin-3-gallate (EGCG), against the methoxy radical, using ferulic acid as antioxidant pattern. The antioxidant activity has been measured by the decrease of the intensity of the spectral bands of the adduct DMPO-OCH3 in the EPR with the amount of antioxidant in the reactive mixture. Tea leaves and buds were extracted with waterless methanol. It has been proved that tea compounds with more antiradical activity against methoxy radical are those with the gallate group, EGCG and ECG. PMID:24885813

  12. Electron paramagnetic resonance spectroscopy of fast neutron-generated defects in GaAs

    NASA Astrophysics Data System (ADS)

    Goltzene, A.; Meyer, B.; Schwab, C.; Greenbaum, S. G.; Wagner, R. J.; Kennedy, T. A.

    1984-12-01

    A series of fast neutron-irradiated GaAs samples (neutron fluence range of 2×1015-2.5×1017 cm-2) has been investigated by electron paramagnetic resonance (EPR) spectroscopy. The EPR spectra at 9 GHz exhibit a broad (˜1 kG) Lorentzian singlet at g≊2.09 superimposed on the AsGa quadruplet. The singlet intensity scales linearly with neutron fluence as does that of the quadruplet. The presence of this new defect has not been reported in as-grown GaAs known to have large concentrations of AsGa defects. EPR measurements at 35, 159, and 337 GHz indicate that the singlet linewidth increases with the microwave frequency.

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

    PubMed

    Maia, Luisa B; Moura, José J G

    2016-01-01

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

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

    NASA Astrophysics Data System (ADS)

    Epel, Boris; Halpern, Howard J.

    2015-05-01

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

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

    PubMed

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

    1987-12-16

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

  16. 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.

  17. The negative effect of soy extract on erythrocyte membrane fluidity: an electron paramagnetic resonance study.

    PubMed

    Ajdžanović, Vladimir; Spasojević, Ivan; Sošić-Jurjević, Branka; Filipović, Branko; Trifunović, Svetlana; Sekulić, Milka; Milošević, Verica

    2011-02-01

    A decrease of erythrocyte membrane fluidity can contribute to the pathophysiology of hypertension. Soy products, which are used as alternative therapeutics in some cardiovascular conditions, contain various isoflavones (genistein, daidzein, and their glucosides, genistin and daidzin), which can incorporate cellular membrane and change its fluidity. The aim of this study was to examine the effects of soy extract (which generally corresponds to the soy products of isoflavone composition) on erythrocyte membrane fluidity at graded depths. We used electron paramagnetic resonance spectroscopy and fatty acid spin probes (5-DS and 12-DS), the spectra of which are dependent on membrane fluidity. After being treated with soy extract, erythrocytes showed a significant (P = 0.016) decrease of membrane fluidity near the hydrophilic surface, while there were no significant changes of fluidity in deeper hydrophobic membrane regions. These results suggest that soy products containing high levels of genistein and isoflavone glucosides may not be suitable for use in hypertension because they decrease erythrocyte membrane fluidity.

  18. 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.

  19. 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

  20. 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.

  1. 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.

  2. The effect of implanting boron on the optical absorption and electron paramagnetic resonance spectra of silica

    NASA Astrophysics Data System (ADS)

    Magruder, R. H.; Stesmans, A.; Weeks, R. A.; Weller, R. A.

    2008-09-01

    Silica samples (type III, Corning 7940) were implanted with B using multiple energies to produce a layer ˜600 nm thick in which the concentration of B ranged from 0.034 to 2.04 at. %. Optical absorption spectra were measured from 1.8 to 6.5 eV. Electron paramagnetic resonance (EPR) measurements were generally made at ˜20.3 and 33 GHz for sample temperatures ranging from 77 to 100 K. Based on the EPR spectra three types of defects, namely, Eγ', the E'-type 73 G split doublet (E73'), and the peroxyradical (POR) were identified. No oxygen-associated hole centers (OHCs) nor specific B-associated paramagnetic defects were detected, not even at the largest B concentration of 2.04 at. %. Unlike previous assignments, there was no correlation between the 4.83 eV optical absorption band and the observed PORs. From these results, we infer that in addition to POR, there is at least one additional Si-related state absorbing in the 4.8-4.9 eV range that is likely diamagnetic. The 5.85 eV optical absorption band is found to be due to the Eγ' and E73' centers, with, in average, quite similar oscillator strengths inferred as before. Both the optical absorption and the electron spin resonance data can be satisfactorily explained without the need for specific B-associated defect site (s). As no OHCs are detected by ESR, these do not seem to make a detectable contribution to the optical spectra.

  3. 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.

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

    PubMed

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

    2011-01-01

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

  5. Isotope effect on electron paramagnetic resonance of boron acceptors in silicon

    NASA Astrophysics Data System (ADS)

    Stegner, A. R.; Tezuka, H.; Andlauer, T.; Stutzmann, M.; Thewalt, M. L. W.; Brandt, M. S.; Itoh, K. M.

    2010-09-01

    The fourfold degeneracy of the boron acceptor ground state in silicon, which is easily lifted by any symmetry-breaking perturbation, allows for a strong inhomogeneous broadening of the boron-related electron paramagnetic resonance (EPR) lines, e.g., by a random distribution of local strains. However, since EPR of boron acceptors in externally unstrained silicon was reported initially, neither the line shape nor the magnitude of the residual broadening observed in samples with high-crystalline purity were compatible with the low concentrations of carbon and oxygen point defects, being the predominant source of random local strain. Adapting a theoretical model which has been applied to understand the acceptor ground-state splitting in the absence of a magnetic field as an effect due to the presence of different silicon isotopes, we show that local fluctuations of the valence-band edge due to different isotopic configurations in the vicinity of the boron acceptors can quantitatively account for all inhomogeneous broadening effects in high-purity Si with a natural isotope composition. Our calculations show that such an isotopic perturbation also leads to a shift in the g value of different boron-related resonances, which we could verify in our experiments. Further, our results provide an independent test and verification of the valence-band offsets between the different Si isotopes determined in previous works.

  6. Electron paramagnetic resonance spectroscopy of Fe3+ ions in amethyst: thermodynamic potentials and magnetic susceptibility

    NASA Astrophysics Data System (ADS)

    Sivaramaiah, Gobburu; Lin, Jinru; Pan, Yuanming

    2011-02-01

    Single-crystal and powder electron paramagnetic resonance (EPR) spectroscopic studies of natural amethyst quartz, before and after isochronal annealing between 573 and 1,173 K, have been made from 90 to 294 K. Single-crystal EPR spectra confirm the presence of two substitutional Fe3+ centers. Powder EPR spectra are characterized by two broad resonance signals at g = ~10.8 and 4.0 and a sharp signal at g = 2.002. The sharp signal is readily attributed to the well-established oxygen vacancy electron center E 1'. However, the two broad signals do not correspond to any known Fe3+ centers in the quartz lattice, but are most likely attributable to Fe3+ clusters on surfaces. The absolute numbers of spins of the Fe3+ species at g = ~10.8 have been calculated from powder EPR spectra measured at temperatures from 90 to 294 K. These results have been used to extract thermodynamic potentials, including Gibbs energy of activation Δ G, activation energy E a, entropy of activation Δ S and enthalpy of activation Δ H for the Fe3+ species in amethyst. In addition, magnetic susceptibilities ( χ) have been calculated from EPR data at different temperatures. A linear relationship between magnetic susceptibility and temperature is consistent with the Curie-Weiss law. Knowledge about the stability and properties of Fe3+ species on the surfaces of quartz is important to better understanding of the reactivity, bioavailability and heath effects of iron in silica particles.

  7. Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional 2H (I=1) nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Antonijevic, Sasa; Wimperis, Stephen

    2005-01-01

    A novel two-dimensional 2H (spin I=1) nuclear magnetic resonance technique is introduced for determination of both quadrupole and chemical/paramagnetic shift tensors and their relative orientation. The new method is based upon the well-known quadrupolar-echo experiment and is designed to refocus the quadrupolar interaction at the end of the t1 evolution period while retaining the modulation introduced by the shift interaction. As a result, a projection of the resulting two-dimensional spectrum onto its F1 dimension yields a shift anisotropy powder lineshape free from any quadrupolar broadening. The chemical/paramagnetic shifts appear in both F1 and F2 dimensions and are thus spread along a +1 frequency gradient; hence, a projection orthogonal to this gradient yields the pure quadrupolar powder lineshape, free from all shift interaction effects. The relative orientation of the quadrupole and shift tensors can be obtained by analysis of the full two-dimensional correlation lineshape. Unlike the well-known double-quantum experiment, the new method is, in principle, equally effective for all values of the quadrupolar splitting, including zero. The properties of the new technique are demonstrated using computer simulation and methods for the extraction of quadrupole and shift tensor parameters are described. The new technique is applied to (diamagnetic) benzoic acid-d1 (C6H5CO2D) and (paramagnetic) copper(II) chloride dihydrate-d4 (CuCl2ṡ2D2O).

  8. Separation of quadrupolar and chemical/paramagnetic shift interactions in two-dimensional 2H (I=1) nuclear magnetic resonance spectroscopy.

    PubMed

    Antonijevic, Sasa; Wimperis, Stephen

    2005-01-22

    A novel two-dimensional (2)H (spin I=1) nuclear magnetic resonance technique is introduced for determination of both quadrupole and chemical/paramagnetic shift tensors and their relative orientation. The new method is based upon the well-known quadrupolar-echo experiment and is designed to refocus the quadrupolar interaction at the end of the t(1) evolution period while retaining the modulation introduced by the shift interaction. As a result, a projection of the resulting two-dimensional spectrum onto its F(1) dimension yields a shift anisotropy powder lineshape free from any quadrupolar broadening. The chemical/paramagnetic shifts appear in both F(1) and F(2) dimensions and are thus spread along a +1 frequency gradient; hence, a projection orthogonal to this gradient yields the pure quadrupolar powder lineshape, free from all shift interaction effects. The relative orientation of the quadrupole and shift tensors can be obtained by analysis of the full two-dimensional correlation lineshape. Unlike the well-known double-quantum experiment, the new method is, in principle, equally effective for all values of the quadrupolar splitting, including zero. The properties of the new technique are demonstrated using computer simulation and methods for the extraction of quadrupole and shift tensor parameters are described. The new technique is applied to (diamagnetic) benzoic acid-d(1) (C(6)H(5)CO(2)D) and (paramagnetic) copper(II) chloride dihydrate-d(4) (CuCl(2).2D(2)O). PMID:15740253

  9. Characterization of the Iron-Sulfur Clusters in Xanthine Dehydrogenase Using Electron Paramagnetic Resonance Spectroscopy and Magnetic Coupling Interactions

    SciTech Connect

    Scott, J. Robert

    2004-02-04

    Xanthine dehydrogenase is a metalloenzyme that is present in numerous eukaryotic and prokaryotic organisms. It contains molybdenum, two different iron-sulfur clusters, and flavin. While the structures of both iron-sulfur clusters were known, it was unclear as to which structure was in which location. Electron paramagnetic resonance spectroscopy probes the paramagnetic qualities of molecules or ions. With this technology we wished to understand which EPR spectrum was associated with which iron-sulfur cluster by looking at magnetic coupling between the paramagnetic Mo(V) oxidation state and the reduced iron-sulfur clusters. We then assigned the clusters to their corresponding locations. The spin-spin interactions observed between Mo(V) and Fe-S I in xanthine dehydrogenase at low temperature show that Fe-S I is the closer site in contrast to Fe-S II.

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

    NASA Astrophysics Data System (ADS)

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

    2014-09-01

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

  11. 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

  12. 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

  13. Zero-field signal in the electron paramagnetic resonance spectrum of Mn{sup +2} in silicate glasses

    SciTech Connect

    Rakhimov, Rakhim R.; Jones, David E.

    2000-07-22

    A 9.4-9.8 GHz electron paramagnetic resonance (EPR) study of Mn{sup +2}-doped Na{sub 2}O-CaO-MgO-SiO{sub 2} glasses has revealed a nonresonant microwave magneto-absorption near zero magnetic field in addition to normal paramagnetic absorption due to Mn{sup +2} ions, electron spin S=5/2. The low-field response has an opposite phase relative to paramagnetic signal and is independent of the mutual orientation of the magnetic field of the microwave H{sub 1} and static magnetic field H. In contrast, the paramagnetic signal is different for perpendicular H{sub 1}(perpendicular sign)H and parallel H{sub 1}(parallel sign)H polarization of the microwave field, which is attributed to enhancement of forbidden magnetic dipolar transitions and suppression of the allowed transitions for parallel polarization. The low-field response is described in terms of microwave dielectric losses that derive from the magneto-induced charge migration in the first coordination sphere of Mn{sup +2}. As opposed to the spin-polarized tunneling that was described in ferromagnets between different valence forms of Mn, the observed effect is due to spin-dependent tunneling that occurs in the vicinity of Mn{sup +2} in a diluted paramagnetic system. (c) 2000 American Institute of Physics.

  14. 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

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

    PubMed

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

    2011-01-01

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

  16. 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.

  17. Electron paramagnetic resonance study of radiation damage in photosynthetic reaction center crystals.

    SciTech Connect

    Utschig, L. M.; Chemerisov, S. D.; Tiede, D. M.; Poluektov, O. G.; Chemical Sciences and Engineering Division

    2008-01-01

    Electron paramagnetic resonance (EPR) was used to simultaneously study radiation-induced cofactor reduction and damaging radical formation in single crystals of the bacterial reaction center (RC). Crystals of Fe-removed/Zn-replaced RC protein from Rhodobacter (R.) sphaeroides R26 were irradiated with varied radiation doses at cryogenic temperature and analyzed for radiation-induced free radical formation and alteration of light-induced photosynthetic electron transfer activity using high-field (HF) D-band (130 GHz) and X-band (9.5 GHz) EPR spectroscopies. These analyses show that the formation of radiation-induced free radicals saturated at doses 1 order of magnitude smaller than the amount of radiation at which protein crystals lose their diffraction quality, while light-induced RC activity was found to be lost at radiation doses at least 1 order of magnitude lower than the dose at which radiation-induced radicals exhibited saturation. HF D-band EPR spectra provide direct evidence for radiation-induced reduction of the quinones and possibly other cofactors. These results demonstrate that substantial radiation damage is likely to have occurred during X-ray diffraction data collection used for photosynthetic RC structure determination. Thus, both radiation-induced loss of photochemical activity in RC crystals and reduction of the quinones are important factors that must be considered when correlating spectroscopic and crystallographic measurements of quinone site structures.

  18. 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.

  19. 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. PMID:26214261

  20. 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.

  1. Electron paramagnetic resonance of the SO{4/3-} radical in barite and celestite

    NASA Astrophysics Data System (ADS)

    Ryabov, I. D.

    1995-09-01

    The electron paramagnetic resonance (EPR) study of gammaor x-ray-irradiated natural barite and celestite has revealed the presence of a radiation center with principal values of the g tensor and the A tensor [MHz] of hyperfine interaction (from the 33S isotope): gxx=1.9963, gyy=2.0073, gzz=2.0025, Axx=434, Ayy=447, Azz=528 in BaSO4, gxx=1.9990, gyy=2.0075, gzz=2.0027, Axx=426, Ayy=439, Azz=520 in SrSO4. The center has been identified as SO{3-/4}radical. The electron centers SO{4/3-}in barite have been found to be produced along with the hole centers SO{4/3-}, and maximum concentration of both centers is reached at a gamma-ray-radiation dose of about 5·105 Gy. UV or thermal treatment causes both centers to disappear. The SO{4/3-}radicals proved to be more thermally stable than the SO{4/3-}radicals: within about 0.5 h the latter disappear at 125° C, whereas the former do so at 180° C.

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

    PubMed

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

    2014-05-01

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

  3. 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.

  4. Simulation of Nitroxide Electron Paramagnetic Resonance Spectra from Brownian Trajectories and Molecular Dynamics Simulations

    PubMed Central

    DeSensi, Susan C.; Rangel, David P.; Beth, Albert H.; Lybrand, Terry P.; Hustedt, Eric J.

    2008-01-01

    A simulated continuous wave electron paramagnetic resonance spectrum of a nitroxide spin label can be obtained from the Fourier transform of a free induction decay. It has been previously shown that the free induction decay can be calculated by solving the time-dependent stochastic Liouville equation for a set of Brownian trajectories defining the rotational dynamics of the label. In this work, a quaternion-based Monte Carlo algorithm has been developed to generate Brownian trajectories describing the global rotational diffusion of a spin-labeled protein. Also, molecular dynamics simulations of two spin-labeled mutants of T4 lysozyme, T4L F153R1, and T4L K65R1 have been used to generate trajectories describing the internal dynamics of the protein and the local dynamics of the spin-label side chain. Trajectories from the molecular dynamics simulations combined with trajectories describing the global rotational diffusion of the protein are used to account for all of the dynamics of a spin-labeled protein. Spectra calculated from these combined trajectories correspond well to the experimental spectra for the buried site T4L F153R1 and the helix surface site T4L K65R1. This work provides a framework to further explore the modeling of the dynamics of the spin-label side chain in the wide variety of labeling environments encountered in site-directed spin labeling studies. PMID:18234808

  5. Paramagnetic hollow silica nanospheres for in vivo targeted ultrasound and magnetic resonance imaging.

    PubMed

    An, Lu; Hu, He; Du, Jing; Wei, Jie; Wang, Li; Yang, Hong; Wu, Dongmei; Shi, Haili; Li, Fenghua; Yang, Shiping

    2014-07-01

    A series of hollow silica nanospheres (HSNSs) with sizes ranging from 100 to 400 nm were synthesized and used for primary ultrasound imaging (US) efficiency assessment. The 400 nm HSNSs were chosen as platform for conjugation with Gd-DTPA and cyclo-arginine-glycine-aspartic acid c(RGD) peptide to construct US and magnetic resonance imaging (MRI) dual-modal contrast agents (CAs): [HSNSs@(DTPA-Gd)-RGD]. The obtained CAs displayed good physiological stability, low cytotoxicity and negligible hemolytic activity in vitro. Furthermore, the passive accumulation and active-targeting of the HSNSs in the tumor site of mice was demonstrated by US and MR imaging, respectively. The qualitative and quantitative biodistribution of the HSNSs showed that they mainly accumulated in the tissues of liver, lung, tumor after intravenous administration and then be excreted from feces. In addition, histological, hematological, blood and biochemical analysis were used to further study toxicity of the HSNSs, and all results indicated that there were no covert toxicity of HSNSs in mice after long exposure times. Findings from this study indicated that the silica-based paramagnetic HSNSs can be used as a platform for long-term targeted imaging and therapy studies safely in vivo.

  6. 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.

  7. Quantitative molecular magnetic resonance imaging of tumor angiogenesis using cNGR-labeled paramagnetic quantum dots.

    PubMed

    Oostendorp, Marlies; Douma, Kim; Hackeng, Tilman M; Dirksen, Anouk; Post, Mark J; van Zandvoort, Marc A M J; Backes, Walter H

    2008-09-15

    The objective of this study was to develop and apply cyclic Asn-Gly-Arg (cNGR)-labeled paramagnetic quantum dots (cNGR-pQDs) for the noninvasive assessment of tumor angiogenic activity using quantitative in vivo molecular magnetic resonance imaging (MRI). cNGR was previously shown to colocalize with CD13, an aminopeptidase that is highly overexpressed on angiogenic tumor endothelium. Because angiogenesis is important for tumor growth and metastatization, its in vivo detection and quantification may allow objective diagnosis of tumor status and evaluation of treatment response. I.v. injection of cNGR-pQDs in tumor-bearing mice resulted in increased quantitative contrast, comprising increased longitudinal relaxation rate and decreased proton visibility, in the tumor rim but not in tumor core or muscle tissue. This showed that cNGR-pQDs allow in vivo quantification and accurate localization of angiogenic activity. MRI results were validated using ex vivo two-photon laser scanning microscopy (TPLSM), which showed that cNGR-pQDs were primarily located on the surface of tumor endothelial cells and to a lesser extent in the vessel lumen. In contrast, unlabeled pQDs were not or only sparsely detected with both MRI and TPLSM, supporting a high specificity of cNGR-pQDs for angiogenic tumor vasculature.

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

    PubMed

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

    2009-05-27

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

  9. 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.

  10. 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.

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

    PubMed Central

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

    2015-01-01

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

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

    PubMed

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

    2012-12-01

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

  13. Electron paramagnetic resonance spectroscopy studies of Eu-Y and coexchanged EuFe-Y zeolites

    SciTech Connect

    Ulla, M.A.; Millman, W.S. ); Aparicio, L.A.; Balse, V.R.; Dumesic, J.A. )

    1990-05-01

    Electron paramagnetic resonance (EPR) was used to probe the oxidation state of europium and the location of divalent europium cations in Eu-Y and EuFe-Y zeolite samples. Europium was present as trivalent cations following treatment in O{sub 2} at 770 K. Treatments in H{sub 2} or CO at 770 K led to formation of divalent cations, and perhaps also caused some reduction to lower oxidation states. Three EPR signals were observed for Eu{sup 2+}, giving rise to effective g values of 3, 4.9, and 6. The first and last signals are interpreted as being due to Eu{sup 2+} cations at sites I and II, respectively, while the latter signal is due to Eu{sup 2+} cations at sites I{prime} and II{prime}. The majority of the Eu{sup 2+} cations are at site I, and the amount of Eu at this site can be increased by reducing the sample in H{sub 2}, compared with reduction in CO. The presence of europium in site I forces the Fe{sup 2+} cations to occupy sites of lower coordination in the sodalite unit (sites I{prime} and II{prime}) and in the supercages (sites II and III{prime}).

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

    PubMed Central

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

    2015-01-01

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

  15. A study of Roman glass by reflectance and electron paramagnetic resonance spectroscopies

    NASA Astrophysics Data System (ADS)

    Mirti, P.; Ferrari, R. P.; Laurenti, E.; Casoli, A.

    1993-08-01

    Reflectance and electron paramagnetic resonance (EPR) spectroscopies were used to study 25 fragments of Roman glass. Colour coordinates were used for an unbiased classification of the glasses in colour groups, which accounted for the presence of blue, blue-green, green, yellow-green, yellow and purple samples. Reflectance spectra were recorded in the 250-2500 nm wavelength range and showed absorption bands characteristic of Fe II, Fe III and Mn III ions; furthermore, Co II and Cu II bands were observed in the spectra of the blue glasses. A decrease of the absorbance ratio of Fe II to Fe III ions was observed moving from blue-green to green and yellow-green glasses; however, yellow fragments still proved to be reduced glasses. EPR spectra displayed the characteristic patterns of Fe III and Mn II ions, with g-values in the 2-5 interval and spectral features depending on the relative content of the two elements. The characteristic pattern of the V IV ion ( g ≈ 2) and signals due to the formation of iron-sulphur complexes ( g ≈ 6) appeared in the spectrum of a dark yellow glass, recorded at 77 K.

  16. In Situ Monitoring of Diffusion of Guest Molecules in Porous Media Using Electron Paramagnetic Resonance Imaging.

    PubMed

    Spitzbarth, Martin; Lemke, Tobias; Drescher, Malte

    2016-01-01

    A method is demonstrated to monitor macroscopic translational diffusion using electron paramagnetic resonance (EPR) imaging. A host-guest system with nitroxide spin probe 3-(2-Iodoacetamido)-2,2,5,5-tetramethyl-1-pyrrolidinyloxy (IPSL) as a guest inside the periodic mesoporous organosilica (PMO) aerogel UKON1-GEL as a host and ethanol as a solvent is used as an example to describe the protocol. Data is shown from a previous publication, where the protocol has been applied to both IPSL and Tris(8-carboxy-2,2,6,6-perdeutero-tetramethyl-benzo[1,2-d:4,5-d']bis(1,3)dithiole) methyl (Trityl) as guest molecules and UKON1-GEL and SILICA-GEL as host systems. A method is shown to prepare aerogel samples that cannot be synthesized directly in the sample tube for measurement due to a size change during synthesis. The aerogel is attached to sample tubes using heat shrink tubing and a pressure cooker to reach the necessary temperature without evaporating the solvent in the process. The method does not assume a clearly defined initial distribution of guest molecules at the start of the measurement. Instead, it requires a reservoir on top of the aerogel and experimentally determines the influx rate during data analysis. The diffusion is monitored continually over a period of 20 hr by recording the 1d spin density profile within the sample. The spectrometer settings for the imaging experiment are described quantitatively. Data analysis software is provided to take the resonator sensitivity profile into account and to numerically solve the diffusion equation. The software determines the macroscopic translational diffusion coefficient by least square minimization of the difference between the experiment and the numerical solution of the diffusion equation. PMID:27685166

  17. New roles of flavoproteins in molecular cell biology: blue-light active flavoproteins studied by electron paramagnetic resonance.

    PubMed

    Schleicher, Erik; Bittl, Robert; Weber, Stefan

    2009-08-01

    Exploring enzymatic mechanisms at a molecular level is one of the major challenges in modern biophysics. Based on enzyme structure data, as obtained by X-ray crystallography or NMR spectroscopy, one can suggest how substrates and products bind for catalysis. However, from the 3D structure alone it is very rarely possible to identify how intermediates are formed and how they are interconverted. Molecular spectroscopy can provide such information and thus supplement our knowledge on the specific enzymatic reaction under consideration. In the case of enzymatic processes in which paramagnetic molecules play a role, EPR and related methods such as electron-nuclear double resonance (ENDOR) are powerful techniques to unravel important details, e.g. the electronic structure or the protonation state of the intermediate(s) carrying (the) unpaired electron spin(s). Here, we review recent EPR/ENDOR studies of blue-light active flavoproteins with emphasis on photolyases that catalyze the enzymatic repair of UV damaged DNA, and on cryptochrome blue-light photoreceptors that act in several species as central components of the circadian clock. PMID:19624734

  18. 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.

  19. 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.

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

    PubMed

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

    2010-01-13

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

  1. New roles of flavoproteins in molecular cell biology: blue-light active flavoproteins studied by electron paramagnetic resonance.

    PubMed

    Schleicher, Erik; Bittl, Robert; Weber, Stefan

    2009-08-01

    Exploring enzymatic mechanisms at a molecular level is one of the major challenges in modern biophysics. Based on enzyme structure data, as obtained by X-ray crystallography or NMR spectroscopy, one can suggest how substrates and products bind for catalysis. However, from the 3D structure alone it is very rarely possible to identify how intermediates are formed and how they are interconverted. Molecular spectroscopy can provide such information and thus supplement our knowledge on the specific enzymatic reaction under consideration. In the case of enzymatic processes in which paramagnetic molecules play a role, EPR and related methods such as electron-nuclear double resonance (ENDOR) are powerful techniques to unravel important details, e.g. the electronic structure or the protonation state of the intermediate(s) carrying (the) unpaired electron spin(s). Here, we review recent EPR/ENDOR studies of blue-light active flavoproteins with emphasis on photolyases that catalyze the enzymatic repair of UV damaged DNA, and on cryptochrome blue-light photoreceptors that act in several species as central components of the circadian clock.

  2. Site selective substitution Pt for Ti in KTiOPO4:Ga crystals revealed by electron paramagnetic resonance

    NASA Astrophysics Data System (ADS)

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

    2014-07-01

    Electron Paramagnetic Resonance at low temperatures has been used to characterize potassium titanyl phosphate (KTiOPO4) 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 KTiOPO4 creating Pt3+ centers. Two different Pt3+ 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 39K and two 31P nuclei in their surroundings. In both Pt(A) and Pt(D) centers, Pt3+ ions substitute for Ti4+ ions, but with a preference to one of two electrically distinct crystallographic positions. The site selective substitution can be controlled by the Ga-doping.

  3. Oxymetry Deep in Tissues With Low-Frequency Electron Paramagnetic Resonance

    NASA Astrophysics Data System (ADS)

    Halpern, Howard J.; Yu, Cheng; Peric, Miroslav; Barth, Eugene; Grdina, David J.; Teicher, Beverly A.

    1994-12-01

    We have measured the oxygen concentration in the body water of murine FSa and NFSa fibrosarcomas using a new method for quantitative oxygen concentration determination deep in the tissues of a living animal. The measurement uses unusually low-frequency electron paramagnetic spectroscopy sensitive to substrate 7 cm deep in tissue, partially deuterated spin probes (spin labels of molecular mass 195, approximating that of glucose) whose distribution compartment can be targeted with facile adduct substitution, and novel analytic techniques. We show that the water-compartment oxygen concentration of the tumors decreases as the tumor size increases and also shows a trend to decrease as radiobiologic hypoxia increases. An oxymetric spectral image of the tumor is presented. The technique will improve with larger human tissue samples. It provides the potential to quantitatively assess tissue hypoxia in ischemic or preischemic states in stroke and myocardial infarction. It will allow direct assessment of tumor hypoxia to determine the usefulness of radiation and chemotherapy adjuvants directed to hypoxic cell compartments.

  4. 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.

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

    PubMed

    Merunka, Dalibor; Peric, Mirna; Peric, Miroslav

    2015-02-19

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-05-01

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

  7. Thermoluminescence, electron paramagnetic resonance and optical absorption in natural and synthetic rhodonite crystals

    NASA Astrophysics Data System (ADS)

    Paião, J. R. B.; Watanabe, S.

    2008-10-01

    Thermoluminescence, electron paramagnetic resonance and optical absorption properties of rhodonite, a natural silicate mineral, have been investigated and compared to those of synthetic crystal, pure and doped. The TL peaks grow linearly for radiation dose up to 4 kGy, and then saturate. In all the synthetic samples, 140 and 340°C TL peaks are observed; the difference occurs in their relative intensities, but only 340°C peak grows strongly for high doses. Al2O3 and Al2O3 + CaO-doped synthetic samples presented several decades intenser TL compared to that of synthetic samples doped with other impurities. A heating rate of 4°C/s has been used in all the TL readings. The EPR spectrum of natural rhodonite mineral has only one huge signal around g = 2.0 with width extending from 1,000 to 6,000 G. This is due to Mn dipolar interaction, a fact proved by numerical calculation based on Van Vleck dipolar broadening expression. The optical absorption spectrum is rich in absorption bands in near-UV, visible and near-IR intervals. Several bands in the region from 540 to 340 nm are interpreted as being due to Mn3+ in distorted octahedral environment. A broad and intense band around 1,040 nm is due to Fe2+. It decays under heating up to 900°C. At this temperature it is reduced by 80% of its original intensity. The pink, natural rhodonite, heated in air starts becoming black at approximately 600°C.

  8. 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.

  9. 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.

  10. Comparative electron paramagnetic resonance study of radical intermediates in turnip peroxidase isozymes.

    PubMed

    Ivancich, A; Mazza, G; Desbois, A

    2001-06-12

    The occurrence of isozymes in plant peroxidases is poorly understood. Turnip roots contain seven season-dependent isoperoxidases with distinct physicochemical properties. In the work presented here, multifrequency electron paramagnetic resonance spectroscopy has been used to characterize the Compound I intermediate obtained by the reaction of turnip isoperoxidases 1, 3, and 7 with hydrogen peroxide. The broad (2500 G) Compound I EPR spectrum of all three peroxidases was consistent with the formation of an exchange-coupled oxoferryl-porphyrinyl radical species. A dramatic pH dependence of the exchange interaction of the [Fe(IV)=O por(*+)] intermediate was observed for all three isoperoxidases and for a pH range of 4.5-7.7. This result provides substantial experimental evidence for previous proposals concerning the protein effect on the ferro- or antiferromagnetic character of the exchange coupling of Compound I based on model complexes. Turnip isoperoxidase 7 exhibited an unexpected pH effect related to the nature of the Compound I radical. At basic pH, a narrow radical species ( approximately 50 G) was formed together with the porphyrinyl radical. The g anisotropy of the narrow radical Delta(g) = 0.0046, obtained from the high-field (190 and 285 GHz) EPR spectrum, was that expected for tyrosyl radicals. The broad g(x) edge of the Tyr* spectrum centered at a low g(x) value (2.00660) strongly argues for a hydrogen-bonded tyrosyl radical in a heterogeneous microenvironment. The relationship between tyrosyl radical formation and the higher redox potential of turnip isozyme 7, as compared to that of isozyme 1, is discussed. PMID:11389600

  11. 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.

  12. Evaluation of the effect of dietary lycopene, the main carotenoid in tomato (Lycopersicon esculentum), on the in vivo renal reducing ability by a radiofrequency electron paramagnetic resonance method.

    PubMed

    Yoshida, Kazutaka; Yokoyama, Hidekatsu; Oteki, Takaaki; Matsumoto, Gaku; Aizawa, Koichi; Inakuma, Takahiro

    2011-04-13

    Although it has been reported that dietary lycopene, the main carotenoid in tomato, improved drug-induced nephropathy, there are no reports on the effect of orally administered lycopene on the in vivo renal reducing (i.e., antioxidant) ability. The radiofrequency electron paramagnetic resonance (EPR) method is a unique technique by which the in vivo reducing ability of an experimental animal can be studied. In this study, the in vivo changes in the renal reducing ability of rats orally administered lycopene were investigated using a 700 MHz EPR spectrometer equipped with a surface-coil-type resonator. Rats were fed either a control diet or a diet containing lycopene. After 2 weeks, in vivo EPR measurements were conducted. The renal reducing ability of lycopene-treated rats was significantly greater than that of the control. This is the first verification of in vivo antioxidant enhancement via dietary lycopene administration. PMID:21381743

  13. Study of ferroelectric phase transition in Pb5Ge3O11 by paramagnetic resonance of Gd3+ centres

    NASA Astrophysics Data System (ADS)

    Vazhenin, V. A.; Rumyantsev, E. L.; Artyomov, M. Yu.; Potapov, A. P.

    2016-06-01

    The temperature dependence of the fine structure of trigonal paramagnetic Gd3+ centres in Pb5Ge3O11 was investigated in a wide temperature range in the vicinity of structural phase transition. The temperature dependence of the squared order parameter has been constructed based on the obtained data. It was shown that for the adequate description of its behaviour, the sixth-power term in polarization must be taken into account in the expansion of the thermodynamic potential. The orientational dependence of anomalous broadening of electron paramagnetic resonance signals in the vicinity of ferroelectric phase transition was studied. By comparison of the observed behaviour with the angular dependences of the line width that are characteristic of various broadening mechanisms, it was inferred that it can be attributed to defect induced statistical dispersion of fine structure triclinic parameters.

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

    PubMed Central

    2015-01-01

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

  15. Electron paramagnetic resonance in irradiated fingernails: variability of dose dependence and possibilities of initial dose assessment.

    PubMed

    Reyes, R A; Romanyukha, Alexander; Olsen, C; Trompier, F; Benevides, L A

    2009-08-01

    The results of electron paramagnetic resonance (EPR) measurements in irradiated fingernails are presented. In total, 83 samples of different fingernails were studied. Five different groups of samples were selected based on the collection time of fingernail samples, their level of mechanical stress, and the number and size of clippings: (1) recently (<24 h) cut, irradiated and measured with EPR without any treatment of samples, and with rigorous control of size and number of clippings (stressed-fresh, controlled); (2) recently (<24 h) cut, irradiated and measured with EPR after application of a special treatment (10 min of water soaking, 5 min of drying time) to reduce the mechanical stress caused by cutting the samples, and with rigorous control of size and number of clippings (unstressed-fresh, controlled); (3) previously (>24 h) cut, stored at room temperature, additionally cut into small pieces immediately prior to study, irradiated and measured with EPR without any treatment of samples, and with rigorous control of size and number of clippings (stressed-old, controlled); (4) previously (>24 h) cut, stored at room temperature, additionally cut into small pieces immediately prior to the study, irradiated and measured with EPR after application of a special treatment to reduce mechanical stress caused by cut, and with rigorous control of size and number of clippings (unstressed-old, controlled); and (5) recently (<24 h) cut, irradiated and measured with EPR after application of a special treatment to reduce the mechanical stress caused by cut, and without rigorous control of size and number of clippings (unstressed-fresh, uncontrolled). Except for the fifth selected group, variability of the dose dependence inside all groups was found to be not statistically significant, although the variability among the different groups was significant. Comparison of the mean dose dependences obtained for each group allowed selection of key factors responsible for radiation

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

    NASA Astrophysics Data System (ADS)

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

    2006-03-01

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

  17. Exploring Structure, Dynamics, and Topology of Nitroxide Spin-Labeled Proteins Using Continuous-Wave Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Altenbach, Christian; López, Carlos J; Hideg, Kálmán; Hubbell, Wayne L

    2015-01-01

    Structural and dynamical characterization of proteins is of central importance in understanding the mechanisms underlying their biological functions. Site-directed spin labeling (SDSL) combined with continuous-wave electron paramagnetic resonance (CW EPR) spectroscopy has shown the capability of providing this information with site-specific resolution under physiological conditions for proteins of any degree of complexity, including those associated with membranes. This chapter introduces methods commonly employed for SDSL and describes selected CW EPR-based methods that can be applied to (1) map secondary and tertiary protein structure, (2) determine membrane protein topology, (3) measure protein backbone flexibility, and (4) reveal the existence of conformational exchange at equilibrium. PMID:26477248

  18. Solid-state nuclear magnetic resonance structural studies of proteins using paramagnetic probes.

    PubMed

    Jaroniec, Christopher P

    2012-01-01

    Determination of three-dimensional structures of biological macromolecules by magic-angle spinning (MAS) solid-state NMR spectroscopy is hindered by the paucity of nuclear dipolar coupling-based restraints corresponding to distances exceeding 5 Å. Recent MAS NMR studies of uniformly (13)C,(15)N-enriched proteins containing paramagnetic centers have demonstrated the measurements of site-specific nuclear pseudocontact shifts and spin relaxation enhancements, which report on electron-nucleus distances up to ~20 Å. These studies pave the way for the application of such long-distance paramagnetic restraints to protein structure elucidation and analysis of protein-protein and protein-ligand interactions in the solid phase. Paramagnetic species also facilitate the rapid acquisition of high resolution and sensitivity multidimensional solid-state NMR spectra of biomacromolecules using condensed data collection schemes, and characterization of solvent-accessible surfaces of peptides and proteins. In this review we discuss some of the latest applications of magic-angle spinning NMR spectroscopy in conjunction with paramagnetic probes to the structural studies of proteins in the solid state.

