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Sample records for nmr relaxation rates

  1. NMR relaxation rate and the libron energy of solid hydrogen

    Science.gov (United States)

    Sugawara, K.; Woollam, J. A.

    1978-01-01

    By taking the rotational relaxation of orthohydrogen (o-H2) in solid hydrogen into account, the authors have theoretically investigated the longitudinal NMR spin lattice relaxation rate of o-H2. The rate is characterized by an anomalous maximum, as a function of temperature, at temperatures close to the mean libron energy of o-H2. Application of the theory for o-H2 concentrations between 42% and 75% reveals a nearly concentration-independent mean libron energy equivalent to about 1 K. This qualitatively and quantitatively contradicts the conclusions of other theories, but agrees with recent experiments.

  2. A comparison of methods for calculating NMR cross-relaxation rates (NOESY and ROESY intensities) in small peptides

    NARCIS (Netherlands)

    Feenstra, K Anton; Peter, Christine; Scheek, Ruud M; van Gunsteren, Wilfred F; Mark, Alan E

    Three methods for calculating nuclear magnetic resonance cross-relaxation rates from molecular dynamics simulations of small flexible molecules have been compared in terms of their ability to reproduce relaxation data obtained experimentally and to produce consistent descriptions of the system. The

  3. Proton NMR relaxation in hydrous melts

    International Nuclear Information System (INIS)

    Braunstein, J.; Bacarella, A.L.; Benjamin, B.M.; Brown, L.L.; Girard, C.

    1976-01-01

    Pulse and continuous wave NMR measurements are reported for protons in hydrous melts of calcium nitrate at temperatures between -4 and 120 0 C. Although measured in different temperature ranges, spin-lattice (T 1 ) and spin-spin (T 2 ) relaxation times appear to be nearly equal to each other and proportional to the self-diffusion coefficients of solute metal cations such as Cd 2+ . At temperatures near 50 0 C, mean Arrhenius coefficients Δ H/sub T 1 / (kcal/mol) are 7.9, 7.3, and 4.8, respectively, for melts containing 2.8, 4.0, and 8.0 moles of water per mole of calcium nitrate, compared to 4.6 kcal/mol for pure water. Temperature dependence of T 1 and T 2 in Ca(NO 3 ) 2 -2.8 H 2 O between -4 and 120 0 C are non-Arrhenius and can be represented by a Fulcher-type equation with a ''zero mobility temperature'' (T 0 ) of 225 0 K, close to the value of T 0 for solute diffusion, electrical conductance and viscosity. Resolution of the relaxation rates into correlation times for intramolecular (rotational) and intermolecular (translational) diffusional motion is discussed in terms of the Bloembergen-Purcell-Pound and more recent models for dipolar relaxation

  4. Relaxation time estimation in surface NMR

    Science.gov (United States)

    Grunewald, Elliot D.; Walsh, David O.

    2017-03-21

    NMR relaxation time estimation methods and corresponding apparatus generate two or more alternating current transmit pulses with arbitrary amplitudes, time delays, and relative phases; apply a surface NMR acquisition scheme in which initial preparatory pulses, the properties of which may be fixed across a set of multiple acquisition sequence, are transmitted at the start of each acquisition sequence and are followed by one or more depth sensitive pulses, the pulse moments of which are varied across the set of multiple acquisition sequences; and apply processing techniques in which recorded NMR response data are used to estimate NMR properties and the relaxation times T.sub.1 and T.sub.2* as a function of position as well as one-dimensional and two-dimension distributions of T.sub.1 versus T.sub.2* as a function of subsurface position.

  5. Pseudogap Behavior of the Nuclear Spin-Lattice Relaxation Rate in FeSe Probed by 77Se-NMR

    Science.gov (United States)

    Shi, Anlu; Arai, Takeshi; Kitagawa, Shunsaku; Yamanaka, Takayoshi; Ishida, Kenji; Böhmer, Anna E.; Meingast, Christoph; Wolf, Thomas; Hirata, Michihiro; Sasaki, Takahiko

    2018-01-01

    We conducted 77Se-nuclear magnetic resonance studies of the iron-based superconductor FeSe in magnetic fields of 0.6 to 19 T to investigate the superconducting and normal-state properties. The nuclear spin-lattice relaxation rate divided by the temperature (T1T)-1 increases below the structural transition temperature Ts but starts to be suppressed below T*, well above the superconducting transition temperature Tc(H), resulting in a broad maximum of (T1T)-1 at Tp(H). This is similar to the pseudogap behavior in optimally doped cuprate superconductors. Because T* and Tp(H) decrease in the same manner as Tc(H) with increasing H, the pseudogap behavior in FeSe is ascribed to superconducting fluctuations, which presumably originate from the theoretically predicted preformed pair above Tc(H).

  6. Exploring catalyst passivation with NMR relaxation.

    Science.gov (United States)

    Robinson, Neil; Gladden, Lynn F; D'Agostino, Carmine

    2017-10-26

    NMR relaxation has recently emerged as a novel and non-invasive tool for probing the surface dynamics of adsorbate molecules within liquid-saturated mesoporous catalysts. The elucidation of such dynamics is of particular relevance to the study and development of solvated green catalytic processes, such as the production of chemicals and fuels from bio-resources. In this paper we develop and implement a protocol using high field 1 H NMR spin-lattice relaxation as a probe of the reorientational dynamics of liquids imbibed within mesoporous oxide materials. The observed relaxation of liquids within mesoporous materials is highly sensitive to the adsorbed surface layer, giving insight into tumbling behaviour of spin-bearing chemical environments at the pore surface. As a prototypical example of relevance to liquid-phase catalytic systems, we examine the mobility of liquid methanol within a range of common catalyst supports. In particular, through the calculation and comparison of a suitable interaction parameter, we assess and quantify changes to these surface dynamics upon replacing surface hydroxyl groups with hydrophobic alkyl chains. Our results indicate that the molecular tumbling of adsorbed methanol is enhanced upon surface passivation due to the suppression of surface-adsorbate hydrogen bonding interactions, and tends towards that of the unrestricted bulk liquid. A complex analysis in which we account for the influence of changing pore structure and surface chemistry upon passivation is discussed. The results presented highlight the use of NMR spin-lattice relaxation measurements as a non-invasive probe of molecular dynamics at surfaces of interest to liquid-phase heterogeneous catalysis.

  7. 129 Xe NMR Relaxation-Based Macromolecular Sensing

    Energy Technology Data Exchange (ETDEWEB)

    Gomes, Muller D. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Dao, Phuong [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Jeong, Keunhong [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Slack, Clancy C. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Vassiliou, Christophoros C. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Finbloom, Joel A. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Francis, Matthew B. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Wemmer, David E. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Physical Biosciences Division; Pines, Alexander [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Materials Sciences Division; Univ. of California, Berkeley, CA (United States). Dept. of Chemistry

    2016-07-29

    A 129Xe NMR relaxation-based sensing approach is reported on that exploits changes in the bulk xenon relaxation rate induced by slowed tumbling of a cryptophane-based sensor upon target binding. The amplification afforded by detection of the bulk dissolved xenon allows sensitive detection of targets. The sensor comprises a xenon-binding cryptophane cage, a target interaction element, and a metal chelating agent. Xenon associated with the target-bound cryptophane cage is rapidly relaxed and then detected after exchange with the bulk. Here we show that large macromolecular targets increase the rotational correlation time of xenon, increasing its relaxation rate. Upon binding of a biotin-containing sensor to avidin at 1.5 μM concentration, the free xenon T2 is reduced by a factor of 4.

  8. Analysis of 2D NMR relaxation data using Chisholm approximations.

    Science.gov (United States)

    Huber, S; Haase, A; Gleich, B

    2017-08-01

    To analyze 2D NMR relaxation data based on a discrete delta-like relaxation map we extended the Padé-Laplace method to two dimensions. We approximate the forward Laplace image of the time domain signal by a Chisholm approximation, i.e. a rational polynomial in two dimensions. The poles and residues of this approximation correspond to the relaxation rates and weighting factors of the underlying relaxation map. In this work we explain the principle ideas of our algorithm and demonstrate its applicability. Therefore we compare the inversion results of the Chisholm approximation and Tikhonov regularization method as a function of SNR when the investigated signal is based on a given discrete relaxation map. Our algorithm proved to be reliable for SNRs larger than 50 and is able to compete with the Tikhonov regularization method. Furthermore we show that our method is also able to detect the simulated relaxation compartments of narrow Gaussian distributions with widths less or equal than 0.05s -1 . Finally we investigate the resolution limit with experimental data. For a SNR of 750 the Chisholm approximation method was able to resolve two relaxation compartments in 8 of 10 cases when both compartments differ by a factor of 1.7. Copyright © 2017 Elsevier Inc. All rights reserved.

  9. Non-uniform sampling of NMR relaxation data

    DEFF Research Database (Denmark)

    Schwarz-Linnet, Troels; Teilum, Kaare

    2016-01-01

    The use of non-uniform sampling of NMR spectra may give significant reductions in the data acquisition time. For quantitative experiments such as the measurement of spin relaxation rates, non-uniform sampling is however not widely used as inaccuracies in peak intensities may lead to errors...... of the multi-dimensional decomposition and iterative re-weighted least-squares algorithms in reconstructing spectra with accurate peak intensities. As long as a single fully sampled spectrum is included in a series of otherwise non-uniform sampled two-dimensional spectra, multi-dimensional decomposition...... in the extracted dynamic parameters. By systematic reducing the coverage of the Nyquist grid of (15)N Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion datasets for four different proteins and performing a full data analysis of the resulting non-uniform sampled datasets, we have compared the performance...

  10. Contribution of proton NMR relaxation to the investigation of ...

    Indian Academy of Sciences (India)

    001 Lisboa, Portugal. *Author for correspondence. Abstract. We present in this work a review concerning wide frequency range T1 proton NMR relaxation studies performed in compounds exhibiting columnar mesophases, namely the Col ho.

  11. Observing Cross-Relaxation with Depth-Resolved 8Li β-NMR

    Science.gov (United States)

    Chow, K. H.; Mansour, A. I.; Fan, I.; Morris, G. D.; Salman, Z.; Dunlop, T.; MacFarlane, W. A.; Kiefl, R. F.; Saadaoui, H.; Mosendz, O.; Kardasz, B.; Heinrich, B.; Jung, J.; Levy, C. D. P.; Pearson, M. R.; Parolin, T. J.; Wang, D.; Hossain, M. D.; Song, Q.; Smadella, M.

    In the paper, we review some of the progress that has been made, at the ISAC β-NMR facility, towards observing 8Li+ high field cross-relaxation phenomena in copper. The clearest observation of these phenomena is via the appearance of peaks in the field dependence of the relaxation rates of the 8Li+ polarization.

  12. NMR relaxation in systems with magnetic nanoparticles: a temperature study.

    Science.gov (United States)

    Issa, Bashar; Obaidat, Ihab M; Hejasee, Rola H; Qadri, Shahnaz; Haik, Yousef

    2014-03-01

    To measure and model nuclear magnetic resonance (NMR) relaxation enhancement due to the presence of gadolinium (Gd)-substituted Zn-Mn ferrite magnetic nanoparticles (MNP) at different temperatures. Relaxation rates were measured at 1.5 T using fast spin echo (FSE) sequences in samples of agarose gel doped with uncoated and polyethylene glycol (PEG)-coated Mn0.5 Zn0.5 Gd0.02 Fe1.98 O4 nanoparticles over the temperature range 8-58°C. Physical characterization of the MNPs synthesized using chemical coprecipitation included scanning (SEM) and transmission (TEM) electron microscopy, inductively coupled plasma (ICP), dynamic light scattering (DLS), and magnetometry. Relaxivity (in s(-1) mM(-1) Fe) for the uncoated and coated particles, respectively, increased as follows: from 2.5 to 3.2 and 0.4 to 0.7 for T1, while for T2 it increased from 162.3 to 253.7 and 59.7 to 82.2 over the temperature range 8-58°C. T2 data were fitted to the echo limited motional regime using one fitting parameter that reflects the degree of agglomeration of particles into a cluster. This parameter was found to increase linearly with temperature and was larger for the PEG-coated particles than the uncoated ones. The increase of 1/T2 with temperature is modeled successfully using echo limited motional regime where both diffusion of the protons and nanoparticle cluster size increase with temperature. Both transverse and longitudinal relaxation efficiencies are reduced by PEG coating at all temperatures. If prediction of relaxation rates under different particle concentrations and operating temperatures is possible then the use of MNP in temperature monitoring and hyperthermia applications may be achieved. Copyright © 2013 Wiley Periodicals, Inc.

  13. Proton NMR relaxation of hydrated insulin powder

    International Nuclear Information System (INIS)

    Sanches, R.; Donoso, J.P.; Mascarenhas, S.; Panepucci, H.C.

    1985-01-01

    Water proton nuclear magnetic relaxation measurements were obtained for hydrated insulin powder as a function of the water content. For samples containing enough water to complete the hydration shell, the data for the spin-lattice and spin-spin relaxation times are consistent with a model in which water molecules exist in two phases, one exhibiting restricted motion and identified with water of hydration and another identified as free water with motions similar to ordinary water. For samples containing only water of hydration, a model for the spin-spin relaxation time is discussed, in which the water molecules relaxation is described in terms for four relaxation times. Estimates are obtained for these relaxation times, in good agreement with the experimental data. (Author) [pt

  14. NMR relaxation studies with MnDPDP

    International Nuclear Information System (INIS)

    Southon, T.E.; Grant, D.; Bjoernerud, A.; Moen, O.M.; Spilling, B.; Martinsen, I.; Refsum, H.

    1997-01-01

    Purpose: Our studies were designed to compare the efficacy of mangafodipir trisodium (MnDPDP, Teslascan) as a tissue-specific MR agent with that of manganese chloride (MnCl 2 ), to compare the efficacy of different doses and rates of administration of MnDPDP, and to collect the data needed for predicting optimum pulse sequences. Material and Methods: The dose response for the relaxation rates R1 and R2 at 0.47 T, and the manganese (Mn) concentrations in rat liver and in the liver, pancreas, heart and adrenals of pigs was determined for both MnDPDP and MnCl 2 administered i.v. Computer simulations were carried out to model the effects of different tissue Mn concentrations and TR on signal intensities and contrast-to-noise ratios. Results: In rat liver and pig organs both compounds produced a positive dose-response in R1 and tissue Mn concentration, and only small or no response in R2. The Mn concentration in rat liver was positively correlated with R1, regardless of the form in which Mn was given, or the rate of administration. Optimal imaging parametes are therefore expected to be different pre- and post-MnDPDP administration. (orig./AJ)

  15. Parameterization of NMR relaxation curves in terms of logarithmic moments of the relaxation time distribution

    Science.gov (United States)

    Petrov, Oleg V.; Stapf, Siegfried

    2017-06-01

    This work addresses the problem of a compact and easily comparable representation of multi-exponential relaxation data. It is often convenient to describe such data in a few parameters, all being of physical significance and easy to interpret, and in such a way that enables a model-free comparison between different groups of samples. Logarithmic moments (LMs) of the relaxation time constitute a set of parameters which are related to the characteristic relaxation time on the log-scale, the width and the asymmetry of an underlying distribution of exponentials. On the other hand, the calculation of LMs does not require knowing the actual distribution function and is reduced to a numerical integration of original data. The performance of this method has been tested on both synthetic and experimental NMR relaxation data which differ in a signal-to-noise ratio, the sampling range and the sampling rate. The calculation of two lower-order LMs, the log-mean time and the log-variance, has proved robust against deficiencies of the experiment such as scattered data point and incomplete sampling. One may consider using them as such to monitor formation of a heterogeneous structure, e.g., in phase separation, vitrification, polymerization, hydration, aging, contrast agent propagation processes. It may also assist in interpreting frequency and temperature dependences of relaxation, revealing a crossover from slow to fast exchange between populations. The third LM was found to be a less reliable quantity due to its susceptibility to the noise and must be used with caution.

  16. Evaluation of algorithms for analysis of NMR relaxation decay curves

    NARCIS (Netherlands)

    Weerd, van der L.; Vergeldt, F.J.; Jager, de P.A.; As, van H.

    2000-01-01

    Quantitative processing of NMR relaxation images depends on the characteristics of the used fitting algorithm. Therefore several common fitting algorithms are compared for decay curves with low signal-to-noise ratios. The use of magnitude data yields a non-zero base line, and is shown to result in

  17. Contribution of proton NMR relaxation to the investigation of ...

    Indian Academy of Sciences (India)

    Centro de Fisica da Materia Condensada (UL), Av. Prof. Gama Pinto 2, 1699 Lisboa Cedex, Portugal. IST (UTL), Av. Rovisco Pais, 1049-001 Lisboa, Portugal. *Author for correspondence. Abstract. We present in this work a review concerning wide frequency range T1 proton NMR relaxation studies performed in compounds ...

  18. β -detected NMR spin relaxation in a thin film heterostructure of ferromagnetic EuO

    Science.gov (United States)

    MacFarlane, W. A.; Song, Q.; Ingle, N. J. C.; Chow, K. H.; Egilmez, M.; Fan, I.; Hossain, M. D.; Kiefl, R. F.; Levy, C. D. P.; Morris, G. D.; Parolin, T. J.; Pearson, M. R.; Saadaoui, H.; Salman, Z.; Wang, D.

    2015-08-01

    We present β -detected NMR measurements of the spin-lattice relaxation of +8Li implanted into an epitaxial heterostructure based on a 100 nm thick film of ferromagnetic (FM) EuO as a function of temperature through its FM transition. In the FM state, the spin-lattice relaxation rate follows the same temperature dependence, determined by magnon scattering mechanisms, observed in the bulk by 153Eu NMR, but above 40 K, the signal is wiped out. We also find that +8Li stopped in material adjacent to the magnetic layer exhibits spin relaxation related to the critical slowing of the Eu spins. A particularly strong relaxation in the Au overlayer suggests an unusual strong nonlocal coupling mechanism to 8Li in the metal.

  19. Automated NMR relaxation dispersion data analysis using NESSY

    Directory of Open Access Journals (Sweden)

    Gooley Paul R

    2011-10-01

    Full Text Available Abstract Background Proteins are dynamic molecules with motions ranging from picoseconds to longer than seconds. Many protein functions, however, appear to occur on the micro to millisecond timescale and therefore there has been intense research of the importance of these motions in catalysis and molecular interactions. Nuclear Magnetic Resonance (NMR relaxation dispersion experiments are used to measure motion of discrete nuclei within the micro to millisecond timescale. Information about conformational/chemical exchange, populations of exchanging states and chemical shift differences are extracted from these experiments. To ensure these parameters are correctly extracted, accurate and careful analysis of these experiments is necessary. Results The software introduced in this article is designed for the automatic analysis of relaxation dispersion data and the extraction of the parameters mentioned above. It is written in Python for multi platform use and highest performance. Experimental data can be fitted to different models using the Levenberg-Marquardt minimization algorithm and different statistical tests can be used to select the best model. To demonstrate the functionality of this program, synthetic data as well as NMR data were analyzed. Analysis of these data including the generation of plots and color coded structures can be performed with minimal user intervention and using standard procedures that are included in the program. Conclusions NESSY is easy to use open source software to analyze NMR relaxation data. The robustness and standard procedures are demonstrated in this article.

  20. Properties of the manganese(II) binding site in ternary complexes of Mnter dot ADP and Mnter dot ATP with chloroplast coupling factor 1: Magnetic field dependence of solvent sup 1 H and sup 2 H NMR relaxation rates

    Energy Technology Data Exchange (ETDEWEB)

    Haddy, A.E.; Frasch, W.D.; Sharp, R.R. (Univ. of Michigan, Ann Arbor (USA))

    1989-05-02

    The influence of the binding of ADP and ATP on the high-affinity Mn(II) binding site of chloroplast coupling factor 1 (CF{sub 1}) was studied by analysis of field-dependent solvent proton and deuteron spin-lattice relaxation data. In order to characterize metal-nucleotide complexes of CF{sub 1} under conditions similar to those of the NMR experiments, the enzyme was analyzed for bound nucleotides and Mn(II) after incubation with AdN and MnCl{sub 2} and removal of labile ligands by extensive gel filtration chromatography. In the field-dependent NMR experiments, the Mn(II) binding site of CF{sub 1} was studied for three mole ratios of added Mn(II) to CF{sub 1}, 0.5, 1.0, and 1.5, in the presence of an excess of either ADP or ATP. The results were extrapolated to zero Mn(II) concentration to characterize the environment of the first Mn(II) binding site of Cf{sub 1}. In the presence of both adenine nucleotides, pronounced changes in the Mn(II) environment relative to that in Mn(II)-CF{sub 1} were evident; the local relaxation rate maxima were more pronounced and shifted to higher field strengths, and the relaxation rate per bound Mn(II) increased at all field strengths. Analysis of the data revealed that the number of exchangeable water molecules liganded to bound Mn(II) increased from one in the binary Mn(II)-CF{sub 1} complex to three and two in the ternary Mn(II)-ADP-CF{sub 1} and Mn(II)-ATP-CF{sub 1} complexes, respectively; these results suggest that a water ligand to bound Mn(II) in the Mn(II)-ADP-CF{sub 1} complex is replaced by the {gamma}-phosphate of ATP in the Mn(II)-ATP-CF{sub 1} complex. A binding model is presented to account for these observations.

  1. Dynamic properties of water in swollen hypercrosslinked polystyrenes, according to NMR relaxation and diffusion data

    Science.gov (United States)

    Babushkina, T. A.; Novikov, V. V.; Koretskaya, V. S.; Klimova, T. P.; Tsyurupa, M. P.; Blinnikova, Z. K.; Davankov, V. A.

    2015-08-01

    Dynamic properties of the water filling of the internal space of hypercrosslinked polystyrene networks are studied via NMR cryoporometry, spin relaxation, and diffusometry. It is found that in the temperature range of 210-240 K, where frozen water melts in the thin pores of the polymer and seems to become a viscous liquid, the main type of molecular motion is rotational and the main relaxation mechanism ( T 1) is spin-rotational interaction between protons. Above 240 K, dipole-dipole coupling is shown to become the main relaxation mechanism T 1. In the temperature range of 210-295 K, the hypercrosslinked polystyrene matrix displays a set of water spin-spin relaxation rates that suggest the structure has cavities (pores) with different sizes and different conditions for the molecular motion of water. We conclude that the shorter (tens of ms) relaxation times T 1 and T 2 of water in the polymer at the temperature above 265 K compared to free water (2-3 s) indicate features of the dynamic characteristics of water in hydrophobic pores (or thin films on the surfaces of granules) that differ from those of free water. The tortuosity coefficients of the water's path of molecular motion are found to change in a symbate manner with a change in the water content in the hypercrosslinked network.

  2. Solution conformation and dynamics of a tetrasaccharide related to the Lewis{sup X} antigen deduced by NMR relaxation measurements

    Energy Technology Data Exchange (ETDEWEB)

    Poveda, Ana [Universidad Autonoma de Madrid, Servicio Interdepartamental de Investigacion (Spain); Asensio, Juan Luis; Martin-Pastor, Manuel; Jimenez-Barbero, Jesus [Instituto de Quimica Organica, CSIC, Grupo de Carbohidratos (Spain)

    1997-07-15

    {sup 1}H-NMR cross-relaxation rates and nonselective longitudinal relaxation times have been obtained at two magnetic fields (7.0 and 11.8 T) and at a variety of temperatures for the branched tetrasaccharide methyl 3-O-{alpha}-N-acetyl-galactosaminyl-{beta}-galactopyranosyl-(1{sup {yields}}4)[3-O-{alpha}-fucosyl] -glucopyranoside (1), an inhibitor of astrocyte growth. In addition, {sup 13}C-NMR relaxation data have also been recorded at both fields. The {sup 1}H-NMR relaxation data have been interpreted using different motional models to obtain proton-proton correlation times. The results indicate that the GalNAc and Fuc rings display more extensive local motion than the two inner Glc and Gal moieties, since those present significantly shorter local correlation times. The{sup 13}C-NMR relaxation parameters have been interpreted in terms of the Lipari-Szabo model-free approach. Thus, order parameters and internal motion correlation times have been deduced. As obtained for the{sup 1}H-NMR relaxation data, the two outer residues possess smaller order parameters than the two inner rings. Internal correlation times are in the order of 100 ps. The hydroxymethyl groups have also different behaviour,with the exocyclic carbon on the glucopyranoside unit showing the highestS{sup 2}. Molecular dynamics simulations using a solvated system have also been performed and internal motion correlation functions have been deduced from these calculations. Order parameters and interproton distances have been compared to those inferred from the NMR measurements. The obtained results are in fair agreement with the experimental data.

  3. Low-frequency spin dynamics and NMR spin-lattice relaxation in antiferromagnetic rings

    Science.gov (United States)

    Itou, T.; Sagane, T.; Oyamada, A.; Maegawa, S.; Igarashi, S.; Yukawa, Y.

    2011-01-01

    We develop a general theory of the spin dynamics of Heisenberg antiferromagnetic rings (HAFRs) that explains the mechanism of NMR spin-lattice relaxation at low temperatures. In HAFRs, the imaginary parts of the q-summed dynamic spin susceptibilities parallel and perpendicular to an applied static field, χsum∥″(ω) and χsum⊥″(ω), are composed of the sum of many slightly broadened δ-functional modes at many frequencies. The NMR relaxation is caused by the quasielastic mode in χsum∥″(ω) at around zero frequency. This quasielastic mode is characterized by two physical quantities, intensity P0∥ and frequency width Γ0∥. Although P0∥ has to date been assumed to be identical to the uniform static susceptibility, we point out that the two quantities are not identical. Without making this unreliable assumption for P0∥, we demonstrate experimentally how P0∥ and Γ0∥ behave, by analyzing the NMR relaxation rates of two different nuclei, H1 and C13, in a real HAFR. This analysis is more rigorous and thus can be used to estimate Γ0∥ and P0∥ more precisely than previously possible. We find that the temperature dependence of P0∥ exhibits activation-type behavior reflecting the first excitation gap. We also find that Γ0∥ decreases monotonically on cooling but saturates to a nonzero value at zero temperature. This strongly suggests that Γ0∥ is dominated not only by the electron-phonon interactions but also by internanomagnet dipole interactions, which have been neglected to date.

  4. Weak self-association of human growth hormone investigated by nitrogen-15 NMR relaxation.

    Science.gov (United States)

    Jensen, Malene Ringkjøbing; Kristensen, Søren M; Keeler, Camille; Christensen, Hans E M; Hodsdon, Michael E; Led, Jens J

    2008-10-01

    The self-association of human growth hormone(hGH) was investigated using 15N NMR relaxation.The investigation relies on the 15N R1 and R2 relaxation rates and the heteronuclear{1H}-15N NOEs of the backbone amide groups at multiple protein concentrations. It is shown that the rotational correlation time of hGH in solution depends strongly on its concentration, indicating a significant degree of self-association.The self-association is reversible and the monomers in the aggregates are noncovalently linked. Extrapolation of the relaxation data to zero concentration predicts a correlation time of 13.4 ns and a rotational diffusion anisotropy of 1.26 for monomeric hGH, in agreement with the rotational diffusion properties estimated by hydrodynamic calculations. Moreover, the extrapolation allows characterization of the backbone dynamics of monomeric hGH without interference from self-association phenomena, and it is found that hGH is considerably more flexible than originally thought. A concerted least-squares analysis of the 15N relaxations and their concentration dependence reveals that the self-association goes beyond a simple monomer-dimer equilibrium, and that tetramers or other multimeric states co-exist in fast exchange with the monomeric and dimeric hGH at sub-millimolar concentrations. Small changes in the 1H and 15N amide chemical shifts suggest that a region around the C-terminus is involved in the oligomer formation.

  5. The eigenmode perspective of NMR spin relaxation in proteins

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, Yury E., E-mail: shapiro@nmrsgi4.ls.biu.ac.il, E-mail: eva.meirovitch@biu.ac.il; Meirovitch, Eva, E-mail: shapiro@nmrsgi4.ls.biu.ac.il, E-mail: eva.meirovitch@biu.ac.il [The Mina and Everard Goodman Faculty of Life Sciences, Bar-Ilan University, Ramat-Gan 52900-02 (Israel)

    2013-12-14

    We developed in recent years the two-body (protein and probe) coupled-rotator slowly relaxing local structure (SRLS) approach for elucidating protein dynamics from NMR spin relaxation. So far we used as descriptors the set of physical parameters that enter the SRLS model. They include the global (protein-related) diffusion tensor, D{sub 1}, the local (probe-related) diffusion tensor, D{sub 2}, and the local coupling/ordering potential, u. As common in analyzes based on mesoscopic dynamic models, these parameters have been determined with data-fitting techniques. In this study, we describe structural dynamics in terms of the eigenmodes comprising the SRLS time correlation functions (TCFs) generated by using the best-fit parameters as input to the Smoluchowski equation. An eigenmode is a weighted exponential with decay constant given by an eigenvalue of the Smoluchowski operator, and weighting factor determined by the corresponding eigenvector. Obviously, both quantities depend on the SRLS parameters as determined by the SRLS model. Unlike the set of best-fit parameters, the eigenmodes represent patterns of motion of the probe-protein system. The following new information is obtained for the typical probe, the {sup 15}N−{sup 1}H bond. Two eigenmodes, associated with the protein and the probe, dominate when the time scale separation is large (i.e., D{sub 2} ≫ D{sub 1}), the tensorial properties are simple, and the local potential is either very strong or very weak. When the potential exceeds these limits while the remaining conditions are preserved, new eigenmodes arise. The multi-exponentiality of the TCFs is associated in this case with the restricted nature of the local motion. When the time scale separation is no longer large, the rotational degrees of freedom of the protein and the probe become statistically dependent (coupled dynamically). The multi-exponentiality of the TCFs is associated in this case with the restricted nature of both the local and the

  6. The eigenmode perspective of NMR spin relaxation in proteins

    Science.gov (United States)

    Shapiro, Yury E.; Meirovitch, Eva

    2013-12-01

    We developed in recent years the two-body (protein and probe) coupled-rotator slowly relaxing local structure (SRLS) approach for elucidating protein dynamics from NMR spin relaxation. So far we used as descriptors the set of physical parameters that enter the SRLS model. They include the global (protein-related) diffusion tensor, D1, the local (probe-related) diffusion tensor, D2, and the local coupling/ordering potential, u. As common in analyzes based on mesoscopic dynamic models, these parameters have been determined with data-fitting techniques. In this study, we describe structural dynamics in terms of the eigenmodes comprising the SRLS time correlation functions (TCFs) generated by using the best-fit parameters as input to the Smoluchowski equation. An eigenmode is a weighted exponential with decay constant given by an eigenvalue of the Smoluchowski operator, and weighting factor determined by the corresponding eigenvector. Obviously, both quantities depend on the SRLS parameters as determined by the SRLS model. Unlike the set of best-fit parameters, the eigenmodes represent patterns of motion of the probe-protein system. The following new information is obtained for the typical probe, the 15N-1H bond. Two eigenmodes, associated with the protein and the probe, dominate when the time scale separation is large (i.e., D2 ≫ D1), the tensorial properties are simple, and the local potential is either very strong or very weak. When the potential exceeds these limits while the remaining conditions are preserved, new eigenmodes arise. The multi-exponentiality of the TCFs is associated in this case with the restricted nature of the local motion. When the time scale separation is no longer large, the rotational degrees of freedom of the protein and the probe become statistically dependent (coupled dynamically). The multi-exponentiality of the TCFs is associated in this case with the restricted nature of both the local and the global motion. The effects of local

  7. Active site dynamics in NADH oxidase from Thermus thermophilus studied by NMR spin relaxation

    International Nuclear Information System (INIS)

    Miletti, Teresa; Farber, Patrick J.; Mittermaier, Anthony

    2011-01-01

    We have characterized the backbone dynamics of NADH oxidase from Thermus thermophilus (NOX) using a recently-developed suite of NMR experiments designed to isolate exchange broadening, together with 15 N R 1 , R 1ρ , and { 1 H}- 15 N steady-state NOE relaxation measurements performed at 11.7 and 18.8 T. NOX is a 54 kDa homodimeric enzyme that belongs to a family of structurally homologous flavin reductases and nitroreductases with many potential biotechnology applications. Prior studies have suggested that flexibility is involved in the catalytic mechanism of the enzyme. The active site residue W47 was previously identified as being particularly important, as its level of solvent exposure correlates with enzyme activity, and it was observed to undergo “gating” motions in computer simulations. The NMR data are consistent with these findings. Signals from W47 are dynamically broadened beyond detection and several other residues in the active site have significant R ex contributions to transverse relaxation rates. In addition, the backbone of S193, whose side chain hydroxyl proton hydrogen bonds directly with the FMN cofactor, exhibits extensive mobility on the ns–ps timescale. We hypothesize that these motions may facilitate structural rearrangements of the active site that allow NOX to accept both FMN and FAD as cofactors.

  8. Histidine side-chain dynamics and protonation monitored by {sup 13}C CPMG NMR relaxation dispersion

    Energy Technology Data Exchange (ETDEWEB)

    Hass, Mathias A. S. [Leiden University, Institute of Chemistry (Netherlands); Yilmaz, Ali [University of Copenhagen, Department of Medicinal Chemistry, Faculty of Pharmaceutical Sciences (Denmark); Christensen, Hans E. M. [Technical University of Denmark, Department of Chemistry (Denmark); Led, Jens J. [University of Copenhagen, Department of Chemistry (Denmark)], E-mail: led@kiku.dk

    2009-08-15

    The use of {sup 13}C NMR relaxation dispersion experiments to monitor micro-millisecond fluctuations in the protonation states of histidine residues in proteins is investigated. To illustrate the approach, measurements on three specifically {sup 13}C labeled histidine residues in plastocyanin (PCu) from Anabaena variabilis (A.v.) are presented. Significant Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion is observed for {sup 13}C{sup {epsilon}}{sup 1} nuclei in the histidine imidazole rings of A.v. PCu. The chemical shift changes obtained from the CPMG dispersion data are in good agreement with those obtained from the chemical shift titration experiments, and the CPMG derived exchange rates agree with those obtained previously from {sup 15}N backbone relaxation measurements. Compared to measurements of backbone nuclei, {sup 13}C{sup {epsilon}}{sup 1} dispersion provides a more direct method to monitor interchanging protonation states or other kinds of conformational changes of histidine side chains or their environment. Advantages and shortcomings of using the {sup 13}C{sup {epsilon}}{sup 1} dispersion experiments in combination with chemical shift titration experiments to obtain information on exchange dynamics of the histidine side chains are discussed.

  9. An investigation into the effects of pore connectivity on T2 NMR relaxation

    Science.gov (United States)

    Ghomeshi, Shahin; Kryuchkov, Sergey; Kantzas, Apostolos

    2018-04-01

    Nuclear Magnetic Resonance (NMR) is a powerful technique used to characterize fluids and flow in porous media. The NMR relaxation curves are closely related to pore geometry, and the inversion of the NMR relaxometry data is known to give useful information with regards to pore size distribution (PSD) through the relative amplitudes of the fluids stored in the small and large pores. While this information is crucial, the main challenge for the successful use of the NMR measurements is the proper interpretation of the measured signals. Natural porous media patterns consist of complex pore structures with many interconnected or "coupled" regions, as well as isolated pores. This connectivity along the throats changes the relaxation distribution and in order to properly interpret this data, a thorough understanding of the effects of pore connectivity on the NMR relaxation distribution is warranted. In this paper we address two main points. The first pertains to the fact that there is a discrepancy between the relaxation distribution obtained from experiments, and the ones obtained from solving the mathematical models of diffusion process in the digitized images of the pore space. There are several reasons that may attribute to this such as the lack of a proper incorporation of surface roughness into the model. However, here we are more interested in the effects of pore connectivity and to understand why the typical NMR relaxation distribution obtained from experiments are wider, while the numerical simulations predict that a wider NMR relaxation distribution may indicate poor connectivity. Secondly, by not taking into account the pore coupling effects, from our experience in interpreting the data, we tend to underestimate the pore volume of small pores and overestimate the amplitudes in the large pores. The role of pore coupling becomes even more prominent in rocks with small pore sizes such as for example in shales, clay in sandstones, and in the microstructures of

  10. Tunneling splitting of magnetic levels in Fe8 detected by 1H NMR cross relaxation

    OpenAIRE

    Furukawa, Y.; Aizawa, K.; Kumagai, K.; Ullu, R.; Lascialfari, A.; Borsa, F.

    2003-01-01

    Measurements of proton NMR and the spin lattice relaxation rate 1/T1 in the octanuclear iron (III) cluster [Fe8(N3C6H15)6O2(OH)12][Br8 9H2O], in short Fe8, have been performed at 1.5 K in a powder sample aligned along the main anisotropy z axis, as a function of a transverse magnetic field (i.e., perpendicular to the main easy axis z). A big enhancement of 1/T1 is observed over a wide range of fields (2.5-5 T), which can be attributed to the tunneling dynamics; in fact, when the tunneling spl...

  11. Measurement and Characterization of Hydrogen-Deuterium Exchange Chemistry Using Relaxation Dispersion NMR Spectroscopy.

    Science.gov (United States)

    Khirich, Gennady; Holliday, Michael J; Lin, Jasper C; Nandy, Aditya

    2018-03-01

    One-dimensional heteronuclear relaxation dispersion NMR spectroscopy at 13 C natural abundance successfully characterized the dynamics of the hydrogen-deuterium exchange reaction occurring at the N ε position in l-arginine by monitoring C δ in varying amounts of D 2 O. A small equilibrium isotope effect was observed and quantified, corresponding to ΔG = -0.14 kcal mol -1 . A bimolecular rate constant of k D = 5.1 × 10 9 s -1 M -1 was determined from the pH*-dependence of k ex (where pH* is the direct electrode reading of pH in 10% D 2 O and k ex is the nuclear spin exchange rate constant), consistent with diffusion-controlled kinetics. The measurement of ΔG serves to bridge the millisecond time scale lifetimes of the detectable positively charged arginine species with the nanosecond time scale lifetime of the nonobservable low-populated neutral arginine intermediate species, thus allowing for characterization of the equilibrium lifetimes of the various arginine species in solution as a function of fractional solvent deuterium content. Despite the system being in fast exchange on the chemical shift time scale, the magnitude of the secondary isotope shift due to the exchange reaction at N ε was accurately measured to be 0.12 ppm directly from curve-fitting D 2 O-dependent dispersion data collected at a single static field strength. These results indicate that relaxation dispersion NMR spectroscopy is a robust and general method for studying base-catalyzed hydrogen-deuterium exchange chemistry at equilibrium.

  12. NMR spin relaxation in proteins: The patterns of motion that dissipate power to the bath

    Science.gov (United States)

    Shapiro, Yury E.; Meirovitch, Eva

    2014-04-01

    We developed in recent years the two-body coupled-rotator slowly relaxing local structure (SRLS) approach for the analysis of NMR relaxation in proteins. The two bodies/rotators are the protein (diffusion tensor D1) and the spin-bearing probe, e.g., the 15N-1H bond (diffusion tensor, D2), coupled by a local potential (u). A Smoluchowski equation is solved to yield the generic time correlation functions (TCFs), which are sums of weighted exponentials (eigenmodes). By Fourier transformation one obtains the generic spectral density functions (SDFs) which underlie the experimental relaxation parameters. The typical paradigm is to characterize structural dynamics in terms of the best-fit values of D1, D2, and u. Additional approaches we pursued employ the SRLS TCFs, SDFs, or eigenmodes as descriptors. In this study we develop yet another perspective. We consider the SDF as function of the angular velocity associated with the fluctuating fields underlying NMR relaxation. A parameter called j-fraction, which represents the relative contribution of eigenmode, i, to a given value of the SDF function at a specific frequency, ω, is defined. j-fraction profiles of the dominant eigenmodes are derived for 0 ≤ ω ≤ 1012 rad/s. They reveal which patterns of motion actuate power dissipation at given ω-values, what are their rates, and what is their relative contribution. Simulations are carried out to determine the effect of timescale separation, D1/D2, axial potential strength, and local diffusion axiality. For D1/D2 ≤ 0.01 and strong local potential of 15 kBT, power is dissipated by global diffusion, renormalized (by the strong potential) local diffusion, and probe diffusion on the surface of a cone (to be called cone diffusion). For D1/D2 = 0.1, power is dissipated by mixed eigenmodes largely of a global-diffusion-type or cone-diffusion-type, and a nearly bare renormalized-local-diffusion eigenmode. For D1/D2 > 0.1, most eigenmodes are of a mixed type. The analysis is

  13. Tunneling splitting of magnetic levels in Fe8 detected by 1H NMR cross relaxation

    Science.gov (United States)

    Furukawa, Y.; Aizawa, K.; Kumagai, K.; Ullu, R.; Lascialfari, A.; Borsa, F.

    2003-05-01

    Measurements of proton NMR and the spin lattice relaxation rate 1/T1 in the octanuclear iron (III) cluster [Fe8(N3C6H15)6O2(OH)12]ṡ[Br8ṡ9H2O], in short Fe8, have been performed at 1.5 K in a powder sample aligned along the main anisotropy z axis, as a function of a transverse magnetic field (i.e., perpendicular to the main easy axis z). A big enhancement of 1/T1 is observed over a wide range of fields (2.5-5 T), which can be attributed to the tunneling dynamics; in fact, when the tunneling splitting of the pairwise degenerate m=±10 states of the Fe8 molecule becomes equal to the proton Larmor frequency a very effective spin lattice relaxation channel for the nuclei is opened. The experimental results are explained satisfactorily by considering the distribution of tunneling splitting resulting from the distribution of the angles in the hard xy plane for the aligned powder, and the results of the direct diagonalization of the model Hamiltonian.

  14. Wettability of quartz surface as observed by NMR transverse relaxation time (T2)

    DEFF Research Database (Denmark)

    Alam, Mohammad Monzurul; Katika, Konstantina; Fabricius, Ida Lykke

    the wettability property of quartz surface by using Nuclear Magnetic Resonance (NMR) method. The principle of this method is that protons in water relax faster when it comes close to solid surface. We observed that quart is highly water wet. A layer of water (bound water) forms on the quartz surface when...

  15. The inverted chevron plot measured by NMR relaxation reveals a native-like unfolding intermediate in acyl-CoA binding protein

    DEFF Research Database (Denmark)

    Teilum, Kaare; Poulsen, F. M.; Akke, M.

    2006-01-01

    under conditions favoring folding, for which the folding rate constant (k f) dominates the relaxation in stopped-flow kinetic measurements. Conversely, k f was determined under conditions favoring unfolding, for which k u dominates stopped-flow data. The rates determined by NMR therefore complement...

  16. Optimization of CPMG sequences to measure NMR transverse relaxation time T2 in borehole applications

    Directory of Open Access Journals (Sweden)

    M. Ronczka

    2012-11-01

    Full Text Available Nuclear Magnetic Resonance (NMR can provide key information such as porosity and permeability for hydrological characterization of geological material. In particular the NMR transverse relaxation time T2 is used to estimate permeability since it reflects a pore-size dependent relaxation process. The measurement sequence (CPMG usually consists of several thousands of electromagnetic pulses to densely record the relaxation process and to avoid relaxation processes that are due to diffusion. These pulses are equidistantly spaced by a time constant tE. In NMR borehole applications the use of CPMG sequences for measuring the transverse relaxation time T2 is limited due to requirements on energy consumption. For measuring T2, it is state-of-the-art to conduct at least two sequences with different echo spacings (tE for recording fast and slow relaxing processes that correspond to different pore-sizes. We focus on conducting only a single CPMG sequence and reducing the amount of energy while obtaining both slow and fast decaying components and minimizing the influence of relaxation due to diffusion. Therefore, we tested the usage of CPMG sequences with an increasing tE and a decreasing number of pulses. A synthetic study as well as laboratory measurements on samples of glass beads and granulate material of different grain size spectra were conducted to evaluate the effects of an increasing tE. We show that T2 distributions are broadened if the number of pulses is decreasing and the mean grain size is increasing, which is mostly an effect of a significantly shortened acquisition time. The shift of T2 distributions to small decay times as a function of tE and the mean grain size distribution is observed. We found that it is possible to conduct CPMG sequences with an increased tE. According to the acquisition time and increasing influence of relaxation due to diffusion, the sequence parameters need to be chosen carefully to avoid misinterpretations.

  17. Joint numerical microscale simulations of multi-phase flow and NMR relaxation behaviour in porous media

    Science.gov (United States)

    Mohnke, O.; Ahrenholz, B.

    2011-12-01

    Nuclear Magnetic Resonance (NMR) is a useful tool for analyzing gas (methane) and fluids (water, oil) in rock formations in order to derive transport and storage properties such as pore-size distributions or relative permeability. Even though there is considerable NMR data available about hydraulic properties of rock formations, this information is only empirical. Thus, the aim of this paper is to present joint NMR and multi-phase flow simulations in micro-scale pore systems derived from micro-CT images to quantify relationships between NMR parameters and transport and storage properties of partially saturated rocks. Hereby, the NMR differential equations were implemented using an advection/diffusion lattice-Boltzmann method (LBM) where the flow field is computed by a coupled LBM CFD solver. The results of numerical imbibition and drainage experiments quantitatively agree with laboratory experiments with regard to frequently found peak shifts and bimodal NMR decay time distributions related to residual water in films and corners as well as to fluids/gases trapped in large pores. This numerical framework enables one to quantitatively describe NMR surface and bulk relaxation processes, diffusive coupling along with the multi-phase flow properties of partially saturated porous systems. Furthermore, it is a viable alternative to the more time-consuming and less controllable laboratory experiments. Such virtual experimental setups can considerably help to benchmark and validate statistical network models to better understand hydraulic properties of partially saturated rocks by using experimentally obtained NMR data.

  18. Cross-Correlated Relaxation of Dipolar Coupling and Chemical-Shift Anisotropy in Magic-Angle Spinning R1ρ NMR Measurements: Application to Protein Backbone Dynamics Measurements

    Science.gov (United States)

    Kurauskas, Vilius; Weber, Emmanuelle; Hessel, Audrey; Ayala, Isabel; Marion, Dominique; Schanda, Paul

    2016-01-01

    Transverse relaxation rate measurements in MAS solid-state NMR provide information about molecular motions occurring on nanoseconds-to-milliseconds (ns-ms) time scales. The measurement of heteronuclear (13C, 15N) relaxation rate constants in the presence of a spin-lock radio-frequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins has been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely (i) the role of CSA/dipolar cross-correlated relaxation (CCR), and (ii) the impact of fast proton spin flips (i.e. proton spin diffusion and relaxation). We show that CSA/D CCR in R1ρ experiments is measurable, and that this cross-correlated relaxation rate constant depends on ns-ms motions, and can thus itself provide insight into dynamics. We find that proton spin-diffusion attenuates this cross-correlated relaxation, due to its decoupling effect on the doublet components. For measurements of dynamics, the use of R1ρ rate constants has practical advantages over the use of CCR rates, and the present manuscript reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation. PMID:27500976

  19. Solid-state NMR paramagnetic relaxation enhancement immersion depth studies in phospholipid bilayers

    KAUST Repository

    Chu, Shidong

    2010-11-01

    A new approach for determining the membrane immersion depth of a spin-labeled probe has been developed using paramagnetic relaxation enhancement (PRE) in solid-state NMR spectroscopy. A DOXYL spin label was placed at different sites of 1-palmitoyl-2-stearoyl-sn-glycero-3-phosphocholine (PSPC) phospholipid bilayers as paramagnetic moieties and the resulting enhancements of the longitudinal relaxation (T1) times of 31P nuclei on the surface of the bilayers were measured by a standard inversion recovery pulse sequence. The 31P NMR spin-lattice relaxation times decrease steadily as the DOXYL spin label moves closer to the surface as well as the concentration of the spin-labeled lipids increase. The enhanced relaxation vs. the position and concentration of spin-labels indicate that PRE induced by the DOXYL spin label are significant to determine longer distances over the whole range of the membrane depths. When these data were combined with estimated correlation times τc, the r-6-weighted, time-averaged distances between the spin-labels and the 31P nuclei on the membrane surface were estimated. The application of using this solid-state NMR PRE approach coupled with site-directed spin labeling (SDSL) may be a powerful method for measuring membrane protein immersion depth. © 2010 Elsevier Inc. All rights reserved.

  20. Molecular motions in thermotropic liquid crystals studied by NMR spin-lattice relaxation

    International Nuclear Information System (INIS)

    Zamar, R.C.; Gonzalez, C.E.; Mensio, O.

    1998-01-01

    Nuclear magnetic resonance relaxation experiments with field cycling techniques proved to be a valuable tool for studying molecular motions in liquid crystals, allowing a very broad Larmor frequency variation, sufficient to separate the cooperative motions from the liquid like molecular diffusion. In new experiments combining NMR field cycling with the Jeener-Broekaert order-transfer pulse sequence, it is possible to measure the dipolar order relaxation time (T 1D ), in addition to the conventional Zeeman relaxation time (T 1Z ) in a frequency range of several decades. When applying this technique to nematic thermotropic liquid crystals, T 1D showed to depend almost exclusively on the order fluctuation of the director mechanism in the whole frequency range. This unique characteristic of T 1D makes dipolar order relaxation experiments specially useful for studying the frequency and temperature dependence of the spectral properties of the collective motions. (author)

  1. Side chain: backbone projections in aromatic and ASX residues from NMR cross-correlated relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Voegeli, Beat, E-mail: beat.voegeli@phys.chem.ethz.ch; Riek, Roland [Swiss Federal Institute of Technology, Laboratory of Physical Chemistry (Switzerland)

    2010-02-15

    The measurements of cross-correlated relaxation rates between H{sup N}-N and C{sup {beta}}-C{sup {gamma}} intraresidual and sequential dipolar interactions is demonstrated in ASN, ASP and aromatic residues. The experiment can be used for deuterated samples and no additional knowledge such as Karplus parametrizations is required for the analysis. The data constitutes a new type of information since no other method relates the C{sup {beta}}-C{sup {gamma}} bond to H{sup N}-N. Using this method the dominant populations of rotamer states of {chi}1 can be readily cross checked provided that {phi} or {psi} are known. In addition, dynamics on all timescales can be probed. As opposed to standard dynamics analysis of isolated bonds, the presented observables depend on relative dynamics with an interesting prospect to analyze correlated fluctuations of the two torsion angles {phi} or {psi} with {chi}1. Experimental rates are compared to single conformer and ensemble representations of GB3 and ubiquitin. In particular, it is found that the recently published ubiquitin ensemble 2k39 improves the agreement obtained for 1UBQ. In general, however, input data restricting ASX and aromatic side chains in structure calculation is sparse highlighting the need for new NMR observables.

  2. Side chain: backbone projections in aromatic and ASX residues from NMR cross-correlated relaxation.

    Science.gov (United States)

    Vögeli, Beat; Riek, Roland

    2010-02-01

    The measurements of cross-correlated relaxation rates between H(N)-N and C(beta)-C(gamma) intraresidual and sequential dipolar interactions is demonstrated in ASN, ASP and aromatic residues. The experiment can be used for deuterated samples and no additional knowledge such as Karplus parametrizations is required for the analysis. The data constitutes a new type of information since no other method relates the C(beta)-C(gamma) bond to H(N)-N. Using this method the dominant populations of rotamer states of chi 1 can be readily cross checked provided that phi or psi are known. In addition, dynamics on all timescales can be probed. As opposed to standard dynamics analysis of isolated bonds, the presented observables depend on relative dynamics with an interesting prospect to analyze correlated fluctuations of the two torsion angles phi or psi with chi 1. Experimental rates are compared to single conformer and ensemble representations of GB3 and ubiquitin. In particular, it is found that the recently published ubiquitin ensemble 2k39 improves the agreement obtained for 1UBQ. In general, however, input data restricting ASX and aromatic side chains in structure calculation is sparse highlighting the need for new NMR observables.

  3. Resonances in field-cycling NMR on molecular crystals. (reversible) Spin dynamics or (irreversible) relaxation?; Resonanzen in Field-Cycling-NMR an Molekuelkristallen. (reversible) Spindynamik oder (irreversible) Relaxation?

    Energy Technology Data Exchange (ETDEWEB)

    Tacke, Christian

    2015-07-01

    Multi spin systems with spin 1/2 nuclei and dipolar coupled quadrupolar nuclei can show so called ''quadrupolar dips''. There are two main reasons for this behavior: polarization transfer and relaxation. They look quite alike and without additional research cannot be differentiated easily in most cases. These two phenomena have quite different physical and theoretical backgrounds. For no or very slow dynamics, polarization transfer will take place, which is energy conserving inside the spin system. This effect can entirely be described using quantum mechanics on the spin system. Detailed knowledge about the crystallography is needed, because this affects the relevant hamiltonians directly. For systems with fast enough dynamics, relaxation takes over, and the energy flows from the spin system to the lattice; thus a more complex theoretical description is needed. This description has to include a dynamic model, usually in the form of a spectral density function. Both models should include detailed modelling of the complete spin system. A software library was developed to be able to model complex spin systems. It allows to simulate polarization transfer or relaxation effects. NMR measurements were performed on the protonic conductor K{sub 3}H(SO{sub 4}){sub 2}. A single crystal shows sharp quadrupolar dips at room temperature. Dynamics could be excluded using relaxation measurements and literature values. Thus, a polarization transfer analysis was used to describe those dips with good agreement. As a second system, imidazolium based molecular crystals were analyzed. The quadrupolar dips were expected to be caused by polarization transfer; this was carefully analyzed and found not to be true. A relaxation based analysis shows good agreement with the measured data in the high temperature area. It leverages a two step spectral density function, which indicates two distinct dynamic processes happening in this system.

  4. NMR relaxation investigation of the native corn starch structure with plasticizers

    Science.gov (United States)

    Cioica, N.; Fechete, R.; Cota, C.; Nagy, E. M.; David, L.; Cozar, O.

    2013-07-01

    The influences of starch, glycerol and water ratios on the structure, morphology and dynamics of starch polymer chains were investigated by NMR relaxation method. The 1H NMR CPMG echo decays and saturation recovery build-up curves were recorded and analyzed using the UPIN algorithm in order to get the spin-spin T2 and spin-lattice T1 relaxation times distributions. Significant differences between the CPMG curves were observed for native starch and the formulas in which water is added, whether these have or not glycerol in composition. For the formula which contains both plasticizers (water and glycerol), the CPMG curves decay slowly, indicating the presence of more mobile components.

  5. NMR measurement of oil shale magnetic relaxation at high magnetic field

    Science.gov (United States)

    Seymour, Joseph D.; Washburn, Kathryn E.; Kirkland, Catherine M.; Vogt, Sarah J.; Birdwell, Justin E.; Codd, Sarah L.

    2013-01-01

    Nuclear magnetic resonance (NMR) at low field is used extensively to provide porosity and pore-size distributions in reservoir rocks. For unconventional resources, due to low porosity and permeability of the samples, much of the signal exists at very short T2 relaxation times. In addition, the organic content of many shales will also produce signal at short relaxation times. Despite recent improvements in low-field technology, limitations still exist that make it difficult to account for all hydrogen-rich constituents in very tight rocks, such as shales. The short pulses and dead times along with stronger gradients available when using high-field NMR equipment provides a more complete measurement of hydrogen-bearing phases due to the ability to probe shorter T2 relaxation times (-5 sec) than can be examined using low-field equipment. Access to these shorter T2 times allows for confirmation of partially resolved peaks observed in low-field NMR data that have been attributed to solid organic phases in oil shales. High-field (300 MHz or 7 T) NMR measurements of spin-spin T2 and spin-lattice T1 magnetic relaxation of raw and artificially matured oil shales have potential to provide data complementary to low field (2 MHz or 0.05T) measurements. Measurements of high-field T2 and T1-T2 correlations are presented. These data can be interpreted in terms of organic matter phases and mineral-bound water known to be present in the shale samples, as confirmed by Fourier transform infrared spectroscopy, and show distributions of hydrogen-bearing phases present in the shales that are similar to those observed in low field measurements.

  6. Secondary relaxations in molecular glasses and polymers studied by 2D {sup 2}H NMR

    Energy Technology Data Exchange (ETDEWEB)

    Micko, Bjoern; Roessler, Ernst [Experimentalphysik II, Universitaet Bayreuth (Germany); Bingemann, Dieter [Department of Chemistry, Williams College, Williamstown, MA (United States)

    2008-07-01

    We present a two-dimensional (2D){sup 2}H exchange NMR study, attempting to clarify the geometry of the molecular motion involved in the secondary relaxation ({beta}-process) of three glass formers: PMMA, polybutadiene and a mixture of decaline and chlorobenzene. Stimulated echo measurements of the orientational correlation function circumscribe the temperature range, in which the {beta}-process is expected to dominate the spectra. In this range we will show by comparison with the spectra of o-terphenyl, which does not show a pronounced {beta}-process, that the {beta}-process is also clearly observable in the 2D NMR spectra below and somewhat above T{sub g}, until upon further heating the structural relaxation ({alpha}-process) enters the time window of the experiment and gives rise to a convergence of the spectra. Whilst the time constants for the studied systems (obtained from dielectric spectroscopy) are very similar on the reduced temperature scale T{sub g}/T, the dielectric relaxation strength differs for each system. In contrast the 2D NMR spectra turn out to be practically identical on the T{sub g}/T scale - which implies strong similarities concerning time scale and underlying geometry of the motion. To get further insight on the reorientation angles involved, simple motional models will be compared against the spectra.

  7. Calculated /sup 13/C NMR relaxation parameters for a restricted internal diffusion model. Application to methionine relaxation in dihydrofolate reductase

    Energy Technology Data Exchange (ETDEWEB)

    London, R.E.; Avitabile, J.

    1978-11-08

    /sup 13/C NMR relaxation parameters, T/sub 1/, T/sub 2/, and NOE, have been calculated based on a model assuming internal rotational diffusion subject to boundary conditions limiting the range of motion. Numerical results are presented as a function of diffusion coefficients D/sub 0/ and D/sub i/ and angle ..beta.. defined as in the free internal rotation calculation, as well as 2theta, the allowed range of motion. Relaxation times vary from values expected in the absence of internal motion to values slightly below those calculated using the free internal rotation model as the range is increased from 0 to 360/sup 0/. The discrepancy in the latter comparison arises from the boundary condition preventing diffusion from 180/sup +/ to 180/sup -/. Changes in T/sub 2/ are typically monotonic or nearly monotonic as a function of theta; however, changes in T/sub 1/ and NOE values are markedly nonmonotonic for D/sub 0/ approx. < 10/sup 6/ s/sup -1/ and for certain values of D/sub i/. Criteria for the applicability of the present calculations to the analysis of /sup 13/C NMR relaxation data obtained in studies of macromolecules undergoing restricted internal motion have been suggested. The results have been generalized to the case of multiple internal rotations, specifically for the problem of one free and one restricted diffusional process. In general, two types of rotation are not commutative. This model has been applied to relaxation data recently obtained for the methionine methyl resonances of specifically /sup 13/C-labeled dihydrofolate reductase obtained from S. faecium. The results indicate that the data can be readily explained by assuming rapid free internal diffusion about the S--CH/sub 3/ bond and restricted internal diffusion about the CH/sub 2/--S bond of methionine, such that for the broadest resonances the motional range is restricted to approx. 90/sup 0/ and for the sharpest resonances the range is >180/sup 0/. Restriction of the motion allows a

  8. NMR spin relaxation in proteins: The patterns of motion that dissipate power to the bath

    Energy Technology Data Exchange (ETDEWEB)

    Shapiro, Yury E., E-mail: eva.meirovitch@biu.ac.il, E-mail: yuryeshapiro@gmail.com; Meirovitch, Eva, E-mail: eva.meirovitch@biu.ac.il, E-mail: yuryeshapiro@gmail.com [The Mina and Everard Goodman Faculty of Life Sciences, Bar-Ilan University, Ramat-Gan 52900-02 (Israel)

    2014-04-21

    We developed in recent years the two-body coupled-rotator slowly relaxing local structure (SRLS) approach for the analysis of NMR relaxation in proteins. The two bodies/rotators are the protein (diffusion tensor D{sub 1}) and the spin-bearing probe, e.g., the {sup 15}N−{sup 1}H bond (diffusion tensor, D{sub 2}), coupled by a local potential (u). A Smoluchowski equation is solved to yield the generic time correlation functions (TCFs), which are sums of weighted exponentials (eigenmodes). By Fourier transformation one obtains the generic spectral density functions (SDFs) which underlie the experimental relaxation parameters. The typical paradigm is to characterize structural dynamics in terms of the best-fit values of D{sub 1}, D{sub 2}, and u. Additional approaches we pursued employ the SRLS TCFs, SDFs, or eigenmodes as descriptors. In this study we develop yet another perspective. We consider the SDF as function of the angular velocity associated with the fluctuating fields underlying NMR relaxation. A parameter called j-fraction, which represents the relative contribution of eigenmode, i, to a given value of the SDF function at a specific frequency, ω, is defined. j-fraction profiles of the dominant eigenmodes are derived for 0 ≤ ω ≤ 10{sup 12} rad/s. They reveal which patterns of motion actuate power dissipation at given ω-values, what are their rates, and what is their relative contribution. Simulations are carried out to determine the effect of timescale separation, D{sub 1}/D{sub 2}, axial potential strength, and local diffusion axiality. For D{sub 1}/D{sub 2} ≤ 0.01 and strong local potential of 15 k{sub B}T, power is dissipated by global diffusion, renormalized (by the strong potential) local diffusion, and probe diffusion on the surface of a cone (to be called cone diffusion). For D{sub 1}/D{sub 2} = 0.1, power is dissipated by mixed eigenmodes largely of a global-diffusion-type or cone-diffusion-type, and a nearly bare renormalized

  9. Wall relaxation rates for an optically pumped NA vapor

    International Nuclear Information System (INIS)

    Swenson, D.R.; Anderson, L.W.

    1986-01-01

    The wall relaxation rates for an optically pumped Na vapor have been measured for a variety of wall surfaces. We find that fluorocarbon rubber (Fluorel, Viton) and organosilicones (silicone rubber, dry film) at a temperature of 250 C have respectively relaxation rates that correspond on the average to 10 to 15 and 200 to 500 bounces before depolarization occurs. 7 refs., 3 figs

  10. Constraints on relaxation rates for N-level quantum systems

    International Nuclear Information System (INIS)

    Schirmer, S.G.; Solomon, A.I.

    2004-01-01

    We study the constraints imposed on the population and phase relaxation rates by the physical requirement of completely positive evolution for open N-level systems. The Lindblad operators that govern the evolution of the system are expressed in terms of observable relaxation rates, explicit formulas for the decoherence rates due to population relaxation are derived, and it is shown that there are additional, nontrivial constraints on the pure dephasing rates for N>2. Explicit, experimentally testable inequality constraints for the decoherence rates are derived for three- and four-level systems, and the implications of the results are discussed for generic ladder, Λ, and V systems and transitions between degenerate energy levels

  11. NMR water-proton spin-lattice relaxation time of human red blood cells and red blood cell suspensions

    International Nuclear Information System (INIS)

    Sullivan, S.G.; Rosenthal, J.S.; Winston, A.; Stern, A.

    1988-01-01

    NMR water-proton spin-lattice relaxation times were studied as probes of water structure in human red blood cells and red blood cell suspensions. Normal saline had a relaxation time of about 3000 ms while packed red blood cells had a relaxation time of about 500 ms. The relaxation time of a red blood cell suspension at 50% hematocrit was about 750 ms showing that surface charges and polar groups of the red cell membrane effectively structure extracellular water. Incubation of red cells in hypotonic saline increases relaxation time whereas hypertonic saline decreases relaxation time. Relaxation times varied independently of mean corpuscular volume and mean corpuscular hemoglobin concentration in a sample population. Studies with lysates and resealed membrane ghosts show that hemoglobin is very effective in lowering water-proton relaxation time whereas resealed membrane ghosts in the absence of hemoglobin are less effective than intact red cells. 9 refs.; 3 figs.; 1 table

  12. Microscopic insights into the NMR relaxation based protein conformational entropy meter

    Science.gov (United States)

    Kasinath, Vignesh; Sharp, Kim A.; Wand, A. Joshua

    2013-01-01

    Conformational entropy is a potentially important thermodynamic parameter contributing to protein function. Quantitative measures of conformational entropy are necessary for an understanding of its role but have been difficult to obtain. An empirical method that utilizes changes in conformational dynamics as a proxy for changes in conformational entropy has recently been introduced. Here we probe the microscopic origins of the link between conformational dynamics and conformational entropy using molecular dynamics simulations. Simulation of seven pro! teins gave an excellent correlation with measures of side-chain motion derived from NMR relaxation. The simulations show that the motion of methyl-bearing side-chains are sufficiently coupled to that of other side chains to serve as excellent reporters of the overall side-chain conformational entropy. These results tend to validate the use of experimentally accessible measures of methyl motion - the NMR-derived generalized order parameters - as a proxy from which to derive changes in protein conformational entropy. PMID:24007504

  13. Relaxation time T/sub 1/ and bound water fraction of muscle by NMR imager

    Energy Technology Data Exchange (ETDEWEB)

    Fukuda, N.; Ikehira, H.; Yamane, T.; Tateno, Y.; Torii, S.; Matsumura, K.

    1986-05-01

    In order to establish the efficacy of NMR-CT in the diagnostic investigation of muscle disorders, proton NMR-CT imaging was performed and muscle longitudinal relaxation (T1) times were measured in 20 Duchenne muscular dystrophy (DMD) patients and normal controls (NC). In addition, the bound water fraction (BWF) was calculated from the measured T1 value in appropriate cases. Results show that in DMD muscle T1 values were above normal in the early clinical stages, declined rapidly with progress of the disease, and reached the same low level as the subcutaneous fat. This decrease of T1 values was not uniform for all muscles, being most prominent in gluteus maximus and least in sartorius and gracilis. In NC muscle BWF increased with maturation under the age of 10 years, and became fixed beyond that. In the early stages of DMD, BWF was below normal.

  14. Study of relaxation times of nanocomposites of starch/montmorillonite employing low field NMR

    International Nuclear Information System (INIS)

    Brito, Luciana M.; Tavares, Maria Ines B.

    2011-01-01

    Due to its various applications and features, especially in therapies for controlled release of pharmaceuticals, polymers are among the most widely used excipients in pharmaceutical technology. One of the most promising nanocomposites is formed from organic polymer and inorganic clay minerals. Nanocomposites of starch/montmorillonite were prepared employing solution intercalation and characterized by proton spin-lattice relaxation time, through NMR relaxometry. The characterization of nanocomposites was done by X-ray diffraction and by nuclear magnetic resonance. The results showed that nanostructured films were obtained by intercalation from solution. Furthermore, the use of low field NMR, T1H, provided more precise information about the movement of materials, being complementary to the results obtained by X-ray diffraction. (author)

  15. Requirements on paramagnetic relaxation enhancement data for membrane protein structure determination by NMR.

    Science.gov (United States)

    Gottstein, Daniel; Reckel, Sina; Dötsch, Volker; Güntert, Peter

    2012-06-06

    Nuclear magnetic resonance (NMR) structure calculations of the α-helical integral membrane proteins DsbB, GlpG, and halorhodopsin show that distance restraints from paramagnetic relaxation enhancement (PRE) can provide sufficient structural information to determine their structure with an accuracy of about 1.5 Å in the absence of other long-range conformational restraints. Our systematic study with simulated NMR data shows that about one spin label per transmembrane helix is necessary for obtaining enough PRE distance restraints to exclude wrong topologies, such as pseudo mirror images, if only limited other NMR restraints are available. Consequently, an experimentally realistic amount of PRE data enables α-helical membrane protein structure determinations that would not be feasible with the very limited amount of conventional NOESY data normally available for these systems. These findings are in line with our recent first de novo NMR structure determination of a heptahelical integral membrane protein, proteorhodopsin, that relied extensively on PRE data. Copyright © 2012 Elsevier Ltd. All rights reserved.

  16. Molecular interpretation of fluorescence solvent relaxation of Patman and 2H NMR experiments in phosphatidylcholine bilayers

    Czech Academy of Sciences Publication Activity Database

    Olžyńska, Agnieszka; Zań, Anna; Jurkiewicz, Piotr; Sýkora, Jan; Gröbner, G.; Langner, M.; Hof, Martin

    2007-01-01

    Roč. 147, č. 2 (2007), s. 69-77 ISSN 0009-3084 R&D Projects: GA AV ČR IAA400400503; GA ČR GA203/05/2308; GA ČR(CZ) GD203/05/H001; GA MŠk(CZ) LC06063 Grant - others:Swedish Research Council(SE) 621-2001-3185 Institutional research plan: CEZ:AV0Z40400503 Source of funding: V - iné verejné zdroje Keywords : solvent relaxation * 2H NMR * Patman * lipid hydration * unsaturated hydrocarbon chain Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.396, year: 2007

  17. NMR longitudinal relaxation enhancement in metal halides by heteronuclear polarization exchange during magic-angle spinning

    Energy Technology Data Exchange (ETDEWEB)

    Shmyreva, Anna A. [Center for Magnetic Resonance, St. Petersburg State University, St. Petersburg 198504 (Russian Federation); Safdari, Majid; Furó, István [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Dvinskikh, Sergey V., E-mail: sergeid@kth.se [Department of Chemistry, KTH Royal Institute of Technology, SE-10044 Stockholm (Sweden); Laboratory of Biomolecular NMR, St. Petersburg State University, St. Petersburg 199034 (Russian Federation)

    2016-06-14

    Orders of magnitude decrease of {sup 207}Pb and {sup 199}Hg NMR longitudinal relaxation times T{sub 1} upon magic-angle-spinning (MAS) are observed and systematically investigated in solid lead and mercury halides MeX{sub 2} (Me = Pb, Hg and X = Cl, Br, I). In lead(II) halides, the most dramatic decrease of T{sub 1} relative to that in a static sample is in PbI{sub 2}, while it is smaller but still significant in PbBr{sub 2}, and not detectable in PbCl{sub 2}. The effect is magnetic-field dependent but independent of the spinning speed in the range 200–15 000 Hz. The observed relaxation enhancement is explained by laboratory-frame heteronuclear polarization exchange due to crossing between energy levels of spin-1/2 metal nuclei and adjacent quadrupolar-spin halogen nuclei. The enhancement effect is also present in lead-containing organometal halide perovskites. Our results demonstrate that in affected samples, it is the relaxation data recorded under non-spinning conditions that characterize the local properties at the metal sites. A practical advantage of fast relaxation at slow MAS is that spectral shapes with orientational chemical shift anisotropy information well retained can be acquired within a shorter experimental time.

  18. Magnetization and 13C NMR spin-lattice relaxation of nanodiamond powder

    Energy Technology Data Exchange (ETDEWEB)

    Levin, E.M.; Fang, X.W.; Bud' ko, S.L.; Straszheim, W.E.; McCallum, R.W.; Schmidt-Rohr, K.