  19. Photoactivation of the flavin cofactor in Xenopus laevis (6–4) photolyase: Observation of a transient tyrosyl radical by time-resolved electron paramagnetic resonance

    PubMed Central

    Weber, Stefan; Kay, Christopher W. M.; Mögling, Heike; Möbius, Klaus; Hitomi, Kenichi; Todo, Takeshi

    2002-01-01

    The light-induced electron transfer reaction of flavin cofactor photoactivation in Xenopus laevis (6–4) photolyase has been studied by continuous-wave and time-resolved electron paramagnetic resonance spectroscopy. When the photoactivation is initiated from the fully oxidized form of the flavin, a neutral flavin radical is observed as a long-lived paramagnetic intermediate of two consecutive single-electron reductions under participation of redox-active amino acid residues. By time-resolved electron paramagnetic resonance, a spin-polarized transient radical-pair signal was detected that shows remarkable differences to the signals observed in the related cyclobutane pyrimidine dimer photolyase enzyme. In (6–4) photolyase, a neutral tyrosine radical has been identified as the final electron donor, on the basis of the characteristic line width, hyperfine splitting pattern, and resonance magnetic field position of the tyrosine resonances of the transient radical pair. PMID:11805294

  20. 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

  1. 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

  2. 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

  3. Diffusion of Paramagnetically Labeled Proteins in Cartilage: Enhancement of the 1-D NMR Imaging Technique

    NASA Astrophysics Data System (ADS)

    Foy, Brent D.; Blake, Joseph

    2001-01-01

    Quantifying the diffusive transport of large molecules in avascular cartilage tissue is important both for planning potential pharamacological treatments and for gaining insight into the molecular-scale structure of cartilage. In this work, the diffusion coefficients of gadolinium-DTPA and Gd-labeled versions of four proteins-lysozyme, trypsinogen, ovalbumin, and bovine serum albumin (BSA) with molecular weights of 14,300, 24,000, 45,000, and 67,000, respectively-have been measured in healthy and degraded calf cartilage. The experimental technique relies on the effect of the paramagnetic on the relaxation properties of the surrounding water, combined with the time course of a 1-dimensional spatial profile of the water signal in the cartilage sample. The enhanced technique presented here does not require a prior measurement of the relaxivity of the paramagnetic compound in the sample of interest. The data are expressed as the ratio of the diffusion coefficient of a compound in cartilage to its diffusion coefficient in water. For healthy cartilage, this ratio was 0.34 ± 0.07 for Gd-DTPA, the smallest compound, and fell to 0.3 ± 0.1 for Gd-lysozyme, 0.08 ± 0.04 for Gd-trypsinogen, and 0.07 ± 0.04 for Gd-ovalbumin. Gd-BSA did not appear to enter healthy cartilage tissue beyond a surface layer. After the cartilage had been degraded by 24-h trypsinization, these ratios were 0.60 ± 0.03 for Gd-DTPA, 0.40 ± 0.08 for Gd-lysozyme, 0.42 ± 0.09 for Gd-trypsinogen, 0.16 ± 0.14 for Gd-ovalbumin, and 0.11 ± 0.05 for Gd-BSA. Thus, degradation of the cartilage led to increases in the diffusion coefficient of up to fivefold for the Gd-labeled proteins. These basic transport parameters yield insights on the nature of pore sizes and chemical-matrix interactions in the cartilage tissue and may prove diagnostically useful for identifying the degree and nature of damage to cartilage.

  4. [Simultaneous magnetic resonance angiographic and tomographic assessment of atherosclerotic plaques of carotid arteries with paramagnetic contrasting by cyclomang].

    PubMed

    Usov, V Yu; Belyanin, M L; Bobrikova, E E; Borodin, O Yu; Shimanovsky, N L; Minenko, T V; Bukhovets, I L; Plotnikov, M P; Kozlov, B N; Shipulin, V M

    2016-01-01

    The authors studied a possibility of simultaneously performing magnetic resonance (MR) angiography of carotid arteries and contrast-enhanced MR tomography of atherosclerotic plaques of carotid arteries. We examined a total of 16 patients presenting with disseminated atherosclerosis and 8 patients of the control group. Quadrature coils for examination of the head were used in order to sequentially perform MR tomography of the brain, MR angiography of carotid arteries and MR tomography of atherosclerotic plaques of carotid arteries with contrasting by 0.5M cyclomang. Angiography was carried out by means of the technique of 3D GR FFE of rapid gradient echo (TR/TE/FA/ST=10 ms/2.7 ms/20°/1.5 mm). MR tomography of the carotid arteries bifurcation was performed in the T1-weighted spin-echo mode: TR=500-900 ms, TE=10 ms, slice sickness 1-3 mm into the matrix 256x256 voxels, with the voxel size measuring 0.2x0.2x2 mm. The average time of passing of the paramagnetic through the blood vessels of the cerebral hemispheres in the control group amounted to 4.23±0.14 s for the left hemisphere and to 4.27±0.15 s for the right one. The mean time of bolus passing in patients with predominantly unilateral stenosis of the internal carotid artery amounted to 4.89±0.23 on the affected side, equalling 4.56±0.19 s on the unaffected side (p>0.05). In bilateral lesions these indices for the left and right hemispheres amounted to 4.98±0.21 s and 5.01±0.16 s (p>0.05), respectively. Contrast-enhanced MR angiography with cyclomang made it possible in all cases to visualize the localization and character of stenosis. The index of stenosis degree calculated for MR-angiogram highly significantly correlated with the indices of the ultrasonographic examination performed according to the ECST technique both for cases of unilateral (r=0.87, p<0.05) and cases of bilateral stenotic lesion (r=0.85, p<0.05). Inhomogeneous soft plaques with high content of lipids had high values of the enhancement

  5. Electron paramagnetic resonance spectroscopy of Cr3+ in hexagonal Cs2NaGaF6 crystals

    NASA Astrophysics Data System (ADS)

    Vrielinck, H.; Khaidukov, N. M.; Callens, F.; Matthys, P.

    Powder samples of hydrothermally grown Cr3+ -doped Cs-2 NaGaF6 crystals have been investigated with electron paramagnetic resonance spectroscopy at X - (9.5 GHz) and Q -band (34 GHz). Analysis of the spectra clearly demonstrates that there are two distinct Cr3+ centres in the Cs2NaGaF6 crystal, having nearly identical g factors, but differing largely from the viewpoint of their zero field splitting. By using the Cr-53 hyperfine spectra observed with electron nuclear double resonance spectroscopy, it is deduced that these centres have opposite signs for the zero field splitting. The spectroscopic properties of the Cr3+ centres in the isostructural Cs2NaGaF6 and Cs2NaAlF6 crystals are compared and discussed.

  6. Native and induced triplet nitrogen-vacancy centers in nano- and micro-diamonds: Half-field electron paramagnetic resonance fingerprint

    NASA Astrophysics Data System (ADS)

    Shames, A. I.; Osipov, V. Yu.; von Bardeleben, H.-J.; Boudou, J.-P.; Treussart, F.; Vul', A. Ya.

    2014-02-01

    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 gHF1 = 4.26 and gHF2 = 4.00 signals. This feature is attributed to "forbidden" ΔMS = 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 D1 = 0.0950 ± 0.002 cm-1 and D2 = 0.030 ± 0.005 cm-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 gHF1 = 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.

  7. Electron Paramagnetic Resonance of MANGANESE(2+), COPPER(2+) and GADOLINIUM(3+) Ions Doping Some - and - Magnetic Single Crystals.

    NASA Astrophysics Data System (ADS)

    Kahrizi, Mojtaba

    X-band EPR measurements on several Mn('2+)-doped single crystals have been made at room and low temperatures. The spin-Hamiltonian parameters are evaluated from the data using a rigorous least-squares-fitting program suitable for electron-nuclear spin coupled systems. The signs of the parameters are determined from the observed relative intensities of EPR lines at liquid helium temperature. The temperature variation of zero-field splitting parameter b(,2)('0), as well as that of the linewidths have been studied. Using the shift of g-values in the paramagnetic Ni('2+) lattices, from those in the corresponding isostructural diagmagnetic lattices, the exchange constant between Mn('2+) -Ni('2+) ions in nickel salts has been estimated. For the case of hosts containing paramagnetic Co('2+) ions the spin-lattice relaxation time was estimated at room and liquid nitrogen temperatures. X-band EPR measurements on Cu('2+) in copper pentakisantipyrine perchlorate were performed at room and low temperatures. The principal values of g and A tensors and their direction cosines were evaluated using a rigorous least-squares fitting technique. Finally, X-band EPR studies of Gd('3+)-doped single crystals of LiYF(,4) and LiYbF(,4) have been made at room and low temperatures. In the case of paramagnetic host LiYbF(,4) the EPR lines broadened very fast as the temperature was lowered from room temperature, and below 270 K no EPR lines were observed. The parameters were evaluated using a least squares fitting method. The temperature variation of the parameters was studied. Using the g-shift in LiYbF(,4) from its value in LiYF(,4) the exchange constant between Gd('3+) and its paramagnetic neighbor ions Yb('3+), was estimated.

  8. Electron-paramagnetic-resonance study of the Sn DX center in direct-gap Ga0.69Al0.31As

    NASA Astrophysics Data System (ADS)

    von Bardeleben, H. J.; Bourgoin, J. C.; Basmaji, P.; Gibart, P.

    1989-09-01

    An electron-paramagnetic-resonance study of the Sn-related DX center in direct-gap Ga0.69Al0.31As shows that the DX center can be transformed by photoexcitation into an excited paramagnetic state, which is metastable at 4 K. This excited state has the characteristics of a strain-split T2 state; its asymmetric line can be decomposed into two Gaussians with the parameters g1=1.92,ΔB1=500 G and g2=1.95,ΔB2=200 G. The photoexcitation spectrum of this paramagnetic state, which is of the Lucovsky type with a threshold at 0.8 eV, is interpreted as an internal A1-T2 transition. No paramagnetic spectrum associated with the ground state of DX has been observed.

  9. 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.

  10. 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.

  11. 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.

  12. 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

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

    NASA Astrophysics Data System (ADS)

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

    2014-03-01

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

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

    PubMed

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

    2015-08-01

    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 a 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.

  15. 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.

  16. 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.

  17. 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

  18. 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

  19. 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.

  20. 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.

  1. Electron paramagnetic resonance studies of Cu 2+ ion in Tetraaqua-di(nicotinamide)Ni(II)-saccharinates single crystals

    NASA Astrophysics Data System (ADS)

    Yerli, Y.; Kazan, S.; Yalçın, O.; Aktaş, B.

    2006-06-01

    X-band (˜9.8 GHz) electron paramagnetic resonance (EPR) measurement at ambient temperature in three mutually perpendicular planes have been carried out on a single crystal of Cu 2+ doped mixed ligand complex of Ni(II) with saccharin and nicotinamide [Ni(Nic) 2(H 2O) 4](sac) 2. The angular dependent spectra showed that the Cu 2+ ion enters Ni 2+ sites in the lattice and distorted local environment of Ni 2+ site. The principal g and A values, covalency parameter ( α' 2), mixing coefficients ( α and β) and Fermi contact term ( K) have been evaluated from the EPR analysis. The ground-state wave function of the Cu 2+ ion has been constructed using the α' 2, α and β values. The nature of the distortion present in the lattice is obtained from the values of the mixing coefficients.

  2. 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

  3. A high-frequency electron paramagnetic resonance spectrometer for multi-dimensional, multi-frequency, and multi-phase pulsed measurements.

    PubMed

    Cho, F H; Stepanov, V; Takahashi, S

    2014-07-01

    We describe instrumentation for a high-frequency electron paramagnetic resonance (EPR) and pulsed electron-electron double resonance (PELDOR) spectroscopy. The instrumentation is operated in the frequency range of 107-120 GHz and 215-240 GHz and in the magnetic field range of 0-12.1 T. The spectrometer consisting of a high-frequency high-power solid-state source, a quasioptical system, a phase-sensitive detection system, a cryogenic-free superconducting magnet, and a (4)He cryostat enables multi-frequency continuous-wave EPR spectroscopy as well as pulsed EPR measurements with a few hundred nanosecond pulses. Here we discuss the details of the design and the pulsed EPR sensitivity of the instrumentation. We also present performance of the instrumentation in unique experiments including PELDOR spectroscopy to probe correlations in an insulating electronic spin system and application of dynamical decoupling techniques to extend spin coherence of electron spins in an insulating solid-state system. PMID:25085176

  4. A high-frequency electron paramagnetic resonance spectrometer for multi-dimensional, multi-frequency, and multi-phase pulsed measurements

    SciTech Connect

    Cho, F. H.; Stepanov, V.; Takahashi, S.

    2014-07-15

    We describe instrumentation for a high-frequency electron paramagnetic resonance (EPR) and pulsed electron-electron double resonance (PELDOR) spectroscopy. The instrumentation is operated in the frequency range of 107−120 GHz and 215−240 GHz and in the magnetic field range of 0−12.1 T. The spectrometer consisting of a high-frequency high-power solid-state source, a quasioptical system, a phase-sensitive detection system, a cryogenic-free superconducting magnet, and a {sup 4}He cryostat enables multi-frequency continuous-wave EPR spectroscopy as well as pulsed EPR measurements with a few hundred nanosecond pulses. Here we discuss the details of the design and the pulsed EPR sensitivity of the instrumentation. We also present performance of the instrumentation in unique experiments including PELDOR spectroscopy to probe correlations in an insulating electronic spin system and application of dynamical decoupling techniques to extend spin coherence of electron spins in an insulating solid-state system.

  5. Electron paramagnetic resonance spectroscopic investigation of the inhibition of the phosphoroclastic system of Clostridium sporogenes by nitrite.

    PubMed

    Payne, M J; Woods, L F; Gibbs, P; Cammack, R

    1990-10-01

    The proposal that nitrite exerts its inhibitory effect on anaerobic bacteria by direct interaction with the iron-sulphur proteins of the phosphoroclastic system was investigated. The effects of nitrate, nitrite with or without ascorbate, and nitric oxide on the growth of Clostridium sporogenes in liquid cultures at pH 7.4, on the rates of hydrogen production, and on the activities of the enzymes pyruvate-ferredoxin oxidoreductase and hydrogenase, and of ferredoxin were investigated. In agreement with previous studies, nitrate was the least effective inhibitor of cell growth, and nitric oxide the most effective. Nitrite reductase activity was very low in C. sporogenes, indicating that the presence of external reducing agents would be necessary for the reduction of nitrite to nitric oxide. Inhibition by nitrite was enhanced by ascorbate; 0.5 mM-nitrite with 10 mM-ascorbate stopped growth completely. In partially-purified preparations 4.1 mM-NaNO2 and equimolar ascorbate caused complete inactivation of hydrogenase activity but only partial (up to 78%) inactivation of pyruvate-ferredoxin oxidoreductase. This agreed with the loss of hydrogen production observed with nitrite in vivo. Inhibition occurred within 5 min, and was irreversible in each case. Electron paramagnetic resonance (EPR) spectroscopy showed that paramagnetic [Fe(NO)2(SR)2] species were formed during growth in the presence of nitrite, and were associated with cells. However, the intensity of these EPR signals did not correlate with the inhibition of cell growth. The [4Fe-4S] clusters in ferredoxin were shown by EPR spectroscopy to be resistant to treatment with 3.6 mM-NaNO2 and 3.6 mM-ascorbate. It is concluded that the effects of nitrite on pre-formed iron-sulphur proteins are not convincing as a basis for the lethal effects on bacterial cells.

  6. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2007-03-01

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

  8. 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.

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

    PubMed

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

    2015-06-01

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

  10. Hyperfine interactions of Ho3+ ions in KY3F10: Electron paramagnetic resonance and optical spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Pytalev, D. S.; Chukalina, E. P.; Popova, M. N.; Shakurov, G. S.; Malkin, B. Z.; Korableva, S. L.

    2012-09-01

    We use high-frequency electron paramagnetic resonance (EPR) and high-resolution optical Fourier spectroscopies to characterize hyperfine interactions of the impurity Ho3+ ions in KY3F10 crystals. Well-resolved hyperfine structure is observed in the EPR spectra for several transitions within the ground 5I8 multiplet of the Ho3+ ion and in the optical spectra for many lines in the infrared and visible ranges. The observed hyperfine patterns and field dependences of the resonance frequencies in the EPR spectra are well reproduced by calculations based on the crystal field (CF) theory. This favors reliability of calculated energies and wave functions of the electron-nuclear states within the ground and excited levels of Ho3+ in KY3F10. Finally, the dc magnetic susceptibility of the concentrated KHo3F10 crystal taken from literature is successfully modeled in the temperature range 0.01-20 K, using CF parameters of the impurity Ho3+ ions in KY3F10.

  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. 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

  13. Potentially diagnostic electron paramagnetic resonance spectra elucidate the underlying mechanism of mitochondrial dysfunction in the deoxyguanosine kinase deficient rat model of a genetic mitochondrial DNA depletion syndrome.

    PubMed

    Bennett, Brian; Helbling, Daniel; Meng, Hui; Jarzembowski, Jason; Geurts, Aron M; Friederich, Marisa W; Van Hove, Johan L K; Lawlor, Michael W; Dimmock, David P

    2016-03-01

    A novel rat model for a well-characterized human mitochondrial disease, mitochondrial DNA depletion syndrome with associated deoxyguanosine kinase (DGUOK) deficiency, is described. The rat model recapitulates the pathologic and biochemical signatures of the human disease. The application of electron paramagnetic (spin) resonance (EPR) spectroscopy to the identification and characterization of respiratory chain abnormalities in the mitochondria from freshly frozen tissue of the mitochondrial disease model rat is introduced. EPR is shown to be a sensitive technique for detecting mitochondrial functional abnormalities in situ and, here, is particularly useful in characterizing the redox state changes and oxidative stress that can result from depressed expression and/or diminished specific activity of the distinct respiratory chain complexes. As EPR requires no sample preparation or non-physiological reagents, it provides information on the status of the mitochondrion as it was in the functioning state. On its own, this information is of use in identifying respiratory chain dysfunction; in conjunction with other techniques, the information from EPR shows how the respiratory chain is affected at the molecular level by the dysfunction. It is proposed that EPR has a role in mechanistic pathophysiological studies of mitochondrial disease and could be used to study the impact of new treatment modalities or as an additional diagnostic tool. PMID:26773591

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

    PubMed Central

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

    2011-01-01

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

  15. 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).

  16. Electron paramagnetic resonance evidence of hydroxyl radical generation and oxidative damage induced by tetrabromobisphenol A in Carassius auratus.

    PubMed

    Shi, Huahong; Wang, Xiaorong; Luo, Yi; Su, Yan

    2005-09-30

    Tetrabromobisphenol A (TBBPA) is one of the most widely used brominated flame retardants (BFRs). To confirm its putative oxidative stress-inducing activity, freshwater fish Carassius auratus were injected intraperitoneally with TBBPA. One experiment lasted 3h to 28 days after a single injection of 100mg/kg TBBPA, and the other lasted 24h after a single injection of 0-300 mg/kg TBBPA. Reactive oxygen species (ROS) were trapped by phenyl-tert-butyl nitrone (PBN) and detected by electron paramagnetic resonance (EPR). Protein carbonyl (PCO) and lipid peroxidation product (LPO) content were also determined. A six-line EPR spectrum was detected in the sample prepared in air, and a multiple one was obtained in nitrogen. The observed spectrum in nitrogen fits the simulation one with PBN/OCH(3) and PBN/CH(3) quite well. As compared to the control group, TBBPA significantly induced ROS production marked by the intensity of the prominent spectra in liver and bile. TBBPA (100mg/kg) also significantly increased PCO content in liver starting 24h and LPO content 3 days after injection. Either PCO or LPO content showed significant relation with ROS production. Based on the hyperfine constants and shape of the spectrum, ROS induced by TBBPA was determined as OH. The results clearly indicated that TBBPA could induce OH generation and result in oxidative damage in liver of C. auratus.

  17. Crystallization and electron paramagnetic resonance characterization of the complex of photosystem I with its natural electron acceptor ferredoxin.

    PubMed Central

    Fromme, Petra; Bottin, Hervé; Krauss, Norbert; Sétif, Pierre

    2002-01-01

    The formation of a transient complex between photosystem I and ferredoxin is involved in the process of ferredoxin photoreduction in oxygenic photosynthetic organisms. Reduced ferredoxin is an essential redox intermediate involved in many assimilatory processes and is necessary for the reduction of NADP(+) to NADPH. Single crystals from a complex of photosystem I with ferredoxin were grown using PEG 400 and CaCl(2) as precipitation agents. The crystals diffract x-rays to a resolution of 7-8 A. The space group was determined to be orthorhombic with the unit cell dimensions a = 194 A, b = 208 A, and c = 354 A. The crystals contain photosystem I and ferredoxin in a 1:1 ratio. Electron paramagnetic resonance (EPR) measurements on these crystals are reported, where EPR signals of the three [4Fe-4S] clusters F(A), F(B), F(X), and the [2Fe-2S] cluster of ferredoxin were detected. From the EPR spectra observed at three particular orientations of the crystal in the magnetic field, the full orientation pattern of the F g-tensor was simulated. This simulation is consistent with the presence of 12 magnetically inequivalent F clusters per unit cell with the C(3) axis of the PSI trimers oriented at (23 degrees, 72 degrees, 77 degrees ) to the unit cell axes. PMID:12324399

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

    PubMed Central

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

    1996-01-01

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

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

    PubMed

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

    1996-11-01

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

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

    PubMed

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

    2016-06-01

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

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

    PubMed

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

    2016-01-01

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

  2. Electron paramagnetic resonance of [(CH3)3NH]CuCl3.2H2O

    NASA Astrophysics Data System (ADS)

    Ritter, Mark B.; Drumheller, John E.; Kite, Terence M.; Snively, Leslie O.; Emerson, Kenneth

    1983-11-01

    The electron paramagnetic resonance of [(CH3)3NH]CuCl3.2H2O has been studied in the temperature range of 4 K to room temperature. This compound is known to behave magnetically as a spin- 1/2 , one-dimensional Heisenberg ferromagnetic with ordering below 1K. In the high-temperature regime the EPR data show a rich angular dependence of the linewidths as the magnetic field is rotated away from the chain. The data were analyzed in manner similar to that used by McGregor and Soos, who used the Blume-Hubbard result for spin dynamics and extracted exchange anisotropies in one dimension. For adequate fit, we reduced the symmetry of symmetric anisotropic exchange to orthorhombic and included the antisymmetric exchange. Isotropic symmetric, dipolar, anisotropic symmetric, and antisymmetric exchange therefore were included with the room temperature results of J0=0.8 K, Dd=0.058 K, De=0.032 K, and d=0.043 K, respectively, and further show about a 12% XY character to the exchange. These results are reasonably consistent with the previous results on this compound. Splitting of the EPR lines indicate that there are two inequivalent chains along the needle axis. Data to 4 K indicate no significant changes in the angle dependence but an anomalous monotonic broadening of the linewidths is observed as temperature is lowered.

  3. Optical absorption and electron paramagnetic resonance of the E{sub {alpha}}{sup '} center in amorphous silicon dioxide

    SciTech Connect

    Buscarino, G.; Boscaino, R.; Agnello, S.; Gelardi, F. M.

    2008-04-15

    We report a combined study by optical absorption (OA) and electron paramagnetic resonance (EPR) spectroscopy on the E{sub {alpha}}{sup '} point defect in amorphous silicon dioxide (a-SiO{sub 2}). This defect has been studied in {beta}-ray irradiated and thermally treated oxygen-deficient a-SiO{sub 2} materials. Our results have pointed out that the E{sub {alpha}}{sup '} center is responsible for an OA Gaussian band peaked at {approx}5.8 eV and having a full width at half maximum of {approx}0.6 eV. The estimated oscillator strength of the related electronic transition is {approx}0.14. Furthermore, we have found that this OA band is quite similar to that of the E{sub {gamma}}{sup '} center induced in the same materials, indicating that the related electronic transitions involve states highly localized on a structure common to both defects: the O{identical_to}Si{sup {center_dot}} moiety.

  4. 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. PMID:26052642

  5. Experimental and Theoretical Electron Paramagnetic Resonance (EPR) Study on the Temperature-Dependent Structural Changes of Methylsulfanylmethane

    PubMed Central

    Tapramaz, Recep; Türkkan, Ercan; Dereli, Ömer

    2011-01-01

    Methylsulfonylmethane (or dimethyl sulfone), a naturally produced and vitally important organosulfur compound in living organisms, was irradiated with gamma rays, and the produced radicals were investigated using electron paramagnetic resonance spectroscopy at different temperatures. The structure and behavior of the radical changed when the temperatures varied. The hyperfine splitting of the CH3 group was small, and the 33S splitting was relatively high between 80 and −50 °C. When the temperature was between −50 and −160 °C, the 33S splitting became small and the CH3 splitting was higher. However, the group kept rotating; therefore, only the isotropic splitting values were measured, and the g-values were anisotropic. When the temperature decreased below −180 °C, the CH3 group stopped rotating, and the hydrogen splitting values became nonequivalent due to an inhomogeneous electron distribution. The observed structures can be explained by referring to both the experimental and theoretically calculated values reported. PMID:21954334

  6. 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.

  7. 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

  8. Electron Paramagnetic Resonance and Fluorescence In Situ Hybridization-Based Investigations of Individual Doses for Persons Living at Metlino in the Upper Reaches of the Techa River

    SciTech Connect

    Degteva, M. O.; Anspaugh, L. R.; Akleyev, A V.; Jacob, Peter; Ivanov, Denis V.; Wieser, Albrecht; Vorobiova, M I.; Shishkina, Elena A.; Shved, Valentina A.; Vozilova, Alexandra; Bayankin, Sergey N.; Napier, Bruce A.

    2005-02-01

    Waterborne releases to the Techa River from the Mayak Production Association in Russia during 1949-1956 resulted in significant doses to persons living downstream; the most contaminated village was Metlino, about 7 km from the site of release. Internal and external doses have been estimated for these residents using the Techa River Dosimetry System-2000 (TRDS-2000); the primary purpose is to support epidemiological studies of the members of the Extended Techa River Cohort. Efforts to validate the calculations of external and internal dose are considered essential. One validation study of the TRDS-2000 system has been performed by the comparison of calculated doses to quartz from bricks in old buildings at Metlino with those measured by luminescence dosimetry. Two additional methods of validation considered here are electron paramagnetic resonance (EPR) measurements of teeth and fluorescence in situ hybridization (FISH) measurements of chromosome translocations in circulating lymphocytes. For electron paramagnetic resonance, 36 measurements on 26 teeth from 16 donors from Metlino were made at the GSF-National Research Center for Environment and Health (16 measurements) and the Institute of Metal Physics (20 measurements); the correlation among measurements made at the two laboratories has been found to be 0.99. Background measurements were also made on 218 teeth (63 molars, 128 premolars, and 27 incisors). Fluorescence in situ hybridization measurements were made for 31 residents of Metlino. These measurements were handicapped by the analysis of a limited number of cells; for several individuals no stable translocations were observed. Fluorescence in situ hybridization measurements were also made for 39 individuals believed to be unexposed. The EPR- and FISH-based estimates agreed well for permanent residents of Metlino: 0.67 +/- 0.21 Gy and 0.48 +/- 0.18 Gy (mean +/- standard error of the mean), respectively. Results of the two experimental methods also agreed well

  9. Kissing G Domains of MnmE Monitored by X-Ray Crystallography and Pulse Electron Paramagnetic Resonance Spectroscopy

    PubMed Central

    Meyer, Simon; Böhme, Sabine; Krüger, André; Steinhoff, Heinz-Jürgen; Klare, Johann P.; Wittinghofer, Alfred

    2009-01-01

    MnmE, which is involved in the modification of the wobble position of certain tRNAs, belongs to the expanding class of G proteins activated by nucleotide-dependent dimerization (GADs). Previous models suggested the protein to be a multidomain protein whose G domains contact each other in a nucleotide dependent manner. Here we employ a combined approach of X-ray crystallography and pulse electron paramagnetic resonance (EPR) spectroscopy to show that large domain movements are coupled to the G protein cycle of MnmE. The X-ray structures show MnmE to be a constitutive homodimer where the highly mobile G domains face each other in various orientations but are not in close contact as suggested by the GDP-AlFx structure of the isolated domains. Distance measurements by pulse double electron-electron resonance (DEER) spectroscopy show that the G domains adopt an open conformation in the nucleotide free/GDP-bound and an open/closed two-state equilibrium in the GTP-bound state, with maximal distance variations of 18 Å. With GDP and AlFx, which mimic the transition state of the phosphoryl transfer reaction, only the closed conformation is observed. Dimerization of the active sites with GDP-AlFx requires the presence of specific monovalent cations, thus reflecting the requirements for the GTPase reaction of MnmE. Our results directly demonstrate the nature of the conformational changes MnmE was previously suggested to undergo during its GTPase cycle. They show the nucleotide-dependent dynamic movements of the G domains around two swivel positions relative to the rest of the protein, and they are of crucial importance for understanding the mechanistic principles of this GAD. PMID:19806182

  10. Theoretical investigations of the electron paramagnetic resonance for Cr 3+ ions at tetragonal sites in K 2ZnF 4 crystal

    NASA Astrophysics Data System (ADS)

    Zeng, Ti-xian; Chen, Jia-jun; Chen, Tai-hong; Dai, Xiao-jing; Liao, Guo

    2010-06-01

    In tetragonal ligand-field, based on the Zhao’s semi-SCF d-orbit wave functions model, the Macfarlane’s perturbation loop method and point-charge crystal field model, the third-order perturbation formulas of electron paramagnetic resonance parameters (zero-field splitting D and g-factors) for 3d 3/7 configuration ions have been constructed. In these formulas, the contributions from configuration interaction, covalency effect, Racah-Trees corrections and local structure distortion (Δ R) have been considered. By using these formulas, the electron paramagnetic resonance parameters of Cr 3+ ion at tetragonal site in K 2ZnF 4 crystal have been calculated. The theoretically calculated values are consistent with the experimentally observed.

  11. 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

  12. 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.

  13. Using nitroxide spin labels. How to obtain T1e from continuous wave electron paramagnetic resonance spectra at all rotational rates.

    PubMed Central

    Haas, D A; Mailer, C; Robinson, B H

    1993-01-01

    Historically, the continuous wave electron paramagnetic resonance (CW-EPR) progressive saturation method has been used to obtain information on the spin-lattice relaxation time (T1e) and those processes, such as motion and spin exchange, that occur on a competitive timescale. For example, qualitative information on local dynamics and solvent accessibility of proteins and nucleic acids has been obtained by this method. However, making quantitative estimates of T1e from CW-EPR spectra have been frustrated by a lack of understanding of the role of T1e (and T2e) in the slow-motion regime. Theoretical simulation of the CW-EPR lineshapes in the slow-motion region under increasing power levels has been used in this work to test whether the saturation technique can produce quantitative estimates of the spin-lattice relaxation rates. A method is presented by which the correct T1e may be extracted from an analysis of the power-saturation rollover curve, regardless of the amount of inhomogeneous broadening or the rates of molecular reorientation. The range of motional correlation times from 10 to 200 ns should be optimal for extracting quantitative estimates of T1e values in spin-labeled biomolecules. The progressive-saturation rollover curve method should find wide application in those areas of biophysics where information on molecular interactions and solvent exposure as well as molecular reorientation rates are desired. PMID:8386009

  14. Study of a DNA Duplex by Nuclear Magnetic Resonance and Molecular Dynamics Simulations. Validation of Pulsed Dipolar Electron Paramagnetic Resonance Distance Measurements Using Triarylmethyl-Based Spin Labels.

    PubMed

    Lomzov, Alexander A; Sviridov, Eugeniy A; Shernuykov, Andrey V; Shevelev, Georgiy Yu; Pyshnyi, Dmitrii V; Bagryanskaya, Elena G

    2016-06-16

    Pulse dipole-dipole electron paramagnetic resonance (EPR) spectroscopy (double electron-electron resonance [DEER] or pulse electron-electron double resonance [PELDOR] and double quantum coherence [DQC]) allows for measurement of distances in biomolecules and can be used at low temperatures in a frozen solution. Recently, the possibility of distance measurement in a nucleic acid at a physiological temperature using pulse EPR was demonstrated. In these experiments, triarylmethyl (TAM) radicals with long memory time of the electron spin served as a spin label. In addition, the duplex was immobilized on modified silica gel particles (Nucleosil DMA); this approach enables measurement of interspin distances close to 4.5 nm. Nevertheless, the possible influence of TAM on the structure of a biopolymer under study and validity of the data obtained by DQC are debated. In this paper, a combination of molecular dynamics (MD) and nuclear magnetic resonance (NMR) methods was used for verification of interspin distances measured by the X-band DQC method. NMR is widely used for structural analysis of biomolecules under natural conditions (room temperature and an aqueous solution). The ultraviolet (UV) melting method and thermal series (1)H NMR in the range 5-95 °C revealed the presence of only the DNA duplex in solution at oligonucleotide concentrations 1 μM to 1.1 mM at temperatures below 40 °C. The duplex structures and conformation flexibility of native and TAM-labeled DNA complexes obtained by MD simulation were the same as the structure obtained by NMR refinement. Thus, we showed that distance measurements at physiological temperatures by the X-band DQC method allow researchers to obtain valid structural information on an unperturbed DNA duplex using terminal TAM spin labels.

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

    PubMed

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

    2010-09-15

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

  16. 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.

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

    PubMed Central

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

    2013-01-01

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

  18. Host spin-lattice relaxation narrowing and the electron paramagnetic resonance of Mn(II) in single crystals of hexakis(pyridine N-oxide)cobalt(II) complexes

    NASA Astrophysics Data System (ADS)

    Murugesan, R.; Thamaraichelvan, A.; Milton Franklin, A.; Ramakrishnan, V.

    The electron paramagnetic resonance spectra of Mn(C5H5NO)6. X2 (X ≡ ClO-4, BF-4 and NO-3) doped in single crystals of isomorphous paramagnetic Co(C5H5NO)6. X2 are studied at various temperatures. Zero-field splitting in all three crystals is axially symmetric and the magnitude of D is unusually large for an octahedral coordination polyhedron with all ligands identical. The sharp resonance of Mn(II) in the paramagnetic host observed at high temperatures is interpreted in terms of random modulation of the dipolar interaction between the guest Mn(II) and host Co(II) ions by the rapid spin-lattice relaxation of Co(II). The spin-lattice relaxation times of Co(II) ions at 300 K, estimated from the temperature dependent linewidth of the Mn(II) resonance, are 24 × 10-12, 28 × 10-12 and 23 × 10-12 s in perchlorate, fluoborate and nitrate crystals respectively. The temperature dependence of the relaxation is of the form 1/(at + bt5) and below 270 K the direct process dominates.

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

    PubMed

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

    2016-06-01

    Fluorine-19 magnetic resonance imaging ((19)F 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 (19)F 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 metallated 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 (19)F T1 can readily be reduced by an order of magnitude and tuned by stoichiometric modulation of the iron concentration. The resulting (19)F MRI detection sensitivity is enhanced by three- to fivefold over previously used tracers at 11.7 T, and is predicted to increase by at least eightfold at the clinical field strength of 3 T. PMID:26974409

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

    NASA Astrophysics Data System (ADS)

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

    2016-06-01

    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 metallated 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 three- to fivefold over previously used tracers at 11.7 T, and is predicted to increase by at least eightfold at the clinical field strength of 3 T.

  1. Electron paramagnetic resonance characteristics of some non-heme low-spin iron(III) complexes

    NASA Astrophysics Data System (ADS)

    Duelund, Lars; Toftlund, Hans

    2000-02-01

    We have recorded the powder EPR-spectra of some near octahedral iron(III) complexes with tridentate ligands donors and analysed their spectra with simple ligand field analysis and for some cases with the angular overlap model (AOM). We have determined the electron praramagnetic resonance (EPR) characteristic of bis 1,4,7-triazacyclonane iron(III)chloride at 4 K and found that it was similar to the characteristics of the so-called 'highly anisotropic low spin' complexes. We have recorded the powder spectra of bis (2,6-bis(benzimidazoly-2-yl)pyridine) iron(III) perchlorate and made an AOM-analyses of the structural similar complex bis-(2,6 (N-carbamoyl)-pyridine) iron(III). With a combination of ligand field analyses and AOM, we could determine the π-donor properties of these ligands. The same approach have been used to determine the π-donor properties of the hydroperoxo ligand. Finally we have recorded the powder EPR-spectrum of [Fe(CN) 6] 3- doped in K 3[Co(CN) 6] and [Co(NH 3) 6][Co(CN) 6] at 4 and 100 K and in water at 4 K. The spectra are interpreted as the effect of a dynamic Jahn-Teller distortion.

  2. Creating traveling waves from standing waves from the gyrotropic paramagnetic properties of Fe{sup 3+} ions in a high-Q whispering gallery mode sapphire resonator

    SciTech Connect

    Benmessai, Karim; Tobar, Michael Edmund; Bazin, Nicholas; Bourgeois, Pierre-Yves; Kersale, Yann; Giordano, Vincent

    2009-05-01

    We report observations of the gyrotropic change in magnetic susceptibility of the Fe{sup 3+} electron paramagnetic resonance at 12.037 GHz (between spin states |1/2> and |3/2>) in sapphire with respect to the applied magnetic field. Measurements were made by observing the response of the high-Q whispering gallery doublet in a Hemex sapphire resonator cooled to 5 K. The doublets initially existed as standing waves at zero field and were transformed to traveling waves due to the gyrotropic response.

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

    PubMed

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

    2015-11-12

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

  4. Electron paramagnetic resonance (EPR) oxygen image hypoxic fraction plus radiation dose strongly correlates with tumor cure in FSa fibrosarcomas

    PubMed Central

    Elas, Martyna; Bell, Rebecca; Hleihel, Danielle; Barth, Eugene D.; McFaul, Colin; Haney, Chad R.; Bielanska, Joanna; Pustelny, Katarzyna; Ahn, Kang-Hyun; Pelizzari, Charles A.; Kocherginsky, Masha; Halpern, Howard J.

    2008-01-01

    Purpose Tumor hypoxia has long been known to produce resistance to radiation. In this study, electron paramagnetic resonance (EPR) oxygen imaging was investigated for its power to predict the success of tumor control depending on tumor oxygenation level and radiation therapy dose. Methods and Materials Thirty-four EPR oxygen images were obtained from the legs of C3H mice bearing 0.5 ml FSa fibrosarcomas under both normal (air breathing) and clamped tumor conditions. Under the same conditions as those during which the images were obtained, tumors were irradiated to a variety doses near the FSa TCD50. Tumor tissue was distinguished from normal tissue using co-registration of the EPR oxygen images with spin-echo MRI images of the tumor and/or stereotactic localization. Tumor voxel statistics in the EPR oxygen image included mean and median pO2, and the fraction of tumor voxels below the specified pO2 values of 3, 6 and 10 torr. Bivariate logistic regression analysis using radiation dose and each of the EPR oxygen image statistics determined which best separated treatment failure from success. Results and Conclusions TCD50 measurements were similar to those found in the literature for this syngeneic tumor. Bivariate analysis of 34 tumors demonstrated that tumor cure correlated with dose (p=0.004) and with <10 torr hypoxic fraction (p=0.023). Together, radiation dose and EPR image hypoxic fraction separate the population of FSa fibrosarcomas which are cured from those which fail, thus predicting curability. PMID:18474313

  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. PMID:25233027

  6. 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.

  7. 2-Chlorophenol induced hydroxyl radical production in mitochondria in Carassius auratus and oxidative stress--an electron paramagnetic resonance study.

    PubMed

    Luo, Yi; Sui, Yun-xia; Wang, Xiao-rong; Tian, Yuan

    2008-04-01

    In our previous study, electron paramagnetic resonance (EPR) evidence of reactive oxygen species (ROS) production in Carassius auratus following 2-chlorophenol (2-CP) administration was provided. To further investigate the potential pathway of ROS production, liver mitochondria of C. auratus was isolated and incubated with 2-CP for 30 min. An EPR analysis indicated ROS was produced, and intensities of ROS increased with increasing concentrations of 2-CP. The ROS was then assigned OH by comparing with Fenton reaction. Either catalase or superoxide dismutase, extinguished OH completely in the mitochondria mixture. These facts suggested that O2(.-) and H2O2 contributed to the formation of OH in mitochondria in C. auratus stressed by 2-CP. Combining previous references and our own data, it is reasonable to suggest that 2-CP is first oxidized by H2O2 present in vivo to form phenoxyl radical under the catalytic action of cellular peroxidase (1); phenoxyl radical oxidizes mitochondria NADH to NAD in the presence of NADH (2); NAD reacts with oxygen in vivo to produce O2(.-) (3); O2(.-) is spontaneously dismutated by SOD to form H2O2 and O2, which creates a renewable supply of H2O2 as the initiators of the chain reactions until NADH is consumed (4); simultaneously with reaction (4), O2(.-) reacts with H2O2 to form OH radical via the Haber-Weiss reaction (5). A strong negative correlation (r=-0.9278, p<0.01) between glutathione (GSH) pool and OH production was observed after fish were i.p. injected with 2-CP (250 mg kg(-1)), indicating the depletion of GSH caused by OH.

  8. An Electron Paramagnetic Resonance Spectroscopic Study of Copper Hopping in Doped Bis(L-histidinato)cadmium Dihydrate

    PubMed Central

    Colaneri, Michael J.; Vitali, Jacqueline; Kirschbaum, Kristin

    2013-01-01

    Electron Paramagnetic Resonance (EPR) spectroscopy was used to study Cu(II) dynamic behavior in a doped biological model crystal; bis(L-histidinato)cadmium dihydrate, in order to gain better insight into copper site stability in metalloproteins. Temperature dependent changes in the low temperature X-band EPR spectra became visible around 100 K and continued up to room temperature. The measured 298 K g-tensor (principal values: 2.17, 2.16, 2.07) and copper hyperfine coupling tensor (principal values: −260, − 190, −37 MHz) were similar to the average of the 77 K tensor values pertaining to two neighboring histidine binding sites. The observed temperature dependence was interpreted using Anderson’s theory of motional narrowing, where the magnetic parameters for the different states are averaged as the copper rapidly hops between sites. The EPR pattern was also found to undergo a sharp sigmoidal-shaped, temperature dependent conversion between two species with a critical temperature Tc ≈ 160 K. The species below Tc hops between the two low temperature site patterns, and the one above Tc represents an average of the molecular spin Hamiltonian coupling tensors of the two 77 K sites. In addition, the low and high temperature species hop between one another, contributing to the dynamic averaging. Spectral simulations using this 4-state model determined a hop rate between the two low temperature sites νh4 = 4.5 × 108 s−1 and between the low and high temperature states νh2 = 1.7 × 108 s−1 at 160 K. An Arrhenius relationship of hop rate and temperature gave energy barriers of ΔE4 = 389 cm−1 and ΔE2 = 656 cm−1 between the two low temperature sites, and between the low and high temperature states, respectively. PMID:23530765

  9. Measuring "free" iron levels in Caenorhabditis elegans using low-temperature Fe(III) electron paramagnetic resonance spectroscopy.

    PubMed

    Pate, Kira T; Rangel, Natalie A; Fraser, Brian; Clement, Matthew H S; Srinivasan, Chandra

    2006-11-15

    Oxidative stress, caused by free radicals within the body, has been associated with the process of aging and many human diseases. Because free radicals, in particular superoxide, are difficult to measure, an alternative indirect method for measuring oxidative stress levels has been used successfully in Escherichia coli and yeast. This method is based on a proposed connection between elevated superoxide levels and release of iron from solvent-exposed [4Fe-4S] enzyme clusters that eventually leads to an increase in hydroxyl radical production. In past studies using bacteria and yeast, a positive correlation was found between superoxide production or oxidative stress due to superoxide within the organism and electron paramagnetic resonance (EPR) detectable "free" iron levels. In the current study, we have developed a reliable and efficient method for measuring "free" iron levels in Caenorhabditis elegans using low-temperature Fe(III) EPR at g=4.3. This method uses synchronized worm cultures grown on plates that are homogenized and treated with desferrioxamine, an Fe(III) chelator, prior to packing the EPR tube. Homogenization was found not to alter "free" iron levels, whereas desferrioxamine treatment significantly raised these levels, indicating the presence of both Fe(II) and Fe(III) in the "free" iron pool. The correlation between free radical levels and the observed "free" iron levels was examined by using heat stress and paraquat treatment. The intensity of the Fe(III) EPR signal, and thus the concentration of the "free" iron pool, varied with the treatments that altered radical levels without changing the total iron levels. This study provides the groundwork needed to uncover the correlation among oxidative stress, "free" iron levels, and longevity in C. elegans.

  10. 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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  12. Electron paramagnetic resonance and theoretical studies of Nb in 4H- and 6H-SiC

    NASA Astrophysics Data System (ADS)

    Tien Son, Nguyen; Thang Trinh, Xuan; Gällström, Andreas; Leone, Stefano; Kordina, Olof; Janzén, Erik; Szász, Krisztián; Ivády, Viktor; Gali, Adam

    2012-10-01

    High purity silicon carbide (SiC) materials are of interest from high-power high temperature applications across recent photo-voltaic cells to hosting solid state quantum bits, where the tight control of electrically, optically, and magnetically active point defects is pivotal in these areas. 4H- and 6H-SiC substrates are grown at high temperatures and the incorporation of transition metal impurities is common. In unintentionally Nb-doped 4H- and 6H-SiC substrates grown by high-temperature chemical vapor deposition, an electron paramagnetic resonance (EPR) spectrum with C1h symmetry and a clear hyperfine (hf) structure consisting of ten equal intensity hf lines was observed. The hf structure can be identified as due to the interaction between the electron spin S = 1/2 and the nuclear spin of 93Nb. Additional hf structures due to the interaction with three Si neighbors were also detected. In 4H-SiC, a considerable spin density of ˜37.4% was found on three Si neighbors, suggesting the defect to be a complex between Nb and a nearby carbon vacancy (VC). Calculations of the 93Nb and 29Si hf constants of the neutral Nb on Si site, NbSi0, and the Nb-vacancy defect, NbSiVC0, support previous reported results that Nb preferentially forms an asymmetric split-vacancy (ASV) defect. In both 4H- and 6H-SiC, only one Nb-related EPR spectrum has been observed, supporting the prediction from calculations that the hexagonal-hexagonal defect configuration of the ASV complex is more stable than others.

  13. Electron paramagnetic resonance radiation dose assessment in fingernails of the victim exposed to high dose as result of an accident.

    PubMed

    Romanyukha, Alexander; Trompier, François; Reyes, Ricardo A; Christensen, Doran M; Iddins, Carol J; Sugarman, Stephen L

    2014-11-01

    In this paper, we report results of radiation dose measurements in fingernails of a worker who sustained a radiation injury to his right thumb while using 130 kVp X-ray for nondestructive testing. Clinically estimated absorbed dose was about 20-25 Gy. Electron paramagnetic resonance (EPR) dose assessment was independently carried out by two laboratories, the Naval Dosimetry Center (NDC) and French Institut de Radioprotection et de Sûreté Nucléaire (IRSN). The laboratories used different equipments and protocols to estimate doses in the same fingernail samples. NDC used an X-band transportable EPR spectrometer, e-scan produced by Bruker BioSpin, and a universal dose calibration curve. In contrast, IRSN used a more sensitive Q-band stationary spectrometer (EMXplus) with a new approach for the dose assessment (dose saturation method), derived by additional dose irradiation to known doses. The protocol used by NDC is significantly faster than that used by IRSN, nondestructive, and could be done in field conditions, but it is probably less accurate and requires more sample for the measurements. The IRSN protocol, on the other hand, potentially is more accurate and requires very small amount of sample but requires more time and labor. In both EPR laboratories, the intense radiation-induced signal was measured in the accidentally irradiated fingernails and the resulting dose assessments were different. The dose on the fingernails from the right thumb was estimated as 14 ± 3 Gy at NDC and as 19 ± 6 Gy at IRSN. Both EPR dose assessments are given in terms of tissue kerma. This paper discusses the experience gained by using EPR for dose assessment in fingernails with a stationary spectrometer versus a portable one, the reasons for the observed discrepancies in dose, and potential advantages and disadvantages of each approach for EPR measurements in fingernails.

  14. Biologic dosimetry for nuclear environments by electron paramagnetic resonance (EPR) methods. Conference paper

    SciTech Connect

    McCreery, M.J.; Swenberg, C.E.; Basso, M.J.; Conklin, J.J.; Hsieh, J.

    1982-06-18

    A number of stable and unstable free radicals are produced by exposure of calcified tissues to ionizing radiation. Identification of the exact molecular nature of these radicals and their kinetic annealing properties awaits further investigation. However, the high stability and the dose-response characteristics of the signal at g = 2.0023 make it very promising for use in biologic dosimetry. A 10-25 mg sample of enamel is enough to determine absorbed dose from 10-10 to the 7th power rads of gamma, X-ray, and accelerated electron exposures. This sample, which is no more than a chip from the ridge of a human tooth, does not expose the living portion of the tooth and so is relatively noninvasive. Investigations to establish a standard method for this procedure and to evaluate neutron dose is in progress. Although the procedures outlined here are relatively noninvasive, this technique affords other approaches that are even less invasive. Unlike optical methods, the sample for EPR analysis does not have to be transparent. It is not even necessary to suspend the sample as a fine powder. As long as the bone or tooth sample is within the dimensional limits of the tuned EPR cavity, it can be analyzed intact. This fact makes in vivo analysis feasible. We are currently making attempts to enlarge the EPR cavity with modification of the corresponding electronic components so that a finger can be analyzed. If this approach is successful, the expedient evaluation of large numbers of casualties might be possible by a method that is noninvasive and nondestructive.

  15. 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

  16. Use of the Relaxometry Technique for Quantification of Paramagnetic Ions in Aqueous Solutions and a Comparison with Other Analytical Methods

    PubMed Central

    Burato, Juliana Soares da Silva; Silva Lobo, Carlos Manuel; Colnago, Luiz Alberto

    2016-01-01

    We have demonstrated that the relaxometry technique is very efficient to quantify paramagnetic ions during in situ electrolysis measurements. Therefore, the goal of this work was to validate the relaxometry technique in the determination of the concentration of the ions contained in electrolytic solutions, Cu2+, Ni2+, Cr3+, and Mn2+, and compare it with other analytical methods. Two different NMR spectrometers were used: a commercial spectrometer with a homogeneous magnetic field and a home-built unilateral sensor with an inhomogeneous magnetic field. Without pretreatment, manganese ions do not have absorption bands in the UV-Visible region, but it is possible to quantify them using relaxometry (the limit of quantification is close to 10−5 mol L−1). Therefore, since the technique does not require chemical indicators and is a cheap and robust method, it can be used as a replacement for some conventional quantification techniques. The relaxometry technique could be applied to evaluate the corrosion of metallic surfaces. PMID:27293437

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

    NASA Astrophysics Data System (ADS)

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

    2015-01-01

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

  18. Role of the coordinating histidine in altering the mixed valency of Cu(A): an electron nuclear double resonance-electron paramagnetic resonance investigation.

    PubMed Central

    Lukoyanov, Dmitriy; Berry, Steven M; Lu, Yi; Antholine, William E; Scholes, Charles P

    2002-01-01

    The binuclear Cu(A) site engineered into Pseudomonas aeruginosa azurin has provided a Cu(A)-azurin with a well-defined crystal structure and a CuSSCu core having two equatorial histidine ligands, His120 and His46. The mutations His120Asn and His120Gly were made at the equatorial His120 ligand to understand the histidine-related modulation to Cu(A), notably to the valence delocalization over the CuSSCu core. For these His120 mutants Q-band electron nuclear double resonance (ENDOR) and multifrequency electron paramagnetic resonance (EPR) (X, C, and S-band), all carried out under comparable cryogenic conditions, have provided markedly different electronic measures of the mutation-induced change. Q-band ENDOR of cysteine C(beta) protons, of weakly dipolar-coupled protons, and of the remaining His46 nitrogen ligand provided hyperfine couplings that were like those of other binuclear mixed-valence Cu(A) systems and were essentially unperturbed by the mutation at His120. The ENDOR findings imply that the Cu(A) core electronic structure remains unchanged by the His120 mutation. On the other hand, multifrequency EPR indicated that the H120N and H120G mutations had changed the EPR hyperfine signature from a 7-line to a 4-line pattern, consistent with trapped-valence, Type 1 mononuclear copper. The multifrequency EPR data imply that the electron spin had become localized on one copper by the His120 mutation. To reconcile the EPR and ENDOR findings for the His120 mutants requires that either: if valence localization to one copper has occurred, the spin density on the cysteine sulfurs and the remaining histidine (His46) must remain as it was for a delocalized binuclear Cu(A) center, or if valence delocalization persists, the hyperfine coupling for one copper must markedly diminish while the overall spin distribution on the CuSSCu core is preserved. PMID:11964261

  19. [Theoretical Investigation of the Electron Paramagnetic Resonance Parameters and Local Structures for Zinc Phosphate Glass Doped with VO2+].

    PubMed

    Li, Chao-ying; Yuang, Xian-Kai; Tu, Qiu; Wang, Wei-yang; Zheng, Xue-mei

    2015-07-01

    As an important model system, 3d(1) ions (VO2+, V4+ et al) have been extensively investigated by means of electron paramagnetic resonance (EPR), and many experimental results of EPR parameters were also measured. The optical absorption and EPR parameters (g factors g||, g⊥ and hyperfine structure constants A||, A⊥) of a tetragonal V4+ center in zinc phosphate glass are theoretically investigated, using the perturbation formulas for a 3d(1) ion in tetragonally compressed octahedra. Since the spin-orbit coupling parameter r (150 cm(-1)) of ligand O2- is close to that ξp(0) (≈248 cm(-1)) of the central 3d(1) ion in zinc phosphate glass doped VO2+, the effect of the spin-orbit coupling parameter ξp(0) on the EPR spectra and optical absorption spectra should be taken into account. In this work, the relationship between the EPR parameters as well as the optical absorption spectra and the local structure of the impurity center are established based on the superposition model. By fitting the calculated EPR parameters and optical absorption spectra for V4+ center in zinc phosphate glass to the experimental data, the local structure parameters of [VO6](8-) cluster are obtained. According to the investigation, the magnitudes of the metal-ligand distances parallel and perpendicular to the C4-axis of [VO6](8-) cluster are, respectively, R|| ≈ 0.175 nm and R⊥ ≈ 0.197 nm, the local structure around the V4+ ions possesses a compressed tetragonal distortion along C4 axis. Theoretical results of EPR parameters and optical absorption spectra are in good agreement with experimental data, the validity of the calculated results has also been discussed. Thus, perturbation method is effective to the studies the EPR parameters and optical spectra of transition-metal 3d ions in crystals. In addition, based on the studies of the hyperfine structure constants (All and A1), one can found that the large value of kappa indicates a large contribution to the hyperfine constant by the

  20. Detection of nitric oxide and superoxide radical anion by electron paramagnetic resonance spectroscopy from cells using spin traps.

    PubMed

    Gopalakrishnan, Bhavani; Nash, Kevin M; Velayutham, Murugesan; Villamena, Frederick A

    2012-01-01

    spin adduct which can be detected by electron paramagnetic resonance (EPR) spectroscopy. The various radical adducts exhibit distinctive spectrum which can be used to identify the radicals being generated and can provide a wealth of information about the nature and kinetics of radical production. The cyclic nitrones, 5,5-dimethyl-pyrroline-N-oxide, DMPO, the phosphoryl-substituted DEPMPO, and the ester-substituted, EMPO and BMPO, have been widely employed as spin traps--the latter spin traps exhibiting longer half-lives for O2•- adduct. Iron (II)-N-methyl-D-glucamine dithiocarbamate, Fe(MGD)2 is commonly used to trap NO due to high rate of adduct formation and the high stability of the spin adduct. PMID:22929836

  1. Electron paramagnetic resonance spectroscopic measurement of Mn2+ binding affinities to the hammerhead ribozyme and correlation with cleavage activity.

    PubMed

    Horton, T E; Clardy, D R; DeRose, V J

    1998-12-22

    Efficient phosphodiester bond cleavage activity by the hammerhead ribozyme requires divalent cations. Toward understanding this metal ion requirement, the Mn2+-binding properties of hammerhead model ribozymes have been investigated under dilute solution conditions, using electron paramagnetic resonance spectroscopy (EPR) to detect free Mn2+ in the presence of added ribozyme. Numbers and affinities of bound Mn2+ were obtained at pH 7.8 (5 mM triethanolamine) in the presence of 0, 0.1, and 1.0 M NaCl for an RNA-DNA model consisting of a 13-nucleotide DNA "substrate" hybridized to a 34-nucleotide RNA "enzyme" [Pley, H. W., Flaherty, K. M., and McKay, D. B. (1994) Nature 372, 68-74]. In 0.1 M NaCl, two classes of Mn2+ sites are found with n1 = 3.7 +/- 0.4, Kd(1) = 4 +/- 1 microM (type 1) and n2 = 5.2 +/- 0.4, Kd(2) = 460 +/- 130 microM (type 2). The high-affinity type 1 sites are confirmed for an active RNA-RNA hybrid (34-nucleotide RNA enzyme:13-nucleotide RNA substrate) by EPR measurements at low Mn2+ concentrations. Decreasing NaCl concentration results in an increased number of bound Mn2+ per hammerhead. By contrast, a binding titration in 1 M NaCl indicates that a single Mn2+ site with apparent Kd approximately 10 microM is populated in low concentrations of Mn2+, and apparent cooperative effects at higher Mn2+ concentrations result in population of a similar total number of Mn2+ sites (n1 = 8-10) as found in 0.1 M NaCl. Mn2+-dependent activity profiles are similar for the active RNA-RNA hybrid in 0.1 and 1 M NaCl. Correlation with binding affinities determined by EPR indicates that hammerhead activity in 0.1 M NaCl is only observed after all four of the high-affinity Mn2+ sites are occupied, rises with population of the type 2 sites, and is independent of Mn2+ concentrations corresponding to > 8-9 Mn2+ bound per hammerhead. Equivalent measurements in 1 M NaCl demonstrate a rise in activity with the cooperative transition observed in the Mn2+ binding curve. These

  2. 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

  3. 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

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

    PubMed Central

    Angiolillo, P J; Vanderkooi, J M

    1995-01-01

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

  5. Characterization of endothelial nitric-oxide synthase and its reaction with ligand by electron paramagnetic resonance spectroscopy.

    PubMed

    Tsai, A L; Berka, V; Chen, P F; Palmer, G

    1996-12-20

    Electron paramagnetic resonance was used to characterize the heme structure of resting endothelial nitric-oxide synthase (eNOS), eNOS devoid of its myristoylation site (G2A mutant), and their heme complexes formed with 16 different ligands. Resting eNOS and the G2A mutant have a mixture of low spin and high spin P450-heme with widely different relaxation behavior and a stable flavin semiquinone radical identified by EPR as a neutral radical. This flavin radical showed efficient electron spin relaxation as a consequence of dipolar interaction with the heme center; P1/2 is independent of Ca2+-calmodulin and tetrahydrobiopterin. Seven of the 16 ligands led to the formation of low spin heme complexes. In order of increasing rhombicity they are pyrimidine, pyridine, thiazole, L-lysine, cyanide, imidazole, and 4-methylimidazole. These seven low spin eNOS complexes fell in a region between the P and O zones on the "truth diagram" originally derived by Blumberg and Peisach (Blumberg, W. E., and Peisach, J. (1971) in Probes and Structure and Function of Macromolecules and Membranes (Chance, B., Yonetani, T., and Mildvan, A. S., eds) Vol. 2, pp. 215-229, Academic Press, New York) and had significant overlap with complexes of chloroperoxidase. A re-definition of the P and O zones is proposed. As eNOS and chloroperoxidase lie closer than do eNOS and P450cam on the truth diagram, it implies that the distal heme environment in eNOS resembles chloroperoxidase more than P450cam. In contrast, 4-ethylpyridine, 4-methylpyrimidine, acetylguanidine, ethylguanidine, 2-aminothiazole, 2amino-4,5-dimethylthiazole, L-histidine, and 7-nitroindazole resulted in high spin heme complexes of eNOS, similar to that observed with L-arginine. This contrasting EPR behavior caused by families of ligands such as imidazole/L-histidine or thiazole/2-aminothiazole confirms the conclusion derived from parallel optical and kinetic studies. The ligands resulting in the low spin complexes bind directly to the

  6. 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

  7. Resonant Wave-Particle Manipulation Techniques

    NASA Astrophysics Data System (ADS)

    Zhmoginov, Andrey I.

    Charged particle dynamics can be altered considerably even by weak electromagnetic waves if some of the particles are in resonance. Depending on the wave parameters, the resonances in the phase space can either be well separated, in which case the particle dynamics is regular almost everywhere, or they can overlap leading to stochastic particle motion in a large volume of the phase space. Although different, both of these regimes allow one to manipulate particle ensembles by arranging resonant interactions with appropriate waves. This thesis is devoted to studying two wave-particle manipulation techniques having potential applications in fusion and laser-plasma interaction research. Specifically, we study the alpha-channeling effect (which relies on stochastic diffusion of resonant particles) and the so-called negative-mass effect (NME) (which involves the conservation of the adiabatic invariant). The alpha-channeling effect entails the use of radio-frequency waves to expel and cool high-energetic alpha particles born in a fusion reactor; the device reactivity can then be increased even further by redirecting the extracted energy to fuel ions. Recently, the alpha-channeling technique, originally proposed for tokamaks, was shown to be suitable for application in mirror machines as well. In the first part of this thesis, we deepen the understanding of issues and possibilities of the alpha-channeling implementation in open-ended reactors. We verify the feasibility of this technique and identify specific waves and supplementary techniques, which can potentially be used for implementing the alpha-channeling in realistic mirror devices. We also propose a new technique for using the alpha-channeling wave energy to catalyze fusion reaction by employing minority ions as a mediator species. In the second part of this thesis, the NME manifesting itself as an unusual response of a resonant particle to external adiabatic perturbations mimicking the behavior of a particle with a

  8. Electron paramagnetic resonance study of ferrous cytochrome P-450/sub scc/-nitric oxide complexes: effects of cholesterol and its analogs

    SciTech Connect

    Tsubaki, M.; Hiwatashi, A.; Ichikawa, Y.; Hori, H.

    1987-07-14

    Electron paramagnetic resonance (EPR) spectra of nitric oxide (NO) complexes of ferrous cytochrome P-450/sub scc/ were measured at 77 K for the first time without using the rapid-mixing and freeze-quenching technique. Without substrate the EPR spectra were very similar to those of cytochrome P-450/sub cam/ (from Pseudomonas putida) and cytochrome P-450/sub LM/ (from rat liver microsomes) with rhombic symmetry; g/sub x/ = 2.071, g/sub z/ = 2.001, g/sub y/ = 1.962, and A/sub z/ = 2.2 mT for /sup 14/NO complexes. Upon addition of substrates, the EPR spectra exhibited many variations having rhombic symmetry in the major component and an additional minor component with less rhombic symmetry. Furthermore, addition of 20(S)-hydroxycholesterol caused a striking change in the EPR spectrum. The component with rhombic symmetry disappeared completely, and the component with less rhombic symmetry dominated (g/sub x/ = 2.027, g/sub z/ = 2.007, g/sub y/ = 1.984, and A/sub z/ = 1.76 mT for /sup 14/NO complexes). These observations suggest the existence of the following physiologically important natures: (1) the conformational flexibility of the active site of the enzyme due to the steric interaction between the substrate and the heme-bound ligand molecule and (2) the importance of the hydroxylation of the cholesterol side chain at the 20S position to proceed the side-chain cleavage reaction in cytochrome P-450/sub scc/.

  9. 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.

  10. Review: Magnetic resonance imaging techniques in ophthalmology

    PubMed Central

    Fagan, Andrew J.

    2012-01-01

    Imaging the eye with magnetic resonance imaging (MRI) has proved difficult due to the eye’s propensity to move involuntarily over typical imaging timescales, obscuring the fine structure in the eye due to the resulting motion artifacts. However, advances in MRI technology help to mitigate such drawbacks, enabling the acquisition of high spatiotemporal resolution images with a variety of contrast mechanisms. This review aims to classify the MRI techniques used to date in clinical and preclinical ophthalmologic studies, describing the qualitative and quantitative information that may be extracted and how this may inform on ocular pathophysiology. PMID:23112569

  11. Low-temperature interquinone electron transfer in photosynthetic reaction centers from Rhodobacter sphaeroides and Blastochloris viridis: characterization of Q(B)- states by high-frequency electron paramagnetic resonance (EPR) and electron-nuclear double resonance (ENDOR).

    PubMed

    Utschig, Lisa M; Thurnauer, Marion C; Tiede, David M; Poluektov, Oleg G

    2005-11-01

    High-frequency electron paramagnetic resonance (HF EPR) techniques have been employed to look for localized light-induced conformational changes in the protein environments around the reduced secondary quinone acceptor (Q(B)(-)) in Rhodobacter sphaeroides and Blastochloris viridis RCs. The Q(A)(-) and Q(B)(-) radical species in Fe-removed/Zn-replaced protonated RCs substituted with deuterated quinones are distinguishable with pulsed D-band (130 GHz) EPR and provide native probes of both the low-temperature Q(A)(-)Q(B) --> Q(A)Q(B)(-) electron-transfer event and the structure of trapped conformational substates. We report here the first spectroscopic evidence that cryogenically trapped, light-induced changes enable low-temperature Q(A)(-)Q(B) --> Q(A)Q(B)(-) electron transfer in the B. viridis RC and the first observation of an inactive, trapped P(+)Q(B)(-) state in both R. sphaeroides and B. viridis RCs that does not recombine at 20 K. The high resolution and orientational selectivity of HF electron-nuclear double resonance (ENDOR) allows us to directly probe protein environments around Q(B)(-) for distinct P(+)Q(B)(-) kinetic RC states by spectrally selecting specific nuclei in isotopically labeled samples. No structural differences in the protein structure near Q(B)(-) or reorientation (within 5 degrees ) of Q(B)(-) was observed with HF ENDOR spectra of two states of P(+)Q(B)(-): "active" and "inactive" states with regards to low-temperature electron transfer. These results reveal a remarkably enforced local protein environment for Q(B) in its reduced semiquinone state and suggest that the conformational change that controls reactivity resides beyond the Q(B) local environment.

  12. Parallel image-acquisition in continuous-wave electron paramagnetic resonance imaging with a surface coil array: Proof-of-concept experiments.

    PubMed

    Enomoto, Ayano; Hirata, Hiroshi

    2014-02-01

    This article describes a feasibility study of parallel image-acquisition using a two-channel surface coil array in continuous-wave electron paramagnetic resonance (CW-EPR) imaging. Parallel EPR imaging was performed by multiplexing of EPR detection in the frequency domain. The parallel acquisition system consists of two surface coil resonators and radiofrequency (RF) bridges for EPR detection. To demonstrate the feasibility of this method of parallel image-acquisition with a surface coil array, three-dimensional EPR imaging was carried out using a tube phantom. Technical issues in the multiplexing method of EPR detection were also clarified. We found that degradation in the signal-to-noise ratio due to the interference of RF carriers is a key problem to be solved.

  13. Electron spin resonance of Ni-doped CuGeO3 in the paramagnetic, spin-Peierls, and antiferromagnetic states: Comparison with nonmagnetic impurities

    NASA Astrophysics Data System (ADS)

    Grenier, B.; Monod, P.; Hagiwara, M.; Matsuda, M.; Katsumata, K.; Clément, S.; Renard, J.-P.; Barra, A. L.; Dhalenne, G.; Revcolevschi, A.

    2002-03-01

    We have performed electron-spin-resonance measurements on single crystals of the doped spin-Peierls compounds CuGe1-ySiyO3 and Cu1-xMxGeO3 with M=Zn, Mg, Ni (x,y<=0.1). The first part of our experiments was performed in the paramagnetic and spin-Peierls phases at 9.5, 95, and 190 GHz. All nonmagnetic impurities (Si, Zn and Mg) were found to hardly affect the position and linewidth of the single line resonance, in spite of the moment formation due to the broken chains. In contrast to Si, Zn, and Mg dopings, the presence of Ni (S=1) at low concentration induces a spectacular shift toward high fields of the ESR line (up to 40% for x=0.002), together with a large broadening. This shift is strictly proportional to the ratio of Ni to Cu susceptibilities: Hence it is strongly enhanced below the spin-Peierls transition. We interpret this shift and the broadening as due to the exchange field induced by the Ni ions onto strongly exchange coupled Cu spins. Second, the antiferromagnetic resonance was investigated in Ni-doped samples. The frequency vs magnetic-field relation of the resonance is well explained by the classical theory with orthorhombic anisotropy, with g values remarkably reduced, in accordance with the study of the spin-Peierls and paramagnetic phases. The easy, second-easy, and hard axes are found to be a, c, and b axes, respectively. These results, which are dominated by the single ion anisotropy of Ni2+, are discussed in comparison with those in the Zn- and Si-doped CuGeO3.

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

    NASA Astrophysics Data System (ADS)

    Williams, Ffrancon

    2009-01-01

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

  15. 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.

  16. A Technique for Adjusting Eigenfrequencies of WGM Resonators

    NASA Technical Reports Server (NTRS)

    Strekalov, Dmitry; Savchenkov, Anatoliy; Maleki, Lute; Matsko, Andrey; Iltchenko, Vladimir; Martin, Jan

    2009-01-01

    A simple technique has been devised for making small, permanent changes in the eigenfrequencies (resonance frequencies) of whispering-gallery-mode (WGM) dielectric optical resonators that have high values of the resonance quality factor (Q). The essence of the technique is to coat the resonator with a thin layer of a transparent polymer having an index of refraction close to that of the resonator material. Successive small frequency adjustments can be made by applying successive coats. The technique was demonstrated on a calcium fluoride resonator to which successive coats of a polymer were applied by use of a hand-made wooden brush. To prevent temperature- related frequency shifts that could interfere with the verification of the effectiveness of this technique, the temperature of the resonator was stabilized by means of a three-stage thermoelectric cooler. Measurements of the resonator spectrum showed the frequency shifts caused by the successive coating layers.

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

    NASA Technical Reports Server (NTRS)

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

    1972-01-01

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

  18. 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

  19. 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

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

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

    Experimental results have been reported on an oversize rectangular waveguide assembly operating nominally at 94 GHz. It was formed using commercially available WR28 waveguide as well as a pair of specially designed tapers with a hyperbolic-cosine shape from WR28 to WR10 waveguide [R. R. Mett et al., Rev. Sci. Instrum. 82, 074704 (2011)]. The oversize section reduces broadband insertion loss for an Electron Paramagnetic Resonance (EPR) probe placed in a 3.36 T magnet. Hyperbolic-cosine tapers minimize reflection of the main mode and the excitation of unwanted propagating waveguide modes. Oversize waveguide is distinguished from corrugated waveguide, overmoded waveguide, or quasi-optic techniques by minimal coupling to higher-order modes. Only the TE10 mode of the parent WR10 waveguide is propagated. In the present work, a new oversize assembly with a gradual 90° twist was implemented. Microwave power measurements show that the twisted oversize waveguide assembly reduces the power loss in the observe and pump arms of a W-band bridge by an average of 2.35 dB and 2.41 dB, respectively, over a measured 1.25 GHz bandwidth relative to a straight length of WR10 waveguide. Network analyzer measurements confirm a decrease in insertion loss of 2.37 dB over a 4 GHz bandwidth and show minimal amplitude distortion of approximately 0.15 dB. Continuous wave EPR experiments confirm these results. The measured phase variations of the twisted oversize waveguide assembly, relative to an ideal distortionless transmission line, are reduced by a factor of two compared to a straight length of WR10 waveguide. Oversize waveguide with proper transitions is demonstrated as an effective way to increase incident power and the return signal for broadband EPR experiments. Detailed performance characteristics, including continuous wave experiment using 1 μM 2,2,6,6-tetramethylpiperidine-1-oxyl in aqueous solution, provided here serve as a benchmark for other broadband low-loss probes in

  1. 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

  2. Effects of diffusion and surface interactions on the line shape of electron paramagnetic resonances in the presence of a magnetic field gradient

    SciTech Connect

    Schaden, M.; Zhao, K. F.; Wu, Z.

    2007-12-15

    In an evanescent wave magnetometer the Zeeman polarization is probed at micrometer to submicrometer distances from the cell surface. The electron paramagnetic resonance lines of an evanescent wave magnetometer in the presence of a magnetic field gradient exhibit edge enhancement seen previously in nuclear magnetic resonance lines. We present a theoretical model that describes quantitatively the shape of the magnetic resonance lines of an evanescent wave magnetometer under a wide range of experimental conditions. It accounts for diffusion broadening in the presence of a magnetic field gradient as well as interactions of spin polarized Rb atoms with the coated Pyrex glass surfaces. Depending on the field gradient, cell thickness, and buffer gas pressure, the resonance line may have the form of a single asymmetric peak or two peaks localized near the front and back surfaces in frequency space. The double-peaked response depends on average characteristics of the surface interactions. Its shape is sensitive to the dwell time, relaxation probability, and average phase shift of adsorbed spin polarized Rb atoms.

  3. X-ray Crystallographic, Multifrequency Electron Paramagnetic Resonance, and Density Functional Theory Characterization of the Ni(P(Cy)2N(tBu)2)2(n+) Hydrogen Oxidation Catalyst in the Ni(I) Oxidation State.

    PubMed

    Niklas, Jens; Westwood, Mark; Mardis, Kristy L; Brown, Tiara L; Pitts-McCoy, Anthony M; Hopkins, Michael D; Poluektov, Oleg G

    2015-07-01

    The Ni(I) hydrogen oxidation catalyst [Ni(P(Cy)2N(tBu)2)2](+) (1(+); P(Cy)2N(tBu)2 = 1,5-di(tert-butyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane) has been studied using a combination of electron paramagnetic resonance (EPR) techniques (X-, Q-, and D-band, electron-nuclear double resonance, hyperfine sublevel correlation spectroscopy), X-ray crystallography, and density functional theory (DFT) calculations. Crystallographic and DFT studies indicate that the molecular structure of 1(+) is highly symmetrical. EPR spectroscopy has allowed determination of the electronic g tensor and the spin density distribution on the ligands, and revealed that the Ni(I) center does not interact strongly with the potentially coordinating solvents acetonitrile and butyronitrile. The EPR spectra and magnetic parameters of 1(+) are found to be distinctly different from those for the related compound [Ni(P(Ph)2N(Ph)2)2](+) (4(+)). One significant contributor to these differences is that the molecular structure of 4(+) is unsymmetrical, unlike that of 1(+). DFT calculations on derivatives in which the R and R' groups are systematically varied have allowed elucidation of structure/substituent relationships and their corresponding influence on the magnetic resonance parameters.

  4. Electron paramagnetic resonance and magnetization in Co doped La{sub 2/3}Ca{sub 1/3}MnO{sub 3}

    SciTech Connect

    Rivadulla, F.; Sande, P.; Causa, M. T.; Hueso, L. E.; Lopez-Quintela, M. A.; Rivas, J.