    2008-02-15

    The bulk magnetization at temperatures of 1.8-400 K and in magnetic fields up to 70 kOe, the ambient temperature {sup 13}C NMR spin-lattice relaxation, T{sub 1,c}, and the elemental composition of three nanodiamond powder samples have been studied. The total magnetization of nanodiamond can be explained in terms of contributions from (1) the diamagnetic effect of carbon, (2) the paramagnetic effect of unpaired electrons present in nanodiamond grains, and (3) ferromagnetic-like and (4) superparamagnetic contributions from Fe-containing particles detected in spatially resolved energy-dispersive spectroscopy. Contributions (1) and (2) are intrinsic to nanodiamond, while contributions (3) and (4) arise from impurities naturally present in detonation nanodiamond samples. {sup 13}C NMR T{sub 1,c} relaxation would be unaffected by the presence of the ferromagnetic particles with the bulk magnetization of {approx} 0.01 emu/g at 300 K. Thus, a reduction of T{sub 1,c} by 3 orders of magnitude compared to natural and synthetic microdiamonds confirms the presence of unpaired electrons in the nanodiamond grains. The spin concentration in nanodiamond powder corresponds to {approx}30 unpaired electrons per {approx}4.6 nm diameter nanodiamond grain.

  19. Temperature-Dependent Oxygen Effect on NMR D-[Formula: see text] Relaxation-Diffusion Correlation of n-Alkanes.

    Science.gov (United States)

    Shikhov, Igor; Arns, Christoph H

    2016-01-01

    Nuclear magnetic resonance (NMR) diffusion-relaxation correlation experiments ( D -[Formula: see text]) are widely used for the petrophysical characterisation of rocks saturated with petroleum fluids both in situ and for laboratory analyses. The encoding for both diffusion and relaxation offers increased fluid typing contrast by discriminating fluids based on their self-diffusion coefficients, while relaxation times provide information about the interaction of solid and fluid phases and associated confinement geometry (if NMR responses of pure fluids at particular temperature and pressure are known). Petrophysical interpretation of D -[Formula: see text] correlation maps is typically assisted by the "standard alkane line"-a relaxation-diffusion correlation valid for pure normal alkanes and their mixtures in the absence of restrictions to diffusing molecules and effects of internal gradients. This correlation assumes fluids are free from paramagnetic impurities. In situations where fluid samples cannot be maintained at air-free state the diffusion-relaxation response of fluids shift towards shorter relaxation times due to oxygen paramagnetic relaxation enhancement. Interpretation of such a response using the "standard alkane line" would be erroneous and is further complicated by the temperature-dependence of oxygen solubility for each component of the alkane mixture. We propose a diffusion-relaxation correlation suitable for interpretation of low-field NMR D -[Formula: see text] responses of normal alkanes and their mixtures saturating rocks over a broad temperature range, in equilibrium with atmospheric air. We review and where necessary revise existing viscosity-relaxation correlations. Findings are applied to diffusion-relaxation dependencies taking into account the temperature dependence of oxygen solubility and solvent vapour pressure. The effect is demonstrated on a partially saturated carbonate rock.

  20. Estimating side-chain order in methyl-protonated, perdeuterated proteins via multiple-quantum relaxation violated coherence transfer NMR spectroscopy

    International Nuclear Information System (INIS)

    Sun Hechao; Godoy-Ruiz, Raquel; Tugarinov, Vitali

    2012-01-01

    Relaxation violated coherence transfer NMR spectroscopy (Tugarinov et al. in J Am Chem Soc 129:1743–1750, 2007) is an established experimental tool for quantitative estimation of the amplitudes of side-chain motions in methyl-protonated, highly deuterated proteins. Relaxation violated coherence transfer experiments monitor the build-up of methyl proton multiple-quantum coherences that can be created in magnetically equivalent spin-systems as long as their transverse magnetization components relax with substantially different rates. The rate of this build-up is a reporter of the methyl-bearing side-chain mobility. Although the build-up of multiple-quantum 1 H coherences is monitored in these experiments, the decay of the methyl signal during relaxation delays occurs when methyl proton magnetization is in a single-quantum state. We describe a relaxation violated coherence transfer approach where the relaxation of multiple-quantum 1 H– 13 C methyl coherences during the relaxation delay period is quantified. The NMR experiment and the associated fitting procedure that models the time-dependence of the signal build-up, are applicable to the characterization of side-chain order in [ 13 CH 3 ]-methyl-labeled, highly deuterated protein systems up to ∼100 kDa in molecular weight. The feasibility of extracting reliable measures of side-chain order is experimentally verified on methyl-protonated, perdeuterated samples of an 8.5-kDa ubiquitin at 10°C and an 82-kDa Malate Synthase G at 37°C.

  1. Intramolecular Energy Relaxation and Statistical Rate Theory

    OpenAIRE

    Okitsugu, KAJIMOTO; Department of Chemistry, Kyoto University

    1994-01-01

    Statistical rate theory is essentially based on the state counting without any restrictions other than the energy and the angular momentum conservation. In this work, two kinds of restrictions are introduced into the statistical theory. The first restriction is related to the intramolecular energy flow within the reacting molecular system. The excess energy of reaction is made distributed with some bias favoring a specific degree of freedom. That is, the statistical weight of each product sta...

  2. NMR diffusion and relaxation studies of 2-nitroimidazole and albumin interactions

    Science.gov (United States)

    Wijesekera, Dj; Willis, Scott A.; Gupta, Abhishek; Torres, Allan M.; Zheng, Gang; Price, William S.

    2018-03-01

    Nitroimidazole derivatives are of current interest in the development of hypoxia targeting agents and show potential in the establishment of quantitative measures of tumor hypoxia. In this study, the binding of 2-nitroimidazole to albumin was probed using NMR diffusion and relaxation measurements. Binding studies were conducted at three different protein concentrations (0.23, 0.30 and 0.38 mM) with drug concentrations ranging from 0.005-0.16 M at 298 K. Quantitative assessments of the binding model were made by evaluating the number of binding sites, n, and association constant, K. These were determined to be 21 ± 3 and 53 ± 4 M- 1, respectively.

  3. relaxGUI: a new software for fast and simple NMR relaxation data analysis and calculation of ps-ns and μs motion of proteins

    International Nuclear Information System (INIS)

    Bieri, Michael; D’Auvergne, Edward J.; Gooley, Paul R.

    2011-01-01

    Investigation of protein dynamics on the ps-ns and μs-ms timeframes provides detailed insight into the mechanisms of enzymes and the binding properties of proteins. Nuclear magnetic resonance (NMR) is an excellent tool for studying protein dynamics at atomic resolution. Analysis of relaxation data using model-free analysis can be a tedious and time consuming process, which requires good knowledge of scripting procedures. The software relaxGUI was developed for fast and simple model-free analysis and is fully integrated into the software package relax. It is written in Python and uses wxPython to build the graphical user interface (GUI) for maximum performance and multi-platform use. This software allows the analysis of NMR relaxation data with ease and the generation of publication quality graphs as well as color coded images of molecular structures. The interface is designed for simple data analysis and management. The software was tested and validated against the command line version of relax.

  4. Molecular interactions in the ionic liquid emim acetate and water binary mixtures probed via NMR spin relaxation and exchange spectroscopy.

    Science.gov (United States)

    Allen, Jesse J; Bowser, Sage R; Damodaran, Krishnan

    2014-05-07

    Interactions of ionic liquids (ILs) with water are of great interest for many potential IL applications. 1-Ethyl-3-methylimidazolium (emim) acetate, in particular, has shown interesting interactions with water including hydrogen bonding and even chemical exchange. Previous studies have shown the unusual behavior of emim acetate when in the presence of 0.43 mole fraction of water, and a combination of NMR techniques is used herein to investigate the emim acetate-water system and the unusual behavior at 0.43 mole fraction of water. NMR relaxometry techniques are used to describe the effects of water on the molecular motion and interactions of emim acetate with water. A discontinuity is seen in nuclear relaxation behavior at the concentration of 0.43 mole fraction of water, and this is attributed to the formation of a hydrogen bonded network. EXSY measurements are used to determine the exchange rates between the H2 emim proton and water, which show a complex dependence on the concentration of the mixture. The findings support and expand our previous results, which suggested the presence of an extended hydrogen bonding network in the emim acetate-water system at concentrations close to 0.50 mole fraction of H2O.

  5. NMR relaxation in spin ice at low temperature due to diffusing emergent monopoles

    Science.gov (United States)

    Henley, Christopher L.

    2013-03-01

    At low temperatures, spin dynamics in ideal spin ice is due mainly to dilute, thermally excited magnetic ``monopole'' excitations. I consider how these will affect the longitudinal (T1) and dephasing (T2) relaxation functions of a nuclear spin in the spin-ice pyrochlore Dy2Ti2O4. Up to the time scale for nearby monopoles to be rearranged, a stretched-exponential form of the relaxation functions is expected, due to averaging over nuclei that have different local environments. ror the dephasing (T2) relaxation, the power of time in the stretched exponential is 3/2 in the case of diffusing monopoles, but 1/2 in the case of fixed, fluctuating magnetic impurities. The flip rate and density of fluctuating spins (whatever their nature) can be extracted from the measured relaxation times T1 and T2, and from known parameters. However, the actual experimental relaxation measured by Kitagawa and Takigawa becomes temperature independent in the very low T limit, and the T2 has a power t 1 / 2 in the exponential, neither of which can be explained by monopoles. I suggest the very low T behavior could be due to magnetic impurities on the (normally nonmagnetic) Ti sites. Supported by NSF grant DMR-1005466.

  6. Quantifying protein dynamics in the ps–ns time regime by NMR relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Hernández, Griselda; LeMaster, David M., E-mail: david.lemaster@health.ny.gov [University at Albany - SUNY, Wadsworth Center, New York State Department of Health and Department of Biomedical Sciences, School of Public Health (United States)

    2016-11-15

    Both {sup 15}N chemical shift anisotropy (CSA) and sufficiently rapid exchange linebroadening transitions exhibit relaxation contributions that are proportional to the square of the magnetic field. Deconvoluting these contributions is further complicated by residue-dependent variations in protein amide {sup 15}N CSA values which have proven difficult to accurately measure. Exploiting recently reported improvements for the implementation of T{sub 1} and T{sub 1ρ} experiments, field strength-dependent studies have been carried out on the B3 domain of protein G (GB3) as well as on the immunophilin FKBP12 and a H87V variant of that protein in which the major conformational exchange linebroadening transition is suppressed. By applying a zero frequency spectral density rescaling analysis to the relaxation data collected at magnetic fields from 500 to 900 MHz {sup 1}H, differential residue-specific {sup 15}N CSA values have been obtained for GB3 which correlate with those derived from solid state and liquid crystalline NMR measurements to a level similar to the correlation among those previously reported studies. Application of this analysis protocol to FKBP12 demonstrated an efficient quantitation of both weak exchange linebroadening contributions and differential residue-specific {sup 15}N CSA values. Experimental access to such differential residue-specific {sup 15}N CSA values should significantly facilitate more accurate comparisons with molecular dynamics simulations of protein motion that occurs within the timeframe of global molecular tumbling.

  7. Spin Liquid State in the 3D Frustrated Antiferromagnet PbCuTe_{2}O_{6}: NMR and Muon Spin Relaxation Studies.

    Science.gov (United States)

    Khuntia, P; Bert, F; Mendels, P; Koteswararao, B; Mahajan, A V; Baenitz, M; Chou, F C; Baines, C; Amato, A; Furukawa, Y

    2016-03-11

    PbCuTe_{2}O_{6} is a rare example of a spin liquid candidate featuring a three-dimensional magnetic lattice. Strong geometric frustration arises from the dominant antiferromagnetic interaction that generates a hyperkagome network of Cu^{2+} ions although additional interactions enhance the magnetic lattice connectivity. Through a combination of magnetization measurements and local probe investigations by NMR and muon spin relaxation down to 20 mK, we provide robust evidence for the absence of magnetic freezing in the ground state. The local spin susceptibility probed by the NMR shift hardly deviates from the macroscopic one down to 1 K pointing to a homogeneous magnetic system with a low defect concentration. The saturation of the NMR shift and the sublinear power law temperature (T) evolution of the 1/T_{1} NMR relaxation rate at low T point to a nonsinglet ground state favoring a gapless fermionic description of the magnetic excitations. Below 1 K a pronounced slowing down of the spin dynamics is witnessed, which may signal a reconstruction of spinon Fermi surface. Nonetheless, the compound remains in a fluctuating spin liquid state down to the lowest temperature of the present investigation.

  8. Interaction of lafutidine in binding to human serum albumin in gastric ulcer therapy: STD-NMR, WaterLOGSY-NMR, NMR relaxation times, Tr-NOESY, molecule docking, and spectroscopic studies.

    Science.gov (United States)

    Yang, Hongqin; Huang, Yanmei; He, Jiawei; Li, Shanshan; Tang, Bin; Li, Hui

    2016-09-15

    In this study, lafutidine (LAF) was used as a model compound to investigate the binding mechanism between antiulcer drugs and human serum albumin (HSA) through various techniques, including STD-NMR, WaterLOGSY-NMR, (1)H NMR relaxation times, tr-NOESY, molecule docking calculation, FT-IR spectroscopy, and CD spectroscopy. The analyses of STD-NMR, which derived relative STD (%) intensities, and WaterLOGSY-NMR, determined that LAF bound to HSA. In particular, the pyridyl group of LAF was in close contact with HSA binding pocket, whereas furyl group had a secondary binding. Competitive STD-NMR and WaterLOGSY-NMR experiments, with warifarin and ibuprofen as site-selective probes, indicated that LAF preferentially bound to site II in the hydrophobic subdomains IIIA of HSA. The bound conformation of LAF at the HSA binding site was further elucidated by transferred NOE effect (tr-NOESY) experiment. Relaxation experiments provided quantitative information about the relationship between the affinity and structure of LAF. The molecule docking simulations conducted with AutoDock and the restraints derived from STD results led to three-dimensional models that were consistent with the NMR spectroscopic data. The presence of hydrophobic forces and hydrogen interactions was also determined. Additionally, FT-IR and CD spectroscopies showed that LAF induced secondary structure changes of HSA. Copyright © 2016 Elsevier Inc. All rights reserved.

  9. The study of NMR relaxation time spectra multi-exponential inversion based on Lloyd–Max optimal quantization

    International Nuclear Information System (INIS)

    Li, Xuewei; Kong, Li; Cheng, Jingjing; Wu, Lei

    2015-01-01

    The multi-exponential inversion of a NMR relaxation signal plays a key role in core analysis and logging interpretation in the formation of porous media. To find an efficient metod of inverting high-resolution relaxation time spectra rapidly, this paper studies the effect of inversion which is based on the discretization of the original echo in a time domain by using a simulation model. This paper analyzes the ill-condition of discrete equations on the basis of the NMR inversion model and method, determines the appropriate number of discrete echoes and acquires the optimal distribution of discrete echo points by the Lloyd–Max optimal quantization method, in considering the inverse precision and computational complexity comprehensively. The result shows that this method can effectively improve the efficiency of the relaxation time spectra inversion while guaranteeing inversed accuracy. (paper)

  10. A minor conformation of a lanthanide tag on adenylate kinase characterized by paramagnetic relaxation dispersion NMR spectroscopy

    International Nuclear Information System (INIS)

    Hass, Mathias A. S.; Liu, Wei-Min; Agafonov, Roman V.; Otten, Renee; Phung, Lien A.; Schilder, Jesika T.; Kern, Dorothee; Ubbink, Marcellus

    2015-01-01

    NMR relaxation dispersion techniques provide a powerful method to study protein dynamics by characterizing lowly populated conformations that are in dynamic exchange with the major state. Paramagnetic NMR is a versatile tool for investigating the structures and dynamics of proteins. These two techniques were combined here to measure accurate and precise pseudocontact shifts of a lowly populated conformation. This method delivers valuable long-range structural restraints for higher energy conformations of macromolecules in solution. Another advantage of combining pseudocontact shifts with relaxation dispersion is the increase in the amplitude of dispersion profiles. Lowly populated states are often involved in functional processes, such as enzyme catalysis, signaling, and protein/protein interactions. The presented results also unveil a critical problem with the lanthanide tag used to generate paramagnetic relaxation dispersion effects in proteins, namely that the motions of the tag can interfere severely with the observation of protein dynamics. The two-point attached CLaNP-5 lanthanide tag was linked to adenylate kinase. From the paramagnetic relaxation dispersion only motion of the tag is observed. The data can be described accurately by a two-state model in which the protein-attached tag undergoes a 23° tilting motion on a timescale of milliseconds. The work demonstrates the large potential of paramagnetic relaxation dispersion and the challenge to improve current tags to minimize relaxation dispersion from tag movements

  11. Sensitivity enhancement using paramagnetic relaxation in MAS solid-state NMR of perdeuterated proteins

    Science.gov (United States)

    Linser, Rasmus; Chevelkov, Veniamin; Diehl, Anne; Reif, Bernd

    2007-12-01

    Previously, Ishii et al., could show that chelated paramagnetic ions can be employed to significantly decrease the recycle delay of a MAS solid-state NMR experiment [N.P. Wickramasinghe, M. Kotecha, A. Samoson, J. Past, Y. Ishii, Sensitivity enhancement in C-13 solid-state NMR of protein microcrystals by use of paramagnetic metal ions for optimizing H-1 T-1 relaxation, J. Magn. Reson. 184 (2007) 350-356]. Application of the method is limited to very robust samples, for which sample stability is not compromised by RF induced heating. In addition, probe integrity might be perturbed in standard MAS PRE experiments due to the use of very short duty cycles. We show that these deleterious effects can be avoided if perdeuterated proteins are employed that have been re-crystallized from D 2O:H 2O = 9:1 containing buffer solutions. The experiments are demonstrated using the SH3 domain of chicken α-spectrin as a model system. The labeling scheme allows to record proton detected 1H, 15N correlation spectra with very high resolution in the absence of heteronuclear dipolar decoupling. Cu-edta as a doping reagent yields a reduction of the recycle delay by up to a factor of 15. In particular, we find that the 1H T1 for the bulk H N magnetization is reduced from 4.4 s to 0.3 s if the Cu-edta concentration is increased from 0 mM to 250 mM. Possible perturbations like chemical shift changes or line broadening due to the paramagnetic chelate complex are minimal. No degradation of our samples was observed in the course of the experiments.

  12. Relaxation time T1, T2 and proton density images in NMR imaging

    International Nuclear Information System (INIS)

    Iwaoka, Hideto; Hirata, Takaaki; Matsuura, Hiroyuki

    1987-01-01

    Pure T 1 , T 2 and proton density (ρ) images can be computed from three or more different NMR images. Computed images can be useful for several reasons: a) they are objective, since they are independent of pulse sequence and scan parameters. b) arbitrary composite images can be synthesized from computed images. c) biochemical information can be obtained from relaxation times, so quantitative diagnosis is possible using T 1 and T 2 images. For these reasons, several methods of producing computed images have been tried. However, with these methods, there are several practical problems such as large systematic error and long total scan time. This paper describes how several sets of NMR pulse sequences and scan parameters were investigated, keeping total scan time constant, to find which of them gave computed images with best resolution and minimum systematic error for a given scan time. Pulse sequences and scan parameters were optimized to yield minimum variance of computed images, using the law of error propagation, for a given range of T 1 , T 2 and ρ. We found that theoretically the combination Inversion Recovery 3 Spin Echo and Saturation Recovery 4 Spin Echo pulse sequence gave the best compromise between scan time and resolution. The effect of slice profile and errors in RF pulses - causes of systematic error - were analyzed in order to find ways to remove or reduce them. Using this method computed T 1 , T 2 and ρ images were obtained for the human head and for various phantoms. Computed values agreed closely with values measured using analytical methods. We conclude from these results that the combination Inversion Recovery 3 Spin Echo and Saturation Recovery 4 Spin Echo pulse sequence gives the best compromise between scan time, resolution and error. (author)

  13. Non-polymeric asymmetric binary glass-formers. II. Secondary relaxation studied by dielectric, 2H NMR, and 31P NMR spectroscopy

    Science.gov (United States)

    Pötzschner, B.; Mohamed, F.; Bächer, C.; Wagner, E.; Lichtinger, A.; Bock, D.; Kreger, K.; Schmidt, H.-W.; Rössler, E. A.

    2017-04-01

    We investigate the secondary (β-) relaxations of an asymmetric binary glass former consisting of a spirobichroman derivative (SBC; Tg = 356 K) as the high-Tg component and the low-Tg component tripropyl phosphate (TPP; Tg = 134 K). The main relaxations are studied in Paper I [B. Pötzschner et al., J. Chem. Phys. 146, 164503 (2017)]. A high Tg contrast of ΔTg = 222 K is put into effect in a non-polymeric system. Component-selective studies are carried out by combining results from dielectric spectroscopy (DS) for mass concentrations cTPP ≥ 60% and those from different methods of 2H and 31P NMR spectroscopy. In the case of NMR, the full concentration range (10% ≤ cTPP ≤ 100%) is covered. The neat components exhibit a β-relaxation (β1 (SBC) and β2 (TPP)). The latter is rediscovered by DS in the mixtures for all concentrations with unchanged time constants. NMR spectroscopy identifies the β-relaxations as being alike to those in neat glasses. A spatially highly restricted motion with angular displacement below ±10° encompassing all molecules is involved. In the low temperature range, where TPP shows the typical 31P NMR echo spectra of the β2-process, very similar spectral features are observed for the (deuterated) SBC component by 2H NMR, in addition to its "own" β1-process observed at high temperatures. Apparently, the small TPP molecules enslave the large SBC molecules to perform a common hindered reorientation. The temperature dependence of the spin-lattice relaxation time of both components is the same and reveals an angular displacement of the SBC molecules somewhat smaller than that of TPP, though the time constants τβ2 are the same. Furthermore, T1(T) of TPP in the temperature region of the β2-process is absolutely the same as in the mixture TPP/polystyrene investigated previously. It appears that the manifestations of the β-process introduced by one component are essentially independent of the second component. Finally, at cTPP ≤ 20% one

  14. Structural and dynamical characterization of piroxicam by 1H- and 13C-NMR relaxation studies

    International Nuclear Information System (INIS)

    Rossi, C.; Casini, A.; Picchi, M.P.; Laschi, F.; Calabria, A.; Marcolongo, R.

    1987-01-01

    Carbon spin-lattice relaxation rates of anti-inflammatory drug, piroxicam, have been measured. These results have been used in determining the reorientational rates of the proton carbon vectors. An analysis of internal motions within the pyridinyl moiety of piroxicam was carried out. Selective proton-carbon nuclear Overhauser effect (NOE) measurements were made in order to determine the solution structure of piroxicam. The effect of indirect NOE arising from exchangeable protons has been analyzed and considered. 20 refs.; 4 figs.; 3 tabs

  15. Manganese-55 NMR and relaxation in single crystals of manganese(12)-Ac and analogs

    Science.gov (United States)

    Harter, Andrew

    This dissertation presents the first single crystal 55Mn NMR characterization of three compounds related to Mn12-acetate [Mn12O12(O2CCH3)16(H 2O)4]·2CH3COOH·4H2O (henceforth Mn12-Ac) that have come to be known as Single-Molecule Magnets (SMMs). This study was undertaken because they exhibit novel phenomena such as quantum mechanical tunneling of their magnetization (QTM), the origin of which is still not fully understood, and also because they have the potential to form elements of magnetic memory storage at the molecular dimensions. The investigations herein involve studies related to both the bonding as well as spin-dynamics in these compounds to much higher precision than in earlier work. These experiments were made possible by the design of a high frequency goniometer probe and a 3He temperature facility. The first single crystal NMR of any Mn12-based molecule was conducted on [Mn12O12(O2CCH2Br) 16(H2O)4]·4CH2Cl2 (Mn12-BrAc). Its 55Mn NMR spectrum, field dependence, angular dependence, and spin-lattice relaxation time (T 1) measurements were conducted. Most importantly, data are presented that (a) confirm the alteration of the magnetic core of these molecules when the samples are crushed into powder (a practice used in earlier studies), (b) show the presence of transverse hyperfine fields at the nuclear site, and (c) do not yield any evidence of temperature independent relaxation below 1 K, suggesting that QTM is not the dominant relaxation mechanism at these temperatures, in contrast to earlier studies. Data from single crystals of Mn12-Ac, the most studied SMM, concur with previous x-ray findings in that isomers are present. Such detailed information was not obtainable with powder samples. T 1-1 measurements over 400 mK--1 K indicate the existence of an energy barrier, in this case ˜1.65 K, which does not fit the current understanding of the electronic energy diagram. This value supports an earlier, yet unexplained observation of such a level by inelastic

  16. Defining the Structural Basis for Allosteric Product Release from E. coli Dihydrofolate Reductase Using NMR Relaxation Dispersion.

    Science.gov (United States)

    Oyen, David; Fenwick, R Bryn; Aoto, Phillip C; Stanfield, Robyn L; Wilson, Ian A; Dyson, H Jane; Wright, Peter E

    2017-08-16

    The rate-determining step in the catalytic cycle of E. coli dihydrofolate reductase is tetrahydrofolate (THF) product release, which can occur via an allosteric or an intrinsic pathway. The allosteric pathway, which becomes accessible when the reduced cofactor NADPH is bound, involves transient sampling of a higher energy conformational state, greatly increasing the product dissociation rate as compared to the intrinsic pathway that obtains when NADPH is absent. Although the kinetics of this process are known, the enzyme structure and the THF product conformation in the transiently formed excited state remain elusive. Here, we use side-chain proton NMR relaxation dispersion measurements, X-ray crystallography, and structure-based chemical shift predictions to explore the structural basis of allosteric product release. In the excited state of the E:THF:NADPH product release complex, the reduced nicotinamide ring of the cofactor transiently enters the active site where it displaces the pterin ring of the THF product. The p-aminobenzoyl-l-glutamate tail of THF remains weakly bound in a widened binding cleft. Thus, through transient entry of the nicotinamide ring into the active site, the NADPH cofactor remodels the enzyme structure and the conformation of the THF to form a weakly populated excited state that is poised for rapid product release.

  17. Vibrational energy transfer in selectively excited diatomic molecules. [Relaxation rates, self-relaxation, upper limits

    Energy Technology Data Exchange (ETDEWEB)

    Dasch, C.J.

    1978-09-01

    Single rovibrational states of HCl(v=2), HBr(v=2), DCl(v=2), and CO(v=2) were excited with a pulsed optical parametric oscillator (OPO). Total vibrational relaxation rates near - resonance quenchers were measured at 295/sup 0/K using time resolved infrared fluorescence. These rates are attributed primarily to V - V energy transfer, and they generally conform to a simple energy gap law. A small deviation was found for the CO(v) + DCl(v') relaxation rates. Upper limits for the self relaxation by V - R,T of HCl(v=2) and HBr(v=2) and for the two quantum exchange between HCl and HBr were determined. The HF dimer was detected at 295/sup 0/K and 30 torr HF pressure with an optoacoustic spectrometer using the OPO. Pulsed and chopped, resonant and non-resonant spectrophones are analyzed in detail. From experiments and first order perturbation theory, these V - V exchange rates appear to behave as a first order perturbation in the vibrational coordinates. The rotational dynamics are known to be complicated however, and the coupled rotational - vibrational dynamics were investigated theoreticaly in infinite order by the Dillon and Stephenson and the first Magnus approximations. Large ..delta..J transitions appear to be important, but these calculations differ by orders of magnitude on specific rovibrational transition rates. Integration of the time dependent semiclassical equations by a modified Gordon method and a rotationally distorted wave approximation are discussed as methods which would treat the rotational motion more accurately. 225 references.

  18. $^{11}$B and $^{27}$Al NMR spin-lattice relaxation and Knight shift study of Mg$_{1-x}$Al$_x$B$_2$. Evidence for anisotropic Fermi surface

    OpenAIRE

    Papavassiliou, G.; Pissas, M.; Karayanni, M.; Fardis, M.; Koutandos, S.; Prassides, K.

    2002-01-01

    We report a detailed study of $^{11}$B and $^{27}$Al NMR spin-lattice relaxation rates ($1/T_1$), as well as of $^{27}$Al Knight shift (K) of Mg$_{1-x}$Al$_x$B$_2$, $0\\leq x\\leq 1$. The obtained ($1/T_1T$) and K vs. x plots are in excellent agreement with ab initio calculations. This asserts experimentally the prediction that the Fermi surface is highly anisotropic, consisting mainly of hole-type 2-D cylindrical sheets from bonding $2p_{x,y}$ boron orbitals. It is also shown that the density ...

  19. 31P NMR probes of chemical dynamics: paramagnetic relaxation enhancement of the (1)H and (31)P NMR resonances of methyl phosphite and methylethyl phosphate anions by selected metal complexes.

    Science.gov (United States)

    Summers, J S; Hoogstraten, C G; Britt, R D; Base, K; Shaw, B R; Ribeiro, A A; Crumbliss, A L

    2001-12-17

    Methyl phosphite ((CH(3)O)P(H)(O)(2)(-); MeOPH) and methylethyl phosphate ((CH(3)O)P(OCH(2)CH(3))(O)(2)(-); MEP) are two members of a class of anionic ligands whose (31)P T(2) relaxation rates are remarkably sensitive to paramagnetic metal ions. The temperature dependence of the (31)P NMR line broadenings caused by the Mn(H(2)O)(6)(2+) ion and a water-soluble manganese(III) porphyrin (Mn(III)TMPyP(5+)) indicates that the extent of paramagnetic relaxation enhancement is a measure of the rate at which the anionic probes come into physical contact with the paramagnetic center (i.e., enter the inner coordination shell); that is, piDeltanu(par) = k(assn)[M], where Deltanu(par) is the difference between the line widths of the resonance in paramagnetic and diamagnetic solutions, and k(assn) is the second-order rate constant for association of the phosphorus ligand with the metal, M. Comparison of the (31)P T(1) and T(2) relaxation enhancements shows that rapid T(2) relaxation by the metal ion is caused by scalar interaction with the electronic spin. Relaxation of the phosphorus-bound proton of MeOPH ((1)H-P) by Mn(III)TMPyP(5+) displayed intermediate exchange kinetics over much of the observable temperature range. The field strength dependence of (1)H-P T(2) enhancement and the independence of the (31)P T(2) support these assertions. As in the case of the (31)P T(2), the (1)H-P T(2) relaxation enhancement results from scalar interaction with the electronic spin. The scalar coupling interpretation of the NMR data is supported by a pulsed EPR study of the interactions of Mn(H(2)O)(6)(2+) with the P-deuterated analogue of methyl phosphite, CH(3)OP((2)H)(O)(2)(-). The electron to (31)P and (2)H nuclear scalar coupling constants were found to be 4.6 and 0.10 MHz, respectively. In contrast, the effects of paramagnetic ions on the methoxy and ethoxy (1)H resonances of MeOPH and MEP are weak, and the evidence suggests that relaxation of these nuclei occurs by a dipolar mechanism

  20. Interaction study of polyisobutylene with paraffins by NMR using the evaluation of spin-lattice relaxation times for hydrogen nuclei

    International Nuclear Information System (INIS)

    Marques, Rosana G.G.; Tavares, Maria I.B.

    2001-01-01

    The evaluation of spin-lattice relaxation times of 1 H for polyisobutylene/paraffin systems, were obtained using the classic inversion recovery technique, and also through Cross Polarization Magic Angle Spinning (CP/MAS) techniques varying the contact time and also by the delayed contact time pulse sequence. NMR results showed that the polyisobutylene/paraffin systems in which high molecular weight paraffins were used, is heterogeneous. However, for paraffins with low molecular weight, the system presents good homogeneity. (author)

  1. An analysis of the NMR-CT image by the measurement of proton-relaxation times in tissue

    International Nuclear Information System (INIS)

    Naruse, Shoji; Horikawa, Yoshiharu; Tanaka, Chuzo; Hirakawa, Kimiyoshi; Nishikawa, Hiroyasu; Shimizu, Koji; Kiri, Motosada.

    1984-01-01

    NMR-CT images were analyzed by measuring the proton-relaxation times in tissues. The NMR-CT images were obtained in 10 normal volunteers and 16 patients with brain tumors with a prototype superconducting magnet (Shimadzu Corp., Japan) operating at 0.2 T and 0.375 T. A smooth T 1 relaxation curve was obtained in each part of the brain and the brain tumor by the use of the data of the NMR-CT image; consequently, the in vivo T 1 value was proved to be reliable. The in vivo T 1 value showed the specific value corresponding to each region of the normal brain in all cases. Cerebral gray matter normally had the longest T 1 value, followed by the medulla oblongata, the pons, and white matter. The T 1 value of each region of the brain varied to the same degree in proportion to the strength of the static magnetic field. The in vivo T 1 values of the brain tumor varied with the histological type. All were longer than any part of the brain parenchyma, being between 480 and 780 msec at 0.2 T. The prolongation of the T 1 value does not always correspond to the degree of the malignancy in a tumor. The in vitro T 1 and T 2 values were also prolonged in all tumors. Although the absolute value of T 1 did not coincide between the in vitro and in vivo data, the tendency of the prolongation was the same between them. This result indicated that the NMR-CT images could be analysed by the use of the data of the in vitro T 1 and T 2 values in the tumor tissues. It is important to analyse the NMR-CT image by both in vivo and in vitro examinations of the relaxation times. (J.P.N.)

  2. Characterization of the overall and internal dynamics of short oligonucleotides by depolarized dynamic light scattering and NMR relaxation measurements

    International Nuclear Information System (INIS)

    Eimer, W.; Williamson, J.R.; Boxer, S.G.; Pecora, R.

    1990-01-01

    The dynamics of three synthetic oligonucleotides d(CG) 4 , d(CG) 6 , and d(CGCGTTGTTCGCG) of different length and shape were studied in solution by depolarized dynamic light scattering (DDLS) and time-resolved nuclear Overhauser effect cross-relaxation measurements. For cylindrically symmetric molecules the DDLS spectrum is dominated by the rotation of the main symmetry axis of the cylinder. The experimental correlation times describe the rotation of the oligonucleotides under hydrodynamic stick boundary conditions. It is shown that the hydrodynamic theory of Tirado and Garcia de la Torre gives good predictions of the rotational diffusion coefficients of cylindrically symmetric molecules of the small axial ratios studied here. These relations are used to calculate the solution dimensions of the DNA fragments from measured correlation times. The DDLS relaxations measurements provide a power method for distinguishing between different conformations of the oligonucleotides. Furthermore, the rotational correlation times are a very sensitive probe of the length of different fragments. The NMR results reflect the anisotropic motion of the molecules as well as the amount of local internal motion present. The experimental correlation time from NMR is determined by the rotation of both the short and long axes of the oligonucleotide. The authors results are compared with those from NMR relaxation measurements on other short oligonucleotides with lengths of up to 20 base pairs. Various dynamic models for the reorientation of the internuclear vector are applied to their interpretation

  3. Histidine side-chain dynamics and protonation monitored by C-13 CPMG NMR relaxation dispersion

    DEFF Research Database (Denmark)

    Hass, M. A. S.; Yilmaz, A.; Christensen, Hans Erik Mølager

    2009-01-01

    the chemical shift titration experiments, and the CPMG derived exchange rates agree with those obtained previously from N-15 backbone relaxation measurements. Compared to measurements of backbone nuclei, C-13(epsilon 1) dispersion provides a more direct method to monitor interchanging protonation states...... or other kinds of conformational changes of histidine side chains or their environment. Advantages and shortcomings of using the C-13(epsilon 1) dispersion experiments in combination with chemical shift titration experiments to obtain information on exchange dynamics of the histidine side chains...

  4. A suite of Mathematica notebooks for the analysis of protein main chain 15N NMR relaxation data

    International Nuclear Information System (INIS)

    Spyracopoulos, Leo

    2006-01-01

    A suite of Mathematica notebooks has been designed to ease the analysis of protein main chain 15 N NMR relaxation data collected at a single magnetic field strength. Individual notebooks were developed to perform the following tasks: nonlinear fitting of 15 N-T 1 and -T 2 relaxation decays to a two parameter exponential decay, calculation of the principal components of the inertia tensor from protein structural coordinates, nonlinear optimization of the principal components and orientation of the axially symmetric rotational diffusion tensor, model-free analysis of 15 N-T 1 , -T 2 , and { 1 H}- 15 N NOE data, and reduced spectral density analysis of the relaxation data. The principle features of the notebooks include use of a minimal number of input files, integrated notebook data management, ease of use, cross-platform compatibility, automatic visualization of results and generation of high-quality graphics, and output of analyses in text format

  5. The effects of some parameters on the calculated 1H NMR relaxation times of cell water

    International Nuclear Information System (INIS)

    Koivula, A.; Suominen, K.; Kiviniitty, K.

    1976-01-01

    The effect of some parameters on the longitudinal and transverse relaxation times is calculated and a comparison between the calculated relaxation times with the results of different measurements is made. (M.S.)

  6. Relaxation rates studies in an argon cylindrical plasma

    International Nuclear Information System (INIS)

    Hernandez, M.A.; Dengra, A.; Colomer, V.

    1986-01-01

    The single Langmuir probe method has been used to determine the relaxation rates of the electron density and temperature in an argon afterglow dc cylindrical plasma. The ion-electron recombination was found to be the fundamental mechanism of density decay during the early afterglow while the ambipolar diffusion controlles the density decay for later afterglow. Electron temperature cooling curves have been interpreted via electron-neutral collisons. Measurements of the electron-ion recombination and the ambipolar diffusion coefficients have been made, as well as of the electron-neutral collision frequency and the momentum transfer cross sections. Good agreement is obtained with previously published data. (author)

  7. Dependence of transmon qubit relaxation rate on readout drive power

    Science.gov (United States)

    Mundhada, S. O.; Shankar, S.; Narla, A.; Zalys-Geller, E.; Girvin, S. M.; Devoret, M. H.

    In circuit QED experiments, microwave drives are applied to the readout mode for qubit measurement, control and to realize various multi-photon processes. These microwave drives have been observed to detrimentally affect the qubit mode by increasing the qubit relaxation rates for both upward and downward transitions. These transitions demolish the qubit state during a measurement, limiting the maximum measurement strength and thus the readout fidelity and speed. Here, we experimentally investigate this effect for transmon qubits coupled to different realizations of the readout mode: 3-dimensional microwave cavities, strip-line resonators and nonlinear readout modes in a waveguide. Work supported by: NSF, ARO, AFOSR and YINQE.

  8. Redox-controlled backbone dynamics of human cytochrome c revealed by 15N NMR relaxation measurements

    International Nuclear Information System (INIS)

    Sakamoto, Koichi; Kamiya, Masakatsu; Uchida, Takeshi; Kawano, Keiichi; Ishimori, Koichiro

    2010-01-01

    Research highlights: → The dynamic parameters for the backbone dynamics in Cyt c were determined. → The backbone mobility of Cyt c is highly restricted due to the covalently bound heme. → The backbone mobility of Cyt c is more restricted upon the oxidation of the heme. → The redox-dependent dynamics are shown in the backbone of Cyt c. → The backbone dynamics of Cyt c would regulate the electron transfer from Cyt c. -- Abstract: Redox-controlled backbone dynamics in cytochrome c (Cyt c) were revealed by 2D 15 N NMR relaxation experiments. 15 N T 1 and T 2 values and 1 H- 15 N NOEs of uniformly 15 N-labeled reduced and oxidized Cyt c were measured, and the generalized order parameters (S 2 ), the effective correlation time for internal motion (τ e ), the 15 N exchange broadening contributions (R ex ) for each residue, and the overall correlation time (τ m ) were estimated by model-free dynamics formalism. These dynamic parameters clearly showed that the backbone dynamics of Cyt c are highly restricted due to the covalently bound heme that functions as the stable hydrophobic core. Upon oxidation of the heme iron in Cyt c, the average S 2 value was increased from 0.88 ± 0.01 to 0.92 ± 0.01, demonstrating that the mobility of the backbone is further restricted in the oxidized form. Such increases in the S 2 values were more prominent in the loop regions, including amino acid residues near the thioether bonds to the heme moiety and positively charged region around Lys87. Both of the regions are supposed to form the interaction site for cytochrome c oxidase (CcO) and the electron pathway from Cyt c to CcO. The redox-dependent mobility of the backbone in the interaction site for the electron transfer to CcO suggests an electron transfer mechanism regulated by the backbone dynamics in the Cyt c-CcO system.

  9. Three-way modelling of NMR relaxation profiles from thawed cod muscle

    DEFF Research Database (Denmark)

    Jensen, Kristina Nedenskov; Guldager, Helle Skov; Jørgensen, Bo Munk

    2002-01-01

    Low-field 1H nuclear magnetic resonance transverse relaxation was used to measure water mobility and distribution in cod stored at -20°C or -30°C for up to 12 months and subsequently from 0 to 21 days in modified atmosphere at +2°C. The relaxation profiles were decomposed by parallel factor......, but not the relaxation times, depended on the frozen storage temperature and on the chilled storage period....

  10. Ligand orientation in a membrane-embedded receptor site revealed by solid-state NMR with paramagnetic relaxation enhancement.

    Science.gov (United States)

    Whittaker, Christopher A P; Patching, Simon G; Esmann, Mikael; Middleton, David A

    2015-03-07

    NMR relaxation enhancement by paramagnetic metals provides powerful restraints on the three-dimensional structures of proteins in solution, and this approach has recently been utilized in several NMR structural investigations of proteins in the solid-state. Here we utilize paramagnetic relaxation enhancement (PRE) by Mn(2+) with cross-polarization magic-angle spinning (CP-MAS) solid-state NMR to investigate the interaction of a membrane-embedded protein the Na,K-ATPase (NKA) with a cardiotonic steroid inhibitor. The inhibitor, a diacetonide derivate of the cardiac glycoside ouabain, with (13)C labelled acetonide groups in the rhamnose sugar and steroid moieties ([(13)C2]ODA), is 1000-fold less potent than the parent compound. It is shown that the (13)C CP-MAS solid-state NMR spectra of the NKA-[(13)C2]ODA complex exhibit distinct signals for the two (13)C labels of the inhibitor when bound to the ouabain site of membrane-embedded NKA. Recent crystal structures of NKA indicate that the catalytic α-subunit binds a single Mn(2+) in a transmembrane site close to the high-affinity ouabain site. Here, complexation of NKA with Mn(2+) broadens the resonance line from the rhamnose group substantially more than the steroid peak, indicating that the rhamnose group is closer to the Mn(2+) site than is the steroid group. These observations agree with computational molecular docking simulations and are consistent with ODA adopting an inverted orientation compared to ouabain in the cardiac glycoside site, with the modified rhamnose group drawn toward the transmembrane centre of the protein. This work demonstrates that PRE can provide unique information on the positions and orientations of ligands within their binding pockets of transmembrane proteins.

  11. An NMR study of 1H, 31P, and 23Na relaxation and molecular dynamics in the polycrystalline sodium salts of adenosine Di- and triphosphate

    Science.gov (United States)

    Reynhardt, E. C.; Jurga, K.; Andrew, E. R.

    Proton spin-lattice relaxation times in the laboratory frame, T1(H),have been measured as a function of frequency and temperature (333K> T > 80 K). The spin-lattice relaxation times in the rotating frame, T1 ϱ(H), have been measured at two different rotating fields while M2(H), the proton second moment, has been extracted from the shape of the FID. In addition, T 1( 31P) and T 1( 23Na) have been measured as functions of temperature at 81 and 50 MHz, respectively. The results demonstrate clearly that the water content of the compounds influences the results to a large extent. It seems that water molecules at some of the lattice sites can be removed from the structure by evacuation, while others are more tightly bound to the ADP and ATP molecules. The more loosely bound water molecules are very mobile and dominate the relaxation results in the high-temperature region via the spin-rotation and dipolar mechanisms. The more tightly bound water molecules rotate about their twofold axes and this motion, characterized by a distribution of correlation times, results in a T1(H) minimum in the low-temperature region. The results have been interpreted in terms of a Fuoss-Kirkwood distribution function. The 23Na spin-lattice relaxation rates are dominated by the quadrupolar interactions, which provide a dominating relaxation mechanism for the proton spins in the rotating frame. In the case of Na 2ATP, T1(P) is independent of the degree of hydration of the sample, but the NaADP T1(H), values are influenced strongly by a change in the water content. An X-ray determination of the lengths of the a axes of the unit cells has provided supporting evidence for the interpretation of the NMR results.

  12. Dependence of transmon qubit relaxation rate on cavity photon population

    Science.gov (United States)

    Mundhada, S. O.; Shankar, S.; Liu, Y.; Hatridge, M.; Narla, A.; Sliwa, K. M.; Girvin, S. M.; Devoret, M. H.

    2015-03-01

    In circuit QED experiments, a qubit is dispersively coupled to a cavity such that the cavity frequency depends on the qubit state. This dispersive shift enables quantum non-demolition readout of the qubit by exciting the cavity with a microwave pulse and detecting the phase shift of the reflected signal. However, this cavity excitation has been observed in experiments to increase the qubit relaxation rate, hence demolishing the qubit state and limiting the maximum measurement strength. Here we experimentally study this effect in a transmon qubit coupled to a three-dimensional superconducting cavity. We also explore alternate qubit circuits designed to mitigate this demolition effect. Work supported by: IARPA, ARO, and NSF.

  13. Non-polymeric asymmetric binary glass-formers. I. Main relaxations studied by dielectric, 2H NMR, and 31P NMR spectroscopy

    Science.gov (United States)

    Pötzschner, B.; Mohamed, F.; Bächer, C.; Wagner, E.; Lichtinger, A.; Minikejew, R.; Kreger, K.; Schmidt, H.-W.; Rössler, E. A.

    2017-04-01

    In Paper I of this series of two papers we study the main relaxations of a binary glass former made of the low-Tg component tripropyl phosphate (TPP, Tg = 134 K) and of a specially synthesized (deuterated) spirobichroman derivative (SBC, Tg = 356 K) as the non-polymeric high-Tg component for the full concentration range. A large Tg contrast of the neat components is put into effect. Dielectric spectroscopy and different techniques of 2H nuclear magnetic resonance (NMR) as well as of 31P NMR spectroscopy allow to selectively probe the dynamics of the components. For all concentrations, two well separated liquid-like processes are identified. The faster α2-process associated with the low-Tg component TPP shows pronounced dynamic heterogeneities reflected by quasi-logarithmic correlation functions at low TPP concentrations. The slower α1-process involves the reorientation of the high-Tg component SBC. Its correlation function is Kohlrausch-like as in neat glass formers. The corresponding time constants and consequently their glass transition temperatures Tg1 and Tg2 differ more the lower the TPP concentration is. Plasticizer and anti-plasticizer effect, respectively, is observed. At low temperatures a situation arises that the TPP molecules isotropically reorient in an arrested SBC matrix (Tg2 TPP gets arrested too. We find indications that a fraction of the TPP molecule takes part in the slower α1-process of the high-Tg component. All the features known from polymer-plasticizer systems are rediscovered in this non-polymeric highly asymmetric binary mixture. In Paper II [B. Pötzschner et al., J. Chem. Phys. 146, 164504 (2017)] we study the secondary (β-) relaxations of the mixtures.

  14. NMR

    International Nuclear Information System (INIS)

    Kneeland, J.B.; Lee, B.C.P.; Whalen, J.P.; Knowles, R.J.R.; Cahill, P.T.

    1984-01-01

    Although still quite new, NMR imaging has already emerged as a safe, noninvasive, painless, and effective diagnostic modality requiring no ionizing radiation. Also, NMR appears already to have established itself as the method of choice for the examination of the brain spinal cord (excluding herniated disks). Another area in which NMR excels is in the examination of the pelvis. The use of surface coils offers the promise of visualizing structures with resolution unobtainable by any other means. In addition, NMR, with its superb visualization of vascular structures and potential ability to measure flow, may soon revolutionize the diagnosis of cardiovascular disease. Finally, NMR, through biochemically and physiologically based T/sub 1/ and T/sub 2/ indices or through spectroscopy, may provide a means of monitoring therapeutic response so as to permit tailoring of treatment to the individual patient. In short, NMR is today probably at the same stage as the x-ray was in Roentgen's day

  15. Application of chemometrics to low-field H-1 NMR relaxation data of intact fish flesh

    DEFF Research Database (Denmark)

    Jepsen, Signe Munk; Pedersen, H.T.; Engelsen, S.B.

    1999-01-01

    The possibilities for application of low-field H-1 nuclear magnetic resonance (NMR) as a rapid method for simultaneous assessment of basic quality parameters in fish were explored. In a first experiment, 200 salmon (Salmo salar) samples mapping the variation over an entire fish were measured by NMR...... and water content in fresh salmon flesh and water-holding capacity in thawed cod flesh respectively. Thus rapid, non-invasive low- field NMR can be used to simultaneously determine both oil and water content of fish flesh. Furthermore, it can predict water- holding capacity of cod flesh, with an R-2 of 0.......9 over the range 30-90%, as determined by a centrifuge test. (C) 1999 Society of Chemical Industry...

  16. A Unique and Simple Approach to Improve Sensitivity in 15N-NMR Relaxation Measurements for NH3+ Groups: Application to a Protein-DNA Complex

    Science.gov (United States)

    Nguyen, Dan; Lokesh, Ganesh L.R.; Volk, David E.; Iwahara, Junji

    2017-01-01

    NMR spectroscopy is a powerful tool for research on protein dynamics. In the past decade, there has been significant progress in the development of NMR methods for studying charged side chains. In particular, NMR methods for lysine side-chain NH3+ groups have been proven to be powerful for investigating the dynamics of hydrogen bonds or ion pairs that play important roles in biological processes. However, relatively low sensitivity has been a major practical issue in NMR experiments on NH3+ groups. In this paper, we present a unique and simple approach to improve sensitivity in 15N relaxation measurements for NH3+ groups. In this approach, the efficiency of coherence transfers for the desired components are maximized, whereas undesired anti-phase or multi-spin order components are purged through pulse schemes and rapid relaxation. For lysine side-chain NH3+ groups of a protein-DNA complex, we compared the data obtained with the previous and new pulse sequences under the same conditions and confirmed that the 15N relaxation parameters were consistent for these datasets. While retaining accuracy in measuring 15N relaxation, our new pulse sequences for NH3+ groups allowed an 82% increase in detection sensitivity of 15N longitudinal and transverse relaxation measurements. PMID:28809801

  17. A Unique and Simple Approach to Improve Sensitivity in15N-NMR Relaxation Measurements for NH₃⁺ Groups: Application to a Protein-DNA Complex.

    Science.gov (United States)

    Nguyen, Dan; Lokesh, Ganesh L R; Volk, David E; Iwahara, Junji

    2017-08-15

    NMR spectroscopy is a powerful tool for research on protein dynamics. In the past decade, there has been significant progress in the development of NMR methods for studying charged side chains. In particular, NMR methods for lysine side-chain NH₃⁺ groups have been proven to be powerful for investigating the dynamics of hydrogen bonds or ion pairs that play important roles in biological processes. However, relatively low sensitivity has been a major practical issue in NMR experiments on NH₃⁺ groups. In this paper, we present a unique and simple approach to improve sensitivity in 15 N relaxation measurements for NH₃⁺ groups. In this approach, the efficiency of coherence transfers for the desired components are maximized, whereas undesired anti-phase or multi-spin order components are purged through pulse schemes and rapid relaxation. For lysine side-chain NH₃⁺ groups of a protein-DNA complex, we compared the data obtained with the previous and new pulse sequences under the same conditions and confirmed that the 15 N relaxation parameters were consistent for these datasets. While retaining accuracy in measuring 15 N relaxation, our new pulse sequences for NH₃⁺ groups allowed an 82% increase in detection sensitivity of 15 N longitudinal and transverse relaxation measurements.

  18. Indirect measurement of the cooperative hydrogen bonding of polymers using NMR quadrupole relaxation and PFG methods

    Czech Academy of Sciences Publication Activity Database

    Kříž, Jaroslav; Dybal, Jiří

    2008-01-01

    Roč. 265, č. 1 (2008), s. 225-232 ISSN 1022-1360. [European Symposium on Polymer Spectroscopy /17./. Seggauberg Leibnitz, 09.9.2007-12.09.2007] R&D Projects: GA AV ČR IAA400500604 Institutional research plan: CEZ:AV0Z40500505 Keywords : cooperative bonding * hydrogen bond * NMR * poly(4-vinylphenol) Subject RIV: CD - Macromolecular Chemistry

  19. Paraffin molecule mobility in channel clathrates of urea on spectroscopic NMR relaxation data

    CERN Document Server

    Kriger, Y G; Chekhova, G N

    2001-01-01

    The temperature dependences of the protons spin-lattice relaxation time (T sub I) in the channel clathrates of urea with paraffins are measured. The data on the T sub I are interpreted within the frames of the model of the paraffins molecules and their fragments orientation in the clathrate channels. The dynamics peculiarities are connected with the disproportion effects of these compounds

  20. Direct binding of ethanol to bovine serum albumin: a fluorescent and 13C NMR multiplet relaxation study.

    Science.gov (United States)

    Avdulov, N A; Chochina, S V; Daragan, V A; Schroeder, F; Mayo, K H; Wood, W G

    1996-01-09

    Molecular mechanisms of ethanol interaction with proteins are not well-understood. In the present study, direct interaction of ethanol with hydrophobic binding sites on fatty acid free bovine serum albumin (BSA) was determined using the fluorescent probe 1-anilinonaphthalene-8-sulfonic acid (1,8-ANS), cis-parinaric acid, and 13C NMR. The affinity of ethanol for BSA (Kd) was (5.21 +/- 0.31) x 10(-2) mol. Ethanol (25-200 mmol) competitively inhibited 1,8-ANS binding to BSA in a concentration-dependent manner with a Ki (concentration of ethanol that decreased 1,8-ANS binding by 50%) of 658 mmol. Preincubation of BSA with ethanol significantly decreased cis-parinaric acid binding to BSA, indicating interaction of ethanol with hydrophobic fatty acid-binding site(s) on BSA. Furthermore, ethanol was found to act on three of the five fatty acid-binding sites on BSA. These data indicated selectivity in the interaction of ethanol with hydrophobic sites on BSA. 13C NMR multiplet relaxation was used to characterize the interaction of ethanol with binding sites on BSA. Detailed analysis of [13C]ethanol relaxation data obtained in the presence of increasing BSA concentrations (25-200 mg/mL) led to the conclusion that the ethanol methyl group, as opposed to its hydroxyl group, binds in a hydrophobic pocket(s) on the protein. Ethanol-induced changes in activity of certain proteins may result from direct binding of ethanol to specific hydrophobic binding sites and/or displacement of endogenous ligands from those sites.

  1. NMR diffusion and relaxation measurements of organic molecules adsorbed in porous media

    International Nuclear Information System (INIS)

    Gjerdaaker, Lars

    2002-01-01

    a bipolar form of the pulsed field gradient has proved to be an efficient method for both reducing the cross-term between the applied and internal gradient and reducing the eddy current dead time. Without the use of a bipolar sequence, the measured diffusivities are likely to be underestimated. In order to get sufficient attenuation of the signal a stimulated-echo sequence together with magnetic field gradients have been used. It was then possible to increase the z-storage period to compensate for insufficient gradient strength. However, the employed diffusion probe and gradient power supply are able to generate magnetic field gradients that make the z-storage period unnecessary. In this work we also present a spin-echo analogue to the 13-interval PFGSTE sequence presented by Cotts et al., a so-called 11-interval bipolar PFGSE sequence. Conclusions: The molecular dynamics of four organic adsorbates confined in porous materials have been investigated. The confinement gives rise to substantial changes in the phase behaviour and molecular dynamics. From the line shape of the confined substances a narrow-line component superimposed on a broad resonance is observed at temperatures well below the transition point of the bulk material. This narrow-line component is, in the freezing region, attributed to the surface layer and the undercooled liquid in the smaller pores that remains unfrozen. In the low-temperature region, the narrow-line component corresponds to the surface layer, while the broad component originates from the crystalline phase at the centre of the pores. The persistent surface layer does not appear to crystallize at all, and a relatively high diffusion rate of this liquid-like phase is observed over a wide temperature range, even well below the transition point of the bulk material. However, with decreasing temperature T2 of the molecules in the surface layer becomes shorter and the contribution to the NMR signal decreases gradually. For pivalic acid and

  2. Temperature dependence of 1H NMR relaxation time, T2, for intact and neoplastic plant tissues

    Science.gov (United States)

    Lewa, Czesław J.; Lewa, Maria

    Temperature dependences of the spin-spin proton relaxation time, T2, have been shown for normal and tumorous tissues collected from kalus culture Nicotiana tabacum and from the plant Kalanchoe daigremontiana. For neoplastic plant tissues, time T2 was increased compared to that for intact plants, a finding similar to that for animal and human tissues. The temperature dependences obtained were compared to analogous relations observed with animal tissues.

  3. Nuclear magnetic relaxation dispersion and 31P-NMR studies of the effect of covalent modification of membrane surfaces with poly(ethylene glycol).

    Science.gov (United States)

    Tilcock, C; Ahkong, Q F; Koenig, S H; Brown, R D; Kabalka, G; Fisher, D

    1992-10-05

    Covalent attachment of methoxypoly(ethylene glycol) (MPEG) 5000 to the surface of unilamellar liposomes composed of egg phosphatidylcholine and dioleoylphosphatidylethanolamine (DOPE) (8:2) containing paramagnetic chelates, either entrapped within the interior volume of the liposomes, or associated with the membrane surface, had no effect upon the measured spin-lattice relaxation rates (1/T1) for water in these systems. 31P-NMR studies indicate no destabilization of dioleoylphosphatidylcholine (DOPC)/(DOPE) (1:1) vesicles following attachment of MPEG. However, in DOPC/DOPE (1:3) mixtures, covalent modification with MPEG results in a destabilization of multilamellar vesicles into smaller vesicular structures. These results indicate that covalent attachment of poly(ethylene glycol) to liposomal magnetic resonance agents may prove a useful method for increasing their utility as vascular MR agents by extending their lifetime in the circulation, without decreasing the relaxivity of paramagnetic species associated with the liposome, but that the presence of PEG covalently attached to the membrane surface may modify the polymorphic phase behavior of the lipid system to which it is covalently linked.

  4. Cadmium-113 NMR spin-lattice relaxation and exchange kinetics in concanavalin A: A double saturation transfer experiment

    Science.gov (United States)

    Ellis, Paul D.; Yang, Ping P.; Palmert, Allen R.

    The field dependence of the 113Cd relaxation rate in cadmium-substituted Concanavalin A was investigated at three magnetic field strengths, 2.3, 4.7, and 9.4 T. Because of the anomalously large relaxation rate observed for the resonance corresponding to free cadmium in the system and our prior knowledge that cadmium is undergoing chemical exchange in this system, a detailed analysis was undertaken of the relaxation data obtained at 9.4 T to investigate the relative importance of chemical exchange dynamics upon the observed relaxation time constants. The differential equations for the resulting restricted three-site exchange network can be solved in closed form by employing a double saturation transfer experiment in conjunction with a saturation-recovery T1 experiment. The analysis of these data demonstrate that chemical exchange processes contribute 14, 75, and 20% to the observed relaxation time constants for the 113Cd resonances for the S1 site, free cadmium and the S2 site respectively. If the possibility of exchange contributions to the NOE were ignored, then the observed field dependence of T1 could not be discussed in terms of conventional single correlation time theories of relaxation. In this case the data could be discussed in terms of correlation times involving overall motion of the protein coupled with correlation times describing "internal motions." These internal motions may be the result of the formation of "abortive" complexes with exogenous ligands for those metalloproteins where the metal can be readily removed from the protein. However, for Con A, it is shown that the weak field dependence observed for the heteronuclear NOE is not due to internal motions, but rather to exchange processes.

  5. The influence of motor cortical stimulus intensity on the relaxation rate of human lower limb muscles

    NARCIS (Netherlands)

    McNeil, C.J.; Bredius, M.S.; Molenaar, J.P.F.; Gandevia, S.C.

    2013-01-01

    Transcranial magnetic stimulation (TMS) allows an in vivo assessment of the rate of muscle relaxation during a voluntary contraction. It is unknown if this method can be applied to lower limb muscles, and the effect of stimulus intensity on relaxation rate has not been investigated in any muscle

  6. Triple resonance 15N NMR relaxation experiments for studies of intrinsically disordered proteins

    Czech Academy of Sciences Publication Activity Database

    Srb, Pavel; Nováček, J.; Kadeřávek, P.; Rabatinová, Alžběta; Krásný, Libor; Žídková, Jitka; Bobálová, Janette; Sklenář, V.; Žídek, L.

    2017-01-01

    Roč. 69, č. 3 (2017), s. 133-146 ISSN 0925-2738 R&D Projects: GA ČR GA13-16842S; GA MŠk(CZ) LO1304 Institutional support: RVO:61388963 ; RVO:61388971 ; RVO:68081715 Keywords : nuclear magnetic resonance * relaxation * non-uniform sampling * intrinsically disordered proteins Subject RIV: CB - Analytical Chemistry, Separation; EE - Microbiology, Virology (MBU-M); CB - Analytical Chemistry, Separation (UIACH-O) OBOR OECD: Analytical chemistry; Microbiology (MBU-M); Analytical chemistry (UIACH-O) Impact factor: 2.410, year: 2016

  7. The influence of motor cortical stimulus intensity on the relaxation rate of human lower limb muscles.

    Science.gov (United States)

    McNeil, Chris J; Bredius, Marlous S; Molenaar, Joery P; Gandevia, Simon C

    2013-07-01

    Transcranial magnetic stimulation (TMS) allows an in vivo assessment of the rate of muscle relaxation during a voluntary contraction. It is unknown if this method can be applied to lower limb muscles, and the effect of stimulus intensity on relaxation rate has not been investigated in any muscle group. The present study sought to address these unknowns. A secondary aim was to test the sensitivity of the method to a change in muscle length by comparing the relaxation rate of the plantar flexor muscles with the gastrocnemius at short and long lengths. Seven subjects performed 21 maximal voluntary isometric contractions (MVCs) of the dorsiflexors (DF) and plantar flexors with a knee angle of either 90° or 180° (PF90 and PF180, respectively). TMS intensity ranged from 40 to 100% stimulator output in intervals of 10%. Relaxation rates increased with stimulus intensity but were equivalent to maximal output at 50 (DF and PF90) or 60% (PF180). MVC torque was greater, and the rate of relaxation was faster for PF180 compared to PF90. The main findings are that TMS can be used to measure relaxation rates of lower limb muscles, and these rates are robust provided the stimulus intensity is above a critical threshold. The dependency of plantar flexor relaxation rate on the length of the fast-twitch gastrocnemius fibers reinforces published temperature and fatigue data which show that the method is sensitive to the contractile properties of the muscle fibers which are actively contributing to torque production.

  8. Superionic phase transitions and nuclear spin phonon relaxation by Raman processes in Me3H(SeO4)2 (Me = Na, K, and Rb) single crystals by 1H and Me NMR

    International Nuclear Information System (INIS)

    Lim, Ae Ran

    2007-01-01

    Me 3 H(SeO 4 ) 2 (Me = Na, K, and Rb) single crystals were grown by the slow evaporation method, and the relaxation times of the 1 H and Me nuclei in these crystals were investigated using FT NMR spectrometry. The 1 H T 1 NMR results for K 3 H(SeO 4 ) 2 and Rb 3 H(SeO 4 ) 2 single crystals were very different from those for Na 3 H(SeO 4 ) 2 crystals. Short 1 H relaxation times were found for K 3 H(SeO 4 ) 2 and Rb 3 H(SeO 4 ) 2 at high temperatures, but not for Na 3 H(SeO 4 ) 2 , which are attributed to the destruction and reconstruction of hydrogen bonds; thus K 3 H(SeO 4 ) 2 and Rb 3 H(SeO 4 ) 2 have superionic phases, whereas Na 3 H(SeO 4 ) 2 does not. The temperature dependence of the relaxation rate for the 23 Na nucleus in Na 3 H(SeO 4 ) 2 crystals was in accord with a Raman process for nuclear spin-lattice relaxation (T 1 -1 ∝T 2 . In contrast, the spin-lattice relaxation rates for the 39 K and 87 Rb nuclei in K 3 H(SeO 4 ) 2 and Rb 3 H(SeO 4 ) 2 single crystals exhibited a very strong temperature dependence, T 1 -1 ∝T 7 . The motions giving rise to this strong temperature dependence may be related to the high electrical conductivities of these crystals at high temperatures

  9. Accurate determination of rates from non-uniformly sampled relaxation data

    International Nuclear Information System (INIS)

    Stetz, Matthew A.; Wand, A. Joshua

    2016-01-01

    The application of non-uniform sampling (NUS) to relaxation experiments traditionally used to characterize the fast internal motion of proteins is quantitatively examined. Experimentally acquired Poisson-gap sampled data reconstructed with iterative soft thresholding are compared to regular sequentially sampled (RSS) data. Using ubiquitin as a model system, it is shown that 25 % sampling is sufficient for the determination of quantitatively accurate relaxation rates. When the sampling density is fixed at 25 %, the accuracy of rates is shown to increase sharply with the total number of sampled points until eventually converging near the inherent reproducibility of the experiment. Perhaps contrary to some expectations, it is found that accurate peak height reconstruction is not required for the determination of accurate rates. Instead, inaccuracies in rates arise from inconsistencies in reconstruction across the relaxation series that primarily manifest as a non-linearity in the recovered peak height. This indicates that the performance of an NUS relaxation experiment cannot be predicted from comparison of peak heights using a single RSS reference spectrum. The generality of these findings was assessed using three alternative reconstruction algorithms, eight different relaxation measurements, and three additional proteins that exhibit varying degrees of spectral complexity. From these data, it is revealed that non-linearity in peak height reconstruction across the relaxation series is strongly correlated with errors in NUS-derived relaxation rates. Importantly, it is shown that this correlation can be exploited to reliably predict the performance of an NUS-relaxation experiment by using three or more RSS reference planes from the relaxation series. The RSS reference time points can also serve to provide estimates of the uncertainty of the sampled intensity, which for a typical relaxation times series incurs no penalty in total acquisition time.

  10. Accurate determination of rates from non-uniformly sampled relaxation data

    Energy Technology Data Exchange (ETDEWEB)

    Stetz, Matthew A.; Wand, A. Joshua, E-mail: wand@upenn.edu [University of Pennsylvania Perelman School of Medicine, Johnson Research Foundation and Department of Biochemistry and Biophysics (United States)

    2016-08-15

    The application of non-uniform sampling (NUS) to relaxation experiments traditionally used to characterize the fast internal motion of proteins is quantitatively examined. Experimentally acquired Poisson-gap sampled data reconstructed with iterative soft thresholding are compared to regular sequentially sampled (RSS) data. Using ubiquitin as a model system, it is shown that 25 % sampling is sufficient for the determination of quantitatively accurate relaxation rates. When the sampling density is fixed at 25 %, the accuracy of rates is shown to increase sharply with the total number of sampled points until eventually converging near the inherent reproducibility of the experiment. Perhaps contrary to some expectations, it is found that accurate peak height reconstruction is not required for the determination of accurate rates. Instead, inaccuracies in rates arise from inconsistencies in reconstruction across the relaxation series that primarily manifest as a non-linearity in the recovered peak height. This indicates that the performance of an NUS relaxation experiment cannot be predicted from comparison of peak heights using a single RSS reference spectrum. The generality of these findings was assessed using three alternative reconstruction algorithms, eight different relaxation measurements, and three additional proteins that exhibit varying degrees of spectral complexity. From these data, it is revealed that non-linearity in peak height reconstruction across the relaxation series is strongly correlated with errors in NUS-derived relaxation rates. Importantly, it is shown that this correlation can be exploited to reliably predict the performance of an NUS-relaxation experiment by using three or more RSS reference planes from the relaxation series. The RSS reference time points can also serve to provide estimates of the uncertainty of the sampled intensity, which for a typical relaxation times series incurs no penalty in total acquisition time.

  11. Accurate determination of rates from non-uniformly sampled relaxation data

    Science.gov (United States)

    Stetz, Matthew A.; Wand, A. Joshua

    2016-01-01

    The application of non-uniform sampling (NUS) to relaxation experiments traditionally used to characterize the fast internal motion of proteins is quantitatively examined. Experimentally acquired Poisson-gap sampled data reconstructed with iterative soft thresholding (IST) are compared to regular sequentially sampled (RSS) data. Using ubiquitin as a model system, it is shown that 25% sampling is sufficient for the determination of quantitatively accurate relaxation rates. When the sampling density is fixed at 25%, the accuracy of rates is shown to increase sharply with the total number of sampled points until eventually converging near the inherent reproducibility of the experiment. Perhaps contrary to some expectations, it is found that accurate peak height reconstruction is not required for the determination of accurate rates. Instead, inaccuracies in rates arise from inconsistencies in reconstruction across the relaxation series that primarily manifest as a non-linearity in the recovered peak height. This indicates that the performance of an NUS relaxation experiment cannot be predicted from comparison of peak heights using a single RSS reference spectrum. The generality of these findings was assessed using three alternative reconstruction algorithms, eight different relaxation measurements, and three additional proteins that exhibit varying degrees of spectral complexity. From these data, it is revealed that non-linearity in peak height reconstruction across the relaxation series is strongly correlated with errors in NUS-derived relaxation rates. Importantly, it is shown that this correlation can be exploited to reliably predict the performance of an NUS-relaxation experiment by using three or more RSS reference planes from the relaxation series. The RSS reference time points can also serve to provide estimates of the uncertainty of the sampled intensity, which for a typical relaxation times series incurs no penalty in total acquisition time. PMID:27393626

  12. Addressing the overlap problem in the quantitative analysis of two dimensional NMR spectra: Application to 15N relaxation measurements

    International Nuclear Information System (INIS)

    Tugarinov, Vitali; Choy, W.-Y.; Kupce, Eriks; Kay, Lewis E.

    2004-01-01

    A quantitative analysis of 2D 1 H- 15 N spectra is often complicated by resonance overlap. Here a simple method is presented for resolving overlapped correlations by recording 2D projection planes from HNCO data sets. Applications are presented involving the measurement of 15 N T 1ρ relaxation rates in a high molecular weight protein, malate synthase G, and in a system that exchanges between folded and unfolded states, the drkN SH3 domain. By supplementing relaxation data recorded in the conventional way as a series of 2D 1 H- 15 N data sets with a series of a pair of projection planes the number of dynamics probes is increased significantly for both systems studied

  13. Ligand-receptor binding affinities from saturation transfer difference (STD) NMR spectroscopy: the binding isotherm of STD initial growth rates.

    Science.gov (United States)

    Angulo, Jesús; Enríquez-Navas, Pedro M; Nieto, Pedro M

    2010-07-12

    The direct evaluation of dissociation constants (K(D)) from the variation of saturation transfer difference (STD) NMR spectroscopy values with the receptor-ligand ratio is not feasible due to the complex dependence of STD intensities on the spectral properties of the observed signals. Indirect evaluation, by competition experiments, allows the determination of K(D), as long as a ligand of known affinity is available for the protein under study. Herein, we present a novel protocol based on STD NMR spectroscopy for the direct measurements of receptor-ligand dissociation constants (K(D)) from single-ligand titration experiments. The influence of several experimental factors on STD values has been studied in detail, confirming the marked impact on standard determinations of protein-ligand affinities by STD NMR spectroscopy. These factors, namely, STD saturation time, ligand residence time in the complex, and the intensity of the signal, affect the accumulation of saturation in the free ligand by processes closely related to fast protein-ligand rebinding and longitudinal relaxation of the ligand signals. The proposed method avoids the dependence of the magnitudes of ligand STD signals at a given saturation time on spurious factors by constructing the binding isotherms using the initial growth rates of the STD amplification factors, in a similar way to the use of NOE growing rates to estimate cross relaxation rates for distance evaluations. Herein, it is demonstrated that the effects of these factors are cancelled out by analyzing the protein-ligand association curve using STD values at the limit of zero saturation time, when virtually no ligand rebinding or relaxation takes place. The approach is validated for two well-studied protein-ligand systems: the binding of the saccharides GlcNAc and GlcNAcbeta1,4GlcNAc (chitobiose) to the wheat germ agglutinin (WGA) lectin, and the interaction of the amino acid L-tryptophan to bovine serum albumin (BSA). In all cases, the

  14. Backbone dynamics of a biologically active human FGF-1 monomer, complexed to a hexasaccharide heparin-analogue, by {sup 15}N NMR relaxation methods

    Energy Technology Data Exchange (ETDEWEB)

    Canales-Mayordomo, Angeles; Fayos, Rosa [Centro de Investigaciones Biologicas, CSIC, Departamento de Estructura y Funcion de Proteinas (Spain); Angulo, Jesus; Ojeda, Rafael [Instituto de Investigaciones Quimicas, CSIC, Grupo de Carbohidratos (Spain); Martin-Pastor, Manuel [Unidad de RM y Unidad de RMN de Biomoleculas Asociada al CSIC, Laboratorio de Estructura e Estructura de Biomoleculas Jose Carracido (Spain); Nieto, Pedro M.; Martin-Lomas, Manuel [Instituto de Investigaciones Quimicas, CSIC, Grupo de Carbohidratos (Spain); Lozano, Rosa; Gimenez-Gallego, Guillermo; Jimenez-Barbero, Jesus [Centro de Investigaciones Biologicas, CSIC, Departamento de Estructura y Funcion de Proteinas (Spain)], E-mail: jjbarbero@cib.csic.es

    2006-08-15

    The binding site and backbone dynamics of a bioactive complex formed by the acidic fibroblast growth factor (FGF-1) and a specifically designed heparin hexasaccharide has been investigated by HSQC and relaxation NMR methods. The comparison of the relaxation data for the free and bound states has allowed showing that the complex is monomeric, and still induces mutagenesis, and that the protein backbone presents reduced motion in different timescale in its bound state, except in certain points that are involved in the interaction with the fibroblast growth factor receptor (FGFR)

  15. Backbone dynamics of a biologically active human FGF-1 monomer, complexed to a hexasaccharide heparin-analogue, by 15N NMR relaxation methods

    International Nuclear Information System (INIS)

    Canales-Mayordomo, Angeles; Fayos, Rosa; Angulo, Jesus; Ojeda, Rafael; Martin-Pastor, Manuel; Nieto, Pedro M.; Martin-Lomas, Manuel; Lozano, Rosa; Gimenez-Gallego, Guillermo; Jimenez-Barbero, Jesus

    2006-01-01

    The binding site and backbone dynamics of a bioactive complex formed by the acidic fibroblast growth factor (FGF-1) and a specifically designed heparin hexasaccharide has been investigated by HSQC and relaxation NMR methods. The comparison of the relaxation data for the free and bound states has allowed showing that the complex is monomeric, and still induces mutagenesis, and that the protein backbone presents reduced motion in different timescale in its bound state, except in certain points that are involved in the interaction with the fibroblast growth factor receptor (FGFR)

  16. Effects of glycosaminoglycan in the nucleus pulposus of cow on the 1H-NMR relaxation times and dynamic viscoelasticity

    International Nuclear Information System (INIS)

    Ohtomo, Satoshi

    1988-01-01

    Nucleus pulposus of the intervertebral disc (NP) has viscoelasticity owing to its high water content. The purpose of this study is to clarify the effects of glycosaminoglycan (GAG) on the mechanical property of NP by examining its interaction with water molecules. Nucleus pulposus of cow discs containing two different amounts of GAG were prepared: non-treated NP and GAG-depleted NP by treatment of hyaluronidase. The 1 H-NMR relaxation times (T 1 , T 2 ) indicating the mobility of water, and dynamic viscoelasticity (|E*|) of those materials were measured. The results suggested that the |E*| value in the normal NP depended on the mobility of water, which is regulated mainly by its interaction with GAG. On the other hand, the |E*| value in the GAG-depleted NP depended not only on the mobility of water but also on the elasticity of the collagen fiber in the NP. In conclusion, GAG plays an important role in the viscoelastic property of the NP by retaining water and by restricting its mobility. (author)

  17. Determination of the Electron Self-Exchange Rates of Blue Copper Proteins by Super-WEFT NMR Spectroscopy

    DEFF Research Database (Denmark)

    Ma, Lixin; Philipp, Else Astrid; Led, Jens J.

    2001-01-01

    Anabaena variabilis plastocyanin, blue copper proteins, electron self-exchange rates, electron transfer, super-WEFT NMR......Anabaena variabilis plastocyanin, blue copper proteins, electron self-exchange rates, electron transfer, super-WEFT NMR...

  18. Relaxation rates of gene expression kinetics reveal the feedback signs of autoregulatory gene networks

    Science.gov (United States)

    Jia, Chen; Qian, Hong; Chen, Min; Zhang, Michael Q.

    2018-03-01

    The transient response to a stimulus and subsequent recovery to a steady state are the fundamental characteristics of a living organism. Here we study the relaxation kinetics of autoregulatory gene networks based on the chemical master equation model of single-cell stochastic gene expression with nonlinear feedback regulation. We report a novel relation between the rate of relaxation, characterized by the spectral gap of the Markov model, and the feedback sign of the underlying gene circuit. When a network has no feedback, the relaxation rate is exactly the decaying rate of the protein. We further show that positive feedback always slows down the relaxation kinetics while negative feedback always speeds it up. Numerical simulations demonstrate that this relation provides a possible method to infer the feedback topology of autoregulatory gene networks by using time-series data of gene expression.

  19. Effect of spatial spin modulation on relaxation and NMR frequencies of sup 5 sup 7 Fe nuclei in ferroelectric antiferromagnetic BiFeO sub 3

    CERN Document Server

    Zalessky, A V; Zvezdin, A K; Gippius, A A; Morozova, E N; Khozeev, D F; Bush, A S; Pokatilov, V S

    2002-01-01

    The NMR spectra on the iron nuclei in the BiFeO sub 3 antiferromagnetic sample enriched by the sup 5 sup 7 Fe (95.43%) with the spatially-modulated magnetic structure are studied. It is established that the cycloid-type spin modulation in the BiFeO sub 3 produces spatial modulation of the nuclear spin-spin relaxation velocity and leads to the spectral nonuniform widening of the NMR local line. It is determined also that the local magnetic moments of the iron ions on various cycloid sections differently depend on temperature which testifies to different character of the spin waves excitation. The analogy of the experimental results with the NMR regularities in the Bloch wall is discussed

  20. Pairwise NMR experiments for the determination of protein backbone dihedral angle Φ based on cross-correlated spin relaxation

    International Nuclear Information System (INIS)

    Takahashi, Hideo; Shimada, Ichio

    2007-01-01

    Novel cross-correlated spin relaxation (CCR) experiments are described, which measure pairwise CCR rates for obtaining peptide dihedral angles Φ. The experiments utilize intra-HNCA type coherence transfer to refocus 2-bond J NCα coupling evolution and generate the N (i)-C α (i) or C'(i-1)-C α (i) multiple quantum coherences which are required for measuring the desired CCR rates. The contribution from other coherences is also discussed and an appropriate setting of the evolution delays is presented. These CCR experiments were applied to 15 N- and 13 C-labeled human ubiquitin. The relevant CCR rates showed a high degree of correlation with the Φ angles observed in the X-ray structure. By utilizing these CCR experiments in combination with those previously established for obtaining dihedral angle Ψ, we can determine high resolution structures of peptides that bind weakly to large target molecules

  1. Combined Diffusion Tensor Imaging and Apparent Transverse Relaxation Rate Differentiate Parkinson Disease and Atypical Parkinsonism.

    Science.gov (United States)

    Du, G; Lewis, M M; Kanekar, S; Sterling, N W; He, L; Kong, L; Li, R; Huang, X

    2017-05-01

    Both diffusion tensor imaging and the apparent transverse relaxation rate have shown promise in differentiating Parkinson disease from atypical parkinsonism (particularly multiple system atrophy and progressive supranuclear palsy). The objective of the study was to assess the ability of DTI, the apparent transverse relaxation rate, and their combination for differentiating Parkinson disease, multiple system atrophy, progressive supranuclear palsy, and controls. A total of 106 subjects (36 controls, 35 patients with Parkinson disease, 16 with multiple system atrophy, and 19 with progressive supranuclear palsy) were included. DTI and the apparent transverse relaxation rate measures from the striatal, midbrain, limbic, and cerebellar regions were obtained and compared among groups. The discrimination performance of DTI and the apparent transverse relaxation rate among groups was assessed by using Elastic-Net machine learning and receiver operating characteristic curve analysis. Compared with controls, patients with Parkinson disease showed significant apparent transverse relaxation rate differences in the red nucleus. Compared to those with Parkinson disease, patients with both multiple system atrophy and progressive supranuclear palsy showed more widespread changes, extending from the midbrain to striatal and cerebellar structures. The pattern of changes, however, was different between the 2 groups. For instance, patients with multiple system atrophy showed decreased fractional anisotropy and an increased apparent transverse relaxation rate in the subthalamic nucleus, whereas patients with progressive supranuclear palsy showed an increased mean diffusivity in the hippocampus. Combined, DTI and the apparent transverse relaxation rate were significantly better than DTI or the apparent transverse relaxation rate alone in separating controls from those with Parkinson disease/multiple system atrophy/progressive supranuclear palsy; controls from those with Parkinson

  2. Determination of the electron self-exchange rates of blue copper proteins by super-WEFT NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Ma Lixin; Philipp, Else; Led, Jens J. [University of Copenhagen, H.C. Orsted Institute, Department of Chemistry (Denmark)

    2001-03-15

    An NMR approach for determining the electron self-exchange (ESE) rate constants in blue copper proteins is presented. The approach uses the paramagnetic relaxation enhancement of resonances in 1D {sup 1}H super-WEFT spectra of partly oxidized (paramagnetic) proteins. These spectra allow a more precise determination of the relevant paramagnetic linebroadenings than conventional 1D {sup 1}H spectra and, thus, permit a more detailed investigation of the applicability of the linebroadenings for determining the electron exchange rates. The approach was used to estimate the ESE rate constant of plastocyanin from Anabaena variabilis. It was found that, although the rate constant can be determined accurately from a series of resonances, precise but erroneous constants are obtained from the resonances of the copper-bound residues, unless a narrow splitting of these resonances caused by the presence of two conformations is taken into account. As demonstrated here, this complication can be overcome by a correct analysis of the paramagnetic broadening of the combined double signals. Because of the high resolution and specific sensitivity of the approach it should be generally applicable to estimate electron transfer rates, k, if the paramagnetic relaxation enhancement R{sub 2p} of the resonances can be determined, and the conditions k<<>k>>R{sub 2p} are fulfilled, {delta}{omega}{sub p} being the frequency separation between corresponding diamagnetic and paramagnetic sites.

  3. Oxygen-17-induced proton relaxation rates for alcohols and alcohol solutions

    Directory of Open Access Journals (Sweden)

    Farrar Thomas C.

    1999-01-01

    Full Text Available The use of 17O enriched samples of alcohols to measure the correlation time of the OH internuclear vector works well when the hydroxyl proton exchanges rapidly. For alcohols such as methanol and ethanol the hydroxyl exchange rate for neat samples is relatively slow even at room temperature and significant systematic errors result if slow exchange effects are not considered. For slow exchange the hydroxyl proton, 17OH, signal is a relatively complex function of the chemical exchange rate of the hydroxyl proton, the OH spin coupling (about 80 Hz for alcohols and water and the relaxation time for the oxygen. The OH linewidth can become so large due to scalar relaxation with the rapidly relaxing oxygen nucleus that the signal becomes very difficult to detect. For neat 17O enriched ethanol at room temperature the oxygen relaxation time is about 3.0 ms and the hydroxyl proton linewidth is over 1000 Hz.

  4. Randomized controlled trial of relaxation music to reduce heart rate in patients undergoing cardiac CT.

    Science.gov (United States)

    Ng, Ming Yen; Karimzad, Yasser; Menezes, Ravi J; Wintersperger, Bernd J; Li, Qin; Forero, Julian; Paul, Narinder S; Nguyen, Elsie T

    2016-10-01

    To evaluate the heart rate lowering effect of relaxation music in patients undergoing coronary CT angiography (CCTA), pulmonary vein CT (PVCT) and coronary calcium score CT (CCS). Patients were randomised to a control group (i.e. standard of care protocol) or to a relaxation music group (ie. standard of care protocol with music). The groups were compared for heart rate, radiation dose, image quality and dose of IV metoprolol. Both groups completed State-Trait Anxiety Inventory anxiety questionnaires to assess patient experience. One hundred and ninety-seven patients were recruited (61.9 % males); mean age 56y (19-86 y); 127 CCTA, 17 PVCT, 53 CCS. No significant difference in heart rate, radiation dose, image quality, metoprolol dose and anxiety scores. 86 % of patients enjoyed the music. 90 % of patients in the music group expressed a strong preference to have music for future examinations. The patient cohort demonstrated low anxiety levels prior to CT. Relaxation music in CCTA, PVCT and CCS does not reduce heart rate or IV metoprolol use. Patients showed low levels of anxiety indicating that anxiolytics may not have a significant role in lowering heart rate. Music can be used in cardiac CT to improve patient experience. • Relaxation music does not reduce heart rate in cardiac CT • Relaxation music does not reduce beta-blocker use in cardiac CT • Relaxation music has no effect on cardiac CT image quality • Low levels of anxiety are present in patients prior to cardiac CT • Patients enjoyed the relaxation music and this results in improved patient experience.

  5. Microscale consolidation analysis of relaxation behavior of single living chondrocytes subjected to varying strain-rates.

    Science.gov (United States)

    Nguyen, Trung Dung; Oloyede, Adekunle; Singh, Sanjleena; Gu, YuanTong

    2015-09-01

    Besides the elastic stiffness, the relaxation behavior of single living cells is also of interest of various researchers when studying cell mechanics. It is hypothesized that the relaxation response of the cells is governed by both intrinsic viscoelasticity of the solid phase and fluid-solid interactions mechanisms. There are a number of mechanical models have been developed to investigate the relaxation behavior of single cells. However, there is lack of model enable to accurately capture both of the mechanisms. Therefore, in this study, the porohyperelastic (PHE) model, which is an extension of the consolidation theory, combined with inverse Finite Element Analysis (FEA) technique was used at the first time to investigate the relaxation response of living chondrocytes. This model was also utilized to study the dependence of relaxation behavior of the cells on strain-rates. The stress-relaxation experiments under the various strain-rates were conducted with the Atomic Force Microscopy (AFM). The results have demonstrated that the PHE model could effectively capture the stress-relaxation behavior of the living chondrocytes, especially at intermediate to high strain-rates. Although this model gave some errors at lower strain-rates, its performance was acceptable. Therefore, the PHE model is properly a promising model for single cell mechanics studies. Moreover, it has been found that the hydraulic permeability of living chondrocytes reduced with decreasing of strain-rates. It might be due to the intracellular fluid volume fraction and the fluid pore pressure gradients of chondrocytes were higher when higher strain-rates applied. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Rotational and translational dynamics and their relation to hydrogen bond lifetimes in an ionic liquid by means of NMR relaxation time experiments and molecular dynamics simulation

    Science.gov (United States)

    Strate, Anne; Neumann, Jan; Overbeck, Viviane; Bonsa, Anne-Marie; Michalik, Dirk; Paschek, Dietmar; Ludwig, Ralf

    2018-05-01

    We report a concerted theoretical and experimental effort to determine the reorientational dynamics as well as hydrogen bond lifetimes for the doubly ionic hydrogen bond +OH⋯O- in the ionic liquid (2-hydroxyethyl)trimethylammonium bis(trifluoromethylsulfonyl)imide [Ch][NTf2] by using a combination of NMR relaxation time experiments, density functional theory (DFT) calculations, and molecular dynamics (MD) simulations. Due to fast proton exchange, the determination of rotational correlation times is challenging. For molecular liquids, 17O-enhanced proton relaxation time experiments have been used to determine the rotational correlation times for the OH vectors in water or alcohols. As an alternative to those expensive isotopic substitution experiments, we employed a recently introduced approach which is providing access to the rotational dynamics from a single NMR deuteron quadrupolar relaxation time experiment. Here, the deuteron quadrupole coupling constants (DQCCs) are obtained from a relation between the DQCC and the δ1H proton chemical shifts determined from a set of DFT calculated clusters in combination with experimentally determined proton chemical shifts. The NMR-obtained rotational correlation times were compared to those obtained from MD simulations and then related to viscosities for testing the applicability of popular hydrodynamic models. In addition, hydrogen bond lifetimes were derived, using hydrogen bond population correlation functions computed from MD simulations. Here, two different time domains were observed: The short-time contributions to the hydrogen lifetimes and the reorientational correlation times have roughly the same size and are located in the picosecond range, whereas the long-time contributions decay with relaxation times in the nanosecond regime and are related to rather slow diffusion processes. The computed average hydrogen bond lifetime is dominated by the long-time process, highlighting the importance and longevity of

  7. Relating PAC damping to EFG fluctuation rates through the PAC relaxation peak

    Energy Technology Data Exchange (ETDEWEB)

    Park, Tyler [Utah Valley University, Department of Physics (United States); Hodges, Jeffery A. [University of Utah, Department of Physics (United States); Moreno, Carlos; Stufflebeam, Michael; Evenson, William E., E-mail: bill@evenson.ch; Matheson, P. [Utah Valley University, Department of Physics (United States); Zacate, M. O. [Northern Kentucky University, Department of Physics and Geology (United States); Collins, Gary S. [Washington State University, Department of Physics and Astronomy (United States)

    2011-07-15

    A perturbed angular correlation (PAC) experiment that measures dynamic damping also needs information about the fundamental quadrupole frequency to relate the damping as a function of temperature to the EFG fluctuation rate. When the experiment is unable to access slow electric field gradient (EFG) fluctuations that show the fundamental quadrupole frequency directly, one needs additional information to determine the hyperfine field parameters and thereby the connection between observed damping and EFG fluctuation rates. One way to solve this problem is to estimate the hyperfine parameters from the fluctuation rate for maximum damping (i.e. at the relaxation peak) or from the rate of maximum damping. This work relates both the maximum damping rate and the fluctuation rate at the relaxation peak to EFG magnitudes (or quadrupole frequencies) for five dynamic N-state symmetric models of fluctuating EFGs.

  8. Relating PAC damping to EFG fluctuation rates through the PAC relaxation peak

    International Nuclear Information System (INIS)

    Park, Tyler; Hodges, Jeffery A.; Moreno, Carlos; Stufflebeam, Michael; Evenson, William E.; Matheson, P.; Zacate, M. O.; Collins, Gary S.

    2011-01-01

    A perturbed angular correlation (PAC) experiment that measures dynamic damping also needs information about the fundamental quadrupole frequency to relate the damping as a function of temperature to the EFG fluctuation rate. When the experiment is unable to access slow electric field gradient (EFG) fluctuations that show the fundamental quadrupole frequency directly, one needs additional information to determine the hyperfine field parameters and thereby the connection between observed damping and EFG fluctuation rates. One way to solve this problem is to estimate the hyperfine parameters from the fluctuation rate for maximum damping (i.e. at the relaxation peak) or from the rate of maximum damping. This work relates both the maximum damping rate and the fluctuation rate at the relaxation peak to EFG magnitudes (or quadrupole frequencies) for five dynamic N-state symmetric models of fluctuating EFGs.

  9. Selective modification of NMR relaxation time in human colorectal carcinoma by using gadolinium-diethylenetriaminepentaacetic acid conjugated with monoclonal antibody 19-9.

    OpenAIRE

    Curtet, C; Tellier, C; Bohy, J; Conti, M L; Saccavini, J C; Thedrez, P; Douillard, J Y; Chatal, J F; Koprowski, H

    1986-01-01

    Monoclonal antibody 19-9 (mAb 19-9) against human colon adenocarcinoma was conjugated with gadolinium X diethylenetriaminepentaacetic acid (Gd X DTPA) and used as a contrast agent in nuclear magnetic resonance (NMR) in an effort to improve tumor target selectivity in nude mice. The data indicate that Gd X DTPA-mAb 19-9 in solution decreased the T1 relaxation of water protons at 90 MHz in direct proportion to the gadolinium concentration, and this effect was greater than in Gd X DTPA solutions...

  10. Music for relaxation: a comparison of musicians and nonmusicians on ratings of selected musical recordings.

    Science.gov (United States)

    Wolfe, David E; O'Connell, Audree S; Waldon, Eric G

    2002-01-01

    The purpose of this study was to determine the kinds of musical selections/CDs to place in a portfolio to be used within a music listening/relaxation program for parents of children in a pediatric hospital. A panel of experts (4 music therapy graduate students and 2 music therapy instructors) listened to a selection of CD recordings (n = 10) which reported to contain music for relaxation. These 10 recordings were chosen based either on words within the title suggestive of sedative/relaxing music, or the literature (booklet) accompanying the CD that contained claims of such therapeutic value. Average number of selections across the 10 recordings was 9.8 with a total of 98 musical selections presented to the panel. A 1 1/2-minute segment from each selection (starting at the beginning of each piece) was played on a stereo CD unit, and time was given to complete a response form following each of the musical selections. The panel was asked to rate the relaxation quality of each piece, and to specify the musical characteristics that enhanced and/or distracted from relaxation. Weekly listening sessions of 40-50 minutes in duration were scheduled across a 10-week time period. Based on the results of the experts, 10 of the 98 musical selections were chosen for presentation to a group of nonmusicians. Again, as with the experts, the nonmusicians listened to 1 1/2-minute segments from each selection and completed a response form similar to the form completed by the panel. Additional questions asked the nonmusicians whether they listened to music for relaxation, and if so, what kind(s) of music they preferred to use for this purpose. Results from the panel of experts and nonmusicians were compiled, and descriptive statistics were used to compare the data. Suggestions were given concerning possible inclusion of musical recordings that may be used in a music listening/ relaxation program for parents of children within a pediatric setting.

  11. Cross-correlated relaxation rates between protein backbone H–X dipolar interactions

    Energy Technology Data Exchange (ETDEWEB)

    Vögeli, Beat, E-mail: beat.vogeli@ucdenver.edu [University of Colorado Denver, Department of Biochemistry and Molecular Genetics (United States)

    2017-03-15

    The relaxation interference between dipole–dipole interactions of two separate spin pairs carries structural and dynamics information. In particular, when compared to individual dynamic behavior of those spin pairs, such cross-correlated relaxation (CCR) rates report on the correlation between the spin pairs. We have recently mapped out correlated motion along the backbone of the protein GB3, using CCR rates among and between consecutive H{sup N}–N and H{sup α}–C{sup α} dipole–dipole interactions. Here, we provide a detailed account of the measurement of the four types of CCR rates. All rates were obtained from at least two different pulse sequences, of which the yet unpublished ones are presented. Detailed comparisons between the different methods and corrections for unwanted pathways demonstrate that the averaged CCR rates are highly accurate and precise with errors of 1.5–3% of the entire value ranges.

  12. Cross-correlated relaxation rates between protein backbone H–X dipolar interactions

    International Nuclear Information System (INIS)

    Vögeli, Beat

    2017-01-01

    The relaxation interference between dipole–dipole interactions of two separate spin pairs carries structural and dynamics information. In particular, when compared to individual dynamic behavior of those spin pairs, such cross-correlated relaxation (CCR) rates report on the correlation between the spin pairs. We have recently mapped out correlated motion along the backbone of the protein GB3, using CCR rates among and between consecutive H N –N and H α –C α dipole–dipole interactions. Here, we provide a detailed account of the measurement of the four types of CCR rates. All rates were obtained from at least two different pulse sequences, of which the yet unpublished ones are presented. Detailed comparisons between the different methods and corrections for unwanted pathways demonstrate that the averaged CCR rates are highly accurate and precise with errors of 1.5–3% of the entire value ranges.

  13. Low-Dimensional Nanoparticle Clustering in Polymer Micelles and Their Transverse Relaxivity Rates

    Science.gov (United States)

    Hickey, Robert J.; Meng, Xin; Zhang, Peijun; Park, So-Jung

    2015-01-01

    One- or two-dimensional arrays of iron oxide nanoparticles were formed in colloidal assemblies of amphiphilic polymers. Electron tomography imaging revealed that nanoparticles are arranged into one-dimensional strings in magneto-micelles or two-dimensional sheets in magneto-core/shell assemblies. The distinct directional assembly behavior was attributed to the interparticle interaction relative to the nanoparticle–polymer interaction, which was modulated by varying the cosolvent used for the solution phase self-assembly. Magneto-core/shell assemblies with varying structural parameters were formed with a range of different sized as-synthesized nanoparticles. The transverse magnetic relaxivity rates (r2) of a series of different assemblies were determined to examine the effect of nanoparticle arrangement on the magnetic relaxivity for their potential applications in MRI. The results indicated that the assembly structure of nanoparticles in polymer micelles significantly affects the r2 of surrounding water, providing a way to control magnetic relaxivity. PMID:23731021

  14. Randomized controlled trial of relaxation music to reduce heart rate in patients undergoing cardiac CT

    International Nuclear Information System (INIS)

    Ng, Ming Yen; Karimzad, Yasser; Menezes, Ravi J.; Wintersperger, Bernd J.; Li, Qin; Forero, Julian; Paul, Narinder S.; Nguyen, Elsie T.

    2016-01-01

    To evaluate the heart rate lowering effect of relaxation music in patients undergoing coronary CT angiography (CCTA), pulmonary vein CT (PVCT) and coronary calcium score CT (CCS). Patients were randomised to a control group (i.e. standard of care protocol) or to a relaxation music group (ie. standard of care protocol with music). The groups were compared for heart rate, radiation dose, image quality and dose of IV metoprolol. Both groups completed State-Trait Anxiety Inventory anxiety questionnaires to assess patient experience. One hundred and ninety-seven patients were recruited (61.9 % males); mean age 56y (19-86 y); 127 CCTA, 17 PVCT, 53 CCS. No significant difference in heart rate, radiation dose, image quality, metoprolol dose and anxiety scores. 86 % of patients enjoyed the music. 90 % of patients in the music group expressed a strong preference to have music for future examinations. The patient cohort demonstrated low anxiety levels prior to CT. Relaxation music in CCTA, PVCT and CCS does not reduce heart rate or IV metoprolol use. Patients showed low levels of anxiety indicating that anxiolytics may not have a significant role in lowering heart rate. Music can be used in cardiac CT to improve patient experience. (orig.)

  15. Randomized controlled trial of relaxation music to reduce heart rate in patients undergoing cardiac CT

    Energy Technology Data Exchange (ETDEWEB)

    Ng, Ming Yen [University of Toronto, Department of Medical Imaging, Toronto General Hospital, Toronto, ON (Canada); The University of Hong Kong, Queen Mary Hospital, Department of Diagnostic Radiology, Hong Kong (China); Karimzad, Yasser; Menezes, Ravi J.; Wintersperger, Bernd J.; Li, Qin; Forero, Julian; Paul, Narinder S.; Nguyen, Elsie T. [University of Toronto, Department of Medical Imaging, Toronto General Hospital, Toronto, ON (Canada)

    2016-10-15

    To evaluate the heart rate lowering effect of relaxation music in patients undergoing coronary CT angiography (CCTA), pulmonary vein CT (PVCT) and coronary calcium score CT (CCS). Patients were randomised to a control group (i.e. standard of care protocol) or to a relaxation music group (ie. standard of care protocol with music). The groups were compared for heart rate, radiation dose, image quality and dose of IV metoprolol. Both groups completed State-Trait Anxiety Inventory anxiety questionnaires to assess patient experience. One hundred and ninety-seven patients were recruited (61.9 % males); mean age 56y (19-86 y); 127 CCTA, 17 PVCT, 53 CCS. No significant difference in heart rate, radiation dose, image quality, metoprolol dose and anxiety scores. 86 % of patients enjoyed the music. 90 % of patients in the music group expressed a strong preference to have music for future examinations. The patient cohort demonstrated low anxiety levels prior to CT. Relaxation music in CCTA, PVCT and CCS does not reduce heart rate or IV metoprolol use. Patients showed low levels of anxiety indicating that anxiolytics may not have a significant role in lowering heart rate. Music can be used in cardiac CT to improve patient experience. (orig.)

  16. Potentiation increases peak twitch torque by enhancing rates of torque development and relaxation.

    Science.gov (United States)

    Froyd, Christian; Beltrami, Fernando Gabe; Jensen, Jørgen; Noakes, Timothy David

    2013-01-01

    The aim of this study was to measure the extent to which potentiation changes in response to an isometric maximal voluntary contraction. Eleven physically active subjects participated in two separate studies. Single stimulus of electrical stimulation of the femoral nerve was used to measure torque at rest in unpotentiated quadriceps muscles (study 1 and 2), and potentiated quadriceps muscles torque in a 10 min period after a 5 s isometric maximal voluntary contraction of the quadriceps muscles (study 1). Additionally, potentiated quadriceps muscles torque was measured every min after a further 10 maximal voluntary contractions repeated every min (study 2). Electrical stimulation repeated several times without previous maximal voluntary contraction showed similar peak twitch torque. Peak twitch torque 4 s after a 5 s maximal voluntary contraction increased by 45±13% (study 1) and by 56±10% (study 2), the rate of torque development by 53±13% and 82±29%, and the rate of relaxation by 50±17% and 59±22%, respectively, but potentiation was lost already two min after a 5 s maximal voluntary contraction. There was a tendency for peak twitch torque to increase for the first five repeated maximal voluntary contractions, suggesting increased potentiation with additional maximal voluntary contractions. Correlations for peak twitch torque vs the rate of torque development and for the rate of relaxation were r(2)= 0.94 and r(2)=0.97. The correlation between peak twitch torque, the rate of torque development and the rate of relaxation suggests that potentiation is due to instantaneous changes in skeletal muscle contractility and relaxation.

  17. Cross-validation of the structure of a transiently formed and low populated FF domain folding intermediate determined by relaxation dispersion NMR and CS-Rosetta.

    Science.gov (United States)

    Barette, Julia; Velyvis, Algirdas; Religa, Tomasz L; Korzhnev, Dmitry M; Kay, Lewis E

    2012-06-14

    We have recently reported the atomic resolution structure of a low populated and transiently formed on-pathway folding intermediate of the FF domain from human HYPA/FBP11 [Korzhnev, D. M.; Religa, T. L.; Banachewicz, W.; Fersht, A. R.; Kay, L.E. Science 2011, 329, 1312-1316]. The structure was determined on the basis of backbone chemical shift and bond vector orientation restraints of the invisible intermediate state measured using relaxation dispersion nuclear magnetic resonance (NMR) spectroscopy that were subsequently input into the database structure determination program, CS-Rosetta. As a cross-validation of the structure so produced, we present here the solution structure of a mimic of the folding intermediate that is highly populated in solution, obtained from the wild-type domain by mutagenesis that destabilizes the native state. The relaxation dispersion/CS-Rosetta structures of the intermediate are within 2 Å of those of the mimic, with the nonnative interactions in the intermediate also observed in the mimic. This strongly confirms the structure of the FF domain folding intermediate, in particular, and validates the use of relaxation dispersion derived restraints in structural studies of invisible excited states, in general.

  18. Simple expressions of the nuclear relaxation rate enhancement due to quadrupole nuclei in slowly tumbling molecules

    Energy Technology Data Exchange (ETDEWEB)

    Fries, Pascal H., E-mail: pascal-h.fries@cea.fr [Université Grenoble Alpes, INAC-SCIB, RICC, F-38000 Grenoble (France); CEA, INAC-SCIB, RICC, F-38000 Grenoble (France); Belorizky, Elie [Université Grenoble Alpes, LIPHY, F-38000 Grenoble (France); CEA, Leti-Clinatec, F-38000 Grenoble (France)

    2015-07-28

    For slowly tumbling entities or quasi-rigid lattices, we derive very simple analytical expressions of the quadrupole relaxation enhancement (QRE) of the longitudinal relaxation rate R{sub 1} of nuclear spins I due to their intramolecular magnetic dipolar coupling with quadrupole nuclei of arbitrary spins S ≥ 1. These expressions are obtained by using the adiabatic approximation for evaluating the time evolution operator of the quantum states of the quadrupole nuclei S. They are valid when the gyromagnetic ratio of the spin S is much smaller than that of the spin I. The theory predicts quadrupole resonant peaks in the dispersion curve of R{sub 1} vs magnetic field. The number, positions, relative intensities, Lorentzian shapes, and widths of these peaks are explained in terms of the following properties: the magnitude of the quadrupole Hamiltonian and the asymmetry parameter of the electric field gradient (EFG) acting on the spin S, the S-I inter-spin orientation with respect to the EFG principal axes, the rotational correlation time of the entity carrying the S–I pair, and/or the proper relaxation time of the spin S. The theory is first applied to protein amide protons undergoing dipolar coupling with fast-relaxing quadrupole {sup 14}N nuclei and mediating the QRE to the observed bulk water protons. The theoretical QRE agrees well with its experimental counterpart for various systems such as bovine pancreatic trypsin inhibitor and cartilages. The anomalous behaviour of the relaxation rate of protons in synthetic aluminium silicate imogolite nano-tubes due to the QRE of {sup 27}Al (S = 5/2) nuclei is also explained.

  19. PROGRESSIVE MUSCLE RELAXATION INCREASE PEAK EXPIRATORY FLOW RATE ON CHRONIC OBSTRUCTIVE PULMONARY DISEASE PATIENTS

    Directory of Open Access Journals (Sweden)

    Tintin Sukartini

    2017-07-01

    Full Text Available Introduction: Limited progressive air flow in Chronic Obstructive Pulmonary Disease (COPD can caused by small airway disease (bronchiolitis obstructive and loss of elasticity of the lung (emphysema. Further it can be decreasing the quality of life in COPD patients because dyspnea and uncomfortable in activity. Progressive muscle relaxation (PMR is one of the relaxation technique that can repair pulmonary ventilation by decreasing chronic constriction of the respiratory muscles. The objective of this study was to analyze the effect of progressive muscle relaxation on raised peak expiratory flow rate (PEFR. Method: A pre-experimental one group pre-post test design was used in this study. Population was all of the COPD patients at Pulmonary Specialist Polyclinic Dr Mohamad Soewandhie Surabaya. There were 8 respondents taken by using purposive sampling. PEFR was counted by using peak flow meter every six day. Data were analyzed by using Paired t-Test with significance level  p≤0.05. Result: The result showed that PMR had significance level on increasing of PEFR (p=0.012. Discussion: It can be concluded that PMR has an effect on raise PEFR. Further studies are recommended to measure the effect of PMR on respiratory rate (RR, heart rate (HR subjective dyspnoe symptoms, forced expiration volume on the first minute (FEV1 and mid maximum flow rate (MMFR in COPD patients.

  20. Realization of a scenario with two relaxation rates in the Hubbard Falicov-Kimball model

    Science.gov (United States)

    Barman, H.; Laad, M. S.; Hassan, S. R.

    2018-02-01

    A single transport relaxation rate governs the decay of both longitudinal and Hall currents in Landau Fermi liquids (FL). Breakdown of this fundamental feature, first observed in two-dimensional cuprates and subsequently in other three-dimensional correlated systems close to the Mott metal-insulator transition, played a pivotal role in emergence of a non-FL (NFL) paradigm in higher dimensions D (>1 ) . Motivated hereby, we explore the emergence of this "two relaxation rates" scenario in the Hubbard Falicov-Kimball model (HFKM) using the dynamical mean-field theory (DMFT). Specializing to D =3 , we find, beyond a critical Falicov-Kimball (FK) interaction, that two distinct relaxation rates governing distinct temperature (T ) dependence of the longitudinal and Hall currents naturally emerges in the NFL metal. Our results show good accord with the experiment in V2 -yO3 near the metal-to-insulator transition (MIT). We rationalize this surprising finding by an analytical analysis of the structure of charge and spin Hamiltonians in the underlying impurity problem, specifically through a bosonization method applied to the Wolff model and connecting it to the x-ray edge problem.

  1. An optimized method for (15)N R(1) relaxation rate measurements in non-deuterated proteins.

    Science.gov (United States)

    Gairí, Margarida; Dyachenko, Andrey; González, M Teresa; Feliz, Miguel; Pons, Miquel; Giralt, Ernest

    2015-06-01

    (15)N longitudinal relaxation rates are extensively used for the characterization of protein dynamics; however, their accurate measurement is hindered by systematic errors. (15)N CSA/(1)H-(15)N dipolar cross-correlated relaxation (CC) and amide proton exchange saturation transfer from water protons are the two main sources of systematic errors in the determination of (15)N R1 rates through (1)H-(15)N HSQC-based experiments. CC is usually suppressed through a train of 180° proton pulses applied during the variable (15)N relaxation period (T), which can perturb water magnetization. Thus CC cancellation is required in such a way as to minimize water saturation effects. Here we examined the level of water saturation during the T period caused by various types of inversion proton pulses to suppress CC: (I) amide-selective IBURP-2; (II) cosine-modulated IBURP-2; (III) Watergate-like blocks; and (IV) non-selective hard. We additionally demonstrate the effect of uncontrolled saturation of aliphatic protons on (15)N R1 rates. In this paper we present an optimized pulse sequence that takes into account the crucial effect of controlling also the saturation of the aliphatic protons during (15)N R1 measurements in non-deuterated proteins. We show that using cosine-modulated IBURP-2 pulses spaced 40 ms to cancel CC in this optimized pulse program is the method of choice to minimize systematic errors coming from water and aliphatic protons saturation effects.

  2. Relaxation-compensated difference spin diffusion NMR for detecting 13C–13C long-range correlations in proteins and polysaccharides

    International Nuclear Information System (INIS)

    Wang, Tuo; Williams, Jonathan K.; Schmidt-Rohr, Klaus; Hong, Mei

    2015-01-01

    The measurement of long-range distances remains a challenge in solid-state NMR structure determination of biological macromolecules. In 2D and 3D correlation spectra of uniformly 13 C-labeled biomolecules, inter-residue, inter-segmental, and intermolecular 13 C– 13 C cross peaks that provide important long-range distance constraints for three-dimensional structures often overlap with short-range cross peaks that only reflect the covalent structure of the molecule. It is therefore desirable to develop new approaches to obtain spectra containing only long-range cross peaks. Here we show that a relaxation-compensated modification of the commonly used 2D 1 H-driven spin diffusion (PDSD) experiment allows the clean detection of such long-range cross peaks. By adding a z-filter to keep the total z-period of the experiment constant, we compensate for 13 C T 1 relaxation. As a result, the difference spectrum between a long- and a scaled short-mixing time spectrum show only long-range correlation signals. We show that one- and two-bond cross peaks equalize within a few tens of milliseconds. Within ∼200 ms, the intensity equilibrates within an amino acid residue and a monosaccharide to a value that reflects the number of spins in the local network. With T 1 relaxation compensation, at longer mixing times, inter-residue and inter-segmental cross peaks increase in intensity whereas intra-segmental cross-peak intensities remain unchanged relative to each other and can all be subtracted out. Without relaxation compensation, the difference 2D spectra exhibit both negative and positive intensities due to heterogeneous T 1 relaxation in most biomolecules, which can cause peak cancellation. We demonstrate this relaxation-compensated difference PDSD approach on amino acids, monosaccharides, a crystalline model peptide, a membrane-bound peptide and a plant cell wall sample. The resulting difference spectra yield clean multi-bond, inter-residue and intermolecular correlation peaks

  3. Stress relaxation of entangled polystyrene solution after constant-rate, uniaxial elongation

    DEFF Research Database (Denmark)

    Matsumiya, Yumi; Masubuchi, Yuichi; Watanabe, Hiroshi

    For an entangled solution of linear polystyrene (PS 545k; M = 545k) in dibutyl phthalate (DBP), the stress relaxation after constant-rate uniaxial elongation was examined with an extensional viscosity fixture mounted on ARES (TA Instruments). The PS concentration, c = 52 wt%, was chosen in a way...... that the entanglement density M/Me of the solution coincided with that of PS 290k melt (M = 290k). After the elongation at the Rouse-based Weissenberg number Wi(R) ~ 3 up to the Hencky strain of 3, the short time stress relaxation of the solution was accelerated by a factor of ~4, which was less significant compared...... but this reduction weakens on an increase of the concentration of un-stretchable solvent molecules. This change of the stretch/orientation reduction of the friction with the solvent concentration appears to be consistent with the monotonic thinning of the steady-state elongational viscosity seen for melts...

  4. [Effects of Monochord Music on Heart Rate Variability and Self-Reports of Relaxation in Healthy Adults].

    Science.gov (United States)

    Gäbel, Christine; Garrido, Natalia; Koenig, Julian; Hillecke, Thomas Karl; Warth, Marco

    Music-based interventions are considered an effective and low-cost treatment option for stress-related symptoms. The present study aimed to examine the trajectories of the psychophysiological response in apparently healthy participants during a music-based relaxation intervention compared to a verbal relaxation exercise. 70 participants were assigned to either receptive live music (experimental group) or a prerecorded verbal relaxation exercise (control group). Self-ratings of relaxation were assessed before and after each intervention on visual analogue scales and the Relaxation Inventory (RI). The heart rate variability (HRV) was continuously recorded throughout the sessions. Statistical analysis focused on HRV parameters indicative of parasympathetic cardiovascular outflow. We found significant quadratic main effects for time on the mean R-R interval (heart rate), the high-frequency power of HRV (indicative of parasympathetic activity), and the self-ratings of relaxation in both groups. A significant group × time interaction was observed for the cognitive tension subscale of the RI. Participants in both groups showed psychophysiological changes indicative of greater relaxation over the course of the interventions. However, differences between groups were only marginal. Music might be effective in relieving stress and promoting relaxation by altering the autonomic nervous system function. Future studies need to explore the long-term outcomes of such interventions. © 2017 S. Karger GmbH, Freiburg.

  5. Strain Rate Dependence of Compressive Yield and Relaxation in DGEBA Epoxies

    Science.gov (United States)

    Arechederra, Gabriel K.; Reprogle, Riley C.; Clarkson, Caitlyn M.; McCoy, John D.; Kropka, Jamie M.; Long, Kevin N.; Chambers, Robert S.

    2015-03-01

    The mechanical response in uniaxial compression of two diglycidyl ether of bisphenol-A epoxies were studied. These were 828DEA (Epon 828 cured with diethanolamine (DEA)) and 828T403 (Epon 828 cured with Jeffamine T-403). Two types of uniaxial compression tests were performed: A) constant strain rate compression and B) constant strain rate compression followed by a constant strain relaxation. The peak (yield) stress was analyzed as a function of strain rate from Eyring theory for activation volume. Runs at different temperatures permitted the construction of a mastercurve, and the resulting shift factors resulted in an activation energy. Strain and hold tests were performed for a low strain rate where a peak stress was lacking and for a higher strain rate where the peak stress was apparent. Relaxation from strains at different places along the stress-strain curve was tracked and compared. Sandia National Laboratories is a multi-program laboratory managed and operated by Sandia Corporation, a wholly owned subsidiary of Lockheed Martin Corporation, for the U.S. Department of Energy's National Nuclear Security Administration under contract DE-AC04-94AL85000.

  6. Relaxation training assisted by heart rate variability biofeedback: Implication for a military predeployment stress inoculation protocol.

    Science.gov (United States)

    Lewis, Gregory F; Hourani, Laurel; Tueller, Stephen; Kizakevich, Paul; Bryant, Stephanie; Weimer, Belinda; Strange, Laura

    2015-09-01

    Decreased heart rate variability (HRV) is associated with posttraumatic stress disorder (PTSD) and depression symptoms, but PTSD's effects on the autonomic stress response and the potential influence of HRV biofeedback in stress relaxation training on improving PTSD symptoms are not well understood. The objective of this study was to examine the impact of a predeployment stress inoculation training (PRESTINT) protocol on physiologic measures of HRV in a large sample of the military population randomly assigned to experimental HRV biofeedback-assisted relaxation training versus a control condition. PRESTINT altered the parasympathetic regulation of cardiac activity, with experimental subjects exhibiting greater HRV, that is, less arousal, during a posttraining combat simulation designed to heighten arousal. Autonomic reactivity was also found to be related to PTSD and self-reported use of mental health services. Future PRESTINT training could be appropriate for efficiently teaching self-help skills to reduce the psychological harm following trauma exposure by increasing the capacity for parasympathetically modulated reactions to stress and providing a coping tool (i.e., relaxation method) for use following a stressful situation. © 2015 Society for Psychophysiological Research.

  7. On the Rate of Relaxation for the Landau Kinetic Equation and Related Models

    Science.gov (United States)

    Bobylev, Alexander; Gamba, Irene M.; Zhang, Chenglong

    2017-08-01

    We study the rate of relaxation to equilibrium for Landau kinetic equation and some related models by considering the relatively simple case of radial solutions of the linear Landau-type equations. The well-known difficulty is that the evolution operator has no spectral gap, i.e. its spectrum is not separated from zero. Hence we do not expect purely exponential relaxation for large values of time t>0. One of the main goals of our work is to numerically identify the large time asymptotics for the relaxation to equilibrium. We recall the work of Strain and Guo (Arch Rat Mech Anal 187:287-339 2008, Commun Partial Differ Equ 31:17-429 2006), who rigorously show that the expected law of relaxation is \\exp (-ct^{2/3}) with some c > 0. In this manuscript, we find an heuristic way, performed by asymptotic methods, that finds this "law of two thirds", and then study this question numerically. More specifically, the linear Landau equation is approximated by a set of ODEs based on expansions in generalized Laguerre polynomials. We analyze the corresponding quadratic form and the solution of these ODEs in detail. It is shown that the solution has two different asymptotic stages for large values of time t and maximal order of polynomials N: the first one focus on intermediate asymptotics which agrees with the "law of two thirds" for moderately large values of time t and then the second one on absolute, purely exponential asymptotics for very large t, as expected for linear ODEs. We believe that appearance of intermediate asymptotics in finite dimensional approximations must be a generic behavior for different classes of equations in functional spaces (some PDEs, Boltzmann equations for soft potentials, etc.) and that our methods can be applied to related problems.

  8. Binding ability of a HHP-tagged protein towards Ni{sup 2+} studied by paramagnetic NMR relaxation: The possibility of obtaining long-range structure information

    Energy Technology Data Exchange (ETDEWEB)

    Jensen, Malene Ringkjo bing [University of Copenhagen, H.C. Orsted Institute, Department of Chemistry (Denmark); Lauritzen, Conni; Dahl, Soren Weis; Pedersen, John [Unizyme Laboratories A/S (Denmark); Led, Jens J. [University of Copenhagen, H.C. Orsted Institute, Department of Chemistry (Denmark)

    2004-06-15

    The binding ability of a protein with a metal binding tag towards Ni{sup 2+} was investigated by longitudinal paramagnetic NMR relaxation, and the possibility of obtaining long-range structure information from the paramagnetic relaxation was explored. A protein with a well-defined solution structure (Escherichia coli thioredoxin) was used as the model system, and the peptide His-His-Pro (HHP) fused to the N-terminus of the protein was used as the metal binding tag. It was found that the tag forms a stable dimer complex with the paramagnetic Ni{sup 2+} ion, where each metal ion binds two HHP-tagged protein molecules. However, it was also found that additional sites in the protein compete with the HHP-tag for the binding of the metal ion. These binding sites were identified as the side chain carboxylate groups of the aspartic and glutamic acid residues. Yet, the carboxylate groups bind the Ni{sup 2+} ions considerably weaker than the HHP-tag, and only protons spatially close to the carboxylate sites are affected by the Ni{sup 2+} ions bound to these groups. As for the protons that are unaffected by the carboxylate-bound Nisupb2+bsup> ions, it was found that the long-range distances derived from the paramagnetic relaxation enhancements are in good agreement with the solution structure of thioredoxin. Specifically, the obtained long-range paramagnetic distance constraints revealed that the dimer complex is asymmetric with different orientations of the two protein molecules relative to the Ni{sup 2+} ion. Abbreviations: NOE - nuclear Overhauser enhancement; E. coli - Escherichia coli; Trx - thioredoxin; IMAC - immobilized metal ion affinity chromatography; HT-DPPI - Polyhistidine-tagged dipeptidyl peptidase I; IPTG - isopropyl-1-thio-galactopyranoside; IR - inversion recovery; RMSD - root mean square deviation.

  9. Inhalation/Exhalation ratio modulates the effect of slow breathing on heart rate variability and relaxation.

    Science.gov (United States)

    Van Diest, Ilse; Verstappen, Karen; Aubert, André E; Widjaja, Devy; Vansteenwegen, Debora; Vlemincx, Elke

    2014-12-01

    Slow breathing is widely applied to improve symptoms of hyperarousal, but it is unknown whether its beneficial effects relate to the reduction in respiration rate per se, or, to a lower inhalation/exhalation (i/e) ratio. The present study examined the effects of four ventilatory patterns on heart rate variability and self-reported dimensions of relaxation. Thirty participants were instructed to breathe at 6 or 12 breaths/min, and with an i/e ratio of 0.42 or 2.33. Participants reported increased relaxation, stress reduction, mindfulness and positive energy when breathing with the low compared to the high i/e ratio. A lower compared to a higher respiration rate was associated only with an increased score on positive energy. A low i/e ratio was also associated with more power in the high frequency component of heart rate variability, but only for the slow breathing pattern. Our results show that i/e ratio is an important modulator for the autonomic and subjective effects of instructed ventilatory patterns.

  10. Quantifying millisecond time-scale exchange in proteins by CPMG relaxation dispersion NMR spectroscopy of side-chain carbonyl groups

    Energy Technology Data Exchange (ETDEWEB)

    Hansen, Alexandar L.; Kay, Lewis E., E-mail: kay@pound.med.utoronto.ca [University of Toronto, Departments of Molecular Genetics, Biochemistry and Chemistry (Canada)

    2011-08-15

    A new pulse sequence is presented for the measurement of relaxation dispersion profiles quantifying millisecond time-scale exchange dynamics of side-chain carbonyl groups in uniformly {sup 13}C labeled proteins. The methodology has been tested using the 87-residue colicin E7 immunity protein, Im7, which is known to fold via a partially structured low populated intermediate that interconverts with the folded, ground state on the millisecond time-scale. Comparison of exchange parameters extracted for this folding 'reaction' using the present methodology with those obtained from more 'traditional' {sup 15}N and backbone carbonyl probes establishes the utility of the approach. The extracted excited state side-chain carbonyl chemical shifts indicate that the Asx/Glx side-chains are predominantly unstructured in the Im7 folding intermediate. However, several crucial salt-bridges that exist in the native structure appear to be already formed in the excited state, either in part or in full. This information, in concert with that obtained from existing backbone and side-chain methyl relaxation dispersion experiments, will ultimately facilitate a detailed description of the structure of the Im7 folding intermediate.

  11. Determination of correlation times from selective and non-selective spin-lattice relaxation rates and their use in drug-drug and drug-albumin interaction studies

    Directory of Open Access Journals (Sweden)

    Tinoco Luzineide Wanderley

    1999-01-01

    Full Text Available The effects of the changes in sample concentration on the NMR chemical shifts and on the selective and non-selective spin-lattice relaxation rates (R1S and R1NS of the three isomers of nitrobenzaldeyde guanyl hydrazone (NBGH pure and with bovine serum albumin (BSA were measured in solution. The results wereused to determine the correlation times (tauc, showing that the degree of intermolecular drug-drug association varies with the nitro group position on the ring and that this degree of association interferes with the interaction of these drugs with BSA. The results suggest that the degree of drug-drug and drug-BSA association are related to the in vitro anti-Trypanosoma cruzi activity of these compounds.

  12. The Effect of Tungsten and Niobium on the Stress Relaxation Rates of Disk Alloy CH98

    Science.gov (United States)

    Gayda, John

    2003-01-01

    Gas turbine engines for future subsonic transports will probably have higher pressure ratios which will require nickel-base superalloy disks with 1300 to 1400 F temperature capability. Several advanced disk alloys are being developed to fill this need. One of these, CH98, is a promising candidate for gas turbine engines and is being studied in NASA s Advanced Subsonic Technology (AST) program. For large disks, residual stresses generated during quenching from solution heat treatment are often reduced by a stabilization heat treatment, in which the disk is heated to 1500 to 1600 F for several hours followed by a static air cool. The reduction in residual stress levels lessens distortion during machining of disks. However, previous work on CH98 has indicated that stabilization treatments decrease creep capability. Additions of the refractory elements tungsten and niobium improve tensile and creep properties after stabilization, while maintaining good crack growth resistance at elevated temperatures. As the additions of refractory elements increase creep capability, they might also effect stress relaxation rates and therefore the reduction in residual stress levels obtained for a given stabilization treatment. To answer this question, the stress relaxation rates of CH98 with and without tungsten and niobium additions are compared in this paper for temperatures and times generally employed in stabilization treatments on modern disk alloys.

  13. Calculation of energy relaxation rates of fast particles by phonons in crystals

    Energy Technology Data Exchange (ETDEWEB)

    Prange, Micah P.; Campbell, Luke W.; Wu, Dangxin; Gao, Fei; Kerisit, Sebastien N.

    2015-03-01

    We present ab initio calculations of the temperature-dependent exchange of energy between a classical charged point-particle and the phonons of a crystalline material. The phonons, which are computed using density functional perturbation theory (DFPT) methods, interact with the mov- ing particle via the Coulomb interaction between the density induced in the material by phonon excitation and the charge of the classical particle. Energy relaxation rates are computed using time- dependent perturbation theory. The method, which is applicable wherever DFPT is, is illustrated with results for CsI, an important scintillator whose performance is affected by electron thermal- ization. We discuss the influence of the form assumed for quasiparticle dispersion on theoretical estimates of electron cooling rates.

  14. Selective modification of NMR relaxation time in human colorectal carcinoma by using gadolinium-diethylenetriaminepentaacetic acid conjugated with monoclonal antibody 19-9.

    Science.gov (United States)

    Curtet, C; Tellier, C; Bohy, J; Conti, M L; Saccavini, J C; Thedrez, P; Douillard, J Y; Chatal, J F; Koprowski, H

    1986-01-01

    Monoclonal antibody 19-9 (mAb 19-9) against human colon adenocarcinoma was conjugated with gadolinium X diethylenetriaminepentaacetic acid (Gd X DTPA) and used as a contrast agent in nuclear magnetic resonance (NMR) in an effort to improve tumor target selectivity in nude mice. The data indicate that Gd X DTPA-mAb 19-9 in solution decreased the T1 relaxation of water protons at 90 MHz in direct proportion to the gadolinium concentration, and this effect was greater than in Gd X DTPA solutions. T1 relaxation time at 90 MHz, measured in tumors removed from nude mice 24 hr after injection of Gd X DTPA-mAb 19-9 (Gd, 20 mumol/kg; 16 DTPA molecules per mAb molecule), was significantly decreased (by 15%) as compared with the control group. Similar results were obtained in tumors from mice injected with Gd X DTPA-mAb 19-9 solutions in which Gd was used at 2, 6, or 10 mumol/kg (16 DTPA molecules per mAb molecule). These doses are lower than those commonly used for Gd X DTPA (10-100 mumol/kg) as contrast agent. Tumor localization by the Gd X DTPA-mAb 19-9 complex containing radioactive Gd (0.3 microCi/microgram of 153Gd) to confirm scintigraphy revealed significant concentrations of the complex (5% of the injected dose per gram of tissue) in the tumor. Scan images recorded in planar scintigraphy at day 5 showed good visualization of tumors. Images PMID:3459174

  15. Refined solution structure and backbone dynamics of 15N-labeled C12A-p8MTCP studied by NMR relaxation

    Energy Technology Data Exchange (ETDEWEB)

    Barthe, Philippe; Chiche, Laurent; Declerck, Nathalie; Delsuc, Marc-Andre [Universite de Montpellier I, Faculte de Pharmacie, Centre de Biochimie Structurale, CNRS-UMR 9955, INSERM-U414 (France); Lefevre, Jean-Francois [Universite Louis Pasteur, CNRS UPR-9003, ESBS (France); Malliavin, Therese [Universite de Montpellier I, Faculte de Pharmacie, Centre de Biochimie Structurale, CNRS-UMR 9955, INSERM-U414 (France); Mispelter, Joel [Centre Universitaire Bat 112, INSERM-U350, Institut Curie, Biologie (France); Stern, Marc-Henri [Hopital Saint-Louis, Unite INSERM-U462 (France); Lhoste, Jean-Marc; Roumestand, Christian [Universite de Montpellier I, Faculte de Pharmacie, Centre de Biochimie Structurale, CNRS-UMR 9955, INSERM-U414 (France)

    1999-12-15

    MTCP1 (for Mature-T-Cell Proliferation) was the first gene unequivocally identified in the group of uncommon leukemias with a mature phenotype. The three-dimensional solution structure of the human p8{sup MTCP} protein encoded by the MTCP1 oncogene has been previously determined by homonuclear proton two-dimensional NMR methods at 600 MHz: it consists of an original scaffold comprising three {alpha}-helices, associated with a new cysteine motif. Two of the helices are covalently paired by two disulfide bridges, forming an {alpha}-hairpin which resembles an antiparallel coiled-coil. The third helix is orientated roughly parallel to the plane defined by the {alpha}-antiparallel motif and appears less well defined. In order to gain more insight into the details of this new scaffold, we uniformly labeled with nitrogen-15 a mutant of this protein (C12A-p8{sup MTCP1}) in which the unbound cysteine at position 12 has been replaced by an alanine residue, thus allowing reproducibly high yields of recombinant protein. The refined structure benefits from 211 additional NOEs, extracted from {sup 15}N-edited 3D experiments, and from a nearly complete set of {phi} angular restraints allowing the estimation of the helical content of the structured part of the protein. Moreover, measurements of {sup 15} N spin relaxation times and heteronuclear {sup 15} N{sup 1}HNOEs provided additional insights into the dynamics of the protein backbone. The analysis of the linear correlation between J(0) and J({omega}) was used to interpret relaxation parameters. It appears that the apparent relative disorder seen in helix III is not simply due to a lack of experimental constraints, but associated with substantial contributions of sub-nanosecond motions in this segment.

  16. Adiabatic fast passage application in solid state NMR study of cross relaxation and molecular dynamics in heteronuclear systems

    Science.gov (United States)

    Baranowski, M.; Woźniak-Braszak, A.; Jurga, K.

    2016-01-01

    The paper presents the benefits of using fast adiabatic passage for the study of molecular dynamics in the solid state heteronuclear systems in the laboratory frame. A homemade pulse spectrometer operating at the frequency of 30.2 MHz and 28.411 MHz for protons and fluorines, respectively, has been enhanced with microcontroller direct digital synthesizer DDS controller [1-4]. This work briefly describes how to construct a low-cost and easy-to-assemble adiabatic extension set for homemade and commercial spectrometers based on recently very popular Arduino shields. The described set was designed for fast adiabatic generation. Timing and synchronization problems are discussed. The cross-relaxation experiments with different initial states of the two spin systems have been performed. Contrary to our previous work [5] where the steady-state NOE experiments were conducted now proton spins 1H are polarized in the magnetic field B0 while fluorine spins 19F are perturbed by selective saturation for a short time and then the system is allowed to evolve for a period in the absence of a saturating field. The adiabatic passage application leads to a reversal of magnetization of fluorine spins and increases the amplitude of the signal.

  17. Mitigating Thermoelastic Dissipation of Flexural Micromechanical Resonators by Decoupling Resonant Frequency from Thermal Relaxation Rate

    Science.gov (United States)

    Zhou, Xin; Xiao, Dingbang; Wu, Xuezhong; Li, Qingsong; Hou, Zhanqiang; He, Kaixuan; Wu, Yulie

    2017-12-01

    This paper reports an alternative design strategy to reduce thermoelastic dissipation (TED) for isothermal-mode micromechanical resonators. This involves hanging lumped masses on a frame structure to decouple the resonant frequency and the effective beamwidth of the resonators, which enables the separation of the thermal relaxation rate and frequency of vibration. This approach is validated using silicon-based micromechanical disklike resonators engineered to isolate TED. A threefold improvement in the quality factor and a tenfold improvement in the decay-time constant is demonstrated. This work proposes a solution for isothermal-mode (flexural) micromechanical resonators to effectively mitigate TED. Specifically, this approach is ideal for designing high-performance gyroscope resonators based on microelectromechanical systems (MEMS) technology. It may pave the way for the next generation inertial-grade MEMS gyroscope, which remains a great challenge and is very appealing.

  18. Hydrogen-1 NMR relaxation time studies in membrane: anesthetic systems; Variacao dos tempos de relaxacao longitudinal de protons em sistemas membranares contendo anestesicos locais

    Energy Technology Data Exchange (ETDEWEB)

    Pinto, L.M.A.; Fraceto, L.; Paula, E. de [Universidade Estadual de Campinas, SP (Brazil). Dept. de Bioquimica; Franzoni, L.; Spisni, A. [Universita degli Studi di Parma, Parma (Italy). Ist. di Chimica Biologica

    1997-12-31

    The study of local anesthetics`(LA) interaction with model phospholipid membranes is justified by the direct correlation between anesthetic`s hydrophobicity and its potency/toxicity. By the same reason, uncharged LA species seems to play a crucial role in anesthesia. Most clinically used LA are small amphiphilics with a protonated amine group (pKa around 8). Although both charged (protonated) and uncharged forms can coexist at physiological pH, it has been shown (Lee, Biochim. Biophys. Acta 514:95, 1978; Screier et al. Biochim. Biophys. Acta 769:231, 1984) that the real anesthetic pka can be down-shifted, due to differential partition into membranes, increasing the ratio of uncharged species at pH 7.4. We have measured {sup 1}H-NMR longitudinal relaxation times (T{sub 1}) for phospholipid and three local anesthetics (tetracaine, lidocaine, benzocaine), in sonicated vesicles at a 3:1 molar ratio. All the LA protons have shown smaller T{sub 1} in this system than in isotropic phases, reflecting LA immobilization caused by insertion in the membrane. T{sub 1} values for the lipid protons in the presence of LA were analyzed, in an attempt to identify specific LA:lipid contact regions. (author) 13 refs., 3 figs., 1 tabs.

  19. High-resolution NMR field-cycling device for full-range relaxation and structural studies of biopolymers on a shared commercial instrument

    International Nuclear Information System (INIS)

    Redfield, Alfred G.

    2012-01-01

    Improvements are described in a shuttling field-cycling device (Redfield in Magn Reson Chem 41:753–768, 2003), designed to allow widespread access to this useful technique by configuring it as a removable module to a commercial 500 MHz NMR instrument. The main improvements described here, leading to greater versatility, high reliability and simple construction, include: shuttling provided by a linear motor driven by an integrated-control servomotor; provision of automated bucking magnets to allow fast two-stage cycling to nearly zero field; and overall control by a microprocessor. A brief review of history and publications that have used the system is followed by a discussion of topics related to such a device including discussion of some future applications. A description of new aspects of the shuttling device follows. The minimum round trip time to 1T and above is less than 0.25 s and to 0.002 T is 0.36 s. Commercial probes are used and sensitivity is that of the host spectrometer reduced only by relaxation during travel. A key element is development of a linkage that prevents vibration of the linear motor from reaching the probe.

  20. Quantification of protein backbone hydrogen-deuterium exchange rates by solid state NMR spectroscopy.

    Science.gov (United States)

    del Amo, Juan-Miguel Lopez; Fink, Uwe; Reif, Bernd

    2010-12-01

    We present the quantification of backbone amide hydrogen-deuterium exchange rates (HDX) for immobilized proteins. The experiments make use of the deuterium isotope effect on the amide nitrogen chemical shift, as well as on proton dilution by deuteration. We find that backbone amides in the microcrystalline α-spectrin SH3 domain exchange rather slowly with the solvent (with exchange rates negligible within the individual (15)N-T (1) timescales). We observed chemical exchange for 6 residues with HDX exchange rates in the range from 0.2 to 5 s(-1). Backbone amide (15)N longitudinal relaxation times that we determined previously are not significantly affected for most residues, yielding no systematic artifacts upon quantification of backbone dynamics (Chevelkov et al. 2008b). Significant exchange was observed for the backbone amides of R21, S36 and K60, as well as for the sidechain amides of N38, N35 and for W41ε. These residues could not be fit in our previous motional analysis, demonstrating that amide proton chemical exchange needs to be considered in the analysis of protein dynamics in the solid-state, in case D(2)O is employed as a solvent for sample preparation. Due to the intrinsically long (15)N relaxation times in the solid-state, the approach proposed here can expand the range of accessible HDX rates in the intermediate regime that is not accessible so far with exchange quench and MEXICO type experiments.

  1. Quantification of protein backbone hydrogen-deuterium exchange rates by solid state NMR spectroscopy

    International Nuclear Information System (INIS)

    Lopez del Amo, Juan-Miguel; Fink, Uwe; Reif, Bernd

    2010-01-01

    We present the quantification of backbone amide hydrogen-deuterium exchange rates (HDX) for immobilized proteins. The experiments make use of the deuterium isotope effect on the amide nitrogen chemical shift, as well as on proton dilution by deuteration. We find that backbone amides in the microcrystalline α-spectrin SH3 domain exchange rather slowly with the solvent (with exchange rates negligible within the individual 15 N-T 1 timescales). We observed chemical exchange for 6 residues with HDX exchange rates in the range from 0.2 to 5 s -1 . Backbone amide 15 N longitudinal relaxation times that we determined previously are not significantly affected for most residues, yielding no systematic artifacts upon quantification of backbone dynamics (Chevelkov et al. 2008b). Significant exchange was observed for the backbone amides of R21, S36 and K60, as well as for the sidechain amides of N38, N35 and for W41ε. These residues could not be fit in our previous motional analysis, demonstrating that amide proton chemical exchange needs to be considered in the analysis of protein dynamics in the solid-state, in case D 2 O is employed as a solvent for sample preparation. Due to the intrinsically long 15 N relaxation times in the solid-state, the approach proposed here can expand the range of accessible HDX rates in the intermediate regime that is not accessible so far with exchange quench and MEXICO type experiments.

  2. Applications de la résonance magnétique nucléaire (RMN en milieu poreux Lissage des courbes de relaxation RMN du domaine du temps par une méthode discrète et continue Nuclear Magnetic Resonance (Nmr Applications in Porous Media Time-Dependent Nmr Relaxation Curve Smoothing Using a Discrete Continuous Method

    Directory of Open Access Journals (Sweden)

    Le Botlan D.

    2006-12-01

    Full Text Available Dans un champ magnétique hétérogène, le signal RMN de précession libre (FID suit une évolution gaussienne. Le traitement du signal par une méthode discrète peut donner des composantes qui ne correspondent pas à un état physique réel. Par contre l'utilisation d'une méthode de déconvolution continue nous a donné des résultats quantitatifs tout à fait satisfaisants permettant de déterminer les distributions de temps de relaxation correspondant à des états intermédiaires entre les phases solides et liquides. La RMN du domaine du temps peut ainsi être considérée comme une méthode analytique complémentaire des techniques habituellement utilisées pour l'étude de composés complexes hétérogènes ATD, ACD, isothermes de sorption, etc. In a heterogeneous magnetic field, the freely precessing NMR signal (FID describes a Gaussian curve. Processing the signal using a discrete method can give rise to components that do not correspond to a real physical state. However, with a continuous deconvolution method, which gives quite satisfactory quantitative results, it is possible to determine the distributions of relaxation times that correspond to intermediate states between solid and liquid phases. Time-dependent NMR can thus be used to supplement the usual analytical methods, such as DTA, DCA and sorption isotherms, for studying complex heterogeneous compounds.

  3. Interaction study of polyisobutylene with paraffins by NMR using the evaluation of spin-lattice relaxation times for hydrogen nuclei; Estudo da interacao do poliisobutileno com parafinas por RMN no estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Marques, Rosana G.G. [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas - CENPES]. E-mail: garrido@cenpes.petrobras.com.br; Tavares, Maria I.B. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas]. E-mail: mibt@ima.ufrj.br

    2001-07-01

    The evaluation of spin-lattice relaxation times of {sup 1}H for polyisobutylene/paraffin systems, were obtained using the classic inversion recovery technique, and also through Cross Polarization Magic Angle Spinning (CP/MAS) techniques varying the contact time and also by the delayed contact time pulse sequence. NMR results showed that the polyisobutylene/paraffin systems in which high molecular weight paraffins were used, is heterogeneous. However, for paraffins with low molecular weight, the system presents good homogeneity. (author)

  4. Nuclear Spin Relaxation

    Indian Academy of Sciences (India)

    IAS Admin

    In the context of nuclear magnetic resonance (NMR), the term relaxation indicates the process by which the magnetic atomic nuclei reach thermal equilibrium with the chaotic molecular environment. In NMR, this process can be very slow, requiring between a fraction of a second to many minutes, depending on the.

  5. Nitrogen Use Efficiency and Carbon Isotope Discrimination Study on NMR151 and NMR152 Mutant Lines Rice at Field Under Different Nitrogen Rates and Water Potentials

    International Nuclear Information System (INIS)

    Ahmad Nazrul Abdul Wahid; Shyful Azizi Abdul Rahman; Abdul Rahim Harun; Latiffah Nordin; Abdul Razak Ruslan; Hazlina Abdullah; Khairuddin Abdul Rahim

    2016-01-01

    This study was conducted to evaluate the nitrogen use efficiency and 13 C isotope discrimination of rice mutant lines viz. NMR151 and NMR152. Both cultivars are developed under rice radiation mutagenesis programme for adaptability to aerobic conditions. In the present study, NMR151 and NMR152 were grown under conditions of varying water potentials and nitrogen levels in a field. Two water potentials and three nitrogen rates in a completely randomized design with three replications were carried out. The rice mutants were grown for 110 days under two water potentials, (i) Field capacity from 0 to 110 DAS [FC], and (ii) Field capacity from 0 to 40 DAS and 30 % dry of field capacity from 41 to 110 DAS [SS] and three nitrogen rates, (i) 0 kg N/ ha (0N), (ii) 60 kg N/ ha (60N), and (iii) 120 kg N/ ha (120N). 15 N isotopic tracer technique was used in this study, whereby the 15 N labeled urea fertilizer 5.20 % atom excess (a.e) was utilized as a tracer for nitrogen use efficiency (NUE) study. 15 N isotope presence in the samples was determined using emission spectrometry and percentage of total nitrogen was determined by the Kjeldahl method. 15 N a.e values of the samples were used in the determination of the NUE. The value of 13 C isotope discrimination (Δ 13 C) in the sample was determined using isotope ratio mass spectrometry (IRMS). The 13 C isotope discrimination technique was used as a tool to identify drought resistance rice cultivars with improves water use efficiency. The growth and agronomy data, viz. plant height, number of tillers, grain yield, straw yield, and 1000 grain weight also were recorded. Results from this study showed nitrogen rates imparted significant effects on yield (grain and straw) plant height, number of tillers and 1000 grain weight. Water potentials had significant effects only on 1000 grain weight and Δ 13 C. The NUE for both mutant lines rice showed no significant different between treatments. Both Rice mutant lines rice NMR151 and NMR

  6. Investigations of effect of phase change mass transfer rate on cavitation process with homogeneous relaxation model

    Energy Technology Data Exchange (ETDEWEB)

    He, Zhixia; Zhang, Liang; Saha, Kaushik; Som, Sibendu; Duan, Lian; Wang, Qian

    2017-12-01

    The super high fuel injection pressure and micro size of nozzle orifice has been an important development trend for the fuel injection system. Accordingly, cavitation transient process, fuel compressibility, amount of noncondensable gas in the fuel and cavitation erosion have attracted more attention. Based on the fact of cavitation in itself is a kind of thermodynamic phase change process, this paper takes the perspective of the cavitation phase change mass transfer process to analyze above mentioned phenomenon. The two-phase cavitating turbulent flow simulations with VOF approach coupled with HRM cavitation model and U-RANS of standard k-ε turbulence model were performed for investigations of cavitation phase change mass transfer process. It is concluded the mass transfer time scale coefficient in the Homogenous Relaxation Model (HRM) representing mass transfer rate should tend to be as small as possible in a condition that ensured the solver stable. At very fast mass transfer rate, the phase change occurs at very thin interface between liquid and vapor phase and condensation occurs more focused and then will contribute predictably to a more serious cavitation erosion. Both the initial non-condensable gas in fuel and the fuel compressibility can accelerate the cavitation mass transfer process.