    2001-06-01

    Spin dynamics of the Mn-site substituted colossal magnetoresistance system were studied by means of electron paramagnetic resonance (EPR) and dc magnetic susceptibility in La{sub 2/3}Ca{sub 1/3}Mn{sub 1{minus}x}Co{sub x}O{sub 3} (0{le}x{le}0.1,{Delta}x=0.025). A dramatic increase in the high temperature limiting value for the EPR linewidth ({Delta}H{sub pp}({infinity})) was observed with doping. Structural analysis revealed that only negligible changes are produced in bond distances and angles at these low doping levels. On the other hand, dipolar contribution to {Delta}H{sub pp}({infinity}) was estimated in a few Gauss. To explain the effect of doping on {Delta}H{sub pp}({infinity}), we propose here a scenario including fast Mn-spin lattice relaxation through paramagnetic Co ions. {copyright} 2001 American Institute of Physics.

  5. The Origin of the Multiline and g = 4.1 Electron Paramagnetic Resonance Signals from the Oxygen-Evolving System of Photosystem II

    PubMed Central

    Hansson, Örjan; Aasa, Roland; Vänngȧrd, Tore

    1987-01-01

    Continuous illumination at 200 K of photosystem (PS) II-enriched membranes generates two electron paramagnetic resonance (EPR) signals that both are connected with the S2 state: a multiline signal at g 2 and a single line at g = 4.1. From measurements at three different X-band frequencies and at 34 GHz, the g tensor of the multiline species was found to be isotropic with g = 1.982. It has an excited spin multiplet at ∼30 cm-1, inferred from the temperature-dependence of the linewidth. The intensity ratio of the g = 4.1 signal to the multiline signal was found to be almost constant from 5 to 23 K. Based on these findings and on spin quantitation of the two signals in samples with and without 4% ethanol, it is concluded that they arise from the ground doublets of paramagnetic species in different PS II centers. It is suggested that the two signals originate from separate PS II electron donors that are in a redox equilibrium with each other in the S2 state and that the g = 4.1 signal arises from monomeric Mn(IV). PMID:19431697

  6. Use of paramagnetic chelated metal derivatives of polysaccharides and spin-labeled polysaccharides as contrast agents in magnetic resonance imaging

    SciTech Connect

    Bligh, S.W.; Harding, C.T.; Sadler, P.J.; Bulman, R.A.; Bydder, G.M.; Pennock, J.M.; Kelly, J.D.; Latham, I.A.; Marriott, J.A. )

    1991-02-01

    Soluble and insoluble polysaccharides were derivatized with diethylenetriaminepentaacetic acid (DTPA) and/or spin-labeled with 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO). Polysaccharides derivatized with DTPA were prepared via cyanogen bromide activation, coupling to a diamine linker, and to DTPA anhydride. Spin-labeled polysaccharides were also prepared via cyanogen bromide activation. The extent of derivatization for dextran (18 kDa) was about 120 glucose units per DTPA, and for cellulose and starch about 15-30 units per DTPA. For spin-labeled polysaccharides, the average loading ranged from 1 nitroxide per 16 glucose units for starch to 181 for dextran (82 kDa). These derivatized paramagnetic polysaccharides were shown to be more effective relaxants than the small paramagnetic molecules alone. Both soluble and insoluble polysaccharide-linker-DTPA-Gd(3) complexes were effectively cleared from the body (rats) after oral administration. After intravenous administration, the biodistribution of dextran-linker-DTPA-Gd(3) complexes differed significantly from that of GdDTPA. Reduction of the nitroxide by ascorbic acid was retarded in the polysaccharide derivatives, particularly in starch derivatized with both nitroxide and linker-DTPA-Cu(2). These agents showed contrast enhancement in the gastrointestinal tract of rabbits.

  7. Single-crystal electron paramagnetic resonance study of cytochrome c3 from Desulfovibrio desulfuricans Norway Strain. Assignment of the heme midpoint redox potentials.

    PubMed

    Guigliarelli, B; Bertrand, P; More, C; Haser, R; Gayda, J P

    1990-11-01

    A single crystal of cytochrome c3 from Desulfovibrio desulfuricans Norway is studied by electron paramagnetic resonance at low temperature. The orientation of the principal axis corresponding to the largest g value is determined for the 12 heme groups in the crystal unit cell. The comparison of these directions to the normals to the heme planes, determined from the crystallographic data at 2.5 A resolution, gives strong evidence for the following assignment of the midpoint redox potentials to the heme groups H1 to H4, defined in the three-dimensional structure: -150 mV is assigned to H3, -300 mV to H4, -330 mV to H1 and -355 mV to H2. This assignment is in agreement with a partial correspondence previously established from an independent study performed on cytochrome c3 in solution. PMID:2172551

  8. Electron Paramagnetic Resonance Characterization of Three Iron-Sulfur Clusters Present in the Nitrogenase Cofactor Maturase NifB from Methanocaldococcus infernus.

    PubMed

    Wilcoxen, Jarett; Arragain, Simon; Scandurra, Alessandro A; Jimenez-Vicente, Emilio; Echavarri-Erasun, Carlos; Pollmann, Stephan; Britt, R David; Rubio, Luis M

    2016-06-22

    NifB utilizes two equivalents of S-adenosyl methionine (SAM) to insert a carbide atom and fuse two substrate [Fe-S] clusters forming the NifB cofactor (NifB-co), which is then passed to NifEN for further modification to form the iron-molybdenum cofactor (FeMo-co) of nitrogenase. Here, we demonstrate that NifB from the methanogen Methanocaldococcus infernus is a radical SAM enzyme able to reductively cleave SAM to 5'-deoxyadenosine radical and is competent in FeMo-co maturation. Using electron paramagnetic resonance spectroscopy we have characterized three [4Fe-4S] clusters, one SAM binding cluster, and two auxiliary clusters probably acting as substrates for NifB-co formation. Nitrogen coordination to one or more of the auxiliary clusters in NifB was observed, and its mechanistic implications for NifB-co dissociation from the maturase are discussed. PMID:27268267

  9. Novel synthesis and structural characterization of a high-affinity paramagnetic kinase probe for the identification of non-ATP site binders by nuclear magnetic resonance.

    SciTech Connect

    Moy, Franklin J.; Lee, Arthur; Gavrin, Lori Krim; Xu, Zhang Bao; Sievers, Annette; Kieras, Elizabeth; Stochaj, Wayne; Mosyak, Lidia; McKew, John; Tsao, Desiree H.H.

    2010-07-23

    To aid in the pursuit of selective kinase inhibitors, we have developed a unique ATP site binder tool for the detection of binders outside the ATP site by nuclear magnetic resonance (NMR). We report here the novel synthesis that led to this paramagnetic spin-labeled pyrazolopyrimidine probe (1), which exhibits nanomolar inhibitory activity against multiple kinases. We demonstrate the application of this probe by performing NMR binding experiments with Lck and Src kinases and utilize it to detect the binding of two compounds proximal to the ATP site. The complex structure of the probe with Lck is also presented, revealing how the probe fits in the ATP site and the specific interactions it has with the protein. We believe that this spin-labeled probe is a valuable tool that holds broad applicability in a screen for non-ATP site binders.

  10. Novel Synthesis and Structural Characterization of a High-Affinity Paramagnetic Kinase Probe for the Identification of Non-ATP Site Binders by Nuclear Magnetic Resonance

    SciTech Connect

    Moy, K.; Lee, A; Krim Gavrin, L; Xu, Z; Sievers, A; Kieras, E; Stochaj, W; Mosyak, L; McKew, J; Tsao, D

    2010-01-01

    To aid in the pursuit of selective kinase inhibitors, we have developed a unique ATP site binder tool for the detection of binders outside the ATP site by nuclear magnetic resonance (NMR). We report here the novel synthesis that led to this paramagnetic spin-labeled pyrazolopyrimidine probe (1), which exhibits nanomolar inhibitory activity against multiple kinases. We demonstrate the application of this probe by performing NMR binding experiments with Lck and Src kinases and utilize it to detect the binding of two compounds proximal to the ATP site. The complex structure of the probe with Lck is also presented, revealing how the probe fits in the ATP site and the specific interactions it has with the protein. We believe that this spin-labeled probe is a valuable tool that holds broad applicability in a screen for non-ATP site binders.

  11. NDI using mm-wave resonant techniques

    SciTech Connect

    Martens, J.S.; Sachtjen, S.; Sorensen, N.R.

    1995-08-01

    Millimeter wave resonant measurements are commonly used for surface and near-surface materials characterization including the detection of cracks and defects, analysis of semiconducting and dielectric materials, and analysis of metallic electrical properties beneath coatings. Recent work has also shown the approach to be useful in evaluating corrosion products and the detection of incipient corrosion and corrosion cracking. In the analysis area, complex permittivity data of the corrosion products can be extracted, usually with accuracy of a few percent or better, to aid in identification of the product and possibly of mechanisms. In the detection area, corrosion-related cracks of order 100{mu}m or less near the surface have been detected and corrosion products have been detected beneath a variety of paints. Surface preparation requirements are minimal, particularly compared to some optical techniques, giving increased hope of field applicability. A number of examples of NDI on aircraft related materials and structures will be presented along with an assessment of detection and accuracy limits.

  12. Ultrasonic signal enhancement by resonator techniques

    NASA Technical Reports Server (NTRS)

    Heyman, J. S.

    1973-01-01

    Ultrasonic resonators increase experimental sensitivity to acoustic dispersion and changes in attenuation. Experimental sensitivity enhancement line shapes are presented which were obtained by modulating the acoustic properties of a CdS resonator with a light beam. Small changes in light level are made to produce almost pure absorptive or dispersive changes in the resonator signal. This effect is due to the coupling of the ultrasonic wave to the CdS conductivity which is proportional to incident light intensity. The resonator conductivity is adjusted in this manner to obtain both dispersive and absorptive sensitivity enhancement line shapes. The data presented verify previous thoretical calculations based on a propagating wave model.

  13. Frequency-Temperature Compensation Techniques for High-Q Microwave Resonators

    NASA Astrophysics Data System (ADS)

    Hartnett, John G.; Tobar, Michael E.

    Low-noise high-stability resonator oscillators based on high-Q monolithic sapphire ``Whispering Gallery'' (WG)-mode resonators have become important devices for telecommunication, radar and metrological applications. The extremely high quality factor of sapphire, of 2 x10^5 at room temperature, 5 x10^7 at liquid nitrogen temperature and 5 x10^9 at liquid helium temperature has enabled the lowest phase noise and highly frequency-stable oscillators in the microwave regime to be constructed. To create an oscillator with exceptional frequency stability, the resonator must have its frequency-temperature dependence annulled at some temperature, as well as a high quality factor. The Temperature Coefficient of Permittivity (TCP) for sapphire is quite large, at 10-100parts per million/K above 77K. This mechanism allows temperature fluctuations to transform to resonator frequency fluctuations.A number of research groups worldwide have investigated various methods of compensating the TCP of a sapphire dielectric resonator at different temperatures. The usual electromagnetic technique of annulment involves the use of paramagnetic impurities contributing an opposite temperature coefficient of the magnetic susceptibility to the TCP. This technique has only been realized successfully in liquid helium environments. Near 4K the thermal expansion and permittivity effects are small and only small quantities of the paramagnetic ions are necessary to compensate the mode frequency. Compensation is due to impurity ions that were incidentally left over from the manufacturing process.Recently, there has been an effort to dispense with the need for liquid helium and make a compact flywheel oscillator for the new generation of primary frequency standards such as the cesium fountain at the Laboratoire Primaire du Temps et des Fréquences (LPTF), France. To achieve the stability limit imposed

  14. 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.

  15. The use of election paramagnetic resonance spectroscopy in early preformulation experiments: the impact of different experimental formulations on the release of a lipophilic spin probe into gastric juice.

    PubMed

    Bittner, B; Isel, H; Mountfield, R J

    2001-03-01

    The lipophilic spin probe TEMPOL-benzoate was dissolved in different experimental formulations, including polyethylene glycol 400 (PEG 400), Miglyol, glycerol monooleate (GMO), and Cremophor RH-40. Samples were measured by electron paramagnetic resonance (EPR) spectroscopy before and after addition to human gastric juice. The distance between the first and the third peak in the EPR spectrum (2a(N)) was measured to monitor the polarity of the spin probe's microenvironment. Moreover, the ratio between the signal amplitudes of the second and the third peak (a/b ratio) was used to monitor the mobility of the spin probe in a certain formulation. Thus, by calculating 2a(N) and the a/b ratio of the EPR spectra it was possible to determine a potential release of the spin probe from different formulations into gastric juice. It was found that oily and surface-active vehicles (Miglyol, Cremophor RH-40, and GMO) were more suitable to protect a lipophilic compound from being released within a gastric environment than PEG 400. Our results demonstrate that EPR spectroscopy seems to be a promising tool in early preformulation experiments to monitor the release of spin probes from formulations of different nature. This kind of experiment can be of value for the optimization of exploratory formulations.

  16. 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.

  17. Artifact suppression in electron paramagnetic resonance imaging of 14N- and 15N-labeled nitroxyl radicals with asymmetric absorption spectra

    NASA Astrophysics Data System (ADS)

    Takahashi, Wataru; Miyake, Yusuke; Hirata, Hiroshi

    2014-10-01

    This article describes an improved method for suppressing image artifacts in the visualization of 14N- and 15N-labeled nitroxyl radicals in a single image scan using electron paramagnetic resonance (EPR). The purpose of this work was to solve the problem of asymmetric EPR absorption spectra in spectral processing. A hybrid function of Gaussian and Lorentzian lineshapes was used to perform spectral line-fitting to successfully separate the two kinds of nitroxyl radicals. This approach can process the asymmetric EPR absorption spectra of the nitroxyl radicals being measured, and can suppress image artifacts due to spectral asymmetry. With this improved visualization method and a 750-MHz continuous-wave EPR imager, a temporal change in the distributions of a two-phase paraffin oil and water/glycerin solution system was visualized using lipophilic and hydrophilic nitroxyl radicals, i.e., 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16-DOXYL stearic acid) and 4-hydroxyl-2,2,6,6-tetramethylpiperidine-d17-1-15N-1-oxyl (TEMPOL-d17-15N). The results of the two-phase separation experiment verified that reasonable artifact suppression could be achieved by the present method that deals with asymmetric absorption spectra in the EPR imaging of 14N- and 15N-labeled nitroxyl radicals.

  18. 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.

  19. Binding of transition metals to monosilicic acid in aqueous and xylem (Cucumis sativus L.) solutions: a low-T electron paramagnetic resonance study.

    PubMed

    Stevic, Nenad; Korac, Jelena; Pavlovic, Jelena; Nikolic, Miroslav

    2016-10-01

    The supplementation of monosilicic acid [Si(OH)4] to the root growing medium is known to protect plants from toxic levels of iron (Fe), copper (Cu) and manganese (Mn), but also to mitigate deficiency of Fe and Mn. However, the physicochemical bases of these alleviating mechanisms are not fully understood. Here we applied low-T electron paramagnetic resonance (EPR) spectroscopy to examine the formation of complexes of Si(OH)4 with Mn(2+), Fe(3+), and Cu(2+) in water and in xylem sap of cucumber (Cucumis sativus L.) grown without or with supply of Si(OH)4. EPR, which is also useful in establishing the redox state of these metals, was combined with measurements of total concentrations of metals in xylem sap by inductive coupled plasma. Our results show that Si(OH)4 forms coordination bonds with all three metals. The strongest interactions of Si(OH)4 appear to be with Cu(2+) (1/1 stoichiometry) which might lead to Cu precipitation. In line with this in vitro findings, Si(OH)4 supply to cucumber resulted in dramatically lower concentration of this metal in the xylem sap. Further, it was demonstrated that Si(OH)4 supplementation causes pro-reductive changes that contribute to the maintenance of Fe and, in particular, Mn in the xylem sap in bioavailable 2+ form. Our results shed more light on the intertwined reactions between Si(OH)4 and transition metals in plant fluids (e.g. xylem sap).

  20. 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.

  1. 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.

  2. 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.

  3. 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.

  4. 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.

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

    PubMed

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

    2013-02-21

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

  6. 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.

  7. Nd3+ ions at the low-symmetry sites of β-Ba B2 O4 single crystals studied by electron paramagnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Bravo, D.; Solé, R.; Aguiló, M.; Díaz, F.; López, F. J.

    2004-11-01

    An electron paramagnetic resonance (EPR) study of Nd3+ ions in single crystals of the low-temperature phase of barium metaborate ( β-BaB2O4 or BBO) is presented. The EPR spectrum shows the existence of various slightly different Nd3+ centers. The g matrices of the three more abundant centers have been determined through the analysis of the angular dependencies of the spectrum in two planes of the crystal. The principal g -axis systems do not allow a straightforward assignment of the centers to a specific lattice cation site because of the low site symmetry ( C1 in all cases). To overcome this problem we have developed a method to calculate principal g -axis systems by constructing and diagonalizing the crystal-field energy matrix for the ground I9/24 level of Nd3+ , including the Zeeman interaction. The superposition model of the crystal field has been employed to estimate the crystal-field Bnm parameters for this ion in BBO, as they are unknown. From this study it is concluded that neodymium is incorporated in the low-symmetry Ba2+ site. Possible reasons for the appearance of different Nd3+ centers are discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2015-11-01

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

  9. 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.

  10. Novel Magnetic Resonance Imaging Techniques in Brain Tumors.

    PubMed

    Nechifor, Ruben E; Harris, Robert J; Ellingson, Benjamin M

    2015-06-01

    Magnetic resonance imaging is a powerful, noninvasive imaging technique with exquisite sensitivity to soft tissue composition. Magnetic resonance imaging is primary tool for brain tumor diagnosis, evaluation of drug response assessment, and clinical monitoring of the patient during the course of their disease. The flexibility of magnetic resonance imaging pulse sequence design allows for a variety of image contrasts to be acquired, including information about magnetic resonance-specific tissue characteristics, molecular dynamics, microstructural organization, vascular composition, and biochemical status. The current review highlights recent advancements and novel approaches in MR characterization of brain tumors.

  11. Brain redox imaging in the pentylenetetrazole (PTZ)-induced kindling model of epilepsy by using in vivo electron paramagnetic resonance and a nitroxide imaging probe.

    PubMed

    Emoto, Miho C; Yamato, Mayumi; Sato-Akaba, Hideo; Yamada, Ken-ichi; Fujii, Hirotada G

    2015-11-01

    Much evidence supports the idea that oxidative stress is involved in the pathogenesis of epilepsy, and therapeutic interventions with antioxidants are expected as adjunct antiepileptic therapy. The aims of this study were to non-invasively obtain spatially resolved redox data from control and pentylenetetrazole (PTZ)-induced kindled mouse brains by electron paramagnetic resonance (EPR) imaging and to visualize the brain regions that are sensitive to oxidative damage. After infusion of the redox-sensitive imaging probe 3-methoxycarbonyl-2,2,5,5-tetramethyl-piperidine-1-oxyl (MCP), a series of EPR images of PTZ-induced mouse heads were measured. Based on the pharmacokinetics of the reduction reaction of MCP in the mouse heads, the pixel-based rate constant of its reduction reaction was calculated as an index of redox status in vivo and mapped as a redox map. The obtained redox map showed heterogeneity in the redox status in PTZ-induced mouse brains compared with control. The co-registered image of the redox map and magnetic resonance imaging (MRI) for both control and PTZ-induced mice showed a clear change in the redox status around the hippocampus after PTZ. To examine the role of antioxidants on the brain redox status, the levels of antioxidants were measured in brain tissues of control and PTZ-induced mice. Significantly lower concentrations of glutathione in the hippocampus of PTZ-kindled mice were detected compared with control. From the results of both EPR imaging and the biochemical assay, the hippocampus was found to be susceptible to oxidative damage in the PTZ-induced animal model of epilepsy.

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

    PubMed Central

    Mett, R. R.; Sidabras, J. W.; Anderson, J. R.; Hyde, J. S.

    2011-01-01

    The two-way insertion loss of a 1 m length of waveguide was reduced by nearly 5 dB over a 4% bandwidth at W-band (94 GHz) for an electron paramagnetic resonance (EPR) spectrometer relative to WR10 waveguide. The waveguide has an oversize section of commercially available rectangular WR28 and a novel pair of tapers that vary in cross section with axial position according to a hyperbolic-cosine (HC) function. The tapers connect conventional rectangular WR10 waveguide to the WR28. For minimum loss, the main mode electric field is parallel to the long side of the WR28. Using mode coupling theory, the position of maximum flare (inflection point) in the taper was optimized with respect to the coupling to higher order modes and the reflection of the main mode. The optimum inflection point position is about one-tenth of the taper length from the small end of the taper. Reflection and coupling were reduced by about 20 dB relative to a pyramidal (linear) taper of the same length. Comb-like dips in the transmission coefficient produced by resonances of the higher order modes in the oversize section were about 0.03 dB. Specially designed high-precision, adjustable WR28 flanges with alignment to about 5 μm were required to keep higher order mode amplitudes arising from the flanges comparable to those from the HC tapers. Minimum return loss was about 30 dB. This paper provides a foundation for further optimization, if needed. Methods are not specific to EPR or the microwave frequency band. PMID:21806211

  13. Strong reduction of V{sup 4+} amount in vanadium oxide/hexadecylamine nanotubes by doping with Co{sup 2+} and Ni{sup 2+} ions: Electron paramagnetic resonance and magnetic studies

    SciTech Connect

    Saleta, M. E.; Troiani, H. E.; Ribeiro Guevara, S.; Ruano, G.; Sanchez, R. D.; Malta, M.; Torresi, R. M.

    2011-05-01

    In this work we present a complete characterization and magnetic study of vanadium oxide/hexadecylamine nanotubes (VO{sub x}/Hexa NT's) doped with Co{sup 2+} and Ni{sup 2+} ions. The morphology of the NT's has been characterized by transmission electron microscopy, while the metallic elements have been quantified by the instrumental neutron activation analysis technique. The static and dynamic magnetic properties were studied by collecting data of magnetization as a function of magnetic field and temperature and by electron paramagnetic resonance. At difference of the majority reports in the literature, we do not observe magnetic dimers in vanadium oxide nanotubes. Also, we observed that the incorporation of metallic ions (Co{sup 2+}, S = 3/2 and Ni{sup 2+}, S = 1) decreases notably the amount of V{sup 4+} ions in the system, from 14-16% (nondoped case) to 2%-4%, with respect to the total vanadium atoms (fact corroborated by XPS experiments) anyway preserving the tubular nanostructure. The method to decrease the amount of V{sup 4+} in the nanotubes improves considerably their potential technological applications as Li-ion batteries cathodes.

  14. Structure and Stability of Pentafluoroaniline and 4-Aminononafluorobiphenyl Radical Anions: Optically Detected Electron Paramagnetic Resonance, Time-Resolved Fluorescence, Time-Resolved Magnetic Field Effect, and Quantum Chemical Study.

    PubMed

    Borovkov, Vsevolod I; Beregovaya, Irina V; Shchegoleva, Lyudmila N; Blinkova, Svetlana V; Ovchinnikov, Dmitry A; Gurskaya, Larisa Yu; Shteingarts, Vitaly D; Bagryansky, Victor A; Molin, Yuriy N

    2015-08-01

    Radical anions (RAs) are the key intermediates of the selective hydrodefluorination of polyfluoroarenes. We used the techniques of optically detected electron paramagnetic resonance (OD EPR), time-resolved fluorescence, time-resolved magnetic field effect (TR MFE), and the density functional theory to study the possibility of RAs formation from 4-aminononafluorobiphenyl (1) and pentafluoroaniline (2) and estimate their lifetimes and decay channels. To our knowledge, both RAs have not been detected earlier. We have registered the OD EPR spectrum for relatively stable in nonpolar solutions 1(-•) but failed to register the spectra for 2(-•). However, we have managed to fix the 2(-•) by the TR MFE method and obtained its hyperfine coupling constants. The lifetime of 2(-•) was found to be only a few nanoseconds. The activation energy of its decay was estimated to be 3.6 ± 0.3 kcal/mol. According to the calculation results, the short lifetime of 2(-•) is due to the RA fast fragmentation with the F(-) elimination from ortho-position to the amine group. The calculated energy barrier, 3.2 kcal/mol, is close to the experimental value. The fragmentation of 2(-•) in a nonpolar solvent is possible due to the stabilization of the incipient F(-) anion by the binding with the amine group proton.

  15. {sup 13}C, {sup 1}H, {sup 6}Li magic-angle spinning nuclear magnetic resonance, electron paramagnetic resonance, and Fourier transform infrared study of intercalation electrodes based in ultrasoft carbons obtained below 3100 K

    SciTech Connect

    Alcantara, R.; Madrigal, F.J.F.; Lavela, P.; Tirado, J.L.; Mateos, J.M.J.; Stoyanova, R.; Zhecheva, E.

    1999-01-01

    The past decade has seen an important development of materials for high-performance energy storage systems. Particularly, the field of electrode materials for advanced lithium batteries has attracted the interest of numerous researchers. Petroleum coke samples of different origins and heat treated at different temperatures below 3100 K have been studied by spectroscopic and electrochemical procedures. According to {sup 13}C and {sup 1}H magic-angle spinning (MAS) nuclear magnetic resonance (NMR), infrared (IR), and electron paramagnetic resonance (EPR) data, aromatic compounds and surface OH groups are present in green coke samples. The preparation of CMB (combustible) sample from 1673 K leads to a low-temperature graphitization process, as shown by the occurrence of multiphase products containing both turbostatic and graphitized solid. This process is accompanied by the loss of aromatic compounds and surface hydroxyls. The optimization of the lithium intercalation electrodes based in the green coke materials was carried out by thermal treatment at 1023 K under dynamic vacuum conditions. Such pretreatment of the electrode material leads to marked enhancement of reversible capacities without the higher temperatures usually required for other soft carbon materials. Finally, the results of {sup 6}Li MAS NMR and EPR have been correlated with the experimental determination of lithium diffusion coefficients and surface properties. On the basis of these results, spin resonance spectroscopies are found to be a powerful tool to discern between the different petroleum coke samples to select the active electrode material with best performance.

  16. 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.

  17. 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

  18. Paramagnetic NMR probes for characterization of the dynamic conformations and interactions of oligosaccharides.

    PubMed

    Kato, Koichi; Yamaguchi, Takumi

    2015-10-01

    Paramagnetism-assisted nuclear magnetic resonance (NMR) techniques have recently been applied to a wide variety of biomolecular systems, using sophisticated immobilization methods to attach paramagnetic probes, such as spin labels and lanthanide-chelating groups, at specific sites of the target biomolecules. This is also true in the field of carbohydrate NMR spectroscopy. NMR analysis of oligosaccharides is often precluded by peak overlap resulting from the lack of variability of local chemical structures, by the insufficiency of conformational restraints from nuclear Overhauser effect (NOE) data due to low proton density, and moreover, by the inherently flexible nature of carbohydrate chains. Paramagnetic probes attached to the reducing ends of oligosaccharides cause paramagnetic relaxation enhancements (PREs) and/or pseudocontact shifts (PCSs) resolve the peak overlap problem. These spectral perturbations can be sources of long-range atomic distance information, which complements the local conformational information derived from J couplings and NOEs. Furthermore, paramagnetic NMR approaches, in conjunction with computational methods, have opened up possibilities for the description of dynamic conformational ensembles of oligosaccharides in solution. Several applications of paramagnetic NMR techniques are presented to demonstrate their utility for characterizing the conformational dynamics of oligosaccharides and for probing the carbohydrate-recognition modes of proteins. These techniques can be applied to the characterization of transient, non-stoichiometric interactions and will contribute to the visualization of dynamic biomolecular processes involving sugar chains.

  19. Membrane Docking of the Synaptotagmin 7 C2A Domain: Electron Paramagnetic Resonance Measurements Show Contributions from Two Membrane Binding Loops

    PubMed Central

    Osterberg, J. Ryan; Chon, Nara Lee; Boo, Arthur; Maynard, Favinn A.; Lin, Hai; Knight, Jefferson D.

    2015-01-01

    The synaptotagmin (Syt) family of proteins plays an important role in vesicle docking and fusion during Ca2+-induced exocytosis in a wide variety of cell types. Its role as a Ca2+ sensor derives primarily from its two C2 domains, C2A and C2B, which insert into anionic lipid membranes upon binding Ca2+. Syt isoforms 1 and 7 differ significantly in their Ca2+ sensitivity; the C2A domain from Syt7 binds Ca2+ and membranes much more tightly than the C2A domain from Syt1, due at least in part to greater contributions from the hydrophobic effect. While the structure and membrane activity of Syt1 have been extensively studied, the structural origins of differences between Syt7 and Syt1 are unknown. The present study used site-directed spin labeling and electron paramagnetic resonance spectroscopy to determine depth parameters for the Syt7 C2A domain, for comparison to analogous previous measurements with Syt1 C2A. In a novel approach, the membrane docking geometry of both Syt1 and Syt7 C2A was modeled by mapping depth parameters onto multiple molecular dynamics simulated structures of the Ca2+-bound protein. The models reveal membrane penetration of Ca2+ binding loops (CBLs) 1 and 3, and membrane binding is more sensitive to mutations in CBL3. On average, Syt7 C2A inserts more deeply in the membrane than Syt1 C2A, although depths vary among the different structural models. This observation provides a partial structural explanation for the hydrophobically driven membrane docking of Syt7 C2A. PMID:26322740

  20. A comparative electron paramagnetic resonance study of the nucleotide-binding domains' catalytic cycle in the assembled maltose ATP-binding cassette importer.

    PubMed

    Grote, Mathias; Bordignon, Enrica; Polyhach, Yevhen; Jeschke, Gunnar; Steinhoff, Heinz-Jürgen; Schneider, Erwin

    2008-09-15

    We present a quantitative analysis of conformational changes of the nucleotide-binding subunits, MalK(2), of the maltose ATP-binding cassette importer MalFGK(2) during the transport cycle. Distance changes occurring between selected residues were monitored in the full transporter by site-directed spin-labeling electron paramagnetic resonance spectroscopy and site-directed chemical cross-linking. We considered S83C and A85C from the conserved Q-loop and V117C located on the outer surface of MalK. Additionally, two native cysteines (C350, C360) were included in the study. On ATP binding, small rearrangements between the native sites, and no distance changes between positions 117 were detected. In contrast, positions 85 come closer together in the ATP-bound state and in the vanadate-trapped intermediate and move back toward the apo-state after ATP hydrolysis. The distance between positions 83 is shown to slightly decrease on ATP binding, and to further decrease after ATP hydrolysis. Results from cross-linking experiments are in agreement with these findings. The data are compared with in silico spin-labeled x-ray structures from both isolated MalK(2) and the MalFGK(2)-E complex. Our results are consistent with a slightly modified "tweezers-like" model of closure and reopening of MalK(2) during the catalytic cycle, and show an unforeseen potential interaction between MalK and the transmembrane subunit MalG.

  1. Intramolecular electron transfer versus substrate oxidation in lactoperoxidase: investigation of radical intermediates by stopped-flow absorption spectrophotometry and (9-285 GHz) electron paramagnetic resonance spectroscopy.

    PubMed

    Fielding, Alistair J; Singh, Rahul; Boscolo, Barbara; Loewen, Peter C; Ghibaudi, Elena M; Ivancich, Anabella

    2008-09-16

    We have combined the information obtained from rapid-scan electronic absorption spectrophotometry and multifrequency (9-295 GHz) electron paramagnetic resonance (EPR) spectroscopy to unequivocally determine the electronic nature of the intermediates in milk lactoperoxidase as a function of pH and to monitor their reactivity with organic substrates selected by their different accessibilities to the heme site. The aim was to address the question of the putative catalytic role of the protein-based radicals. This experimental approach allowed us to discriminate between the protein-based radical intermediates and [Fe(IV)=O] species, as well as to directly detect the oxidation products by EPR. The advantageous resolution of the g anisotropy of the Tyr (*) EPR spectrum at high fields showed that the tyrosine of the [Fe(IV)=O Tyr (*)] intermediate has an electropositive and pH-dependent microenvironment [g(x) value of 2.0077(0) at pH >or= 8.0 and 2.0066(2) at 4.0

  2. 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.

  3. Binding of transition metals to monosilicic acid in aqueous and xylem (Cucumis sativus L.) solutions: a low-T electron paramagnetic resonance study.

    PubMed

    Stevic, Nenad; Korac, Jelena; Pavlovic, Jelena; Nikolic, Miroslav

    2016-10-01

    The supplementation of monosilicic acid [Si(OH)4] to the root growing medium is known to protect plants from toxic levels of iron (Fe), copper (Cu) and manganese (Mn), but also to mitigate deficiency of Fe and Mn. However, the physicochemical bases of these alleviating mechanisms are not fully understood. Here we applied low-T electron paramagnetic resonance (EPR) spectroscopy to examine the formation of complexes of Si(OH)4 with Mn(2+), Fe(3+), and Cu(2+) in water and in xylem sap of cucumber (Cucumis sativus L.) grown without or with supply of Si(OH)4. EPR, which is also useful in establishing the redox state of these metals, was combined with measurements of total concentrations of metals in xylem sap by inductive coupled plasma. Our results show that Si(OH)4 forms coordination bonds with all three metals. The strongest interactions of Si(OH)4 appear to be with Cu(2+) (1/1 stoichiometry) which might lead to Cu precipitation. In line with this in vitro findings, Si(OH)4 supply to cucumber resulted in dramatically lower concentration of this metal in the xylem sap. Further, it was demonstrated that Si(OH)4 supplementation causes pro-reductive changes that contribute to the maintenance of Fe and, in particular, Mn in the xylem sap in bioavailable 2+ form. Our results shed more light on the intertwined reactions between Si(OH)4 and transition metals in plant fluids (e.g. xylem sap). PMID:27502949

  4. Analysis of saturation transfer electron paramagnetic resonance spectra of a spin-labeled integral membrane protein, band 3, in terms of the uniaxial rotational diffusion model.

    PubMed Central

    Hustedt, E J; Beth, A H

    1995-01-01

    Algorithms have been developed for the calculation of saturation transfer electron paramagnetic resonance (ST-EPR) spectra of a nitroxide spin-label assuming uniaxial rotational diffusion, a model that is frequently used to describe the global rotational dynamics of large integral membrane proteins. One algorithm explicitly includes terms describing Zeeman overmodulation effects, whereas the second more rapid algorithm treats these effects approximately using modified electron spin-lattice and spin-spin relaxation times. Simulations are presented to demonstrate the sensitivity of X-band ST-EPR spectra to the rate of uniaxial rotational diffusion and the orientation of the nitroxide probe with respect to the diffusion axis. Results obtained by using the algorithms presented, which are based on the transition-rate formalism, are in close agreement with those obtained by using an eigenfunction expansion approach. The effects of various approximations used in the simulation algorithms are considered in detail. Optimizing the transition-rate formalism to model uniaxial rotational diffusion results in over an order of magnitude reduction in computation time while allowing treatment of nonaxial A- and g-tensors. The algorithms presented here are used to perform nonlinear least-squares analyses of ST-EPR spectra of the anion exchange protein of the human erythrocyte membrane, band 3, which has been affinity spin-labeled with a recently developed dihydrostilbene disulfonate derivative, [15N,2H13]-SL-H2DADS-MAL. These results suggest that all copies of band 3 present in intact erythrocytes undergo rotational diffusion about the membrane normal axis at a rate consistent with a band 3 dimer. PMID:8534811

  5. Manganese binding properties of human calprotectin under conditions of high and low calcium: X-ray crystallographic and advanced electron paramagnetic resonance spectroscopic analysis.

    PubMed

    Gagnon, Derek M; Brophy, Megan Brunjes; Bowman, Sarah E J; Stich, Troy A; Drennan, Catherine L; Britt, R David; Nolan, Elizabeth M

    2015-03-01

    The antimicrobial protein calprotectin (CP), a hetero-oligomer of the S100 family members S100A8 and S100A9, is the only identified mammalian Mn(II)-sequestering protein. Human CP uses Ca(II) ions to tune its Mn(II) affinity at a biologically unprecedented hexahistidine site that forms at the S100A8/S100A9 interface, and the molecular basis for this phenomenon requires elucidation. Herein, we investigate the remarkable Mn(II) coordination chemistry of human CP using X-ray crystallography as well as continuous-wave (CW) and pulse electron paramagnetic resonance (EPR) spectroscopies. An X-ray crystallographic structure of Mn(II)-CP containing one Mn(II), two Ca(II), and two Na(I) ions per CP heterodimer is reported. The CW EPR spectrum of Ca(II)- and Mn(II)-bound CP prepared with a 10:0.9:1 Ca(II):Mn(II):CP ratio is characterized by an unusually low zero-field splitting of 485 MHz (E/D = 0.30) for the S = 5/2 Mn(II) ion, consistent with the high symmetry of the His6 binding site observed crystallographically. Results from electron spin-echo envelope modulation and electron-nuclear double resonance experiments reveal that the six Mn(II)-coordinating histidine residues of Ca(II)- and Mn(II)-bound CP are spectroscopically equivalent. The observed (15)N (I = 1/2) hyperfine couplings (A) arise from two distinct classes of nitrogen atoms: the coordinating ε-nitrogen of the imidazole ring of each histidine ligand (A = [3.45, 3.71, 5.91] MHz) and the distal δ-nitrogen (A = [0.11, 0.18, 0.42] MHz). In the absence of Ca(II), the binding affinity of CP for Mn(II) drops by two to three orders of magnitude and coincides with Mn(II) binding at the His6 site as well as other sites. This study demonstrates the role of Ca(II) in enabling high-affinity and specific binding of Mn(II) to the His6 site of human calprotectin. PMID:25597447

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

    PubMed

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

    2016-07-01

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

  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. 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.

  9. 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

    2015-12-01

    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.

  10. 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

    2015-12-01

    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. PMID:26125988

  11. The active site of the [FeFe]-hydrogenase from Desulfovibrio desulfuricans. I. Light sensitivity and magnetic hyperfine interactions as observed by electron paramagnetic resonance.

    PubMed

    Albracht, Simon P J; Roseboom, Winfried; Hatchikian, E Claude

    2006-01-01

    The hydrogen-activating cluster (H cluster) in [FeFe]-hydrogenases consists of two moieties. The [2Fe]H subcluster is a (L)(CO)(CN)Fe(mu-RS2)(mu-CO)Fe(CysS)(CO)(CN) centre. The Cys-bound Fe is called Fe1, the other iron Fe2. The Cys-thiol forms a bridge to a [4Fe-4S] cluster, the [4Fe-4S]H subcluster. We report that electron paramagnetic resonance (EPR) spectra of the 57Fe-enriched enzyme from Desulfovibrio desulfuricans in the H(ox)-CO state are consistent with a magnetic hyperfine interaction of the unpaired spin with all six Fe atoms of the H cluster. In contrast to the inactive aerobic enzyme, the active enzyme is easily destroyed by light. The [2Fe]H subcluster in some enzyme molecules loses CO by photolysis, whereupon other molecules firmly bind the released CO to form the H(ox)-CO state giving rise to the so-called axial 2.06 EPR signal. Though not destroyed by light, the H(ox)-CO state is affected by it. As demonstrated in the accompanying paper [49] two of the intrinsic COs, both bound to Fe2, can be exchanged by extrinsic 13CO during illumination at 2 degrees C. We found that only one of the three 13COs, the one at the extrinsic position, gives an EPR-detectable isotropic superhyperfine interaction of 0.6 mT. At 30 K both the inhibiting extrinsic CO bound to Fe2 and one more CO can be photolysed. EPR spectra of the photolysed products are consistent with a 3d7 system of Fe with the formal oxidation state +1. The damaged enzyme shows a light-sensitive g = 5 signal which is ascribed to an S = 3/2 form of the [2Fe](H) subcluster. The light sensitivity of the enzyme explains the occurrence of the g = 5 signal and the axial 2.06 signal in published EPR spectra of nearly all preparations studied thus far.

  12. Electronic structure of the Mn-cofactor of modified bacterial reaction centers measured by electron paramagnetic resonance and electron spin echo envelope modulation spectroscopies.

    PubMed

    Tufts, A A; Flores, M; Olson, T L; Williams, J C; Allen, J P

    2014-05-01

    The electronic structure of a Mn(II) ion bound to highly oxidizing reaction centers of Rhodobacter sphaeroides was studied in a mutant modified to possess a metal binding site at a location comparable to the Mn4Ca cluster of photosystem II. The Mn-binding site of the previously described mutant, M2, contains three carboxylates and one His at the binding site (Thielges et al., Biochemistry 44:389-7394, 2005). The redox-active Mn-cofactor was characterized using electron paramagnetic resonance (EPR) and electron spin echo envelope modulation (ESEEM) spectroscopies. In the light without bound metal, the Mn-binding mutants showed an EPR spectrum characteristic of the oxidized bacteriochlorophyll dimer and reduced quinone whose intensity was significantly reduced due to the diminished quantum yield of charge separation in the mutant compared to wild type. In the presence of the metal and in the dark, the EPR spectrum measured at the X-band frequency of 9.4 GHz showed a distinctive spin 5/2 Mn(II) signal consisting of 16 lines associated with both allowed and forbidden transitions. Upon illumination, the amplitude of the spectrum is decreased by over 80 % due to oxidation of the metal upon electron transfer to the oxidized bacteriochlorophyll dimer. The EPR spectrum of the Mn-cofactor was also measured at the Q-band frequency of 34 GHz and was better resolved as the signal was composed of the six allowed electronic transitions with only minor contributions from other transitions. A fit of the Q-band EPR spectrum shows that the Mn-cofactor is a high spin Mn(II) species (S = 5/2) that is six-coordinated with an isotropic g-value of 2.0006, a weak zero-field splitting and E/D ratio of approximately 1/3. The ESEEM experiments showed the presence of one (14)N coordinating the Mn-cofactor. The nitrogen atom is assigned to a His by comparing our ESEEM results to those previously reported for Mn(II) ions bound to other proteins and on the basis of the X-ray structure of the M2

  13. Probing Structural Dynamics and Topology of the KCNE1 Membrane Protein in Lipid Bilayers via Site-Directed Spin Labeling and Electron Paramagnetic Resonance Spectroscopy.

    PubMed

    Sahu, Indra D; Craig, Andrew F; Dunagan, Megan M; Troxel, Kaylee R; Zhang, Rongfu; Meiberg, Andrew G; Harmon, Corrinne N; McCarrick, Robert M; Kroncke, Brett M; Sanders, Charles R; Lorigan, Gary A

    2015-10-20

    KCNE1 is a single transmembrane protein that modulates the function of voltage-gated potassium channels, including KCNQ1. Hereditary mutations in the genes encoding either protein can result in diseases such as congenital deafness, long QT syndrome, ventricular tachyarrhythmia, syncope, and sudden cardiac death. Despite the biological significance of KCNE1, the structure and dynamic properties of its physiologically relevant native membrane-bound state are not fully understood. In this study, the structural dynamics and topology of KCNE1 in bilayered lipid vesicles was investigated using site-directed spin labeling (SDSL) and electron paramagnetic resonance (EPR) spectroscopy. A 53-residue nitroxide EPR scan of the KCNE1 protein sequence including all 27 residues of the transmembrane domain (45-71) and 26 residues of the N- and C-termini of KCNE1 in lipid bilayered vesicles was analyzed in terms of nitroxide side-chain motion. Continuous wave-EPR spectral line shape analysis indicated the nitroxide spin label side-chains located in the KCNE1 TMD are less mobile when compared to the extracellular region of KCNE1. The EPR data also revealed that the C-terminus of KCNE1 is more mobile when compared to the N-terminus. EPR power saturation experiments were performed on 41 sites including 18 residues previously proposed to reside in the transmembrane domain (TMD) and 23 residues of the N- and C-termini to determine the topology of KCNE1 with respect to the 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC)/1-palmitoyl-2-oleoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (POPG) lipid bilayers. The results indicated that the transmembrane domain is indeed buried within the membrane, spanning the width of the lipid bilayer. Power saturation data also revealed that the extracellular region of KCNE1 is solvent-exposed with some of the portions partially or weakly interacting with the membrane surface. These results are consistent with the previously published solution NMR

  14. 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

  15. 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

  16. 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

  17. Structure of the P700(+ )A1(-) radical pair intermediate in photosystem I by high time resolution multifrequency electron paramagnetic resonance: analysis of quantum beat oscillations.

    PubMed

    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

    2001-05-01

    The geometry of the secondary radical pair P700(+)A1(-), in photosystem I (PSI) from the deuterated and 15N-substituted cyanobacterium Synechococcus lividus, has been determined by high time resolution electron paramagnetic resonance (EPR), performed at three different microwave frequencies. Structural information is extracted from light-induced quantum beats observed in the transverse magnetization of P700(+)A1(-) at early times after laser excitation. A computer analysis of the two-dimensional Q-band experiment provides the orientation of the various magnetic tensors of with respect to a magnetic reference frame. The orientation of the cofactors of the primary donor in the g-tensor system of is then evaluated by analyzing time-dependent X-band EPR spectra, extracted from a two-dimensional data set. Finally, the cofactor arrangement of P700(+)A1(-) in the photosynthetic membrane is deduced from angular-dependent W-band spectra, observed for a magnetically aligned sample. Thus, the orientation of the g-tensor of P700(+) with respect to a chlorophyll based reference system could be determined. The angle between the g1(z) axis and the chlorophyll plane normal is found to be 29 +/- 7 degrees, while the g1(y) axis lies in the chlorophyll plane. In addition, a complete structural model for the reduced quinone acceptor, A1(-), is evaluated. In this model, the quinone plane of is found to be inclined by 68 +/- 7 degrees relative to the membrane plane, while the P700(+)-A1(-) axis makes an angle of 35 +/- 6 degrees with the membrane normal. All of these values refer to the charge separated state, observed at low temperatures, where forward electron transfer to the iron-sulfur centers is partially blocked. Preliminary room temperature studies of P700(+)A1(-), employing X-band quantum beat oscillations, indicate a different orientation of A1(-) in its binding pocket. A comparison with crystallographic data provides information on the electron-transfer pathway in PSI. It

  18. 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

  19. 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

  20. Experimental Test of New Technique to Overcome Spin Depolarizing Resonances

    SciTech Connect

    Raymond, R. S.; Chao, A. W.; Krisch, A. D.; Leonova, M. A.; Morozov, V. S.; Sivers, D. W.; Wong, V. K.; Ganshvili, A.; Gebel, R.; Lehrach, A.; Lorentz, B.; Maier, R.; Prasuhn, D.; Stockhorst, H.; Welsch, D.; Hinterberger, F.; Kondratenko, A. M.

    2009-08-04

    We recently tested a new spin resonance crossing technique, Kondratenko Crossing (KC) by sweeping an rf solenoid's frequency through an rf-induced spin resonance with both the KC an traditional Fast Crossing (FC) patterns. Using both rf bunched and unbunched 1.85 GeV/c polarized deuterons stored in COSY, we varied the parameters of both crossing patterns. Compared to FC with the same crossing speed, KC reduced the depolarization by measured factors of 4.7+-0.3 and 19+-{sub 5}{sup 12} for unbunched and bunched beams, respectively. This clearly showed the large potential benefit of Kondratenko Crossing over Fast Crossing.

  1. [Use of paramagnetic ions in the study of intercellular water transport by nuclear magnetic resonance with pulsed gradient ofthe magnetic field].

    PubMed

    Evarestov, A S; Anisimov, A V; Samuilova, I F

    1984-01-01

    A methodical approach to the studies of water transport in biological cells by NMR method with impulse gradient of the magnetic field is proposed. It allows to exclude experimentally water transport through the plasmalemma, without touching upon transport along intercellular contacts. The effect is achieved by preliminary introduction of paramagnetic ions into intercellular space.

  2. Surface Plasmon Resonance: A Versatile Technique for Biosensor Applications

    PubMed Central

    Nguyen, Hoang Hiep; Park, Jeho; Kang, Sebyung; Kim, Moonil

    2015-01-01

    Surface plasmon resonance (SPR) is a label-free detection method which has emerged during the last two decades as a suitable and reliable platform in clinical analysis for biomolecular interactions. The technique makes it possible to measure interactions in real-time with high sensitivity and without the need of labels. This review article discusses a wide range of applications in optical-based sensors using either surface plasmon resonance (SPR) or surface plasmon resonance imaging (SPRI). Here we summarize the principles, provide examples, and illustrate the utility of SPR and SPRI through example applications from the biomedical, proteomics, genomics and bioengineering fields. In addition, SPR signal amplification strategies and surface functionalization are covered in the review. PMID:25951336

  3. A study of C-13-enriched chemical vapor deposited diamond film by means of C-13 nuclear magnetic resonance, electron paramagnetic resonance, and dynamic nuclear polarization

    NASA Astrophysics Data System (ADS)

    Lock, Herman; Wind, Robert A.; Maciel, Gary E.; Johnson, Curtis E.

    1993-09-01

    The results are presented of a study, based on EPR and various NMR techniques, of the effect on the nature of CVD diamond films of the addition of O2 to the methane-hydrogen mixture used to produce the film. The addition of oxygen to the feed gas results in a reduction of the number of unpaired electron spins, roughly from 10 exp 18 spins/g up to 10 exp 17 spins/g. There is a small aromatic signal in the dynamic nuclear polarization (DNP)-cross polarization (CP)-magic angle spinning (MAS) C-13 spectrum and a small peak at 28 ppm in the 14 T DP-MAS C-13 spectrum for only the diamond film sample grown without O2 present in the feed gas. The combination of DNP and CP at 1.4 T enables one to obtain a useful DNP-CP-MAS C-13 spectrum, ostensibly probing only the surface and intergrain boundary regions, in a matter of hours.

  4. Munitions classification using an Acoustic Resonance Spectroscopic technique

    SciTech Connect

    Roberts, R.S.; Chen, J.T.; Vela, O.A.; Lewis, P.S.

    1993-12-01

    In support of the Bilateral Chemical Weapons Agreement between the United States and Russia, Los Alamos National Laboratory has developed a nondestructive evaluation (NDE) technique that discriminates between different types of artillery munitions. This NDE classification technique allows on-site inspectors to rapidly classify the munitions as chemical or high explosive, and furthermore discriminates between various subclasses of these types of munitions. This technique, based on acoustic resonance measurements, has been successfully demonstrated on a wide variety of high explosive and chemical munitions. The technique consists of building templates of spectral features from sets of known munitions. Spectral features of unknown munitions are compared with a library of templates, and the degree of match between the features and the templates is used to classify the munition. This paper describes the technique, including the feature extraction, clustering and classification algorithms.

  5. Magnetic resonance elastography (MRE) in cancer: Technique, analysis, and applications

    PubMed Central

    Pepin, Kay M.; Ehman, Richard L.; McGee, Kiaran P.

    2015-01-01

    Tissue mechanical properties are significantly altered with the development of cancer. Magnetic resonance elastography (MRE) is a noninvasive technique capable of quantifying tissue mechanical properties in vivo. This review describes the basic principles of MRE and introduces some of the many promising MRE methods that have been developed for the detection and characterization of cancer, evaluation of response to therapy, and investigation of the underlying mechanical mechanisms associated with malignancy. PMID:26592944

  6. Total body water measurements using resonant cavity perturbation techniques

    NASA Astrophysics Data System (ADS)

    Stone, Darren A.; Robinson, Martin P.

    2004-05-01

    A recent paper proposed a novel technique for determining the total body water (TBW) of patients suffering with abnormal hydration levels, using a resonant cavity perturbation method. Current techniques to measure TBW are limited by resolution and technical constraints. However, this new method involves measuring the dielectric properties of the body, by placing a subject in a large cavity resonator and measuring the subsequent change in its resonant frequency, fres and its Q-factor. Utilizing the relationship that water content correlates to these dielectric properties, it has been shown that the measured response of these parameters enables determination of TBW. Results are presented for a preliminary study using data estimated from anthropometric measurements, where volunteers were asked to lie and stand in an electromagnetic screened room, before and after drinking between 1 and 2 l of water, and in some cases, after voiding the bladder. Notable changes in the parameters were observed; fres showed a negative shift and Q was reduced. Preliminary calibration curves using estimated values of water content have been developed from these results, showing that for each subject the measured resonant frequency is a linear function of TBW. Because the gradients of these calibration curves correlate to the mass-to-height-ratio of the volunteers, it has proved that a system in which TBW can be unequivocally obtained is possible. Measured values of TBW have been determined using this new pilot-technique, and the values obtained correlate well with theoretical values of body water (r = 0.87) and resolution is very good (750 ml). The results obtained are measurable, repeatable and statistically significant. This leads to confidence in the integrity of the proposed technique.

  7. Magnetic resonance elastography (MRE) in cancer: Technique, analysis, and applications.

    PubMed

    Pepin, Kay M; Ehman, Richard L; McGee, Kiaran P

    2015-11-01

    Tissue mechanical properties are significantly altered with the development of cancer. Magnetic resonance elastography (MRE) is a noninvasive technique capable of quantifying tissue mechanical properties in vivo. This review describes the basic principles of MRE and introduces some of the many promising MRE methods that have been developed for the detection and characterization of cancer, evaluation of response to therapy, and investigation of the underlying mechanical mechanisms associated with malignancy. PMID:26592944

  8. Disappearance of electron-hole asymmetry in nanoparticles of Nd{sub 1−x}Ca{sub x}MnO{sub 3}(x=0.6,0.4): magnetization and electron paramagnetic resonance evidence

    SciTech Connect

    Bhagyashree, K. S. Bhat, S. V.

    2015-05-07

    We study and compare magnetic and electron paramagnetic resonance behaviors of bulk and nanoparticles of Nd{sub 1−x}Ca{sub x}MnO{sub 3} in hole doped (x=0.4;NCMOH) and electron doped (x=0.6;NCMOE) samples. NCMOH in bulk form shows a complex temperature dependence of magnetization M(T), with a charge ordering transition at ∼250 K, an antiferromagnetic (AFM) transition at ∼150 K, and a transition to a canted AFM phase/mixed phase at ∼80 K. Bulk NCMOE behaves quite differently with just a charge ordering transition at ∼280 K, thus providing a striking example of the so called electron-hole asymmetry. While our magnetization data on bulk samples are consistent with the earlier reports, the new results on the nanoparticles bring out drastic effects of size reduction. They show that M(T) behaviors of the two nanosamples are essentially similar in addition to the absence of the charge order in them thus providing strong evidence for vanishing of the electron-hole asymmetry in nanomanganites. This conclusion is further corroborated by electron paramagnetic resonance studies which show that the large difference in the “g” values and their temperature dependences found for the two bulk samples disappears as they approach a common behavior in the corresponding nanosamples.

  9. Various diffusion magnetic resonance imaging techniques for pancreatic cancer

    PubMed Central

    Tang, Meng-Yue; Zhang, Xiao-Ming; Chen, Tian-Wu; Huang, Xiao-Hua

    2015-01-01

    Pancreatic cancer is one of the most common malignant tumors and remains a treatment-refractory cancer with a poor prognosis. Currently, the diagnosis of pancreatic neoplasm depends mainly on imaging and which methods are conducive to detecting small lesions. Compared to the other techniques, magnetic resonance imaging (MRI) has irreplaceable advantages and can provide valuable information unattainable with other noninvasive or minimally invasive imaging techniques. Advances in MR hardware and pulse sequence design have particularly improved the quality and robustness of MRI of the pancreas. Diffusion MR imaging serves as one of the common functional MRI techniques and is the only technique that can be used to reflect the diffusion movement of water molecules in vivo. It is generally known that diffusion properties depend on the characterization of intrinsic features of tissue microdynamics and microstructure. With the improvement of the diffusion models, diffusion MR imaging techniques are increasingly varied, from the simplest and most commonly used technique to the more complex. In this review, the various diffusion MRI techniques for pancreatic cancer are discussed, including conventional diffusion weighted imaging (DWI), multi-b DWI based on intra-voxel incoherent motion theory, diffusion tensor imaging and diffusion kurtosis imaging. The principles, main parameters, advantages and limitations of these techniques, as well as future directions for pancreatic diffusion imaging are also discussed. PMID:26753059

  10. Juvenile angiofibroma: imaging by magnetic resonance, CT and conventional techniques.

    PubMed

    Lloyd, G A; Phelps, P D

    1986-08-01

    Thirty patients with histologically verified angiofibromata have been investigated over a period of 14 years. They have been examined by conventional radiographic techniques and computerized tomography, and more recently 4 patients have been scanned by magnetic resonance. CT studies of patients with small tumours have shown that the point of origin is at the sphenopalatine foramen. The tumour enlarges the foramen and erodes bone locally giving rise to characteristic signs both on plain X-ray and on CT scan. The value of magnetic resonance imaging is assessed and it is concluded that in the presence of the characteristic 'antral sign' on plain X-ray, 3-plane magnetic resonance is now the method of choice to show the extent of the tumour pre-operatively. Magnetic resonance can also show the vascular nature of the angiofibroma by the demonstration of large vessels, shown as dark areas of negative signal within the tumour mass. With this new method of investigation available, angiography should now only be performed if embolization is deemed necessary prior to surgical removal of the angiofibroma.

  11. Magnetic Resonance Spectroscopy: Principles and Techniques: Lessons for Clinicians.

    PubMed

    Tognarelli, Joshua M; Dawood, Mahvish; Shariff, Mohamed I F; Grover, Vijay P B; Crossey, Mary M E; Cox, I Jane; Taylor-Robinson, Simon D; McPhail, Mark J W

    2015-12-01

    Magnetic resonance spectroscopy (MRS) provides a non-invasive 'window' on biochemical processes within the body. Its use is no longer restricted to the field of research, with applications in clinical practice increasingly common. MRS can be conducted at high magnetic field strengths (typically 11-14 T) on body fluids, cell extracts and tissue samples, with new developments in whole-body magnetic resonance imaging (MRI) allowing clinical MRS at the end of a standard MRI examination, obtaining functional information in addition to anatomical information. We discuss the background physics the busy clinician needs to know before considering using the technique as an investigative tool. Some potential applications of hepatic and cerebral MRS in chronic liver disease are also discussed.

  12. Brain perfusion: computed tomography and magnetic resonance techniques.

    PubMed

    Copen, William A; Lev, Michael H; Rapalino, Otto

    2016-01-01

    Cerebral perfusion imaging provides assessment of regional microvascular hemodynamics in the living brain, enabling in vivo measurement of a variety of different hemodynamic parameters. Perfusion imaging techniques that are used in the clinical setting usually rely upon X-ray computed tomography (CT) or magnetic resonance imaging (MRI). This chapter reviews CT- and MRI-based perfusion imaging techniques, with attention to image acquisition, clinically relevant aspects of image postprocessing, and fundamental differences between CT- and MRI-based techniques. Correlations with cerebrovascular physiology and potential clinical applications of perfusion imaging are reviewed, focusing upon the two major classes of neurologic disease in which perfusion imaging is most often performed: primary perfusion disorders (including ischemic stroke, transient ischemic attack, and reperfusion syndrome), and brain tumors.

  13. 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.

  14. Functional magnetic resonance imaging: imaging techniques and contrast mechanisms.

    PubMed Central

    Howseman, A M; Bowtell, R W

    1999-01-01

    Functional magnetic resonance imaging (fMRI) is a widely used technique for generating images or maps of human brain activity. The applications of the technique are widespread in cognitive neuroscience and it is hoped they will eventually extend into clinical practice. The activation signal measured with fMRI is predicated on indirectly measuring changes in the concentration of deoxyhaemoglobin which arise from an increase in blood oxygenation in the vicinity of neuronal firing. The exact mechanisms of this blood oxygenation level dependent (BOLD) contrast are highly complex. The signal measured is dependent on both the underlying physiological events and the imaging physics. BOLD contrast, although sensitive, is not a quantifiable measure of neuronal activity. A number of different imaging techniques and parameters can be used for fMRI, the choice of which depends on the particular requirements of each functional imaging experiment. The high-speed MRI technique, echo-planar imaging provides the basis for most fMRI experiments. The problems inherent to this method and the ways in which these may be overcome are particularly important in the move towards performing functional studies on higher field MRI systems. Future developments in techniques and hardware are also likely to enhance the measurement of brain activity using MRI. PMID:10466145

  15. Advanced Morphological and Functional Magnetic Resonance Techniques in Glaucoma

    PubMed Central

    Mastropasqua, Rodolfo; Agnifili, Luca; Mattei, Peter A.; Caulo, Massimo; Fasanella, Vincenzo; Navarra, Riccardo; Mastropasqua, Leonardo; Marchini, Giorgio

    2015-01-01

    Glaucoma is a multifactorial disease that is the leading cause of irreversible blindness. Recent data documented that glaucoma is not limited to the retinal ganglion cells but that it also extends to the posterior visual pathway. The diagnosis is based on the presence of signs of glaucomatous optic neuropathy and consistent functional visual field alterations. Unfortunately these functional alterations often become evident when a significant amount of the nerve fibers that compose the optic nerve has been irreversibly lost. Advanced morphological and functional magnetic resonance (MR) techniques (morphometry, diffusion tensor imaging, arterial spin labeling, and functional connectivity) may provide a means for observing modifications induced by this fiber loss, within the optic nerve and the visual cortex, in an earlier stage. The aim of this systematic review was to determine if the use of these advanced MR techniques could offer the possibility of diagnosing glaucoma at an earlier stage than that currently possible. PMID:26167474

  16. Novel technique in the segmentation of magnetic resonance image

    NASA Astrophysics Data System (ADS)

    Chan, Kwok-Leung

    1996-04-01

    In this investigation, automatic image segmentation is carried out on magnetic resonance image (MRI). A novel technique based on the maximum minimum measure is devised. The measure is improved by combining the smoothing and counting processes, and then normalizing the number of maximum and minimum positions over the region of interest (ROI). Two parameters (MM_H and MM_V) are generated and used for the segmentation. The technique is tested on some brain MRIs of a human male from the Visible Human Project of the National Library of Medicine, National Institutes of Health, USA. Preliminary results indicate that the maximum minimum measure can provide effective parameters for human tissue characterization and image segmentation with an added advantage of faster computation.

  17. Theoretical studies of the local structures and electron paramagnetic resonance parameters for Cu2+ center in Zn(C3H3O4)2(H2O)2 single crystal

    NASA Astrophysics Data System (ADS)

    Zhang, Hua-Ming; Xiao, Wen-Bo; Wan, Xiong

    2014-07-01

    The electron paramagnetic resonance (EPR) parameters (g factors gxx, gyy, gzz and hyperfine structure constants Axx, Ayy, Azz) are interpreted by taking account of the admixture of d-orbitals in the ground state wave function of the Cu2+ ion in a Zn(C3H3O4)2(H2O)2 (DABMZ) single crystal. Based on the calculation, local structural parameters of the impurity Cu2+ center were obtained (i.e. Ra≈1.92 Å, Rb≈1.96 Å, Rc≈1.99 Å). The theoretical EPR parameters based on the above Cu2+-O2- bond lengths in the DABMZ crystal show good agreement with the observed values and some improvements have been made as compared with those in the previous studies.

  18. 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.

  19. Electron paramagnetic resonance study of alinement induced by magnetic fields in two smectic-A liquid crystals not exhibiting nematic phases

    NASA Technical Reports Server (NTRS)

    Fryburg, G. C.; Gelerinter, E.

    1972-01-01

    Using vanadyl acetylacetonate (VAAC) as a paramagnetic probe, the molecular ordering in two smectic-A liquid crystals that do not display nematic phases were studied. Reproducible alinement was attained by slow cooling throughout the isotropic smectic-A transition in dc magnetic fields of 1.1 and 2.15 teslas. The degree of order attained is small for a smectic-A liquid crystal. Measurements were made of the variation of the average hyperfine splitting of the alined samples as a function of orientation relative to the dc magnetic field of the spectrometer. This functional dependence is in agreement with the theoretical prediction except where the viscosity of the liquid crystal becomes large enough to slow the tumbling of the VAAC, as indicated by asymmetry in the end lines of the spectrum.

  20. Quantitative Proton Magnetic Resonance Techniques for Measuring Fat

    PubMed Central

    Harry, Houchun; Kan, Hermien E.

    2014-01-01

    Accurate, precise, and reliable techniques for quantifying body and organ fat distributions are important tools in physiology research. They are critically needed in studies of obesity and diseases involving excess fat accumulation. Proton magnetic resonance methods address this need by providing an array of relaxometry-based (T1, T2) and chemical-shift-based approaches. These techniques can generate informative visualizations of regional and whole-body fat distributions, yield measurements of fat volumes within specific body depots, and quantify fat accumulation in abdominal organs and muscles. MR methods are commonly used to investigate the role of fat in nutrition and metabolism, to measure the efficacy of short and long-term dietary and exercise interventions, to study the implications of fat in organ steatosis and muscular dystrophies, and to elucidate pathophysiological mechanisms in the context of obesity and its comorbidities. The purpose of this review is to provide a summary of mainstream MR strategies for fat quantification. The article will succinctly describe the principles that differentiate water and fat proton signals, summarize advantages and limitations of various techniques, and offer a few illustrative examples. The article will also highlight recent efforts in MR of brown adipose tissue and conclude by briefly discussing some future research directions. PMID:24123229

  1. Resonant frequency calculations using a hybrid perturbation-Galerkin technique

    NASA Technical Reports Server (NTRS)

    Geer, James F.; Andersen, Carl M.

    1991-01-01

    A two-step hybrid perturbation Galerkin technique is applied to the problem of determining the resonant frequencies of one or several degrees of freedom nonlinear systems involving a parameter. In one step, the Lindstedt-Poincare method is used to determine perturbation solutions which are formally valid about one or more special values of the parameter (e.g., for large or small values of the parameter). In step two, a subset of the perturbation coordinate functions determined in step one is used in Galerkin type approximation. The technique is illustrated for several one degree of freedom systems, including the Duffing and van der Pol oscillators, as well as for the compound pendulum. For all of the examples considered, it is shown that the frequencies obtained by the hybrid technique using only a few terms from the perturbation solutions are significantly more accurate than the perturbation results on which they are based, and they compare very well with frequencies obtained by purely numerical methods.

  2. Resonant frequency calculations using a hybrid perturbation-Galerkin technique

    NASA Technical Reports Server (NTRS)

    Geer, James F.; Andersen, Carl M.

    1991-01-01

    A two-step hybrid perturbation Galerkin technique is applied to the problem of determining the resonant frequencies of one or several degree of freedom nonlinear systems involving a parameter. In one step, the Lindstedt-Poincare method is used to determine perturbation solutions which are formally valid about one or more special values of the parameter (e.g., for large or small values of the parameter). In step two, a subset of the perturbation coordinate functions determined in step one is used in Galerkin type approximation. The technique is illustrated for several one degree of freedom systems, including the Duffing and van der Pol oscillators, as well as for the compound pendulum. For all of the examples considered, it is shown that the frequencies obtained by the hybrid technique using only a few terms from the perturbation solutions are significantly more accurate than the perturbation results on which they are based, and they compare very well with frequencies obtained by purely numerical methods.

  3. Magnetic resonance techniques for investigation of multiple sclerosis

    NASA Astrophysics Data System (ADS)

    MacKay, Alex; Laule, Cornelia; Li, David K. B.; Meyers, Sandra M.; Russell-Schulz, Bretta; Vavasour, Irene M.

    2014-11-01

    Multiple sclerosis (MS) is a common neurological disease which can cause loss of vision and balance, muscle weakness, impaired speech, fatigue, cognitive dysfunction and even paralysis. The key pathological processes in MS are inflammation, edema, myelin loss, axonal loss and gliosis. Unfortunately, the cause of MS is still not understood and there is currently no cure. Magnetic resonance imaging (MRI) is an important clinical and research tool for MS. 'Conventional' MRI images of MS brain reveal bright lesions, or plaques, which demark regions of severe tissue damage. Conventional MRI has been extremely valuable for the diagnosis and management of people who have MS and also for the assessment of therapies designed to reduce inflammation and promote repair. While conventional MRI is clearly valuable, it lack pathological specificity and, in some cases, sensitivity to non-lesional pathology. Advanced MR techniques have been developed to provide information that is more sensitive and specific than what is available with clinical scanning. Diffusion tensor imaging and magnetization transfer provide a general but non-specific measure of the pathological state of brain tissue. MR spectroscopy provides concentrations of brain metabolites which can be related to specific pathologies. Myelin water imaging was designed to assess brain myelination and has proved useful for measuring myelin loss in MS. To combat MS, it is crucial that the pharmaceutical industry finds therapies which can reverse the neurodegenerative processes which occur in the disease. The challenge for magnetic resonance researchers is to design imaging techniques which can provide detailed pathological information relating to the mechanisms of MS therapies. This paper briefly describes the pathologies of MS and demonstrates how MS-associated pathologies can be followed using both conventional and advanced MR imaging protocols.

  4. Novel nuclear magnetic resonance techniques for studying biological molecules

    SciTech Connect

    Laws, David D.

    2000-06-01

    Over the fifty-five year history of Nuclear Magnetic Resonance (NMR), considerable progress has been made in the development of techniques for studying the structure, function, and dynamics of biological molecules. The majority of this research has involved the development of multi-dimensional NMR experiments for studying molecules in solution, although in recent years a number of groups have begun to explore NMR methods for studying biological systems in the solid-state. Despite this new effort, a need still exists for the development of techniques that improve sensitivity, maximize information, and take advantage of all the NMR interactions available in biological molecules. In this dissertation, a variety of novel NMR techniques for studying biomolecules are discussed. A method for determining backbone ({phi}/{psi}) dihedral angles by comparing experimentally determined {sup 13}C{sub a}, chemical-shift anisotropies with theoretical calculations is presented, along with a brief description of the theory behind chemical-shift computation in proteins and peptides. The utility of the Spin-Polarization Induced Nuclear Overhauser Effect (SPINOE) to selectively enhance NMR signals in solution is examined in a variety of systems, as are methods for extracting structural information from cross-relaxation rates that can be measured in SPINOE experiments. Techniques for the production of supercritical and liquid laser-polarized xenon are discussed, as well as the prospects for using optically pumped xenon as a polarizing solvent. In addition, a detailed study of the structure of PrP 89-143 is presented. PrP 89-143 is a 54 residue fragment of the prion proteins which, upon mutation and aggregation, can induce prion diseases in transgenic mice. Whereas the structure of the wild-type PrP 89-143 is a generally unstructured mixture of {alpha}-helical and {beta}-sheet conformers in the solid state, the aggregates formed from the PrP 89-143 mutants appear to be mostly {beta}-sheet.

  5. 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

  6. Acceptor-oxygen vacancy defect dipoles and fully coordinated defect centers in a ferroelectric perovskite lattice: Electron paramagnetic resonance analysis of Mn2+ in single crystal BaTiO3

    NASA Astrophysics Data System (ADS)

    Maier, R. A.; Pomorski, T. A.; Lenahan, P. M.; Randall, C. A.

    2015-10-01

    Defect dipoles are significant point defects in perovskite oxides as a result of their impact on oxygen vacancy dynamics. Electron paramagnetic resonance (EPR) was used to investigate the local defect structure of single crystal BaTiO3 doped with manganese. These results, along with a re-analysis of literature data, do not support the conclusion that transition metal-oxygen vacancy nearest neighbor defect dipoles ( M nT i ″ - VO • • ) × in ferroelectric BaTiO3 are majority defect centers as previously reported. Local symmetry analysis of the zero-field splitting term of the spin Hamiltonian supports the assignment of fully coordinated defect centers as opposed to defect dipoles for resonance signals at geff ˜ 2. A newly discovered defect center with g⊥ ˜ 6 is observed in the manganese doped system, and it is argued that this defect center belongs to an associated defect complex or defect dipole. This newly reported strong axial defect center, however, is present in small, minor concentrations compared to the well-known Mn2+ center with zero-field splitting of D ˜ 645 MHz. In regard to relative concentration, it is concluded that the dominant point defect related to the Mn2+ ion doped in BaTiO3 corresponds to B-site substitution with six nearest neighbor anions in octahedral coordination.

  7. Paramagnetic shimming for wide-range variable-field NMR.

    PubMed

    Ichijo, Naoki; Takeda, Kazuyuki; Takegoshi, K

    2014-09-01

    We propose a new passive shimming strategy for variable-field NMR experiments, in which the magnetic field produced by paramagnetic shim pieces placed inside the magnet bore compensates the inhomogeneity of a variable-field magnet for a wide range of magnet currents. Paramagnetic shimming is demonstrated in (7)Li, (87)Rb, and (45)Sc NMR of a liquid solution sample in magnetic fields of 3.4, 4.0, and 5.4T at a fixed carrier frequency of 56.0MHz. Since both the main-field inhomogeneity and the paramagnetic magnetization are proportional to the main-magnet current, the resonance lines are equally narrowed by the improved field homogeneity with an identical configuration of the paramagnetic shim pieces. Paramagnetic shimming presented in this work opens the possibility of high-resolution variable-field NMR experiments. PMID:25080372

  8. 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.

  9. 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…

  10. 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)

  11. 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.

  12. In vivo evaluation of different alterations of redox status by studying pharmacokinetics of nitroxides using magnetic resonance techniques

    PubMed Central

    Bačić, Goran; Pavićević, Aleksandra; Peyrot, Fabienne

    2015-01-01

    Free radicals, particularly reactive oxygen species (ROS), are involved in various pathologies, injuries related to radiation, ischemia-reperfusion or ageing. Unfortunately, it is virtually impossible to directly detect free radicals in vivo, but the redox status of the whole organism or particular organ can be studied in vivo by using magnetic resonance techniques (EPR and MRI) and paramagnetic stable free radicals – nitroxides. Here we review results obtained in vivo following the pharmacokinetics of nitroxides on experimental animals (and a few in humans) under various conditions. The focus was on conditions where the redox status has been altered by induced diseases or harmful agents, clearly demonstrating that various EPR/MRI/nitroxide combinations can reliably detect metabolically induced changes in the redox status of organs. These findings can improve our understanding of oxidative stress and provide a basis for studying the effectiveness of interventions aimed to modulate oxidative stress. Also, we anticipate that the in vivo EPR/MRI approach in studying the redox status can play a vital role in the clinical management of various pathologies in the years to come providing the development of adequate equipment and probes. PMID:26827126

  13. 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.

  14. 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.

  15. The Structure of Vimentin Linker 1 and Rod 1B Domains Characterized by Site-directed Spin-labeling Electron Paramagnetic Resonance (SDSL-EPR) and X-ray Crystallography*

    PubMed Central

    Aziz, Atya; Hess, John F.; Budamagunta, Madhu S.; Voss, John C.; Kuzin, Alexandre P.; Huang, Yuanpeng J.; Xiao, Rong; Montelione, Gaetano T.; FitzGerald, Paul G.; Hunt, John F.

    2012-01-01

    Despite the passage of ∼30 years since the complete primary sequence of the intermediate filament (IF) protein vimentin was reported, the structure remains unknown for both an individual protomer and the assembled filament. In this report, we present data describing the structure of vimentin linker 1 (L1) and rod 1B. Electron paramagnetic resonance spectra collected from samples bearing site-directed spin labels demonstrate that L1 is not a flexible segment between coiled-coils (CCs) but instead forms a rigid, tightly packed structure. An x-ray crystal structure of a construct containing L1 and rod 1B shows that it forms a tetramer comprising two equivalent parallel CC dimers that interact with one another in the form of a symmetrical anti-parallel dimer. Remarkably, the parallel CC dimers are themselves asymmetrical, which enables them to tetramerize rather than undergoing higher order oligomerization. This functionally vital asymmetry in the CC structure, encoded in the primary sequence of rod 1B, provides a striking example of evolutionary exploitation of the structural plasticity of proteins. EPR and crystallographic data consistently suggest that a very short region within L1 represents a minor local distortion in what is likely to be a continuous CC from the end of rod 1A through the entirety of rod 1B. The concordance of this structural model with previously published cross-linking and spectral data supports the conclusion that the crystallographic oligomer represents a native biological structure. PMID:22740688

  16. Characterization of the coral allene oxide synthase active site with UV-visible absorption, magnetic circular dichroism, and electron paramagnetic resonance spectroscopy: evidence for tyrosinate ligation to the ferric enzyme heme iron.