  7. Relating PAC damping to EFG fluctuation rates through the PAC relaxation peak. Dynamic N-state symmetric models

    Science.gov (United States)

    Park, Tyler; Hodges, Jeffery A.; Moreno, Carlos; Stufflebeam, Michael; Evenson, William E.; Matheson, P.; Zacate, M. O.; Collins, Gary S.

    2011-07-01

    A perturbed angular correlation (PAC) experiment that measures dynamic damping also needs information about the fundamental quadrupole frequency to relate the damping as a function of temperature to the EFG fluctuation rate. When the experiment is unable to access slow electric field gradient (EFG) fluctuations that show the fundamental quadrupole frequency directly, one needs additional information to determine the hyperfine field parameters and thereby the connection between observed damping and EFG fluctuation rates. One way to solve this problem is to estimate the hyperfine parameters from the fluctuation rate for maximum damping (i.e. at the relaxation peak) or from the rate of maximum damping. This work relates both the maximum damping rate and the fluctuation rate at the relaxation peak to EFG magnitudes (or quadrupole frequencies) for five dynamic N-state symmetric models of fluctuating EFGs.

  8. Determination of rate constants of N-alkylation of primary amines by 1H NMR spectroscopy.

    Science.gov (United States)

    Li, Chenghong

    2013-09-05

    Macromolecules containing N-diazeniumdiolates of secondary amines are proposed scaffolds for controlled nitrogen oxide (NO) release medical applications. Preparation of these compounds often involves converting primary amine groups to secondary amine groups through N-alkylation. However, N-alkylation results in not only secondary amines but tertiary amines as well. Only N-diazeniumdiolates of secondary amines are suitable for controlled NO release; therefore, the yield of secondary amines is crucial to the total NO load of the carrier. In this paper, (1)H NMR spectroscopy was used to estimate the rate constants for formation of secondary amine (k1) and tertiary amine (k2) for alkylation reagents such as propylene oxide (PO), methyl acrylate (MA), and acrylonitrile (ACN). At room temperature, the ratio of k2/k1 for the three reactions was found to be around 0.50, 0.026, and 0.0072.

  9. A study of the effect of relaxing music on heart rate recovery after exercise among healthy students.

    Science.gov (United States)

    Tan, Fuitze; Tengah, Asrin; Nee, Lo Yah; Fredericks, Salim

    2014-05-01

    Music has been employed in various clinical settings to reduce anxiety. However, meta-analysis has shown music to have little influence on haemodynamic parameters. This study aimed at investigating the effect of relaxing music on heart rate recovery after exercise. Twenty-three student volunteers underwent treadmill exercise and were assessed for heart rate recovery and saliva analysis; comparing exposure to sedative music with exposure to silence during the recovery period immediately following exercise. No differences were found between music and non-music exposure regarding: heart rate recovery, resting pulse rate, and salivary cortisol. Music was no different to silence in affecting these physiological measures, which are all associated with anxiety. Relaxing music unaccompanied by meditation techniques or other such interventions may not have a major role in reducing anxiety in certain experimental settings. Copyright © 2014 Elsevier Ltd. All rights reserved.

  10. NMR studies of the equilibria and reaction rates in aqueous solutions of formaldehyde.

    Science.gov (United States)

    Rivlin, Michal; Eliav, Uzi; Navon, Gil

    2015-03-26

    Formaldehyde has an important role in the chemical industry and in biological sciences. In dilute aqueous solutions of formaldehyde only traces of the molecular formaldehyde are present and the predominant species are methylene glycol and in lower concentrations, dimethylene glycol. The chemical equilibria and reaction rates of the hydration of formaldehyde in H2O and D2O solutions at low concentrations were studied by (1)H and (13)C NMR at various conditions of pH (1.8-7.8) and temperature (278-333 K). These measurements became possible by direct detection of formaldehyde (13)C and (1)H peaks. The equilibrium and rate constants of the dimerization reaction of methylene glycol were also measured. The rate constants for both the hydration and the dimerization reactions were measured by a new version of the conventional selective inversion transfer method. This study, together with previous published work, completes the description of dynamics and equilibria of all the processes occurring in dilute aqueous formaldehyde solutions.

  11. Using Nice-Ohvms Lineshapes to Study Relaxation Rates and Transition Dipole Moments

    Science.gov (United States)

    Hodges, James N.; McCall, Benjamin J.

    2016-06-01

    Noise Immune Cavity Enhanced Optical Heterodyne Velocity Modulation Spectroscopy (NICE-OHVMS) is a successful technique that we have developed to sensitively, precisely, and accurately record transitions of molecular ions. It has been used exclusively as a method for precise transition frequency measurement via saturation and fitting of the resultant Lamb dips. NICE-OHVMS has been employed to improve the uncertainties on H_3^+, CH_5^+, HeH^+, and OH^+, reducing the transition frequency uncertainties by two orders of magnitude. Because NICE-OHVMS is a saturation technique, this provides a unique opportunity to access information about the ratio of the transition dipole moment to the relaxation rate of the transition. This can be done in two ways, either through comparison of Lamb dip depth to the transition profile or comparison of the absorption intensity and dispersion intensity. Due to the complexity of the modulation scheme, there are many parameters that affect the apparent intensity of the recorded lineshape. A complete understanding of the lineshape is required to make the measurements of interest. Here we present a model that accounts for the heterodyne modulation and velocity modulation, assuming that the fundamental lineshape is represented by a Voigt profile. Fits to data are made and interpreted in order to extract the saturation parameter. K.N. Crabtree et al., Chem. Phys. Lett. 551, 1 (2012). J.N. Hodges et al., J. Chem. Phys. 139, 164201 (2013). A.J. Perry et al., J. Mol. Spectrosc. 317, 71 (2015). A.J. Perry et al., J. Chem. Phys. 141, 101101 (2014). C.R. Marcus et al., Astrophys. J. 817, 138 (2016).

  12. Maximum rate of pressure development and maximal relaxation rate of respiratory muscles in patients with cystic fibrosis.

    Science.gov (United States)

    Dassios, Theodore G; Doudounakis, Stavros; Dimitriou, Gabriel

    2013-03-01

    Respiratory muscle function in patients with cystic fibrosis (CF) has been studied by measurement of maximal inspiratory pressure (P(Imax)), maximal expiratory pressure (P(Emax)), and the pressure-time index of the respiratory muscles (PTI(mus)). The maximum rate of pressure development (MRPD) during P(Imax) (MRPD-P(Imax)), MRPD during P(Emax) (MRPD-P(Emax)), maximal relaxation rate (MRR) during P(Imax) (MRR-P(imax)), and MRR during P(Emax) (MRR-P(Emax)) have not been studied in CF. Our aim was to study MRPD and MRR and investigate their possible application as accessory indices of respiratory muscle function in patients with CF. FEVY, FVC, and maximal expiratory flow between 25% and 75% of vital capacity, body mass index (BMI), upper arm muscle area, P(imax), P(Emax), PTI(mus), MRPD-P(Imax), MRPD-P(Emax), MRR-P(imax), and MRR-P(Emax) were assessed in 123 CF patients and in a control group of 123 healthy subjects matched for age and sex. MRR-P(Emax) was significantly increased and MRPD-P(Emax) was significantly decreased in the CF patients, compared to the healthy controls. In the CF patients MRR-P(Imax) was significantly related to PTI(mus) (P = .02), FEV1 (P = .03), FVC (P = .001), BMI (P muscle area (P muscle area (P respiratory effort, compared to controls. The differences in MRR-P(imax) and MRPD-P(Imax) between the controls and the complete group of CF patients were not significant. MRPD and MRR were significantly related to nutritional and pulmonary function impairment in CF patients. MRPD strongly correlated to maximal respiratory muscle pressures, and MRR strongly correlated to PTI(mus) in patients with CF. These findings suggest that CF patients are at increased risk of respiratory muscle fatigue. Regular determination of MRPD and MRR may be clinically useful in CF patients and help to initiate inspiratory muscle training and noninvasive ventilation.

  13. 31-P Relaxation times of metabolic compounds in tumors grafted in nude mice

    International Nuclear Information System (INIS)

    Remy, C.; Benabid, A.L.; Jacrot, M.; Riondel, J.; Albrand, J.P.; Decorps, M.

    1985-08-01

    The observation that water proton relaxation rates were longer in tumors than in normal tissues provided a basis for the detection of human tumors by the NMR imaging technique. To evaluate the potentiality of 31-P NMR spectroscopy as a diagnostic tool of the pathological state of tissues, T1 and T2 relaxation times have been measured for the phosphates of ATP, inorganic phosphate (Pi), phosphomonoesters (PME) and phosphocreatine (PCr) in the 31-P NMR spectra obtained in vivo for normal rat brain and rat brain tumors implanted in nude mice

  14. Noninvasive detection of nanoparticle clustering by water proton NMR

    Energy Technology Data Exchange (ETDEWEB)

    Taraban, Marc B.; Truong, Huy C.; Ilavsky, Jan; DePaz, Roberto A.; Lobo, Brian; Yu, Y. Bruce

    2017-06-01

    It is shown that water proton NMR can detect uncontrolled clustering of inert nanoparticles (NPs) formulated as aqueous suspensions. The clustering of NPs causes the compartmentalization of water molecules, leading to accelerated proton spin de-coherence, and hence, much faster water transverse relaxation rates. The results suggest that water proton NMR can be used to noninvasively inspect NP products by commercial end users and researchers.

  15. NMR-based screening method for transglutaminases: rapid analysis of their substrate specificities and reaction rates.

    Science.gov (United States)

    Shimba, Nobuhisa; Yokoyama, Kei-ichi; Suzuki, Ei-ichiro

    2002-03-13

    Incorporation of inter- or intramolecular covalent cross-links into food proteins with microbial transglutaminase (MTG) improves the physical and textural properties of many food proteins such as tofu, boiled fish paste, and sausage. Other transglutaminases (TGases) are expected to be used in the same way, and also to extend the scope of industrial applications to materials, drugs, and so on. The TGases have great diversity, not only in amino acid sequence and size, but also in their substrate specificities and catalytic activities, and therefore, it is quite difficult to estimate their reactivity. We have developed an NMR-based method using the enzymatic labeling technique (ELT) for simultaneous analysis of the substrate specificities and reaction rates of TGases. It is quite useful for comparing the existing TGases and for screening new TGases or TGases variants. This method has shown that MTG is superior for industrial use because of its lower substrate specificity compared with those of guinea pig liver transglutaminase (GTG) and red sea bream liver transglutaminase (FTG). We have also found that an MTG variant lacking an N-terminal aspartic acid residue has higher activity than that of the native enzyme.

  16. The spin lattice relaxation of 8Li in simple metals

    Science.gov (United States)

    Hossain, M. D.; Saadaoui, H.; Parolin, T. J.; Song, Q.; Wang, D.; Smadella, M.; Chow, K. H.; Egilmez, M.; Fan, I.; Kiefl, R. F.; Kreitzman, S. R.; Levy, C. D. P.; Morris, G. D.; Pearson, M. R.; Salman, Z.; MacFarlane, W. A.

    2009-04-01

    We report the modification to the linear temperature dependence of the Korringa nuclear spin-lattice relaxation rate of an implanted NMR probe in silver, as it makes a thermally activated site change. We develop a simple model of this phenomenon, which is found in a number of metals including Au and Nb.

  17. Strange metal from Gutzwiller correlations in infinite dimensions: Transverse transport, optical response, and rise of two relaxation rates

    Science.gov (United States)

    Ding, Wenxin; Žitko, Rok; Shastry, B. Sriram

    2017-09-01

    Using two approaches to strongly correlated systems, the extremely correlated Fermi liquid theory and the dynamical mean field theory, we compute the transverse transport coefficients, namely, the Hall constants RH and Hall angles θH, and the longitudinal and transverse optical response of the U =∞ Hubbard model in the limit of infinite dimensions. We focus on two successive low-temperature regimes, the Gutzwiller-correlated Fermi liquid (GCFL) and the Gutzwiller-correlated strange metal (GCSM). We find that the Hall angle cotθH is proportional to T2 in the GCFL regime, while upon warming into the GCSM regime it first passes through a downward bend and then continues as T2. Equivalently, RH is weakly temperature dependent in the GCFL regime, but becomes strongly temperature dependent in the GCSM regime. Drude peaks are found for both the longitudinal optical conductivity σx x(ω ) and the optical Hall angles tanθH(ω ) below certain characteristic energy scales. By comparing the relaxation rates extracted from fitting to the Drude formula, we find that in the GCFL regime there is a single relaxation rate controlling both longitudinal and transverse transport, while in the GCSM regime two different relaxation rates emerge. We trace the origin of this behavior to the dynamical particle-hole asymmetry of the Dyson self-energy, arguably a generic feature of doped Mott insulators.

  18. beta-NMR of isolated lithium in nearly ferromagnetic palladium.

    Science.gov (United States)

    Parolin, T J; Salman, Z; Chakhalian, J; Song, Q; Chow, K H; Hossain, M D; Keeler, T A; Kiefl, R F; Kreitzman, S R; Levy, C D P; Miller, R I; Morris, G D; Pearson, M R; Saadaoui, H; Wang, D; MacFarlane, W A

    2007-01-26

    The temperature dependence of the frequency shift and spin-lattice relaxation rate of isolated, nonmagnetic (8)Li impurities implanted in a nearly ferromagnetic host (Pd) are measured by means of beta-detected nuclear magnetic resonance (beta-NMR). The shift is negative, very large, and increases monotonically with decreasing T in proportion to the bulk susceptibility of Pd for T > T* approximately 100 K. Below T*, an additional shift occurs which we attribute to the response of Pd to the defect. The relaxation rate is much slower than expected for the large shift and is linear with T below T*, showing no sign of additional relaxation mechanisms associated with the defect.

  19. Disproportional plastome-wide increase of substitution rates and relaxed purifying selection in genes of carnivorous Lentibulariaceae.

    Science.gov (United States)

    Wicke, Susann; Schäferhoff, Bastian; dePamphilis, Claude W; Müller, Kai F

    2014-03-01

    Carnivorous Lentibulariaceae exhibit the most sophisticated implementation of the carnivorous syndrome in plants. Their unusual lifestyle coincides with distinct genomic peculiarities such as the smallest angiosperm nuclear genomes and extremely high nucleotide substitution rates across all genomic compartments. Here, we report the complete plastid genomes from each of the three genera Pinguicula, Utricularia, and Genlisea, and investigate plastome-wide changes in their molecular evolution as the carnivorous syndrome unfolds. We observe a size reduction by up to 9% mostly due to the independent loss of genes for the plastid NAD(P)H dehydrogenase and altered proportions of plastid repeat DNA, as well as a significant plastome-wide increase of substitution rates and microstructural changes. Protein-coding genes across all gene classes show a disproportional elevation of nonsynonymous substitutions, particularly in Utricularia and Genlisea. Significant relaxation of purifying selection relative to noncarnivores occurs in the plastid-encoded fraction of the photosynthesis ATP synthase complex, the photosystem I, and in several other photosynthesis and metabolic genes. Shifts in selective regimes also affect housekeeping genes including the plastid-encoded polymerase, for which evidence for relaxed purifying selection was found once during the transition to carnivory, and a second time during the diversification of the family. Lentibulariaceae significantly exhibit enhanced rates of nucleotide substitution in most of the 130 noncoding regions. Various factors may underlie the observed patterns of relaxation of purifying selection and substitution rate increases, such as reduced net photosynthesis rates, alternative paths of nutrient uptake (including organic carbon), and impaired DNA repair mechanisms.

  20. Effects of Loading Rate on the Relaxation and Recovery Ability of an Epoxy-Based Shape Memory Polymer

    Directory of Open Access Journals (Sweden)

    Amber J.W. McClung

    2017-03-01

    Full Text Available The majority of aerospace structural composites use thermoset resins for their processing flexibility, temperature capability, and environmental durability. In this study, the recovery behavior of Veriflex-E, an epoxy-based, thermosetting, thermally-triggered shape memory polymer (SMP resin, is investigated in glassy (25 °C and rubbery (130 °C states, as a function of shape memory cycles, and as a means to evaluate its potential as a resin for a shape memory composite. At 25 °C, Veriflex-E exhibits a promising high elastic modulus and a positive, nonlinear strain rate sensitivity in monotonic loading. At 130 °C, the strain rate sensitivity in monotonic loading decreases. Stress relaxation after storage in the deformed temporary state and subsequent shape recovery is of particular interest, a challenge to measure, and has not been widely reported for SMPs. The current experimental program measures the influence of strain rate changes in the 10−4–10−2 s−1 range on the stress relaxation response of the material, as well as on the strain recovery behavior at both 25 °C and 130 °C. As expected, the post-relaxation strain is larger with faster loading. Unexpectedly, the total strain recovered after shape memory cycling is more similar to the low temperature deformation. Overall, the results suggest that, while being influenced by both the loading rate and the test temperature, Veriflex-E is a promising candidate for a shape memory composite which could enable adaptive structures.

  1. Endo- vs. exogenous shocks and relaxation rates in book and music “sales”

    Science.gov (United States)

    Lambiotte, R.; Ausloos, M.

    2006-04-01

    In this paper, we analyse the response of music and book sales to an external field and a buyer herding. We distinguish endogenous and exogenous shocks. We focus on some case studies, whose data have been collected from ranking on amazon.com. We show that an ensemble of equivalent systems quantitatively respond in a same way to a similar “external shock”, indicating roads to universality features. In contrast to Sornette et al. [Phys. Rev. Lett. 93 (2004) 228701] who seemed to find power-law behaviours, in particular at long times, a law interpreted in terms of an epidemic activity, we observe that the relaxation process can be as well seen as an exponential one that saturates toward an asymptotic state, itself different from the pre-shock state. By studying an ensemble of 111 shocks, on books or records, we show that exogenous and endogenous shocks are discriminated by their short-time behaviour: the relaxation time seems to be twice shorter in endogenous shocks than in exogenous ones. We interpret the finding through a simple thermodynamic model with a dissipative force.

  2. Hydrate Shell Growth Measured Using NMR.

    Science.gov (United States)

    Haber, Agnes; Akhfash, Masoumeh; Loh, Charles K; Aman, Zachary M; Fridjonsson, Einar O; May, Eric F; Johns, Michael L

    2015-08-18

    Benchtop nuclear magnetic resonance (NMR) pulsed field gradient (PFG) and relaxation measurements were used to monitor the clathrate hydrate shell growth occurring in water droplets dispersed in a continuous cyclopentane phase. These techniques allowed the growth of hydrate inside the opaque exterior shell to be monitored and, hence, information about the evolution of the shell's morphology to be deduced. NMR relaxation measurements were primarily used to monitor the hydrate shell growth kinetics, while PFG NMR diffusion experiments were used to determine the nominal droplet size distribution (DSD) of the unconverted water inside the shell core. A comparison of mean droplet sizes obtained directly via PFG NMR and independently deduced from relaxation measurements showed that the assumption of the shell model-a perfect spherical core of unconverted water-for these hydrate droplet systems is correct, but only after approximately 24 h of shell growth. Initially, hydrate growth is faster and heat-transfer-limited, leading to porous shells with surface areas larger than that of spheres with equivalent volumes. Subsequently, the hydrate growth rate becomes mass-transfer-limited, and the shells become thicker, spherical, and less porous.

  3. An optimized method for {sup 15}N R{sub 1} relaxation rate measurements in non-deuterated proteins

    Energy Technology Data Exchange (ETDEWEB)

    Gairí, Margarida, E-mail: mgairi@rmn.ub.edu [University of Barcelona (CCiTUB), NMR Facility, Scientific and Technological Centers (Spain); Dyachenko, Andrey [Institute for Research in Biomedicine (IRB) (Spain); González, M. Teresa; Feliz, Miguel [University of Barcelona (CCiTUB), NMR Facility, Scientific and Technological Centers (Spain); Pons, Miquel [University of Barcelona, Biomolecular NMR Laboratory and Organic Chemistry Department (Spain); Giralt, Ernest, E-mail: ernest.giralt@irbbarcelona.org [Institute for Research in Biomedicine (IRB) (Spain)

    2015-06-15

    {sup 15}N longitudinal relaxation rates are extensively used for the characterization of protein dynamics; however, their accurate measurement is hindered by systematic errors. {sup 15}N CSA/{sup 1}H–{sup 15}N dipolar cross-correlated relaxation (CC) and amide proton exchange saturation transfer from water protons are the two main sources of systematic errors in the determination of {sup 15}N R{sub 1} rates through {sup 1}H–{sup 15}N HSQC-based experiments. CC is usually suppressed through a train of 180° proton pulses applied during the variable {sup 15}N relaxation period (T), which can perturb water magnetization. Thus CC cancellation is required in such a way as to minimize water saturation effects. Here we examined the level of water saturation during the T period caused by various types of inversion proton pulses to suppress CC: (I) amide-selective IBURP-2; (II) cosine-modulated IBURP-2; (III) Watergate-like blocks; and (IV) non-selective hard. We additionally demonstrate the effect of uncontrolled saturation of aliphatic protons on {sup 15}N R{sub 1} rates. In this paper we present an optimized pulse sequence that takes into account the crucial effect of controlling also the saturation of the aliphatic protons during {sup 15}N R{sub 1} measurements in non-deuterated proteins. We show that using cosine-modulated IBURP-2 pulses spaced 40 ms to cancel CC in this optimized pulse program is the method of choice to minimize systematic errors coming from water and aliphatic protons saturation effects.

  4. Polymers under mechanical stress- an NMR investigation

    Energy Technology Data Exchange (ETDEWEB)

    Boehme, Ute; Scheler, Ulrich [Leibniz Institute of Polymer Research Dresden (Germany); Xu, Bo; Leisen, Johannes; Beckham, Haskell W. [Georgia Institute of Technology, Atlanta, Georgia (United States)

    2010-07-01

    Low-field NMR using permanent magnets in Halbach arrangements permit NMR investigation without the limits present in high-field NMR. The lower field in conjunction with confined stray field permit the application of NMR, in particular relaxation NMR in a stretching apparatus and a rheometer. Crystalline and amorphous fraction of semi-crystalline polymers are distinguished by their transverse relaxation times. Upon mechanical load the relaxation times of the amorphous fraction changes as seen in in-situ measurements on polypropylene rods. During the formation of a neck the crystalline fraction becomes more prominent.

  5. NMR relaxometry as a versatile tool to study Li ion dynamics in potential battery materials.

    Science.gov (United States)

    Kuhn, A; Kunze, M; Sreeraj, P; Wiemhöfer, H D; Thangadurai, V; Wilkening, M; Heitjans, P

    2012-04-01

    NMR spin relaxometry is known to be a powerful tool for the investigation of Li(+) dynamics in (non-paramagnetic) crystalline and amorphous solids. As long as significant structural changes are absent in a relatively wide temperature range, with NMR spin-lattice (as well as spin-spin) relaxation measurements information on Li self-diffusion parameters such as jump rates and activation energies are accessible. Diffusion-induced NMR relaxation rates are governed by a motional correlation function describing the ion dynamics present. Besides the mean correlation rate of the dynamic process, the motional correlation function (i) reflects deviations from random motion (so-called correlation effects) and (ii) gives insights into the dimensionality of the hopping process. In favorable cases, i.e., when temperature- and frequency-dependent NMR relaxation rates are available over a large dynamic range, NMR spin relaxometry is able to provide a comprehensive picture of the relevant Li dynamic processes. In the present contribution, we exemplarily present two recent variable-temperature (7)Li NMR spin-lattice relaxation studies focussing on Li(+) dynamics in crystalline ion conductors which are of relevance for battery applications, viz. Li(7) La(3)Zr(2)O(12) and Li(12)Si(7). Copyright © 2012 Elsevier Inc. All rights reserved.

  6. NMR Studies of Lithium Iodide Based Solid Electrolytes

    DEFF Research Database (Denmark)

    Dupree, R.; Howells, R. J.; Hooper, A.

    1983-01-01

    In mixture of LiI with γAl2O3 the ionic conductivity is found to increase by up to three orders of magnitude over pure LiI. NMR measurements of7Li relaxation times were performed on both anhydrous LiI and a mixture of LiI with 30m/o γAl2O3. The relaxation is found to be purely dipolar in origin...... for the pure halide with correlation times consistent with conductivity data. However two relaxation rates are found in the composite material which indicate that 50% of the7Li ions are in a radically different environment....

  7. Spin-lattice relaxation times and knight shift in InSb and InAs

    International Nuclear Information System (INIS)

    Braun, P.; Grande, S.

    1976-01-01

    For a dominant contact interaction between nuclei and conduction electrons the relaxation rate is deduced. The extreme cases of degenerate and non-degenerate semiconductors are separately discussed. At strong degeneracy the product of the Knight shift and relaxation time gives the Korringa relation for metals. Measurements of the NMR spin-lattice relaxation times of 115 InSb and 115 InAs were made between 4.2 and 300 K for strongly degenerated samples. The different relaxation mechanisms are discussed and the experimental and theoretical results are compared. (author)

  8. Complex methyl groups dynamics in [(CH3)4P]3Sb2Br9 (PBA) from low to high temperatures by proton spin-lattice relaxation and narrowing of proton NMR spectrum.

    Science.gov (United States)

    Latanowicz, L; Medycki, W; Jakubas, R

    2009-11-01

    Molecular dynamics of a polycrystalline sample of [(CH(3))(4)P](3)Sb(2)Br(9) (PBA) has been studied on the basis of the T(1) (24.7 MHz) relaxation time measurement, the proton second moment of NMR and the earlier published T(1) (90 MHz) relaxation times. The study was performed in a wide range of temperatures (30-337 K). The tunnel splitting omega(T) of the methyl groups was estimated as of low frequency (from kHz to few MHz). The proton spin pairs of the methyl group are known to perform a complex internal motion being a resultant of four components. Three of them involve mass transportation over and through the potential barrier and are characterized by the correlation times tau(3) and tau(T)of the jumps over the barrier and tunnel jumps in the threefold potential of the methyl group and tau(iso) the correlation time of isotropic rotation of the whole TMP cation. For tau(3) and tau(iso) the Arrhenius temperature dependence was assumed, while for tau(T)--the Schrödinger one. The fourth motion causes fluctuations of the tunnel splitting frequency, omega(T), and it is related to the lifetime of the methyl spin at the energy level. The correlation function for this fourth motion (tau(omega) correlation time) has been proposed by Müller-Warmuth et al. In this paper a formula for the correlation function and spectral density of the complex motion made of the above-mentioned four components was derived and used in interpretation of the T(1) relaxation time. The second moment of proton NMR line at temperatures below 50K is four times lower than its value for the rigid structure. The three components of the internal motion characterized by tau(T), tau(H), and tau(iso) were proved to reduce the second moment of the NMR line. The tunnel jumps of the methyl group reduce M(2) at almost 0K, the classical jumps over the barrier reduce M(2) in the vicinity of 50K, while the isotropic motion near 150K. Results of the study on the dynamics of CH(3) groups of TMP cation based on

  9. Optimizing Water Exchange Rates and Rotational Mobility for High-Relaxivity of a Novel Gd-DO3A Derivative Complex Conjugated to Inulin as Macromolecular Contrast Agents for MRI.

    Science.gov (United States)

    Granato, Luigi; Vander Elst, Luce; Henoumont, Celine; Muller, Robert N; Laurent, Sophie

    2018-02-01

    Thanks to the understanding of the relationships between the residence lifetime τ M of the coordinated water molecules to macrocyclic Gd-complexes and the rotational mobility τ R of these structures, and according to the theory for paramagnetic relaxation, it is now possible to design macromolecular contrast agents with enhanced relaxivities by optimizing these two parameters through ligand structural modification. We succeeded in accelerating the water exchange rate by inducing steric compression around the water binding site, and by removing the amide function from the DOTA-AA ligand [1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid mono(p-aminoanilide)] (L) previously designed. This new ligand 10[2(1-oxo-1-p-propylthioureidophenylpropyl]-1,4,7,10-tetraazacyclodecane-1,4,7-tetraacetic acid (L 1 ) was then covalently conjugated to API [O-(aminopropyl)inulin] to get the complex API-(GdL 1 )x with intent to slow down the rotational correlation time (τ R ) of the macromolecular complex. The evaluation of the longitudinal relaxivity at different magnetic fields and the study of the 17 O-NMR at variable temperature of the low-molecular-weight compound (GdL 1 ) showed a slight decrease of the τ M value (τM310 = 331 ns vs. τM310 = 450 ns for the GdL complex). Consequently to the increase of the size of the API-(GdL 1 )x complex, the rotational correlation time becomes about 360 times longer compared to the monomeric GdL 1 complex (τ R  = 33,700 ps), which results in an enhanced proton relaxivity. © 2018 Wiley-VHCA AG, Zurich, Switzerland.

  10. How does relaxing the algorithm for autism affect DSM-V prevalence rates?

    Science.gov (United States)

    Matson, Johnny L; Hattier, Megan A; Williams, Lindsey W

    2012-08-01

    Although it is still unclear what causes autism spectrum disorders (ASDs), over time researchers and clinicians have become more precise with detecting and diagnosing ASD. Many diagnoses, however, are based on the criteria established within the Diagnostic and Statistical Manual of Mental Disorders (DSM); thus, any change in these diagnostic criteria can have a great effect upon children with ASD and their families. It is predicted that the prevalence of ASD diagnoses will dramatically decrease with the adoption of the proposed DSM-5 criteria in 2013. The aim of this current study was to inspect the changes in prevalence first using a diagnostic criteria set which was modified slightly from the DSM-5 criteria (Modified-1 criteria) and again using a set of criteria which was relaxed even a bit more (Modified-2 criteria). Modified-1 resulted in 33.77 % fewer toddlers being diagnosed with ASD compared to the DSM-IV, while Modified-2 resulted in only a 17.98 % decrease in ASD diagnoses. Children diagnosed with the DSM-5 criteria exhibited the greatest levels of autism symptomatology, but the Mod-1, Mod-2, and DSM-IV groups still demonstrated significant impairments. Implications of these findings are discussed.

  11. Correlation of heart rate and radionuclide index of left ventricular contraction and relaxation

    International Nuclear Information System (INIS)

    Adachi, Haruhiko; Sugihara, Hiroki; Nakagawa, Hiroaki; Inagaki, Suetsugu; Kubota, Yasushi; Nakagawa, Masao

    1990-01-01

    Since the cardiac function indices derived from radionuclide ventriculography (RNV) are considered to depend on the heart rate, we studied the relationship between systolic or diastolic indices and heart rates in patients with normal RNV and devised a method of correcting these indices according to the heart rate. For the systolic indices, the heart rate showed significant correlation with ET (r=-0.640), PER (r=0.791) and TPE (r=-0.401) but not with EF, 1/3 EF, MNSER or 1/3 MNSER. For the diastolic indices, the heart rate correlated well with FT (r=-0.938), RFT (r=-0.736), SFT (r=-0.803), 1/3 FF (r=-0.758), PFR (r=0.759), 1/3 PFR (r=0.742) and TPF (r=-0.389) but not with AFT, 1/3 MNDFR or AFF. These results indicate that many systolic and diastolic indices derived from RNV are affected by the heart rate, So when cardiac function is evaluated with the use of radionuclide indices, those which are independent of the heart rate should be used, or they should be corrected for the heart rate. As a method of correction, we proposed a rotating method obtained by manipulation of the regression equation of heart rates and indices. This new method is certain and easier to use when the correcting equations are set into a computer program. (author)

  12. A carbon-13 NMR spin-lattice relaxation study of the molecular conformation of the nootropic drug 2-oxopyrrolidin-1-ylacetamide

    Science.gov (United States)

    Baldo, M.; Grassi, A.; Guidoni, L.; Nicolini, M.; Pappalardo, G. C.; Viti, V.

    The spin-lattice relaxation times ( T1) of carbon-13 resonances of the drug 2-oxopyrrolidin- 1-ylacetamide ( 2OPYAC) were determined in CDCl 3 + DMSO and H 2O solutions to investigate the internal conformational flexibility. The measured T1s for the hydrogen-bearing carbon atoms of the 2-pyrrolidone ring fragment were diagnostic of a rigid conformation with respect to the acetamide linked moiety. The model of anisotropic reorientation of a rigid body was used to analyse the measured relaxation data in terms of a single conformation. Owing to the small number of T1 data available the fitting procedure for each of the possible conformations failed. The structure corresponding to the rigid conformation was therefore considered to be the one that is strongly stabilized by internal hydrogen bonding as predicted on the basis of theoretical MO ab initio quantum chemical calculations.

  13. Cross-relaxation of 8Li + in copper

    Science.gov (United States)

    Mansour, A. I.; Morris, G. D.; Salman, Z.; Chow, K. H.; Dunlop, T.; Jung, J.; Fan, I.; MacFarlane, W. A.; Kiefl, R. F.; Parolin, T. J.; Saadaoui, H.; Wang, D.; Hossain, M. D.; Song, Q.; Smadella, M.; Mosendz, O.; Kardasz, B.; Heinrich, B.; Levy, C. D. P.; Pearson, M. R.

    2009-04-01

    The “cross-relaxation” method (also called “level-crossing resonance” or “avoided level-crossing”) is a powerful technique that can be used to provide detailed structural and site information on impurities in materials. In this paper, we report on the development of the cross-relaxation technique for Li+8 at the β-detected nuclear magnetic resonance ( β-NMR) facility located in TRIUMF in Vancouver. The measurements were carried out on a Cu single crystal where the relaxation rate of the Li8 polarization was monitored as a function of the applied longitudinal magnetic field. The occurrence of cross-relaxation, at a particular magnetic field, between the Li8 and the surrounding nuclei is evident as a resonant enhancement of the relaxation rate at the level crossing field. We discuss inferences about the site and structure of Li+8 in Cu from this data.

  14. Oxygen Mapping within Healthy and Acutely Infarcted Brain Tissue in Humans Using the NMR Relaxation of Lipids: A Proof-Of-Concept Translational Study.

    Science.gov (United States)

    Colliez, Florence; Safronova, Marta M; Magat, Julie; Joudiou, Nicolas; Peeters, André P; Jordan, Bénédicte F; Gallez, Bernard; Duprez, Thierry

    2015-01-01

    The clinical applicability of brain oxygenation mapping using the MOBILE (Mapping of Oxygen By Imaging Lipids relaxation Enhancement) magnetic resonance (MR) technique was assessed in the clinical setting of normal brain and of acute cerebral ischemia as a founding proof-of-concept translational study. Changes in the oxygenation level within healthy brain tissue can be detected by analyzing the spin-lattice proton relaxation ('Global T1' combining water and lipid protons) because of the paramagnetic properties of molecular oxygen. It was hypothesized that selective measurement of the relaxation of the lipid protons ('Lipids T1') would result in enhanced sensitivity of pO2 mapping because of higher solubility of oxygen in lipids than in water, and this was demonstrated in pre-clinical models using the MOBILE technique. In the present study, 12 healthy volunteers and eight patients with acute (48-72 hours) brain infarction were examined with the same clinical 3T MR system. Both Lipids R1 (R1 = 1/T1) and Global R1 were significantly different in the infarcted area and the contralateral unaffected brain tissue, with a higher statistical significance for Lipids R1 (median difference: 0.408 s-1; pbrain tissue of stroke patients were not significantly different from the R1 values calculated in the brain tissue of healthy volunteers. The main limitations of the present prototypic version of the MOBILE sequence are the long acquisition time (4 min), hampering robustness of data in uncooperative patients, and a 2 mm slice thickness precluding accurate measurements in small infarcts because of partial volume averaging effects.

  15. Oxygen Mapping within Healthy and Acutely Infarcted Brain Tissue in Humans Using the NMR Relaxation of Lipids: A Proof-Of-Concept Translational Study.

    Directory of Open Access Journals (Sweden)

    Florence Colliez

    Full Text Available The clinical applicability of brain oxygenation mapping using the MOBILE (Mapping of Oxygen By Imaging Lipids relaxation Enhancement magnetic resonance (MR technique was assessed in the clinical setting of normal brain and of acute cerebral ischemia as a founding proof-of-concept translational study. Changes in the oxygenation level within healthy brain tissue can be detected by analyzing the spin-lattice proton relaxation ('Global T1' combining water and lipid protons because of the paramagnetic properties of molecular oxygen. It was hypothesized that selective measurement of the relaxation of the lipid protons ('Lipids T1' would result in enhanced sensitivity of pO2 mapping because of higher solubility of oxygen in lipids than in water, and this was demonstrated in pre-clinical models using the MOBILE technique. In the present study, 12 healthy volunteers and eight patients with acute (48-72 hours brain infarction were examined with the same clinical 3T MR system. Both Lipids R1 (R1 = 1/T1 and Global R1 were significantly different in the infarcted area and the contralateral unaffected brain tissue, with a higher statistical significance for Lipids R1 (median difference: 0.408 s-1; p<0.0001 than for Global R1 (median difference: 0.154 s-1; p = 0.027. Both Lipids R1 and Global R1 values in the unaffected contralateral brain tissue of stroke patients were not significantly different from the R1 values calculated in the brain tissue of healthy volunteers. The main limitations of the present prototypic version of the MOBILE sequence are the long acquisition time (4 min, hampering robustness of data in uncooperative patients, and a 2 mm slice thickness precluding accurate measurements in small infarcts because of partial volume averaging effects.

  16. NMR spectroscopic study and DFT calculations of GIAO NMR ...

    African Journals Online (AJOL)

    1H, proton coupled and decoupled 13C, DEPT, HETCOR NMR spectra, the magnitude of one bond 1JCH coupling constants and 13C NMR spin-lattice relaxation time (T1) of 1,9-diaminononane (danon, C9H22N2) have been reported for the first time. 1H, 13C NMR chemical shifts and 1JCH coupling constants of danon ...

  17. Institute of Physics, A Mickiewicz University, Ul. Umultowska 85, 61-614 Poznan, Poland: ? NMR relaxation in supercooled di-methyl phthalate

    Science.gov (United States)

    Suchanski, W.; Szczesiak, E.; Jurga, S.

    1998-07-01

    Spin-lattice relaxation times 0953-8984/10/28/006/img2 and nuclear Overhauser enhancement factors (NOE) for the individual ring carbons in di-methyl phthalate (DMF) were measured over a wide range of temperatures. The results show that the reorientational correlation function corresponding to the global dynamics in supercooled liquid can be well described by a Davidson-Cole distribution. The viscosity dependence of the reorientational correlation time 0953-8984/10/28/006/img3 derived is analysed to investigate the adequacy of the modified Debye equation to description of the microscopic behaviour of supercooled systems.

  18. Anthocyanin Incorporated Dental Copolymer: Bacterial Growth Inhibition, Mechanical Properties, and Compound Release Rates and Stability by 1H NMR

    Directory of Open Access Journals (Sweden)

    Halyna Hrynash

    2014-01-01

    Full Text Available Objective. To evaluate bacterial growth inhibition, mechanical properties, and compound release rate and stability of copolymers incorporated with anthocyanin (ACY; Vaccinium macrocarpon. Methods. Resin samples were prepared (Bis-GMA/TEGDMA at 70/30 mol% and incorporated with 2 w/w% of either ACY or chlorhexidine (CHX, except for the control group. Samples were individually immersed in a bacterial culture (Streptococcus mutans for 24 h. Cell viability (n=3 was assessed by counting the number of colony forming units on replica agar plates. Flexural strength (FS and elastic modulus (E were tested on a universal testing machine (n=8. Compound release and chemical stability were evaluated by UV spectrophotometry and 1H NMR (n=3. Data were analyzed by one-way ANOVA and Tukey’s test (α = 0.05. Results. Both compounds inhibited S. mutans growth, with CHX being most effective (P<0.05. Control resin had the lowest FS and E values, followed by ACY and CHX, with statistical difference between control and CHX groups for both mechanical properties (P<0.05. The 24 h compound release rates were ACY: 1.33 μg/mL and CHX: 1.92 μg/mL. 1H NMR spectra suggests that both compounds remained stable after being released in water. Conclusion. The present findings indicate that anthocyanins might be used as a natural antibacterial agent in resin based materials.

  19. Direct measurement of the electron-phonon relaxation rate in thin copper films

    Energy Technology Data Exchange (ETDEWEB)

    Taskinen, L.J.; Karvonen, J.T.; Maasilta, I.J. [NanoScience Center, Department of Physics, P.O. Box 35, FIN-40014 University of Jyvaeskylae (Finland); Kivioja, J.M. [Low Temperature Laboratory, Helsinki University of Technology, P.O. Box 2200, 02015 HUT Helsinki (Finland)

    2004-11-01

    We have used normal metal-insulator-superconductor (NIS) tunnel junction pairs, known as SINIS structures, for ultrasensitive thermometry at sub-Kelvin temperatures. With the help of these thermometers, we have developed an ac-technique to measure the electron-phonon (e-p) scattering rate directly, without any other material or geometry dependent parameters, based on overheating the electron gas. The technique is based on Joule heating the electrons in the frequency range DC-10 MHz, and measuring the electron temperature in DC. Because of the nonlinearity of the electron-phonon coupling with respect to temperature, even the DC response will be affected, when the heating frequency reaches the natural cut-off determined by the e-p scattering rate. Results on thin Cu films show a T{sup 4} behavior for the scattering rate, in agreement with indirect measurement of similar samples and numerical modeling of the non-linear response. (copyright 2004 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim) (orig.)

  20. Direct measurement of the electron-phonon relaxation rate in thin metal films

    Science.gov (United States)

    Maasilta, Ilari; Kivioja, Jani

    2005-03-01

    We have used normal metal-insulator-superconductor (NIS) tunnel junctions for ultrasensitive thermometry at sub-Kelvin temperatures. With the help of these thermometers, we have developed an ac-technique to measure the electron-phonon (e-p) scattering rate directly, without any other material or geometry dependent parameters, based on overheating the electron gas. The technique is based on Joule heating the electrons in the frequency range DC-10 MHz, and measuring the electron temperature in DC. Because of the nonlinearity of the electron-phonon coupling with respect to temperature, even the DC response will be affected, when the heating frequency reaches the natural cut-off determined by the e-p scattering rate. Results on thin Cu films show a T^4 behavior for the scattering rate, in agreement with indirect measurement of similar samples and numerical modeling of the non-linear response.ootnotetextL. J. Taskinen, J. M. Kivioja, J. T. Karvonen, and I. J. Maasilta, phys. stat. sol. (c) 1, 2856 (2004). ,ootnotetextJ. T. Karvonen, L. J. Taskinen, I. J. Maasilta, phys. stat. sol. (c) 1, 2799 (2004).

  1. Phosphorus-31 NMR magnetization transfer measurements of metabolic reaction rates in the rat heart and kidney in vivo

    International Nuclear Information System (INIS)

    Koretsky, A.P.

    1984-01-01

    31 P NMR is a unique tool to study bioenergetics in living cells. The application of magnetization transfer techniques to the measurement of steady-state enzyme reaction rates provides a new approach to understanding the regulation of high energy phosphate metabolism. This dissertation is concerned with the measurement of the rates of ATP synthesis in the rat kidney and of the creatine kinase catalyzed reaction in the rat heart in situ. The theoretical considerations of applying magnetization transfer techniques to intact organs are discussed with emphasis on the problems associated with multiple exchange reactions and compartmentation of reactants. Experimental measurements of the ATP synthesis rate were compared to whole kidney oxygen consumption and Na + reabsorption rates to derive ATP/O values. The problems associated with ATP synthesis rate measurements in kidney, e.g. the heterogeneity of the inorganic phosphate resonance, are discussed and experiments to overcome these problems proposed. In heart, the forward rate through creatine kinase was measured to be larger than the reverse rate. To account for the difference in forward and reverse rates a model is proposed based on the compartmentation of a small pool of ATP

  2. High-resolution magic angle spinning proton NMR analysis of human prostate tissue with slow spinning rates.

    Science.gov (United States)

    Taylor, Jennifer L; Wu, Chin-Lee; Cory, David; Gonzalez, R Gilberto; Bielecki, Anthony; Cheng, Leo L

    2003-09-01

    The development of high-resolution magic angle spinning (HR-MAS) NMR spectroscopy for intact tissue analysis and the correlations between the measured tissue metabolites and disease pathologies have inspired investigations of slow-spinning methodologies to maximize the protection of tissue pathology structures from HR-MAS centrifuging damage. Spinning sidebands produced by slow-rate spinning must be suppressed to prevent their complicating the spectral region of metabolites. Twenty-two human prostatectomy samples were analyzed on a 14.1T spectrometer, with HR-MAS spinning rates of 600 Hz, 700 Hz, and 3.0 kHz, a repetition time of 5 sec, and employing various rotor-synchronized suppression methods, including DANTE, WATERGATE, TOSS, and PASS pulse sequences. Among them, DANTE, as the simplest scheme, has shown the most potential in suppression of tissue water signals and spinning sidebands, as well as in quantifying metabolic concentrations. Copyright 2003 Wiley-Liss, Inc.

  3. The effect of dissolved oxygen on the relaxation rates of blood plasma: Implications for hyperoxia calibrated BOLD.

    Science.gov (United States)

    Ma, Yuhan; Berman, Avery J L; Pike, G Bruce

    2016-12-01

    To determine the contribution of paramagnetic dissolved oxygen in blood plasma to blood-oxygenation-level-dependent (BOLD) signal changes in hyperoxic calibrated BOLD studies. Bovine blood plasma samples were prepared with partial pressures of oxygen (pO 2 ) ranging from 110 to 600 mmHg. R 1 , R 2 , and R 2 * of the plasma with dissolved oxygen were measured using quantitative MRI sequences at 3 Tesla. Simulations were performed to predict the relative effects of dissolved oxygen and deoxyhemoglobin changes in hyperoxia calibrated BOLD. The relaxivities of dissolved oxygen in plasma were found to be r 1, O2 =1.97 ± 0.09 ×10 -4 s -1 mmHg -1 , r 2, O2 =2.3 ± 0.7 ×10 -4 s -1 mmHg -1 , and r 2, O2 * = 2.3 ± 0.7 ×10 -4 s -1 mmHg -1 . Simulations predict that neither the transverse nor longitudinal relaxation rates of dissolved oxygen contribute significantly to the BOLD signal during hyperoxia. During hyperoxia, the increases in R 2 and R 2 * of blood from dissolved oxygen in plasma are considerably less than the decreases in R 2 and R 2 * from venous deoxyhemoglobin. R 1 effects due to dissolved oxygen are also predicted to be negligible. As a result, dissolved oxygen in arteries should not contribute significantly to the hyperoxic calibrated BOLD signal. Magn Reson Med 76:1905-1911, 2016. © 2015 International Society for Magnetic Resonance in Medicine. © 2015 International Society for Magnetic Resonance in Medicine.

  4. Is meditation always relaxing? Investigating heart rate, heart rate variability, experienced effort and likeability during training of three types of meditation.

    Science.gov (United States)

    Lumma, Anna-Lena; Kok, Bethany E; Singer, Tania

    2015-07-01

    Meditation is often associated with a relaxed state of the body. However, meditation can also be regarded as a type of mental task and training, associated with mental effort and physiological arousal. The cardiovascular effects of meditation may vary depending on the type of meditation, degree of mental effort, and amount of training. In the current study we assessed heart rate (HR), high-frequency heart rate variability (HF-HRV) and subjective ratings of effort and likeability during three types of meditation varying in their cognitive and attentional requirements, namely breathing meditation, loving-kindness meditation and observing-thoughts meditation. In the context of the ReSource project, a one-year longitudinal mental training study, participants practiced each meditation exercise on a daily basis for 3 months. As expected HR and effort were higher during loving-kindness meditation and observing-thoughts meditation compared to breathing meditation. With training over time HR and likeability increased, while HF-HRV and the subjective experience of effort decreased. The increase in HR and decrease in HF-HRV over training was higher for loving-kindness meditation and observing-thoughts meditation compared to breathing meditation. In contrast to implicit beliefs that meditation is always relaxing and associated with low arousal, the current results show that core meditations aiming at improving compassion and meta-cognitive skills require effort and are associated with physiological arousal compared to breathing meditation. Overall these findings can be useful in making more specific suggestions about which type of meditation is most adaptive for a given context and population. Copyright © 2015 Elsevier B.V. All rights reserved.

  5. NMR spin-lattice relaxation study of 7Li and 93Nb nuclei in Ti- or Fe-doped LiNbO3:Mg single crystals

    Directory of Open Access Journals (Sweden)

    Tae Ho Yeom

    2016-04-01

    Full Text Available In this study, to understand the effects of paramagnetic impurities, we investigated the temperature dependent of the spin-lattice relaxation times of pure LiNbO3, LiNbO3:Mg, LiNbO3:Mg/Ti, LiNbO3:Mg/Fe, and LiNbO3:Mg/Fe (thermally treated at 500°C single crystals. The results for the LiNbO3:Mg single crystals doped with Fe3+ or Ti3+ are discussed with respect to the site distribution and atomic mobility of Li and Nb. In addition, the effects of a thermal treatment on LiNbO3:Mg/Fe single crystals were examined based on the T1 analysis of 7Li and 93Nb. It was found that the presence of impurities in the crystals induced systematic changes of activation energies concerning atomic mobility.

  6. Characterization of mu s-ms dynamics of proteins using a combined analysis of N-15 NMR relaxation and chemical shift: Conformational exchange in plastocyanin induced by histidine protonations

    DEFF Research Database (Denmark)

    Hass, M. A. S.; Thuesen, Marianne Hallberg; Christensen, Hans Erik Mølager

    2004-01-01

    variabilis (A.v. PCu) (Ma, L.; Hass, M. A. S.; Vierick, N.; Kristensen, S. M.; Ulstrup, J.; Led, J. J. Biochemistry 2003, 42, 320-330). The R-1 and R-2 relaxation rates of the backbone N-15 nuclei were measured at a series of pH and temperatures on an 15N labeled sample of A.v. PCu, and the 15 N chemical...

  7. The spin lattice relaxation of {sup 8}Li in simple metals

    Energy Technology Data Exchange (ETDEWEB)

    Hossain, M.D.; Saadaoui, H. [Department of Physics, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Parolin, T.J. [Chemistry Department, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Song, Q.; Wang, D.; Smadella, M. [Department of Physics, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Chow, K.H.; Egilmez, M.; Fan, I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Kiefl, R.F. [Department of Physics, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Canadian Institute of Advanced Research (Canada); Kreitzman, S.R.; Levy, C.D.P.; Morris, G.D.; Pearson, M.R. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Salman, Z. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Clarendon Laboratory, Department of Physics, Oxford University, Parks Road, Oxford OX1 3PU (United Kingdom); MacFarlane, W.A., E-mail: wam@chem.ubc.c [Chemistry Department, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada)

    2009-04-15

    We report the modification to the linear temperature dependence of the Korringa nuclear spin-lattice relaxation rate of an implanted NMR probe in silver, as it makes a thermally activated site change. We develop a simple model of this phenomenon, which is found in a number of metals including Au and Nb.

  8. Crystal structure, NMR study, dc-conductivity and dielectric relaxation studies of a new compound [C2H10N2]Cd(SCN)2Cl2

    Science.gov (United States)

    Saidi, K.; Kamoun, S.; Ayedi, H. F.; Gargouri, M.

    2012-06-01

    The crystal structure, the solid NMR spectroscopy and the complex impedance study have been carried out on [C2H10N2]CdCl2(SCN)2. Characterization by single crystal X-ray crystallography shows that the cadmium atoms have à 2N2S2Cl hexa-coordination sphere, exhibiting pseudo-octahedral geometry. The cadmium atoms are bridged by two thiocyanate ions generating 1-D polymeric-chains. These chains are themselves interconnected by means of N-H…Cl(NCS) hydrogen bonds originating from the organic cation [(NH3)2(CH2)2]2+. 111Cd isotropic chemical shifts span a range of 268ppm. The cadmium atom exhibits multiplets that result from 111Cd-14N spin-spin coupling. Examination of 111Cd and 13C MAS line shapes shows direct measurement of the indirect spin-spin coupling constant 2J(111Cd, 14N) = 105Hz and the dipolar coupling constant of 1381Hz . Impedance spectroscopy measurements of [C2H10N2]CdCl2(SCN)2 have been studied from 209Hz to 5 MHz over the temperature range 300-370 K. The Cole-Cole (Z" versus Z') plots are fitted to two equivalent circuits models. The formalism of complex permittivity and impedance were employed to analyze the experimental data. The dc conductivity follows the Arrhenius relation with an activation energy Ea = 0.54 (3) eV.

  9. Crystal structure, NMR study, dc-conductivity and dielectric relaxation studies of a new compound [C2H10N2]Cd(SCN2Cl2

    Directory of Open Access Journals (Sweden)

    Gargouri M.

    2012-06-01

    Full Text Available The crystal structure, the solid NMR spectroscopy and the complex impedance study have been carried out on [C2H10N2]CdCl2(SCN2. Characterization by single crystal X-ray crystallography shows that the cadmium atoms have à 2N2S2Cl hexa-coordination sphere, exhibiting pseudo-octahedral geometry. The cadmium atoms are bridged by two thiocyanate ions generating 1-D polymeric-chains. These chains are themselves interconnected by means of N-H…Cl(NCS hydrogen bonds originating from the organic cation [(NH32(CH22]2+. 111Cd isotropic chemical shifts span a range of 268ppm. The cadmium atom exhibits multiplets that result from 111Cd-14N spin-spin coupling. Examination of 111Cd and 13C MAS line shapes shows direct measurement of the indirect spin-spin coupling constant 2J(111Cd, 14N = 105Hz and the dipolar coupling constant of 1381Hz . Impedance spectroscopy measurements of [C2H10N2]CdCl2(SCN2 have been studied from 209Hz to 5 MHz over the temperature range 300-370 K. The Cole-Cole (Z” versus Z’ plots are fitted to two equivalent circuits models. The formalism of complex permittivity and impedance were employed to analyze the experimental data. The dc conductivity follows the Arrhenius relation with an activation energy Ea = 0.54 (3 eV.

  10. Determination of muscle protein synthesis rates in fish using (2)H2O and (2)H NMR analysis of alanine.

    Science.gov (United States)

    Marques, Cátia; Viegas, Filipa; Rito, João; Jones, John; Viegas, Ivan

    2016-09-15

    Following administration of deuterated water ((2)H2O), the fractional synthetic rate (FSR) of a given endogenous protein can be estimated by (2)H-enrichment quantification of its alanine residues. Currently, this is measured by mass spectrometry following a derivatization procedure. Muscle FSR was measured by (1)H/(2)H NMR analysis of alanine from seabass kept for 6 days in 5% (2)H-enriched saltwater, following acid hydrolysis and amino acid isolation by cation-exchange chromatography of muscle tissue. The analysis is simple and robust, and provides precise measurements of excess alanine (2)H-enrichment in the 0.1-0.4% range from 50 mmol of alanine recovered from muscle protein. Copyright © 2016 Elsevier Inc. All rights reserved.

  11. Whole-core analysis by 13C NMR

    International Nuclear Information System (INIS)

    Vinegar, H.J.; Tutunjian, P.N.; Edelstein, W.A.; Roemer, P.B.

    1991-01-01

    This paper reports on a whole-core nuclear magnetic resonance (NMR) system that was used to obtain natural abundance 13 C spectra. The system enables rapid, nondestructive measurements of bulk volume of movable oil, aliphatic/aromatic ratio, oil viscosity, and organic vs. carbonate carbon. 13 C NMR can be used in cores where the 1 H NMR spectrum is too broad to resolve oil and water resonances separately. A 5 1/4-in. 13 C/ 1 H NMR coil was installed on a General Electric (GE) CSI-2T NMR imager/spectrometer. With a 4-in.-OD whole core, good 13 C signal/noise ratio (SNR) is obtained within minutes, while 1 H spectra are obtained in seconds. NMR measurements have been made of the 13 C and 1 H density of crude oils with a wide range of API gravities. For light- and medium-gravity oils, the 13 C and 1 H signal per unit volume is constant within about 3.5%. For heavy crudes, the 13 C and 1 H density measured by NMR is reduced by the shortening of spin-spin relaxation time. 13 C and 1 H NMR spin-lattice relaxation times were measured on a suite of Cannon viscosity standards, crude oils (4 to 60 degrees API), and alkanes (C 5 through C 16 ) with viscosities at 77 degrees F ranging from 0.5 cp to 2.5 x 10 7 cp. The 13 C and 1 H relaxation times show a similar correlation with viscosity from which oil viscosity can be estimated accurately for viscosities up to 100 cp. The 13 C surface relaxation rate for oils on water-wet rocks is very low. Nonproton decoupled 13 C NMR is shown to be insensitive to kerogen; thus, 13 C NMR measures only the movable hydrocarbon content of the cores. In carbonates, the 13 C spectrum also contains a carbonate powder pattern useful in quantifying inorganic carbon and distinguishing organic from carbonate carbon

  12. Analysing the response in R2* relaxation rate of intracranial tumours to hyperoxic and hypercapnic respiratory challenges: initial results

    International Nuclear Information System (INIS)

    Mueller, A.; Traeber, F.; Koenig, R.; Willinek, W.A.; Schild, H.H.; Muertz, P.; Remmele, S.; Wenningmann, I.; Clusmann, H.; Flacke, S.; Gieseke, J.

    2011-01-01

    To investigate the response in R2 * relaxation rate of human intracranial tumours during hyperoxic and hypercapnic respiratory challenges. In seven patients with different intracranial tumours, cerebral R2 * changes during carbogen and CO 2 /air inhalation were monitored at 3 T using a dynamic multigradient-echo sequence of high temporal and spatial resolution. The R2 * time series of each voxel was tested for significant change. Regions of interest were analysed with respect to response amplitude and velocity. The tumours showed heterogeneous R2 * responses with large interindividual variability. In the 'contrast-enhancing' area of five patients and in the 'non-tumoral' tissue most voxels showed a decrease in R2 * for carbogen. For the 'contrast-enhancing' area of two patients hardly any responses were found. In areas of 'necrosis' and perifocal 'oedema' typically voxels with R2 * increase and no response were found for both gases. For tissue responding to CO 2 /air, the R2 * changes were of the same order of magnitude as those for carbogen. The response kinetic was generally attenuated in tumoral tissue. The spatially resolved determination of R2 * changes reveals the individual heterogeneous response characteristic of intracranial human tumours during hyperoxic and hypercapnic respiratory challenges. (orig.)

  13. Investigation of the Temperature Dependence of the Acceptor Center Relaxation Rate in Silicon by the mu^-SR-Method

    CERN Document Server

    Mamedov, T N; Stojkov, A V; Andrianov, D G; Gerlach, D; Zimmermann, U; Gorelkin, V N; Kormann, O; Major, J V; Shevchik, M

    2000-01-01

    Results on the temperature dependence of the residual polarization of negative muons in silicon with phosphorus (3.2 cdot 10^12, 2.3 cdot 10^15 and 4.5 cdot 10^18 cm^-3) and aluminium (2 cdot 10^14 and 2.4 cdot 10^18 cm^-3) impurities are presented. The measurements were carried out in a transverse to the direction of the muon spin magnetic field of 2000 Oe in the temperature range 4.2-300 K. The temperature dependence of the relaxation rate of the magnetic moment of the Al shallow acceptor centre in undeformed silicon is determined for the first time. The constant of the hyperfine interaction between the magnetic moment of the muon and that of the electron shell of the muonic atom A_hf/2pi approx 3 cdot 10^7 s^-1) and the coefficient for capture of free electrons by a neutral aluminium atom in silicon (beta (Al^0) approx 7 cdot 10^-14 cm^3 s^-1 at 30 K) are estimated.

  14. Study of cultured fibroblasts in vivo using NMR

    Energy Technology Data Exchange (ETDEWEB)

    Karczmar, G.S.

    1984-08-01

    The goal was to study the compartmentation of phosphorylated glycolytic intermediates in intact Chicken Embryo Fibroblasts (CEFs) using /sup 31/P NMR at 109 MHz. A technique for maintaining functional cells at high densities in an NMR magnet is described. Signals were detected from cytoplasmic inorganic phosphate (P/sub i/), ATP, NAD, NADH, phosphorylcholine and phosphorylethanolamine. The effect of external glucose on cytoplasmic pools of phosphates was studied. When cells were perfused with glucose-free medium the rate of glycolysis decreased, the amplitudes of the ATP resonances decreased, and the P/sub i/ intensity increased. The quantity of NMR-detectable P/sub i/ produced was significantly greater than the quantity of NMR-detectable ATP which was lost. Experiments with /sup 32/P labeled P/sub i/ showed that as the concentration of glucose in the medium was increase, the amount of phosphate sequestered in the cells increased. We conclude that there is a pool of P/sub i/ which is not detected by high resolution NMR and that the size of this pool increases as the rate of glycolysis increase. Longtitudinal relaxation times of intracellular phosphates in normal, transformed, and primary CEFs were measured. The results demonstrate that relaxation times of phosphates are sensitive to structural and metabolic changes which occur when cells are grown in culture. 59 references. 31 figures.

  15. High resolution NMR theory and chemical applications

    CERN Document Server

    Becker, Edwin D

    1969-01-01

    High Resolution NMR: Theory and Chemical Applications focuses on the applications of nuclear magnetic resonance (NMR), as well as chemical shifts, lattices, and couplings. The book first offers information on the theory of NMR, including nuclear spin and magnetic moment, spin lattice relaxation, line widths, saturation, quantum mechanical description of NMR, and ringing. The text then ponders on instrumentation and techniques and chemical shifts. Discussions focus on the origin of chemical shifts, reference compounds, empirical correlations of chemical shifts, modulation and phase detection,

  16. Optimized "detectors" for dynamics analysis in solid-state NMR

    Science.gov (United States)

    Smith, Albert A.; Ernst, Matthias; Meier, Beat H.

    2018-01-01

    Relaxation in nuclear magnetic resonance (NMR) results from stochastic motions that modulate anisotropic NMR interactions. Therefore, measurement of relaxation-rate constants can be used to characterize molecular-dynamic processes. The motion is often characterized by Markov processes using an auto-correlation function, which is assumed to be a sum of multiple decaying exponentials. We have recently shown that such a model can lead to severe misrepresentation of the real motion, when the real correlation function is more complex than the model. Furthermore, multiple distributions of motion may yield the same set of dynamics data. Therefore, we introduce optimized dynamics "detectors" to characterize motions which are linear combinations of relaxation-rate constants. A detector estimates the average or total amplitude of motion for a range of motional correlation times. The information obtained through the detectors is less specific than information obtained using an explicit model, but this is necessary because the information contained in the relaxation data is ambiguous, if one does not know the correct motional model. On the other hand, if one has a molecular dynamics trajectory, one may calculate the corresponding detector responses, allowing direct comparison to experimental NMR dynamics analysis. We describe how to construct a set of optimized detectors for a given set of relaxation measurements. We then investigate the properties of detectors for a number of different data sets, thus gaining an insight into the actual information content of the NMR data. Finally, we show an example analysis of ubiquitin dynamics data using detectors, using the DIFRATE software.

  17. Relaxation and exchange dynamics of hyperpolarized 129Xe in human blood.

    Science.gov (United States)

    Norquay, Graham; Leung, General; Stewart, Neil J; Tozer, Gillian M; Wolber, Jan; Wild, Jim M

    2015-08-01

    (129) Xe-blood NMR was performed over the full blood oxygenation range to evaluate (129) Xe relaxation and exchange dynamics in human blood. Hyperpolarized (129) Xe was equilibrated with blood and isolated plasma, and NMR was performed at 1.5 T. The (129) Xe relaxation rate was found to increase nonlinearly with decreasing blood oxygenation. Three constants were extrapolated: rsO2 =  11.1, a "relaxivity index" characterizing the rate of change of (129) Xe relaxation as a function of blood oxygenation, and 1/T1oHb  =  0.13 s(-1) and 1/T1dHb = 0.42 s(-1) , the (129) Xe relaxation rates in oxygenated blood and deoxygenated blood, respectively. In addition, rate constants, ka =  0.022 ms(-1) and kb =  0.062 ms(-1) , were determined for xenon diffusing between red blood cells (RBCs) and plasma (hematocrit  =  48%). The (129) Xe-O2 relaxivity in plasma, rO2 = 0.075 s(-1) mM(-1) , and the (129) Xe relaxation rate in isolated plasma (without dissolved O2 ), 1/T1,b0 = 0.046 s(-1) , were also calculated. Finally, intrinsic (129) Xe-RBC relaxation rates, 1/T1,aoHb = 0.19 s(-1) and 1/T1,adHb = 0.84 s(-1) , in oxygenated blood and deoxygenated blood, respectively, were calculated. The relaxation and exchange analysis performed in this study should provide a sound experimental basis upon which to design future MR experiments for dissolved xenon transport from the lungs to distal tissues. © 2014 Wiley Periodicals, Inc.

  18. [Quantitative magnetic resonance imaging of brain iron deposition: comparison between quantitative susceptibility mapping and transverse relaxation rate (R2*) mapping].

    Science.gov (United States)

    Guan, Ji-Jing; Feng, Yan-Qiu

    2018-03-20

    To evaluate the accuracy and sensitivity of quantitative susceptibility mapping (QSM) and transverse relaxation rate (R2*) mapping in the measurement of brain iron deposition. Super paramagnetic iron oxide (SPIO) phantoms and mouse models of Parkinson's disease (PD) related to iron deposition in the substantia nigra (SN) underwent 7.0 T magnetic resonance (MR) scans (Bruker, 70/16) with a multi-echo 3D gradient echo sequence, and the acquired data were processed to obtain QSM and R2*. Linear regression analysis was performed for susceptibility and R2* in the SPIO phantoms containing 5 SPIO concentrations (30, 15, 7.5, 3.75 and 1.875 µg/mL) to evaluate the accuracy of QSM and R2* in quantitative iron analysis. The sensitivities of QSM and R2* mapping in quantitative detection of brain iron deposition were assessed using mouse models of PD induced by 1-methyl-4-phenyl-1,2,3,6-tetrahy-dropyridine (MPTP) in comparison with the control mice. In SPIO phantoms, QSM provided a higher accuracy than R2* mapping and their goodness-of-fit coefficients (R 2 ) were 0.98 and 0.89, respectively. In the mouse models of PD and control mice, the susceptibility of the SN was significantly higher in the PD models (5.19∓1.58 vs 2.98∓0.88, n=5; Pbrain iron deposition than R2*, and the susceptibility derived by QSM can be a potentially useful biomarker for studying PD.

  19. Measurement of backbone hydrogen-deuterium exchange in the type III secretion system needle protein PrgI by solid-state NMR

    Science.gov (United States)

    Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam

    2017-10-01

    In this report we present site-specific measurements of amide hydrogen-deuterium exchange rates in a protein in the solid state phase by MAS NMR. Employing perdeuteration, proton detection and a high external magnetic field we could adopt the highly efficient Relax-EXSY protocol previously developed for liquid state NMR. According to this method, we measured the contribution of hydrogen exchange on apparent 15N longitudinal relaxation rates in samples with differing D2O buffer content. Differences in the apparent T1 times allowed us to derive exchange rates for multiple residues in the type III secretion system needle protein.

  20. Beryllium fluoride exchange rate accelerated by Mg²⁺ as discovered by ¹⁹F NMR.

    Science.gov (United States)

    Liu, Yixiang; Mao, Xi-an; Liu, Maili; Jiang, Ling

    2015-01-08

    Beryllium fluoride is widely used as a phosphoryl analogue in macromolecular studies, which are not only fluoride-sensitive but also magnesium-dependent. The beryllium fluorides are a mixture of different species including BeF3(-) and BeF4(2-) exchanging under thermodynamic equilibrium in neutral aqueous solutions. In the cases of mimicking phosphate group transfer, both beryllium fluoride and the magnesium ion are generally needed. However, the impact of magnesium on the bioactivity of beryllium fluoride is not clear. We have found by (19)F NMR spectroscopy that Mg(2+) can severely affect the chemical exchange kinetics between BeF3(-) and BeF4(2-). When the F(-) concentration is relatively low, the presence of 10.0 mM Mg(2+) can accelerate the exchange rate 3-4 fold. However, when the F(-) concentration is relatively high, the Mg(2+) effect on the chemical exchange vanishes. On the basis of these findings, we proposed a possible mechanism that BeF4(2-) and Mg(2+) form an ion pair that affects the distribution of beryllium fluoride species and thus the activity in the solution.

  1. Application of pulsed-gradient 31P NMR on frog muscle to measure the diffusion rates of phosphorus compounds in cells

    International Nuclear Information System (INIS)

    Yoshizaki, K.; Seo, Y.; Nishikawa, H.; Morimoto, T.

    1982-01-01

    Pulsed-gradient 31 P NMR was used to measure the diffusion rates of phosphorus compounds in aqueous solution and in living muscles. The diffusion rates of creatine phosphate and inorganic phosphate in intact frog muscle cells were reduced by a factor of approx. 2 from those in aqueous solution, which suggests that the apparent intracellular viscosity is approx. 2 times larger than in aqueous solution

  2. Direct synthesis of magnetite nanoparticles from iron(II) carboxymethylcellulose and their performance as NMR contrast agents

    Science.gov (United States)

    da Silva, Delmarcio Gomes; Hiroshi Toma, Sergio; de Melo, Fernando Menegatti; Carvalho, Larissa Vieira C.; Magalhães, Alvicler; Sabadini, Edvaldo; dos Santos, Antônio Domingues; Araki, Koiti; Toma, e. Henrique E.

    2016-01-01

    Iron(II) carboxymethylcellulose (CMC) has been successfully employed in the synthesis of hydrophylic magnetite nanoparticles stabilized with a biopolymer coating, aiming applications in NMR imaging. The new method encompasses a convenient one-step synthetic procedure, allowing a good size control and yielding particles of about 10 nm (core size). In addition to the biocompatibility, the nanoparticles have promoted a drastic reduction in the transverse relaxation time (T2) of the water protons. The relaxivity rates have been investigated as a function of the nanoparticles concentration, showing a better performance in relation to the common NMR contrast agents available in the market.

  3. 13C NMR studies of the molecular flexibility of antidepressants

    International Nuclear Information System (INIS)

    Munro, S.L.; Andrews, P.R.; Craik, D.J.; Gale, D.J.