    PubMed

    Abraham, B D; Sono, M; Boutaud, O; Shriner, A; Dawson, J H; Brash, A R; Gaffney, B J

    2001-02-20

    Coral allene oxide synthase (AOS), a hemoprotein with weak sequence homology to catalase, is the N-terminal domain of a naturally occurring fusion protein with an 8R-lipoxygenase. AOS converts 8R-hydroperoxyeicosatetraenoic acid to the corresponding allene oxide. The UV--visible absorption and magnetic circular dichroism spectra of ferric AOS and of its cyanide and azide complexes, and the electron paramagnetic resonance spectra of native AOS (high-spin, g = 6.56, 5.22, 2.00) and of its cyanide adduct (low-spin, g = 2.86, 2.24, 1.60) closely resemble the corresponding spectra of bovine liver catalase (BLC). These results provide strong evidence for tyrosinate ligation to the heme iron of AOS as has been established for catalases. On the other hand, the positive circular dichroism bands in the Soret region for all three derivatives of ferric AOS are almost the mirror image of those in catalase. In addition, the cyanide affinity of native AOS (K(d) = 10 mM at pH 7) is about 3 orders of magnitude lower than that of BLC. Thus, while these results conclusively support a common tyrosinate-ligated heme in AOS as in catalase, significant differences exist in the interaction between their respective heme prosthetic groups and protein environments, and in the access of small molecules to the heme iron. PMID:11329294

  17. 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

  18. Development of adaptive resonator techniques for high-power lasers

    SciTech Connect

    An, J; Brase, J; Carrano, C; Dane, C B; Flath, L; Fochs, S; Hurd, R; Kartz, M; Sawvel, R

    1999-07-12

    The design of an adaptive wavefront control system for a high-power Nd:Glass laser will be presented. Features of this system include: an unstable resonator in confocal configuration, a multi-module slab amplifier, and real-time intracavity adaptive phase control using deformable mirrors and high-speed wavefront sensors. Experimental results demonstrate the adaptive correction of an aberrated passive resonator (no gain).

  19. Experimental study of liquid level gauge for liquid hydrogen using Helmholtz resonance technique

    NASA Astrophysics Data System (ADS)

    Nakano, Akihiro; Nishizu, Takahisa

    2016-07-01

    The Helmholtz resonance technique was applied to a liquid level gauge for liquid hydrogen to confirm the applicability of the technique in the cryogenic industrial field. A specially designed liquid level gauge that has a Helmholtz resonator with a small loudspeaker was installed in a glass cryostat. A swept frequency signal was supplied to the loudspeaker, and the acoustic response was detected by measuring the electrical impedance of the loudspeaker's voice coil. The penetration depth obtained from the Helmholtz resonance frequency was compared with the true value, which was read from a scale. In principle, the Helmholtz resonance technique is available for use with liquid hydrogen, however there are certain problems as regards practical applications. The applicability of the Helmholtz resonance technique to liquid hydrogen is discussed in this study.

  20. End-to-End Thiocyanato-Bridged Helical Chain Polymer and Dichlorido-Bridged Copper(II) Complexes with a Hydrazone Ligand: Synthesis, Characterisation by Electron Paramagnetic Resonance and Variable-Temperature Magnetic Studies, and Inhibitory Effects on Human Colorectal Carcinoma Cells.

    PubMed

    Das, Kuheli; Datta, Amitabha; Sinha, Chittaranjan; Huang, Jui-Hsien; Garribba, Eugenio; Hsiao, Ching-Sheng; Hsu, Chin-Lin

    2012-04-01

    The reactions of the tridentate hydrazone ligand, N'-[1-(pyridin-2-yl)ethylidene]acetohydrazide (HL), obtained by condensation of 2-acetylpyridine with acetic hyadrazide, with copper nitrate trihydrate in the presence of thiocyanate, or with CuCl2 produce two distinct coordination compounds, namely a one-dimensional helical coordination chain of [CuL(NCS)] n (1) units, and a doubly chlorido-bridged dinuclear complex [Cu2L2Cl2] (2) (where L=CH3C(O)=N-N=CCH3C5H4N). Single-crystal X-ray structural determination studies reveal that in complex 1, a deprotonated hydrazone ligand L(-) coordinates a copper(II) ion that is bridged to two neighbouring metal centres by SCN(-) anions, generating a one-dimensional helical coordination chain. In complex 2, two symmetry-related, adjacent copper(II) coordination entities are doubly chlorido-bridged, producing a dicopper entity with a Cu⋅⋅⋅Cu distance of 3.402 (1) Å. The two coordination compounds have been fully characterised by elemental analysis, spectroscopic techniques including IR, UV-vis and electron paramagnetic resonance, and variable-temperature magnetic studies. The biological effects of 1 and 2 on the viability of human colorectal carcinoma cells (COLO-205 and HT-29) were evaluated using an MTT assay, and the results indicate that these complexes induce a decrease in cell-population growth of human colorectal carcinoma cells with apoptosis.

  1. Metal-Metal Interactions in Trinuclear Copper(II) Complexes [Cu3(RCOO)4(H2TEA)2] and Binuclear [Cu2(RCOO)2(H2TEA)2]. Syntheses and Combined Structural, Magnetic, High-Field Electron Paramagnetic Resonance, and Theoretical Studies.

    PubMed

    Ozarowski, Andrew; Calzado, Carmen J; Sharma, Raj Pal; Kumar, Santosh; Jezierska, Julia; Angeli, Celestino; Spizzo, Federico; Ferretti, Valeria

    2015-12-21

    The trinuclear [Cu3(RCOO)4(H2TEA)2] copper(II) complexes, where RCOO(-) = 2-furoate (1), 2-methoxybenzoate (2), and 3-methoxybenzoate (3, 4), as well as dimeric species [Cu2(H2TEA)2(RCOO)2]·2H2O, have been prepared by adding triethanolamine (H3TEA) at ambient conditions to hydrated Cu(RCOO)2 salts. The newly synthesized complexes have been characterized by elemental analyses, spectroscopic techniques (IR and UV-visible), magnetic susceptibility, single crystal X-ray structure determination and theoretical calculations, using a Difference Dedicated Configuration Interaction approach for the evaluation of magnetic coupling constants. In 1 and 2, the central copper atom lies on an inversion center, while in the polymorphs 3 and 4, the three metal centers are crystallographically independent. The zero-field splitting parameters of the trimeric compounds, D and E, were derived from high-field, high-frequency electron paramagnetic resonance spectra at temperatures ranging from 3 to 290 K and were used for the interpretation of the magnetic data. It was found that the dominant interaction between the terminal and central Cu sites J12 is ferromagnetic in nature in all complexes, even though differences have been found between the symmetrical or quasi-symmetrical complexes 1-3 and non-symmetrical complex 4, while the interaction between the terminal centers, J23, is negligible.

  2. In-Situ Characterization of Tissue Blood Flow, Blood Content, and Water State Using New Techniques in Magnetic Resonance Imaging.

    NASA Astrophysics Data System (ADS)

    Conturo, Thomas Edward

    Tissue blood flow, blood content, and water state have been characterized in-situ with new nuclear magnetic resonance imaging techniques. The sensitivities of standard techniques to the physiologic tissue parameters spin density (N_{rm r}) and relaxation times (T_1 and T_2 ) are mathematically defined. A new driven inversion method is developed so that tissue T_1 and T_2 changes produce cooperative intensity changes, yielding high contrast, high signal to noise, and sensitivity to a wider range of tissue parameters. The actual tissue parameters were imaged by automated collection of multiple-echo data having multiple T _1 dependence. Data are simultaneously fit by three-parameters to a closed-form expression, producing lower inter-parameter correlation and parameter noise than in separate T_1 or T_2 methods or pre-averaged methods. Accurate parameters are obtained at different field strengths. Parametric images of pathology demonstrate high sensitivity to tissue heterogeneity, and water content is determined in many tissues. Erythrocytes were paramagnetically labeled to study blood content and relaxation mechanisms. Liver and spleen relaxation were enhanced following 10% exchange of animal blood volumes. Rapid water exchange between intracellular and extracellular compartments was validated. Erythrocytes occupied 12.5% of renal cortex volume, and blood content was uniform in the liver, spleen and kidney. The magnitude and direction of flow velocity was then imaged. To eliminate directional artifacts, a bipolar gradient technique sensitized to flow in different directions was developed. Phase angle was reconstructed instead of intensity since the former has a 2pi -fold higher dynamic range. Images of flow through curves demonstrated secondary flow with a centrifugally-biased laminar profile and stationary velocity peaks along the curvature. Portal vein flow velocities were diminished or reversed in cirrhosis. Image artifacts have been characterized and removed. The

  3. Surface Plasmon Resonance: An Introduction to a Surface Spectroscopy Technique

    ERIC Educational Resources Information Center

    Tang, Yijun; Zeng, Xiangqun; Liang, Jennifer

    2010-01-01

    Surface plasmon resonance (SPR) has become an important optical biosensing technology in the areas of biochemistry, biology, and medical sciences because of its real-time, label-free, and noninvasive nature. The high cost of commercial devices and consumables has prevented SPR from being introduced in the undergraduate laboratory. Here, we present…

  4. 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.

  5. Nuclear magnetic resonance contrast agents

    DOEpatents

    Smith, P.H.; Brainard, J.R.; Jarvinen, G.D.; Ryan, R.R.

    1997-12-30

    A family of contrast agents for use in magnetic resonance imaging and a method of enhancing the contrast of magnetic resonance images of an object by incorporating a contrast agent of this invention into the object prior to forming the images or during formation of the images. A contrast agent of this invention is a paramagnetic lanthanide hexaazamacrocyclic molecule, where a basic example has the formula LnC{sub 16}H{sub 14}N{sub 6}. Important applications of the invention are in medical diagnosis, treatment, and research, where images of portions of a human body are formed by means of magnetic resonance techniques. 10 figs.

  6. Nuclear magnetic resonance contrast agents

    DOEpatents

    Smith, Paul H.; Brainard, James R.; Jarvinen, Gordon D.; Ryan, Robert R.

    1997-01-01

    A family of contrast agents for use in magnetic resonance imaging and a method of enhancing the contrast of magnetic resonance images of an object by incorporating a contrast agent of this invention into the object prior to forming the images or during formation of the images. A contrast agent of this invention is a paramagnetic lanthanide hexaazamacrocyclic molecule, where a basic example has the formula LnC.sub.16 H.sub.14 N.sub.6. Important applications of the invention are in medical diagnosis, treatment, and research, where images of portions of a human body are formed by means of magnetic resonance techniques.

  7. Effects of hydrostatic pressure and temperature on the electron paramagnetic resonance spectrum of off-centre Jahn Teller [CuF4F4]6- complexes in SrF2 crystal

    NASA Astrophysics Data System (ADS)

    Ulanov, V. A.; Krupski, M.; Hoffmann, S. K.; Zaripov, M. M.

    2003-02-01

    Pressure and temperature variations of the spin-Hamiltonian parameters and electron paramagnetic resonance (EPR) linewidths of non-central Jahn-Teller [CuF4F4]6- complexes in SrF2 crystal were studied by continuous-wave EPR. It was found that the static spin-Hamiltonian parameters, found at T = 85 K and at normal pressure (gparallel = 2.491, gbot = 2.083, aparallel = 360, abot = 26, Ax'' = 96, Ay'' = 99, Az'' = 403 and betaexp = 17°), are slightly changed with hydrostatic pressure and, at T = 85 K and P = 550 MPa, become equal to gparallel = 2.489, gbot = 2.083, aparallel = 348, abot = 27, Ax'' = 99, Ay'' = 102, Az'' = 406 and betaexp = 20° (a and A values in megahertz, x''-, y''-and z''-axes are eigenvectors of the super-hyperfine tensor A, betaexp is the experimental value of the angle between the C4 symmetry axis of the complex and the x''-axis). With increasing temperature the well-resolved EPR spectrum of the complex is transformed continuously into a single broad line both at normal pressure and at a hydrostatic pressure of 550 MPa. But in the first case the coalescence point corresponds to 220-230 K while in the second case it is 195-205 K. Treatment using the linear combination of atomic orbitals representation of molecular orbitals (LCAO MO) model was performed to establish some relations between variations of the spin-Hamiltonian parameters and pressure-induced changes in the molecular structure of the complex. To get some additional information about the molecular structure of the complex and variations of its structural parameters with pressure, treatment using the rigid-ion model was performed. Experimental and theoretical results are discussed in the framework of the Jahn-Teller model of the complex.

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

    PubMed

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

    2015-11-01

    The extradiol-cleaving dioxygenase homoprotocatechuate 2,3-dioxygenase (HPCD) binds substrate homoprotocatechuate (HPCA) and O2 sequentially in adjacent ligand sites of the active site Fe(II). 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 Fe(III) center coupled to an SR = 1/2 radical to give a ground state with total spin S = 2 (J > 40 cm(-1)) in Hexch = JŜ1·ŜR. Density functional theory (DFT) property calculations for structural models suggest that Int1 is a (HPCA semiquinone(•))Fe(III)(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 (57)Fe electric field gradient and the zero-field splitting tensors (D = 1.6 cm(-1), E/D = 0.05) were determined. This information was used to predict hyperfine splittings from bound (17)OOH. DFT reactivity analysis suggests that Int1 can evolve from a ferromagnetically coupled Fe(III)-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

  9. Arsenic speciation in newberyite (MgHPO(4)·3H(2)O) determined by synchrotron X-ray absorption and electron paramagnetic resonance spectroscopies: implications for the fate of arsenic in green fertilizers.

    PubMed

    Lin, Jinru; Chen, Ning; Pan, Yuanming

    2014-06-17

    Newberyite (MgHPO4·3H2O), a biomineral and common constituent in guano deposits, is an important decomposition product of struvite that is an increasingly popular green fertilizer recovered from wastewaters. Two samples of newberyite containing 1099 and 25 ppm As have been obtained at pH = 6.4, by using Na2HAsO4·7H2O and NaAsO2 as the dopant, respectively (i.e., Synthesis 1 and Synthesis 2). Synchrotron arsenic K-edge X-ray absorption spectroscopic data of newberyite from Synthesis 1 show that As(5+) is dominant and has a local environment typical of the arsenate species. Single-crystal electron paramagnetic resonance (EPR) spectra of gamma-ray-irradiated newberyite from Synthesis 1 contain two arsenic-associated oxyradicals: [AsO3](2-) and [AsO2](2-) derived from As(5+) and As(3+), respectively, at the P site. Quantitative analyses of powder EPR spectra allow determinations of the As(5+) and As(3+) contents in newberyite from Synthesis 1 and Synthesis 2. Elevated concentrations of arsenic also occur in natural newberyite transformed from struvite in guano deposits and record the accumulation of this metalloid in the food chain. Therefore, newberyite, which sequesters As during crystallization and retains this metalloid during the transformation from struvite, can attenuate arsenic contamination from green fertilizers in moderately acidic soils. Also, the capacity for accommodating both As(5+) and As(3+) in the crystal lattice coupled with simple chemistry and easy crystallization at ambient conditions makes newberyite an attractive material for remediation of arsenic contamination in aqueous environments.

  10. Structural effects of insulin-loading into HII mesophases monitored by electron paramagnetic resonance (EPR), small angle X-ray spectroscopy (SAXS), and attenuated total reflection Fourier transform spectroscopy (ATR-FTIR).

    PubMed

    Mishraki, Tehila; Ottaviani, Maria Francesca; Shames, Alexander I; Aserin, Abraham; Garti, Nissim

    2011-06-30

    Insulin entrapment within a monoolein-based reverse hexagonal (H(II)) mesophase was investigated under temperature-dependent conditions at acidic (pH 3) and basic (pH 8) conditions. Studying the structure of the host H(II) system and the interactions of insulin under temperature-dependent conditions has great impact on the enhancement of its thermal stabilization and controlled release for the purposes of transdermal delivery. Small angle X-ray spectroscopy (SAXS) measurements show that pH variation and/or insulin entrapment preserve the hexagonal structure and do not influence the lattice parameter. Attenuated total reflection Fourier transform spectroscopy (ATR-FTIR) spectra indicate that, although insulin interacts with hydroxyl groups of GMO in the interface region, it is not affected by pH variations. Hence different microenvironments within the H(II) mesophase were monitored by a computer-aided electron paramagnetic resonance (EPR) analysis using 5-doxylstearic acid (5-DSA) as a pH-dependent probe. The microviscosity, micropolarity, order of systems, and distribution of the probes in different microenvironments were influenced by three factors: temperature, pH, and insulin solubilization. When the temperature is increased, microviscosity and order parameters decreased at both pH 3 and 8, presenting different decrease trends. It was found that, at pH 3, the protein perturbs the lipid structure while "pushing aside" the un-ionized 5-DSA probe to fit into the narrow water cylinders. At the interface region (pH 8), the probe was distributed in two differently structured environments that significantly modifies by increasing temperature. Insulin loading within the H(II) mesophase decreased the order and microviscosity of both the microenvironments and increased their micropolarity. Finally, the EPR analysis also provides information about the unfolding/denaturation of insulin within the channel at high temperatures.

  11. Low dimensional quantum paramagnets

    NASA Astrophysics Data System (ADS)

    Hong, Tao

    A quantum paramagnet is a material with interacting spins that possesses a paramagnetic ground state and an energy gap to all excitations. This dissertation focuses on studying the magnetic excitation spectrum and the quantum critical phenomena of such low dimensional quantum paramagnet systems. Inelastic neutron scattering (INS) measurements of Cu(Quinoxaline)Br 2 was performed on a partially deuterated powder sample. Magnetic neutron scattering was identified above an energy gap of 1.9 meV. Consideration of the sharp spectral max imum and wave vector dependence of the scattering and polymeric structure further identifies the material as a two-legged spin-1/2 ladder. The continuous uniform transformation theory provides an excellent account of the data with leg exchange J‖ =2.0 meV and the rung exchange J⊥ =3.3 meV. INS study of (2,3 - dimethylpyridinium)2CuBr4 (DIMPY) in both powder and single crystalline form are presented to understand the origin of the spin gap and what is the right spin Hamiltonian. Magnetic excitations are found above a 0.3 meV energy gap. The excitation only disperses along the a-direction with a bandwidth that exceeds 1.7 meV. The conclusion to be a S=1/2 two-legged spin ladder is supported by the material structure and INS measurement. External magnetic field drives the system into a critical region and induced low energy excitation continuum above critical field was studied. Piperazinium Hexachlorodicuprate (PHCC) is a two-dimensional antiferromagnet. We studied the behavior in the vicinity of the quantum critical point (QCP) where the spin gap is closed by an applied magnetic field by INS. The energy and damping of the low energy excitations were measured in the vicinity of the QCP where both quantities become strongly temperature dependent, which can be successfully described by a selfconsistent Hartree-Fock theory of strongly interacting bosons developed by Sachdev and Dunkel. A preliminary study of hydrostatic pressure effects

  12. Coal thickness gauge using RRAS techniques, part 1. [radiofrequency resonance absorption

    NASA Technical Reports Server (NTRS)

    Rollwitz, W. L.; King, J. D.

    1978-01-01

    A noncontacting sensor having a measurement range of 0 to 6 in or more, and with an accuracy of 0.5 in or better is needed to control the machinery used in modern coal mining so that the thickness of the coal layer remaining over the rock is maintained within selected bounds. The feasibility of using the radiofrequency resonance absorption (RRAS) techniques of electron magnetic resonance (EMR) and nuclear magnetic resonance (NMR) as the basis of a coal thickness gauge is discussed. The EMR technique was found, by analysis and experiments, to be well suited for this application.

  13. Electron paramagnetic resonance line shifts and line shape changes due to heisenberg spin exchange and dipole-dipole interactions of nitroxide free radicals in liquids 8. Further experimental and theoretical efforts to separate the effects of the two interactions.

    PubMed

    Peric, Mirna; Bales, Barney L; Peric, Miroslav

    2012-03-22

    The work in part 6 of this series (J. Phys. Chem. A 2009, 113, 4930), addressing the task of separating the effects of Heisenberg spin exchange (HSE) and dipole-dipole interactions (DD) on electron paramagnetic resonance (EPR) spectra of nitroxide spin probes in solution, is extended experimentally and theoretically. Comprehensive measurements of perdeuterated 2,2,6,6-tetramethyl-4-oxopiperidine-1-oxyl (pDT) in squalane, a viscous alkane, paying special attention to lower temperatures and lower concentrations, were carried out in an attempt to focus on DD, the lesser understood of the two interactions. Theoretically, the analysis has been extended to include the recent comprehensive treatment by Salikhov (Appl. Magn. Reson. 2010, 38, 237). In dilute solutions, both interactions (1) introduce a dispersion component, (2) broaden the lines, and (3) shift the lines. DD introduces a dispersion component proportional to the concentration and of opposite sign to that of HSE. Equations relating the EPR spectral parameters to the rate constants due to HSE and DD have been derived. By employing nonlinear least-squares fitting of theoretical spectra to a simple analytical function and the proposed equations, the contributions of the two interactions to items 1-3 may be quantified and compared with the same parameters obtained by fitting experimental spectra. This comparison supports the theory in its broad predictions; however, at low temperatures, the DD contribution to the experimental dispersion amplitude does not increase linearly with concentration. We are unable to deduce whether this discrepancy is due to inadequate analysis of the experimental data or an incomplete theory. A new key aspect of the more comprehensive theory is that there is enough information in the experimental spectra to find items 1-3 due to both interactions; however, in principle, appeal must be made to a model of molecular diffusion to separate the two. The permanent diffusion model is used to

  14. Paramagnetic centers in particulate formed from the oxidative pyrolysis of 1-methylnaphthalene in the presence of Fe(III)2O3 nanoparticles

    PubMed Central

    Herring, Paul; Khachatryan, Lavrent; Lomnicki, Slawomir; Dellinger, Barry

    2015-01-01

    The identity of radical species associated with particulate formed from the oxidative pyrolysis of 1-methylnaphthalene (1-MN) was investigated using low temperature matrix isolation electron paramagnetic resonance spectroscopy (LTMI-EPR), a specialized technique that provided a method of sampling and analysis of the gas-phase paramagnetic components. A superimposed EPR signal was identified to be a mixture of organic radicals (carbon and oxygen-centered) and soot. The carbon-centered radicals were identified as a mixture of the resonance-stabilized indenyl, cyclopentadienyl, and naphthalene 1-methylene radicals through the theoretical simulation of the radical’s hyperfine structure. Formation of these radical species was promoted by the addition of Fe(III)2O3 nanoparticles. Enhanced formation of resonance stabilized radicals from the addition of Fe(III)2O3 nanoparticles can account for the observed increased sooting tendency associated with Fe(III)2O3 nanoparticle addition. PMID:25673882

  15. Methods for magnetic resonance analysis using magic angle technique

    DOEpatents

    Hu, Jian Zhi; Wind, Robert A.; Minard, Kevin R.; Majors, Paul D.

    2011-11-22

    Methods of performing a magnetic resonance analysis of a biological object are disclosed that include placing the object in a main magnetic field (that has a static field direction) and in a radio frequency field; rotating the object at a frequency of less than about 100 Hz around an axis positioned at an angle of about 54.degree.44' relative to the main magnetic static field direction; pulsing the radio frequency to provide a sequence that includes a phase-corrected magic angle turning pulse segment; and collecting data generated by the pulsed radio frequency. In particular embodiments the method includes pulsing the radio frequency to provide at least two of a spatially selective read pulse, a spatially selective phase pulse, and a spatially selective storage pulse. Further disclosed methods provide pulse sequences that provide extended imaging capabilities, such as chemical shift imaging or multiple-voxel data acquisition.

  16. Magnetic Resonance Imaging: Principles and Techniques: Lessons for Clinicians

    PubMed Central

    Grover, Vijay P.B.; Tognarelli, Joshua M.; Crossey, Mary M.E.; Cox, I. Jane; Taylor-Robinson, Simon D.; McPhail, Mark J.W.

    2015-01-01

    The development of magnetic resonance imaging (MRI) for use in medical investigation has provided a huge forward leap in the field of diagnosis, particularly with avoidance of exposure to potentially dangerous ionizing radiation. With decreasing costs and better availability, the use of MRI is becoming ever more pervasive throughout clinical practice. Understanding the principles underlying this imaging modality and its multiple applications can be used to appreciate the benefits and limitations of its use, further informing clinical decision-making. In this article, the principles of MRI are reviewed, with further discussion of specific clinical applications such as parallel, diffusion-weighted, and magnetization transfer imaging. MR spectroscopy is also considered, with an overview of key metabolites and how they may be interpreted. Finally, a brief view on how the use of MRI will change over the coming years is presented. PMID:26628842

  17. Magnetic Resonance Elastography and Other Magnetic Resonance Imaging Techniques in Chronic Liver Disease: Current Status and Future Directions

    PubMed Central

    Tan, Cher Heng; Venkatesh, Sudhakar Kundapur

    2016-01-01

    Recent advances in the noninvasive imaging of chronic liver disease have led to improvements in diagnosis, particularly with magnetic resonance imaging (MRI). A comprehensive evaluation of the liver may be performed with the quantification of the degree of hepatic steatosis, liver iron concentration, and liver fibrosis. In addition, MRI of the liver may be used to identify complications of cirrhosis, including portal hypertension, ascites, and the development of hepatocellular carcinoma. In this review article, we discuss the state of the art techniques in liver MRI, namely, magnetic resonance elastography, hepatobiliary phase MRI, and liver fat and iron quantification MRI. The use of these advanced techniques in the management of chronic liver diseases, including non-alcoholic fatty liver disease, will be elaborated. PMID:27563019

  18. Magnetic Resonance Elastography and Other Magnetic Resonance Imaging Techniques in Chronic Liver Disease: Current Status and Future Directions.

    PubMed

    Tan, Cher Heng; Venkatesh, Sudhakar Kundapur

    2016-09-15

    Recent advances in the noninvasive imaging of chronic liver disease have led to improvements in diagnosis, particularly with magnetic resonance imaging (MRI). A comprehensive evaluation of the liver may be performed with the quantification of the degree of hepatic steatosis, liver iron concentration, and liver fibrosis. In addition, MRI of the liver may be used to identify complications of cirrhosis, including portal hypertension, ascites, and the development of hepatocellular carcinoma. In this review article, we discuss the state of the art techniques in liver MRI, namely, magnetic resonance elastography, hepatobiliary phase MRI, and liver fat and iron quantification MRI. The use of these advanced techniques in the management of chronic liver diseases, including nonalcoholic fatty liver disease, will be elaborated. PMID:27563019

  19. Single crystal electron paramagnetic resonance spectra of Cu(II) ions in Cu(tyrosine)(2): a study of weak exchange interactions mediated by resonance assisted hydrogen bonds (RAHB).

    PubMed

    Paredes-García, Verónica; Santana, Ricardo C; Madrid, Rosa; Baldo, Bianca; Vega, Andrés; Spodine, Evgenia

    2012-09-01

    EPR measurements have been performed on single crystals of [Cu(L-tyrosine)(2)](∞) at 33.8 GHz and at room temperature. The EPR spectra display partially resolved EPR lines for most orientations of the magnetic field in the ab plane, and only one resonance for orientations close to the crystal axes, while only a single line is observed along any direction in the ca and cb crystal planes. This behavior is a result of the selective collapse of the resonances corresponding to the four copper sites in the unit cell produced by the exchange interactions between the copper ions. The magnitudes of the exchange interactions between the copper ions were evaluated from the angular variation of the line width and the collapse of the EPR lines. The value |J(AD)/k(B)|=0.8 K between neighboring copper atoms at 4.942 Å is assigned to a syn-anti equatorial-apical carboxylate bridge with a total bond length of 6.822 Å, while the small value |J(AB)/k(B)|=0.004 K is assigned to a long bridge of 11 atoms with a total bond length of 19.186 Å, that includes one resonance assisted hydrogen bond (RAHB). This finding is discussed in terms of values obtained for similar paths in other model compounds and in proteins.

  20. 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.

  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. High-frequency electron paramagnetic resonance analysis of the oxidation state and local structure of Ni and Mn ions in Ni,Mn-codoped LiCoO(2).

    PubMed

    Stoyanova, R; Barra, A-L; Yoncheva, M; Zhecheva, E; Shinova, E; Tzvetkova, P; Simova, S

    2010-02-15

    High-frequency electron paramagnetic resonance (HF-EPR) spectroscopy was employed to examine the oxidation state and local structure of Ni and Mn ions in Ni,Mn-codoped LiCoO(2). The assignment of EPR signals was based on Mg,Mn-codoped LiCoO(2) and Ni-doped LiCoO(2) used as Mn(4+) and low-spin Ni(3+) EPR references. Complementary information on the oxidation state of transition-metal ions was obtained by solid-state (6,7)Li NMR spectroscopy. For slightly doped oxides (LiCo(1-x)Ni(x)Mn(x)O(2) with x < 0.05), nickel and manganese substitute for cobalt in the CoO(2) layers and are stabilized as Ni(3+) and Mn(4+) ions. The local structure of Mn(4+) ions was determined by modeling of the axial zero-field-splitting parameter in the framework of the Newman superposition model. It has been found that the local trigonal distortion around Mn(4+) is smaller in comparison with that of the host site. To achieve a local compensation of Mn(4+) charge, several defect models are discussed. With an increase in the total dopant content (LiCo(1-x)Ni(x)Mn(x)O(2) and 0.05

  3. X-Band Electron Paramagnetic Resonance Comparison of Mononuclear Mn(IV)-oxo and Mn(IV)-hydroxo Complexes and Quantum Chemical Investigation of Mn(IV) Zero-Field Splitting.

    PubMed

    Leto, Domenick F; Massie, Allyssa A; Colmer, Hannah E; Jackson, Timothy A

    2016-04-01

    X-band electron paramagnetic resonance (EPR) spectroscopy was used to probe the ground-state electronic structures of mononuclear Mn(IV) complexes [Mn(IV)(OH)2(Me2EBC)](2+) and [Mn(IV)(O)(OH)(Me2EBC)](+). These compounds are known to effect C-H bond oxidation reactions by a hydrogen-atom transfer mechanism. They provide an ideal system for comparing Mn(IV)-hydroxo versus Mn(IV)-oxo motifs, as they differ by only a proton. Simulations of 5 K EPR data, along with analysis of variable-temperature EPR signal intensities, allowed for the estimation of ground-state zero-field splitting (ZFS) and (55)Mn hyperfine parameters for both complexes. From this analysis, it was concluded that the Mn(IV)-oxo complex [Mn(IV)(O)(OH)(Me2EBC)](+) has an axial ZFS parameter D (D = +1.2(0.4) cm(-1)) and rhombicity (E/D = 0.22(1)) perturbed relative to the Mn(IV)-hydroxo analogue [Mn(IV)(OH)2(Me2EBC)](2+) (|D| = 0.75(0.25) cm(-1); E/D = 0.15(2)), although the complexes have similar (55)Mn values (a = 7.7 and 7.5 mT, respectively). The ZFS parameters for [Mn(IV)(OH)2(Me2EBC)](2+) were compared with values obtained previously through variable-temperature, variable-field magnetic circular dichroism (VTVH MCD) experiments. While the VTVH MCD analysis can provide a reasonable estimate of the magnitude of D, the E/D values were poorly defined. Using the ZFS parameters reported for these complexes and five other mononuclear Mn(IV) complexes, we employed coupled-perturbed density functional theory (CP-DFT) and complete active space self-consistent field (CASSCF) calculations with second-order n-electron valence-state perturbation theory (NEVPT2) correction, to compare the ability of these two quantum chemical methods for reproducing experimental ZFS parameters for Mn(IV) centers. The CP-DFT approach was found to provide reasonably acceptable values for D, whereas the CASSCF/NEVPT2 method fared worse, considerably overestimating the magnitude of D in several cases. Both methods were poor in

  4. X-Band Electron Paramagnetic Resonance Comparison of Mononuclear Mn(IV)-oxo and Mn(IV)-hydroxo Complexes and Quantum Chemical Investigation of Mn(IV) Zero-Field Splitting.

    PubMed

    Leto, Domenick F; Massie, Allyssa A; Colmer, Hannah E; Jackson, Timothy A

    2016-04-01

    X-band electron paramagnetic resonance (EPR) spectroscopy was used to probe the ground-state electronic structures of mononuclear Mn(IV) complexes [Mn(IV)(OH)2(Me2EBC)](2+) and [Mn(IV)(O)(OH)(Me2EBC)](+). These compounds are known to effect C-H bond oxidation reactions by a hydrogen-atom transfer mechanism. They provide an ideal system for comparing Mn(IV)-hydroxo versus Mn(IV)-oxo motifs, as they differ by only a proton. Simulations of 5 K EPR data, along with analysis of variable-temperature EPR signal intensities, allowed for the estimation of ground-state zero-field splitting (ZFS) and (55)Mn hyperfine parameters for both complexes. From this analysis, it was concluded that the Mn(IV)-oxo complex [Mn(IV)(O)(OH)(Me2EBC)](+) has an axial ZFS parameter D (D = +1.2(0.4) cm(-1)) and rhombicity (E/D = 0.22(1)) perturbed relative to the Mn(IV)-hydroxo analogue [Mn(IV)(OH)2(Me2EBC)](2+) (|D| = 0.75(0.25) cm(-1); E/D = 0.15(2)), although the complexes have similar (55)Mn values (a = 7.7 and 7.5 mT, respectively). The ZFS parameters for [Mn(IV)(OH)2(Me2EBC)](2+) were compared with values obtained previously through variable-temperature, variable-field magnetic circular dichroism (VTVH MCD) experiments. While the VTVH MCD analysis can provide a reasonable estimate of the magnitude of D, the E/D values were poorly defined. Using the ZFS parameters reported for these complexes and five other mononuclear Mn(IV) complexes, we employed coupled-perturbed density functional theory (CP-DFT) and complete active space self-consistent field (CASSCF) calculations with second-order n-electron valence-state perturbation theory (NEVPT2) correction, to compare the ability of these two quantum chemical methods for reproducing experimental ZFS parameters for Mn(IV) centers. The CP-DFT approach was found to provide reasonably acceptable values for D, whereas the CASSCF/NEVPT2 method fared worse, considerably overestimating the magnitude of D in several cases. Both methods were poor in

  5. Resonant cavity based time-domain multiplexing techniques for coherently combined fiber laser systems

    NASA Astrophysics Data System (ADS)

    Zhou, T.; Ruppe, J.; Stanfield, P.; Nees, J.; Wilcox, R.; Galvanauskas, A.

    2015-10-01

    This paper describes novel time-domain multiplexing techniques that use various resonant cavity configurations for increasing pulse energy extraction per each parallel amplification channel of a coherently combined array. Two different techniques are presented: a so-called N2 coherent array combining technique, applicable to a periodic pulse train, and a coherent pulse stacking amplification (CPSA) technique, applicable to a pulse burst. The first technique is a coherent combining technique, which achieves simultaneous beam combining and time-domain pulse multiplexing/down-counting using traveling-wave Fabry-Perot type resonators. The second technique is purely a time-domain pulse multiplexing technique, used with either a single amplifier or an amplifier array, which uses traveling-wave Gires-Tourmois type resonators. The importance of these techniques is that they can enable stacking of very large number of pulses, thus increasing effective amplified-pulse duration potentially by 102 to 103 times, and reducing fiber array size by the corresponding factor. This could lead to very compact coherently combined arrays even for generating very high pulse energies in the range of 1 to 100 J.

  6. Neurocysticercosis: evaluation with advanced magnetic resonance techniques and atypical forms.

    PubMed

    do Amaral, Lázaro Luís Faria; Ferreira, Rafael Martins; da Rocha, Antônio José; Ferreira, Nelson Paes Diniz Fortes

    2005-04-01

    Neurocysticercosis (NCC) is the most common helminthic infection of the central nervous system, but its diagnosis remains difficult. The purpose of this article is to perform a critical analysis of the literature and show our experience in the evaluation of NCC. We discuss the advanced MR technique applications such as diffusion and perfusion-weighted imaging, spectroscopy, cisternography with FLAIR, and supplemental O2 and 3D-CISS. The typical manifestations of NCC are described; emphasis is given to the unusual presentations. The atypical forms of neurocysticercosis were divided into: intraventricular, subarachnoid, spinal, orbital, and intraparenchymatous. Special attention was also given to reactivation of previously calcified lesions and neurocysticercosis associated with mesial temporal sclerosis.

  7. 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

  8. Paramagnetic state of the isolated gold impurity in silicon

    NASA Astrophysics Data System (ADS)

    Son, N. T.; Gregorkiewicz, T.; Ammerlaan, C. A. J.

    1992-11-01

    The paper reports on the observation of the electron paramagnetic resonance spectrum of the isolated substitutional gold impurity in silicon. The spectrum has orthorhombic I (C2v) symmetry and an effective spin S=1/2. It has been detected in silver-doped samples with gold being introduced as contamination of the isotope used for diffusion. Parameters of the spectrum are given and an electronic model is proposed. With the results of the current study the puzzling question concerning paramagnetism of the isolated gold impurity in silicon appears to be clarified.

  9. Production and EPR characterization of exohedrally perfluoroalkylated paramagnetic lanthanum metallofullerenes: (La@C 82)-(C 8F 17) 2

    NASA Astrophysics Data System (ADS)

    Tagmatarchis, Nikos; Taninaka, Atsushi; Shinohara, Hisanori

    2002-04-01

    A strategy to chemically derivatize the outer sphere of endohedral metallofullerenes by using a fluorous synthesis-partitioning approach has been developed. The newly synthesized materials were found to be paramagnetic species and were characterized by electron paramagnetic resonance spectroscopy (EPR), laser desorption time-of-flight spectrometry (LD-TOF) and electronic absorption spectroscopy (UV-VIS-NIR). The fluorous-phase partitioning method (or liquid-liquid extraction), successfully applied for the first time in fullerene chemistry, aided by multi-stage recycling high performance liquid chromatography (HPLC) resulted in their isolation in isomer-free form. The present study opens the way to organic transformations of fullerene-based materials as a powerful separation technique.

  10. Investigating real-time activation of adenosine receptors by bioluminescence resonance energy transfer technique

    NASA Astrophysics Data System (ADS)

    Huang, Yimei; Yang, Hongqin; Zheng, Liqin; Chen, Jiangxu; Wang, Yuhua; Li, Hui; Xie, Shusen

    2013-02-01

    Adenosine receptors play important roles in many physiological and pathological processes, for example regulating myocardial oxygen consumption and the release of neurotransmitters. The activations of adenosine receptors have been studied by some kinds of techniques, such as western blot, immunohistochemistry, etc. However, these techniques cannot reveal the dynamical response of adenosine receptors under stimulation. In this paper, bioluminescence resonance energy transfer technique was introduced to study the real-time activation of adenosine receptors by monitoring the dynamics of cyclic adenosine monophosphate (cAMP) level. The results showed that there were significant differences between adenosine receptors on real-time responses under stimulation. Moreover, the dynamics of cAMP level demonstrated that competition between adenosine receptors existed. Taken together, our study indicates that monitoring the dynamics of cAMP level using bioluminescence resonance energy transfer technique could be one potential approach to investigate the mechanism of competitions between adenosine receptors.

  11. [Update on cardiac imaging techniques. Echocardiography, cardiac magnetic resonance and multidetector computed tomography].

    PubMed

    de Vinuesa, Pastora Gallego García; del Castillo, Sonia Velasco; Torres, Río Aguilar; Bardera, Juan C Paré

    2008-02-01

    This review of progress in cardiac imaging techniques summarizes the most significant development reported in the last year on different echocardiographic techniques and their application in a range of settings, from the treatment of heart failure to their use in intraoperative monitoring and guiding interventional procedures. Large sections are devoted to recent developments in three-dimensional imaging and, because of its clinical importance, to magnetic resonance imaging. Finally, there is a comprehensive update on the use of multidetector computed tomography in cardiology.

  12. 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

  13. Electron Paramagnetic Resonance Studies of Single Crystals of Manganese Ion-Doped Ammonium Sulfate, Gadolinium Ion-Doped Ammonium Praseodymium SULFATE.WATER, Vanadium Oxide Ion-Doped M Ammonium SULFATE.WATER

    NASA Astrophysics Data System (ADS)

    Sun, Jiansheng

    Detailed X-band electron paramagnetic resonance (EPR) measurements on single crystals of Mn^ {2+}-doped (NH_4)_2 SO_4, Gd^ {3+}-doped NH_4Pr(SO _4)_2cdot4H _2O, VO^{2+} -doped M(NH_4)_2(SO _4)_2cdot6H_2 O (M = Cd, Co, Mg, Fe, Zn) and Mg(ND_4) _2(SO_4)_2cdot 6D_2O, and Cu^ {2+}-doped MNa_2(SO _4)_2cdot4H _2O (M = Mg, Co) are made at variable temperatures. The spin-Hamiltonian parameters for Mn^{2+ }, Gd^{3+}, VO^{2+} and Cu ^{2+} ions are evaluated using a least-squares-fitting procedure. The positions and local symmetries of the impurity ions in these hosts have been well deduced. The ferroelectric transition in (NH_4) _2SO_4 has been extensively studied via the splittings of Mn^{2+ } EPR lines, leading to the determination of the critical exponent beta. The existence of two inequivalent sublattices in the (NH _4)_2SO_4 crystal is confirmed. Temperature variation of Gd^{3+ } EPR spectra reveal two first-order phase transitions in the NH_4Pr(SO _4)_2cdot4H_2 O crystal. The host-ion spin-lattice relaxation (SLR) times (tau) of Pr^ {3+} have been estimated via the EPR linewidths of Gd^{3+} impurity ions using an appropriate expression. The predominant processes of SLR of Pr^{3+} host -ions have been deduced. The superhyperfine structures of VO^ {2+} EPR spectra in the hydrated Tutton -salt hosts M(NH_4)_2(SO _4)_2cdot6H_2 O have been well explained by comparison with the VO^{2+} EPR spectra in the deuterated host crystal Mg(ND_4)_2 (SO_4)_2cdot6D _2O. Using the VO^ {2+} EPR and optical-absorption spectra, the bonding coefficients of the (VO(H_2 O)_5]^{2+ } complex have been estimated. The systematics of EPR of the VO^{2+} ion in this series of Tutton salts is analyzed. The impurity-host exchange-interaction constant of VO^{2+}-Fe ^{2+} pair is determined in the Fe(NH_4)_2(SO_4) _2cdot6H_2O host, using the g-shift due to the exchange interaction and the shape of the crystal at liquid-helium temperature. The tau values of Fe^ {2+} and Co^{2+} in the Fe(NH_4)_2(SO _4

  14. 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

  15. Photodarkening and paramagnetism in ultraviolet exposed lead lanthanum zirconate ceramics

    NASA Astrophysics Data System (ADS)

    Seager, C. H.; Warren, W. L.

    1993-06-01

    Electron paramagnetic resonance (EPR) and photothermal deflection spectroscopy (PDS) have been utilized to characterize samples of lead lanthanum zirconate titanate (PLZT) ceramics before and after ultraviolet (uv) irradiation. We find a variety of EPR resonances in the unirradiated samples, including those attributable to Cu+2, Fe+3, Pb+3, and Ti+3 ions. The dark optical absorption spectra show broad, exponential subgap absorption tails which increase in magnitude with decreasing grain size. In addition, some of the larger grain ceramics show a prominent absorption enhancement which seems to correlate well with the density of Ti+3 centers. During and after uv illumination with light near the PLZT band gap, substantial increases are seen in the density of paramagnetic Ti+3 and Pb+3 ions, and a broad absorption peak appears at ˜2.6 eV. The spatial distribution of the induced absorption correlates well with the location of the absorbed uv, suggesting that photoproduced carrier pairs are trapped at Ti+4 and Pb+2 ions producing the observed paramagnetism. The Ti+3 EPR spectra can be successfully fit using the crystal-field-splitting parameters derived from the PDS data. We also observe that both the paramagnetism and the induced absorption are readily bleached by light absorbed in the spectral region where the photoinduced peak is located. We suggest that this effect is due to photoionization of the localized charges.

  16. Experimental Test of a New Technique to Overcome Spin-Depolarizing Resonances

    SciTech Connect

    Morozov, V. S.; Chao, A. W.; Krisch, A. D.; Leonova, M. A.; Raymond, R. S.; Sivers, D. W.; Wong, V. K.; Garishvili, A.; Gebel, R.; Lehrach, A.; Lorentz, B.; Maier, R.; Prasuhn, D.; Stockhorst, H.; Welsch, D.; Hinterberger, F.; Kondratenko, A. M.

    2009-06-19

    We recently tested a new spin resonance crossing technique, Kondratenko Crossing (KC), by sweeping an rf-solenoid's frequency through an rf-induced spin resonance with both the KC and traditional fast crossing (FC) patterns. Using both rf bunched and unbunched 1.85 GeV/c polarized deuterons stored in COSY, we varied the parameters of both crossing patterns. Compared to FC with the same crossing speed, KC reduced the depolarization by measured factors of 4.7+-0.3 and 19{sub -5}{sup +12} for unbunched and bunched beams, respectively. This clearly showed the large potential benefit of Kondratenko Crossing over fast crossing.

  17. Resonance frequencies and Young's modulus determination of magnetorheological elastomers using the photoacoustic technique

    NASA Astrophysics Data System (ADS)

    Daniel Macias, J.; Ordonez-Miranda, J.; Alvarado-Gil, J. J.

    2012-12-01

    A simple and reliable methodology for determining the Young's modulus of magnetorheological elastomers is proposed based on the resonance frequencies of the amplitude of the photoacoustic signal. An explicit expression for the pressure changes within a photoacoustic cell, due to the thermal expansion of the air and the elastic bending of a clamped circular elastic membrane, is derived and analyzed. It is found that the resonance behavior of the amplitude of the photoacoustic signal is due to the contribution of the axial bending of its thickness. It is also shown that the Young's modulus of the membrane is proportional to its density, the square of its resonance frequencies and the fourth power of its radius, and inversely proportional to the square of its thickness. The application of the proposed approach to membranes made up of spherical microparticles of carbonyl iron powder embedded in a matrix of silicone rubber with weight concentrations of 0%, 5.2%, and 13.7% yields accurate and reproducible results, which are in good agreement with reported data in the literature. The highest accuracy on the measurement of the resonance frequencies and therefore on the Young's modulus is found for the first resonance peak. When a magnetic field is applied to the samples to modify their stiffness, it is observed that the Young's modulus increases with the magnetic field. This novel application of the photoacoustic technique opens the possibility of performing mechanical characterization of a broad diversity of magnetorheological membranes.

  18. Clinical decision support systems for brain tumor characterization using advanced magnetic resonance imaging techniques.

    PubMed

    Tsolaki, Evangelia; Kousi, Evanthia; Svolos, Patricia; Kapsalaki, Efthychia; Theodorou, Kyriaki; Kappas, Constastine; Tsougos, Ioannis

    2014-04-28

    In recent years, advanced magnetic resonance imaging (MRI) techniques, such as magnetic resonance spectroscopy, diffusion weighted imaging, diffusion tensor imaging and perfusion weighted imaging have been used in order to resolve demanding diagnostic problems such as brain tumor characterization and grading, as these techniques offer a more detailed and non-invasive evaluation of the area under study. In the last decade a great effort has been made to import and utilize intelligent systems in the so-called clinical decision support systems (CDSS) for automatic processing, classification, evaluation and representation of MRI data in order for advanced MRI techniques to become a part of the clinical routine, since the amount of data from the aforementioned techniques has gradually increased. Hence, the purpose of the current review article is two-fold. The first is to review and evaluate the progress that has been made towards the utilization of CDSS based on data from advanced MRI techniques. The second is to analyze and propose the future work that has to be done, based on the existing problems and challenges, especially taking into account the new imaging techniques and parameters that can be introduced into intelligent systems to significantly improve their diagnostic specificity and clinical application.

  19. Extracting Information about the Rotator Cuff from Magnetic Resonance Images Using Deterministic and Random Techniques

    PubMed Central

    De Los Ríos, F. A.; Paluszny, M.

    2015-01-01

    We consider some methods to extract information about the rotator cuff based on magnetic resonance images; the study aims to define an alternative method of display that might facilitate the detection of partial tears in the supraspinatus tendon. Specifically, we are going to use families of ellipsoidal triangular patches to cover the humerus head near the affected area. These patches are going to be textured and displayed with the information of the magnetic resonance images using the trilinear interpolation technique. For the generation of points to texture each patch, we propose a new method that guarantees the uniform distribution of its points using a random statistical method. Its computational cost, defined as the average computing time to generate a fixed number of points, is significantly lower as compared with deterministic and other standard statistical techniques. PMID:25650281

  20. Characterizing Oxygen Local Environments in Paramagnetic Battery Materials via (17)O NMR and DFT Calculations.

    PubMed

    Seymour, Ieuan D; Middlemiss, Derek S; Halat, David M; Trease, Nicole M; Pell, Andrew J; Grey, Clare P

    2016-08-01

    Experimental techniques that probe the local environment around O in paramagnetic Li-ion cathode materials are essential in order to understand the complex phase transformations and O redox processes that can occur during electrochemical delithiation. While Li NMR is a well-established technique for studying the local environment of Li ions in paramagnetic battery materials, the use of (17)O NMR in the same materials has not yet been reported. In this work, we present a combined (17)O NMR and hybrid density functional theory study of the local O environments in Li2MnO3, a model compound for layered Li-ion batteries. After a simple (17)O enrichment procedure, we observed five resonances with large (17)O shifts ascribed to the Fermi contact interaction with directly bonded Mn(4+) ions. The five peaks were separated into two groups with shifts at 1600 to 1950 ppm and 2100 to 2450 ppm, which, with the aid of first-principles calculations, were assigned to the (17)O shifts of environments similar to the 4i and 8j sites in pristine Li2MnO3, respectively. The multiple O environments in each region were ascribed to the presence of stacking faults within the Li2MnO3 structure. From the ratio of the intensities of the different (17)O environments, the percentage of stacking faults was found to be ca. 10%. The methodology for studying (17)O shifts in paramagnetic solids described in this work will be useful for studying the local environments of O in a range of technologically interesting transition metal oxides. PMID:27404908

  1. Dynamic neutron scattering on incoherent systems using efficient resonance spin flip techniques

    SciTech Connect

    Häussler, Wolfgang; Kredler, Lukas

    2014-05-15

    We have performed numerical ray-tracing Monte-Carlo-simulations of incoherent dynamic neutron scattering experiments. We intend to optimize the efficiency of incoherent measurements depending on the fraction of neutrons scattered without and with spin flip at the sample. In addition to conventional spin echo, we have numerically and experimentally studied oscillating intensity techniques. The results point out the advantages of these different spin echo variants and are an important prerequisite for neutron resonance spin echo instruments like RESEDA (FRM II, Munich), to choose the most efficient technique depending on the scattering vector range and the properties of the sample system under study.

  2. Enhanced Wireless Power Transmission Using Strong Paramagnetic Response

    PubMed Central

    Ahn, Dukju; Kiani, Mehdi; Ghovanloo, Maysam

    2015-01-01

    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. PMID:26120144

  3. Numerical and experimental investigation of a low-frequency measurement technique: differential acoustic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Yin, Hanjun; Zhao, Jianguo; Tang, Genyang; Ma, Xiaoyi; Wang, Shangxu

    2016-06-01

    Differential acoustic resonance spectroscopy (DARS) has been developed to determine the elastic properties of saturated rocks within the kHz frequency range. This laboratory technique is based on considerations from perturbation theory, wherein the resonance frequencies of the resonant cavity with and without a perturbation sample are used to estimate the acoustic properties of the test sample. In order to better understand the operating mechanism of DARS and therefore optimize the procedure, it is important to develop an accurate and efficient numerical model. Accordingly, this study presents a new multiphysics model by coupling together considerations from acoustics, solid mechanics, and electrostatics. The numerical results reveal that the newly developed model can successfully simulate the acoustic pressure field at different resonance modes, and that it can accurately reflect the measurement process. Based on the understanding of the DARS system afforded by the numerical simulation, we refine the system configuration by utilizing cavities of different lengths and appropriate radii to broaden the frequency bandwidth and ensure testing accuracy. Four synthetic samples are measured to test the performance of the optimized DARS system, in conjunction with ultrasonic and static measurements. For nonporous samples, the estimated bulk moduli are shown to be independent of the different measurement methods (i.e. DARS or ultrasonic techniques). In contrast, for sealed porous samples, the differences in bulk moduli between the low- and high-frequency techniques can be clearly observed; this discrepancy is attributed to frequency dispersion. In summary, the optimized DARS system with an extended frequency range of 500–2000 Hz demonstrates considerable utility in investigating the frequency dependence of the acoustic properties of reservoir rocks.

  4. Numerical and experimental investigation of a low-frequency measurement technique: differential acoustic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Yin, Hanjun; Zhao, Jianguo; Tang, Genyang; Ma, Xiaoyi; Wang, Shangxu

    2016-06-01

    Differential acoustic resonance spectroscopy (DARS) has been developed to determine the elastic properties of saturated rocks within the kHz frequency range. This laboratory technique is based on considerations from perturbation theory, wherein the resonance frequencies of the resonant cavity with and without a perturbation sample are used to estimate the acoustic properties of the test sample. In order to better understand the operating mechanism of DARS and therefore optimize the procedure, it is important to develop an accurate and efficient numerical model. Accordingly, this study presents a new multiphysics model by coupling together considerations from acoustics, solid mechanics, and electrostatics. The numerical results reveal that the newly developed model can successfully simulate the acoustic pressure field at different resonance modes, and that it can accurately reflect the measurement process. Based on the understanding of the DARS system afforded by the numerical simulation, we refine the system configuration by utilizing cavities of different lengths and appropriate radii to broaden the frequency bandwidth and ensure testing accuracy. Four synthetic samples are measured to test the performance of the optimized DARS system, in conjunction with ultrasonic and static measurements. For nonporous samples, the estimated bulk moduli are shown to be independent of the different measurement methods (i.e. DARS or ultrasonic techniques). In contrast, for sealed porous samples, the differences in bulk moduli between the low- and high-frequency techniques can be clearly observed; this discrepancy is attributed to frequency dispersion. In summary, the optimized DARS system with an extended frequency range of 500-2000 Hz demonstrates considerable utility in investigating the frequency dependence of the acoustic properties of reservoir rocks.

  5. Barnett effect in paramagnetic states

    NASA Astrophysics Data System (ADS)

    Ono, Masao; Chudo, Hiroyuki; Harii, Kazuya; Okayasu, Satoru; Matsuo, Mamoru; Ieda, Jun'ichi; Takahashi, Ryo; Maekawa, Sadamichi; Saitoh, Eiji

    2015-11-01

    We report the observation of the Barnett effect in paramagnetic states by mechanically rotating gadolinium (Gd) metal with a rotational frequency of up to 1.5 kHz above the Curie temperature. An in situ magnetic measurement setup comprising a high-speed rotational system and a fluxgate magnetic sensor was developed for the measurement. Temperature dependence of the observed magnetization follows that of paramagnetic susceptibility, indicating that any emergent magnetic field is proportional to the rotational frequency and is independent of temperature. From the proportionality constant of the emergent field, the gyromagnetic ratio of Gd is calculated to be -29 ±5 GHz /T . This study revisits the primordial issue of magnetism with modern technologies to shed new light on the fundamental spin-rotation coupling.

  6. Paramagnetically induced gapful topological superconductors

    NASA Astrophysics Data System (ADS)

    Daido, Akito; Yanase, Youichi

    2016-08-01

    We propose a generic scenario for realizing gapful topological superconductors (TSCs) from gapless spin-singlet superconductors (SCs). Noncentrosymmetric nodal SCs in two dimensions are shown to be gapful under a Zeeman field, as a result of the cooperation of inversion-symmetry breaking and time-reversal-symmetry breaking. In particular, non-s -wave SCs acquire a large excitation gap. Such paramagnetically induced gapful SCs may be classified into TSCs in the symmetry class D specified by the Chern number. We show nontrivial Chern numbers over a wide parameter range for spin-singlet SCs. A variety of the paramagnetically induced gapful TSCs are demonstrated, including D +p -wave TSC, extended S +p -wave TSC, p +D +f -wave TSC, and s +P -wave TSC. Natural extension toward three-dimensional Weyl SCs is also discussed.

  7. Finite pulse effects in CPMG pulse trains on paramagnetic materials.

    PubMed

    Leskes, Michal; Grey, Clare P

    2015-09-14

    The Carr-Purcell-Meiboom-Gill (CPMG) sequence is commonly used in high resolution NMR spectroscopy and in magnetic resonance imaging for the measurement of transverse relaxation in systems that are subject to diffusion in internal or external gradients and is superior to the Hahn echo measurement, which is more sensitive to diffusion effects. Similarly, it can potentially be used to study dynamic processes in electrode materials for lithium ion batteries. Here we compare the (7)Li signal decay curves obtained with the CPMG and Hahn echo sequences under static conditions (i.e., in the absence of magic angle spinning) in paramagnetic materials with varying transition metal ion concentrations. Our results indicate that under CPMG pulse trains the lifetime of the (7)Li signal is substantially extended and is correlated with the strength of the electron-nuclear interaction. Numerical simulations and analytical calculations using Floquet theory suggest that the combination of large interactions and a train of finite pulses, results in a spin locking effect which significantly slows the signal's decay. While these effects complicate the interpretation of CPMG-based investigations of diffusion and chemical exchange in paramagnetic materials, they may provide a useful approach to extend the signal's lifetime in these often fast relaxing systems, enabling the use of correlation experiments. Furthermore, these results highlight the importance of developing a deeper understanding of the effects of the large paramagnetic interactions during multiple pulse experiments in order to extend the experimental arsenal available for static and in situ NMR investigations of paramagnetic materials.

  8. A biofilm microreactor system for simultaneous electrochemical and nuclear magnetic resonance techniques.

    PubMed

    Renslow, R S; Babauta, J T; Majors, P D; Mehta, H S; Ewing, R J; Ewing, T W; Mueller, K T; Beyenal, H

    2014-01-01

    Nuclear magnetic resonance (NMR) techniques are ideally suited for the study of biofilms and for probing their microenvironments because these techniques allow for noninvasive interrogation and in situ monitoring with high resolution. By combining NMR with simultaneous electrochemical techniques, it is possible to sustain and study live biofilms respiring on electrodes. Here, we describe a biofilm microreactor system, including a reusable and a disposable reactor, that allows for simultaneous electrochemical and NMR techniques (EC-NMR) at the microscale. Microreactors were designed with custom radio frequency resonator coils, which allowed for NMR measurements of biofilms growing on polarized gold electrodes. For an example application of this system we grew Geobacter sulfurreducens biofilms on electrodes. EC-NMR was used to investigate growth medium flow velocities and depth-resolved acetate concentration inside the biofilm. As a novel contribution we used Monte Carlo error analysis to estimate the standard deviations of the acetate concentration measurements. Overall, we found that the disposable EC-NMR microreactor provided a 9.7 times better signal-to-noise ratio over the reusable reactor. The EC-NMR biofilm microreactor system can ultimately be used to correlate extracellular electron transfer rates with metabolic reactions and explore extracellular electron transfer mechanisms.

  9. A biofilm microreactor system for simultaneous electrochemical and nuclear magnetic resonance techniques

    SciTech Connect

    Renslow, Ryan S.; Babauta, Jerome T.; Majors, Paul D.; Mehta, Hardeep S.; Ewing, R. James; Ewing, Thomas; Mueller, Karl T.; Beyenal, Haluk

    2014-03-01

    In order to fully understand electrochemically active biofilms and the limitations to their scale-up in industrial biofilm reactors, a complete picture of the microenvironments inside the biofilm is needed. Nuclear magnetic resonance (NMR) techniques are ideally suited for the study of biofilms and for probing their microenvironments because these techniques allow for non-invasive interrogation and in situ monitoring with high resolution. By combining NMR with simultaneous electrochemical techniques, it is possible to sustain and study live electrochemically active biofilms. Here, we introduce a novel biofilm microreactor system that allows for simultaneous electrochemical and NMR techniques (EC-NMR) at the microscale. Microreactors were designed with custom radiofrequency resonator coils, which allowed for NMR measurements of biofilms growing on polarized gold electrodes. For an example application of this system, we grew Geobacter sulfurreducens biofilms. NMR was used to investigate growth media flow velocities, which were compared to simulated laminar flow, and electron donor concentrations inside the biofilms. We use Monte Carlo error analysis to estimate standard deviations of the electron donor concentration measurements within the biofilm. The EC-NMR biofilm microreactor system can ultimately be used to correlate extracellular electron transfer rates with metabolic reactions and explore extracellular electron transfer mechanisms.

  10. Fabrication of Capacitive Acoustic Resonators Combining 3D Printing and 2D Inkjet Printing Techniques

    PubMed Central

    Haque, Rubaiyet Iftekharul; Ogam, Erick; Loussert, Christophe; Benaben, Patrick; Boddaert, Xavier

    2015-01-01

    A capacitive acoustic resonator developed by combining three-dimensional (3D) printing and two-dimensional (2D) printed electronics technique is described. During this work, a patterned bottom structure with rigid backplate and cavity is fabricated directly by a 3D printing method, and then a direct write inkjet printing technique has been employed to print a silver conductive layer. A novel approach has been used to fabricate a diaphragm for the acoustic sensor as well, where the conductive layer is inkjet-printed on a pre-stressed thin organic film. After assembly, the resulting structure contains an electrically conductive diaphragm positioned at a distance from a fixed bottom electrode separated by a spacer. Measurements confirm that the transducer acts as capacitor. The deflection of the diaphragm in response to the incident acoustic single was observed by a laser Doppler vibrometer and the corresponding change of capacitance has been calculated, which is then compared with the numerical result. Observation confirms that the device performs as a resonator and provides adequate sensitivity and selectivity at its resonance frequency. PMID:26473878

  11. Fabrication of capacitive acoustic resonators combining 3D printing and 2D inkjet printing techniques.

    PubMed

    Haque, Rubaiyet Iftekharul; Ogam, Erick; Loussert, Christophe; Benaben, Patrick; Boddaert, Xavier

    2015-10-14

    A capacitive acoustic resonator developed by combining three-dimensional (3D) printing and two-dimensional (2D) printed electronics technique is described. During this work, a patterned bottom structure with rigid backplate and cavity is fabricated directly by a 3D printing method, and then a direct write inkjet printing technique has been employed to print a silver conductive layer. A novel approach has been used to fabricate a diaphragm for the acoustic sensor as well, where the conductive layer is inkjet-printed on a pre-stressed thin organic film. After assembly, the resulting structure contains an electrically conductive diaphragm positioned at a distance from a fixed bottom electrode separated by a spacer. Measurements confirm that the transducer acts as capacitor. The deflection of the diaphragm in response to the incident acoustic single was observed by a laser Doppler vibrometer and the corresponding change of capacitance has been calculated, which is then compared with the numerical result. Observation confirms that the device performs as a resonator and provides adequate sensitivity and selectivity at its resonance frequency.

  12. Direct imaging of neural currents using ultra-low field magnetic resonance techniques

    DOEpatents

    Volegov, Petr L.; Matlashov, Andrei N.; Mosher, John C.; Espy, Michelle A.; Kraus, Jr., Robert H.

    2009-08-11

    Using resonant interactions to directly and tomographically image neural activity in the human brain using magnetic resonance imaging (MRI) techniques at ultra-low field (ULF), the present inventors have established an approach that is sensitive to magnetic field distributions local to the spin population in cortex at the Larmor frequency of the measurement field. Because the Larmor frequency can be readily manipulated (through varying B.sub.m), one can also envision using ULF-DNI to image the frequency distribution of the local fields in cortex. Such information, taken together with simultaneous acquisition of MEG and ULF-NMR signals, enables non-invasive exploration of the correlation between local fields induced by neural activity in cortex and more `distant` measures of brain activity such as MEG and EEG.

  13. Parametric techniques for characterizing myocardial tissue by magnetic resonance imaging (part 1): T1 mapping.

    PubMed

    Perea Palazón, R J; Ortiz Pérez, J T; Prat González, S; de Caralt Robira, T M; Cibeira López, M T; Solé Arqués, M

    2016-01-01

    The development of myocardial fibrosis is a common process in the appearance of ventricular dysfunction in many heart diseases. Magnetic resonance imaging makes it possible to accurately evaluate the structure and function of the heart, and its role in the macroscopic characterization of myocardial fibrosis by late enhancement techniques has been widely validated clinically. Recent studies have demonstrated that T1-mapping techniques can quantify diffuse myocardial fibrosis and the expansion of the myocardial extracellular space in absolute terms. However, further studies are necessary to validate the usefulness of this technique in the early detection of tissue remodeling at a time when implementing early treatment would improve a patient's prognosis. This article reviews the state of the art for T1 mapping of the myocardium, its clinical applications, and its limitations.

  14. Parametric techniques for characterizing myocardial tissue by magnetic resonance imaging (part 1): T1 mapping.

    PubMed

    Perea Palazón, R J; Ortiz Pérez, J T; Prat González, S; de Caralt Robira, T M; Cibeira López, M T; Solé Arqués, M

    2016-01-01

    The development of myocardial fibrosis is a common process in the appearance of ventricular dysfunction in many heart diseases. Magnetic resonance imaging makes it possible to accurately evaluate the structure and function of the heart, and its role in the macroscopic characterization of myocardial fibrosis by late enhancement techniques has been widely validated clinically. Recent studies have demonstrated that T1-mapping techniques can quantify diffuse myocardial fibrosis and the expansion of the myocardial extracellular space in absolute terms. However, further studies are necessary to validate the usefulness of this technique in the early detection of tissue remodeling at a time when implementing early treatment would improve a patient's prognosis. This article reviews the state of the art for T1 mapping of the myocardium, its clinical applications, and its limitations. PMID:26944850

  15. Inspection technique for cleaved optical fiber ends based on Fabry-Perot resonator

    NASA Astrophysics Data System (ADS)

    Kihara, Mitsuru; Watanabe, Hiroshi; Yajima, Yuichi; Toyonaga, Masanobu

    2011-05-01

    We present a novel inspection technique for cleaved optical fiber ends based on the Fabry-Perot resonator. The technique uses mainly laser diodes, an optical power meter, 3-dB coupler, and XY lateral adjustment stage. It can be achieved more easily than current imaging processing that uses a charge coupled device camera and video monitor. The inspected fiber end is considered failed or successful depending on whether both the measured return losses from the fiber end at two wavelengths are equal to ~14.7 dB. Experimentally obtained fiber end images were in good agreement with scanning electron microscope observation images. Thus, the proposed technique provides a simple and cost-effective way to inspect cleaved optical fiber ends.

  16. Review of pyroelectric thermal energy harvesting and new MEMs based resonant energy conversion techniques

    SciTech Connect

    Hunter, Scott Robert; Lavrik, Nickolay V; Mostafa, Salwa; Rajic, Slobodan; Datskos, Panos G

    2012-01-01

    Harvesting electrical energy from thermal energy sources using pyroelectric conversion techniques has been under investigation for over 50 years, but it has not received the attention that thermoelectric energy harvesting techniques have during this time period. This lack of interest stems from early studies which found that the energy conversion efficiencies achievable using pyroelectric materials were several times less than those potentially achievable with thermoelectrics. More recent modeling and experimental studies have shown that pyroelectric techniques can be cost competitive with thermoelectrics and, using new temperature cycling techniques, has the potential to be several times as efficient as thermoelectrics under comparable operating conditions. This paper will review the recent history in this field and describe the techniques that are being developed to increase the opportunities for pyroelectric energy harvesting. The development of a new thermal energy harvester concept, based on temperature cycled pyroelectric thermal-to-electrical energy conversion, are also outlined. The approach uses a resonantly driven, pyroelectric capacitive bimorph cantilever structure that can be used to rapidly cycle the temperature in the energy harvester. The device has been modeled using a finite element multi-physics based method, where the effect of the structure material properties and system parameters on the frequency and magnitude of temperature cycling, and the efficiency of energy recycling using the proposed structure, have been modeled. Results show that thermal contact conductance and heat source temperature differences play key roles in dominating the cantilever resonant frequency and efficiency of the energy conversion technique. This paper outlines the modeling, fabrication and testing of cantilever and pyroelectric structures and single element devices that demonstrate the potential of this technology for the development of high efficiency thermal

  17. A fluorescent, paramagnetic and PEGylated gold/silica nanoparticle for MRI, CT and fluorescence imaging

    PubMed Central

    van Schooneveld, Matti M.; Cormode, David P.; Koole, Rolf; van Wijngaarden, J. Timon; Calcagno, Claudia; Skajaa, Torjus; Hilhorst, Jan; ’t Hart, Dannis C.; Fayad, Zahi A.; Mulder, Willem J. M.; Meijerink, Andries

    2013-01-01

    An important challenge in medical diagnostics is to design all-in-one contrast agents that can be detected with multiple techniques such as magnetic resonance imaging (MRI), X-ray computed tomography (CT), positron emission tomography (PET), single photon emission tomography (SPECT) or fluorescence imaging (FI). Although many dual labeled agents have been proposed, mainly for combined MRI/FI, constructs for three imaging modalities are scarce. Here gold/silica nanoparticles with a poly(ethylene glycol), paramagnetic and fluorescent lipid coating were synthesized, characterized and applied as trimodal contrast agents to allow for nanoparticle-enhanced imaging of macrophage cells in vitro via MRI, CT and FI, and mice livers in vivo via MRI and CT. This agent can be a useful tool in a multitude of applications, including cell tracking and target-specific molecular imaging, and is a step in the direction of truly multi-modal imaging. PMID:20812290

  18. [Magnetic resonance imaging postprocessing techniques in the study of brain connectivity].

    PubMed

    de la Iglesia-Vayá, M; Molina-Mateo, J; Escarti-Fabra, M J; Martí-Bonmatí, L; Robles, M; Meneu, T; Aguilar, E J; Sanjuán, J

    2011-01-01

    Brain connectivity is a key concept for understanding brain function. Current methods to detect and quantify different types of connectivity with neuroimaging techniques are fundamental for understanding the pathophysiology of many neurologic and psychiatric disorders. This article aims to present a critical review of the magnetic resonance imaging techniques used to measure brain connectivity within the context of the Human Connectome Project. We review techniques used to measure: a) structural connectivity b) functional connectivity (main component analysis, independent component analysis, seed voxel, meta-analysis), and c) effective connectivity (psychophysiological interactions, causal dynamic models, multivariate autoregressive models, and structural equation models). These three approaches make it possible to combine and use different statistical techniques to elaborate mathematical models in the attempt to understand the functioning of the brain. The findings obtained with these techniques must be validated by other techniques for analyzing structural and functional connectivity. This information is integrated in the Human Connectome Project where all these approaches converge to provide a representation of all the different models of connectivity. PMID:21477826

  19. Development of techniques in magnetic resonance and structural studies of the prion protein

    SciTech Connect

    Bitter, Hans-Marcus L.

    2000-07-01

    Magnetic resonance is the most powerful analytical tool used by chemists today. Its applications range from determining structures of large biomolecules to imaging of human brains. Nevertheless, magnetic resonance remains a relatively young field, in which many techniques are currently being developed that have broad applications. In this dissertation, two new techniques are presented, one that enables the determination of torsion angles in solid-state peptides and proteins, and another that involves imaging of heterogenous materials at ultra-low magnetic fields. In addition, structural studies of the prion protein via solid-state NMR are described. More specifically, work is presented in which the dependence of chemical shifts on local molecular structure is used to predict chemical shift tensors in solid-state peptides with theoretical ab initio surfaces. These predictions are then used to determine the backbone dihedral angles in peptides. This method utilizes the theoretical chemicalshift tensors and experimentally determined chemical-shift anisotropies (CSAs) to predict the backbone and side chain torsion angles in alanine, leucine, and valine residues. Additionally, structural studies of prion protein fragments are described in which conformationally-dependent chemical-shift measurements were made to gain insight into the structural differences between the various conformational states of the prion protein. These studies are of biological and pathological interest since conformational changes in the prion protein are believed to cause prion diseases. Finally, an ultra-low field magnetic resonance imaging technique is described that enables imaging and characterization of heterogeneous and porous media. The notion of imaging gases at ultra-low fields would appear to be very difficult due to the prohibitively low polarization and spin densities as well as the low sensitivities of conventional Faraday coil detectors. However, Chapter 5 describes how gas imaging

  20. Magnetic resonance imaging of multiple sclerosis: a study of pulse-technique efficacy

    SciTech Connect

    Runge, V.M.; Price, A.C.; Kirshner, H.S.; Allen, J.H.; Partain, C.L.; James, A.E. Jr.

    1984-11-01

    Forty-two patients with the clinical diagnosis of multiple sclerosis were examined by proton magnetic resonance imaging (MRI) at 0.5 T. An extensive protocol was used to facilitate a comparison of the efficacy of different pulse techniques. Results were also compared in 39 cases with high-resolution x-ray computed tomography (CT). MRI revealed characteristic abnormalities in each case, whereas CT was positive in only 15 of 33 patients. Cerebral abnormalities were best shown with the T2-weighted spin-echo sequence: brainstem lesions were best defined on the inversion-recovery sequence.

  1. Cancer detection based on Raman spectra super-paramagnetic clustering

    NASA Astrophysics Data System (ADS)

    González-Solís, José Luis; Guizar-Ruiz, Juan Ignacio; Martínez-Espinosa, Juan Carlos; Martínez-Zerega, Brenda Esmeralda; Juárez-López, Héctor Alfonso; Vargas-Rodríguez, Héctor; Gallegos-Infante, Luis Armando; González-Silva, Ricardo Armando; Espinoza-Padilla, Pedro Basilio; Palomares-Anda, Pascual

    2016-08-01

    The clustering of Raman spectra of serum sample is analyzed using the super-paramagnetic clustering technique based in the Potts spin model. We investigated the clustering of biochemical networks by using Raman data that define edge lengths in the network, and where the interactions are functions of the Raman spectra's individual band intensities. For this study, we used two groups of 58 and 102 control Raman spectra and the intensities of 160, 150 and 42 Raman spectra of serum samples from breast and cervical cancer and leukemia patients, respectively. The spectra were collected from patients from different hospitals from Mexico. By using super-paramagnetic clustering technique, we identified the most natural and compact clusters allowing us to discriminate the control and cancer patients. A special interest was the leukemia case where its nearly hierarchical observed structure allowed the identification of the patients's leukemia type. The goal of this study is to apply a model of statistical physics, as the super-paramagnetic, to find these natural clusters that allow us to design a cancer detection method. To the best of our knowledge, this is the first report of preliminary results evaluating the usefulness of super-paramagnetic clustering in the discipline of spectroscopy where it is used for classification of spectra.

  2. Myocardial tagging by cardiovascular magnetic resonance: evolution of techniques--pulse sequences, analysis algorithms, and applications.