    1986-01-01

    The solution dynamics of a series of clinically potent antidepressants have been investigated by measuring 13 C NMR relaxation parameters. Correlation times and internal motional rates were calculated from spin-lattice relaxation times and nuclear Overhauser effects for the protonated carbons in mianserin, imipramine-like antidepressants, and amitriptyline-like antidepressants. These data were interpreted in terms of overall molecular tumbling, internal rotations, and inherent flexibility of these structures. Of particular interest was the conformational variability of the tricyclic nucleus of the tricyclic antidepressants, where the data indicated a fivefold difference in mobility of the dimethylene bridge of imipramine-like antidepressants relative to amitriptyline-like compounds. The implications of such a difference in internal motions is discussed in relation to previous NMR studies and to the reported differences in pharmacological activity of these antidepressants

  4. Untangle soil-water-mucilage interactions: 1H NMR Relaxometry is lifting the veil

    Science.gov (United States)

    Brax, Mathilde; Buchmann, Christian; Schaumann, Gabriele Ellen

    2017-04-01

    Mucilage is mainly produced at the root tips and has a high water holding capacity derived from highly hydrophilic gel-forming substances. The objective of the MUCILAGE project is to understand the mechanistic role of mucilage for the regulation of water supply for plants. Our subproject investigates the chemical and physical properties of mucilage as pure gel and mixed with soil. 1H-NMR Relaxometry and PFG NMR represent non-intrusive powerful methods for soil scientific research by allowing quantification of the water distribution as well as monitoring of the water mobility in soil pores and gel phases.Relaxation of gel water differs from the one of pure water due to additional interactions with the gel matrix. Mucilage in soil leads to a hierarchical pore structure, consisting of the polymeric biohydrogel network surrounded by the surface of soil particles. The two types of relaxation rates 1/T1 and 1/T2 measured with 1H-NMR relaxometry refer to different relaxation mechanisms of water, while PFG-NMR measures the water self-diffusion coefficient. The objective of our study is to distinguish in situ water in gel from pore water in a simplified soil system, and to determine how the "gel effect" affects both relaxation rates and the water self-diffusion coefficient in porous systems. We demonstrate how the mucilage concentration and the soil solution alter the properties of water in the respective gel phases and pore systems in model soils. To distinguish gel-inherent processes from classical processes, we investigated the variations of the water mobility in pure chia mucilage under different conditions by using 1H-NMR relaxometry and PFG NMR. Using model soils, the signals coming from pore water and gel water were differentiated. We combined the equations describing 1H-NMR relaxation in porous systems and our experimental results, to explain how the presence of gel in soil affects 1H-NMR relaxation. Out of this knowledge we propose a method, which determines in

  5. β-NMR of Isolated Lithium in Nearly Ferromagnetic Palladium

    Science.gov (United States)

    Parolin, T. J.; Salman, Z.; Chakhalian, J.; Song, Q.; Chow, K. H.; Hossain, M. D.; Keeler, T. A.; Kiefl, R. F.; Kreitzman, S. R.; Levy, C. D. P.; Miller, R. I.; Morris, G. D.; Pearson, M. R.; Saadaoui, H.; Wang, D.; Macfarlane, W. A.

    2007-01-01

    The temperature dependence of the frequency shift and spin-lattice relaxation rate of isolated, nonmagnetic Li8 impurities implanted in a nearly ferromagnetic host (Pd) are measured by means of β-detected nuclear magnetic resonance (β-NMR). The shift is negative, very large, and increases monotonically with decreasing T in proportion to the bulk susceptibility of Pd for T>T*≈100K. Below T*, an additional shift occurs which we attribute to the response of Pd to the defect. The relaxation rate is much slower than expected for the large shift and is linear with T below T*, showing no sign of additional relaxation mechanisms associated with the defect.

  6. Direct synthesis of magnetite nanoparticles from iron(II) carboxymethylcellulose and their performance as NMR contrast agents

    Energy Technology Data Exchange (ETDEWEB)

    Gomes da Silva, Delmarcio; Hiroshi Toma, Sergio; Menegatti de Melo, Fernando [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Carvalho, Larissa Vieira C.; Magalhães, Alvicler; Sabadini, Edvaldo [Instituto de Química, Universidade Estadual de Campinas – UNICAMP, Campinas, SP (Brazil); Domingues dos Santos, Antônio [Instituto de Física, Universidade de São Paulo, São Paulo, SP (Brazil); Araki, Koiti [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil); Toma, Henrique E., E-mail: henetoma@iq.usp.br [Instituto de Química, Universidade de São Paulo, São Paulo, SP (Brazil)

    2016-01-01

    Iron(II) carboxymethylcellulose (CMC) has been successfully employed in the synthesis of hydrophylic magnetite nanoparticles stabilized with a biopolymer coating, aiming applications in NMR imaging. The new method encompasses a convenient one-step synthetic procedure, allowing a good size control and yielding particles of about 10 nm (core size). In addition to the biocompatibility, the nanoparticles have promoted a drastic reduction in the transverse relaxation time (T{sub 2}) of the water protons. The relaxivity rates have been investigated as a function of the nanoparticles concentration, showing a better performance in relation to the common NMR contrast agents available in the market. - Highlights: • Stable, hydrophylic magnetic nanoparticles have been obtained. • Direct use of iron(II) carboxymethylcellulose improves the synthesis. • The magnetic nanoparticles exhibit high spin–spin relaxivity. • The particles promote dark contrast by decreasing the T{sub 2} relaxation time.

  7. NMR Analysis of Amide Hydrogen Exchange Rates in a Pentapeptide-Repeat Protein from A. thaliana.

    Science.gov (United States)

    Xu, Shenyuan; Ni, Shuisong; Kennedy, Michael A

    2017-05-23

    At2g44920 from Arabidopsis thaliana is a pentapeptide-repeat protein (PRP) composed of 25 repeats capped by N- and C-terminal α-helices. PRP structures are dominated by four-sided right-handed β-helices typically consisting of mixtures of type II and type IV β-turns. PRPs adopt repeated five-residue (Rfr) folds with an Rfr consensus sequence (STAV)(D/N)(L/F)(S/T/R)(X). Unlike other PRPs, At2g44920 consists exclusively of type II β-turns. At2g44920 is predicted to be located in the thylakoid lumen although its biochemical function remains unknown. Given its unusual structure, we investigated the biophysical properties of At2g44920 as a representative of the β-helix family to determine if it had exceptional global stability, backbone dynamics, or amide hydrogen exchange rates. Circular dichroism measurements yielded a melting point of 62.8°C, indicating unexceptional global thermal stability. Nuclear spin relaxation measurements indicated that the Rfr-fold core was rigid with order parameters ranging from 0.7 to 0.9. At2g44920 exhibited a striking range of amide hydrogen exchange rates spanning 10 orders of magnitude, with lifetimes ranging from minutes to several months. A weak correlation was found among hydrogen exchange rates, hydrogen bonding energies, and amino acid solvent-accessible areas. Analysis of contributions from fast (approximately picosecond to nanosecond) backbone dynamics to amide hydrogen exchange rates revealed that the average order parameter of amides undergoing fast exchange was significantly smaller compared to those undergoing slow exchange. Importantly, the activation energies for amide hydrogen exchange were found to be generally higher for the slowest exchanging amides in the central Rfr coil and decreased toward the terminal coils. This could be explained by assuming that the concerted motions of two preceding or following coils required for hydrogen bond disruption and amide hydrogen exchange have a higher activation energy

  8. Hyperfine fields in thin Pd films by beta-detected NMR

    Science.gov (United States)

    Parolin, T. J.; Salman, Z.; Chakhalian, J.; Song, Q.; Chow, K. H.; Morris, G. D.; Egilmez, M.; Fan, I.; Hossain, M. D.; Keeler, T. A.; Kiefl, R. F.; Kreitzman, S. R.; Levy, C. D. P.; Mansour, A. I.; Miller, R. I.; Pearson, M. R.; Saadaoui, H.; Smadella, M.; Wang, D.; Xu, M.; MacFarlane, W. A.

    2009-04-01

    Using low energy beta-detected nuclear magnetic resonance (βNMR), the Knight shift and spin-lattice relaxation rate of dilute 8Li+ implanted into a 28 nm Pd film on a MgO substrate were studied as a function of temperature. The shift of the resonance is negative, but much smaller in magnitude than observed in two other much thicker samples. The corresponding spin-lattice relaxation rates are found to be linear with temperature T, but are roughly 50% slower than the rates measured in a Pd foil. Potential explanations are discussed.

  9. Hyperfine fields in thin Pd films by beta-detected NMR

    Energy Technology Data Exchange (ETDEWEB)

    Parolin, T.J. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Salman, Z. [Department of Physics, Oxford University, Parks Road, Oxford OX1 3PU (United Kingdom); ISIS Facility, Rutherford Appleton Laboratory, Chilton, Oxfordshire OX11 0QX (United Kingdom); Chakhalian, J. [Department of Physics, University of Arkansas, Fayetteville, AR 72701 (United States); Song, Q. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Chow, K.H. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Morris, G.D. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Egilmez, M.; Fan, I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Hossain, M.D.; Keeler, T.A. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Kiefl, R.F. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Canadian Institute for Advanced Research, Toronto, ON, M5G 1Z8 (Canada); Kreitzman, S.R.; Levy, C.D.P. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Mansour, A.I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Miller, R.I.; Pearson, M.R. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Saadaoui, H.; Smadella, M.; Wang, D. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Xu, M. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada)

    2009-04-15

    Using low energy beta-detected nuclear magnetic resonance (betaNMR), the Knight shift and spin-lattice relaxation rate of dilute {sup 8}Li{sup +} implanted into a 28 nm Pd film on a MgO substrate were studied as a function of temperature. The shift of the resonance is negative, but much smaller in magnitude than observed in two other much thicker samples. The corresponding spin-lattice relaxation rates are found to be linear with temperature T, but are roughly 50% slower than the rates measured in a Pd foil. Potential explanations are discussed.

  10. NMR relaxation study of sickle cell disease

    International Nuclear Information System (INIS)

    Losada, J.; Gilart, F.; Cabal, C.; Fleitas, H.; Valiente, L.; Robier, J.

    1989-01-01

    Spin-echo methods have been developed for the fast determination in vitro of the complete polymerization time of Hbs momomers under standard deoxygenation conditions, and for the determination of amount of so-called irreversibly sickled cells (ISC). (author). 4 refs.; 2 figs.; 1 tab

  11. THE PARTICIPATION OF THE NITRERGIC PATHWAY IN INCREASED RATE OF TRANSITORY RELAXATION OF LOWER ESOPHAGEAL SPHINCTER INDUCED BY RECTAL DISTENSION IN DOGS

    Directory of Open Access Journals (Sweden)

    Michel Santos PALHETA

    2014-04-01

    Full Text Available Context The rectal distension in dogs increases the rate of transitory lower esophageal sphincter relaxation considered the main factor causing gastroesophageal reflux. Objectives The aim of this study was evaluate the participation of the nitrergic pathway in the increased transitory lower esophageal sphincter relaxation rate induced by rectal distension in anesthetized dogs. Methods Male mongrel dogs (n = 21, weighing 10-15 kg, were fasted for 12 hours, with water ad libitum. Thereafter, they were anesthetized (ketamine 10 mg.Kg-1 + xylazine 20 mg.Kg-1, so as to carry out the esophageal motility evaluation protocol during 120 min. After a 30-minute basal period, the animals were randomly intravenous treated whith: saline solution 0.15M (1ml.Kg-1, L-NAME (3 mg.Kg-1, L-NAME (3 mg.Kg-1 + L-Arginine (200 mg.Kg-1, glibenclamide (1 mg.Kg-1 or methylene blue (3 mg.Kg-1. Forty-five min after these pre-treatments, the rectum was distended (rectal distension, 5 mL.Kg-1 or not (control with a latex balloon, with changes in the esophageal motility recorded over 45 min. Data were analyzed using ANOVA followed by Student Newman-Keuls test. Results In comparison to the respective control group, rectal distension induces an increase in transitory lower esophageal sphincter relaxation. Pre-treatment with L-NAME or methylene blue prevents (P<0.05 this phenomenon, which is reversible by L-Arginine plus L-NAME. However, pretreating with glibenclamide failed to abolish this process. Conclusions Therefore, these experiments suggested, that rectal distension increases transitory lower esophageal sphincter relaxation in dogs via through nitrergic pathways.

  12. Characterization of Chemical Exchange Using Relaxation Dispersion of Hyperpolarized Nuclear Spins.

    Science.gov (United States)

    Liu, Mengxiao; Kim, Yaewon; Hilty, Christian

    2017-09-05

    Chemical exchange phenomena are ubiquitous in macromolecules, which undergo conformational change or ligand complexation. NMR relaxation dispersion (RD) spectroscopy based on a Carr-Purcell-Meiboom-Gill pulse sequence is widely applied to identify the exchange and measure the lifetime of intermediate states on the millisecond time scale. Advances in hyperpolarization methods improve the applicability of NMR spectroscopy when rapid acquisitions or low concentrations are required, through an increase in signal strength by several orders of magnitude. Here, we demonstrate the measurement of chemical exchange from a single aliquot of a ligand hyperpolarized by dissolution dynamic nuclear polarization (D-DNP). Transverse relaxation rates are measured simultaneously at different pulsing delays by dual-channel 19 F NMR spectroscopy. This two-point measurement is shown to allow the determination of the exchange term in the relaxation rate expression. For the ligand 4-(trifluoromethyl)benzene-1-carboximidamide binding to the protein trypsin, the exchange term is found to be equal within error limits in neutral and acidic environments from D-DNP NMR spectroscopy, corresponding to a pre-equilibrium of trypsin deprotonation. This finding illustrates the capability for determination of binding mechanisms using D-DNP RD. Taking advantage of hyperpolarization, the ligand concentration in the exchange measurements can reach on the order of tens of μM and protein concentration can be below 1 μM, i.e., conditions typically accessible in drug discovery.

  13. Comparison of Physiological and Psychological Relaxation Using Measurements of Heart Rate Variability, Prefrontal Cortex Activity, and Subjective Indexes after Completing Tasks with and without Foliage Plants.

    Science.gov (United States)

    Park, Sin-Ae; Song, Chorong; Oh, Yun-Ah; Miyazaki, Yoshifumi; Son, Ki-Cheol

    2017-09-20

    The objective of this study was to compare physiological and psychological relaxation by assessing heart rate variability (HRV), prefrontal cortex activity, and subjective indexes while subjects performed a task with and without foliage plants. In a crossover experimental design, 24 university students performed a task transferring pots with and without a foliage plant for 3 min. HRV and oxyhemoglobin (oxy-Hb) concentration in the prefrontal cortex were continuously measured. Immediately thereafter, subjective evaluation of emotions was performed using a modified semantic differential (SD) method and a profile of mood state questionnaire (POMS). Results showed that the natural logarithmic (ln) ratio of low frequency/high frequency, as an estimate of sympathetic nerve activity, was significantly lower while performing the task with foliage plants for the average 3 min measurement interval. Oxy-Hb concentration in the left prefrontal cortex showed a tendency to decrease in the 2-3 min interval in the task with foliage plants compared to the task without plants. Moreover, significant psychological relaxation according to POMS score and SD was demonstrated when the task involved foliage plants. In conclusion, the task involving foliage plants led to more physiological and psychological relaxation compared with the task without foliage plants.

  14. Comparison of Physiological and Psychological Relaxation Using Measurements of Heart Rate Variability, Prefrontal Cortex Activity, and Subjective Indexes after Completing Tasks with and without Foliage Plants

    Directory of Open Access Journals (Sweden)

    Sin-Ae Park

    2017-09-01

    Full Text Available The objective of this study was to compare physiological and psychological relaxation by assessing heart rate variability (HRV, prefrontal cortex activity, and subjective indexes while subjects performed a task with and without foliage plants. In a crossover experimental design, 24 university students performed a task transferring pots with and without a foliage plant for 3 min. HRV and oxyhemoglobin (oxy-Hb concentration in the prefrontal cortex were continuously measured. Immediately thereafter, subjective evaluation of emotions was performed using a modified semantic differential (SD method and a profile of mood state questionnaire (POMS. Results showed that the natural logarithmic (ln ratio of low frequency/high frequency, as an estimate of sympathetic nerve activity, was significantly lower while performing the task with foliage plants for the average 3 min measurement interval. Oxy-Hb concentration in the left prefrontal cortex showed a tendency to decrease in the 2–3 min interval in the task with foliage plants compared to the task without plants. Moreover, significant psychological relaxation according to POMS score and SD was demonstrated when the task involved foliage plants. In conclusion, the task involving foliage plants led to more physiological and psychological relaxation compared with the task without foliage plants.

  15. Ratiometric analysis in hyperpolarized NMR (I): test of the two-site exchange model and the quantification of reaction rate constants.

    Science.gov (United States)

    Li, Lin Z; Kadlececk, Stephen; Xu, He N; Daye, Dania; Pullinger, Benjamin; Profka, Harrilla; Chodosh, Lewis; Rizi, Rahim

    2013-10-01

    Conventional methods for the analysis of in vivo hyperpolarized (13) C NMR data from the lactate dehydrogenase (LDH) reaction usually make assumptions on the stability of rate constants and/or the validity of the two-site exchange model. In this study, we developed a framework to test the validity of the assumption of stable reaction rate constants and the two-site exchange model in vivo via ratiometric fitting of the time courses of the signal ratio L(t)/P(t). Our analysis provided evidence that the LDH enzymatic kinetics observed by hyperpolarized NMR are in near-equilibrium and satisfy the two-site exchange model for only a specific time window. In addition, we quantified both the forward and reverse exchange rate constants of the LDH reaction for the transgenic and mouse xenograft models of breast cancer using the ratio fitting method developed, which includes only two modeling parameters and is less sensitive to the influence of instrument settings/protocols, such as flip angles, degree of polarization and tracer dosage. We further compared the ratio fitting method with a conventional two-site exchange modeling method, i.e. the differential equation fitting method, using both the experimental and simulated hyperpolarized NMR data. The ratio fitting method appeared to fit better than the differential equation fitting method for the reverse rate constant on the mouse tumor data, with less relative errors on average, whereas the differential equation fitting method also resulted in a negative reverse rate constant for one tumor. The simulation results indicated that the accuracy of both methods depends on the width of the transport function, noise level and rate constant ratio; one method may be more accurate than the other based on the experimental/biological conditions aforementioned. We were able to categorize our tumor models into specific conditions of the computer simulation and to estimate the errors of rate quantification. We also discussed possible

  16. Rapid monitoring of iron-chelating therapy in thalassemia major by a new cardiovascular MR measure: the reduced transverse relaxation rate

    Science.gov (United States)

    Kim, Daniel; Jensen, Jens H.; Wu, Ed X.; Feng, Li; Au, Wing-Yan; Cheung, Jerry S.; Ha, Shau-Yin; Sheth, Sujit S.; Brittenham, Gary M.

    2011-01-01

    In iron overload, almost all the excess iron is stored intracellularly as rapidly mobilizable ferritin iron and slowly exchangeable hemosiderin iron. Increases in cytosolic iron may produce oxidative damage that ultimately results in cardiomyocyte dysfunction. Because intracellular ferritin iron is evidently in equilibrium with the low-molecular-weight cytosolic iron pool, measurements of ferritin iron potentially provide a clinically useful indicator of changes in cytosolic iron. The cardiovascular magnetic resonance (CMR) index of cardiac iron used clinically, the effective transverse relaxation rate (R2*), is principally influenced by hemosiderin iron and changes only slowly over several months, even with intensive iron-chelating therapy. Another conventional CMR index of cardiac iron, the transverse relaxation rate (R2), is sensitive to both hemosiderin iron and ferritin iron. We have developed a new MRI measure, the ‘reduced transverse relaxation rate’ (RR2), and have proposed in previous studies that this measure is primarily sensitive to ferritin iron and largely independent of hemosiderin iron in phantoms mimicking ferritin iron and human liver explants. We hypothesized that RR2 could detect changes produced by 1 week of iron-chelating therapy in patients with transfusion-dependent thalassemia. We imaged 10 patients with thalassemia major at 1.5 T in mid-ventricular short-axis planes of the heart, initially after suspending iron-chelating therapy for 1 week and subsequently after resuming oral deferasirox. After resuming iron-chelating therapy, significant decreases were observed in the mean myocardial RR2 (7.8%, p 0.90). Although the difference between changes in RR2 and R2 was not significant (p > 0.3), RR2 was consistently more sensitive than R2 (and R2*) to the resumption of iron-chelating therapy, as judged by the effect sizes of relaxation rate differences detected. Although further studies are needed, myocardial RR2 may be a promising

  17. Dynamics of unloaded and green tea extract loaded lecithin based liposomal dispersions investigated by nuclear magnetic resonance T2relaxation.

    Science.gov (United States)

    Kirtil, Emrah; Dag, Damla; Guner, Selen; Unal, Kubra; Oztop, Mecit H

    2017-09-01

    Liposomes are lipid bilayer vesicles that can be used as encapsulation systems for bioactive agents to provide increased protection against environmental stresses (such as pH or temperature extremes). Time Domain Nuclear Magnetic Resonance (TD-NMR) that is based on differentiation of specimen contents with respect to magnetic relaxation rates provides detailed information on amount, state and distribution of water and oil and provide reproducible results on the samples. These make TD-NMR particularly suitable for time-dependent monitoring of emulsion system dynamics. In this study, spin-spin (T 2 ) relaxation times and relaxation spectra were used for characterizing green tea extract loaded and unloaded liposomes prepared with soy (S75) and egg lecithins (E80) by different preparation methods (such as homogenization type, pressure and solvent type). Mean particle sizes of liposomes were found to be the most influential factor in shaping mono-exponential T 2 relaxation times. The differences in particle sizes of E80 and S75 samples along with samples with different homogenization pressures could be monitored with T 2 relaxation times. Additionally, T 2 relaxation times were found to be correlated with particle shape irregularity, and chemical instability of samples due to lipid oxidation. With relaxation spectrum analysis, particular components in the sample could be distinguished (internal/external water and lipid bilayers), which gave more elaborate results on mechanisms of instability. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. Nuclear spin relaxation in liquids theory, experiments, and applications

    CERN Document Server

    Kowalewski, Jozef

    2006-01-01

    Nuclear magnetic resonance (NMR) is widely used across many fields because of the rich data it produces, and some of the most valuable data come from the study of nuclear spin relaxation in solution. While described to varying degrees in all major NMR books, spin relaxation is often perceived as a difficult, if not obscure, topic, and an accessible, cohesive treatment has been nearly impossible to find.Collecting relaxation theory, experimental techniques, and illustrative applications into a single volume, this book clarifies the nature of the phenomenon, shows how to study it, and explains why such studies are worthwhile. Coverage ranges from basic to rigorous theory and from simple to sophisticated experimental methods, and the level of detail is somewhat greater than most other NMR texts. Topics include cross-relaxation, multispin phenomena, relaxation studies of molecular dynamics and structure, and special topics such as relaxation in systems with quadrupolar nuclei and paramagnetic systems.Avoiding ove...

  19. Relaxing music prevents stress-induced increases in subjective anxiety, systolic blood pressure, and heart rate in healthy males and females.

    Science.gov (United States)

    Knight, W E; Rickard PhD, N S

    2001-01-01

    Previous research suggests that while subjective anxiety is reduced by relaxing music, the effect of music on physiological stress indices is less consistent. In the current study, the effect of relaxing music on participants' subjective and physiological response to stress was explored, with attention paid to methodological factors and mediating variables that might have contributed to inconsistencies in previous studies. Undergraduate students (43 females & 44 males) were exposed to a cognitive stressor task involving preparation for an oral presentation either in the presence of Pachelbel's Canon in D major, or in silence. Measures of subjective anxiety, heart rate, blood pressure, cortisol, and salivary IgA were obtained during rest and after presentation of the stressor. The stressor caused significant increases in subjective anxiety, heart rate, and systolic blood pressure in male and female controls. These stress-induced increases were each prevented by exposure to music, and this effect was independent of gender. Music also enhanced baseline salivary IgA levels in the absence of any stress-induced effects. These findings provide experimental support for claims that music is an effective anxiolytic treatment, the robustness of which is demonstrated by retention of the effect in the presence of a range of potentially mediating variables.

  20. The change of longitudinal relaxation rate in oxygen enhanced pulmonary MRI depends on age and BMI but not diffusing capacity of carbon monoxide in healthy never-smokers.

    Directory of Open Access Journals (Sweden)

    Simon Sven Ivan Kindvall

    Full Text Available Oxygen enhanced pulmonary MRI is a promising modality for functional lung studies and has been applied to a wide range of pulmonary conditions. The purpose of this study was to characterize the oxygen enhancement effect in the lungs of healthy, never-smokers, in light of a previously established relationship between oxygen enhancement and diffusing capacity of carbon monoxide in the lung (DL,CO in patients with lung disease.In 30 healthy never-smoking volunteers, an inversion recovery with gradient echo read-out (Snapshot-FLASH was used to quantify the difference in longitudinal relaxation rate, while breathing air and 100% oxygen, ΔR1, at 1.5 Tesla. Measurements were performed under multiple tidal inspiration breath-holds.In single parameter linear models, ΔR1 exhibit a significant correlation with age (p = 0.003 and BMI (p = 0.0004, but not DL,CO (p = 0.33. Stepwise linear regression of ΔR1 yields an optimized model including an age-BMI interaction term.In this healthy, never-smoking cohort, age and BMI are both predictors of the change in MRI longitudinal relaxation rate when breathing oxygen. However, DL,CO does not show a significant correlation with the oxygen enhancement. This is possibly because oxygen transfer in the lung is not diffusion limited at rest in healthy individuals. This work stresses the importance of using a physiological model to understand results from oxygen enhanced MRI.

  1. Calculation of the expected zero-field muon relaxation rate in the geometrically frustrated rare earth pyrochlore Gd(2)Sn(2)O(7) antiferromagnet.

    Science.gov (United States)

    McClarty, P A; Cosman, J N; Del Maestro, A G; Gingras, M J P

    2011-04-27

    The magnetic insulator Gd(2)Sn(2)O(7) is one of many geometrically frustrated magnetic materials known to exhibit a nonzero muon spin polarization relaxation rate, λ(T), down to the lowest temperature (T) studied. Such behaviour is typically interpreted as signalling the presence of persistent spin dynamics (PSD) of the host material. In the case of Gd(2)Sn(2)O(7), such PSD comes as a surprise since magnetic specific heat measurements suggest conventional gapped magnons, which would naively lead to an exponentially vanishing λ(T) as T → 0. In contrast to most materials that display PSD, the ordered phase of Gd(2)Sn(2)O(7) is well characterized and both the nature and the magnitude of the interactions have been inferred from the magnetic structure and the temperature dependence of the magnetic specific heat. Based on this understanding, the temperature dependence of the muon spin polarization relaxation through the scattering of spin waves (magnons) is calculated. The result explicitly shows that, despite the unusual extensive number of weakly dispersive (gapped) excitations characterizing Gd(2)Sn(2)O(7), a remnant of the zero modes of the parent frustrated pyrochlore Heisenberg antiferromagnet, the temperature dependence of the calculated λ(T) differs dramatically from the experimental one. Indeed, the calculation conforms to the naive expectation of an exponential collapse of λ(T) at temperatures below ∼ 0.7 K. This result, for the first time, illustrates crisply and quantitatively the paradox that presents itself with the pervasive occurrence of PSD in highly frustrated magnetic systems as evinced by muon spin relaxation measurements.

  2. Relationships Between Base-Catalyzed Hydrolysis Rates or Glutathione Reactivity for Acrylates and Methacrylates and Their NMR Spectra or Heat of Formation

    Directory of Open Access Journals (Sweden)

    Yoshinori Kadoma

    2012-05-01

    Full Text Available The NMR chemical shift, i.e., the π-electron density of the double bond, of acrylates and methacrylates is related to the reactivity of their monomers. We investigated quantitative structure-property relationships (QSPRs between the base-catalyzed hydrolysis rate constants (k1 or the rate constant with glutathione (GSH (log kGSH for acrylates and methacrylates and the 13C NMR chemical shifts of their α,β-unsaturated carbonyl groups (δCα and δCβ or heat of formation (Hf calculated by the semi-empirical MO method. Reported data for the independent variables were employed. A significant linear relationship between k1 and δCβ, but not δCα, was obtained for methacrylates (r2 = 0.93, but not for acrylates. Also, a significant relationship between k1 and Hf was obtained for both acrylates and methacrylates (r2 = 0.89. By contrast, log kGSH for acrylates and methacrylates was linearly related to their δCβ (r2 = 0.99, but not to Hf. These findings indicate that the 13C NMR chemical shifts and calculated Hf values for acrylates and methacrylates could be valuable for estimating the hydrolysis rate constants and GSH reactivity of these compounds. Also, these data for monomers may be an important tool for examining mechanisms of reactivity.

  3. Deuteron relaxation in the system Arkopal 9-D2O

    International Nuclear Information System (INIS)

    Pasterna, G.; Kupka, T.; Weglarz, W.; Blicharski, J.S.

    1994-01-01

    The NMR spectra and relaxation time T 1 for D 2 O - polyether liquid crystal solutions have been performed. The concentration and temperature changes in liquid crystal structure have been observed and discussed

  4. Restricted lithium ion dynamics in PEO-based block copolymer electrolytes measured by high-field nuclear magnetic resonance relaxation

    Science.gov (United States)

    Huynh, Tan Vu; Messinger, Robert J.; Sarou-Kanian, Vincent; Fayon, Franck; Bouchet, Renaud; Deschamps, Michaël

    2017-10-01

    The intrinsic ionic conductivity of polyethylene oxide (PEO)-based block copolymer electrolytes is often assumed to be identical to the conductivity of the PEO homopolymer. Here, we use high-field 7Li nuclear magnetic resonance (NMR) relaxation and pulsed-field-gradient (PFG) NMR diffusion measurements to probe lithium ion dynamics over nanosecond and millisecond time scales in PEO and polystyrene (PS)-b-PEO-b-PS electrolytes containing the lithium salt LiTFSI. Variable-temperature longitudinal (T1) and transverse (T2) 7Li NMR relaxation rates were acquired at three magnetic field strengths and quantitatively analyzed for the first time at such fields, enabling us to distinguish two characteristic time scales that describe fluctuations of the 7Li nuclear electric quadrupolar interaction. Fast lithium motions [up to O (ns)] are essentially identical between the two polymer electrolytes, including sub-nanosecond vibrations and local fluctuations of the coordination polyhedra between lithium and nearby oxygen atoms. However, lithium dynamics over longer time scales [O (10 ns) and greater] are slower in the block copolymer compared to the homopolymer, as manifested experimentally by their different transverse 7Li NMR relaxation rates. Restricted dynamics and altered thermodynamic behavior of PEO chains anchored near PS domains likely explain these results.

  5. Enhanced ultrafast relaxation rate in the Weyl semimetal phase of MoTe2 measured by time- and angle-resolved photoelectron spectroscopy

    Science.gov (United States)

    Crepaldi, A.; Autès, G.; Gatti, G.; Roth, S.; Sterzi, A.; Manzoni, G.; Zacchigna, M.; Cacho, C.; Chapman, R. T.; Springate, E.; Seddon, E. A.; Bugnon, Ph.; Magrez, A.; Berger, H.; Vobornik, I.; Kalläne, M.; Quer, A.; Rossnagel, K.; Parmigiani, F.; Yazyev, O. V.; Grioni, M.

    2017-12-01

    MoTe2 has recently been shown to realize in its low-temperature phase the type-II Weyl semimetal (WSM). We investigated by time- and angle- resolved photoelectron spectroscopy (tr-ARPES) the possible influence of the Weyl points on the electron dynamics above the Fermi level EF, by comparing the ultrafast response of MoTe2 in the trivial and topological phases. In the low-temperature WSM phase, we report an enhanced relaxation rate of electrons optically excited to the conduction band, which we interpret as a fingerprint of the local gap closure when Weyl points form. By contrast, we find that the electron dynamics of the related compound WTe2 is slower and temperature independent, consistent with a topologically trivial nature of this material. Our results shows that tr-ARPES is sensitive to the small modifications of the unoccupied band structure accompanying the structural and topological phase transition of MoTe2.

  6. Nonlinear fractional relaxation

    Indian Academy of Sciences (India)

    Abstract. We define a nonlinear model for fractional relaxation phenomena. We use ε-expansion method to analyse this model. By studying the fundamental solutions of this model we find that when t → 0 the model exhibits a fast decay rate and when t → ∞ the model exhibits a power-law decay. By analysing the frequency ...

  7. Impurity effects in a S=1/2 Heisenberg spin chain probed by {sup 63}Cu NMR

    Energy Technology Data Exchange (ETDEWEB)

    Utz, Yannic; Bruening, Eva Maria; Hammerath, Franziska; Rudisch, Christian; Grafe, Hans-Joachim; Mohan, Ashwin; Hess, Christian; Nishimoto, Satoshi; Drechsler, Stefan-Ludwig; Buechner, Bernd [IFW Dresden (Germany); Saint-Martin, Romuald; Revcolevschi, Alexandre [LPCES, Orsay (France)

    2013-07-01

    We present {sup 63}Cu NMR measurements on undoped, Ni doped and Mg doped SrCuO{sub 2} single crystals. SrCuO{sub 2} is a good realization of a one-dimensional S=1/2 Heisenberg spin chain. This is confirmed by the theoretically-expected temperature independent NMR spin-lattice relaxation rate T{sup -1}{sub 1}. Doping with Ni, which can be regarded as a S=1 impurity, has a major impact on the magnetic properties of the spin chains. On the one hand, this is manifested by unusual features in the NMR spectra below 100 K, revealing the existence of an impurity-induced local alternating magnetisation. On the other hand, exponentially decaying spin lattice relaxation rates towards low temperatures indicate the opening of a spin gap similar to Ca doped SrCuO{sub 2}. Mg doping (S=0) has, however, no influence on the magnetic properties of the spin chains. Neither the NMR spectra nor the spin lattice relaxation rates differ from those measured on pure SrCuO{sub 2}. While the different impact of Ni and Mg doping on the spin chains could be explained by their different impurity spins, the opening of a spin gap in case of Ni doping is totally unexpected and not yet understood.

  8. EPR studies of the Mo-enzyme aldehyde oxidoreductase from Desulfovibrio gigas: an application of the Bloch-Wangsness-Redfield theory to a system containing weakly-coupled paramagnetic redox centers with different relaxation rates.

    Science.gov (United States)

    González, Pablo J; Barrera, Guillermo I; Rizzi, Alberto C; Moura, José J G; Passeggi, Mario C G; Brondino, Carlos D

    2009-10-01

    Electron transfer proteins and redox enzymes containing paramagnetic redox centers with different relaxation rates are widespread in nature. Despite both the long distances and chemical paths connecting these centers, they can present weak magnetic couplings produced by spin-spin interactions such as dipolar and isotropic exchange. We present here a theoretical model based on the Bloch-Wangsness-Redfield theory to analyze the dependence with temperature of EPR spectra of interacting pairs of spin 1/2 centers having different relaxation rates, as is the case of the molybdenum-containing enzyme aldehyde oxidoreductase from Desulfovibrio gigas. We analyze the changes of the EPR spectra of the slow relaxing center (Mo(V)) induced by the faster relaxing center (FeS center). At high temperatures, when the relaxation time T(1) of the fast relaxing center is very short, the magnetic coupling between centers is averaged to zero. Conversely, at low temperatures when T(1) is longer, no modulation of the coupling between metal centers can be detected.

  9. Effects of progressive relaxation and classical music on measurements of attention, relaxation, and stress responses.

    Science.gov (United States)

    Scheufele, P M

    2000-04-01

    The present experiment examined relaxation using different experimental conditions to test whether the effects of individual elements of relaxation could be measured, whether specific effects were revealed, or whether relaxation resulted from a generalized "relaxation response." Sixty-seven normal, male volunteers were exposed to a stress manipulation and then to one of two relaxation (Progressive Relaxation, Music) or control (Attention Control, Silence) conditions. Measurements of attention, relaxation, and stress responses were obtained during each phase of the experiment. All four groups exhibited similar performance on behavioral measures of attention that suggested a reduction in physiological arousal following their relaxation or control condition, as well as a decreased heart rate. Progressive Relaxation, however, resulted in the greatest effects on behavioral and self-report measures of relaxation, suggesting that cognitive cues provided by stress management techniques contribute to relaxation.

  10. Effect of wrist posture, rate of force development/relaxation, and isotonic contractions on finger force independence.

    Science.gov (United States)

    May, Stephen E; Keir, Peter J

    2018-02-01

    The multi-articular anatomy and inter-connections of the extrinsic finger muscles suggests that wrist posture may affect enslaved finger forces. The purpose of this study was to determine the effects of (i) wrist posture on enslaved finger forces during ramp and isotonic exertions, and (ii) the rate of force development on enslaved forces and error. Twelve men performed 3 repetitions of isometric finger flexion and extension force with index and ring fingers with the wrist in 30° flexion, neutral, and 30° extension. Trials consisted of an isotonic contraction at 25% of maximum, and two ramp contractions performed at 25% MVC/s and 10% MVC/s up to 50% MVC, returning to zero at the same rate. Electromyography was recorded from compartments of extensor digitorum (ED) and flexor digitorum superficialis and analyzed at 25% MVC. Wrist posture significantly affected enslaving effect (EE) during extension exertions (F 4, 44  > 2.6, p < .05) with higher EE, error, and muscle activity of ED in wrist extension. Contraction condition significantly affected EE for index and ring finger exertions (p = .001). In fingers adjacent to the task finger, descending phase EE was higher than ascending phase, independent of muscle activity. Mechanical factors such as posture, and neural factors both contribute to enslaved finger actions. Copyright © 2017 Elsevier Ltd. All rights reserved.

  11. Applications of NMR in biological metabolic research

    International Nuclear Information System (INIS)

    Nie Jiarui; Li Xiuqin; He Chunjian

    1989-01-01

    The nuclear magnetic resonance has become a powerful means of studying biological metabolism in non-invasive and non-destructive way. Being used to study the metabolic processes of living system in normal physiological conditions as well as in molecular level, the method is better than other conventional approaches. Using important parameters such as NMR-chemical shifts, longitudinal relaxation time and transverse relaxation time, it is possible to probe the metabolic processes as well as conformation, concentration, transportation and distribution of reacting and resulting substances. The NMR spectroscopy of 1 H, 31 P and 13 C nuclei has already been widely used in metabolic researches

  12. Flow NMR of complex systems

    Energy Technology Data Exchange (ETDEWEB)

    Scheler, U.; Bagusat, F. [Leibniz-Inst. fuer Polymerforschung Dresden e.V., Dresden (Germany)

    2007-07-01

    A combination of NMR imaging and pulsed field gradient (PFG) NMR is applied to investigate flow. NMR longitudinal relaxation is used to generate contrast in a binary system of oil and water. The spatial distribution of each component and its flow pattern are measured separately. As a model a Couette cell with an additional area of high shear is used as model geometry. While a flat smooth interface is found at rest, the interface become bent under rotation, finally emulgation starts because of the velocity differences between the components. Flow from a submillimeter tube into a wide box and out of the box is investigated as well to understand shear-induced mixing and demixing. (orig.)

  13. Study of cultured fibroblasts in vivo using NMR

    Energy Technology Data Exchange (ETDEWEB)

    Karczmar, G.S.

    1984-01-01

    The goal of this thesis was to study the compartmentation of phosphorylated glycolytic intermediates in intact Chicken Embryo Fibroblasts (CEFs) using /sup 31/P NMR at 109 MHz. Because glycolysis is regulated differently in normal and virally transformed CEFs, NMR experiments were performed on both types of cells. A technique for maintaining functional cells at high densities in an NMR magnet is described. Signals were detected from cytoplasmic inorganic phosphate (P/sub i/), ATP, NAD, NADH, phosphorylcholine and phosphorylethanolamine. The effect of external glucose on cytoplasmic pools of phosphates was studied. However, experiments with /sup 32/P labelled P/sub i/ showed that as the concentration of glucose in the medium was increased, the amount of phosphate sequestered in the cells increased. They conclude that there is a pool of P/sub i/ which is not detected by high resolution of NMR and that the size of this pool increases as the rate of glycolysis increases. These effects were found only in cultured cells; the data for transformed and normal cells were similar. Longitudinal relaxation times of intracellular phosphates in normal, transformed, and primary CEFs were measured.

  14. Refinement of the protein backbone angle ψ in NMR structure calculations

    International Nuclear Information System (INIS)

    Sprangers, R.; Bottomley, M.J.; Linge, J.P.; Schultz, J.; Nilges, M.; Sattler, M.

    2000-01-01

    Cross-correlated relaxation rates involving the C α -H α dipolar interaction and the carbonyl (C') chemical shift anisotropy (CSA) have been measured using two complementary 3D experiments. We show that the protein backbone angle ψ can be directly refined against such cross-correlated relaxation rates (Γ HαCα,C' ) and the three-bond H/D isotope effect on the C α chemical shifts ( 3 ΔC α (ND) ). By simultaneously using both experimental parameters as restraints during NMR structure calculations, a unique value for the backbone angle ψ is defined. We have applied the new refinement method to the α-Spectrin SH3 domain (a β-sheet protein) and to the Sgs1p HRDC domain (an α-helical protein) and show that the quality of the NMR structures is substantially improved, judging from the atomic coordinate precision and the Ramachandran map. In addition, the ψ-refined NMR structures of the SH3 domain deviate less from the 1.8 A crystal structure, suggesting an improved accuracy. The proposed refinement method can be used to significantly improve the quality of NMR structures and will be applicable to larger proteins

  15. Natural relaxation

    Science.gov (United States)

    Marzola, Luca; Raidal, Martti

    2016-11-01

    Motivated by natural inflation, we propose a relaxation mechanism consistent with inflationary cosmology that explains the hierarchy between the electroweak scale and Planck scale. This scenario is based on a selection mechanism that identifies the low-scale dynamics as the one that is screened from UV physics. The scenario also predicts the near-criticality and metastability of the Standard Model (SM) vacuum state, explaining the Higgs boson mass observed at the Large Hadron Collider (LHC). Once Majorana right-handed neutrinos are introduced to provide a viable reheating channel, our framework yields a corresponding mass scale that allows for the seesaw mechanism as well as for standard thermal leptogenesis. We argue that considering singlet scalar dark matter extensions of the proposed scenario could solve the vacuum stability problem and discuss how the cosmological constant problem is possibly addressed.

  16. The effect of a broad activation energy distribution on deuteron spin-lattice relaxation.

    Science.gov (United States)

    Ylinen, E E; Punkkinen, M; Birczyński, A; Lalowicz, Z T

    2015-10-01

    Deuteron NMR spectra and spin-lattice relaxation were studied experimentally in zeolite NaY(2.4) samples containing 100% or 200% of CD3OH or CD3OD molecules of the total coverage of Na atoms in the temperature range 20-150K. The activation energies describing the methyl and hydroxyl motions show broad distributions. The relaxation data were interpreted by improving a recent model (Stoch et al., 2013 [16]) in which the nonexponential relaxation curves are at first described by a sum of three exponentials with adjustable relaxation rates and weights. Then a broad distribution of activation energies (the mean activation energy A0 and the width σ) was assumed for each essentially different methyl and hydroxyl position. The correlation times were calculated from the Arrhenius equation (containing the pre-exponential factor τ0), individual relaxation rates computed and classified into three classes, and finally initial relaxation rates and weights for each class formed. These were compared with experimental data, motional parameters changed slightly and new improved rates and weights for each class calculated, etc. This method was improved by deriving for the deuterons of the A and E species methyl groups relaxation rates, which depend explicitly on the tunnel frequency ωt. The temperature dependence of ωt and of the low-temperature correlation time were obtained by using the solutions of the Mathieu equation for a threefold potential. These dependencies were included in the simulations and as the result sets of A0, σ and τ0 obtained, which describe the methyl and hydroxyl motions in different positions in zeolite. Copyright © 2015 Elsevier Inc. All rights reserved.

  17. Quantum mechanical alternative to Arrhenius equation in the interpretation of proton spin-lattice relaxation data for the methyl groups in solids

    KAUST Repository

    Bernatowicz, Piotr

    2015-10-01

    Theory of nuclear spin-lattice relaxation in methyl groups in solids has been a recurring problem in nuclear magnetic resonance (NMR) spectroscopy. The current view is that, except for extreme cases of low torsional barriers where special quantum effects are at stake, the relaxation behaviour of the nuclear spins in methyl groups is controlled by thermally activated classical jumps of the methyl group between its three orientations. The temperature effects on the relaxation rates can be modelled by Arrhenius behaviour of the correlation time of the jump process. The entire variety of relaxation effects in protonated methyl groups has recently been given a consistently quantum mechanical explanation not invoking the jump model regardless of the temperature range. It exploits the damped quantum rotation (DQR) theory originally developed to describe NMR line shape effects for hindered methyl groups. In the DQR model, the incoherent dynamics of the methyl group include two quantum rate, i.e., coherence-damping processes. For proton relaxation only one of these processes is relevant. In this paper, temperature-dependent proton spin-lattice relaxation data for the methyl groups in polycrystalline methyltriphenyl silane and methyltriphenyl germanium, both deuterated in aromatic positions, are reported and interpreted in terms of the DQR model. A comparison with the conventional approach exploiting the phenomenological Arrhenius equation is made. The present observations provide further indications that incoherent motions of molecular moieties in condensed phase can retain quantum character over much broad temperature range than is commonly thought.

  18. {sup 15}N relaxation study of the cold shock protein CspB at various solvent viscosities

    Energy Technology Data Exchange (ETDEWEB)

    Zeeb, Markus; Jacob, Maik H. [Universitaet Bayreuth, Laboratorium fuer Biochemie (Germany); Schindler, Thomas [Hoffmann LaRoche AG (Switzerland); Balbach, Jochen [Universitaet Bayreuth, Laboratorium fuer Biochemie (Germany)], E-mail: jochen.balbach@uni-bayreuth.de

    2003-11-15

    For a detailed NMR study of the dynamics of the cold shock protein CspB from Bacillus subtilis, we determined {sup 15}N transverse and longitudinal relaxation rates and heteronuclear nuclear Overhauser effects at different solvent viscosities. Up to a relative viscosity of 2, which is equivalent to 27% ethylene glycol (EG), the overall correlation time follows the linear Stokes-Einstein equation. At a relative viscosity of 6 (70% EG) the correlation time deviates from linearity by 30%, indicating that CspB tumbles at a higher rate as expected from the solvent viscosity probably due to a preferential binding of water molecules at the protein surface. The corresponding hydrodynamic radii, determined by NMR diffusion experiments, show no variation with viscosity. The amplitudes of intramolecular motions on a sub-nanosecond time scale revealed by an extended Lipari-Szabo analysis were mainly independent of the solvent viscosity. The lower limit of the NMR 'observation window' for the internal correlation time shifts above 0.5 ns at 70% EG, which is directly reflected in the experimentally derived internal correlation times. Chemical exchange contributions to the transverse relaxation rates derived from the Lipari-Szabo approach coincide with the experimentally determined values from the transverse {sup 1}H-{sup 15}N dipolar/{sup 15}N chemical shift anisotropy relaxation interference. These contributions originate from fast protein folding reactions on a millisecond timescale, which get retarded at increased solvent viscosities.

  19. Alternating spin chain compound AgVOAsO4 probed by 75As NMR

    Science.gov (United States)

    Ahmed, N.; Khuntia, P.; Ranjith, K. M.; Rosner, H.; Baenitz, M.; Tsirlin, A. A.; Nath, R.

    2017-12-01

    75As NMR measurements were performed on a polycrystalline sample of spin-1/2 alternating spin chain Heisenberg antiferromagnet AgVOAsO4. The temperature-dependent NMR shift K (T ) , which is a direct measure of the intrinsic spin susceptibility, agrees very well with the spin-1/2 alternating-chain model, justifying the assignment of the spin lattice. From the analysis of K (T ) , magnetic exchange parameters were estimated as follows: the leading exchange J /kB≃38.4 K and the alternation ratio α =J'/J ≃0.69 . The transferred hyperfine coupling between the 75As nucleus and V4 + spins obtained by comparing the NMR shift with the bulk susceptibility amounts to Ahf≃3.3 TμB. The effect of interchain couplings on the low-temperature activated behavior of K (T ) and the spin-lattice relaxation rate 1 /T1 is identified.

  20. 27Al NMR studies of NpPd5Al2

    International Nuclear Information System (INIS)

    Chudo, H.; Sakai, H.; Tokunaga, Y.; Kambe, S.; Aoki, D.; Homma, Y.; Shiokawa, Y.; Haga, Y.; Ikeda, S.; Matsuda, T.D.; Onuki, Y.; Yasuoka, H.

    2009-01-01

    We present 27 Al NMR studies for a single crystal of the Np-based superconductor NpPd 5 Al 2 (T c =4.9K). We have observed a five-line 27 Al NMR spectrum with a center line and four satellite lines separated by first-order nuclear quadrupole splittings. The Knight shift clearly drops below T c . The temperature dependence of the 27 Al nuclear spin-lattice relaxation rate shows no coherence peak below T c , indicating that NpPd 5 Al 2 is an unconventional superconductor with an anisotropic gap. The analysis of the present NMR data provides evidence for strong-coupling d-wave superconductivity in NpPd 5 Al 2 .

  1. The characterisation of polymers using pulsed NMR

    International Nuclear Information System (INIS)

    Charlesby, A.

    1983-01-01

    Broad line pulsed NMR is applied to obtain information on radiation-induced polymer changes and other aspects of polymer science based on the interpretation of spin-spin relaxation curves. Calculations are made to determine the molecular weight, the crosslink density of simple, low molecular weight, flexible polymers. For higher molecular weight polymers, a conclusion can be drawn on the concentrations of entangled and crosslinked units by means of pulsed NMR. Some typical applications of the technique are illustrated by the examples of polyethylenes, rubbers, filled polymeric systems and aqueous polyethylene oxide solutions. The morphology of polymers can be followed by pulsed NMR. (V.N.)

  2. Prognostic Significance of Transverse Relaxation Rate (R2* in Blood Oxygenation Level-Dependent Magnetic Resonance Imaging in Patients with Invasive Breast Cancer.

    Directory of Open Access Journals (Sweden)

    Hye Young Choi

    Full Text Available To examine the relationship between magnetic resonance transverse relaxation rate (R2* and prognostic factors.A total of 159 women with invasive ductal carcinomas (IDCs underwent breast magnetic resonance imaging (MRI including blood oxygenation level-dependent (BOLD sequence at 3 T. The distribution of the measured R2* values were analyzed, and the correlation between R2* and various prognostic factors (age, tumor size, histologic grade, lymphovascular invasion, and axillary lymph node status, as well as expression of estrogen receptor, progesterone receptor, human epidermal growth factor receptor 2, p53, and Ki-67 were retrospectively assessed using patient medical records.The baseline R2* values of the IDCs were very heterogeneous with wide range among the patients. The mean R2* value was (32.8 ± 14.0 Hz with a median of 29.3 Hz (range 13.5-109.4 Hz. In multivariate analysis, older age was associated with decreased R2* value (P = 0.011 and IDCs with p53-overexpression showed higher R2* values than those without p53-overexpression group (P = 0.031. Other prognostic factors were not significantly correlated with R2* value.In this study, R2* values were significantly correlated with age and expression of p53. Further studies are necessary to determine the prognostic value of BOLD-MRI.

  3. Cross relaxation in nitroxide spin labels

    DEFF Research Database (Denmark)

    Marsh, Derek

    2016-01-01

    Cross relaxation, and mI-dependence of the intrinsic electron spin-lattice relaxation rate We, are incorporated explicitly into the rate equations for the electron-spin population differences that govern the saturation behaviour of 14N- and 15N-nitroxide spin labels. Both prove important in spin......-label EPR and ELDOR, particularly for saturation recovery studies. Neither for saturation recovery, nor for CW-saturation EPR and CW-ELDOR, can cross relaxation be described simply by increasing the value of We, the intrinsic spin-lattice relaxation rate. Independence of the saturation recovery rates from...... the hyperfine line pumped or observed follows directly from solution of the rate equations including cross relaxation, even when the intrinsic spin-lattice relaxation rate We is mI-dependent....

  4. NMR study of strongly correlated electron systems

    Science.gov (United States)

    Kitaoka, Y.; Tou, H.; Zheng, G.-q.; Ishida, K.; Asayama, K.; Kobayashi, T. C.; Kohda, A.; Takeshita, N.; Amaya, K.; Onuki, Y.; Geibel, G.; Schank, C.; Steglich, F.

    1995-02-01

    Various types of ground states in strongly correlated electron systems have been systematically investigated by means of NMR/NQR at low temperatures under high magnetic field and pressure. We focus on two well-known heavy-electron families, CeCu 2X 2 (X = Si and Ge) (Ce(122)) and UM 2Al 3 (M = Ni and Pd) (U(123)). The Cu NQR experiments on CeCu 2X 2 under high pressure indicate that the physical property of CeCu 2Ge 2 at high pressure, i.e. above the transition at 7.6 GPa from antiferromagnetic (AF) to superconductivity, are clearly related to tha CeCu 2Si 2 at ambient pressure. In addition to the H-T phase diagram established below 7 T, NMR and specific heat experiments on polycrystal CeCu 2.05Si 2 have revealed the presence of a new phase above 7 T. In a high-quality polycrystal of UPd 2Al 3 with a record high- Tc of 2 K at ambient pressure and the narrowest Al NQR line width, the nuclear-spin lattice relaxation rate, 27(1/ T1) measured in zero field has been found to obey the T3 law down to 0.13 K, giving strong evidence that the energy gap vanishes along lines on the Fermi surface. Thus it seems that all heavy-electron superconductors exhibit lines of zero gap, regardless of their different magnetic properties.

  5. Computer Code for Interpreting 13C NMR Relaxation Measurements with Specific Models of Molecular Motion: The Rigid Isotropic and Symmetric Top Rotor Models and the Flexible Symmetric Top Rotor Model

    Science.gov (United States)

    2017-01-01

    for a rigid symmetric top rotor can be derived by replacing τc in eq 8 with an effective correlation time that relates the 13C–1H relaxation vector...of internal motions (θ = ε = 0°), the expression that is derived from substituting τc in eq 8 with τe reduces to the symmetric top rotor J(ω) in eq... SYMMETRIC TOP ROTOR MODELS AND THE FLEXIBLE SYMMETRIC TOP ROTOR MODEL ECBC-TR-1428 Terry J. Henderson RESEARCH AND TECHNOLOGY DIRECTORATE

  6. Comparative NMR investigation of the Re-based borides

    Science.gov (United States)

    Lue, C. S.; Tao, Y. F.; Su, T. H.

    2008-07-01

    We report a systematic study of the rhenium-based borides, ReB2 , Re7B3 , and Re3B , by means of the B11 nuclear magnetic resonance (NMR) spectroscopy. While Re7B3 and Re3B are superconductors, ReB2 exhibits no superconducting signature but is of current interest due to its superhard mechanical property. Since the major focus of this investigation is their electronic characteristics in the normal states, we performed the measurements at temperatures between 77 and 295 K. For Re7B3 and Re3B , s -character electrons were found to be responsible for the observed B11 NMR Knight shift and spin-lattice relaxation rate (1/T1) . From T1 analysis, we thus deduce the partial Bs Fermi-level density of states (DOS) of both borides. On the other hand, the relaxation rate of ReB2 is mainly associated with p electrons, similar to the cases of OsB2 and RuB2 . In addition, the extracted B2p Fermi-level DOS is in good agreement with the theoretical prediction from band-structure calculations.

  7. Fluid-Rock Characterization and Interactions in NMR Well Logging

    Energy Technology Data Exchange (ETDEWEB)

    Hirasaki, George J.; Mohanty, Kishore K.

    2003-02-10

    The objective of this project was to characterize the fluid properties and fluid-rock interactions that are needed for formation evaluation by NMR well logging. The advances made in the understanding of NMR fluid properties are summarized in a chapter written for an AAPG book on NMR well logging. This includes live oils, viscous oils, natural gas mixtures, and the relation between relaxation time and diffusivity.

  8. Heteronuclear relaxation in time-dependent spin systems: 15N-T1ρ dispersion during adiabatic fast passage

    International Nuclear Information System (INIS)

    Konrat, Robert; Tollinger, Martin

    1999-01-01

    A novel NMR experiment comprising adiabatic fast passage techniques for the measurement of heteronuclear self-relaxation rates in fully 15N-enriched proteins is described. Heteronuclear self-relaxation is monitored by performing adiabatic fast passage (AFP) experiments at variable adiabaticity (e.g., variation of RF spin-lock field intensity). The experiment encompasses gradient- selection and sensitivity-enhancement. It is shown that transverse relaxation rates derived with this method are in good agreement with the ones measured by the classical Carr-Purcell-Meiboom-Gill (CPMG) sequences. An application of this method to the study of the carboxyl-terminal LIM domain of quail cysteine and glycine-rich protein qCRP2(LIM2) is presented

  9. Cross-relaxation of {sup 8}Li{sup +} in copper

    Energy Technology Data Exchange (ETDEWEB)

    Mansour, A.I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Morris, G.D. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Salman, Z. [Clarendon Laboratory, Department of Physics, Oxford University, Parks Road, Oxford OX1 3PU (United Kingdom); ISIS Facility, Rutherford-Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); Chow, K.H., E-mail: kimchow@phys.ualberta.c [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Dunlop, T.; Jung, J.; Fan, I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); MacFarlane, W.A. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada); Kiefl, R.F. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Canada Institute for Advanced Research, Toronto, ON, M5G 1Z8 (Canada); Parolin, T.J. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada); Saadaoui, H.; Wang, D.; Hossain, M.D.; Song, Q.; Smadella, M. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Mosendz, O.; Kardasz, B.; Heinrich, B. [Simon Fraser University, 8888 University Drive, Burnaby, BC, V5A 1S6 (Canada); Levy, C.D.P.; Pearson, M.R. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada)

    2009-04-15

    The 'cross-relaxation' method (also called 'level-crossing resonance' or 'avoided level-crossing') is a powerful technique that can be used to provide detailed structural and site information on impurities in materials. In this paper, we report on the development of the cross-relaxation technique for {sup 8}Li{sup +} at the beta-detected nuclear magnetic resonance (beta-NMR) facility located in TRIUMF in Vancouver. The measurements were carried out on a <110> Cu single crystal where the relaxation rate of the {sup 8}Li polarization was monitored as a function of the applied longitudinal magnetic field. The occurrence of cross-relaxation, at a particular magnetic field, between the {sup 8}Li and the surrounding nuclei is evident as a resonant enhancement of the relaxation rate at the level crossing field. We discuss inferences about the site and structure of {sup 8}Li{sup +} in Cu from this data.

  10. Breathing and Relaxation

    Science.gov (United States)

    ... Home Health Insights Stress & Relaxation Breathing and Relaxation Breathing and Relaxation Make an Appointment Ask a Question ... level is often dependent on his or her breathing pattern. Therefore, people with chronic lung conditions may ...

  11. Effects of environmental hypercapnia on animal physiology: a 13C NMR study of protein synthesis rates in the marine invertebrate Sipunculus nudus.

    Science.gov (United States)

    Langenbuch, M; Bock, C; Leibfritz, D; Pörtner, H O

    2006-08-01

    Global climate change is associated with a progressive rise in ocean CO(2) concentrations (hypercapnia) and, consequently, a drop in seawater pH. However, a comprehensive picture of the physiological mechanisms affected by chronic CO(2) stress in marine biota is still lacking. Here we present an analysis of protein biosynthesis rates in isolated muscle of the marine invertebrate Sipunculus nudus, a sediment dwelling worm living at various water depths. We followed the incorporation of (13)C-labelled phenylalanine into muscular protein via high-resolution NMR spectroscopy. Protein synthesis decreased by about 60% at a medium pH of 6.70 and a consequently lowered intracellular pH (pHi). The decrease in protein synthesis rates is much stronger than the concomitant suppression of protein degradation (60% versus 10-15%) possibly posing a threat to the cellular homeostasis of structural as well as functional proteins. Considering the progressive rise in ocean CO(2) concentrations, permanent disturbances of cellular protein turnover might seriously affect growth and reproductive performance in many marine organisms with as yet unexplored impacts on species density and composition in marine ecosystems.

  12. Determination of glucose exchange rates and permeability of erythrocyte membrane in preeclampsia and subsequent oxidative stress-related protein damage using dynamic-{sup 19}F-NMR

    Energy Technology Data Exchange (ETDEWEB)

    Dickinson, Elizabeth, E-mail: elizabeth.dickinson@york.ac.uk [University of York, Department of Chemistry (United Kingdom); Arnold, John R. P. [Selby College (United Kingdom); Fisher, Julie [University of Leeds, School of Chemistry (United Kingdom)

    2017-02-15

    The cause of the pregnancy condition preeclampsia (PE) is thought to be endothelial dysfunction caused by oxidative stress. As abnormal glucose tolerance has also been associated with PE, we use a fluorinated-mimic of this metabolite to establish whether any oxidative damage to lipids and proteins in the erythrocyte membrane has increased cell membrane permeability. Data were acquired using {sup 19}F Dynamic-NMR (DNMR) to measure exchange of 3-fluoro-3-deoxyglucose (3-FDG) across the membrane of erythrocytes from 10 pregnant women (5 healthy control women, and 5 from women suffering from PE). Magnetisation transfer was measured using the 1D selective inversion and 2D EXSY pulse sequences, over a range of time delays. Integrated intensities from these experiments were used in matrix diagonalisation to estimate the values of the rate constants of exchange and membrane permeability. No significant differences were observed for the rate of exchange of 3-FDG and membrane permeability between healthy pregnant women and those suffering from PE, leading us to conclude that no oxidative damage had occurred at this carrier-protein site in the membrane.

  13. Enzymatic conversion of sucrose to glucose and its anomerization by quantitative NMR spectroscopy: Application of a simple consecutive reaction rates approach

    Science.gov (United States)

    Singh, Jaideep; Her, Cheenou; Krishnan, V. V.

    2018-02-01

    The anomerization of carbohydrates is an essential process that determines the relative stabilization of stereoisomers in an aqueous solution. In a typical real-time enzyme kinetics experiment, the substrate (sucrose) is converted to glucose and fructose by the enzyme invertase. The product (α-D-glucose) starts to convert to β-D-glucose immediately by hydrolysis. Though the anomerization process is independent of the enzyme catalysis, the progress curve describing the production of β-D-glucose from α-D-glucose is directly affected by the kinetics of consecutive reactions. When α-D-glucose is continually converted to β-D-glucose, by the enzymatic action, the time course of both α- and β-D-glucose is influenced by the enzyme kinetics. Thus, a reversible first-order rate equation is not adequate to model the reaction mechanism, leading to erroneous results on the rates of formation of the glucose anomers. In this manuscript, we incorporate an approximate method to address consecutive general reactions involving enzyme kinetics and first-order reaction processes. The utility of the approach is demonstrated in the real-time NMR measurement of the anomerization process of α-D-glucose (enzymatically produced from sucrose) to β-D-glucose, as a function of invertase enzyme concentration. Variable temperature experiments were used to estimate the thermodynamic parameters of the anomerization process and are consistent with literature values.

  14. Recovery of Underwater Resonances by Magnetization Transferred NMR Spectroscopy (RECUR-NMR)

    Science.gov (United States)

    Liu, Maili; Tang, Huiru; Nicholson, Jeremy K.; Lindon, John C.

    2001-11-01

    A method for detecting small molecule NMR resonances under a water peak in biological samples is presented. After high-efficiency solvent suppression using double WATERGATE, either a TOCSY- or ROESY-based coherence transfer sequence is applied to reestablish the resonances close to, or under, water through magnetization transfer using scalar or dipolar coupling, respectively. The use of the TOCSY and ROESY methods ensures an in-phase magnetization transfer, which makes the new approach readily extended for the measurement of transverse relaxation times, internuclear ROEs, and ROE buildup rates. An extension of the new approach for J-resolved spectroscopy is also presented and tested using a sample of human blood plasma.

  15. Relaxed states of tokamak plasmas

    International Nuclear Information System (INIS)

    Kucinski, M.Y.; Okano, V.

    1993-01-01

    The relaxed states of tokamak plasmas are studied. It is assumed that the plasma relaxes to a quasi-steady state which is characterized by a minimum entropy production rate, compatible with a number of prescribed conditions and pressure balance. A poloidal current arises naturally due to the anisotropic resistivity. The minimum entropy production theory is applied, assuming the pressure equilibrium as fundamental constraint on the final state. (L.C.J.A.)

  16. Detailing magnetic field strength dependence and segmental artifact distribution of myocardial effective transverse relaxation rate at 1.5, 3.0, and 7.0 T.

    Science.gov (United States)

    Meloni, Antonella; Hezel, Fabian; Positano, Vincenzo; Keilberg, Petra; Pepe, Alessia; Lombardi, Massimo; Niendorf, Thoralf

    2014-06-01

    Realizing the challenges and opportunities of effective transverse relaxation rate (R2 *) mapping at high and ultrahigh fields, this work examines magnetic field strength (B0 ) dependence and segmental artifact distribution of myocardial R2 * at 1.5, 3.0, and 7.0 T. Healthy subjects were considered. Three short-axis views of the left ventricle were examined. R2 * was calculated for 16 standard myocardial segments. Global and mid-septum R2 * were determined. For each segment, an artifactual factor was estimated as the deviation of segmental from global R2 * value. The global artifactual factor was significantly enlarged at 7.0 T versus 1.5 T (P = 0.010) but not versus 3.0 T. At 7.0 T, the most severe susceptibility artifacts were detected in the inferior lateral wall. The mid-septum showed minor artifactual factors at 7.0 T, similar to those at 1.5 and 3.0 T. Mean R2 * increased linearly with the field strength, with larger changes for global heart R2 * values. At 7.0 T, segmental heart R2 * analysis is challenging due to macroscopic susceptibility artifacts induced by the heart-lung interface and the posterior vein. Myocardial R2 * depends linearly on the magnetic field strength. The increased R2 * sensitivity at 7.0 T might offer means for susceptibility-weighted and oxygenation level-dependent MR imaging of the myocardium. Copyright © 2013 Wiley Periodicals, Inc.

  17. The energy barrier to reorientational motion of the trifluoromethyl group in lithium trifluoromethanesulphonate and its complex with poly(ethylene oxide): a comparison between modelling and NMR relaxation measurements

    Science.gov (United States)

    Moore, Elaine A.; Mortimer, Michael; Wigglesworth, Christopher; Williams, Martin A. K.

    1999-07-01

    Molecular modelling is used to calculate the barrier heights to reorientation for the trifluoromethyl group, CF 3, in both lithium trifluoromethanesulphonate, LiCF 3SO 3, and the crystalline complex of this salt with poly(ethylene oxide), PEO. The calculated barrier heights are compared with those determined from 19F spin-lattice relaxation studies. In the case of LiCF 3SO 3, fluorine-fluorine non-bonded interactions are shown to play a dominant role in determining the barrier height to CF 3 group reorientation and optimised Lennard-Jones parameters for this interaction are determined. In the crystalline complex, PEO 3·LiCF 3SO 3, it is suggested that CF 3 group reorientation is strongly influenced by segmental motions of the PEO chain.

  18. Interfaces in polymer nanocomposites – An NMR study

    Energy Technology Data Exchange (ETDEWEB)

    Böhme, Ute; Scheler, Ulrich, E-mail: scheler@ipfdd.de [Leibniz-Institut für Polymerforschung Dresden e.V., Hohe Str. 6, 01069 Dresden (Germany)

    2016-03-09

    Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. {sup 1}H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T{sub 2} is most suited. In this presentation we report on two applications of T{sub 2} measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of the polymer dynamics in the melt under shear flow.

  19. Interfaces in polymer nanocomposites – An NMR study

    International Nuclear Information System (INIS)

    Böhme, Ute; Scheler, Ulrich

    2016-01-01

    Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. 1 H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T 2 is most suited. In this presentation we report on two applications of T 2 measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of the polymer dynamics in the melt under shear flow.

  20. Predicting acoustic relaxation absorption in gas mixtures for extraction of composition relaxation contributions.

    Science.gov (United States)

    Liu, Tingting; Wang, Shu; Zhu, Ming

    2017-12-01

    The existing molecular relaxation models based on both parallel relaxation theory and series relaxation theory cannot extract the contributions of gas compositions to acoustic relaxation absorption in mixtures. In this paper, we propose an analytical model to predict acoustic relaxation absorption and clarify composition relaxation contributions based on the rate-determining energy transfer processes in molecular relaxation in excitable gases. By combining parallel and series relaxation theory, the proposed model suggests that the vibration-translation process of the lowest vibrational mode in each composition provides the primary deexcitation path of the relaxation energy, and the rate-determining vibration-vibration processes between the lowest mode and others dominate the coupling energy transfer between different modes. Thus, each gas composition contributes directly one single relaxation process to the molecular relaxation in mixture, which can be illustrated by the decomposed acoustic relaxation absorption spectrum of the single relaxation process. The proposed model is validated by simulation results in good agreement with experimental data such as N 2 , O 2 , CO 2 , CH 4 and their mixtures.

  1. Measuring the χ1 torsion angle in protein by CH-CH cross-correlated relaxation: A new resolution-optimised experiment

    International Nuclear Information System (INIS)

    Carlomagno, Teresa; Bermel, Wolfgang; Griesinger, Christian

    2003-01-01

    Here we introduce an experiment with high sensitivity and resolution for the measurement of CH-CH dipolar-dipolar cross-correlated relaxation rates (CCRR) in protein side-chains. The new methodology aims to the determination of structural and dynamical parameters around the torsion angle χ 1 by measuring C α H α -C β H β cross-correlated relaxation rates. The method is validated on the protein ubiquitin: the χ 1 angles determined from the CCRR data are compared with the χ 1 angles of a previously determined NMR structure. The agreement between the two data sets is excellent for most residues. The few discrepancies that were found between the CCR-derived χ 1 angles and the angles of the previously determined NMR structure could be explained by taking internal motion into account. The new methodology represents a very powerful tool to determine both structure and dynamics of protein side-chains in only one experiment

  2. Solid-state NMR basic principles and practice

    CERN Document Server

    Apperley, David C; Hodgkinson, Paul

    2014-01-01

    Nuclear Magnetic Resonance (NMR) has proved to be a uniquely powerful and versatile tool for analyzing and characterizing chemicals and materials of all kinds. This book focuses on the latest developments and applications for "solid-state" NMR, which has found new uses from archaeology to crystallography to biomaterials and pharmaceutical science research. The book will provide materials engineers, analytical chemists, and physicists, in and out of lab, a survey of the techniques and the essential tools of solid-state NMR, together with a practical guide on applications. In this concise introduction to the growing field of solid-state nuclear magnetic resonance spectroscopy The reader will find: * Basic NMR concepts for solids, including guidance on the spin-1/2 nuclei concept * Coverage of the quantum mechanics aspects of solid state NMR and an introduction to the concept of quadrupolar nuclei * An understanding relaxation, exchange and quantitation in NMR * An analysis and interpretation of NMR data, with e...

  3. Intermolecular nuclear relaxation in paramagnetic solutions: from free radicals to rare earths

    Energy Technology Data Exchange (ETDEWEB)

    Belorizky, E. [Universite Joseph-Fourier, Lab. de Spectrometrie Physique, CNRS-UMR 5588, 38 - Saint Martin d' Heres (France); Fries, P.H.; Rast, S. [CEA Grenoble, Laboratoire de Reconnaissance ionique, Service de Chimie Inorganique et Biologique UMR 5046, Dept. de Recherche Fondamentale sur la Matiere Condensee, 38 (France)

    2001-11-01

    The principles of the intermolecular relaxation of a nuclear spin by its fluctuating magnetic dipolar interactions with the electronic spins of the paramagnetic surrounding species in solution are briefly recalled. It is shown that a very high dynamic nuclear polarization (DNP) of solvent protons is obtained by saturating allowed transitions of free radicals with a hyperfine structure, and that this effect can be used in efficient Earth field magnetometers. Recent work on trivalent lanthanide Ln{sup 3+} aqua complexes in heavy water solutions is discussed, including paramagnetic shift and relaxation rate measurements of the {sup 1}H NMR lines of probe solutes. This allows a determination of the effective electronic magnetic moments of the various Ln{sup 3+} ions in these complexes, and an estimation of their longitudinal and transverse electronic relaxation times T{sub 1e} and T{sub 2e}. Particular attention is given to Gd(III) hydrated chelates which can serve as contrast agents in magnetic resonance imaging (MRI). The full experimental electronic paramagnetic resonance (EPR) spectra of these complexes can be interpreted within the Redfield relaxation theory. Monte-Carlo simulations are used to explore situations beyond the validity of the Redfield approximation. For each Gd(III) complex, the EPR study leads to an accurate prediction of T{sub 1e}, which can be also derived from an independent relaxation dispersion study of the protons of the probe solutes. (authors)

  4. Diffusion and spatially resolved NMR in Berea and Venezuelan oil reservoir rocks.

    Science.gov (United States)

    Murgich, J; Corti, M; Pavesi, L; Voltini, F

    1992-01-01

    Conventional and spatially resolved proton NMR and relaxation measurements are used in order to study the molecular motions and the equilibrium and nonequilibrium diffusion of oils in Berea sandstone and Venezuelan reservoir rocks. In the water-saturated Berea a single line with T*2 congruent to 150 microseconds is observed, while the relaxation recovery is multiexponential. In an oil reservoir rock (Ful 13) a single narrow line is present while a distribution of relaxation rates is evidenced from the recovery plots. On the contrary, in the Ful 7 sample (extracted at a deeper depth in a different zone) two NMR components are present, with 3.5 and 30 KHz linewidths, and the recovery plot exhibits biexponential law. No echo signal could be reconstructed in the oil reservoir rocks. These findings can be related to the effects in the micropores, where motions at very low frequency can occur in a thin layer. From a comparison of the diffusion constant in water-saturated Berea, D congruent to 5*10(-6) cm2/sec, with the ones in model systems, the average size of the pores is estimated around 40 A. The density profiles at the equilibrium show uniform distribution of oils or of water, and the relaxation rates appear independent from the selected slice. The nonequilibrium diffusion was studied as a function of time in a Berea cylinder with z axis along H0, starting from a thin layer of oil at the base, and detecting the spin density profiles d(z,t) with slice-selection techniques. Simultaneously, the values of T1's were measured locally, and the distribution of the relaxation rates was observed to be present in any slice.(ABSTRACT TRUNCATED AT 250 WORDS)

  5. What is the surface specific area of porous cement-based material? A nuclear magnetic relaxation dispersion approach.

    Science.gov (United States)

    Barberon, F; Korb, J-P; Petit, D; Morin, V; Bermejo, E

    2003-01-01

    We propose a new NMR method to measure and follow the evolution of the surface specific area, Sp, of a porous cement-based material. This method, that does not require any preliminary drying process, uses nuclear magnetic relaxation dispersion (NMRD), the measurement of spin-lattice relaxation rate as a function of magnetic field strength or nuclear Larmor frequency. The method is applied for three different mortars samples prepared by mixing cement, sand, silica fume, water and superplasticizer with a water to cement ratio w/c=0.25, 0.38 and 0.65, respectively. The evolution of Sp grows linearly with the degree of advancement of chemical reactions measured by thermal heating and we evidence two relaxation processes independent of the w/c ratio.

  6. Fluid-Rock Characterization and Interactions in NMR Well Logging

    Energy Technology Data Exchange (ETDEWEB)

    George J. Hirasaki; Kishore K. Mohanty

    2005-09-05

    The objective of this report is to characterize the fluid properties and fluid-rock interactions that are needed for formation evaluation by NMR well logging. The advances made in the understanding of NMR fluid properties are summarized in a chapter written for an AAPG book on NMR well logging. This includes live oils, viscous oils, natural gas mixtures, and the relation between relaxation time and diffusivity. Oil based drilling fluids can have an adverse effect on NMR well logging if it alters the wettability of the formation. The effect of various surfactants on wettability and surface relaxivity are evaluated for silica sand. The relation between the relaxation time and diffusivity distinguishes the response of brine, oil, and gas in a NMR well log. A new NMR pulse sequence in the presence of a field gradient and a new inversion technique enables the T{sub 2} and diffusivity distributions to be displayed as a two-dimensional map. The objectives of pore morphology and rock characterization are to identify vug connectivity by using X-ray CT scan, and to improve NMR permeability correlation. Improved estimation of permeability from NMR response is possible by using estimated tortuosity as a parameter to interpolate between two existing permeability models.

  7. Pulsed NMR studies of water under extreme conditions

    Energy Technology Data Exchange (ETDEWEB)

    DeFries, Timothy Hatmaker [Univ. of Illinois, Urbana-Champaign, IL (United States)

    1978-01-01

    The dynamic structure of water and heavy water was studied using NMR spin-lattice relaxation and self-diffusion techniques. For both compounds, the relaxation rate is proportional to the ratio of viscosity to absolute temperature at constant density. The coupling between rotational and translational motions decreases with increasing temperature and increasing density. The temperature and density dependence of the deuteron quadrupole coupling constant in D2O was determined. The proton spin-lattice relaxation times of supercritical H2O were measured from 400 to 700°C and to 1 kbar. The times were found to be roughly proportional to density and were found to decrease with temperature. The angular momentum correlation times tauJ were calculated and compared with the times between collisions for a hard sphere fluid, the Enskog times, tauE. The values of tauEtauJ were roughly 6 at 400°C and low densities. The values decreased at higher densities and higher temperatures. The proton spin-lattice relaxation times of H2O were also measured from 90 to 350°C up to 2 to 5 kbar. The data clearly show the change from dipolar to spin-rotation relaxation as a function of temperature and density. Both the low and the high temperature results agree with the idea that it is the strong and anisotropic intermolecular potential which causes the dynamic behavior of water to be so different from that of normal liquids.

  8. High-resolution solid-state NMR study of isotactic polypropylenes

    Directory of Open Access Journals (Sweden)

    O. Fricova

    2012-03-01

    Full Text Available The high-resolution solid-state 13C NMR spectra were recorded for metallocene (m and Ziegler-Natta (ZN isotactic polypropylenes (iPP in pelletized form using cross polarization (CP and magic angle spinning (MAS techniques within the temperature range of 20–160°C. Besides the CP MAS experiments also the MAS 13C NMR spectra (without CP, MAS 1H NMR spectra and rotating frame spin-lattice relaxation times T1ρ (13C were measured at elevated temperatures. With the rise of temperature the splitting of CH2, CH and CH3 signals into two components was detected in 13C NMR spectra and assigned to amorphous and crystalline phases. The temperature dependences of chemical shifts and integral intensities obtained from the deconvoluted spectra provided information on the main chain and CH3 groups motions in amorphous and crystalline regions of studied samples. While T1ρ (13C values show that the rate of segmental motion in amorphous regions in m-iPP and ZN-iPP is virtually the same, larger linewidths in 13C and 1H NMR spectra indicate somewhat larger restraints of the motion in amorphous regions of ZN-iPP.

  9. Nuclear spin relaxation/resonance of 8Li in Al

    Science.gov (United States)

    Wang, D.; Salman, Z.; Chow, K. H.; Fan, I.; Hossain, M. D.; Keeler, T. A.; Kiefl, R. F.; Levy, C. D. P.; Mansour, A. I.; Morris, G. D.; Pearson, M. R.; Parolin, T. J.; Saadaoui, H.; Smadella, M.; Song, Q.; MacFarlane, W. A.

    2009-04-01

    A low energy beam of spin polarized 8Li has been used to study the behaviour of isolated 8Li implanted into a 150 nm thick film of Al on an MgO substrate. The spin relaxation rate 1/T1 and β-NMR lineshape were measured as a function of temperature in a large magnetic field of 4.1 T. The resonances from different sites are unresolved due to the large nuclear dipolar interaction with the host 27Al magnetic dipole moments. Nevertheless the temperature variation of the site averaged 1/T1 and Knight shift show evidence for a transition between the octahedral O and substitutional S sites at about 150 K, as observed in other fcc metals.

  10. Early non-destructive biofouling detection in spiral wound RO Membranes using a mobile earth's field NMR

    KAUST Repository

    Fridjonsson, E.O.

    2015-04-20

    We demonstrate the use of Earth\\'s field (EF) Nuclear Magnetic Resonance (NMR) to provide early non-destructive detection of active biofouling of a commercial spiral wound reverse osmosis (RO) membrane module. The RO membrane module was actively biofouled to different extents, by the addition of biodegradable nutrients to the feed stream, as revealed by a subtle feed-channel pressure drop increase. Easily accessible EF NMR parameters (signal relaxation parameters T1, T2 and the total NMR signal modified to be sensitive to stagnant fluid only) were measured and analysed in terms of their ability to detect the onset of biofouling. The EF NMR showed that fouling near the membrane module entrance significantly distorted the flow field through the whole membrane module. The total NMR signal is shown to be suitable for non-destructive early biofouling detection of spiral wound membrane modules, it was readily deployed at high (operational) flow rates, was particularly sensitive to flow field changes due to biofouling and could be deployed at any position along the membrane module axis. In addition to providing early fouling detection, the mobile EF NMR apparatus could also be used to (i) evaluate the production process of spiral wound membrane modules, and (ii) provide an in-situ determination of module cleaning process efficiency.

  11. Vesicle to micelle transition in the ternary mixture of L121/SDS/D2O: NMR, EPR and SANS studies.

    Science.gov (United States)

    Prameela, G K S; Phani Kumar, B V N; Reddy, R Ravikanth; Pan, A; Subramanian, J; Kumar, Sugam; Aswal, V K; Kohlbrecher, Joachim; Mandal, A B; Moulik, S P

    2017-12-06

    Subtle changes in the microstructure and dynamics of the triblock copolymer L121, (ethylene oxide) 5 (propylene oxide) 68 (ethylene oxide) 5 i.e., E 5 P 68 E 5 , and sodium dodecylsulfate (SDS) system in aqueous medium were investigated using high-resolution nuclear magnetic resonance (NMR), electron paramagnetic resonance (EPR) and small-angle neutron scattering (SANS) methods. NMR self-diffusion measurements helped us to understand the nature of binding of SDS with L121, and the formation of their mixed aggregates. These results showed that even at low [SDS] (∼2 mM), the addition of L121 stabilized the dynamics of SDS. Furthermore, the increase in [SDS] resulted in progressive changes in the diffusion behavior of both SDS and L121. 13 C chemical shift analysis revealed that preferential binding of L121 occurred on the SDS micelle surface. Deuterium ( 2 H) NMR spin-relaxation data evidenced that the formed mixed aggregates were non-spherical in terms of relaxation rate changes, and slowed the dynamics. The rotational correlation times of mixed aggregates were estimated from EPR analysis. A SANS study indicated the presence of uni- and multi-lamellar vesicles of L121 at low [SDS]. The vesicles transformed to mixed L121-SDS micelles in the presence of a higher [SDS]. This was supported by the measurements of 2 H NMR spin-relaxation and EPR rotational correlation times.

  12. An NMR study of the molecular mobility in BeSO 4·4H 2O

    Science.gov (United States)

    Larsson, K.; Tegenfeldt, J.

    1988-05-01

    Molecular and ionic mobility in the solid hydrate BeSO 4·H 2O has been studied by 1H-NMR spectroscopy. Spin-lattice relaxation rates in the laboratory and rotating frames, T-11 and T-11π, have been measured as a function of temperature for polycrystalline samples, and as a function of orientation for a single crystal. One dynamical process has been clearly identified as being responsible for the rotating frame relaxation: an H 2O flip motion with an activation energy of 58 kJ mol -1. The pre-exponential factor of the Arrhenius relation for the correlation time of this motion is 4.3 × 10 -16 s. A second process, responsible for the laboratory frame spin-lattice relaxation is observed, but cannot be identified unambiguously.

  13. Multiscale nuclear magnetic relaxation dispersion of complex liquids in bulk and confinement.

    Science.gov (United States)

    Korb, Jean-Pierre

    2018-02-01

    The nuclear magnetic relaxation dispersion (NMRD) technique consists of measurement of the magnetic-field dependence of the longitudinal nuclear-spin-lattice relaxation rate 1/T 1 . Usually, the acquisition of the NMRD profiles is made using a fast field cycling (FFC) NMR technique that varies the magnetic field and explores a very large range of Larmor frequencies (10 kHz relaxation is sensitive. The FFC technique thus offers opportunities on multiple scales of both time and distance for characterizing the molecular dynamics and transport properties of complex liquids in bulk or embedded in confined environments. This review presents the principles, theories and applications of NMRD for characterizing fundamental properties such as surface correlation times, diffusion coefficients and dynamical surface affinity (NMR wettability) for various confined liquids. The basic longitudinal and transverse relaxation equations are outlined for bulk liquids. The nuclear relaxation of a liquid confined in pores is considered in detail in order to find the biphasic fast exchange relations for a liquid at proximity of a solid surface. The physical-chemistry of liquids at solid surfaces induces striking differences between NMRD profiles of aprotic and protic (water) liquids embedded in calibrated porous disordered materials. A particular emphasis of this review concerns the extension of FFC NMR relaxation to industrial applications. For instance, it is shown that the FFC technique is sufficiently rapid for following the progressive setting of cement-based materials (plasters, cement pastes, concretes). The technique also allows studies of the dynamics of hydrocarbons in proximity of asphaltene nano-aggregates and macro-aggregates in heavy crude oils as a function of the concentration of asphaltenes. It also gives new information on the wettability of petroleum fluids (brine and oil) embedded in shale oil rocks. It is useful for understanding the relations and correlations

  14. Fast hydrogen exchange affects 15N relaxation measurements in intrinsically disordered proteins

    International Nuclear Information System (INIS)

    Kim, Seho; Wu, Kuen-Phon; Baum, Jean

    2013-01-01

    Unprotected amide protons can undergo fast hydrogen exchange (HX) with protons from the solvent. Generally, NMR experiments using the out-and-back coherence transfer with amide proton detection are affected by fast HX and result in reduced signal intensity. When one of these experiments, 1 H– 15 N HSQC, is used to measure the 15 N transverse relaxation rate (R 2 ), the measured R 2 rate is convoluted with the HX rate (k HX ) and has higher apparent R 2 values. Since the 15 N R 2 measurement is important for analyzing protein backbone dynamics, the HX effect on the R 2 measurement is investigated and described here by multi-exponential signal decay. We demonstrate these effects by performing 15 N R 2 CPMG experiments on α-synuclein, an intrinsically disordered protein, in which the amide protons are exposed to solvent. We show that the HX effect on R 2 CPMG can be extracted by the derived equation. In conclusion, the HX effect may be pulse sequence specific and results from various sources including the J coupling evolution, the change of steady state water proton magnetization, and the D 2 O content in the sample. To avoid the HX effect on the analysis of relaxation data of unprotected amides, it is suggested that NMR experimental conditions insensitive to the HX should be considered or that intrinsic R 2 CPMG values be obtained by methods described herein.

  15. A mixed relaxed clock model

    Science.gov (United States)

    2016-01-01

    Over recent years, several alternative relaxed clock models have been proposed in the context of Bayesian dating. These models fall in two distinct categories: uncorrelated and autocorrelated across branches. The choice between these two classes of relaxed clocks is still an open question. More fundamentally, the true process of rate variation may have both long-term trends and short-term fluctuations, suggesting that more sophisticated clock models unfolding over multiple time scales should ultimately be developed. Here, a mixed relaxed clock model is introduced, which can be mechanistically interpreted as a rate variation process undergoing short-term fluctuations on the top of Brownian long-term trends. Statistically, this mixed clock represents an alternative solution to the problem of choosing between autocorrelated and uncorrelated relaxed clocks, by proposing instead to combine their respective merits. Fitting this model on a dataset of 105 placental mammals, using both node-dating and tip-dating approaches, suggests that the two pure clocks, Brownian and white noise, are rejected in favour of a mixed model with approximately equal contributions for its uncorrelated and autocorrelated components. The tip-dating analysis is particularly sensitive to the choice of the relaxed clock model. In this context, the classical pure Brownian relaxed clock appears to be overly rigid, leading to biases in divergence time estimation. By contrast, the use of a mixed clock leads to more recent and more reasonable estimates for the crown ages of placental orders and superorders. Altogether, the mixed clock introduced here represents a first step towards empirically more adequate models of the patterns of rate variation across phylogenetic trees. This article is part of the themed issue ‘Dating species divergences using rocks and clocks’. PMID:27325829

  16. Onsager relaxation of toroidal plasmas

    International Nuclear Information System (INIS)

    Samain, A.; Nguyen, F.

    1997-01-01

    The slow relaxation of isolated toroidal plasmas towards their thermodynamical equilibrium is studied in an Onsager framework based on the entropy metric. The basic tool is a variational principle, equivalent to the kinetic equation, involving the profiles of density, temperature, electric potential, electric current. New minimization procedures are proposed to obtain entropy and entropy production rate functionals. (author)

  17. Solid-state NMR of polymers

    International Nuclear Information System (INIS)

    Mirau, P.

    2001-01-01

    Nuclear magnetic resonance (NMR) spectroscopy has emerged as one of the most important methods for the solid-state characterisation of polymers. The popularity of NMR is due to the fact that many molecular level features can be measured from the NMR spectra, including the polymer chain conformation, the morphology and the dynamics. The spectral features and relaxation times are affected by local interactions, so they provide information about the structure of polymers on a length scale (2-200 A) that is difficult to measure by other methods. In favourable cases, the NMR experiments provide a molecular-level explanation for the transitions observed by differential scanning calorimetry (DSC) and other methods, and the NMR properties can often be related to the bulk properties. Solid-state NMR has long been of interest in polymer science, and the first solid-state NMR studies of polymers were reported approximately a year after the discovery of nuclear resonance in bulk matter. It was reported in this initial study that the proton line width for natural rubber at room temperature is more like that of a mobile liquid than of a solid, but that the resonance broadens near the glass transition temperature (T g ). This was recognised as being related to a change in chain dynamics above and below the T g . NMR methods developed rapidly after these initial observations, first for polymers in solution and, more recently, for polymers in the solid-state. Solid-state NMR studies of polymers were developed more slowly than their solution-state counterparts because solid-state NMR requires more specialised equipment. Solid-state NMR is now such an important tool that most modern spectrometers are capable of performing these studies. The interest in the NMR of solid polymers is due in part to the fact that most polymers are used in the solid state, and in many cases the NMR properties can be directly related to the macroscopic properties. Polymers have restricted mobility in

  18. Nuclear spin-lattice relaxation in carbon nanostructures

    Energy Technology Data Exchange (ETDEWEB)

    Panich, A.M., E-mail: pan@bgu.ac.i [Department of Physics, Ben-Gurion University of the Negev, P.O. Box 653, Beer Sheva 84105 (Israel); Sergeev, N.A. [Institute of Physics, University of Szczecin, 70-451 Szczecin (Poland)

    2010-04-15

    Interpretation of nuclear spin-lattice relaxation data in the carbon nanostructures is usually based on the analysis of fluctuations of dipole-dipole interactions of nuclear spins and anisotropic electron-nuclear interactions responsible for chemical shielding, which are caused by molecular dynamics. However, many nanocarbon systems such as fullerene and nanotube derivatives, nanodiamonds and carbon onions reveal noticeable amount of paramagnetic defects with unpaired electrons originating from dangling bonds. The interaction between nuclear and electron spins strongly influences the nuclear spin-lattice relaxation, but usually is not taken into account, thus the relaxation data are not correctly interpreted. Here we report on the temperature dependent NMR spectra and spin-lattice relaxation measurements of intercalated fullerenes C{sub 60}(MF{sub 6}){sub 2} (M=As and Sb), where nuclear relaxation is caused by both molecular rotation and interaction between nuclei and unpaired electron spins. We present a detailed theoretical analysis of the spin-lattice relaxation data taking into account both these contributions. Good agreement between the experimental data and calculations is obtained. The developed approach would be useful in interpreting the NMR relaxation data in different nanostructures and their intercalation compounds.

  19. Tuning the relaxation rates of dual-mode T1/T2 nanoparticle contrast agents: a study into the ideal system

    Science.gov (United States)

    Keasberry, Natasha A.; Bañobre-López, Manuel; Wood, Christopher; Stasiuk, Graeme. J.; Gallo, Juan; Long, Nicholas. J.

    2015-09-01

    Magnetic resonance imaging (MRI) is an excellent imaging modality. However the low sensitivity of the technique poses a challenge to achieving an accurate image of function at the molecular level. To overcome this, contrast agents are used; typically gadolinium based agents for T1 weighted imaging, or iron oxide based agents for T2 imaging. Traditionally, only one imaging mode is used per diagnosis although several physiological situations are known to interfere with the signal induced by the contrast agents in each individual imaging mode acquisition. Recently, the combination of both T1 and T2 imaging capabilities into a single platform has emerged as a tool to reduce uncertainties in MR image analysis. To date, contradicting reports on the effect on the contrast of the coupling of a T1 and T2 agent have hampered the application of these specialised probes. Herein, we present a systematic experimental study on a range of gadolinium-labelled magnetite nanoparticles envisioned to bring some light into the mechanism of interaction between T1 and T2 components, and advance towards the design of efficient (dual) T1 and T2 MRI probes. Unexpected behaviours observed in some of the constructs will be discussed. In this study, we demonstrate that the relaxivity of such multimodal probes can be rationally tuned to obtain unmatched potentials in MR imaging, exemplified by preparation of the magnetite-based nanoparticle with the highest T2 relaxivity described to date.Magnetic resonance imaging (MRI) is an excellent imaging modality. However the low sensitivity of the technique poses a challenge to achieving an accurate image of function at the molecular level. To overcome this, contrast agents are used; typically gadolinium based agents for T1 weighted imaging, or iron oxide based agents for T2 imaging. Traditionally, only one imaging mode is used per diagnosis although several physiological situations are known to interfere with the signal induced by the contrast agents in

  20. Flow NMR of polymers in external fields

    Energy Technology Data Exchange (ETDEWEB)

    Boehme, Ute; Bagusat, Frank; Scheler, Ulrich [Leibniz Institute of Polymer Research Dresden (Germany)

    2008-07-01

    Pulsed-field gradient NMR is applied to study the motion of polymers in an external electric field and under mechanical shear. The application of an electric field drives motion of charged species. In conjunction with the diffusion coefficient from the electrophoretic mobility the effective charge per molecule is derived. The electric field applicable in the aqueous system is too weak to deform the polymer or even abstract counterions. In a shear flow established in a Couette cell partial orientation of polymer chains is measured via residual dipolar couplings. The entire flow field in a non-symmetric flow cell is monitored by a combination of PFG NMR and NMR imaging exhibiting regions of high shear and locally low shear, where polymers relax.

  1. Analysis of diffusion and relaxation behavior of water in apple parenchyma cells

    NARCIS (Netherlands)

    Sibgatullin, T.; Anisimov, A.V.; Jager, de P.A.

    2007-01-01

    It has been demonstrated by an example of apple parenchymal cells that NMR spectroscopy can be used to analyze the relaxation and diffusion of water molecules in plant cells. With small diffusion times, three relaxation components have been distinguished, which correspond to water in a vacuole, in

  2. Some exercises in quantitative NMR imaging

    International Nuclear Information System (INIS)

    Bakker, C.J.G.

    1985-01-01

    The articles represented in this thesis result from a series of investigations that evaluate the potential of NMR imaging as a quantitative research tool. In the first article the possible use of proton spin-lattice relaxation time T 1 in tissue characterization, tumor recognition and monitoring tissue response to radiotherapy is explored. The next article addresses the question whether water proton spin-lattice relaxation curves of biological tissues are adequately described by a single time constant T 1 , and analyzes the implications of multi-exponentiality for quantitative NMR imaging. In the third article the use of NMR imaging as a quantitative research tool is discussed on the basis of phantom experiments. The fourth article describes a method which enables unambiguous retrieval of sign information in a set of magnetic resonance images of the inversion recovery type. The next article shows how this method can be adapted to allow accurate calculation of T 1 pictures on a pixel-by-pixel basis. The sixth article, finally, describes a simulation procedure which enables a straightforward determination of NMR imaging pulse sequence parameters for optimal tissue contrast. (orig.)

  3. Mechanical relaxation in glasses

    International Nuclear Information System (INIS)

    Hiki, Y.

    2004-01-01

    The basic properties of glasses and the characteristics of mechanical relaxation in glasses were briefly reviewed, and then our studies concerned were presented. Experimental methods adopted were viscosity, internal friction, ultrasonic attenuation, and Brillouin scattering measurements. The specimens used were several kinds of inorganic, organic, and metallic glasses. The measurements were mainly carried out from the room temperature up to the glass transition temperature, and the relaxation time was determined as a function of temperature. The 'double relaxation' composed of two Arrhenius-type relaxations was observed in many materials. In both relaxations, the 'compensation effect' showing a correlation of the pre-exponential factor and the activation energy was observed. These results were explained by considering the 'complex relaxation' due to cooperative motions of atoms or group of atoms. Values of activation energy near the glass transition determined by the various experimental methods were compared with each other

  4. Relaxation of polarized nuclei in superconducting rhodium

    DEFF Research Database (Denmark)

    Knuuttila, T.A.; Tuoriniemi, J.T.; Lefmann, K.

    2000-01-01

    Nuclear spin lattice relaxation rates were measured in normal and superconducting (sc) rhodium with nuclear polarizations up to p = 0.55. This was sufficient to influence the sc state of Rh, whose T, and B-c, are exceptionally low. Because B-c ... is unchanged, the nuclear spin entropy was fully sustained across the sc transition. The relaxation in the sc state was slower at all temperatures without the coherence enhancement close to T-c. Nonzero nuclear polarization strongly reduced the difference between the relaxation rates in the sc and normal...

  5. Integration of screening and identifying ligand(s) from medicinal plant extracts based on target recognition by using NMR spectroscopy

    OpenAIRE

    sprotocols

    2015-01-01

    Authors: Yalin Tang, Qian Shang, Junfeng Xiang, Qianfan Yang, Qiuju Zhou, Lin Li, Hong Zhang, Qian Li, Hongxia Sun, Aijiao Guan, Wei Jiang & Wei Gai ### Abstract This protocol presents the screening of ligand(s) from medicinal plant extracts based on target recognition by using NMR spectroscopy. A detailed description of sample preparation and analysis process is provided. NMR spectroscopies described here are 1H NMR, diffusion-ordered spectroscopy (DOSY), relaxation-edited NMR, 1H–1...

  6. 1H NMR of High-Potential Iron-Sulfur Protein from the Purple Non-Sulfur Bacterium Rhodoferax fermentans

    DEFF Research Database (Denmark)

    Ciurli, Stefano; Cremonini, Mauro Andrea; Kofod, Pauli

    1996-01-01

    residues bound to the [4Fe-4S]3+/2+ cluster have been performed using one-dimensional NOE and exchange spectroscopy experiments. 1H-NMR hyperfine shifts and relaxation rates of cluster-bound Cys β-CH2 protons indicate that in the [4Fe-4S]3+ cluster one iron ion can be formally described as Fe(III), while...... electron density corresponding to one electron is unevenly delocalized onto the remaining three iron ions. This delocalization is effected by means of two different electronic distributions interconverting rapidly on the NMR time scale. The mechanism of paramagnetic proton relaxation, studied by analyzing...... longitudinal relaxation rates of Cys β-CH2 protons in HiPIPs from six different sources as a function of the Fe-S-Cβ-Cα dihedral angle, indicate that the major contribution is due to a dipolar metal-centered mechanism, with a non-negligeable contribution from a ligand-centered dipolar mechanism which involves...

  7. Assessment of chemical exchange in tryptophan–albumin solution through {sup 19}F multicomponent transverse relaxation dispersion analysis

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Ping-Chang, E-mail: pingchang.lin@howard.edu [Howard University, Department of Radiology, College of Medicine (United States)

    2015-06-15

    A number of NMR methods possess the capability of probing chemical exchange dynamics in solution. However, certain drawbacks limit the applications of these NMR approaches, particularly, to a complex system. Here, we propose a procedure that integrates the regularized nonnegative least squares (NNLS) analysis of multiexponential T{sub 2} relaxation into Carr–Purcell–Meiboom–Gill (CPMG) relaxation dispersion experiments to probe chemical exchange in a multicompartmental system. The proposed procedure was validated through analysis of {sup 19}F T{sub 2} relaxation data of 6-fluoro-DL-tryptophan in a two-compartment solution with and without bovine serum albumin. Given the regularized NNLS analysis of a T{sub 2} relaxation curve acquired, for example, at the CPMG frequency υ{sub CPMG} = 125, the nature of two distinct peaks in the associated T{sub 2} distribution spectrum indicated 6-fluoro-DL-tryptophan either retaining the free state, with geometric mean */multiplicative standard deviation (MSD) = 1851.2 ms */1.51, or undergoing free/albumin-bound interconversion, with geometric mean */MSD = 236.8 ms */1.54, in the two-compartment system. Quantities of the individual tryptophan species were accurately reflected by the associated T{sub 2} peak areas, with an interconversion state-to-free state ratio of 0.45 ± 0.11. Furthermore, the CPMG relaxation dispersion analysis estimated the exchange rate between the free and albumin-bound states in this fluorinated tryptophan analog and the corresponding dissociation constant of the fluorinated tryptophan–albumin complex in the chemical-exchanging, two-compartment system.

  8. Charge carrier effective mass and concentration derived from combination of Seebeck coefficient and 125Te NMR measurements in complex tellurides

    Science.gov (United States)

    Levin, E. M.

    2016-06-01

    Thermoelectric materials utilize the Seebeck effect to convert heat to electrical energy. The Seebeck coefficient (thermopower), S , depends on the free (mobile) carrier concentration, n , and effective mass, m*, as S ˜m*/n2 /3 . The carrier concentration in tellurides can be derived from 125Te nuclear magnetic resonance (NMR) spin-lattice relaxation measurements. The NMR spin-lattice relaxation rate, 1 /T1 , depends on both n and m* as 1 /T1˜(m*)3/2n (within classical Maxwell-Boltzmann statistics) or as 1 /T1˜(m*)2n2 /3 (within quantum Fermi-Dirac statistics), which challenges the correct determination of the carrier concentration in some materials by NMR. Here it is shown that the combination of the Seebeck coefficient and 125Te NMR spin-lattice relaxation measurements in complex tellurides provides a unique opportunity to derive the carrier effective mass and then to calculate the carrier concentration. This approach was used to study A gxS bxG e50-2xT e50 , well-known GeTe-based high-efficiency tellurium-antimony-germanium-silver thermoelectric materials, where the replacement of Ge by [Ag+Sb] results in significant enhancement of the Seebeck coefficient. Values of both m* and n derived using this combination show that the enhancement of thermopower can be attributed primarily to an increase of the carrier effective mass and partially to a decrease of the carrier concentration when the [Ag+Sb] content increases.

  9. NMR of lignins

    Science.gov (United States)

    John Ralph; Larry L. Landucci

    2010-01-01

    This chapter will consider the basic aspects and findings of several forms of NMR spectroscopy, including separate discussions of proton, carbon, heteronuclear, and multidimensional NMR. Enhanced focus will be on 13C NMR, because of its qualitative and quantitative importance, followed by NMR’s contributions to our understanding of lignin...

  10. Parallelizing acquisitions of solid-state NMR spectra with multi-channel probe and multi-receivers: applications to nanoporous solids.

    Science.gov (United States)

    Martineau, Charlotte; Decker, Frank; Engelke, Frank; Taulelle, Francis

    2013-01-01

    A five-channel ((1)H, (19)F, (31)P, (27)Al, (13)C) 2.5 mm magic-angle-spinning (MAS) nuclear magnetic resonance (NMR) probe is used in combination with three separate receivers for the parallel acquisitions of one (1D) and two-dimensional (2D) NMR spectra in model fluorinated aluminophosphate and porous Al-based metal-organic framework (MOF). Possible combinations to record simultaneously spectra using this set-up are presented, including (i) parallel acquisitions of quantitative 1D NMR spectra of solids containing nuclei with contrasted T1 relaxation rates and (ii) parallel acquisitions of 2D heteronuclear NMR spectra. In solids containing numerous different NMR-accessible nuclei, the number of NMR experiments that have to be acquired to get accurate structural information is high. The strategy we present here, i.e. the multiplication of both the number of irradiation channels in the probe and the number of parallel receivers, offers one possibility to optimize this measurement time. © 2013 Elsevier Inc. All rights reserved.

  11. Coexistence of spin frozen state and persistent spin dynamics in NaSrCo{sub 2}F{sub 7} as probed by μSR and NMR

    Energy Technology Data Exchange (ETDEWEB)

    Dengre, Shanu; Sarkar, Rajib; Braeuninger, Sascha Albert; Brueckner, Felix; Materne, Philipp; Klauss, Hans-Henning [Institute for Solid State Physics, TU Dresden (Germany); Krizan, Jason W.; Cava, Robert J. [Department of Chemistry, Princeton University, Princeton, NJ (United States); Luetkens, Hubertus; Baines, Chris [Laboratory for Muon-Spin Spectroscopy, Paul Scherrer Institute, Villigen (Switzerland)

    2016-07-01

    {sup 23}Na -and {sup 19}F NMR, and μSR experiments are performed to explore the microscopic properties of NaSrCo{sub 2}F{sub 7}, which is a newly discovered magnetically frustrated pyrochlore with weak bond disorder and with a frustration index of f = 42. While {sup 23}Na and {sup 19}F NMR experiments clearly suggest the presence of quasi static field distribution below ∝3 K as reflected in the huge NMR line broadening and wipe out effect of NMR signal intensity, μSR experiments on the other hand remains passive to this spin frozen state. Both NMR and μSR results indicate the slowing down of the magnetic (spin) fluctuations upon cooling towards the NMR spin frozen state. μSR relaxation rate increases slightly below ∝ 3 K, and remains not only constant down to 20 mK, but also stands independent in longitudinal magnetic field upto 4000 G implying that the spin fluctuations are dynamic. These observations suggest the coexistence of partial spin frozen state and persistent spin dynamics in NaSrCo{sub 2}F{sub 7}.

  12. Contribution of proton NMR relaxation to the investigation of ...

    Indian Academy of Sciences (India)

    Author Affiliations. A C Ribeiro1 P J Sebastiao1 C Cruz1. Centro de Fisica da Materia Condensada (UL), Av. Prof. Gama Pinto 2, 1699 Lisboa Cedex, Portugal IST (UTL), Av. Rovisco Pais, 1049-001 Lisboa, Portugal ...

  13. High-Sensitivity Rheo-NMR Spectroscopy for Protein Studies.

    Science.gov (United States)

    Morimoto, Daichi; Walinda, Erik; Iwakawa, Naoto; Nishizawa, Mayu; Kawata, Yasushi; Yamamoto, Akihiko; Shirakawa, Masahiro; Scheler, Ulrich; Sugase, Kenji

    2017-07-18

    Shear stress can induce structural deformation of proteins, which might result in aggregate formation. Rheo-NMR spectroscopy has the potential to monitor structural changes in proteins under shear stress at the atomic level; however, existing Rheo-NMR methodologies have insufficient sensitivity to probe protein structure and dynamics. Here we present a simple and versatile approach to Rheo-NMR, which maximizes sensitivity by using a spectrometer equipped with a cryogenic probe. As a result, the sensitivity of the instrument ranks highest among the Rheo-NMR spectrometers reported so far. We demonstrate that the newly developed Rheo-NMR instrument can acquire high-quality relaxation data for a protein under shear stress and can trace structural changes in a protein during fibril formation in real time. The described approach will facilitate rheological studies on protein structural deformation, thereby aiding a physical understanding of shear-induced amyloid fibril formation.

  14. Study of poly butadiene molecular mobility by NMR in the solid state

    International Nuclear Information System (INIS)

    Coelho, Maria Rita G.; San Gil, Rosane A.S.; Tavares, Maria Ines B.

    1995-01-01

    This work has aimed to study commercial poly butadiene using 13 C NMR spectroscopy in the solid state through relaxation time investigation, in order to characterize its molecular mobility in the solid state and structure. NMR spectra are presented and analysed and chemical shifts are also observed and discussed

  15. Relaxation of Anisotropic Glasses

    DEFF Research Database (Denmark)

    Deubener, Joachim; Martin, Birgit; Wondraczek, Lothar

    2004-01-01

    . When the load was removed at room temperature a permanent optical anisotropy (birefringence) was observed only perpendicular to cylinder axis and the pressure direction indicating complete elimination of thermal stresses. Relaxation of structural anisotropy was studied from reheating experiments using...... the energy release, thermo-mechanical and optical relaxation behaviour are drawn....

  16. β-NMR study of isolated 8Li+ in the enhanced paramagnet platinum

    Science.gov (United States)

    Ofer, Oren; Chow, K. H.; Fan, I.; Egilmez, M.; Parolin, T. J.; Hossain, M. D.; Jung, J.; Salman, Z.; Kiefl, R. F.; Levy, C. D. P.; Morris, G. D.; Pearson, M. R.; Saadaoui, H.; Song, Q.; Wang, D.; MacFarlane, W. A.

    2012-08-01

    We report β-detected nuclear magnetic resonance (β-NMR) measurements of 8Li+ implanted into high purity Pt. The frequency of the 8Li β-NMR resonance and the spin-lattice relaxation rates 1/T1 were measured at temperatures ranging from 3 to 300 K. Remarkably, both the spin-lattice relaxation rate and the Knight shift K depend linearly on temperature T although the bulk susceptibility does not. K is found to scale with the Curie-Weiss dependence of the Pt susceptibility extrapolated to low temperatures. This is attributed to a defect response of the enhanced paramagnetism of Pt, i.e., the presence of the interstitial Li+ locally relieves the tendency for the Curie-Weiss susceptibility to saturate at low T. We propose that the low temperature saturation in χ of Pt may be related to an interband coupling between the s and d bands that is disrupted locally by the presence of the Li+.

  17. An NMR study of sodium poly(acrylate) adsorption on rutile

    International Nuclear Information System (INIS)

    Evershed, P.G.

    2000-05-01

    Adsorption of sodium poly(acrylate) (PA) on rutile particles in aqueous dispersion was studied. Two different molecular weights of PA (2,100 and 30,000) and two different grades of rutile were used. Various pHs, ionic strengths, and PA concentrations were investigated. The main technique employed was measurement of the transverse NMR relaxation of the solvent using the CPMG pulse sequence. Other techniques used to augment these results include electroacoustics, scanning electron microscopy, and measurement of the adsorbed amount of PA by a fluorescence spectroscopy technique using the dye acridine orange. Adsorption of small ions such as Na + , K + , Cl - , and NO 3 - to the particle surface was found to have a significant effect on the measured transverse relaxation rate, that was dependent on the pH and the concentration of the ions. There was usually an additional effect on the relaxation due to the adsorbed PA, but only qualitative rather than quantitative information about the adsorption could be deduced. At pH 4 especially, it could be seen that the results were consistent with the common assertion that polymers adsorb in a flat conformation at low concentration, and only become looped when all of the surface sites are full. At pH 10 it was found that the relaxation rate for the longer chain PA samples fluctuated over time, indicating metastable PA conformations. There were also unusual trends in the relaxation rate for these samples, which could be due to a previously proposed small ion complexation mechanism for PA adsorption at high pH in this system. It is possible that an extensive and comprehensive study using this technique, investigating all of the relevant parameters, especially the effect of small ion adsorption, may allow a quantitative description of the adsorbed conformation. (author)

  18. Effect of residual stress relaxation by means of local rapid induction heating on stress corrosion cracking behavior and electrochemical characterization of welded Ti-6Al-4V alloy under slow strain rate test

    Science.gov (United States)

    Liu, Yan; Tang, Shawei; Liu, Guangyi; Sun, Yue; Hu, Jin

    2017-05-01

    In this study, a welded Ti-6Al-4V alloy was treated by means of local rapid induction heating in order to relax the residual stress existed in the weldment. The welded samples were heat treated at the different temperatures. The stress corrosion cracking behavior and electrochemical characterization of the as-welded samples before and after the post weld heat treatment as a function of residual stress were investigated. Electrochemical impedance spectroscopy measurements of the samples under slow strain rate test were performed in a LiCl-methanol solution. The results demonstrated that the residual stress in the as-welded sample was dramatically reduced after the post weld heat treatment, and the residual stress decreased with the increase in the heat treatment temperature. The stress corrosion cracking susceptibility and electrochemical activity of the as-welded sample were significantly reduced after the heat treatment due to the relaxation of the residual stress, which gradually decreased with the decreasing value of the residual stress distributed in the heat treated samples.

  19. Permeability Estimation in Chalk Using NMR and a Modified Kozeny Equation

    DEFF Research Database (Denmark)

    Meireles, Leonardo Teixeira Pinto; Alam, Mohammad Monzurul; Fabricius, Ida Lykke

    2017-01-01

    calibration. To translate the T2 relaxation distribution into pore size, an analogy is made between the NMR T2 data and the MICP output. Specific surface data acquired by the Brunauer Emmett Teller method (BET) was used to aid the interpretation of the surface relaxivity. The model was tested in a chalk...

  20. MR fingerprinting using the quick echo splitting NMR imaging technique.

    Science.gov (United States)

    Jiang, Yun; Ma, Dan; Jerecic, Renate; Duerk, Jeffrey; Seiberlich, Nicole; Gulani, Vikas; Griswold, Mark A

    2017-03-01

    The purpose of the study is to develop a quantitative method for the relaxation properties with a reduced radio frequency (RF) power deposition by combining magnetic resonance fingerprinting (MRF) technique with quick echo splitting NMR imaging technique (QUEST). A QUEST-based MRF sequence was implemented to acquire high-order echoes by increasing the gaps between RF pulses. Bloch simulations were used to calculate a dictionary containing the range of physically plausible signal evolutions using a range of T 1 and T 2 values based on the pulse sequence. MRF-QUEST was evaluated by comparing to the results of spin-echo methods. The specific absorption rate (SAR) of MRF-QUEST was compared with the clinically available methods. MRF-QUEST quantifies the relaxation properties with good accuracy at the estimated head SAR of 0.03 W/kg. T 1 and T 2 values estimated by MRF-QUEST are in good agreement with the traditional methods. The combination of the MRF and the QUEST provides an accurate quantification of T 1 and T 2 simultaneously with reduced RF power deposition. The resulting lower SAR may provide a new acquisition strategy for MRF when RF energy deposition is problematic. Magn Reson Med 77:979-988, 2017. © 2016 International Society for Magnetic Resonance in Medicine. © 2016 International Society for Magnetic Resonance in Medicine.

  1. Delta Relaxation Enhanced Magnetic Resonance

    Science.gov (United States)

    Alford, Jamu K.

    Generally speaking, targeted molecular imaging has always been difficult to perform with magnetic resonance. The difficulty does not arise with the magnetic resonance imaging (MRI) technique or equipment itself, but rather with the targeted contrast agents, which the method requires. Also referred to as activatable contrast agents, or MRI probes, targeted contrast agents are pharmaceuticals that will selectively bind to a particular biological (target) molecule. They are used to highlight a certain tissue or the difference between healthy and diseased tissue. Unfortunately, nearly all MRI probes are non-specific, causing localized increases in MR image intensity in both the unbound and target-bound states. Therefore, brightening in a conventional MRI image, following probe injection, does not positively indicate the presence of the target molecule. Herein, a novel method known as delta relaxation enhanced magnetic resonance (dreMR, pronounced "dreamer") is presented that utilizes variable magnetic field technology to produce image contrast related to the dependence of the sample's longitudinal relaxation rates upon the strength of the main magnetic field of the MRI scanner. Since only bound contrast agent shows significant magnetic field dependence, it is an indicator of the bound probe, which is in turn a marker for the target molecule. This work details the development of the dreMR method, focusing on the specialized hardware necessary to provide a clinical, static-field MRI the ability to modulate its main magnetic field throughout an MRI sequence. All modifications were performed in such a manner that the host MRI system was not degraded or permanently modified in any way. The three parts of this technology are: the insertable electromagnet, the power supply system and the control system. The insertable electromagnet modifies the magnetic field, the power system drives the electromagnet, and the control system generates the magnetic field waveform envelope and

  2. 209Bi NMR in heavy-electron system YbBiPt

    International Nuclear Information System (INIS)

    Reyes, A.P.; Le, L.P.; Heffner, R.H.; Ahrens, E.T.; Fisk, Z.; Canfield, P.C.

    1994-01-01

    Bismuth NMR Knight shift and spin lattice relaxation rate 1/T 1 are reported between 35--325K in the low-carrier heavy fermion system YbBiPt. The Knight shift is strongly temperature dependent and negative. Its temperature dependence tracks the bulk susceptibility with a hyperfine coupling constant A hf = -7.89 kOe/μB. At low temperatures 1/T 1 exhibits a dramatic increase, such that the average 4f spin correlation time τ f shows a crossover behavior at about 75K. The rate 1/τ f is proportional to temperature, but with a different proportionality constant above and below about 75K. The linear temperature dependence is consistent with non-interacting 4f local moments which are relaxed via Korringa-type scattering with the conduction electrons. Below 75K, we infer that the reduced thermal excitation of a higher crystal-field multiplet is responsible for the dramatic decrease in the rate of 4f relaxation

  3. Recent excitements in protein NMR: Large proteins and biologically ...

    Indian Academy of Sciences (India)

    The advent of Transverse Relaxation Optimized SpectroscopY (TROSY) and perdeuteration allowed biomolecularNMR spectroscopists to overcome the size limitation barrier (~20 kDa) in de novo structure determination of proteins.The utility of these techniques was immediately demonstrated on large proteins and protein ...

  4. Separation of components of a broad 1H-NMR composite signal by means of nutation experiments under low amplitude radiofrequency fields. Application to the water signal in synthetic clays

    International Nuclear Information System (INIS)

    Trausch, G.

    2006-11-01

    Nowadays, geologic nuclear waste storage is envisioned according to a multi-layer model which implies clays. The latter exhibit retention capacities and low permeability to water; that is why they are considered as a good candidate for engineered barriers to radioactive waste disposal. The present work here aims at studying transport phenomena which involve water molecules in three samples of synthetic clays (two of them exhibiting a Pake doublet) by means of Nuclear Magnetic Resonance (NMR). The first chapter describes structural properties of clays and presents the state-of-art of NMR and other experimental techniques used for such systems. The second chapter deals with the interpretation and the simulation of each conventional proton spectrum. These simulations allow us to evidence and to characterize a chemical exchange phenomenon. The third chapter is dedicated to original nutation experiments performed under low radiofrequency field in the case of broad NMR signal. It is shown that this type of NMR experiment can yield the number and the proportion of each species contributing to the whole signal. These results are exploited in the fourth chapter for processing relaxation and diffusion experiments. Finally, the diffusion coefficients obtained by NMR are divided by a factor 4 with respect to pure water while relaxation rates are two orders of magnitude greater. (author)

  5. Selective observation of the Cu(I)-amicyanin metal site by paramagnetic NMR on partially oxidised samples

    International Nuclear Information System (INIS)

    Salgado, Jesus; Kalverda, Arnout P.; Canters, Gerard W.

    1997-01-01

    The relaxation enhancement caused by paramagnetic copper(II) is used to observe selectively the metal site of copper(I)-amicyanin by one- and two-dimensional NMR spectroscopy. The paramagnetic effect is communicated to the diamagnetic protein through the electron self-exchange reaction in partially oxidised samples, and can be used for the selective detection of protons around the metal. Relaxation-selective NMR pulse sequences, like super-WEFT and WEFT-NOESY, are used to achieve the desired selection of the signals. The spectra obtained show well-resolved signals corresponding to protons within a radius of∼7 A from the metal, including almost all protons from the coordinated residues. A significant increase in resolution as well as selection of the most relevant part of the protein (close to the active centre) are the principal advantages of this technique, which can be used to obtain specific information about the metal site in blue copper proteins, to assist in the assignment of their NMR spectra and to determine functional properties like the electron self-exchange rate

  6. Magnetic excitations in the t - J model: application to neutron and NMR experiments in high Tc materials

    International Nuclear Information System (INIS)

    Grempel, D.R.; Lavagna, M.

    1992-01-01

    We study the dynamic magnetic susceptibility of the two-dimensional t-J model using a mean-field bond slave boson approach coupled to self-consistent spin-fluctuation theory. The spectrum of the magnetic fluctuation exhibits interesting temperature dependence that is a consequence of lattice effects. We apply our results to the interpretation of recent neutron and NMR measurements on YBa 2 Cu 3 O 6+x systems. Our predictions for the temperature dependence of the nuclear spin relaxation rate are in good agreement with experiment. (author)

  7. Relaxation of the one child policy and trends in caesarean section rates and birth outcomes in China between 2012 and 2016: observational study of nearly seven million health facility births.

    Science.gov (United States)

    Liang, Juan; Mu, Yi; Li, Xiaohong; Tang, Wen; Wang, Yanping; Liu, Zheng; Huang, Xiaona; Scherpbier, Robert W; Guo, Sufang; Li, Mingrong; Dai, Li; Deng, Kui; Deng, Changfei; Li, Qi; Kang, Leni; Zhu, Jun; Ronsmans, Carine

    2018-03-05

    To examine how the relaxation of the one child policy and policies to reduce caesarean section rates might have affected trends over time in caesarean section rates and perinatal and pregnancy related mortality in China. Observational study. China's National Maternal Near Miss Surveillance System (NMNMSS). 6 838 582 births at 28 completed weeks or more of gestation or birth weight ≥1000 g in 438 hospitals in the NMNMSS between 2012 and 2016. Obstetric risk was defined using a modified Robson classification. The main outcome measures were changes in parity and age distributions and relative frequency of each Robson group, crude and adjusted trends over time in caesarean section rates within each risk category (using Poisson regression with a robust variance estimator), and trends in perinatal and pregnancy related mortality over time. Caesarean section rates declined steadily between 2012 and 2016 (crude relative risk 0.91, 95% confidence interval 0.89 to 0.93), reaching an overall hospital based rate of 41.1% in 2016. The relaxation of the one child policy was associated with an increase in the proportion of multiparous births (from 34.1% in 2012 to 46.7% in 2016), and births in women with a uterine scar nearly doubled (from 9.8% to 17.7% of all births). Taking account of these changes, the decline in caesarean sections was amplified over time (adjusted relative risk 0.82, 95% confidence interval 0.81 to 0.84). Caesarean sections declined noticeably in nulliparous women (0.75, 0.73 to 0.77) but also declined in multiparous women without a uterine scar (0.65, 0.62 to 0.77). The decrease in caesarean section rates was most pronounced in hospitals with the highest rates in 2012, consistent with the government's policy of targeting hospitals with the highest rates. Perinatal mortality declined from 10.1 to 7.2 per 1000 births over the same period (0.87, 0.83 to 0.91), and there was no change in pregnancy related mortality over time. China is the only country that

  8. NMR of geophysical drill cores with a mobile Halbach scanner

    International Nuclear Information System (INIS)

    Talnishnikh, E.

    2007-01-01

    This thesis is devoted to a mobile NMR with an improved Halbach scanner. This is a lightweight tube-shaped magnet with sensitive volume larger and a homogeneity of the magnetic field higher than the previous prototype version. The improved Halbach scanner is used for analysis of water-saturated drill cores and plugs with diameters up to 60 mm. To provide the analysis, the standard 1D technique with the CPMG sequence as well as 2D correlation experiments were successfully applied and adapted to study properties of fluid-saturated sediments. Afterwards the Halbach scanner was calibrated to fast non-destructive measurements of porosity, relaxation time distributions, and estimation of permeability. These properties can be calculated directly from the NMR data using the developed methodology. Any independent measurements of these properties with other methods are not needed. One of the main results of this work is the development of a new NMR on-line core scanner for measurements of porosity in long cylindrical and semi cylindrical drill cores. Also dedicated software was written to operate the NMR on-line core scanner. The physical background of this work is the study of the diffusion influence on transverse relaxation. The diffusion effect in the presence of internal gradients in porous media was probed by 1D and 2D experiments. The transverse relaxation time distributions obtained from 1D and from 2D experiments are comparable but different in fine details. Two new methodologies were developed based on the results of this study. First is the methodology quantifying the influence of diffusion in the internal gradients of water-saturated sediments on transverse relaxation from 2D correlation experiments. The second one is the correction of the permeability estimation from the NMR data taking in account the influence of the diffusion. Furthermore, PFG NMR technique was used to study restricted diffusion in the same kind of samples. Preliminary results are reported

  9. NMR of geophysical drill cores with a mobile Halbach scanner

    Energy Technology Data Exchange (ETDEWEB)

    Talnishnikh, E.

    2007-08-21

    This thesis is devoted to a mobile NMR with an improved Halbach scanner. This is a lightweight tube-shaped magnet with sensitive volume larger and a homogeneity of the magnetic field higher than the previous prototype version. The improved Halbach scanner is used for analysis of water-saturated drill cores and plugs with diameters up to 60 mm. To provide the analysis, the standard 1D technique with the CPMG sequence as well as 2D correlation experiments were successfully applied and adapted to study properties of fluid-saturated sediments. Afterwards the Halbach scanner was calibrated to fast non-destructive measurements of porosity, relaxation time distributions, and estimation of permeability. These properties can be calculated directly from the NMR data using the developed methodology. Any independent measurements of these properties with other methods are not needed. One of the main results of this work is the development of a new NMR on-line core scanner for measurements of porosity in long cylindrical and semi cylindrical drill cores. Also dedicated software was written to operate the NMR on-line core scanner. The physical background of this work is the study of the diffusion influence on transverse relaxation. The diffusion effect in the presence of internal gradients in porous media was probed by 1D and 2D experiments. The transverse relaxation time distributions obtained from 1D and from 2D experiments are comparable but different in fine details. Two new methodologies were developed based on the results of this study. First is the methodology quantifying the influence of diffusion in the internal gradients of water-saturated sediments on transverse relaxation from 2D correlation experiments. The second one is the correction of the permeability estimation from the NMR data taking in account the influence of the diffusion. Furthermore, PFG NMR technique was used to study restricted diffusion in the same kind of samples. Preliminary results are reported

  10. Relaxation Techniques for Health

    Science.gov (United States)

    ... combined with guided imagery and breathing exercises. Self-Hypnosis In self-hypnosis programs, people are taught to produce the relaxation ... have shown that women who were taught self-hypnosis have a decreased need for pain medicine during ...

  11. NMR-spectroscopy

    International Nuclear Information System (INIS)

    Lundin, A.G.; Fedin, Eh.I.

    1986-01-01

    Physical foundations are given and the most important areas of nuclear magnetic resonance (NMR) application in physics, chemistry, biology are described. A detailed review of the investigations conducted and the NMR applications in different science and technology fields is presented. The method basic experimental variants, including such new ones as high resolution in a solid body; rare isotope resonance; two-dimensional and multi-quantum fourier-spectroscopy; large molecule NMR; NMR tomography and NMR intrascopy etc. are considered. The instruments are briefly described. NMR is characterized as one of the most important investigation methods of the material composition, its molecular and crystal structure, visualization of the living organism and nonmetallic object inner structure

  12. NMR detects molecular interactions of graphene with aromatic and aliphatic hydrocarbons in water

    Science.gov (United States)

    Bichenkova, Elena V.; Raju, Arun P. A.; Burusco, Kepa K.; Kinloch, Ian A.; Novoselov, Kostya S.; Clarke, David J.

    2018-03-01

    Polyaromatic carbon is widely held to be strongly diamagnetic and hydrophobic, with textbook van der Waals and ‘π-stacked’ binding of hydrocarbons, which disrupt their self-assembled supramolecular structures. The NMR of organic molecules sequestered by polyaromatic carbon is expected to be dominated by shielding from the orbital diamagnetism of π electrons. We report the first evidence of very different polar and magnetic behavior in water, wherein graphene remained well-dispersed after extensive dialysis and behaved as a 1H-NMR-silent ghost. Magnetic effects dominated the NMR of organic structures which interacted with graphene, with changes in spin-spin coupling, vast increase in relaxation, line broadening and decrease in NMR peak heights when bound to graphene. However, the interactions were weak, reversible and did not disrupt organic self-assemblies reliant on hydrophobic ‘π-stacking’, even when substantially sequestered on the surface of graphene by the high surface area available. Interacting assemblies of aromatic molecules retained their strongly-shielded NMR signals and remained within self-assembled structures, with slower rates of diffusion from association with graphene, but with no further shielding from graphene. Binding to graphene was selective for positively-charged organic assemblies, weaker for non-aromatic and negligible for strongly-negatively-charged molecules, presumably repelled by a negative zeta potential of graphene in water. Stronger binders, or considerable excess of weaker binders readily reversed physisorption, with no evidence of structural changes from chemisorption. The fundamental nature of these different electronic interactions between organic and polyaromatic carbon is considered with relevance to electronics, charge storage, sensor, medical, pharmaceutical and environmental research.

  13. On the invariance of spatially inhomogeneous relaxation processes

    Energy Technology Data Exchange (ETDEWEB)

    Eliazar, Iddo [Department of Technology Management, Holon Institute of Technology, PO Box 305, Holon 58102 (Israel); Benichou, Olivier, E-mail: eliazar@post.tau.ac.il, E-mail: benichou@lptmc.jussieu.fr [UPMC Universite de Paris 06, UMR 7600 Laboratoire de Physique Theorique de la Matiere Condensee, 4 Place Jussieu, F-75005 Paris (France)

    2012-01-13

    We consider a general relaxation model based on an ensemble of particles propagating randomly in a general space. The particles' trajectories are independent and identically distributed copies of an arbitrary random spatial curve, and each particle has its own parameter triplet: initiation epoch, velocity and relaxation coefficient. The relaxation rate of each particle is dynamic-depending on its spatial location and quantified by an arbitrary spatial 'landscape function'. We study the relaxation rate of the entire ensemble and characterize the class of Poissonian randomizations of the particles' parameters that render the ensemble's relaxation rate invariant with respect to both the particles' trajectories and the landscape function. The invariant relaxation rates turn out to be governed by power laws and display a statistical behavior analogous to anomalous diffusion. Applications range from chemical reactions to target search and intelligence sifting. (paper)

  14. NMR of newly accessible nuclei. Volume 2; chemically and biochemically important elements

    International Nuclear Information System (INIS)

    Laszlo, P.

    1983-01-01

    This two-volume work constitutes a state-of-the-art review of multinuclear magnetic resonance. It features contributions by an international group of eminent scientists and emphasizes methods of study. Volume 1 discusses the fundamental principles of recent developments in NMR and special applications selected for their timeliness and importance. In Volume 2 the contributions provide a systematic survey of the most important nuclei and families of nuclei in the periodic table. This organization ensures in-depth coverage of the subject and facilitates more effective retrieval of information. An important feature of this work is the special emphasis on the exploitation of relaxation processes, both as a new dimension of NMR that became prominent in the 1960s and 1970s and as a source of information on significant parameters for studying the thermodynamics and kinetics of binding. Thus, in these volumes, the ''three dimensions'' of a spectral line-frequency, scalar couplings, and relaxation rates are treated not as discrete entities, but as inseparable elements in a single informational continuum

  15. Nuclear spin relaxation of 8Li in a thin film of La 0.67Ca 0.33MnO 3

    Science.gov (United States)

    Miller, R. I.; Arseneau, D.; Chow, K. H.; Daviel, S.; Engelbertz, A.; Hossain, MD.; Keeler, T.; Kiefl, R. F.; Kreitzman, S.; Levy, C. D. P.; Morales, P.; Morris, G. D.; MacFarlane, W. A.; Parolin, T. J.; Poutissou, R.; Saadaoui, H.; Salman, Z.; Wang, D.; Wei, J. Y. T.

    2006-03-01

    We report β-NMR measurements of the nuclear spin relaxation rate (1/T1) in a thin film of La 0.67Ca 0.33MnO 3 (LCMO) using a low-energy beam of spin-polarized 8Li. In a small magnetic field of 150 G, there is a broad peak in 1/T1 near the Curie temperature (Tc=259 K) and a dramatic decrease in 1/T1 at lower temperatures. This is attributed to a critical slowing down of the spin fluctuations near Tc and freezing of the magnetic excitations at low temperatures, respectively. In addition, there is a small amplitude, slow relaxing component at high temperatures, which we attribute to 8Li in the SrTiO 3 substrate. There is an indication that the spin relaxation rate in the substrate is also peaked at Tc due to close proximity to the magnetic film. These results establish that low-energy β-NMR can be used as a probe of magnetic fluctuations in magnetic thin films over a wide range of temperatures.

  16. Enhancing the detection of edges and non-differentiable points in an NMR spectrum using delayed-acquisition

    Science.gov (United States)

    Gong, Zhaoyuan; Walls, Jamie D.

    2018-02-01

    Delayed-acquisition, which is a common technique for improving spectral resolution in Fourier transform based spectroscopies, typically relies upon differences in T2 relaxation rates that are often due to underlying differences in dynamics and/or complexities of the spin systems being studied. After an acquisition delay, the broad signals from fast T2 -relaxing species are more suppressed relative to the sharp signals from slow T2 -relaxing species. In this paper, an alternative source of differential "dephasing" under delayed-acquisition is demonstrated that is based solely upon the mathematical properties of the line shape and is independent of the underlying spin dynamics and/or complexity. Signals associated with frequencies where the line shape either changes sharply and/or is non-differentiable at some finite order dephase at a much slower rate than those signals associated with frequencies where the line shape is smooth. Experiments employing delayed-acquisition to study interfaces in biphasic samples, to measure spatially-dependent longitudinal relaxation, and to highlight sharp features in NMR spectra are presented.

  17. Proton relaxation relationships of human and animal tissues in vitro. Changes due to autolysis and fixing

    International Nuclear Information System (INIS)

    Grodd, W.; Schmitt, W.G.H.

    1983-01-01

    The results of measurements of proton relaxation times of various tissues from rats, pigs and humans are reported; these were obtained by a resonance spectroscope at 20 MHz and 40 0 C. There were specific differences in both relaxation times (T 1 and T 2 ) of the liver and spleen. There was a difference of more than 150 ms in the longitudinal relaxation time between grey and white cerebral tissue. Autolytic changes show an increase in both relaxation times. Fixation produced a reduction in T 1 only. The significance of these findings for NMR tomography is discussed. (orig.) [de

  18. β-detected NMR of 8Li in the normal state of 2H- NbSe2

    Science.gov (United States)

    Wang, D.; Hossain, M. D.; Salman, Z.; Arseneau, D.; Chow, K. H.; Daviel, S.; Keeler, T. A.; Kiefl, R. F.; Kreitzman, S. R.; Levy, C. D. P.; Morris, G. D.; Miller, R. I.; MacFarlane, W. A.; Parolin, T. J.; Saadaoui, H.

    2006-03-01

    β-NMR of isolated 8Li has been investigated in the normal state of 2H- NbSe2. In a high magnetic field of 3 T a single resonance is observed with a Gaussian line width of 3.5 kHz. The line shape varies weakly as function of magnetic field and temperature but has a strong orientation dependence. The nuclear electric quadrupole splitting is unresolved implying that the electric field gradients are 10-100 times smaller than in other non-cubic crystals. The nuclear spin relaxation rate is also anomalously small but varies linearly with temperature as expected for Korringa relaxation in a metal. These results suggest that Li adopts an interstitial position between the weakly coupled NbSe2 layers and away from the conduction band.

  19. {beta}-detected NMR of {sup 8}Li in the normal state of 2H-NbSe{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Wang, D. [Department of Physics and Astronomy, University of B.C., Vancouver, V6T1Z1 (Canada); Hossain, M.D. [Department of Physics and Astronomy, University of B.C., Vancouver, V6T1Z1 (Canada); Salman, Z. [TRIUMF, 4004 Wesbrook Mall, University of B.C., Vancouver, V6T2A3 (Canada); Arseneau, D. [TRIUMF, 4004 Wesbrook Mall, University of B.C., Vancouver, V6T2A3 (Canada); Chow, K.H. [Department of Physics, University of Alberta, Edmonton Alberta, T6G2J1 (Canada); Daviel, S. [TRIUMF, 4004 Wesbrook Mall, University of B.C., Vancouver, V6T2A3 (Canada); Keeler, T.A. [Department of Physics and Astronomy, University of B.C., Vancouver, V6T1Z1 (Canada); Kiefl, R.F. [Department of Physics and Astronomy, University of B.C., Vancouver, V6T1Z1 (Canada)]. E-mail: kiefl@triumf.ca; Kreitzman, S.R. [TRIUMF, 4004 Wesbrook Mall, University of B.C., Vancouver, V6T2A3 (Canada); Levy, C.D.P. [TRIUMF, 4004 Wesbrook Mall, University of B.C., Vancouver, V6T2A3 (Canada); Morris, G.D. [TRIUMF, 4004 Wesbrook Mall, University of B.C., Vancouver, V6T2A3 (Canada); Miller, R.I. [TRIUMF, 4004 Wesbrook Mall, University of B.C., Vancouver, V6T2A3 (Canada); MacFarlane, W.A. [Department of Chemistry, University of B.C., Vancouver, V6T1Z1 (Canada); Parolin, T.J. [Department of Chemistry, University of B.C., Vancouver, V6T1Z1 (Canada); Saadaoui, H. [Department of Physics and Astronomy, University of B.C., Vancouver, V6T1Z1 (Canada)

    2006-03-31

    {beta}-NMR of isolated {sup 8}Li has been investigated in the normal state of 2H-NbSe{sub 2}. In a high magnetic field of 3T a single resonance is observed with a Gaussian line width of 3.5kHz. The line shape varies weakly as function of magnetic field and temperature but has a strong orientation dependence. The nuclear electric quadrupole splitting is unresolved implying that the electric field gradients are 10-100 times smaller than in other non-cubic crystals. The nuclear spin relaxation rate is also anomalously small but varies linearly with temperature as expected for Korringa relaxation in a metal. These results suggest that Li adopts an interstitial position between the weakly coupled NbSe{sub 2} layers and away from the conduction band.

  20. Study of paramagnetic contrast agents for NMR imaging: theoretical and experimental aspects (the case of Mn2+ ion)

    International Nuclear Information System (INIS)

    Chavoix, M.E.

    1984-06-01

    The use of contrast enhancing agents and the evaluation of magnetic properties of tissues, extend the diagnostic usefulness of Nuclear Magnetic Resonance (NMR) imaging. From this point of view, proton T 1 (spin-lattice) relaxation times of rat tissue, following parenteral administration of Mn(II) to increase the relaxation rate (R 1 =1/T 1 ), have been studied at 20 MHz. Differenciation of free (MF) and bound (Mb) manganese in these tissues was thus determined by measuring, total exogenous Mn ++ ions by Atomic Absorption spectrometry and free (non protein complexed) ions by Electron Spin Resonance Analysis. From these results, the diffusion of Mn ++ into various organs, was evaluated 15 min. after injection. A significant difference in the fixation of manganese occured between the liver and the pancreas with uptakes of 50% and 1% of the administration dose respectively [fr

  1. The effect of silica fume on early hydration of white Portland cement via fast field cycling-NMR relaxometry

    Science.gov (United States)

    Badea, Codruţa.; Bede, Andrea; Ardelean, Ioan

    2017-12-01

    Fast Field Cycling (FFC) nuclear magnetic resonance (NMR) relaxometry is used to monitor the influence introduced on the hydration process by the addition of silica fume in a cement paste mixture, prepared with white Portland cement. The FFC relaxometry technique was implemented due to its sensitivity to a wider range of molecular motions, which gives more information than other relaxometry techniques performed at a fixed frequency. This unique feature of FFC relaxometry allows better separation of the surface and bulk contributions from the global measured relaxation rate. The relaxation process is dominated by the interaction of water protons with the paramagnetic centers located on the surface of cement grains. In the frame of a two-phase exchange model, this allows the monitoring of the influence of an addition of silica fume on the evolution of surface-to-volume ratio during the early hydration stages.

  2. Characterization of threonine side chain dynamics in an antifreeze protein using natural abundance {sup 13}C NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Daley, Margaret E.; Sykes, Brian D. [University of Alberta, Department of Biochemistry, CIHR Group in Protein Structure and Function and Protein Engineering Network of Centres of Excellence (Canada)

    2004-06-15

    The dynamics of threonine side chains of the Tenebrio molitor antifreeze protein (TmAFP) were investigated using natural abundance {sup 13}C NMR. In TmAFP, the array of threonine residues on one face of the protein is responsible for conferring its ability to bind crystalline ice and inhibit its growth. Heteronuclear longitudinal and transverse relaxation rates and the {sup 1}H-{sup 13}C NOE were determined in this study. The C{alpha}H relaxation measurements were compared to the previously measured {sup 15}N backbone parameters and these are found to be in agreement. For the analysis of the threonine side chain motions, the model of restricted rotational diffusion about the {chi}{sub 1} dihedral angle was employed [London and Avitabile (1978) J. Am. Chem. Soc., 100, 7159-7165]. We demonstrate that the motion experienced by the ice binding threonine side chains is highly restricted, with an approximate upper limit of less than {+-}25 deg.

  3. Prediction of stress relaxation under multiaxial stresses

    International Nuclear Information System (INIS)

    Sandstroem, R.; Malen, K.; Otterberg, R.

    1981-01-01

    Computations have been made of the relaxation of residual stresses in a thick walled tube under conditions corresponding to commercial stress relief heat treatment of the nuclear reactor pressure vessel steel A533B. The distribution of residual stresses which were introduced was peaked around a given radius in the tube. The relax- ation of the equivalent stresses followed almost exactly a uniaxial behavior. The relaxation rate of the hydrostatic stress was of about the same order or slower than that of the equivalent stress. The time dependence of the hydrostatic stress was mainly controlled by the initial magnitude of hydrostatic stress whereas the degree of the constraint and thereby the boundary conditions at the tube walls had only a small influence. The relaxation rate decreased with increasing initial magnitude of the hydrostatic stress. The computed relaxation behaviour under multiaxial stress could be rationalized in terms of a developed model. This model was also suc- cessfully applied to Gott's measurements on stress relaxation during stress relief heat treatment of a welded joint between 130 mm thick plates of A533B where the stress state was highly triaxial. (Authors)

  4. Some nitrogen-14 NMR studies in solids

    Energy Technology Data Exchange (ETDEWEB)

    Pratum, T.K.

    1983-11-01

    The first order quadrupolar perturbation of the /sup 14/N NMR spectrum yields information regarding the static and dynamic properties of the surrounding electronic environment. Signal to noise problems caused by long /sup 14/N longitudinal relaxation times (T/sub 1/) and small equilibrium polarizations are reduced by rotating frame cross polarization (CP) experiments between /sup 14/N and /sup 1/H. Using quadrupolar echo and CP techniques, the /sup 14/N quadrupolar coupling constants (e/sup 2/qQ/h) and asymmetry parameters (eta) have been obtained for a variety of tetraalkylammonium compounds by observation of their quadrupolar powder patterns at various temperatures. For choline chloride and iodide the /sup 14/N NMR powder patterns exhibit the effects of anisotropic molecular motion, while choline bromide spectra show no such effects.