    PubMed

    Ibrahim, El-Sayed H

    2011-01-01

    Cardiovascular magnetic resonance (CMR) tagging has been established as an essential technique for measuring regional myocardial function. It allows quantification of local intramyocardial motion measures, e.g. strain and strain rate. The invention of CMR tagging came in the late eighties, where the technique allowed for the first time for visualizing transmural myocardial movement without having to implant physical markers. This new idea opened the door for a series of developments and improvements that continue up to the present time. Different tagging techniques are currently available that are more extensive, improved, and sophisticated than they were twenty years ago. Each of these techniques has different versions for improved resolution, signal-to-noise ratio (SNR), scan time, anatomical coverage, three-dimensional capability, and image quality. The tagging techniques covered in this article can be broadly divided into two main categories: 1) Basic techniques, which include magnetization saturation, spatial modulation of magnetization (SPAMM), delay alternating with nutations for tailored excitation (DANTE), and complementary SPAMM (CSPAMM); and 2) Advanced techniques, which include harmonic phase (HARP), displacement encoding with stimulated echoes (DENSE), and strain encoding (SENC). Although most of these techniques were developed by separate groups and evolved from different backgrounds, they are in fact closely related to each other, and they can be interpreted from more than one perspective. Some of these techniques even followed parallel paths of developments, as illustrated in the article. As each technique has its own advantages, some efforts have been made to combine different techniques together for improved image quality or composite information acquisition. In this review, different developments in pulse sequences and related image processing techniques are described along with the necessities that led to their invention, which makes this

  3. Myocardial tagging by Cardiovascular Magnetic Resonance: evolution of techniques--pulse sequences, analysis algorithms, and applications

    PubMed Central

    2011-01-01

    Cardiovascular magnetic resonance (CMR) tagging has been established as an essential technique for measuring regional myocardial function. It allows quantification of local intramyocardial motion measures, e.g. strain and strain rate. The invention of CMR tagging came in the late eighties, where the technique allowed for the first time for visualizing transmural myocardial movement without having to implant physical markers. This new idea opened the door for a series of developments and improvements that continue up to the present time. Different tagging techniques are currently available that are more extensive, improved, and sophisticated than they were twenty years ago. Each of these techniques has different versions for improved resolution, signal-to-noise ratio (SNR), scan time, anatomical coverage, three-dimensional capability, and image quality. The tagging techniques covered in this article can be broadly divided into two main categories: 1) Basic techniques, which include magnetization saturation, spatial modulation of magnetization (SPAMM), delay alternating with nutations for tailored excitation (DANTE), and complementary SPAMM (CSPAMM); and 2) Advanced techniques, which include harmonic phase (HARP), displacement encoding with stimulated echoes (DENSE), and strain encoding (SENC). Although most of these techniques were developed by separate groups and evolved from different backgrounds, they are in fact closely related to each other, and they can be interpreted from more than one perspective. Some of these techniques even followed parallel paths of developments, as illustrated in the article. As each technique has its own advantages, some efforts have been made to combine different techniques together for improved image quality or composite information acquisition. In this review, different developments in pulse sequences and related image processing techniques are described along with the necessities that led to their invention, which makes this

  4. Influence of paramagnetic melanin on the MRI contrast in melanoma: a combined high-field (11.7 T) MRI and EPR study.

    PubMed

    Godechal, Q; Mignion, L; Karroum, O; Magat, J; Danhier, P; Morandini, R; Ghanem, G E; Leveque, P; Gallez, B

    2014-01-01

    Melanoma is the most dangerous form of skin cancer and its incidence is rising each year. Because the current methods of diagnosis based on the visual aspect of the tumor show limitations, several new techniques are emerging to help in this diagnosis, amongst which are magnetic resonance imaging (MRI) and electron paramagnetic resonance (EPR). The origin of the typical contrast pattern observable in melanoma in T1 - and T2 -weighted images remains to be elucidated and is a source of controversy. In addition, melanin could create sufficient magnetic inhomogeneities to allow its visualization on T2 *-weighted images using high-field MRI. In order to elucidate the possible role of melanin in the MRI contrast of melanoma, the present study was designed to correlate the paramagnetic content in melanin pigment to the contrast on T1 -, T2 - and T2 *-weighted images. MR images were obtained in vivo at 11.7 T using four types of experimental tumors with different pigmentations (B16, HBL, LND1 melanomas and KHT sarcomas). The paramagnetic content in melanin pigment was measured by EPR. No significant correlation was observed between the content in melanin and the relaxation times T1 , T2 and T2 *, emphasizing that the presence of pigment alone has negligible effect on the MRI contrast.

  5. Paramagnetic Meissner effect in Nb

    NASA Astrophysics Data System (ADS)

    Kostić, P.; Veal, B.; Paulikas, A. P.; Welp, U.; Todt, V. R.; Gu, C.; Geiser, U.; Williams, J. M.; Carlson, K. D.; Klemm, R. A.

    1996-01-01

    The paramagnetic Meissner effect (PME), or Wohlleben effect, in which the field-cooled magnetization of superconducting samples is paramagnetic below Tc, has been reported to occur in some samples of a variety of high-Tc cuprate superconductors. It has been proposed that the effect arose in granular hole-doped cuprates from current loops with π phase shifts of the superconducting order parameter at some grain-boundary junctions. It is argued that such behavior would be expected to occur in a d-wave superconductor, but not in a conventional s-wave superconductor. To test this hypothesis, we have searched for the occurrence of the effect in Nb, and have confirmed a recent report by Minhaj et al. of its occurrence in some Nb samples. For these studies, the effects of stray fields and field gradients in the measurement volume of the superconducting quantum interference device magnetometer have been carefully considered to rule out the possibility that measurement artifacts might be responsible for the apparent paramagnetic behavior in Nb. The M(T) and M(H) curves obtained in Nb samples that show the PME also show remarkably strong resemblance to those curves reported for the cuprate materials exhibiting the PME. Evidence is presented that the effect arises from inhomogeneously trapped flux, and is strongly influenced by sample geometry and surface effects. These results suggest that, for the effect to be observable, Tc on the sample surface must be different from the bulk Tc. The occurrence of the PME in Nb strongly suggests that the observation of this effect is unrelated to d-wave superconductivity.

  6. Paramagnetism in X-irradiated chalcogenide glasses and crystals

    NASA Astrophysics Data System (ADS)

    Taylor, P. C.; Strom, U.; Bishop, S. G.

    1982-11-01

    In semiconducting chalcogenide glasses, X-irradiation at 77 K produces paramagnetic responses which are similar to those produced by optical excitation at band gap energies. These Electron Spin Resonance (ESR) signals can be bleached with light of less than band gap energies. There is evidence that X-irradiation at low temperature creates a greater density of metastable centers which can subsequently be populated or depopulated (rendered paramagnetic) optically, by excitation with low intensities (of about 10 mW/sq cm) of band-gap light. In addition to the usual, optically induced responses, X-irradiation in the chalcogenide glasses also produces signals attributable to impurities such as copper and iron. In pure crystalline As2Se, X-irradiation at 77 K produces only centers associated with Cu(2+) impurities.

  7. Refractive index dispersion of swift heavy ion irradiated BFO thin films using Surface Plasmon Resonance technique

    NASA Astrophysics Data System (ADS)

    Paliwal, Ayushi; Sharma, Savita; Tomar, Monika; Singh, Fouran; Gupta, Vinay

    2016-07-01

    Swift heavy ion irradiation (SHI) is an effective technique to induce defects for possible modifications in the material properties. There is growing interest in studying the optical properties of multiferroic BiFeO3 (BFO) thin films for optoelectronic applications. In the present work, BFO thin films were prepared by sol-gel spin coating technique and were irradiated using the 15 UD Pelletron accelerator with 100 MeV Au9+ ions at a fluence of 1 × 1012 ions cm-2. The as-grown films became rough and porous on ion irradiation. Surface Plasmon Resonance (SPR) technique has been identified as a highly sensitive and powerful technique for studying the optical properties of a dielectric material. Optical properties of BFO thin films, before and after irradiation were studied using SPR technique in Otto configuration. Refractive index is found to be decreasing from 2.27 to 2.14 on ion irradiation at a wavelength of 633 nm. Refractive index dispersion of BFO thin film (from 405 nm to 633 nm) before and after ion radiation was examined.

  8. Dimensional characterization of a quasispherical resonator by microwave and coordinate measurement techniques

    NASA Astrophysics Data System (ADS)

    Underwood, R.; Flack, D.; Morantz, P.; Sutton, G.; Shore, P.; de Podesta, M.

    2011-02-01

    We describe the dimensional characterization of copper quasisphere NPL-Cranfield 2. The quasisphere is assembled from two hemispheres such that the internal shape is a triaxial ellipsoid, the major axes of which have nominal radii 62.000 mm, 62.031 mm and 62.062 mm. The artefact has been manufactured using diamond-turning technology and shows a deviation from design form of less than ±1 µm over most of its surface. Our characterization involves both coordinate measuring machine (CMM) experiments and microwave resonance spectroscopy. We have sought to reduce the dimensional uncertainty below the maximum permissible error of the CMM by comparative measurements with silicon and Zerodur spheres of known volume. Using this technique we determined the equivalent radius with an uncertainty of u(k = 1) = 114 nm, a fractional uncertainty of 1.8 parts in 106. Due to anisotropy of the probe response, we could only determine the eccentricities of the quasihemispheres with a fractional uncertainty of approximately 2%. Our microwave characterization uses the TM11 to TM18 resonances. We find the equivalent radius inferred from analysis of these modes to be consistent within ±4 nm with an overall uncertainty u(k = 1) = 11 nm. We discuss corrections for surface conductivity, waveguide perturbations and dielectric surface layers. We find that the CMM radius estimates derived from each hemisphere cannot be used to accurately predict the equivalent radius of the assembled resonator for two reasons. Firstly, the equatorial flanges are flat only to within ±1 µm, leading to an equatorial 'gap' whose dimension cannot be reliably estimated. Secondly, the resonator undergoes significant elastic distortion when the bolts connecting the hemispheres are tightened. We provide CMM and microwave measurements to support these conclusions in addition to finite-element modelling. Finally, we consider the implications of this work on a forthcoming experiment to determine the Boltzmann constant

  9. Development of a rapid and efficient magnetic resonance imaging technique for analysis of body fat distribution.

    PubMed

    Barnard, M L; Schwieso, J E; Thomas, E L; Bell, J D; Saeed, N; Frost, G; Bloom, S R; Hajnal, J V

    1996-06-01

    Fast scan magnetic resonance imaging techniques for adipose tissue (AT) quantification were compared to a conventional T1-weighted spin-echo (SE) sequence (TR = 500 ms, TE = 20 ms), imaging a mid-abdominal slice. A rapid T1-weighted SE sequence (TR = 36 ms, TE = 14 ms) was optimal, with minimal distortion (field, motion, flow artefact). Tissue contrast was higher and visceral AT was clearly differentiated. Quantification of all AT compartments (total, subcutaneous, internal, visceral) showed close agreement with the T1-weighted SE sequence and reproducibility was high (coefficient of variation < 4.7%). For AT quantification in a whole subject, this fast technique allows each image to be acquired serially at the magnet isocenter, as the subject is moved through the scanner (serial isocenter scanning, SIS). This method provides minimal image distortion and allows rapid coverage of the whole body. PMID:9015802

  10. Characterizing Si:P quantum dot qubits with spin resonance techniques.

    PubMed

    Wang, Yu; Chen, Chin-Yi; Klimeck, Gerhard; Simmons, Michelle Y; Rahman, Rajib

    2016-01-01

    Quantum dots patterned by atomically precise placement of phosphorus donors in single crystal silicon have long spin lifetimes, advantages in addressability, large exchange tunability, and are readily available few-electron systems. To be utilized as quantum bits, it is important to non-invasively characterise these donor quantum dots post fabrication and extract the number of bound electron and nuclear spins as well as their locations. Here, we propose a metrology technique based on electron spin resonance (ESR) measurements with the on-chip circuitry already needed for qubit manipulation to obtain atomic scale information about donor quantum dots and their spin configurations. Using atomistic tight-binding technique and Hartree self-consistent field approximation, we show that the ESR transition frequencies are directly related to the number of donors, electrons, and their locations through the electron-nuclear hyperfine interaction.

  11. Development of a rapid and efficient magnetic resonance imaging technique for analysis of body fat distribution.

    PubMed

    Barnard, M L; Schwieso, J E; Thomas, E L; Bell, J D; Saeed, N; Frost, G; Bloom, S R; Hajnal, J V

    1996-06-01

    Fast scan magnetic resonance imaging techniques for adipose tissue (AT) quantification were compared to a conventional T1-weighted spin-echo (SE) sequence (TR = 500 ms, TE = 20 ms), imaging a mid-abdominal slice. A rapid T1-weighted SE sequence (TR = 36 ms, TE = 14 ms) was optimal, with minimal distortion (field, motion, flow artefact). Tissue contrast was higher and visceral AT was clearly differentiated. Quantification of all AT compartments (total, subcutaneous, internal, visceral) showed close agreement with the T1-weighted SE sequence and reproducibility was high (coefficient of variation < 4.7%). For AT quantification in a whole subject, this fast technique allows each image to be acquired serially at the magnet isocenter, as the subject is moved through the scanner (serial isocenter scanning, SIS). This method provides minimal image distortion and allows rapid coverage of the whole body.

  12. Magnetic Resonance Techniques Applied to the Diagnosis and Treatment of Parkinson's Disease.

    PubMed

    de Celis Alonso, Benito; Hidalgo-Tobón, Silvia S; Menéndez-González, Manuel; Salas-Pacheco, José; Arias-Carrión, Oscar

    2015-01-01

    Parkinson's disease (PD) affects at least 10 million people worldwide. It is a neurodegenerative disease, which is currently diagnosed by neurological examination. No neuroimaging investigation or blood biomarker is available to aid diagnosis and prognosis. Most effort toward diagnosis using magnetic resonance (MR) has been focused on the use of structural/anatomical neuroimaging and diffusion tensor imaging (DTI). However, deep brain stimulation, a current strategy for treating PD, is guided by MR imaging (MRI). For clinical prognosis, diagnosis, and follow-up investigations, blood oxygen level-dependent MRI, DTI, spectroscopy, and transcranial magnetic stimulation have been used. These techniques represent the state of the art in the last 5 years. Here, we focus on MR techniques for the diagnosis and treatment of Parkinson's disease. PMID:26191037

  13. Characterizing Si:P quantum dot qubits with spin resonance techniques

    PubMed Central

    Wang, Yu; Chen, Chin-Yi; Klimeck, Gerhard; Simmons, Michelle Y.; Rahman, Rajib

    2016-01-01

    Quantum dots patterned by atomically precise placement of phosphorus donors in single crystal silicon have long spin lifetimes, advantages in addressability, large exchange tunability, and are readily available few-electron systems. To be utilized as quantum bits, it is important to non-invasively characterise these donor quantum dots post fabrication and extract the number of bound electron and nuclear spins as well as their locations. Here, we propose a metrology technique based on electron spin resonance (ESR) measurements with the on-chip circuitry already needed for qubit manipulation to obtain atomic scale information about donor quantum dots and their spin configurations. Using atomistic tight-binding technique and Hartree self-consistent field approximation, we show that the ESR transition frequencies are directly related to the number of donors, electrons, and their locations through the electron-nuclear hyperfine interaction. PMID:27550779

  14. Characterizing Si:P quantum dot qubits with spin resonance techniques.

    PubMed

    Wang, Yu; Chen, Chin-Yi; Klimeck, Gerhard; Simmons, Michelle Y; Rahman, Rajib

    2016-01-01

    Quantum dots patterned by atomically precise placement of phosphorus donors in single crystal silicon have long spin lifetimes, advantages in addressability, large exchange tunability, and are readily available few-electron systems. To be utilized as quantum bits, it is important to non-invasively characterise these donor quantum dots post fabrication and extract the number of bound electron and nuclear spins as well as their locations. Here, we propose a metrology technique based on electron spin resonance (ESR) measurements with the on-chip circuitry already needed for qubit manipulation to obtain atomic scale information about donor quantum dots and their spin configurations. Using atomistic tight-binding technique and Hartree self-consistent field approximation, we show that the ESR transition frequencies are directly related to the number of donors, electrons, and their locations through the electron-nuclear hyperfine interaction. PMID:27550779

  15. Magnetic Resonance Techniques Applied to the Diagnosis and Treatment of Parkinson’s Disease

    PubMed Central

    de Celis Alonso, Benito; Hidalgo-Tobón, Silvia S.; Menéndez-González, Manuel; Salas-Pacheco, José; Arias-Carrión, Oscar

    2015-01-01

    Parkinson’s disease (PD) affects at least 10 million people worldwide. It is a neurodegenerative disease, which is currently diagnosed by neurological examination. No neuroimaging investigation or blood biomarker is available to aid diagnosis and prognosis. Most effort toward diagnosis using magnetic resonance (MR) has been focused on the use of structural/anatomical neuroimaging and diffusion tensor imaging (DTI). However, deep brain stimulation, a current strategy for treating PD, is guided by MR imaging (MRI). For clinical prognosis, diagnosis, and follow-up investigations, blood oxygen level-dependent MRI, DTI, spectroscopy, and transcranial magnetic stimulation have been used. These techniques represent the state of the art in the last 5 years. Here, we focus on MR techniques for the diagnosis and treatment of Parkinson’s disease. PMID:26191037

  16. Characterizing Si:P quantum dot qubits with spin resonance techniques

    NASA Astrophysics Data System (ADS)

    Wang, Yu; Chen, Chin-Yi; Klimeck, Gerhard; Simmons, Michelle Y.; Rahman, Rajib

    2016-08-01

    Quantum dots patterned by atomically precise placement of phosphorus donors in single crystal silicon have long spin lifetimes, advantages in addressability, large exchange tunability, and are readily available few-electron systems. To be utilized as quantum bits, it is important to non-invasively characterise these donor quantum dots post fabrication and extract the number of bound electron and nuclear spins as well as their locations. Here, we propose a metrology technique based on electron spin resonance (ESR) measurements with the on-chip circuitry already needed for qubit manipulation to obtain atomic scale information about donor quantum dots and their spin configurations. Using atomistic tight-binding technique and Hartree self-consistent field approximation, we show that the ESR transition frequencies are directly related to the number of donors, electrons, and their locations through the electron-nuclear hyperfine interaction.

  17. Optical detection of paramagnetic centres: From crystals to glass-ceramics

    NASA Astrophysics Data System (ADS)

    Rogulis, Uldis

    2016-07-01

    An unambiguous attribution of the absorption spectra to definite paramagnetic centres identified by the EPR techniques in the most cases is problematic. This problem may be solved by applying of a direct measurement techniques—the EPR detected via the magnetic circular dichroism, or briefly MCD-EPR. The present survey reports on the advantages and disadvantages applying the MCD-EPR techniques to simple and complex paramagnetic centres in crystals as well as glasses and glass-ceramics.

  18. Fiber optic profenofos sensor based on surface plasmon resonance technique and molecular imprinting.

    PubMed

    Shrivastav, Anand M; Usha, Sruthi P; Gupta, Banshi D

    2016-05-15

    A successful approach for the fabrication and characterization of an optical fiber sensor for the detection of profenofos based on surface plasmon resonance (SPR) and molecular imprinting is introduced. Molecular imprinting technology is used for the creation of three dimensional binding sites having complementary shape and size of the specific template molecule over a polymer for the recognition of the same. Binding of template molecule with molecularly imprinted polymer (MIP) layer results in the change in the dielectric nature of the sensing surface (polymer) and is identified by SPR technique. Spectral interrogation method is used for the characterization of the sensing probe. The operating profenofos concentration range of the sensor is from 10(-4) to 10(-1)µg/L. A red shift of 18.7 nm in resonance wavelength is recorded for this profenofos concentration range. The maximum sensitivity of the sensor is 12.7 nm/log (µg/L) at 10(-4)µg/L profenofos concentration. Limit of detection (LOD) of the sensor is found to be 2.5×10(-6)µg/L. Selectivity measurements predict the probe highly selective for the profenofos molecule. Besides high sensitivity due to SPR technique and selectivity due to molecular imprinting, proposed sensor has numerous other advantages like immunity to electromagnetic interference, fast response, low cost and capability of online monitoring and remote sensing of analyte due to the fabrication of the probe on optical fiber.

  19. Fiber optic profenofos sensor based on surface plasmon resonance technique and molecular imprinting.

    PubMed

    Shrivastav, Anand M; Usha, Sruthi P; Gupta, Banshi D

    2016-05-15

    A successful approach for the fabrication and characterization of an optical fiber sensor for the detection of profenofos based on surface plasmon resonance (SPR) and molecular imprinting is introduced. Molecular imprinting technology is used for the creation of three dimensional binding sites having complementary shape and size of the specific template molecule over a polymer for the recognition of the same. Binding of template molecule with molecularly imprinted polymer (MIP) layer results in the change in the dielectric nature of the sensing surface (polymer) and is identified by SPR technique. Spectral interrogation method is used for the characterization of the sensing probe. The operating profenofos concentration range of the sensor is from 10(-4) to 10(-1)µg/L. A red shift of 18.7 nm in resonance wavelength is recorded for this profenofos concentration range. The maximum sensitivity of the sensor is 12.7 nm/log (µg/L) at 10(-4)µg/L profenofos concentration. Limit of detection (LOD) of the sensor is found to be 2.5×10(-6)µg/L. Selectivity measurements predict the probe highly selective for the profenofos molecule. Besides high sensitivity due to SPR technique and selectivity due to molecular imprinting, proposed sensor has numerous other advantages like immunity to electromagnetic interference, fast response, low cost and capability of online monitoring and remote sensing of analyte due to the fabrication of the probe on optical fiber. PMID:26706813

  20. Biochemical component identification by light scattering techniques in whispering gallery mode optical resonance based sensor

    NASA Astrophysics Data System (ADS)

    Saetchnikov, Vladimir A.; Tcherniavskaia, Elina A.; Saetchnikov, Anton V.; Schweiger, Gustav; Ostendorf, Andreas

    2014-03-01

    Experimental data on detection and identification of variety of biochemical agents, such as proteins (albumin, interferon, C reactive protein), microelements (Na+, Ca+), antibiotic of different generations, in both single and multi component solutions under varied in wide range concentration are represented. Analysis has been performed on the light scattering parameters of whispering gallery mode (WGM) optical resonance based sensor with dielectric microspheres from glass and PMMA as sensitive elements fixed by spin - coating techniques in adhesive layer on the surface of substrate or directly on the coupling element. Sensitive layer was integrated into developed fluidic cell with a digital syringe. Light from tuneable laser strict focusing on and scattered by the single microsphere was detected by a CMOS camera. The image was filtered for noise reduction and integrated on two coordinates for evaluation of integrated energy of a measured signal. As the entrance data following signal parameters were used: relative (to a free spectral range) spectral shift of frequency of WGM optical resonance in microsphere and relative efficiency of WGM excitation obtained within a free spectral range which depended on both type and concentration of investigated agents. Multiplexing on parameters and components has been realized using spatial and spectral parameters of scattered by microsphere light with developed data processing. Biochemical component classification and identification of agents under investigation has been performed by network analysis techniques based on probabilistic network and multilayer perceptron. Developed approach is demonstrated to be applicable both for single agent and for multi component biochemical analysis.

  1. Magnetic resonance imaging: Review of imaging techniques and overview of liver imaging

    PubMed Central

    Maniam, Santhi; Szklaruk, Janio

    2010-01-01

    Magnetic resonance imaging (MRI) of the liver is slowly transitioning from a problem solving imaging modality to a first line imaging modality for many diseases of the liver. The well established advantages of MRI over other cross sectional imaging modalities may be the basis for this transition. Technological advancements in MRI that focus on producing high quality images and fast imaging, increasing diagnostic accuracy and developing newer function-specific contrast agents are essential in ensuring that MRI succeeds as a first line imaging modality. Newer imaging techniques, such as parallel imaging, are widely utilized to shorten scanning time. Diffusion weighted echo planar imaging, an adaptation from neuroimaging, is fast becoming a routine part of the MRI liver protocol to improve lesion detection and characterization of focal liver lesions. Contrast enhanced dynamic T1 weighted imaging is crucial in complete evaluation of diseases and the merit of this dynamic imaging relies heavily on the appropriate timing of the contrast injection. Newer techniques that include fluoro-triggered contrast enhanced MRI, an adaptation from 3D MRA imaging, are utilized to achieve good bolus timing that will allow for optimum scanning. For accurate interpretation of liver diseases, good understanding of the newer imaging techniques and familiarity with typical imaging features of liver diseases are essential. In this review, MR sequences for a time efficient liver MRI protocol utilizing newer imaging techniques are discussed and an overview of imaging features of selected common focal and diffuse liver diseases are presented. PMID:21160685

  2. Resonant fiber optic gyro based on a sinusoidal wave modulation and square wave demodulation technique.

    PubMed

    Wang, Linglan; Yan, Yuchao; Ma, Huilian; Jin, Zhonghe

    2016-04-20

    New developments are made in the resonant fiber optic gyro (RFOG), which is an optical sensor for the measurement of rotation rate. The digital signal processing system based on the phase modulation technique is capable of detecting the weak frequency difference induced by the Sagnac effect and suppressing the reciprocal noise in the circuit, which determines the detection sensitivity of the RFOG. A new technique based on the sinusoidal wave modulation and square wave demodulation is implemented, and the demodulation curve of the system is simulated and measured. Compared with the past technique using sinusoidal modulation and demodulation, it increases the slope of the demodulation curve by a factor of 1.56, improves the spectrum efficiency of the modulated signal, and reduces the occupancy of the field-programmable gate array resource. On the basis of this new phase modulation technique, the loop is successfully locked and achieves a short-term bias stability of 1.08°/h, which is improved by a factor of 1.47. PMID:27140098

  3. Detection of Bacterial Magnetofossils with Ferromagnetic Resonance and Rock Magnetic Techniques

    NASA Astrophysics Data System (ADS)

    Kirschvink, J. L.; Kim, S.; Weiss, B.

    2001-12-01

    Intracellular biomineralization of magnetite is a biochemical process used by members of the Bacteria, Protist, and Animal kingdoms, and the fossil remains of this process on Earth (termed magnetofossils) have been documented in sediments as old as the ~2 Byr Gunflint Chert. Magnetofossils 4 Byr old have also been reported from carbonates in the Martian meteorite ALH84001; if this interpretation is correct, they represent the oldest evidence for life yet found. Past techniques for identification of bacterial magnetofossils have relied on the use of particle extraction and high-resolution electron microscopy (HRTEM). Because these techniques are time-consuming and fairly complex, they are not appropriate for screening large volumes of sediments on Earth and could not be used remotely on a Martian lander. For this reason, we have been testing a variety of ferromagnetic resonance and low-temperature rock magnetic techniques to determine if they are capable of identifying correctly rock samples known to contain abundant magnetofossils. An instrument capable of making such a determination, if deployed on the Martian surface, could be extraordinarily valuable for selecting samples for return to Earth. Several features of the ferromagnetic resonance (FMR) spectra have signatures only displayed by pure samples of magnetite from the magnetotactic bacteria, and from samples known to contain abundant magnetofossils. These unique features apparently arise from the elongated shape and narrow size distribution of the single-domain magnetite produced by these bacteria. Preliminary results from ALH84001 carbonates also have these features. We are also currently obtaining FMR spectra and low-temperature rock magnetic data on samples of Archean and Early Proterozoic sediments from Australia to search for older evidence of intracellular magnetite biomineralization on Earth.

  4. 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)

  5. Novel Technique for Cardiac Electromechanical Mapping with Magnetic Resonance Imaging Tagging and an Epicardial Electrode Sock

    PubMed Central

    Faris, Owen P.; Evans, Frank J.; Ennis, Daniel B.; Helm, Patrick A.; Taylor, Joni L.; Chesnick, A. Scott; Guttman, Michael A.; Ozturk, Cengizhan; Mcveigh, Elliot R.

    2005-01-01

    Near-simultaneous measurements of electrical and mechanical activation over the entire ventricular surface are now possible using magnetic resonance imaging tagging and a multielectrode epicardial sock. This new electromechanical mapping technique is demonstrated in the ventricularly paced canine heart. A 128-electrode epicardial sock and pacing electrodes were placed on the hearts of four anesthetized dogs. In the magnetic resonance scanner, tagged cine images (8–15 ms/frame) and sock electrode recordings (1000 Hz) were acquired under right-ventricular pacing and temporally referenced to the pacing stimulus. Electrical recordings were obtained during intermittent breaks in image acquisition, so that both data sets represented the same physiologic state. Since the electrodes were not visible in the images, electrode recordings and cine images were spatially registered with Gd-DTPA markers attached to the sock. Circumferential strain was calculated at locations corresponding to electrodes. For each electrode location, electrical and mechanical activation times were calculated and relationships between the two activation patterns were demonstrated. This method holds promise for improving understanding of the relationships between the patterns of electrical activation and contraction in the heart. PMID:12723684

  6. Development of a dispersive read-out technique for quantum measurements of nanomechanical resonators

    NASA Astrophysics Data System (ADS)

    Rouxinol, Francisco; Lahaye, Matthew; Hao, Hugo; Shim, Seung-Bo

    2013-03-01

    Over the last decade, there has been an active effort to prepare and measure mechanical structures in the quantum regime for the purpose of sensing weak forces and for studying fundamental topics in quantum mechanics such as quantum measurement, entanglement and decoherence in new macroscopic limits. One promsing tool for such studies is the qubit-coupled mechanical resonator. In this work we discuss some of our first results towards the development of a nanoelectromechanical system that integrates a charge-type superconducting qubit as a detector to probe the number-states of a nanomechanical mode. In our system the qubit-coupled nanoresonator is embedded in a superconducting microwave resonator (SMR); the SMR then serves to perform spectroscopic measurements of the qubit to infer the number-state statistics of the nanoresonator in a manner analogous to dispersive measurement techniques used in circuit and cavity QED to probe the number-states of electromagnetic cavities. We will discuss the design and measurement of our latest generation devices and the prospects for achieving single-phonon measurement resolution with this system. This work is supported by NSF-DMR Career Award 1056423 and funding from the College of Arts and Sciences at Syracuse University.

  7. Magnetic flocculation of paramagnetic particles

    SciTech Connect

    Tsouris, C.; Scott, T.C.

    1994-09-01

    An experimental apparatus has been assembled for the flocculation study of paramagnetic particles under the influence of a strong magnetic field. A magnetic field of strength up to 6 T is generated by a cryogenic magnet operating near liquid helium temperatures. Experimental information is obtained from fluctuation and intensity measurements of light passing through a particle suspension located in a uniform magnetic field. Particle flocculation is described by a Brownian flocculation model in which hydrodynamic, van der Waals, double-layer, and magnetic forces are incorporated for the estimation of the particle flocculation rate. A population-balance model is employed in conjunction with the flocculation model to predict the evolution of the particle size and composition or magnetic susceptibility with time. The effects of magnetic-field strength, magnetic susceptibility of the particles, particle size, and zeta potential are investigated. Results show that particle size and magnetic susceptibility each play an important role in the selective flocculation of particles of different properties.

  8. [New technique of magnetic resonance imaging to evaluate peripheral circulation in diabetic patients].

    PubMed

    Suzuki, Eiji

    2006-11-01

    Waveform analysis at the popliteal artery using the new technique of gated two-dimensional cine-mode phase-contrast magnetic resonance imaging is beneficial to assess peripheral circulation in both normal and diseased arteries. The normal subjects had a typically triphasic waveform, which could be clearly separated into systolic, and early and late diastolic phases of the cardiac cycle. Diabetic patients are reported to have two types of insufficient arterial blood flow to the lower limbs associated with the vessel wall properties. Firstly, patients with atherosclerotic occlusion in the lower-leg arteries distal to the aortic bifurcation, resulting in a low ankle-brachial index, show an abnormal monophasic waveform. Secondly, patients with stiffer arteries characteristically show abnormal flow reversal in late diastole, suggesting higher vascular resistance.

  9. Resonance ultrasonic vibrations in Cz-Si wafers as a possible diagnostic technique in ion implantation

    NASA Astrophysics Data System (ADS)

    Zhao, Z. Y.; Ostapenko, S.; Anundson, R.; Tvinnereim, M.; Belyaev, A.; Anthony, M.

    2001-07-01

    The semiconductor industry does not have effective metrology for well implants. The ability to measure such deep level implants will become increasingly important as we progress along the technology road map. This work explores the possibility of using the acoustic whistle effect on ion implanted silicon wafers. The technique detects the elastic stress and defects in silicon wafers by measuring the sub-harmonic f/2 resonant vibrations on a wafer induced via backside contact to create standing waves, which are measured by a non-contact ultrasonic probe. Preliminary data demonstrates that it is sensitive to implant damage, and there is a direct correlation between this sub-harmonic acoustic mode and some of the implant and anneal conditions. This work presents the results of a feasibility study to assess and quantify the correspondent whistle effect to implant damage, residual damage after annealing and intrinsic defects.

  10. Evaluation of Possible Nuclear Magnetic Resonance Diagnostic Techniques for Tokamak Experiments

    SciTech Connect

    S.J. Zweben; T.W. Kornack; D. Majeski; G. Schilling; C.H. Skinner; R. Wilson

    2002-08-05

    Potential applications of nuclear magnetic resonance (NMR) diagnostic techniques to tokamak experiments are evaluated. NMR frequencies for hydrogen isotopes and low-Z nuclei in such experiments are in the frequency range approximately equal to 20-200 MHz, so existing RF [radio-frequency] antennas could be used to rotate the spin polarization and to make the NMR measurements. Our tentative conclusion is that such measurements are possible if highly spin polarized H or (superscript)3He gas sources (which exist) are used to fuel these plasmas. In addition, NMR measurements of the surface layers of the first wall (without plasma) may also be possible, e.g., to evaluate the inventory of tritium inside the vessel.

  11. Demonstration of the stabilization technique for nonplanar optical resonant cavities utilizing polarization

    SciTech Connect

    Akagi, T.; Araki, S.; Funahashi, Y.; Honda, Y.; Okugi, T.; Omori, T.; Shimizu, H.; Terunuma, N.; Urakawa, J.; Miyoshi, S.; Takahashi, T. Tanaka, R.; Uesugi, Y.; Yoshitama, H.; Sakaue, K.; Washio, M.

    2015-04-15

    Based on our previously developed scheme to stabilize nonplanar optical resonant cavities utilizing polarization caused by a geometric phase in electromagnetic waves traveling along a twisted path, we report an application of the technique for a cavity installed in the Accelerator Test Facility, a 1.3-GeV electron beam accelerator at KEK, in which photons are generated by laser-Compton scattering. We successfully achieved a power enhancement of 1200 with 1.4% fluctuation, which means that the optical path length of the cavity has been controlled with a precision of 14 pm under an accelerator environment. In addition, polarization switching utilizing a geometric phase of the nonplanar cavity was demonstrated.

  12. Demonstration of the stabilization technique for nonplanar optical resonant cavities utilizing polarization

    NASA Astrophysics Data System (ADS)

    Akagi, T.; Araki, S.; Funahashi, Y.; Honda, Y.; Miyoshi, S.; Okugi, T.; Omori, T.; Shimizu, H.; Sakaue, K.; Takahashi, T.; Tanaka, R.; Terunuma, N.; Uesugi, Y.; Urakawa, J.; Washio, M.; Yoshitama, H.

    2015-04-01

    Based on our previously developed scheme to stabilize nonplanar optical resonant cavities utilizing polarization caused by a geometric phase in electromagnetic waves traveling along a twisted path, we report an application of the technique for a cavity installed in the Accelerator Test Facility, a 1.3-GeV electron beam accelerator at KEK, in which photons are generated by laser-Compton scattering. We successfully achieved a power enhancement of 1200 with 1.4% fluctuation, which means that the optical path length of the cavity has been controlled with a precision of 14 pm under an accelerator environment. In addition, polarization switching utilizing a geometric phase of the nonplanar cavity was demonstrated.

  13. Further Evaluation of the Neutron Resonance Transmission Analysis (NRTA) Technique for Assaying Plutonium in Spent Fuel

    SciTech Connect

    J. W. Sterbentz; D. L. Chichester

    2011-09-01

    This is an end-of-year report (Fiscal Year (FY) 2011) for the second year of effort on a project funded by the National Nuclear Security Administration's Office of Nuclear Safeguards (NA-241). The goal of this project is to investigate the feasibility of using Neutron Resonance Transmission Analysis (NRTA) to assay plutonium in commercial light-water-reactor spent fuel. This project is part of a larger research effort within the Next-Generation Safeguards Initiative (NGSI) to evaluate methods for assaying plutonium in spent fuel, the Plutonium Assay Challenge. The second-year goals for this project included: (1) assessing the neutron source strength needed for the NRTA technique, (2) estimating count times, (3) assessing the effect of temperature on the transmitted signal, (4) estimating plutonium content in a spent fuel assembly, (5) providing a preliminary assessment of the neutron detectors, and (6) documenting this work in an end of the year report (this report). Research teams at Los Alamos National Laboratory (LANL), Lawrence Berkeley National Laboratory (LBNL), Pacific Northwest National Laboratory (PNNL), and at several universities are also working to investigate plutonium assay methods for spent-fuel safeguards. While the NRTA technique is well proven in the scientific literature for assaying individual spent fuel pins, it is a newcomer to the current NGSI efforts studying Pu assay method techniques having just started in March 2010; several analytical techniques have been under investigation within this program for two to three years or more. This report summarizes work performed over a nine month period from January-September 2011 and is to be considered a follow-on or add-on report to our previous published summary report from December 2010 (INL/EXT-10-20620).

  14. Improvement of (31)P NMR spectral resolution by 8-hydroxyquinoline precipitation of paramagnetic Fe and Mn in environmental samples.

    PubMed

    Ding, Shiming; Xu, Di; Li, Bin; Fan, Chengxin; Zhang, Chaosheng

    2010-04-01

    Solution (31)P nuclear magnetic resonance (NMR) spectroscopy is currently the main method for the characterization of phosphorus (P) forms in environment samples. However, identification and quantification of P compounds may be hampered by poor resolution of spectra caused by paramagnetic Fe and Mn. In this study, a novel technique was developed to improve spectral resolution by removing paramagnetic Fe and Mn from alkaline extracts via 8-hydroxyquinoline (8-HOQ) precipitation. Batch experiments showed that both Fe and Mn were effectively removed by the precipitation at pH 9.0, with the removal efficiencies of 83-91% for Fe and 67-78% for Mn from the extracts of five different environmental samples, while little effect was found on concentration of total P. The (31)P NMR analysis of a model P solution showed that addition of 8-HOQ and its precipitation with metal ions did not alter P forms. Further analyses of the five extracts with (31)P NMR spectroscopy demonstrated that the