  5. Fully automated system for pulsed NMR measurements

    International Nuclear Information System (INIS)

    Cantor, D.M.

    1977-01-01

    A system is described which places many of the complex, tedious operations for pulsed NMR experiments under computer control. It automatically optimizes the experiment parameters of pulse length and phase, and precision, accuracy, and measurement speed are improved. The hardware interface between the computer and the NMR instrument is described. Design features, justification of the choices made between alternative design strategies, and details of the implementation of design goals are presented. Software features common to all the available experiments are discussed. Optimization of pulse lengths and phases is performed via a sequential search technique called Uniplex. Measurements of the spin-lattice and spin-spin relaxation times and of diffusion constants are automatic. Options for expansion of the system are explored along with some of the limitations of the system

  6. Some nitrogen-14 NMR studies in solids

    International Nuclear Information System (INIS)

    Pratum, T.K.

    1983-11-01

    The first order quadrupolar perturbation of the 14 N NMR spectrum yields information regarding the static and dynamic properties of the surrounding electronic environment. Signal to noise problems caused by long 14 N longitudinal relaxation times (T 1 ) and small equilibrium polarizations are reduced by rotating frame cross polarization (CP) experiments between 14 N and 1 H. Using quadrupolar echo and CP techniques, the 14 N quadrupolar coupling constants (e 2 qQ/h) and asymmetry parameters (eta) have been obtained for a variety of tetraalkylammonium compounds by observation of their quadrupolar powder patterns at various temperatures. For choline chloride and iodide the 14 N NMR powder patterns exhibit the effects of anisotropic molecular motion, while choline bromide spectra show no such effects

  7. {beta}-nmr of Palladium foil

    Energy Technology Data Exchange (ETDEWEB)

    Parolin, T.J. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Salman, Z. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Chakhalian, J. [Max-Plank Institute for Solid State Research, D-70569 Stuttgart (Germany); Wang, D. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Keeler, T.A. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Hossain, Md. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Kiefl, R.F. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Canadian Institute for Advanced Research (Canada); Chow, K.H. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2J1 (Canada); Morris, G.D. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Miller, R.I. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); MacFarlane, W.A. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada)]. E-mail: wam@chem.ubc.ca

    2006-03-31

    Beta-detected NMR ({beta}-nmr) of low-energy implanted {sup 8}Li{sup +} was studied in metallic palladium. The resonance was found to have a large negative shift with respect to the reference signal in the cubic insulator MgO. This shift exhibited significant temperature dependence on cooling below room temperature, approximately proportionate to the temperature-dependent spin susceptibility of pure Pd. Thus it is tentatively attributed to a Knight shift (K) caused by a large negative hyperfine coupling; a phenomenon common in transition metal ions, but not in alkalis. However, the spin-lattice relaxation of {sup 8}Li is much slower than expected from the Korringa law for such a large K. We compare results from samples of very different thicknesses: 12.5{mu}m foil and a 100nm thin film.

  8. NMR imaging of the cardiovascular system

    International Nuclear Information System (INIS)

    Canby, R.C.; Evanochko, W.T.; Pohost, G.M.

    1986-01-01

    Proton nuclear magnetic resonance (NMR) imaging permits high-resolution tomographic and three-dimensional images of the human body to be obtained without exposure to ionizing radiation. Such imaging not only yields anatomic resolution comparable to X-ray examinations but also provides a potential means to discriminate between healthy tissue and diseased tissue. This potential is based on certain NMR properties known as relaxation times, which determine, in part, the signal intensity in an image. These properties are related to such factors as the sizes and concentrations of proteins and mobile lipids and the compartmentalization of the protons of water. Although NMR imaging (also called magnetic resonance imaging, MRI) is becoming widely available for clinical use, application to the cardiovascular system, though promising, remains primarily a research tool. Gated proton NMR imaging can generate cardiac images with excellent morphologic detail and contrast; however, its ultimate importance as a cardiovascular diagnostic modality will depend on the development of several unique applications. These applications are discussed in this paper

  9. O17 and V51 NMR for the zigzag spin-1 chain compound CaV2O4

    Science.gov (United States)

    Zong, X.; Suh, B. J.; Niazi, A.; Yan, J. Q.; Schlagel, D. L.; Lograsso, T. A.; Johnston, D. C.

    2008-01-01

    V51 NMR studies on CaV2O4 single crystals and O17 NMR studies on O17 -enriched powder samples are reported. The temperature dependences of the O17 NMR linewidth and nuclear spin-lattice relaxation rate give strong evidence for a long-range antiferromagnetic transition at TN=78K in the powder. Magnetic susceptibility measurements show that TN=69K in the crystals. A zero-field V51 NMR signal was observed at low temperatures ( f≈237MHz at 4.2K ) in the crystals. The field-swept spectra with the field in different directions suggest the presence of two antiferromagnetic substructures. Each substructure is collinear, with the easy axes of the two substructures separated by an angle of 19(1)°, and with their average direction pointing approximately along the b axis of the crystal structure. The two spin substructures contain equal numbers of spins. The temperature dependence of the ordered moment, measured up to 45K , shows the presence of an energy gap EG in the antiferromagnetic spin wave excitation spectrum. Antiferromagnetic spin wave theory suggests that EG/kB lies between 64 and 98K .

  10. Stress corrosion crack initiation of Zircaloy-4 cladding tubes in an iodine vapor environment during creep, relaxation, and constant strain rate tests

    Science.gov (United States)

    Jezequel, T.; Auzoux, Q.; Le Boulch, D.; Bono, M.; Andrieu, E.; Blanc, C.; Chabretou, V.; Mozzani, N.; Rautenberg, M.

    2018-02-01

    During accidental power transient conditions with Pellet Cladding Interaction (PCI), the synergistic effect of the stress and strain imposed on the cladding by thermal expansion of the fuel, and corrosion by iodine released as a fission product, may lead to cladding failure by Stress Corrosion Cracking (SCC). In this study, internal pressure tests were conducted on unirradiated cold-worked stress-relieved Zircaloy-4 cladding tubes in an iodine vapor environment. The goal was to investigate the influence of loading type (constant pressure tests, constant circumferential strain rate tests, or constant circumferential strain tests) and test temperature (320, 350, or 380 °C) on iodine-induced stress corrosion cracking (I-SCC). The experimental results obtained with different loading types were consistent with each other. The apparent threshold hoop stress for I-SCC was found to be independent of the test temperature. SEM micrographs of the tested samples showed many pits distributed over the inner surface, which tended to coalesce into large pits in which a microcrack could initiate. A model for the time-to-failure of a cladding tube was developed using finite element simulations of the viscoplastic mechanical behavior of the material and a modified Kachanov's damage growth model. The times-to-failure predicted by this model are consistent with the experimental data.

  11. Detection of the sulfhydryl groups in proteins with slow hydrogen exchange rates and determination of their proton/deuteron fractionation factors using the deuterium-induced effects on the 13C(beta) NMR signals.

    Science.gov (United States)

    Takeda, Mitsuhiro; Jee, JunGoo; Terauchi, Tsutomu; Kainosho, Masatsune

    2010-05-05

    A method for identifying cysteine (Cys) residues with sulfhydryl (SH) groups exhibiting slow hydrogen exchange rates has been developed for proteins in aqueous media. The method utilizes the isotope shifts of the C(beta) chemical shifts induced by the deuteration of the SH groups. The 18.2 kDa E. coli peptidyl prolyl cis-trans isomerase b (EPPIb), which was selectively labeled with [3-(13)C;3,3-(2)H(2)]Cys, showed much narrower line widths for the (13)C(beta) NMR signals, as compared to those of the proteins labeled with either [3-(13)C]Cys or (3R)-[3-(13)C;3-(2)H]Cys. The (13)C(beta) signals of the two Cys residues of EPPIb, i.e. Cys-31 and Cys-121, labeled with [3-(13)C;3,3-(2)H(2)]Cys, split into four signals in H(2)O/D(2)O (1:1) at 40 degrees C and pH 7.5, indicating that the exchange rates of the side-chain SH's and the backbone amides are too slow to average the chemical shift differences of the (13)C(beta) signals, due to the two- and three-bond isotope shifts. By virtue of the well-separated signals, the proton/deuteron fractional factors for both the SH and amide groups of the two Cys residues in EPPIb could be directly determined, as approximately 0.4-0.5 for [SD]/[SH] and 0.9-1.0 for [ND]/[NH], by the relative intensities of the NMR signals for the isotopomers. The proton NOE's of the two slowly exchanging SH's were clearly identified in the NOESY spectra and were useful for the determining the local structure of EPPIb around the Cys residues.

  12. Earthquake sequence simulations of a fault in a viscoelastic material with a spectral boundary integral equation method: The effect of interseismic stress relaxation on a behavior of a rate-weakening patch

    Science.gov (United States)

    Miyake, Y.; Noda, H.

    2017-12-01

    Earthquake sequences involve many processes in a wide range of time scales, from quasistatic loading to dynamic rupture. At a depth of brittle-plastic transitional and deeper, rock behaves as a viscous fluid in a long timescale, but as an elastic material in a short timescale. Viscoelastic stress relaxation may be important in the interseismic periods at the depth, near the deeper limit of the seismogenic layer or the region of slow slip events (SSEs) [Namiki et al., 2014 and references therein]. In the present study, we implemented the viscoelastic effect (Maxwell material) in fully-dynamic earthquake sequence simulations using a spectral boundary integral equation method (SBIEM) [e.g., Lapusta et al., 2000]. SBIEM is efficient in calculation of convolutional terms for dynamic stress transfer, and the problem size is limited by the amount of memory available. Linear viscoelasticity could be implemented by convolution of slip rate history and Green's function, but this method requires additional memory and thus not suitable for the implementation to the present code. Instead, we integrated the evolution of "effective slip" distribution, which gives static stress distribution when convolved with static elastic Green's function. This method works only for simple viscoelastic property distributions, but such models are suitable for numerical experiments aiming basic understanding of the system behavior because of the virtue of SBIEM, the ability of fine on-fault spatial resolution and efficient computation utilizing the fast Fourier transformation. In the present study, we examined the effect of viscoelasticity on earthquake sequences of a fault with a rate-weakening patch. A series of simulations with various relaxation time tc revealed that as decreasing tc, recurrence intervals of earthquakes increases and seismicity ultimately disappears. As long as studied, this transition to aseismic behavior is NOT associated with SSEs. In a case where the rate-weakening patch

  13. Transport and NMR characteristics of the skutterudite-related compound Ca3Rh4Sn13

    Science.gov (United States)

    Tseng, C. W.; Kuo, C. N.; Li, B. S.; Wang, L. M.; Gippius, A. A.; Kuo, Y. K.; Lue, C. S.

    2018-02-01

    We report the electronic properties of the Yb3Rh4Sn13-type single crystalline Ca3Rh4Sn13 by means of the electrical resistivity, Hall coefficient, Seebeck coefficient, thermal conductivity, as well as 119Sn nuclear magnetic resonance (NMR) measurements. The negative sign of the Hall coefficient and Seebeck coefficient at low temperatures suggests that the n-type carriers dominate the electrical transport in Ca3Rh4Sn13, in contrast to the observations in Sr3Rh4Sn13 which has a p-type conduction. Such a finding indicates a significant difference in the electronic features between these two stannides. Furthermore, we analyzed the temperature-dependent 119Sn NMR spin-lattice relaxation rate for Ca3Rh4Sn13, (Sr0.7Ca0.3)3Rh4Sn13, and Sr3Rh4Sn13 to examine the change of the electronic Fermi-level density of states (DOS) in (Sr1-xCax)3Rh4Sn13. It indicates that the Sn 5s partial Fermi-level DOS enhances with increasing the Ca content, being consistent with the trend of the superconducting temperature. Since the total Fermi-level DOS usually obeys the same trend of the partial Fermi-level DOS, the NMR analysis provides microscopic evidence for the correlation between the electronic DOS and superconductivity of the (Sr1-xCax)3Rh4Sn13 system.

  14. Novel 1H NMR approach to quantitative tissue oximetry using hexamethyldisiloxane.

    Science.gov (United States)

    Kodibagkar, Vikram D; Cui, Weina; Merritt, Matthew E; Mason, Ralph P

    2006-04-01

    19F NMR spin-lattice relaxometry of hexafluorobenzene (HFB) has been shown to be a highly sensitive indicator of tumor oxygenation. In this study hexamethyldisiloxane (HMDSO) was identified as a proton NMR analog, and its potential as a probe for investigating dynamic changes in tissue oxygen tension (pO2) was evaluated. HMDSO has a single proton resonance (delta= -0.3 ppm) and the spin-lattice relaxation rate, Rl (= 1/T1) exhibits a linear dependence on pO2: R1 (s(-1)) = 0.1126 + 0.0013* pO2 (torr) at 37 degrees C. To demonstrate application in vivo, HMDSO was administered into healthy rat thigh muscle (100 microl) and tumors (50 microl). Local pO2 was determined by using pulse-burst saturation recovery (PBSR) 1H NMR spectroscopy to assess R1. Water and fat signals were effectively suppressed by frequency-selective excitation of the HMDSO resonance. Rat thigh muscle had a mean baseline pO2 of 35 +/- 11 torr, with a typical stability of +/-3 torr over 20 min, when the rats breathed air. Altering the inhaled gas to oxygen produced a significant increase in pO2 to 100-200 torr. In tumors, altering the inspired gas also produced significant (albeit generally smaller) changes. This new pO2 reporter molecule offers a potentially valuable new tool for investigating pO2 in vivo. (c) 2006 Wiley-Liss, Inc.

  15. Excited-state relaxation of some aminoquinolines

    Directory of Open Access Journals (Sweden)

    2006-01-01

    Full Text Available The absorption and fluorescence spectra, fluorescence quantum yields and lifetimes, and fluorescence rate constants ( k f of 2-amino-3-( 2 ′ -benzoxazolylquinoline (I, 2-amino-3-( 2 ′ -benzothiazolylquinoline (II, 2-amino-3-( 2 ′ -methoxybenzothiazolyl-quinoline (III, 2-amino-3-( 2 ′ -benzothiazolylbenzoquinoline (IV at different temperatures have been measured. The shortwavelength shift of fluorescence spectra of compounds studied (23–49 nm in ethanol as the temperature decreases (the solvent viscosity increases points out that the excited-state relaxation process takes place. The rate of this process depends essentially on the solvent viscosity, but not the solvent polarity. The essential increasing of fluorescence rate constant k f (up to about 7 times as the solvent viscosity increases proves the existence of excited-state structural relaxation consisting in the mutual internal rotation of molecular fragments of aminoquinolines studied, followed by the solvent orientational relaxation.

  16. Relaxation in magnetic nanostructures

    International Nuclear Information System (INIS)

    Novak, M.A.; Folly, W.S.D.; Sinnecker, J.P.; Soriano, S.

    2005-01-01

    Nanostructured magnetic materials present a wide range of magnetic relaxation phenomena. One problem in studying nanomagnetic granular materials is the strong dependence of the relaxation with the anisotropy barrier which, even for systems with narrow size distributions, brings difficulties in the analysis of the experimental data. Molecular magnetism, with the chemists' bottom-up approach to build molecular nanostructures, provides this field with some beautiful model systems, well ordered crystals of single molecule magnets, single molecule chains, molecular magnetic multilayers and others novelties to appear. Most of these systems present slow relaxation and the study of these well-characterized nanomaterials may elucidate many features that are difficult to grasp in the non molecular materials

  17. Caracterização dos constituintes poliméricos da Maytenus ilicifolia por relaxação nuclear de ¹H por RMN no estado sólido Characterization of Maytenus ilicifolia Samples by ¹H NMR relaxation in the solid state

    Directory of Open Access Journals (Sweden)

    Mônica S. de M. Preto

    2011-01-01

    , verificação de autenticidade e/ou avaliação de eventual adulteração nesse tipo de amostra. Pelos resultados obtidos foi possível diferenciar as duas amostras comerciais por comparação com a amostra controle.The Maytenus ilicifolia (espinheira-santa is a popular medicinal plant with different uses. It is native of South America and can be found in Brazil. In the Brazilian market it is possible found products labeled as M. ilicifolia. So far, the studies published in the literature involve the modification of the natural materials and do not concern the comparison between commercial the raw natural materials. Different non-destructive NMR techniques can be used to study natural materials. In this work it is presented a characterization study by Fast Field Cycling of the ¹H spin-lattice relaxation time (T1 NMR, in the frequency range 100 kHz-10 MHz. The results obtained in two commercial M. ilicifolia samples and one control sample collected in natura are compared. It was intended to study the possibility to elaborate a characterization method using FFCNMR suitable for the verification of authenticity and/or evaluation of tampering on products. The differences detected by FFCNMR relaxometry were confirmed by thermogravimetric analysis and infrared spectroscopy.

  18. High resolution β-NMR study of L8i+ implanted in gold

    Science.gov (United States)

    Parolin, T. J.; Salman, Z.; Chow, K. H.; Song, Q.; Valiani, J.; Saadaoui, H.; O'Halloran, A.; Hossain, M. D.; Keeler, T. A.; Kiefl, R. F.; Kreitzman, S. R.; Levy, C. D. P.; Miller, R. I.; Morris, G. D.; Pearson, M. R.; Smadella, M.; Wang, D.; Xu, M.; Macfarlane, W. A.

    2008-06-01

    We report the behavior of low energy L8i+ implanted into gold as revealed by beta-detected NMR. At an external magnetic field of 3 T, two narrow resonances are observed, which are attributed to Li in the octahedral interstitial and the substitutional lattice sites. The Knight shifts for these two resonances are found to be temperature independent with values of +141(4) and +73(5)ppm , respectively. The spin-lattice relaxation rate in high magnetic fields at 290 K is slow, consistent with the Korringa relation; however, the rate increases dramatically for magnetic fields below about 2 mT. We attribute this to interaction of the L8i spin with the host lattice nuclear spins.

  19. Rindler fluid with weak momentum relaxation

    Science.gov (United States)

    Khimphun, Sunly; Lee, Bum-Hoon; Park, Chanyong; Zhang, Yun-Long

    2018-01-01

    We realize the weak momentum relaxation in Rindler fluid, which lives on the time-like cutoff surface in an accelerating frame of flat spacetime. The translational invariance is broken by massless scalar fields with weak strength. Both of the Ward identity and the momentum relaxation rate of Rindler fluid are obtained, with higher order correction in terms of the strength of momentum relaxation. The Rindler fluid with momentum relaxation could also be approached through the near horizon limit of cutoff AdS fluid with momentum relaxation, which lives on a finite time-like cutoff surface in Anti-de Sitter(AdS) spacetime, and further could be connected with the holographic conformal fluid living on AdS boundary at infinity. Thus, in the holographic Wilson renormalization group flow of the fluid/gravity correspondence with momentum relaxation, the Rindler fluid can be considered as the Infrared Radiation(IR) fixed point, and the holographic conformal fluid plays the role of the ultraviolet(UV) fixed point.

  20. Improving the double quantum filtered COSY experiment by "Moving Tube" NMR.

    Science.gov (United States)

    Donovan, Kevin J; Allen, Mary; Martin, Rachel W; Shaka, A J

    2012-06-01

    Most 2D NMR spectra show artifacts that become increasingly more prominent as the relaxation delay between transients is decreased. Additionally, "rushing" a 2D experiment may lead to reduced sensitivity. It is shown here how to collect a DQF-COSY spectrum in less time, without artifacts, and with improved sensitivity, by a hardware solution we call Moving Tube NMR (MT NMR): the sample volume is physically moved out of the receiver coil after each transient and replaced by a fresh aliquot that is nearer to the equilibrium magnetization M(0). MT NMR was implemented with an automated mechanism that gave accurate and reproducible vertical tube movement, and a very long 5mm outer diameter (OD) NMR tube to hold a larger sample volume. Comparison of conventional and MT NMR DQF-COSY showed increased sensitivity and far reduced artifacts in the latter. The so-called t(1)-noise in the MT spectrum was no worse than in the conventional spectrum, pointing to the excellent specifications of the long 5mm OD tube, and the good mechanical handling of the automated drive. Thus, MT NMR could improve throughput for routine 2D NMR experiments without reducing sensitivity or adding artifacts, if sufficient sample is available. MT NMR could also be useful in cases of limited solubility, or for nuclei with long T(1) relaxation times. Copyright © 2012 Elsevier Inc. All rights reserved.

  1. Control of dipolar relaxation in external fields

    Science.gov (United States)

    Pasquiou, B.; Bismut, G.; Beaufils, Q.; Crubellier, A.; Maréchal, E.; Pedri, P.; Vernac, L.; Gorceix, O.; Laburthe-Tolra, B.

    2010-04-01

    We study dipolar relaxation in both ultracold thermal and Bose-condensed Cr atom gases. We show three different ways to control dipolar relaxation, making use of either a static magnetic field, an oscillatory magnetic field, or an optical lattice to reduce the dimensionality of the gas from three-dimensional (3D) to two-dimensional (2D). Although dipolar relaxation generally increases as a function of a static magnetic-field intensity, we find a range of nonzero magnetic-field intensities where dipolar relaxation is strongly reduced. We use this resonant reduction to accurately determine the S=6 scattering length of Cr atoms: a6=103±4a0. We compare this new measurement to another new determination of a6, which we perform by analyzing the precise spectroscopy of a Feshbach resonance in d-wave collisions, yielding a6=102.5±0.4a0. These two measurements provide, by far, the most precise determination of a6 to date. We then show that, although dipolar interactions are long-range interactions, dipolar relaxation only involves the incoming partial wave l=0 for large enough magnetic-field intensities, which has interesting consequences on the stability of dipolar Fermi gases. We then study ultracold Cr gases in a one-dimensional (1D) optical lattice resulting in a collection of independent 2D gases. We show that dipolar relaxation is modified when the atoms collide in reduced dimensionality at low magnetic-field intensities, and that the corresponding dipolar relaxation rate parameter is reduced by a factor up to 7 compared to the 3D case. Finally, we study dipolar relaxation in the presence of rf oscillating magnetic fields, and we show that both the output channel energy and the transition amplitude can be controlled by means of the rf frequency and Rabi frequency.

  2. Nuclear spin relaxation/resonance of {sup 8}Li in Al

    Energy Technology Data Exchange (ETDEWEB)

    Wang, D. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Salman, Z. [Clarendon Laboratory, Department of Physics, Oxford University, Parks Road, Oxford OX1 3PU (United Kingdom); ISIS Facility, Rutherford-Appleton Laboratory, Chilton, Didcot, Oxon OX11 0QX (United Kingdom); Chow, K.H.; Fan, I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Hossain, M.D.; Keeler, T.A. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Kiefl, R.F., E-mail: kiefl@triumf.c [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Canadian Institute for Advanced Research (Canada); Levy, C.D.P. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Mansour, A.I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Morris, G.D.; Pearson, M.R. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Parolin, T.J. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada); Saadaoui, H.; Smadella, M.; Song, Q. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); MacFarlane, W.A. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z3 (Canada)

    2009-04-15

    A low energy beam of spin polarized {sup 8}Li has been used to study the behaviour of isolated {sup 8}Li implanted into a 150 nm thick film of Al on an MgO substrate. The spin relaxation rate 1/T{sub 1} and beta-NMR lineshape were measured as a function of temperature in a large magnetic field of 4.1 T. The resonances from different sites are unresolved due to the large nuclear dipolar interaction with the host {sup 27}Al magnetic dipole moments. Nevertheless the temperature variation of the site averaged 1/T{sub 1} and Knight shift show evidence for a transition between the octahedral O and substitutional S sites at about 150 K, as observed in other fcc metals.

  3. Non-Invasive Detection of Adulterated Olive Oil in Full Bottles Using Time-Domain NMR Relaxometry

    OpenAIRE

    Santos, Poliana M.; Kock, Flávio Vinicius C.; Santos, Maiara S.; Lobo, Carlos Manuel S.; Carvalho, André S.; Colnago, Luiz Alberto

    2017-01-01

    A fast procedure using time-domain nuclear magnetic resonance (TD-NMR) to detect olive oil adulteration with polyunsaturated vegetable oils in filled bottles is proposed. The 1H transverse relaxation times (T2) of 37 commercial samples were measured using low-field nuclear magnetic resonance (LF-NMR) spectrometer and a unilateral nuclear magnetic resonance (UNMR) sensor. Results obtained with LF-NMR revealed better feasibility when compared with the UNMR sensor, with higher signal-to-noise (S...

  4. [Optimization of experimental parameters for quantitative NMR (qNMR) and its application in quantitative analysis of traditional Chinese medicines].

    Science.gov (United States)

    Ma, Xiao-Li; Zou, Ping-Ping; Lei, Wei; Tu, Peng-Fei; Jiang, Yong

    2014-09-01

    Quantitative NMR (qNMR) is a technology based on the principle of NMR. This technology does not need the references of the determined components, which supplies a solution for the problem of reference scarcity in the quantitative analysis of traditional Chinese medicines. Moreover, this technology has the advantages of easy operation, non-destructiveness for the determined sample, high accuracy and repeatability, in comparison with HPLC, LC-MS and GC-MS. NMR technology has achieved quantum leap in sensitivity and accuracy with the development of NMR hardware. In addition, the choice of appropriate experimental parameters of the pre-treatment and measurement procedure as well as the post-acquisition processing is also important for obtaining high-quality and reproducible NMR spectra. This review summarizes the principle of qHNMR, the various experimental parameters affecting the accuracy and the precision of qHNMR, such as signal to noise ratio, relaxation delay, pulse width, acquisition time, window function, phase correction and baseline correction, and their corresponding optimized methods. Moreover, the application of qHNMR in the fields of quantitation of single or multi-components of traditional Chinese medicines, the purity detection of references, and the quality analysis of foods has been discussed. In addition, the existing questions and the future application prospects of qNMR in natural product areas are also presented.

  5. Hydraulic characterisation of iron-oxide-coated sand and gravel based on nuclear magnetic resonance relaxation mode analyses

    Directory of Open Access Journals (Sweden)

    S. Costabel

    2018-03-01

    Full Text Available The capability of nuclear magnetic resonance (NMR relaxometry to characterise hydraulic properties of iron-oxide-coated sand and gravel was evaluated in a laboratory study. Past studies have shown that the presence of paramagnetic iron oxides and large pores in coarse sand and gravel disturbs the otherwise linear relationship between relaxation time and pore size. Consequently, the commonly applied empirical approaches fail when deriving hydraulic quantities from NMR parameters. Recent research demonstrates that higher relaxation modes must be taken into account to relate the size of a large pore to its NMR relaxation behaviour in the presence of significant paramagnetic impurities at its pore wall. We performed NMR relaxation experiments with water-saturated natural and reworked sands and gravels, coated with natural and synthetic ferric oxides (goethite, ferrihydrite, and show that the impact of the higher relaxation modes increases significantly with increasing iron content. Since the investigated materials exhibit narrow pore size distributions, and can thus be described by a virtual bundle of capillaries with identical apparent pore radius, recently presented inversion approaches allow for estimation of a unique solution yielding the apparent capillary radius from the NMR data. We found the NMR-based apparent radii to correspond well to the effective hydraulic radii estimated from the grain size distributions of the samples for the entire range of observed iron contents. Consequently, they can be used to estimate the hydraulic conductivity using the well-known Kozeny–Carman equation without any calibration that is otherwise necessary when predicting hydraulic conductivities from NMR data. Our future research will focus on the development of relaxation time models that consider pore size distributions. Furthermore, we plan to establish a measurement system based on borehole NMR for localising iron clogging and controlling its remediation

  6. Hydraulic characterisation of iron-oxide-coated sand and gravel based on nuclear magnetic resonance relaxation mode analyses

    Science.gov (United States)

    Costabel, Stephan; Weidner, Christoph; Müller-Petke, Mike; Houben, Georg

    2018-03-01

    The capability of nuclear magnetic resonance (NMR) relaxometry to characterise hydraulic properties of iron-oxide-coated sand and gravel was evaluated in a laboratory study. Past studies have shown that the presence of paramagnetic iron oxides and large pores in coarse sand and gravel disturbs the otherwise linear relationship between relaxation time and pore size. Consequently, the commonly applied empirical approaches fail when deriving hydraulic quantities from NMR parameters. Recent research demonstrates that higher relaxation modes must be taken into account to relate the size of a large pore to its NMR relaxation behaviour in the presence of significant paramagnetic impurities at its pore wall. We performed NMR relaxation experiments with water-saturated natural and reworked sands and gravels, coated with natural and synthetic ferric oxides (goethite, ferrihydrite), and show that the impact of the higher relaxation modes increases significantly with increasing iron content. Since the investigated materials exhibit narrow pore size distributions, and can thus be described by a virtual bundle of capillaries with identical apparent pore radius, recently presented inversion approaches allow for estimation of a unique solution yielding the apparent capillary radius from the NMR data. We found the NMR-based apparent radii to correspond well to the effective hydraulic radii estimated from the grain size distributions of the samples for the entire range of observed iron contents. Consequently, they can be used to estimate the hydraulic conductivity using the well-known Kozeny-Carman equation without any calibration that is otherwise necessary when predicting hydraulic conductivities from NMR data. Our future research will focus on the development of relaxation time models that consider pore size distributions. Furthermore, we plan to establish a measurement system based on borehole NMR for localising iron clogging and controlling its remediation in the gravel pack of

  7. Functional studies using NMR

    International Nuclear Information System (INIS)

    McCready, V.R.; Leach, M.O.; Sutton; Ell, P.

    1986-01-01

    The object of this book is to discuss and evaluate an area of Nuclear Magnetic Resonance which to date has been less emphasized than it might be, namely the use of NMR for functional studies. The book commences with a discussion of the areas in which the NMR techniques might be needed due to deficiencies in other techniques. The physics of NMR especially relating to functional measurement are then explained. Technical factors in producing functional images are discussed and the use of paramagnetic substances for carrying out flow studies are detailed. Particular attention is paid to specific studies in the various organs. The book ends with a survey of imaging in each organ and the relation of NMR images to other techniques such as ultrasound, nuclear medicine and X-rays

  8. Functional studies using NMR

    International Nuclear Information System (INIS)

    McCready, V.R.; Leach, M.; Ell, P.J.

    1987-01-01

    This volume is based on a series of lectures delivered at a one-day teaching symposium on functional and metabolic aspects of NMR measurements held at the Middlesex Hospital Medical School on 1st September 1985 as a part of the European Nuclear Medicine Society Congress. Currently the major emphasis in medical NMR in vivo is on its potential to image and display abnormalities in conventional radiological images, providing increased contrast between normal and abnormal tissue, improved definition of vasculature, and possibly an increased potential for differential diagnosis. Although these areas are undeniably of major importance, it is probable that NMR will continue to complement conventional measurement methods. The major potential benefits to be derived from in vivo NMR measurements are likely to arise from its use as an instrument for functional and metabolic studies in both clinical research and in the everyday management of patients. It is to this area that this volume is directed

  9. Rating

    OpenAIRE

    Karas, Vladimír

    2006-01-01

    Charakteristika ratingu. Dělení a druhy ratingu (rating emise × rating emitenta; dlouhodobý rating × krátkodobý rating; mezinárodní rating × lokální rating). Obecné požadavky kladené na rating. Proces tvorby ratingu. Vyžádaný rating. Nevyžádaný rating. Ratingový proces na bázi volně přístupných informací. Uplatňované ratingové systémy. Ratingová kriteria. Využití a interpretace ratingové známky. Funkce ratingu. Rating v souvislosti s BASEL II. Rating v souvislosti s hospodářskými krizemi....

  10. Lithium diffusion in spinel Li4Ti5O12 and LiTi2O4 films detected with 8Liβ -NMR

    Science.gov (United States)

    Sugiyama, Jun; Umegaki, Izumi; Uyama, Takeshi; McFadden, Ryan M. L.; Shiraki, Susumu; Hitosugi, Taro; Salman, Zaher; Saadaoui, Hassan; Morris, Gerald D.; MacFarlane, W. Andrew; Kiefl, Robert F.

    2017-09-01

    Diffusion of Li+ in (111) oriented thin films of the spinels Li4Ti5O12 and LiTi2O4 has been studied with 8Liβ -detected NMR in the temperature range between 5 and 310 K. In Li4Ti5O12 , the spin-lattice relaxation rate (1 /T1 ) versus temperature shows a clear maximum around 100 K (=Tmax ) which we attribute to magnetic freezing of dilute Ti3 + local magnetic moments, consistent with the results of magnetization and muon spin relaxation (μ+SR ) measurements. The decrease in 1 /T1 with temperature above Tmax indicates that Li+ starts to diffuse with a thermal activation energy (Ea) of 0.11(1) eV. In LiTi2O4 , on the contrary, as temperature increases from 200 K, 1 /T1 increases monotonically up to 310 K. This suggests that Li also starts to diffuse above 200 K with Ea=0.16 (2 ) eV in LiTi2O4 . Comparison with conventional Li-NMR on Li4Ti5O12 implies that both β -NMR and μ+SR sense short-range Li motion, i.e., a jump diffusion of Li+ to the nearest neighboring sites.

  11. Solid state proton spin-lattice relaxation in four structurally related organic molecules

    International Nuclear Information System (INIS)

    Beckmann, Peter A.; Burbank, Kendra S.; Lau, Matty M.W.; Ree, Jessica N.; Weber, Tracy L.

    2003-01-01

    We report and interpret the temperature dependence of the proton spin-lattice relaxation rate at 8.50 and 22.5 MHz in four polycrystalline solids composed of structurally related molecules: 2-ethylanthracene, 2-t-butylanthracene, 2-ethylanthraquinone, and 2-t-butylanthraquinone. We have been unable to grow single crystals and therefore do not know the crystal structures. Hence, we use the NMR relaxometry data to make predictions about the solid state structures. As expected, we are able to conclude that the ethyl groups do not reorient in the solid state but that the t-butyl groups do. The anthraquinones have a ''simpler'' structure than the anthracenes. The best dynamical models suggest that there is a unique crystallographic site for the t-butyl groups in 2-t-butylanthraquinone and two sites, each with half the molecules, for the ethyl groups in 2-ethylanthraquinone. There are also two sites in 2-ethylanthracene, but with unequal weights, suggesting four sites in the unit cell with lower symmetry than the two anthraquinones. Finally, the observed relaxation rate data in 2-t-butylanthracene is very complex and its interpretation demonstrates the uniqueness problem that arises in interpreting relaxometry data without the knowledge of the crystal structure

  12. Hair Dye and Hair Relaxers

    Science.gov (United States)

    ... For Consumers Consumer Information by Audience For Women Hair Dye and Hair Relaxers Share Tweet Linkedin Pin it More sharing ... products. If you have a bad reaction to hair dyes and relaxers, you should: Stop using the ...

  13. Study of lignin standard-substances type biphenyl by {sup 13} C NMR; Estudo de substancias-modelo de lignina do tipo bifenila, por RMN de {sup 13} C

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Marcia Alves; Drumond, Mariza Guimaraes; Veloso, Dorila Pilo [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Dept. de Quimica

    1995-12-31

    Lignins structural study by NMR has utilized standard-substances spectral comparative analysis. This work has present relaxation time studies for lignin standard-substance, and {sup 13} C NMR chemical shift values were also shown and compared for several compounds. NMR spectra were commented besides experimental data analysis 2 figs., 4 tabs.

  14. The “long tail” of the protein tumbling correlation function: observation by {sup 1}H NMR relaxometry in a wide frequency and concentration range

    Energy Technology Data Exchange (ETDEWEB)

    Roos, Matthias [Martin-Luther-Universität Halle-Wittenberg, Institut für Physik (Germany); Hofmann, Marius [Universität Bayreuth, Lehrstuhl Experimentalphysik II, Universitätsstr. 30 (Germany); Link, Susanne; Ott, Maria; Balbach, Jochen [Martin-Luther-Universität Halle-Wittenberg, Institut für Physik (Germany); Rössler, Ernst [Universität Bayreuth, Lehrstuhl Experimentalphysik II, Universitätsstr. 30 (Germany); Saalwächter, Kay, E-mail: kay.saalwaechter@physik.uni-halle.de; Krushelnitsky, Alexey, E-mail: krushelnitsky@physik.uni-halle.de [Martin-Luther-Universität Halle-Wittenberg, Institut für Physik (Germany)

    2015-12-15

    Inter-protein interactions in solution affect the auto-correlation function of Brownian tumbling not only in terms of a simple increase of the correlation time, they also lead to the appearance of a weak slow component (“long tail”) of the correlation function due to a slowly changing local anisotropy of the microenvironment. The conventional protocol of correlation time estimation from the relaxation rate ratio R{sub 1}/R{sub 2} assumes a single-component tumbling correlation function, and thus can provide incorrect results as soon as the “long tail” is of relevance. This effect, however, has been underestimated in many instances. In this work we present a detailed systematic study of the tumbling correlation function of two proteins, lysozyme and bovine serum albumin, at different concentrations and temperatures using proton field-cycling relaxometry combined with R{sub 1ρ} and R{sub 2} measurements. Unlike high-field NMR relaxation methods, these techniques enable a detailed study of dynamics on a time scale longer than the normal protein tumbling correlation time and, thus, a reliable estimate of the parameters of the “long tail”. In this work we analyze the concentration dependence of the intensity and correlation time of the slow component and perform simulations of high-field {sup 15}N NMR relaxation data demonstrating the importance of taking the “long tail” in the analysis into account.

  15. THEORY OF RELAXATION PROCESSES IN FERROMAGNETIC INSULATORS

    Science.gov (United States)

    Contents: Simplified description of ferromagnetic relaxation Detailed treatment of magnons Relaxation frequency calculations Summary of relaxation processes in YIG Summary of experimental results for YIG

  16. UC Merced NMR Instrumentation Acquisition

    Science.gov (United States)

    2015-06-18

    UC Merced NMR Instrumentation Acquisition For the UC Merced NMR Instrumentation Acquisition proposal, a new 400 MHz and an upgraded 500 MHz NMR...valid OMB control number. PLEASE DO NOT RETURN YOUR FORM TO THE ABOVE ADDRESS. University of California - Merced 5200 North Lake Road Merced , CA 95343...UC Merced NMR Instrumentation Acquisition Report Title For the UC Merced NMR Instrumentation Acquisition proposal, a new 400 MHz and an upgraded 500

  17. A Comparison of Relaxation Strategies.

    Science.gov (United States)

    Matthews, Doris B.

    Some researchers argue that all relaxation techniques produce a single relaxation response while others support a specific-effects hypothesis which suggests that progressive relaxation affects the musculoskeletal system and that guided imagery affects cognitive changes. Autogenics is considered a technique which is both somatic and cognitive. This…

  18. Relaxation from particle production

    Energy Technology Data Exchange (ETDEWEB)

    Hook, Anson; Marques-Tavares, Gustavo [Stanford Institute for Theoretical Physics, Stanford University, Stanford, CA 94305 (United States)

    2016-12-20

    We consider using particle production as a friction force by which to implement a “Relaxion” solution to the electroweak hierarchy problem. Using this approach, we are able to avoid superplanckian field excursions and avoid any conflict with the strong CP problem. The relaxation mechanism can work before, during or after inflation allowing for inflationary dynamics to play an important role or to be completely decoupled.

  19. MAGNETIC RELAXATION IN RARE EARTH DOPED GARNET.

    Science.gov (United States)

    in resonance measurements by the constant low temperature linewidth due to two magnon scattering. In contrast, the PPI relaxation rate is independent...of two magnon scattering. The 4.5K doublet may well be related to a near crossing of energy levels which probably causes the anomalous low temperature peaks in delta H and resonance field observed by Dillon. (Author)

  20. Momentum constraint relaxation

    International Nuclear Information System (INIS)

    Marronetti, Pedro

    2006-01-01

    Full relativistic simulations in three dimensions invariably develop runaway modes that grow exponentially and are accompanied by violations of the Hamiltonian and momentum constraints. Recently, we introduced a numerical method (Hamiltonian relaxation) that greatly reduces the Hamiltonian constraint violation and helps improve the quality of the numerical model. We present here a method that controls the violation of the momentum constraint. The method is based on the addition of a longitudinal component to the traceless extrinsic curvature A ij -tilde, generated by a vector potential w i , as outlined by York. The components of w i are relaxed to solve approximately the momentum constraint equations, slowly pushing the evolution towards the space of solutions of the constraint equations. We test this method with simulations of binary neutron stars in circular orbits and show that it effectively controls the growth of the aforementioned violations. We also show that a full numerical enforcement of the constraints, as opposed to the gentle correction of the momentum relaxation scheme, results in the development of instabilities that stop the runs shortly

  1. Solid state NMR study of cumbaru flour

    International Nuclear Information System (INIS)

    Nogueira, Jose S.; Bathista, Andre L.B.S.; Silva, Emerson O.; Priante Filho, Nicolau; Tavares, Maria I.B.

    2001-01-01

    The polysaccharide obtained by seed of Dipteryx alata Vog, has been characterised by 13 C solid state, using the basic routine techniques, like MAS and CPMAS and by the proton spin-lattice relaxation time in the rotating frame parameter (T 1 H ρ). Knowing that the chemical structure and molecular dynamic are extremely necessary route to obtain information on the polysaccharides, this work contributes to the classification of the seed containing in the cumbaru fruit to get response on its application. To obtain the initial responses for our purposes some solid state NMR techniques were chosen. The CPMAS 13 C NMR spectrum of the polysaccharide was investigated to know if it has some crystallinity. The MAS 13 C NMR spectrum showed the presence of domains with distinct molecular mobility, because these domains will differ basically in the distribution size and chain packing. The variable contact time experiment was used to analyse the distribution form of 13 C decays, which give us more information about sample heterogeneity. The T 1 H ρHr values were obtained from the variable contact time and by delayed contact time experiment, because these parameter indicate the order of polysaccharides. From the values of this parameter, we found that this polysaccharide is completely non-ordered. (author)

  2. K + -induced relaxation in vascular smooth muscle of alloxan ...

    African Journals Online (AJOL)

    The effects of different concentration of intracellular potassium (K+), on rate of relaxation were studied in isolated aortae of normal and diabetic rats. The relaxation responses induced by raised extracellular potassium concentration was attenuated in aortic rings from diabetic rats. Possible reasons are discussed in the text.

  3. Abrupt relaxation in high-spin molecules

    International Nuclear Information System (INIS)

    Chang, C.-R.; Cheng, T.C.

    2000-01-01

    Mean-field model suggests that the rate of resonant quantum tunneling in high-spin molecules is not only field-dependent but also time-dependent. The relaxation-assisted resonant tunneling in high-spin molecules produces an abrupt magnetization change during relaxation. When the applied field is very close to the resonant field, a time-dependent interaction field gradually shifts the energies of different collective spin states, and magnetization tunneling is observed as two energies of the spin states coincide

  4. Changes in seed water status as characterized by NMR in developing soybean seed grown under moisture stress conditions

    Energy Technology Data Exchange (ETDEWEB)

    Krishnan, P., E-mail: pkrishnan@iari.res.in; Singh, Ravender; Verma, A.P.S.; Joshi, D.K.; Singh, Sheoraj

    2014-02-21

    Highlights: • In developing soybean seeds, moisture stress resulted in more proportion of water to bound state. • These changes are further corroborated by concomitant changes in seed metabolites. • Thus there exists a moisture stress and development stage dependence of seed tissue water status. - Abstract: Changes in water status of developing seeds of Soybean (Glycine max L. Merrill.) grown under different moisture stress conditions were characterized by proton nuclear magnetic resonance (NMR)- spin–spin relaxation time (T{sub 2}). A comparison of the seed development characteristics, composition and physical properties indicated that, characteristics like seed weight, seed number/ear, rate of seed filling increased with development stages but decreased with moisture stress conditions. The NMR- spin–spin relaxation (T{sub 2}) component like bound water increased with seed maturation (40–50%) but decreased with moisture stress conditions (30–40%). The changes in seed water status to increasing levels of moisture stress and seed maturity indicates that moisture stress resulted in more proportion of water to bound state and intermediate state and less proportion of water in free-state. These changes are further corroborated by significant changes in protein and starch contents in seeds under high moisture stress treatments. Thus seed water status during its development is not only affected by development processes but also by moisture stress conditions. This study strongly indicated a clear moisture stress and development stage dependence of seed tissue water status in developing soybean seeds.

  5. Changes in seed water status as characterized by NMR in developing soybean seed grown under moisture stress conditions

    International Nuclear Information System (INIS)

    Krishnan, P.; Singh, Ravender; Verma, A.P.S.; Joshi, D.K.; Singh, Sheoraj

    2014-01-01

    Highlights: • In developing soybean seeds, moisture stress resulted in more proportion of water to bound state. • These changes are further corroborated by concomitant changes in seed metabolites. • Thus there exists a moisture stress and development stage dependence of seed tissue water status. - Abstract: Changes in water status of developing seeds of Soybean (Glycine max L. Merrill.) grown under different moisture stress conditions were characterized by proton nuclear magnetic resonance (NMR)- spin–spin relaxation time (T 2 ). A comparison of the seed development characteristics, composition and physical properties indicated that, characteristics like seed weight, seed number/ear, rate of seed filling increased with development stages but decreased with moisture stress conditions. The NMR- spin–spin relaxation (T 2 ) component like bound water increased with seed maturation (40–50%) but decreased with moisture stress conditions (30–40%). The changes in seed water status to increasing levels of moisture stress and seed maturity indicates that moisture stress resulted in more proportion of water to bound state and intermediate state and less proportion of water in free-state. These changes are further corroborated by significant changes in protein and starch contents in seeds under high moisture stress treatments. Thus seed water status during its development is not only affected by development processes but also by moisture stress conditions. This study strongly indicated a clear moisture stress and development stage dependence of seed tissue water status in developing soybean seeds

  6. Asymptotic representation of relaxation oscillations in lasers

    CERN Document Server

    Grigorieva, Elena V

    2017-01-01

    In this book we analyze relaxation oscillations in models of lasers with nonlinear elements controlling light dynamics. The models are based on rate equations taking into account periodic modulation of parameters, optoelectronic delayed feedback, mutual coupling between lasers, intermodal interaction and other factors. With the aim to study relaxation oscillations we present the special asymptotic method of integration for ordinary differential equations and differential-difference equations. As a result, they are reduced to discrete maps. Analyzing the maps we describe analytically such nonlinear phenomena in lasers as multistability of large-amplitude relaxation cycles, bifurcations of cycles, controlled switching of regimes, phase synchronization in an ensemble of coupled systems and others. The book can be fruitful for students and technicians in nonlinear laser dynamics and in differential equations.

  7. Beta-detected NMR study of the local magnetic field in epitaxial GaAs:Mn

    Science.gov (United States)

    Song, Q.; Chow, K. H.; Miller, R. I.; Fan, I.; Hossain, M. D.; Kiefl, R. F.; Kreitzman, S. R.; Levy, C. D. P.; Parolin, T. J.; Pearson, M. R.; Salman, Z.; Saadaoui, H.; Smadella, M.; Wang, D.; Yu, K. M.; Liu, X.; Furdyna, J. K.; MacFarlane, W. A.

    2009-04-01

    A low energy beam of spin polarized 8Li + has been employed to study the magnetic field distribution in an epitaxial thin film of 5.4% Mn doped GaAs(180 nm) on a (1 0 0) GaAs substrate via beta-detected NMR. The spectrum is a strong function of the implantation energy in the range 28-3 keV. In the magnetic layer, there is no indication of a missing fraction, and even more remarkable, there is a broad negatively shifted resonance. The spin lattice relaxation rate is, however, much faster in the Mn doped layer than in the substrate. A sharp peak characteristic of nonmagnetic GaAs is observed down to the lowest implantation energy, for which none of the Li should reach the substrate. This unexpected depth dependence is discussed.

  8. B11 NMR in the layered diborides OsB2 and RuB2

    Science.gov (United States)

    Suh, B. J.; Zong, X.; Singh, Y.; Niazi, A.; Johnston, D. C.

    2007-10-01

    B11 nuclear magnetic resonance (NMR) measurements have been performed on B11 enriched OsB2 and RuB2 polycrystalline powder samples in an external field of 4.7T and in the temperature range, 4.2Krelaxation rate T1-1 follows a Korringa law in the whole temperature range investigated with T1T=600 and 680sK for OsB2 and RuB2 , respectively. The experimental results indicate that a p character dominates the conduction electron wave function at the B site with a negligibly small s character in both compounds.

  9. Beta-detected NMR study of the local magnetic field in epitaxial GaAs:Mn

    Energy Technology Data Exchange (ETDEWEB)

    Song, Q., E-mail: susan@phas.ubc.c [Department of Physics, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Chow, K.H. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Miller, R.I. [TRIMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Fan, I. [Department of Physics, University of Alberta, Edmonton, AB, T6G 2G7 (Canada); Hossain, M.D. [Department of Physics, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Kiefl, R.F. [Department of Physics, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Canadian Institute of Advanced Research (Canada); Kreitzman, S.R.; Levy, C.D.P. [TRIMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Parolin, T.J. [Chemistry Department, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Pearson, M.R.; Salman, Z. [TRIMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Saadaoui, H.; Smadella, M.; Wang, D. [Department of Physics, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Yu, K.M. [Lawrence Berkeley National Laboratory, 1 Cyclotron Road, Berkeley, CA 94720 (United States); Liu, X.; Furdyna, J.K. [Department of Physics, University of Notre Dame, Notre Dame, IN 46556 (United States); MacFarlane, W.A. [Chemistry Department, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada)

    2009-04-15

    A low energy beam of spin polarized {sup 8}Li{sup +} has been employed to study the magnetic field distribution in an epitaxial thin film of 5.4% Mn doped GaAs(180 nm) on a (1 0 0) GaAs substrate via beta-detected NMR. The spectrum is a strong function of the implantation energy in the range 28-3 keV. In the magnetic layer, there is no indication of a missing fraction, and even more remarkable, there is a broad negatively shifted resonance. The spin lattice relaxation rate is, however, much faster in the Mn doped layer than in the substrate. A sharp peak characteristic of nonmagnetic GaAs is observed down to the lowest implantation energy, for which none of the Li should reach the substrate. This unexpected depth dependence is discussed.

  10. Teaching NMR Using Online Textbooks

    Directory of Open Access Journals (Sweden)

    Joseph P. Hornak

    1999-12-01

    Full Text Available Nuclear magnetic resonance (NMR spectroscopy has almost become an essential analytical tool for the chemist. High-resolution one- and multi-dimensional NMR, timedomain NMR, and NMR microscopy are but a few of the NMR techniques at a chemist's disposal to determine chemical structure and dynamics. Consequently, even small chemistry departments are finding it necessary to provide students with NMR training and experience in at least some of these techniques. The hands-on experience is readily provided with access to state-of-the-art commercial spectrometers. Instruction in the principles of NMR is more difficult to achieve as most instructors try to teach NMR using single organic or analytical chemistry book chapters with static figures. This paper describes an online textbook on NMR spectroscopy called The Basics of NMR (http://www.cis.rit.edu/htbooks/nmr/ suitable for use in teaching the principles of NMR spectroscopy. The book utilizes hypertext and animations to present the principles of NMR spectroscopy. The book can be used as a textbook associated with a lecture or as a stand-alone teaching tool. Conference participants are encouraged to review the textbook and evaluate its suitability for us in teaching NMR spectroscopy to undergraduate chemistry majors.

  11. Nuclear spin relaxation of {sup 8}Li in a thin film of La{sub 0.67}Ca{sub 0.33}MnO{sub 3}

    Energy Technology Data Exchange (ETDEWEB)

    Miller, R.I. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, Canada V6T 2A3 (Canada); Arseneau, D. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Chow, K.H. [Department of Physics, University of Alberta, Edmonton, Alta., T6G 2J1 (Canada); Daviel, S. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Engelbertz, A. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Hossain, MD. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Keeler, T. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Kiefl, R.F. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada)]|[Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, Canada V6T 1Z1 (Canada)]|[Canadian Institute for Advanced Research, Toronto, Ont., Canada M5G 1Z8 (Canada)]. E-mail: kiefl@triumf.ca; Kreitzman, S. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Levy, C.D.P. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Morales, P. [Department of Physics, University of Toronto, Toronto, Ont., M5S 1A7 (Canada); Morris, G.D. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); MacFarlane, W.A. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada): Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Parolin, T.J. [Department of Chemistry, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Poutissou, R. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Saadaoui, H.; Wang, D. [Department of Physics and Astronomy, University of British Columbia, Vancouver, BC, V6T 1Z1 (Canada); Salman, Z. [TRIUMF, 4004 Wesbrook Mall, Vancouver, BC, V6T 2A3 (Canada); Wei, J.Y.T. [Canadian Institute for Advanced Research, Toronto, Ont., M5G 1Z8 (Canada)]|[Department of Physics, University of Toronto, Toronto, Ont., M5S 1A7 (Canada)

    2006-03-31

    We report {beta}-NMR measurements of the nuclear spin relaxation rate (1/T{sub 1}) in a thin film of La{sub 0.67}Ca{sub 0.33}MnO{sub 3} (LCMO) using a low-energy beam of spin-polarized {sup 8}Li. In a small magnetic field of 150G, there is a broad peak in 1/T{sub 1} near the Curie temperature (T{sub c}=259K) and a dramatic decrease in 1/T{sub 1} at lower temperatures. This is attributed to a critical slowing down of the spin fluctuations near T{sub c} and freezing of the magnetic excitations at low temperatures, respectively. In addition, there is a small amplitude, slow relaxing component at high temperatures, which we attribute to {sup 8}Li in the SrTiO{sub 3} substrate. There is an indication that the spin relaxation rate in the substrate is also peaked at T{sub c} due to close proximity to the magnetic film. These results establish that low-energy {beta}-NMR can be used as a probe of magnetic fluctuations in magnetic thin films over a wide range of temperatures.

  12. Thermometry of hot spot using NMR for hyperthermia

    International Nuclear Information System (INIS)

    Amemiya, Yoshifumi; Kamimura, Yoshitsugu

    1983-01-01

    Lately noticed hyperthermia in cancer therapy requires non-invasive measurement of the temperature at the warmed site in the deep portion of human body. Nuclear magnetic relaxation time of NMR is also usable for cancer diagnosis. For coordination of these two techniques, it was judged suitable to measure temperature by NMR so that cancer diagnosis and treatment and evaluation of therapeutic effect might be incorporated into one system. This report dealt with concrete procedures of measuring the temperature of deep portions by NMR. Computations revealed that the coefficient of temperature of the thermal equilibrium magnetization was useful, that magnetic field focusing was the most effective imaging technique and that temperature rise in areas about 2 cm in radius could be measured without large errors. (Chiba, N.)

  13. Multinuclear NMR studies of hemoproteins and their model compounds

    International Nuclear Information System (INIS)

    Lee, H.C.

    1988-01-01

    Nuclear magnetic resonance (NMR) in both solution and solid state has been used to study the active site structure of various hemoproteins, and the nature of the iron-oxygen bond in oxyhemoglobin. The first iron-57 NMR spectra of a metalloprotein, carbonmonoxymyoglobin, has been obtained, yielding the isotropic chemical shift, the anisotropy of the chemical shielding tensor and the rotational correlation time of the protein. The oxygen-17 NMR signals from CO ligands bound to oxygen-transport hemoproteins are much narrower than expected, and the lineshape is non-Lorentzian. The results indicate that the unusual linewidths and lineshapes originate from the multiexponential nature of quadrupolar relaxation outside of the extreme narrowing limit, permitting determinations of the oxygen-17 nuclear quadrupole coupling constants and the rotational correlation time of the proteins

  14. Repeatability and reliability of muscle relaxation properties induced by motor cortical stimulation.

    Science.gov (United States)

    Molenaar, Joery P; Voermans, Nicol C; de Jong, Lysanne A; Stegeman, Dick F; Doorduin, Jonne; van Engelen, Baziel G

    2018-03-15

    Impaired muscle relaxation is a feature of many neuromuscular disorders. However, there are few tests available to quantify muscle relaxation. Transcranial magnetic stimulation (TMS) of the motor cortex can induce muscle relaxation by abruptly inhibiting corticospinal drive. The aim of our study is to investigate if repeatability and reliability of TMS-induced relaxation is greater than voluntary relaxation. Furthermore, effects of sex, cooling and fatigue on muscle relaxation properties were studied. Muscle relaxation of deep finger flexors was assessed in twenty-five healthy subjects (14 M and 11 F, aged 39.1{plus minus}12.7 and 45.3{plus minus}8.7 years old, respectively) using handgrip dynamometry. All outcome measures showed greater repeatability and reliability in TMS-induced relaxation compared to voluntary relaxation. The within-subject coefficient of variability of normalized peak relaxation rate was lower in TMS-induced relaxation than in voluntary relaxation (3.0 vs 19.7% in men, and 6.1 vs 14.3% in women). The repeatability coefficient was lower (1.3 vs 6.1 s -1 in men and 2.3 vs 3.1 s -1 in women), and the intraclass correlation coefficient was higher (0.95 vs 0.53 in men and 0.78 vs 0.69 in women), for TMS-induced relaxation compared to voluntary relaxation. TMS enabled to demonstrate slowing effects of sex, muscle cooling, and muscle fatigue on relaxation properties that voluntary relaxation could not. In conclusion, repeatability and reliability of TMS-induced muscle relaxation was greater compared to voluntary muscle relaxation. TMS-induced muscle relaxation has the potential to be used in clinical practice for diagnostic purposes and therapy effect monitoring in patients with impaired muscle relaxation.

  15. Microprocessorized NMR measurement

    International Nuclear Information System (INIS)

    Rijllart, A.

    1984-01-01

    An MC68000 CAMAC microprocessor system for fast and accurate NMR signal measurement will be presented. A stand-alone CAMAC microprocessor system (MC68000 STAC) with a special purpose interface sweeps a digital frequency synthesizer and digitizes the NMR signal with a 16-bit ADC of 17 μs conversion time. It averages the NMR signal data over many sweeps and then transfers it through CAMAC to a computer for calculation of the signal parameters. The computer has full software control over the timing and sweep settings of this signal averager, and thus allows optimization of noise suppression. Several of these processor systems can be installed in the same crate for parallel processing, and the flexibility of the STAC also allows easy adaptation to other applications such as transient recording or phase-sensitive detection. (orig.)

  16. Structural NMR assignment

    International Nuclear Information System (INIS)

    Procter, J.B.; Torda, A.E.

    1999-01-01

    Full text: General automated NMR assignment approaches are aimed at full heteronuclear assignment, which is needed for structure determination. Usually, full assignment requires at least as much spectral information as is used for structure generation. For large proteins, obtaining sufficient spectral information may require a number of sample preparations and many spectra, resulting in a significant overhead for the use of NMR in biochemical investigation. For a protein of biochemical interest one may already have an x-ray crystal structure, but spectral assignment is still needed to use NMR as a structural probe for ligand binding studies. In this situation it may be possible to use much less spectral information to make an assignment based purely on the correspondence of structural data to the measurements contained in a few simple spectra. We introduce a framework to accomplish this 'structural assignment', and give some observations on the practical requirements for a structural assignment to succeed

  17. The in-vitro study of human blood leukemic cells by pulsed NMR

    International Nuclear Information System (INIS)

    Zulkarnaen, M.; Munawir; Wibowo, Tono; Suyitno, Gogot

    1983-01-01

    The diagram of leukemic cells in human blood has been studied by using the NMR longitudinal relaxation technique. The observation was treated in whole blood, serum and blood cell. Every result was compared with previous observation and show that the values of the proton longitudinal relaxation in the leukemic whole blood almost twice or more that of normal blood, while in the serum and the blood cell, the values are nearly the same. (author)

  18. Determining the sizes of micropores in activated charcoals by the pulsed NMR method

    Science.gov (United States)

    Gogelashvili, G. Sh.; Khozina, E. V.; Vartapetyan, R. Sh.; Ladychuk, D. V.; Grunin, Yu. B.

    2011-07-01

    The pulsed NMR method was used to measure the nuclear spin-spin relaxation of protons of water adsorbed in micropores of activated charcoal (AC) samples with different porous structures. A correlation was found between the spin-spin relaxation time of water protons in AC with completely filled micropores and the volume density of water primary adsorption centers in the AC samples. An equation for approximating obtained dependences is proposed that allows us to determine the volume of micropores in AC.

  19. Direct 13C-detection for carbonyl relaxation studies of protein dynamics.

    Science.gov (United States)

    Pasat, Gabriela; Zintsmaster, John S; Peng, Jeffrey W

    2008-08-01

    We describe a method that uses direct 13C-detection for measuring rotating-frame carbonyl (13CO) relaxation rates to describe protein functional dynamics. Key advantages of method include the following: (i) unique access to 13CO groups that lack a scalar-coupled 15N-1H group; (ii) insensitivity to 15N/1H exchange-broadening that can derail 1H-detected 15N and HNCO methods; (iii) avoidance of artifacts caused by incomplete water suppression. We demonstrate the approach for both backbone and side-chain 13CO groups. Accuracy of the 13C-detected results is supported by their agreement with those obtained from established HNCO-based approaches. Critically, we show that the 13C-detection approach provides access to the 13CO groups of functionally important residues that are invisible via 1H-detected HNCO methods because of exchange-broadening. Hence, the 13C-based method fills gaps inherent in canonical 1H-detected relaxation experiments, and thus provides a novel complementary tool for NMR studies of biomolecular flexibility.

  20. Variational formulation of relaxed and multi-region relaxed magnetohydrodynamics

    Science.gov (United States)

    Dewar, R. L.; Yoshida, Z.; Bhattacharjee, A.; Hudson, S. R.

    2015-12-01

    > Ideal magnetohydrodynamics (IMHD) is strongly constrained by an infinite number of microscopic constraints expressing mass, entropy and magnetic flux conservation in each infinitesimal fluid element, the latter preventing magnetic reconnection. By contrast, in the Taylor relaxation model for formation of macroscopically self-organized plasma equilibrium states, all these constraints are relaxed save for the global magnetic fluxes and helicity. A Lagrangian variational principle is presented that leads to a new, fully dynamical, relaxed magnetohydrodynamics (RxMHD), such that all static solutions are Taylor states but also allows state with flow. By postulating that some long-lived macroscopic current sheets can act as barriers to relaxation, separating the plasma into multiple relaxation regions, a further generalization, multi-region relaxed magnetohydrodynamics (MRxMHD) is developed.

  1. Progressive muscle relaxation, yoga stretching, and ABC relaxation theory.

    Science.gov (United States)

    Ghoncheh, Shahyad; Smith, Jonathan C

    2004-01-01

    This study compared the psychological effects of progressive muscle relaxation (PMR) and yoga stretching (hatha) exercises. Forty participants were randomly divided into two groups and taught PMR or yoga stretching exercises. Both groups practiced once a week for five weeks and were given the Smith Relaxation States Inventory before and after each session. As hypothesized, practitioners of PMR displayed higher levels of relaxation states (R-States) Physical Relaxation and Disengagement at Week 4 and higher levels of Mental Quiet and Joy as a posttraining aftereffect at Week 5. Contrary to what was hypothesized, groups did not display different levels of R-States Energized or Aware. Results suggest the value of supplementing traditional somatic conceptualizations of relaxation with the psychological approach embodied in ABC relaxation theory. Clinical and research implications are discussed. Copyright 2003 Wiley Periodicals, Inc. J Clin Psychol.

  2. Separation of components of a broad 1H-NMR composite signal by means of nutation experiments under low amplitude radiofrequency fields. Application to the water signal in synthetic clays; Developpement et mise en oeuvre d'une nouvelle methode fondee sur le phenomene de nutation pour la decomposition d'un signal composite de resonance magnetique nucleaire. Application au signal 1h de l'eau dans des argiles synthetiques

    Energy Technology Data Exchange (ETDEWEB)

    Trausch, G

    2006-11-15

    Nowadays, geologic nuclear waste storage is envisioned according to a multi-layer model which implies clays. The latter exhibit retention capacities and low permeability to water; that is why they are considered as a good candidate for engineered barriers to radioactive waste disposal. The present work here aims at studying transport phenomena which involve water molecules in three samples of synthetic clays (two of them exhibiting a Pake doublet) by means of Nuclear Magnetic Resonance (NMR). The first chapter describes structural properties of clays and presents the state-of-art of NMR and other experimental techniques used for such systems. The second chapter deals with the interpretation and the simulation of each conventional proton spectrum. These simulations allow us to evidence and to characterize a chemical exchange phenomenon. The third chapter is dedicated to original nutation experiments performed under low radiofrequency field in the case of broad NMR signal. It is shown that this type of NMR experiment can yield the number and the proportion of each species contributing to the whole signal. These results are exploited in the fourth chapter for processing relaxation and diffusion experiments. Finally, the diffusion coefficients obtained by NMR are divided by a factor 4 with respect to pure water while relaxation rates are two orders of magnitude greater. (author)

  3. Li dynamics in carbon-rich polymer-derived SiCN ceramics probed by NMR

    Science.gov (United States)

    Baek, Seung-Ho; Reinold, Lukas; Graczyk-Zajac, Magdalena; Riedel, Ralf; Hammerath, Franziska; Buechner, Bernd; Grafe, Hajo

    2014-03-01

    We report 7Li, 29Si, and 13C NMR studies of two different carbon-rich SiCN ceramics SiCN-1 and SiCN-3 derived from the preceramic polymers polyphenylvinylsilylcarbodiimide and polyphenylvinylsilazane, respectively. From the spectral analysis of the three nuclei at room temperature, we find that only the 13C spectrum is strongly influenced by Li insertion/extraction, suggesting that carbon phases are the major electrochemically active sites for Li storage. Temperature and Larmor frequency (ωL) dependences of the 7Li linewidth and spin-lattice relaxation rates T1-1 are described by an activated law with the activation energy EA of 0.31 eV and the correlation time τ0 in the high temperature limit of 1.3 ps. The 3 / 2 power law dependence of T1-1 on ωL which deviates from the standard Bloembergen, Purcell, and Pound (BPP) model implies that the Li motion on the μs timescale is governed by continuum diffusion mechanism rather than jump diffusion. On the other hand, the rotating frame relaxation rate T1ρ-1 results suggest that the slow motion of Li on the ms timescale may be affected by complex diffusion and/or non-diffusion processes.

  4. Dynamics of relaxed inflation

    Science.gov (United States)

    Tangarife, Walter; Tobioka, Kohsaku; Ubaldi, Lorenzo; Volansky, Tomer

    2018-02-01

    The cosmological relaxation of the electroweak scale has been proposed as a mechanism to address the hierarchy problem of the Standard Model. A field, the relaxion, rolls down its potential and, in doing so, scans the squared mass parameter of the Higgs, relaxing it to a parametrically small value. In this work, we promote the relaxion to an inflaton. We couple it to Abelian gauge bosons, thereby introducing the necessary dissipation mechanism which slows down the field in the last stages. We describe a novel reheating mechanism, which relies on the gauge-boson production leading to strong electro-magnetic fields, and proceeds via the vacuum production of electron-positron pairs through the Schwinger effect. We refer to this mechanism as Schwinger reheating. We discuss the cosmological dynamics of the model and the phenomenological constraints from CMB and other experiments. We find that a cutoff close to the Planck scale may be achieved. In its minimal form, the model does not generate sufficient curvature perturbations and additional ingredients, such as a curvaton field, are needed.

  5. International symposium on NMR spectroscopy

    International Nuclear Information System (INIS)

    The publication consists of 32 papers and presentations from the field of NMR spectroscopy applications submitted to the International Symposium on NMR Spectroscopy held at Smolenice between 29 Sep and 3 Oct, 1980. (B.S.)

  6. Dynamics and relaxation in confined medium. Application to 129Xe magnetic relaxation in Vycor

    International Nuclear Information System (INIS)

    Pasquier, Virginie

    1995-01-01

    Porous media morphology and topology drive the exploration of pore space by fluid. So, analysis of transport process, associated with relaxation mechanism, allows indirect study of pore geometry. The purpose of this work is to understand better the relation between geometry and transport. This study involves two parts: a modelization and prediction step is followed by an experimental application of magnetic relaxation. Numerical simulations and analytical models allow to quantify the influence on the solid interface of the dynamical behavior of confined gas in disordered porous media (granular structure and porous network) or in common geometry (cylindrical and lamellar interfaces). The formalism of diffusion propagator is a powerful tool to quantify the influence of the pore geometry on the diffusion of confined gas. The propagator holds all dynamical information on the system; it also predicts the temporal evolution of the autocorrelation functions of the Hamiltonian describing local coupling. In an intermediate time scale, magnetic relaxation shows complex diffusional regime: the autocorrelation functions decrease in a power law with a exponent smaller than d/2 (where d is the Euclidian dimension of the system). This behavior is analogous to dynamic in low-dimensional space, but here arises from surface correlations of the porous media. The long-time behavior of the autocorrelation functions retrieves the asymptotic decrease t -d/2 . Moreover, atypical behavior is observed for the Knudsen diffusion between infinite planes. It turns out that 129 Xe NMR is a appropriate technique to characterize organization and diffusion of gas confined in Vycor. Systematic studies of temperature and pressure effect on the 129 Xe chemical shift allow to specify the Xe/solid interaction. The analysis of the relaxation measurements, thanks to the numerical development, confirms conclusions arising from the study of diffusion propagator. (author) [fr

  7. Electron spin-lattice relaxation in fractals

    International Nuclear Information System (INIS)

    Shrivastava, K.N.

    1986-08-01

    We have developed the theory of the spin-fracton interaction for paramagnetic ions in fractal structures. The interaction is exponentially damped by the self-similarity length of the fractal and by the range dimensionality d Φ . The relaxation time of the spin due to the absorption and emission of the fracton has been calculated for a general dimensionality called the Raman dimensionality d R , which for the fractons differs from the Hausdorff (fractal) dimensionality, D, as well as from the Euclidean dimensionality, d. The exponent of the energy level separation in the relaxation rate varies with d R d Φ /D. We have calculated the spin relaxation rate due to a new type of Raman process in which one fracton is absorbed to affect a spin transition from one electronic level to another and later another fracton is emitted along with a spin transition such that the difference in the energies of the two fractons is equal to the electronic energy level separation. The temperature and the dimensionality dependence of such a process has been found in several approximations. In one of the approximations where the van Vleck relaxation rate for a spin in a crystal is known to vary with temperature as T 9 , our calculated variation for fractals turns out to be T 6.6 , whereas the experimental value for Fe 3+ in frozen solutions of myoglobin azide is T 6.3 . Since we used d R =4/3 and the fracton range dimensionality d Φ =D/1.8, we expect to measure the dimensionalities of the problem by measuring the temperature dependence of the relaxation times. We have also calculated the shift of the paramagnetic resonance transition for a spin in a fractal for general dimensionalities. (author)

  8. Relaxing music for anxiety control.

    Science.gov (United States)

    Elliott, Dave; Polman, Remco; McGregor, Richard

    2011-01-01

    The purpose of this investigation was to determine the characteristics of relaxing music for anxiety control. Undergraduate students (N=84) were instructed to imagine themselves in an anxiety producing situation while listening to a selection of 30 music compositions. For each composition, level of relaxation, the factors that either enhanced or detracted from its relaxing potential and the emotional labels attached were assessed. Participants were also asked to state which music components (e.g., tempo, melody) were most conducive to relaxation. Additional information was obtained through the use of a focus group of 6 undergraduate music students. This paper presents details on the characteristics of relaxing-music for anxiety control and emotional labels attached to the relaxing compositions. Furthermore, an importance value has been attached to each of the music components under scrutiny, thus providing an indication of which music components should receive greatest attention when selecting music for anxiety control.

  9. Autonomous driving in NMR.

    Science.gov (United States)

    Perez, Manuel

    2017-01-01

    The automatic analysis of NMR data has been a much-desired endeavour for the last six decades, as it is the case with any other analytical technique. This need for automation has only grown as advances in hardware; pulse sequences and automation have opened new research areas to NMR and increased the throughput of data. Full automatic analysis is a worthy, albeit hard, challenge, but in a world of artificial intelligence, instant communication and big data, it seems that this particular fight is happening with only one technique at a time (let this be NMR, MS, IR, UV or any other), when the reality of most laboratories is that there are several types of analytical instrumentation present. Data aggregation, verification and elucidation by using complementary techniques (e.g. MS and NMR) is a desirable outcome to pursue, although a time-consuming one if performed manually; hence, the use of automation to perform the heavy lifting for users is required to make the approach attractive for scientists. Many of the decisions and workflows that could be implemented under automation will depend on the two-way communication with databases that understand analytical data, because it is desirable not only to query these databases but also to grow them in as much of an automatic manner as possible. How these databases are designed, set up and the data inside classified will determine what workflows can be implemented. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  10. NMR, water and plants

    NARCIS (Netherlands)

    As, van H.

    1982-01-01

    This Thesis describes the application of a non-destructive pulsed proton NMR method mainly to measure water transport in the xylem vessels of plant stems and in some model systems. The results are equally well applicable to liquid flow in other biological objects than plants, e.g. flow of blood and

  11. NMR of unfolded proteins

    Indian Academy of Sciences (India)

    Unknown

    2005-01-03

    Jan 3, 2005 ... out' response to environmental changes with structural complexity ... of 3D structure at atomic resolution of folded proteins ...... 5.14 HIV-1 protease. NMR identification of local structural preferences in. HIV-1 protease in the 'unfolded state' at 6 M gua- nidine hydrochloride has been reported.49 Analyses.

  12. Single-sided NMR

    CERN Document Server

    Casanova, Federico; Blümich, Bernhard

    2011-01-01

    Single-Sided NMR describes the design of the first functioning single-sided tomograph, the related measurement methods, and a number of applications. One of the key advantages to this method is the speed at which the images are obtained.

  13. ABC relaxation theory and the factor structure of relaxation states, recalled relaxation activities, dispositions, and motivations.

    Science.gov (United States)

    Smith, J C; Wedell, A B; Kolotylo, C J; Lewis, J E; Byers, K Y; Segin, C M

    2000-06-01

    ABC Relaxation Theory proposes 15 psychological relaxation-related states (R-States): Sleepiness, Disengagement, Physical Relaxation, Mental Quiet, Rested/Refreshed, At Ease/At Peace, Energized, Aware, Joy, Thankfulness and Love, Prayerfulness, Childlike Innocence, Awe and Wonder, Mystery, and Timeless/Boundless/Infinite. The present study summarizes the results of 13 separate factor analyses of immediate relaxation-related states, states associated with recalled relaxation activities, relaxation dispositions, and relaxation motivations on a combined sample of 1,904 individuals (group average ages ranged from 28-40 yr.). Four exploratory factor analyses of Smith Relaxation Inventories yielded 15 items that most consistently and exclusively load (generally at least .70) on six replicated factors. These items included happy, joyful, energized, rested, at peace, warm, limp, silent, quiet, dozing, drowsy, prayerful, mystery, distant, and indifferent. Subsequent factor analyses restricted to these items and specifying six factors were performed on 13 different data sets. Each yielded the same six-factor solution: Factor 1: Centered Positive Affect, Factor 2: Sleepiness, Factor 3: Disengagement, Factor 4: Physical Relaxation, Factor 5: Mental Quiet, and Factor 6: Spiritual. Implications for ABC Relaxation Theory are discussed.

  14. Relaxation and Meditation with Music

    OpenAIRE

    ČAPKOVÁ, Jana

    2011-01-01

    The thesis introduces an importance of a mental hygiene and its chosen methods - relaxation and meditation with music. The theoretical part is focused on a description of the basic relaxation and meditation techniques and curative effects of music. It deals with a music therapy, its meaning, types, methods and history in terms of the importance of music healing relaxation effects on the mental, physical as well as spiritual health. The practical part includes a usage of these methods in pract...

  15. Stress relaxation and estimation of activation volume in a ...

    Indian Academy of Sciences (India)

    Unknown

    ). The testing was carried out in displacement control for stress relaxation testing at a strain rate of 3%/min. An active capacitor transducer measured the displacement of specimen with a sensitivity of 367 µm/V. 3. Results and discussion.

  16. NMR for chemists and biologists

    CERN Document Server

    Carbajo, Rodrigo J

    2013-01-01

    This book offers a concise introduction to the field of nuclear magnetic resonance or NMR. It presents the basic foundations of NMR in a non-mathematical way and provides an overview of both recent and important biological applications of NMR.

  17. Fetal responses to induced maternal relaxation during pregnancy

    OpenAIRE

    DiPietro, Janet A.; Costigan, Kathleen A.; Nelson, Priscilla; Gurewitsch, Edith D.; Laudenslager, Mark L.

    2007-01-01

    Fetal responses to induced maternal relaxation during the 32nd week of pregnancy were recorded in 100 maternal-fetal pairs using a digitized data collection system. The 18-minute guided imagery relaxation manipulation generated significant changes in maternal heart rate, skin conductance, respiration period, and respiratory sinus arrhythmia. Significant alterations in fetal neurobehavior were observed, including decreased fetal heart rate (FHR), increased FHR variability, suppression of fetal...

  18. Study of poly butadiene molecular mobility by NMR in the solid state; Estudo da mobilidade molecular do polibutadieno por RMN no estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Coelho, Maria Rita G.; San Gil, Rosane A.S. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica; Tavares, Maria Ines B. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas

    1995-12-31

    This work has aimed to study commercial poly butadiene using {sup 13} C NMR spectroscopy in the solid state through relaxation time investigation, in order to characterize its molecular mobility in the solid state and structure. NMR spectra are presented and analysed and chemical shifts are also observed and discussed 3 refs., 3 figs., 1 tab.

  19. Spin-flip relaxation via optical phonon scattering in quantum dots

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Zi-Wu, E-mail: zwwang@semi.ac.cn [Tianjin Key Laboratory of Low Dimensional Materials Physics and Preparing Technology, Department of Physics, Tianjin University, Tianjin 300072 (China); Liu, Lei [Suzhou Institute of Nano-tech and Nano-bionics, CAS, Suzhou 215125 (China); Li, Shu-Shen [Institute of Semiconductor, CAS, Beijing 100083 (China)

    2013-12-14

    Based on the spin-orbit coupling admixture mechanism, we theoretically investigate the spin-flip relaxation via optical phonon scattering in quantum dots by considering the effect of lattice relaxation due to the electron-acoustic phonon deformation potential coupling. The relaxation rate displays a cusp-like structure (or a spin hot spot) that becomes more clearly with increasing temperature. We also calculate the relaxation rate of the spin-conserving process, which follows a Gaussian form and is several orders of magnitude larger than that of spin-flip process. Moreover, we find that the relaxation rate displays the oscillatory behavior due to the interplay effects between the magnetic and spatial confinement for the spin-flip process not for the spin-conserving process. The trends of increasing and decreasing temperature dependence of the relaxation rates for two relaxation processes are obtained in the present model.

  20. Relaxation Techniques for Trauma.

    Science.gov (United States)

    Scotland-Coogan, Diane; Davis, Erin

    2016-01-01

    Physiological symptoms of posttraumatic stress disorder (PTSD) manifest as increased arousal and reactivity seen as anger outburst, irritability, reckless behavior with no concern for consequences, hypervigilance, sleep disturbance, and problems with focus (American Psychiatric Association, 2013 ). In seeking the most beneficial treatment for PTSD, consideration must be given to the anxiety response. Relaxation techniques are shown to help address the physiological manifestations of prolonged stress. The techniques addressed by the authors in this article include mindfulness, deep breathing, yoga, and meditation. By utilizing these techniques traditional therapies can be complemented. In addition, those who are averse to the traditional evidence-based practices or for those who have tried traditional therapies without success; these alternative interventions may assist in lessening physiological manifestations of PTSD. Future research studies assessing the benefits of these treatment modalities are warranted to provide empirical evidence to support the efficacy of these treatments.

  1. Nuclear magnetic resonance (NMR): application to examine liver tissues during invasion of the Liver fluke in cattle

    International Nuclear Information System (INIS)

    Wranicz, M.; Podbielski, T.; Grabiec, S.

    1989-01-01

    The T 1 and T 2 relaxation times of protons of hydrogen in the liver parenchyma and biliary ducts in normal and parazitized by the Liver fluke cows were determined. A method of the NMR in which a lenght or relaxation time is an index was applied. The value of this index is characteristic for determined physiological and pathological states of cells and it reveals changes which developed in body cells. It was found that tissues of cows parazitized by the Liver fluke (parenchyma and biliary ducts) and healthy ones differ significantly by the lenght of relaxation times. Parazitized tissues show a longer relaxation time than tissues of normal cows. (author)

  2. Quantitative measurement of water diffusion lifetimes at a protein/DNA interface by NMR

    International Nuclear Information System (INIS)

    Gruschus, James M.; Ferretti, James A.

    2001-01-01

    Hydration site lifetimes of slowly diffusing water molecules at the protein/DNA interface of the vnd/NK-2 homeodomain DNA complex were determined using novel three-dimensional NMR techniques. The lifetimes were calculated using the ratios of ROE and NOE cross-relaxation rates between the water and the protein backbone and side chain amides. This calculation of the lifetimes is based on a model of the spectral density function of the water-protein interaction consisting of three timescales of motion: fast vibrational/rotational motion, diffusion into/out of the hydration site, and overall macromolecular tumbling. The lifetimes measured ranged from approximately 400 ps to more than 5 ns, and nearly all the slowly diffusing water molecules detected lie at the protein/DNA interface. A quantitative analysis of relayed water cross-relaxation indicated that even at very short mixing times, 5 ms for ROESY and 12 ms for NOESY, relay of magnetization can make a small but detectable contribution to the measured rates. The temperature dependences of the NOE rates were measured to help discriminate direct dipolar cross-relaxation from chemical exchange. Comparison with several X-ray structures of homeodomain/DNA complexes reveals a strong correspondence between water molecules in conserved locations and the slowly diffusing water molecules detected by NMR. A homology model based on the X-ray structures was created to visualize the conserved water molecules detected at the vnd/NK-2 homeodomain DNA interface. Two chains of water molecules are seen at the right and left sides of the major groove, adjacent to the third helix of the homeodomain. Two water-mediated hydrogen bond bridges spanning the protein/DNA interface are present in the model, one between the backbone of Phe8 and a DNA phosphate, and one between the side chain of Asn51 and a DNA phosphate. The hydrogen bond bridge between Asn51 and the DNA might be especially important since the DNA contact made by the invariant

  3. 8Li β-NMR study of epitaxial LixCoO2 films

    Science.gov (United States)

    Sugiyama, J.; Harada, M.; Oki, H.; Shiraki, S.; Hitosugi, T.; Ofer, O.; Salman, Z.; Song, Q.; Wang, D.; Saadaoui, H.; Morris, G. D.; Chow, K. H.; MacFarlane, W. A.; Kiefl, R. F.

    2014-12-01

    In order to investigate the diffusive motion of Li+ in a thin film electrode material for Li-ion batteries, we have measured β-NMR spectra of 8Li+ ions implanted into epitaxial films of Li0.7CoO2 and LiCoO2 in the temperature range between 10 and 310 K. Below 100 K, the spin-lattice relaxation rate (1/T1) in the Li0.7CoO2 film increased with decreasing temperature, indicating the appearance and evolution of localized magnetic moments, as observed with μ+SR. As temperature is increased from 100 K, 1/T1 starts to increase above ~ 200 K, where both Li- NMR and μ+SR also sensed an increase in 1/T1 due to Li-diffusion. Interestingly, such diffusive behavior was found to depend on the implantation energy, possibly because the surface of the film is decomposed due to chemical instability of the Li0.7CoO2 phase in air. Such diffusive behavior was not observed for the LiCoO2 film up to 310 K.

  4. NMR evidence for peculiar spin gaps in a doped S=1/2 Heisenberg spin chain

    Energy Technology Data Exchange (ETDEWEB)

    Utz, Yannic; Rudisch, Christian; Hammerath, Franziska; Grafe, Hans-Joachim; Mohan, Ashwin; Ribeiro, Patrick; Hess, Christian; Wolter, Anja; Kataev, Vladislav; Nishimoto, Satoshi; Drechsler, Stefan-Ludwig; Buechner, Bernd [IFW Dresden (Germany); Singh, Surjeet [Indian Institute of Science Education and Research, Pune (India); Saint-Martin, Romuald; Revcolevschi, Alexandre [Laboratoire de Physico-Chimie de l' Etat Solide, Universite Paris-Sud, Orsay (France)

    2012-07-01

    We present {sup 63}Cu Nuclear Magnetic Resonance (NMR) measurements on undoped, Ca-doped and Ni-doped SrCuO{sub 2} single crystals. SrCuO{sub 2} is a good realization of a one-dimensional S=1/2 Heisenberg spin chain. This is manifested by the theoretically-expected temperature-independent NMR spin-lattice relaxation rate T{sub 1}{sup -1}. In Sr{sub 0.9}Ca{sub 0.1}CuO{sub 2} an exponential decrease of T{sub 1}{sup -1} below 90 K evidences the opening of a gap in the spin excitation spectrum, which amounts to {Delta}=50 K. DMRG calculations are presented to discuss the origin of this spin gap. New results on SrCu{sub 0.99}Ni{sub 0.01}O{sub 2} also indicate the presence of a spin gap, which is twice as large as in Sr{sub 0.9}Ca{sub 0.1}CuO{sub 2}, despite the minor doping level of Ni compared to Ca. We discuss different possible impacts of Ca (S=0) and Ni (S=1) doping on structural and magnetic properties of the parent compound.

  5. Precession relaxation of viscoelastic oblate rotators

    Science.gov (United States)

    Frouard, Julien; Efroimsky, Michael

    2018-01-01

    Perturbations of all sorts destabilize the rotation of a small body and leave it in a non-principal spin state. In such a state, the body experiences alternating stresses generated by the inertial forces. This yields nutation relaxation, i.e. evolution of the spin towards the principal rotation about the maximal-inertia axis. Knowledge of the time-scales needed to damp the nutation is crucial in studies of small bodies' dynamics. In the literature hitherto, nutation relaxation has always been described with aid of an empirical quality factor Q introduced to parametrize the energy dissipation rate. Among the drawbacks of this approach was its inability to describe the dependence of the relaxation rate upon the current nutation angle. This inability stemmed from our lack of knowledge of the quality factor's dependence on the forcing frequency. In this article, we derive our description of nutation damping directly from the rheological law obeyed by the material. This renders us the nutation damping rate as a function of the current nutation angle, as well as of the shape and the rheological parameters of the body. In contradistinction from the approach based on an empirical Q factor, our development gives a zero damping rate in the spherical-shape limit. Our method is generic and applicable to any shape and to any linear rheological law. However, to simplify the developments, here we consider a dynamically oblate rotator with a Maxwell rheology.

  6. The GNAT: A new tool for processing NMR data.

    Science.gov (United States)

    Castañar, Laura; Poggetto, Guilherme Dal; Colbourne, Adam A; Morris, Gareth A; Nilsson, Mathias

    2018-02-02

    The GNAT (General NMR Analysis Toolbox) is a free and open-source software package for processing, visualising, and analysing NMR data. It supersedes the popular DOSY Toolbox, which has a narrower focus on diffusion NMR. Data import of most common formats from the major NMR platforms is supported, as well as a GNAT generic format. Key basic processing of NMR data (e.g., Fourier transformation, baseline correction, and phasing) is catered for within the program, as well as more advanced techniques (e.g., reference deconvolution and pure shift FID reconstruction). Analysis tools include DOSY and SCORE for diffusion data, ROSY T 1 /T 2 estimation for relaxation data, and PARAFAC for multilinear analysis. The GNAT is written for the MATLAB® language and comes with a user-friendly graphical user interface. The standard version is intended to run with a MATLAB installation, but completely free-standing compiled versions for Windows, Mac, and Linux are also freely available. © 2018 The Authors Magnetic Resonance in Chemistry Published by John Wiley & Sons Ltd.

  7. Time domain NMR evaluation of poly(vinyl alcohol) xerogels

    Energy Technology Data Exchange (ETDEWEB)

    Rodrigues, Elton Jorge da Rocha; Cavalcante, Maxwell de Paula; Tavares, Maria Ines Bruno, E-mail: mibt@ima.ufrj.br [Universidade Federal do Rio de Janeiro (IMA/UFRJ), Rio de Janeiro, RJ (Brazil). Centro de Tecnologia. Instituto de Macromoleculas Professora Eloisa Mano

    2016-05-15

    Poly(vinyl alcohol) (PVA)-based chemically cross-linked xerogels, both neat and loaded with nanoparticulate hydrophilic silica (SiO{sub 2}), were obtained and characterized mainly through time domain NMR experiments (TD-NMR). Fourier-transform infrared (FT-IR) and wide angle X-ray diffraction (WAXD) analyses were employed as secondary methods. TD-NMR, through the interpretation of the spin-lattice relaxation constant values and related information, showed both cross-linking and nanoparticle influences on PVA matrix. SiO{sub 2} does not interact chemically with the PVA chains, but has effect on its molecular mobility, as investigated via TD-NMR. Apparent energy of activation, spin-lattice time constant and size of spin domains in the sample have almost linear dependence with the degree of cross-linking of the PVA and are affected by the addition of SiO{sub 2}. These three parameters were derived from a single set of TD-NMR experiments, which demonstrates the versatility of the technique for characterization of inorganic-organic hybrid xerogels, an important class of materials. (author)

  8. Backbone dynamics of a bacterially expressed peptide from the receptor binding domain of Pseudomonas aeruginosa pilin strain PAK from heteronuclear 1H-15N NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Campbell, A. Patricia [University of Washington, Department of Medicinal Chemistry, School of Pharmacy (United States); Spyracopoulos, Leo [Department of Biochemistry (Canada); Irvin, Randall T. [University of Alberta, Department of Medical Microbiology and Immunology (Canada); Sykes, Brian D. [Department of Biochemistry (Canada)

    2000-07-15

    The backbone dynamics of a {sup 15}N-labeled recombinant PAK pilin peptide spanning residues 128-144 in the C-terminal receptor binding domain of Pseudomonas aeruginosa pilin protein strain PAK (Lys{sup 128}-Cys-Thr-Ser-Asp-Gln-Asp-Glu-Gln-Phe-Ile-Pro-Lys-Gly-Cys-Ser-Lys{sup 144}) were probed by measurements of {sup 15}N NMR relaxation. This PAK(128-144) sequence is a target for the design of a synthetic peptide vaccine effective against multiple strains of P. aeruginosa infection. The {sup 15}N longitudinal (T{sub 1}) and transverse (T{sub 2}) relaxation rates and the steady-state heteronuclear {l_brace}{sup 1}H{r_brace}-{sup 15}N NOE were measured at three fields (7.04, 11.74 and 14.1 Tesla), five temperatures (5, 10, 15, 20, and 25 deg. C ) and at pH 4.5 and 7.2. Relaxation data was analyzed using both the 'model-free' formalism [Lipari, G. and Szabo, A. (1982) J. Am. Chem. Soc., 104, 4546-4559 and 4559-4570] and the reduced spectral density mapping approach [Farrow, N.A., Szabo, A., Torchia, D.A. and Kay, L.E. (1995) J. Biomol. NMR, 6, 153-162]. The relaxation data, spectral densities and order parameters suggest that the type I and type II {beta}-turns spanning residues Asp{sup 134}-Glu-Gln-Phe{sup 137} and Pro{sup 139}-Lys-Gly-Cys{sup 142}, respectively, are the most ordered and structured regions of the peptide. The biological implications of these results will be discussed in relation to the role that backbone motions play in PAK pilin peptide immunogenicity, and within the framework of developing a pilin peptide vaccine capable of conferring broad immunity across P. aeruginosa strains.

  9. Estimation of water retention parameters from nuclear magnetic resonance relaxation time distributions.

    Science.gov (United States)

    Costabel, Stephan; Yaramanci, Ugur

    2013-04-01

    [1] For characterizing water flow in the vadose zone, the water retention curve (WRC) of the soil must be known. Because conventional WRC measurements demand much time and effort in the laboratory, alternative methods with shortened measurement duration are desired. The WRC can be estimated, for instance, from the cumulative pore size distribution (PSD) of the investigated material. Geophysical applications of nuclear magnetic resonance (NMR) relaxometry have successfully been applied to recover PSDs of sandstones and limestones. It is therefore expected that the multiexponential analysis of the NMR signal from water-saturated loose sediments leads to a reliable estimation of the WRC. We propose an approach to estimate the WRC using the cumulative NMR relaxation time distribution and approximate it with the well-known van-Genuchten (VG) model. Thereby, the VG parameter n , which controls the curvature of the WRC, is of particular interest, because it is the essential parameter to predict the relative hydraulic conductivity. The NMR curves are calibrated with only two conventional WRC measurements, first, to determine the residual water content and, second, to define a fixed point that relates the relaxation time to a corresponding capillary pressure. We test our approach with natural and artificial soil samples and compare the NMR-based results to WRC measurements using a pressure plate apparatus and to WRC predictions from the software ROSETTA. We found that for sandy soils n can reliably be estimated with NMR, whereas for samples with clay and silt contents higher than 10% the estimation fails. This is the case when the hydraulic properties of the soil are mainly controlled by the pore constrictions. For such samples, the sensitivity of the NMR method for the pore bodies hampers a plausible WRC estimation. Citation: Costabel, S., and U. Yaramanci (2013), Estimation of water retention parameters from nuclear magnetic resonance relaxation time distributions, Water

  10. OCT-based approach to local relaxations discrimination from translational relaxation motions

    Science.gov (United States)

    Matveev, Lev A.; Matveyev, Alexandr L.; Gubarkova, Ekaterina V.; Gelikonov, Grigory V.; Sirotkina, Marina A.; Kiseleva, Elena B.; Gelikonov, Valentin M.; Gladkova, Natalia D.; Vitkin, Alex; Zaitsev, Vladimir Y.

    2016-04-01

    Multimodal optical coherence tomography (OCT) is an emerging tool for tissue state characterization. Optical coherence elastography (OCE) is an approach to mapping mechanical properties of tissue based on OCT. One of challenging problems in OCE is elimination of the influence of residual local tissue relaxation that complicates obtaining information on elastic properties of the tissue. Alternatively, parameters of local relaxation itself can be used as an additional informative characteristic for distinguishing the tissue in normal and pathological states over the OCT image area. Here we briefly present an OCT-based approach to evaluation of local relaxation processes in the tissue bulk after sudden unloading of its initial pre-compression. For extracting the local relaxation rate we evaluate temporal dependence of local strains that are mapped using our recently developed hybrid phase resolved/displacement-tracking (HPRDT) approach. This approach allows one to subtract the contribution of global displacements of scatterers in OCT scans and separate the temporal evolution of local strains. Using a sample excised from of a coronary arteria, we demonstrate that the observed relaxation of local strains can be reasonably fitted by an exponential law, which opens the possibility to characterize the tissue by a single relaxation time. The estimated local relaxation times are assumed to be related to local biologically-relevant processes inside the tissue, such as diffusion, leaking/draining of the fluids, local folding/unfolding of the fibers, etc. In general, studies of evolution of such features can provide new metrics for biologically-relevant changes in tissue, e.g., in the problems of treatment monitoring.

  11. NMR study of the molecular nanomagnet [Fe8(N3C6H15)6O2(OH)12]·[Br8·9H2O] in the high-spin magnetic ground state

    International Nuclear Information System (INIS)

    Furukawa, Y.; Kumagai, K.; Lascialfari, A.; Aldrovandi, S.; Borsa, F.; Sessoli, R.; Gatteschi, D.

    2001-01-01

    The magnetic molecular cluster [Fe 8 (N 3 C 6 H 15 ) 6 O 2 (OH) 12 ] 8+ [Br 8 ·9H 2 O] 8- , in short Fe8, has been investigated at low temperature by 1 H-NMR and relaxation measurements. Some measurements of 2 D-NMR in partially deuterated Fe8 clusters will also be reported. Upon decreasing temperature the NMR spectra display a very broad and structured signal which is the result of the internal local fields at the proton sites due to the local moments of the Fe(III) ions in the total S=10 magnetic ground state. The proton and deuteron NMR spectra have been analyzed and the different resonance peaks have been attributed to the different proton groups in the molecule. The simulation of the spectra by using a dipolar hyperfine field and the accepted model for the orientation of the Fe(III) local moments do not agree with the experiments even when the magnitude of the local Fe(III) moments is allowed to vary. It is concluded that a positive contact hyperfine interaction of the same order of magnitude as the dipolar interaction is present for all proton sites except the water molecules. The temperature and magnetic field dependence of the nuclear spin-lattice relaxation rate is ascribed to the fluctuations of the local Fe(III) moments, which follow rigidly the fluctuations of the total ground state magnetization of the nanomagnet. By using a simple model already utilized for the Mn12 cluster, we derive the value of the spin phonon coupling constant which determines the lifetime broadening of the different magnetic quantum number m substates of the S=10 ground state. It is shown that the lifetime broadening decreases rapidly on lowering the temperature. When the lifetime becomes longer than the reciprocal of the frequency shift of the proton lines a structure emerges in the NMR spectrum reflecting the ''frozen'' local moment configuration

  12. Irradiation creep, stress relaxation and a mechanical equation of state

    International Nuclear Information System (INIS)

    Foster, J.P.

    1976-01-01

    Irradiation creep and stress relaxation data are available from the United Kingdom for 20 percent CW M316, 20 percent CW FV 548 and FHT PE16 using pure torsion in the absence of swelling at 300 0 C. Irradiation creep models were used to calculate the relaxation and permanent deflection of the stress relaxation tests. Two relationships between irradiation creep and stress relaxation were assessed by comparing the measured and calculated stress relaxation and permanent deflection. The results show that for M316 and FV548, the stress relaxation and deflection may be calculated using irradiation creep models when the stress rate term arising from the irradiation creep model is set equal to zero. In the case of PE16, the inability to calculate the stress relaxation and permanent deflection from the irradiation creep data was attributed to differences in creep behavior arising from lot-to-lot variations in alloying elements and impurity content. A modification of the FV548 and PE16 irradiation creep coefficients was necessary in order to calculate the stress relaxation and deflection. The modifications in FV548 and PE16 irradiation creep properties reduces the large variation in the transient or incubation parameter predicted by irradiation creep tests for M316, FV548 and PE16

  13. Magnetic relaxation in anisotropic magnets

    DEFF Research Database (Denmark)

    Lindgård, Per-Anker

    1971-01-01

    The line shape and the kinematic and thermodynamic slowing down of the critical and paramagnetic relaxation in axially anisotropic materials are discussed. Kinematic slowing down occurs only in the longitudinal relaxation function. The thermodynamic slowing down occurs in either the transverse...

  14. Electrode reactions in slowly relaxing media

    Science.gov (United States)

    Matyushov, Dmitry V.; Newton, Marshall D.

    2017-11-01

    Standard models of reaction kinetics in condensed materials rely on the Boltzmann-Gibbs distribution for the population of reactants at the top of the free energy barrier separating them from the products. While energy dissipation and quantum effects at the barrier top can potentially affect the transmission coefficient entering the rate pre-exponential factor, much stronger dynamical effects on the reaction barrier are caused by the breakdown of ergodicity for populating the reaction barrier (violation of the Boltzmann-Gibbs statistics). When the spectrum of medium modes coupled to the reaction coordinate includes fluctuations slower than the reaction rate, such nuclear motions dynamically freeze on the reaction time scale and do not contribute to the activation barrier. Here we consider the consequences of this scenario for electrode reactions in slowly relaxing media. Changing the electrode overpotential speeds the electrode electron transfer up, potentially cutting through the spectrum of nuclear modes coupled to the reaction coordinate. The reorganization energy of electrochemical electron transfer becomes a function of the electrode overpotential, switching between the thermodynamic value at low rates to the nonergodic limit at higher rates. The sharpness of this transition depends on the relaxation spectrum of the medium. The reorganization energy experiences a sudden drop with increasing overpotential for a medium with a Debye relaxation but becomes a much shallower function of the overpotential for media with stretched exponential dynamics. The latter scenario characterizes the electron transfer in ionic liquids. The analysis of electrode reactions in room-temperature ionic liquids shows that the magnitude of the free energy of nuclear solvation is significantly below its thermodynamic limit. This result applies to reaction times faster than microseconds and is currently limited by the available dielectric relaxation data.

  15. International school on high field NMR spectroscopy for solids and liquids

    Energy Technology Data Exchange (ETDEWEB)

    Marion, D.; Meier, B.; Keeler, J.; Berthault, P.; Vedrine, P.; Grandinetti, P.; Delsuc, M.A.; Spiess, H

    2006-07-01

    The aim of the school is to offer high-level pedagogical courses on a wide range of liquid- and solid-state NMR concepts and techniques: theory, instrumentation (magnets and probes), data acquisition, processing and analysis, measurement of dipolar and quadrupolar couplings, spin relaxation and hyper-polarization. This document gathers only the slides of most presentations.

  16. NMR Studies of Peroxidases.

    Science.gov (United States)

    Veitch, Nigel Charles

    Available from UMI in association with The British Library. Requires signed TDF. Peroxidases are a haem-containing group of enzymes with a wide diversity of function within biological systems. While a common characteristic is the ability to catalyse the conversion of hydrogen peroxide to water, it is the accompanying processes of hormone synthesis and degradation which have generated such a high level of interest. However, information at the molecular level is limited to a single well-resolved crystal structure, that of yeast cytochrome c peroxidase. This thesis presents a strategy for the investigation of peroxidase structure and function based on proton nuclear magnetic resonance spectroscopy, a technique which has the ability to address aspects of both protein structure and protein dynamics in solution. The application of one- and two-dimensional NMR techniques has been developed in the context of plant peroxidases, notably the isoenzyme HRP-C derived from the horseradish root. Characterisation of the proton NMR spectra of HRP -C in resting and ligated states provided new information enabling the structure of the binding site for aromatic donor molecules, such as indole-3-propionic, ferulic and benzhydroxamic acids, to be resolved. In order to overcome difficulties encountered with a protein of the complexity of peroxidase, additional information was obtained from chemical shift parameters and the use of peroxidase variants produced by site-directed mutagenesis. A comparative study using NMR spectroscopy was undertaken for wild-type recombinant HRP-C expressed in Escherichia coli, and two protein variants with substitutions made to residues located on the distal side of the haem pocket, Phe41 to Val and Arg38 to Lys. NMR analyses of a plant peroxidase from barley grains and the fungal peroxidase from Coprinus cinereus were also successful using methods conceived with HRP-C. Examination of three specifically constructed recombinant protein variants of C. cinereus

  17. NMR, water and plants

    International Nuclear Information System (INIS)

    As, H. van.

    1982-01-01

    This thesis describes the application of a non-destructive pulsed proton NMR method mainly to measure water transport in the xylem vessels of plant stems and in some model systems. The results are equally well applicable to liquid flow in other biological objects than plants, e.g. flow of blood and other body fluids in human and animals. The method is based on a pulse sequence of equidistant π pulses in combination with a linear magnetic field gradient. (Auth.)

  18. Assessment of structural changes of human teeth by low-field nuclear magnetic resonance (NMR)

    International Nuclear Information System (INIS)

    Ni, Qingwen; Chen, Shuo

    2010-01-01

    A technique of low-field pulsed proton nuclear magnetic resonance (NMR) spin relaxation is described for assessment of age-related structural changes (dentin and pulp) of human teeth in vitro. The technique involves spin–spin relaxation measurement and inversion spin–spin spectral analysis methods. The spin–spin relaxation decay curve is converted into a T 2 distribution spectrum by a sum of single exponential decays. The NMR spectra from the extracted dentin-portion-only and dental pulp-cells-only were compared with the whole extracted teeth spectra, for the dentin and pulp peak assignments. While dentin and pulp are highly significant parameters in determining tooth quality, variations in these parameters with age can be used as an effective tool for estimating tooth quality. Here we propose an NMR calibration method—the ratio of the amount of dentin to the amount of pulp obtained from NMR T 2 distribution spectra can be used for measuring the age-related structural changes in teeth while eliminating any variations in size of teeth. Eight teeth (third molars) extracted from humans, aged among 17–67 years old, were tested in this study. It is found that the intensity ratio of dentin to pulp sensitively changes from 0.48 to 3.2 approaching a linear growth with age. This indicates that age-related structural changes in human teeth can be detected using the low-field NMR technique

  19. Rotational dynamics account for pH-dependent relaxivities of PAMAM dendrimeric, Gd-based potential MRI contrast agents.

    Science.gov (United States)

    Laus, Sabrina; Sour, Angélique; Ruloff, Robert; Tóth, Eva; Merbach, André E

    2005-05-06

    The EPTPA5) chelate, which ensures fast water exchange in GdIII complexes, has been coupled to three different generations (5, 7, and 9) of polyamidoamine (PAMAM) dendrimers through benzylthiourea linkages (H5EPTPA = ethylenepropylenetriamine-N,N,N',N'',N''-pentaacetic acid). The proton relaxivities measured at pH 7.4 for the dendrimer complexes G5-(GdEPTPA)111, G7-(GdEPTPA)253 and G9-(GdEPTPA)1157 decrease with increasing temperature, indicating that, for the first time for dendrimers, slow water exchange does not limit relaxivity. At a given field and temperature, the relaxivity increases from G5 to G7, and then slightly decreases for G9 (r1 = 20.5, 28.3 and 27.9 mM(-1) s(-1), respectively, at 37 degrees C, 30 MHz). The relaxivities show a strong and reversible pH dependency for all three dendrimer complexes. This originates from the pH-dependent rotational dynamics of the dendrimer skeleton, which was evidenced by a combined variable-temperature and multiple-field 17O NMR and 1H relaxivity study performed at pH 6.0 and 9.9 on G5-(GdEPTPA)111. The longitudinal 17O and 1H relaxation rates of the dendrimeric complex are strongly pH-dependent, whereas they are not for the [Gd(EPTPA)(H2O)]2- monomer chelate. The longitudinal 17O and 1H relaxation rates have been analysed by the Lipari-Szabo spectral density functions and correlation times have been calculated for the global motion of the entire macromolecule (tau(gO)) and the local motion of the GdIII chelates on the surface (tau(lO)), correlated by means of an order parameter S2. The dendrimer complex G5-(GdEPTPA)111 has a considerably higher tau(gO) under acidic than under basic conditions (tau(298)gO = 4040 ps and 2950 ps, respectively), while local motions are less influenced by pH (tau(298)lO = 150 and 125 ps). The order parameter, characterizing the rigidity of the macromolecule, is also higher at pH 6.0 than at pH 9.9 (S2 = 0.43 vs 0.36, respectively). The pH dependence of the global correlation time can be

  20. Nuclear magnetic relaxation studies of semiconductor nanocrystals and solids

    Energy Technology Data Exchange (ETDEWEB)

    Sachleben, Joseph Robert [Lawrence Berkeley Lab., CA (United States); California Univ., Berkeley, CA (United States). Dept. of Chemistry

    1993-09-01

    Semiconductor nanocrystals, small biomolecules, and 13C enriched solids were studied through the relaxation in NMR spectra. Surface structure of semiconductor nanocrystals (CdS) was deduced from high resolution 1H and 13C liquid state spectra of thiophenol ligands on the nanocrystal surfaces. The surface coverage by thiophenol was found to be low, being 5.6 and 26% for nanocrystal radii of 11.8 and 19.2 Å. Internal motion is estimated to be slow with a correlation time > 10-8 s-1. The surface thiophenol ligands react to form a dithiophenol when the nanocrystals were subjected to O2 and ultraviolet. A method for measuring 14N-1H J-couplings is demonstrated on pyridine and the peptide oxytocin; selective 2D T1 and T2 experiments are presented for measuring relaxation times in crowded spectra with overlapping peaks in 1D, but relaxation effects interfere. Possibility of carbon-carbon cross relaxation in 13C enriched solids is demonstrated by experiments on zinc acetate and L-alanine.

  1. Biomolecules: Fluctuations and relaxations

    Science.gov (United States)

    Parak, F.; Ostermann, A.; Gassmann, A.; Scherk, C.; Chong, S.-H.; Kidera, A.; Go, N.

    1999-10-01

    The normal-mode refinement of X-ray crystallographic data opened a new possibility to analyze the mean-square displacements in a protein molecule. A comparison of the X-ray structure of myoglobin at several temperatures with Mössbauer data is performed. In the low-temperature regime below 180 K the iron mean-square displacements obtained by Mössbauer spectroscopy are in good agreement with a normal-mode analysis. The X-ray mean-square displacements at the position of the iron, after the motion originated from the external degrees of freedom are subtracted, have practically the same temperature dependence as those from Mössbauer spectroscopy. The difference between the X-ray mean-square displacements and those predicted by normal-mode analysis measures the distribution of molecules into conformational substates. Above 180 K the Mössbauer effect indicates fluctuations between conformational substates. The relaxation from a Fe(III) conformation to a Fe(II) conformation is shown for superoxide dismutase of Propionibacterium shermanii.

  2. Non-monotonic behaviour in relaxation dynamics of image restoration

    International Nuclear Information System (INIS)

    Ozeki, Tomoko; Okada, Masato

    2003-01-01

    We have investigated the relaxation dynamics of image restoration through a Bayesian approach. The relaxation dynamics is much faster at zero temperature than at the Nishimori temperature where the pixel-wise error rate is minimized in equilibrium. At low temperature, we observed non-monotonic development of the overlap. We suggest that the optimal performance is realized through premature termination in the relaxation processes in the case of the infinite-range model. We also performed Markov chain Monte Carlo simulations to clarify the underlying mechanism of non-trivial behaviour at low temperature by checking the local field distributions of each pixel

  3. Characterization of Oat (Avena nuda L.) β-Glucan Cryogelation Process by Low-Field NMR.

    Science.gov (United States)

    Wu, Jia; Li, Linlin; Wu, Xiaoyan; Dai, Qiaoling; Zhang, Ru; Zhang, Yi

    2016-01-13

    Low-field nuclear magnetic resonance (LF-NMR) is a useful method in studying the water distribution and mobility in heterogeneous systems. This technique was used to characterize water in an oat β-glucan aqueous system during cryogelation by repeated freeze-thaw treatments. The results indicated that microphase separation occurred during cryogelation, and three water components were determined in the cryostructure. The spin-spin relaxation time was analyzed on the basis of chemical exchange and diffusion exchange theory. The location of each water component was identified in the porous microstructure of the cryogel. The pore size measured from the SEM image is in accordance with that estimated from relaxation time. The formation of cryogel is confirmed by rheological method. The results suggested that the cryogelation process of the polysaccharide could be monitored by LF-NMR through the evolution of spin-spin relaxation characteristics.

  4. Nuclear spin relaxation of methane in solid xenon

    Science.gov (United States)

    Sugimoto, Takeru; Arakawa, Ichiro; Yamakawa, Koichiro

    2018-03-01

    Nuclear spin relaxation of methane in solid xenon has been studied by infrared spectroscopy. From the analysis of the temporal changes of the rovibrational peaks, the rates of the nuclear spin relaxation of I = 2 ← 1 correlated to the rotational relaxation of J = 0 ← 1 were obtained at temperatures of 5.1-11.5 K. On the basis of the temperature dependence of the relaxation rate, the activation energy of the indirect two-phonon process was determined to be 50 ± 6 K, which is in good agreement with the rotational transition energies of J = 2 ← 1 and J = 3 ← 1. Taking into account this result and the spin degeneracy, we argue that the lowest J = 3 level in which the I = 1 and I = 2 states are degenerate acts as the intermediate point of the indirect process.

  5. Relaxed states with plasma flow

    International Nuclear Information System (INIS)

    Avinash, K.; Taylor, J.B.

    1991-01-01

    In the theory of relaxation, a turbulent plasma reaches a state of minimum energy subject to constant magnetic helicity. In this state the plasma velocity is zero. Attempts have been made by introducing a number of different constraints, to obtain relaxed states with plasma flow. It is shown that these alternative constraints depend on two self-helicities, one for ions, and one for electrons. However, whereas there are strong arguments for the effective invariance of the original magnetic-helicity, these arguments do not apply to the self-helicities. Consequently the existence of relaxed states with flow remains in doubt. (author)

  6. Can Black Hole Relax Unitarily?

    Science.gov (United States)

    Solodukhin, S. N.

    2005-03-01

    We review the way the BTZ black hole relaxes back to thermal equilibrium after a small perturbation and how it is seen in the boundary (finite volume) CFT. The unitarity requires the relaxation to be quasi-periodic. It is preserved in the CFT but is not obvious in the case of the semiclassical black hole the relaxation of which is driven by complex quasi-normal modes. We discuss two ways of modifying the semiclassical black hole geometry to maintain unitarity: the (fractal) brick wall and the worm-hole modification. In the latter case the entropy comes out correctly as well.

  7. NMR imaging of the spine

    Energy Technology Data Exchange (ETDEWEB)

    Han, J.S. (Case Western Reserve Univ. School of Medicine, Cleveland, OH); Kaufman, B.; El Yousef, S.J.; Benson, J.E.; Bonstelle, C.T.; Alfidi, R.J.; Haaga, J.R.; Yeung, H.; Huss, R.G.

    1983-12-01

    The usefulness of nuclear magnetic resonance (NMR) images in the evaluation of spinal disorders below the craniocervical junction was studied. Six normal subjects and 41 patients with various spinal abnormalities were examined. NMR proved capable of demonstrating important normal and pathologic anatomic structures; it was useful in the evaluation of syringohydromyelia and cystic spinal cord tumors, and the bright signal intensity of lipoma was quite impressive. In the evaluation of herniated disk, NMR images offered a new perspective by visualizing abnormal degradation of the signal intensity of the nucleus pulposus itself. NMR images were least valuable in the evaluation of spondylosis and spinal stenosis. Although NMR imaging of the spine is still in a very early developmental stage, the absence of both ionizing radiation and risks associated with contrast material makes it especially attractive as a new diagnostic method. This limited experience with currently available equipment suggests that, with technical refinement, the efficacy of NMR of the spine will increase.

  8. Analysis of porous media and objects of cultural heritage by mobile NMR

    International Nuclear Information System (INIS)

    Haber, Agnes

    2012-01-01

    Low-field NMR techniques are used to study porous system, from simple to complex structures, and objects of cultural heritage. It is shown that NMR relaxometry can be used to study the fluid dynamics inside a porous system. A simple theoretical model for multi-site relaxation exchange NMR is used to extract exchange kinetic parameters when applied on a model porous systems. It provides a first step towards the study of more complex systems, where continuous relaxation distributions are present, such as soil systems or building materials. Moisture migration is observed in the soil systems with the help of 1D and 2D NMR relaxometry methods. In case of the concrete samples, the difference in composition makes a significant difference in the ability of water uptake. The single-sided NMR sensor proves to be a useful tool for on-site measurements. This is very important also in the case of the cultural heritage objects, as most of the objects can not be moved out of their environment. Mobile NMR turns out to be a simple but reliable and powerful tool to investigate moisture distributions and pore structures in porous media as well as the conservation state and history of objects of cultural heritage.

  9. NMR studies on inter- and intramolecular interactions in polymer melts

    International Nuclear Information System (INIS)

    Kehr, Marcus

    2007-01-01

    Polymer chain dynamics may be subdivided into three time regimes: Local motions, chain modes, and global motions. Local motions are characterized by the segment fluctuation time τ s . On the other hand, the so-called terminal chain relaxation time τ t indicates the onset of the dominance of global center-of-mass motions. For the chain mode regime in between, τ s t , model theories predict anomalous power laws for the time dependence of the mean-squared segment displacement and the frequency dependence of the spin-lattice relaxation time which are often taken to be indicative for the model assumptions. It was therefore of interest to probe the mean-squared segment displacement as a function of time and the frequency dependence of the spin-lattice relaxation time in ranges as wide as possible. A formalism was presented permitting the evaluation of the relative mean-squared displacement of molecules from the interchain contribution to spin-lattice relaxation dispersion of dipolar coupled spins. The only condition for the applicability was the subdiffusive power law character of the time dependence of the mean-squared displacement as it is typical for the chain mode regime in polymer liquids. Using field-cycling NMR relaxometry, an effective diffusion time range from nano- to almost milliseconds was probed. The interchain and intrachain spin-lattice relaxation contribution could be distinguished with the aid of isotopic dilution, that is mixtures of undeuterated and deuterated molecules. Experiments have been performed with melts of polyethyleneoxide and polybutadiene with molecular weights above the critical value. The mean-squared segment displacements have been evaluated as a function of time over five decades. The data could be described by a power law. The extrapolation to the much longer time scale of ordinary field-gradient NMR diffusometry gave good coincidence with literature data. The total time range thus covered nine decades. Deuteron field-cycling NMR

  10. Use of the Strong Collision Model to Calculate Spin Relaxation

    Science.gov (United States)

    Wang, D.; Chow, K. H.; Smadella, M.; Hossain, M. D.; MacFarlane, W. A.; Morris, G. D.; Ofer, O.; Morenzoni, E.; Salman, Z.; Saadaoui, H.; Song, Q.; Kiefl, R. F.

    The strong collision model is used to calculate spin relaxation of a muon or polarized radioactive nucleus in contact with a fluctuating environment. We show that on a time scale much longer than the mean time between collisions (fluctuations) the longitudinal polarization decays exponentially with a relaxation rate equal to a sum of Lorentzians-one for each frequency component in the static polarization function ps(t).

  11. An Initialization Technique for the Waveform-Relaxation Circuit Simulation

    OpenAIRE

    Habib, S. E.-D.; Al-Karim, G. J.

    1999-01-01

    This paper reports the development of the Cairo University Waveform Relaxation (CUWORX) simulator. In order to accelerate the convergence of the waveform relaxation (WR) in the presence of logic feedback, CUWORK is initialized via a logic simulator. This logic initialization scheme is shown to be highly effective for digital synchronous circuits. Additionally, this logic initialization scheme preserves fully the multi-rate properties of the WR algorithm.

  12. Microplastic relaxations of single and polycrystalline molybdenum

    Energy Technology Data Exchange (ETDEWEB)

    Pichl, W.; Weiss, B. [Wien Univ. (Austria). Inst. fuer Materialphysik; Chen, D.L.

    1998-05-01

    The microplasticity of high-purity molybdenum single crystals and of Mo polycrystals of technical purity has been investigated by relaxation step tests in uniaxial compression. A new model for the evaluation of relaxation tests in the microplastic range of b.c.c metals is presented which takes into account the decrease of the mobile dislocation density due to exhaustion of non-screw dislocations. The model allows an independent determination of the activation volume and of the microstructure parameters controlling dislocation exhaustion. The results indicate that in the high-purity single crystals the deformation rate is controlled by interactions of non-screw dislocations with the grown-in network. In the polycrystals additional interactions with impurity atoms seem to occur. In the single crystals the activity and subsequent exhaustion of two different glide systems was observed, followed by a gradual onset of screw dislocation motion. (orig.) 26 refs.

  13. Modelling Creep (Relaxation of the Urinary Bladder

    Directory of Open Access Journals (Sweden)

    Zdravkovic Nebojsa

    2017-12-01

    Full Text Available We first present the results of an experiment in which the passive properties of the urinary bladder were investigated using strips of rabbit bladder. Under the assumption that the urinary bladder had orthopaedic characteristics, the strips were taken in the longitudinal and in the circumferential directions. The material was subjected to uniaxial tension, and stress-stretch curves were generated for various rates of deformation. We found that the rates did not have a significantly effect on the passive response of the material. Additionally, the stress-stretch dependence during relaxation of the material when exposed to isometric conditions was determined experimentally.

  14. 1H NMR methods for the noninvasive study of metabolism and other processes involving small molecules in intact erythrocytes

    International Nuclear Information System (INIS)

    Rabenstein, D.L.

    1984-01-01

    1 H NMR methods are described with which resolved resonances can be obtained for many of the small molecules in intact erythrocytes. In one method, the more intense hemoglobin resonances are suppressed by transfer of saturation throughout the hemoglobin spin system by cross relaxation following a selective saturation pulse. In a second method, the hemoglobin resonances are eliminated with the spin-echo pulse sequence by using a between-pulse delay time long enough for complete elimination of the hemoglobin resonances by spin-spin relaxation. Selected examples of the study of erythrocyte biochemistry by 1 H NMR are discussed. (Auth.)

  15. Relaxation Pathways in Metallic Glasses

    Science.gov (United States)

    Gallino, Isabella; Busch, Ralf

    2017-11-01

    At temperatures below the glass transition temperature, physical properties of metallic glasses, such as density, viscosity, electrical resistivity or enthalpy, slowly evolve with time. This is the process of physical aging that occurs among all types of glasses and leads to structural changes at the microscopic level. Even though the relaxation pathways are ruled by thermodynamics as the glass attempts to re-attain thermodynamic equilibrium, they are steered by sluggish kinetics at the microscopic level. Understanding the structural and dynamic pathways of the relaxing glassy state is still one of the grand challenges in materials physics. We review some of the recent experimental advances made in understanding the nature of the relaxation phenomenon in metallic glasses and its implications to the macroscopic and microscopic properties changes of the relaxing glass.

  16. Processing DOSY NMR Data by Chemometric Methods

    NARCIS (Netherlands)

    Huo, R.

    2006-01-01

    DOSY NMR can be used as a non-invasive separation method for complex mixtures. It is more and more attractive for industrial laboratories, for the main advantage DOSY NMR over routine separation methods such as LC-NMR is easy and economical implementation. With NMR instruments, DOSY NMR data can be

  17. General expressions for R1ρ relaxation for N-site chemical exchange and the special case of linear chains.

    Science.gov (United States)

    Koss, Hans; Rance, Mark; Palmer, Arthur G

    2017-01-01

    Exploration of dynamic processes in proteins and nucleic acids by spin-locking NMR experiments has been facilitated by the development of theoretical expressions for the R 1 ρ relaxation rate constant covering a variety of kinetic situations. Herein, we present a generalized approximation to the chemical exchange, R ex , component of R 1 ρ for arbitrary kinetic schemes, assuming the presence of a dominant major site population, derived from the negative reciprocal trace of the inverse Bloch-McConnell evolution matrix. This approximation is equivalent to first-order truncation of the characteristic polynomial derived from the Bloch-McConnell evolution matrix. For three- and four-site chemical exchange, the first-order approximations are sufficient to distinguish different kinetic schemes. We also introduce an approach to calculate R 1 ρ for linear N-site schemes, using the matrix determinant lemma to reduce the corresponding 3N×3N Bloch-McConnell evolution matrix to a 3×3 matrix. The first- and second order-expansions of the determinant of this 3×3 matrix are closely related to previously derived equations for two-site exchange. The second-order approximations for linear N-site schemes can be used to obtain more accurate approximations for non-linear N-site schemes, such as triangular three-site or star four-site topologies. The expressions presented herein provide powerful means for the estimation of R ex contributions for both low (CEST-limit) and high (R 1 ρ -limit) radiofrequency field strengths, provided that the population of one state is dominant. The general nature of the new expressions allows for consideration of complex kinetic situations in the analysis of NMR spin relaxation data. Copyright © 2016 Elsevier Inc. All rights reserved.

  18. Negative magnetic relaxation in superconductors

    Directory of Open Access Journals (Sweden)

    Krasnoperov E.P.

    2013-01-01

    Full Text Available It was observed that the trapped magnetic moment of HTS tablets or annuli increases in time (negative relaxation if they are not completely magnetized by a pulsed magnetic field. It is shown, in the framework of the Bean critical-state model, that the radial temperature gradient appearing in tablets or annuli during a pulsed field magnetization can explain the negative magnetic relaxation in the superconductor.

  19. Finite element models of non-Newtonian crater relaxation

    Science.gov (United States)

    Thomas, Paul J.; Schubert, Gerald

    1987-01-01

    The effects of a non-Newtonian rheology on the profiles of relaxing craters (such as those seen on the surfaces of the icy Galilean and Saturnian satellites) were studied. Two-dimensional finite element simulations of non-Newtonian viscous flow were performed, and the results were compared with those associated with Newtonian rheology. Viscous relaxation of craters in a non-Newtonian medium was significantly different from that in a Newtonian medium. Crater rims are observed to relax at a more rapid rate in a non-Newtonian region as a result of the movement of the low viscosity region to underneath the crater rim after the initial relaxation of the bowl. Significant differences are also found when central depth is plotted as a function of time. For a Newtonian medium, crater relaxation is exponential in form. In contrast, non-Newtonian crater relaxation is initially rapid, in response to the large initial stresses and small viscosities; however, as stresses decrease, this relaxation becomes extremely gradual.

  20. A quantum relaxation-time approximation for finite fermion systems

    Energy Technology Data Exchange (ETDEWEB)

    Reinhard, P.-G., E-mail: paul-gerhard.reinhard@fau.de [Institut für Theoretische Physik, Universität Erlangen, D-91058 Erlangen (Germany); Suraud, E. [Université de Toulouse, UPS, Laboratoire de Physique Théorique, IRSAMC, F-31062 Toulouse Cedex (France); Laboratoire de Physique Théorique, Université Paul Sabatier, CNRS, F-31062 Toulouse Cédex (France); Physics Department, University at Buffalo, The State University New York, Buffalo, NY 14260 (United States)

    2015-03-15

    We propose a relaxation time approximation for the description of the dynamics of strongly excited fermion systems. Our approach is based on time-dependent density functional theory at the level of the local density approximation. This mean-field picture is augmented by collisional correlations handled in relaxation time approximation which is inspired from the corresponding semi-classical picture. The method involves the estimate of microscopic relaxation rates/times which is presently taken from the well established semi-classical experience. The relaxation time approximation implies evaluation of the instantaneous equilibrium state towards which the dynamical state is progressively driven at the pace of the microscopic relaxation time. As test case, we consider Na clusters of various sizes excited either by a swift ion projectile or by a short and intense laser pulse, driven in various dynamical regimes ranging from linear to strongly non-linear reactions. We observe a strong effect of dissipation on sensitive observables such as net ionization and angular distributions of emitted electrons. The effect is especially large for moderate excitations where typical relaxation/dissipation time scales efficiently compete with ionization for dissipating the available excitation energy. Technical details on the actual procedure to implement a working recipe of such a quantum relaxation approximation are given in appendices for completeness.

  1. Nuclear spin-lattice relaxation in nitroxide spin-label EPR

    DEFF Research Database (Denmark)

    Marsh, Derek

    2016-01-01

    that the definition of nitrogen nuclear relaxation rate Wn commonly used in the CW-EPR literature for 14N-nitroxyl spin labels is inconsistent with that currently adopted in time-resolved EPR measurements of saturation recovery. Redefinition of the normalised 14N spin-lattice relaxation rate, b = Wn/(2We), preserves...... of spin-lattice relaxation in this three-level system. Expressions for CW-saturation EPR with the revised definitions are summarised. Data on nitrogen nuclear spin-lattice relaxation times are compiled according to the three-level scheme for 14N-relaxation: T1 n = 1/Wn. Results are compared and contrasted...... the expressions used for CW-EPR, whilst rendering them consistent with expressions for saturation recovery rates in pulsed EPR. Furthermore, values routinely quoted for nuclear relaxation times that are deduced from EPR spectral diffusion rates in 14N-nitroxyl spin labels do not accord with conventional analysis...

  2. nmr spectroscopic study and dft calculations of giao nmr shieldings

    African Journals Online (AJOL)

    Preferred Customer

    NMR is a sensitive and versatile probe of molecular-scale structure and dynamics in solids and liquids. It has been widely used in chemistry, materials and geochemistry [21-23] and it enables one to get faster and easier structural information. The standard 1D and 2D hetero and homonuclear NMR experiments are enough ...

  3. Relaxation processes in Aeolian transport

    Directory of Open Access Journals (Sweden)

    Selmani Houssem

    2017-01-01

    Full Text Available We investigate experimentally the relaxation process toward the equilibrium regime of saltation transport in the context of spatial inhomogeneous conditions. The relaxation length associated to this process is an important length in aeolian transport. This length stands for the distance needed for the particle flux to adapt to a change in flow conditions or in the boundary conditions at the bed. Predicting the value of this length under given conditions of transport remains an open and important issue. We conducted wind tunnel experiments to document the influence of the upstream particle flux and wind speed on the relaxation process toward the saturated transport state. In the absence of upstream particle flux, data show that the relaxation length is independent of the wind strength (except close to the threshold of transport. In contrast, in the case of a finite upstream flux, the relaxation length exhibits a clear increase with increasing air flow velocity. Moreover, in the latter the relaxation is clearly non-monotonic and presents an overshoot.

  4. Broad line NMR study of modified polypropylene fibres

    International Nuclear Information System (INIS)

    Olcak, D.; Sevcovic, L.; Mucha, L.

    1999-01-01

    Study of drawn fibres prepared from an isostatic polypropylene modified by an ethylene aminoalkylacrylate copolymer has been done using the broad line of 1 H NMR. NMR spectra were measured on the set of fibres prepared with a draw ratio λ from 1 to 5.5 at two temperatures, one of them corresponding to the onset of segmental motion and the other one is the minddle of the temperature interval as determined by decrease of the second moment M 2 . Decomposition of the spectra into elementary components related to the amorphous, intermediate and crystalline regions of partially crystalline polymers has been made. The drawing of the fibres was found to enhance the chain mobility in the amorphous region and to restrain the molecular motion in the intermediate region. Such behaviour well supports conclusions predicted in the earlier study based on the spin-lattice relaxation time T 1 and dynamic mechanical data treated using the WLF theory. (Authors)

  5. Spin-lattice relaxation of magnetic centers in molecular crystals at low temperature

    OpenAIRE

    Ho, Le Tuan Anh; Chibotaru, Liviu F.

    2017-01-01

    We study the spin-phonon relaxation rate of both Kramers and non-Kramers molecular magnets in strongly diluted samples at low temperature. Using the "rotational" contribution to the spin-phonon Hamiltonian, universal formulae for the relaxation rate are obtained. Intriguingly, these formulae are all entirely expressed via measurable or \\emph{ab initio} computable physical quantities. Moreover, they are also independent of the energy gaps to excited states involved in the relaxation process. T...

  6. THz Dynamic Nuclear Polarization NMR.

    Science.gov (United States)

    Nanni, Emilio A; Barnes, Alexander B; Griffin, Robert G; Temkin, Richard J

    2011-08-29

    Dynamic nuclear polarization (DNP) increases the sensitivity of nuclear magnetic resonance (NMR) spectroscopy by using high frequency microwaves to transfer the polarization of the electrons to the nuclear spins. The enhancement in NMR sensitivity can amount to a factor of well above 100, enabling faster data acquisition and greatly improved NMR measurements. With the increasing magnetic fields (up to 23 T) used in NMR research, the required frequency for DNP falls into the THz band (140-600 GHz). Gyrotrons have been developed to meet the demanding specifications for DNP NMR, including power levels of tens of watts; frequency stability of a few megahertz; and power stability of 1% over runs that last for several days to weeks. Continuous gyrotron frequency tuning of over 1 GHz has also been demonstrated. The complete DNP NMR system must include a low loss transmission line; an optimized antenna; and a holder for efficient coupling of the THz radiation to the sample. This paper describes the DNP NMR process and illustrates the THz systems needed for this demanding spectroscopic application. THz DNP NMR is a rapidly developing, exciting area of THz science and technology.

  7. NMR imaging studies of coal

    Energy Technology Data Exchange (ETDEWEB)

    Ma, Z.R.; Zhang, P.Z.; Ding, G.L.; Li, L.Y.; Ye, C.H. [University of Science and Technology, Beijing (China). Dept. of Chemistry

    1996-06-01

    The permeation transportation and swelling behavior of solvents into coal are investigated by NMR imaging using pyridine-d{sub 5} and acetone-d{sub 6}. Images of coal swollen with deuterated solvents illuminate proton distributions of mobile phases within the coal macromolecular networks. More information about the chemical and physical structure of coal can be obtained using NMR imaging techniques.

  8. NMR imaging of osteoarticular pathology

    Energy Technology Data Exchange (ETDEWEB)

    Frocrain, L.; Duvauferrier, R.; Gagey, N. and others

    1987-01-01

    NMR imaging is assuming an increasingly important role in the diagnosis of osteo-articular disorders. Semiological descriptions of the mean pathological disorders of the locomotor system are presented. Some investigation strategies are proposed to compare NMR imaging with other imaging techniques in various pathological states.

  9. NMR in pulsed magnetic field

    KAUST Repository

    Abou-Hamad, Edy

    2011-09-01

    Nuclear magnetic resonance (NMR) experiments in pulsed magnetic fields up to 30.4 T focused on 1H and 93Nb nuclei are reported. Here we discuss the advantage and limitation of pulsed field NMR and why this technique is able to become a promising research tool. © 2011 Elsevier Inc. All Rights Reserved.

  10. Quantum Information Processing by NMR

    Indian Academy of Sciences (India)

    Keywords. NMR; quantum information processing; quantum computing; qubits; pseudopure states; quantum; pseudopure states; quantum gates; quantum simulations; decoherence. ... T S Mahesh1. Department of Physics and NMR Research Center, Indian Institute of Science Education and Research, Pune 411 008, India ...

  11. Resistive NMR of intracranial hematomas

    Energy Technology Data Exchange (ETDEWEB)

    Zimmerman, R.A.; Bilaniuk, L.T.; Grossman, R.I.; Levine, R.S.; Lynch, R.; Goldberg, H.I.; Samuel, L.; Edelstein, W.; Bottomley, P.; Redington, R.W.

    1985-01-01

    Comparison between computed tomography and nuclear magnetic resonance imaging in 17 patients with intracranial hematomas indicate a distinct role for NMR in evaluating the stable patient with hematoma. NMR is useful for delineating the extent of the hematoma, the relationship of the hematoma to brain anatomy, and the presence of hematoma at a time when the hematoma is isodense on CT.

  12. A novel improved method for analysis of 2D diffusion-relaxation data-2D PARAFAC-Laplace decomposition

    NARCIS (Netherlands)

    Tonning, E.; Polders, D.; Callaghan, P.T.; Engelsen, S.B.

    2007-01-01

    This paper demonstrates how the multi-linear PARAFAC model can with advantage be used to decompose 2D diffusion¿relaxation correlation NMR spectra prior to 2D-Laplace inversion to the T2¿D domain. The decomposition is advantageous for better interpretation of the complex correlation maps as well as

  13. 13C solid state NMR investigation of natural resins components

    International Nuclear Information System (INIS)

    Tavares, Maria I.B.; Bathista, Andre L.B.S.; Silva, Emerson O.; Priante Filho, Nicolau; Nogueira, Jose S.

    2001-01-01

    The objective of this work is to establish and analytical methodology as a routine using solid state nuclear magnetic resonance (NMR) techniques to investigate the mainly chemical components presented in natural resins in bulk. And also to evaluate the molecular behaviour of these resins. The routine solid state techniques allow us to assign the main compounds presented in the resins. Therefore, applying specialised techniques, like variable contact time, delayed contact time, dephasing time and proton spin lattice relaxation time in the rotating frame (T 1 H ρ), more information about chemical structure and molecular dynamic is available

  14. ^51V NMR Study of the Magnetic Structure of the Frustrated Zig-Zag Spin-1 Chain Compound CaV2O4

    Science.gov (United States)

    Zong, X.; Suh, B. J.; Niazi, A.; Johnston, D. C.

    2007-03-01

    ^51V NMR measurements have been performed on a single crystal of orthorhombic (at room temperature) CaV2O4 in zero applied magnetic field and with a small perturbing field up to H = 2 T, at temperatures well below the N'eel temperature TN= 78 K@. The c-axis is parallel to the chains. At H = 0, a broad ^51V NMR spectrum with a peak at 237 MHz was observed. The effective local hyperfine field Heff = 21.2 T corresponding to the peak frequency 237 MHz is in good agreement with expectation for the V^3+ S = 1 spin state. In Hc, the spectrum splits into two parts that are equally separated from the peak position at zero field. The separation of the parts depends strongly both on the magnitude and direction of H with respect to the crystal axes. Our NMR results are consistent with a collinear antiferromagnetic spin structure with the spin direction along the b-axis, which together with the magnetization data suggest that the antiferromagnetic long-range order arises from an order-from-disorder mechanism. We also present the temperature and orientation dependence of the spin-lattice relaxation rate 1/T1.

  15. sup 5 sup 9 Co-NMR studies on La sub 4 Co sub 3 O sub 1 sub 0 sub + subdelta

    CERN Document Server

    Miyashita, T; Fukamachi, T; Masuda, H; Sato, M

    2002-01-01

    Samples of La sub 4 Co sub 3 O sub 1 sub 0 sub + subdelta with delta - 0.1, 0.3 and 0.6 have been prepared. For delta - 0.1, the crossover-like changes of the spin state at approx 100 K and approx 550 K have been confirmed by the measurements of the magnetic susceptibility. At approx 550 K, we have observed for the sample the anomalous T-dependence of the electrical resistivity and the thermoelectric power. Its NMR spectra exhibit the very large broadening at low temperatures due to the antiferromagnetic ordering. NMR spectra of the sample with delta - 0.6 show that there exist two kinds of Co atoms: The NMR signal intensity of one of the two with the larger relaxation rate 1/T sub 2 decreases, while the intensity of the other with the smaller 1/T sub 2 increases, with decreasing T below 100 K, which indicates that the spectra of the latter are from the Co sup 3 sup + in the low spin state. The T-dependence of 1/T sub 1 shows the existence of the energy difference between the low spin (spin S=0) and intermedi...

  16. Copper NMR and hole depletion in the normal state of Y1-xPrxBa2Cu3O7

    International Nuclear Information System (INIS)

    MacLaughlin, D.E.; Reyes, A.P.; Takigawa, M.; Hammel, P.C.; Heffner, R.H.; Thompson, J.D.; Crow, J.E.

    1990-01-01

    Normal-state copper NMR spectra and spin-lattice relaxation rates 1/T 1 have been measured in the planar cuprate system YBa 2 Cu 3 O 7 . With Pr doping the Knight shift K decreases and develops a temperature dependence at both plane and chain sites. Analysis of the bulk susceptibility and NMR data indicate that pair breaking and hole depletion both take part in the suppression of the superconducting transition temperature T c . The Knight shift behavior resembles that in oxygen-deficient YBa 2 Cu 3 O 7-y , as does the temperature dependence of 1/T 1 for plane Cu sites and magnetic field perpendicular to the c axis. This agreement leads to a consistent picture of the role of antiferromagnetic fluctuations in these materials. An analysis of the data in the framework of the phenomenological theory of Millis, Monien, and Pines is given. In the end compound PrBa 2 Cu 3 O 7 the NMR signal from plane Cu sites indicates antiferromagnetic (AF) ordering at a Neel temperature ∼280 K, and in the AF state yields an internal field similar to those found in AF YBa 2 Cu 3 O 6 and La 2 CuO 4 . 32 refs., 7 figs

  17. Hypnotizability modulates the cardiovascular correlates of subjective relaxation.

    Science.gov (United States)

    Santarcangelo, Enrica L; Paoletti, Giulia; Balocchi, Rita; Carli, Giancarlo; Morizzo, Carmela; Palombo, Carlo; Varanini, Maurizio

    2012-01-01

    Mean values and the spectral variability of heart rate (HRV), blood pressure, and skin blood flow were studied in high and low hypnotizable subjects during simple relaxation. Similar subjective relaxation was reported by highs and lows. A parasympathetic prevalence (indicated by a higher High-Frequency component of HRV and a lower High/Low-Frequency ratio) and lower renin-angiotensin activity (indicated by a lower Very-Low-Frequency component of HRV) could be attributed to highs with respect to lows. Hypnotizability did not affect blood pressure and its variability and modulated the skin blood flow across the session only in lows. The findings confirm that relaxation cannot be defined solely on cardiovascular parameters and also indicate that hypnotizability modulates cardiovascular activity during simple relaxation and suggest it may have a protective role against cardiovascular disease.

  18. Comparative analysis of complete mitochondrial genomes suggests that relaxed purifying selection is driving high nonsynonymous evolutionary rate of the NADH2 gene in whitefish (Coregonus ssp.)

    DEFF Research Database (Denmark)

    Jacobsen, Magnus W.; Rodrigues da Fonseca, Rute Andreia; Bernatchez, Louis

    2016-01-01

    Several studies have recently reported evidence for positive selection acting on the mitochondrial genome (mitogenome), emphasizing its potential role in adaptive divergence and speciation. In this study we searched 107 full mitogenomes of recently diverged species and lineages of whitefish...... evolution in ND2 by (i) mapping amino acid changes to a protein model structure which showed that they were located away from key functional residues of the protein, (ii) locating them in the sequences of other species of fish (Salmonidae, Anguillidae, Scombridae and Percidae) only to find pronounced...... overlap of nonsynonymous regions. We thus conclude that relaxed purifying selection is driving the evolution of ND2 by affecting mostly regions that have lower functional relevance....

  19. Thermal relaxation of molecular oxygen in collisions with nitrogen atoms

    Energy Technology Data Exchange (ETDEWEB)

    Andrienko, Daniil A., E-mail: daniila@umich.edu; Boyd, Iain D. [Department of Aerospace Engineering, University of Michigan, 1320 Beal Ave., Ann Arbor, Michigan 48108 (United States)

    2016-07-07

    Investigation of O{sub 2}–N collisions is performed by means of the quasi-classical trajectory method on the two lowest ab initio potential energy surfaces at temperatures relevant to hypersonic flows. A complete set of bound–bound and bound–free transition rates is obtained for each precollisional rovibrational state. Special attention is paid to the vibrational and rotational relaxations of oxygen as a result of chemically non-reactive interaction with nitrogen atoms. The vibrational relaxation of oxygen partially occurs via the formation of an intermediate NO{sub 2} complex. The efficient energy randomization results in rapid vibrational relaxation at low temperatures, compared to other molecular systems with a purely repulsive potential. The vibrational relaxation time, computed by means of master equation studies, is nearly an order of magnitude lower than the relaxation time in N{sub 2}–O collisions. The rotational nonequilibrium starts to play a significant effect at translational temperatures above 8000 K. The present work provides convenient relations for the vibrational and rotational relaxation times as well as for the quasi-steady dissociation rate coefficient and thus fills a gap in data due to a lack of experimental measurements for this system.

  20. Thermal relaxation of molecular oxygen in collisions with nitrogen atoms.

    Science.gov (United States)

    Andrienko, Daniil A; Boyd, Iain D

    2016-07-07

    Investigation of O2-N collisions is performed by means of the quasi-classical trajectory method on the two lowest ab initio potential energy surfaces at temperatures relevant to hypersonic flows. A complete set of bound-bound and bound-free transition rates is obtained for each precollisional rovibrational state. Special attention is paid to the vibrational and rotational relaxations of oxygen as a result of chemically non-reactive interaction with nitrogen atoms. The vibrational relaxation of oxygen partially occurs via the formation of an intermediate NO2 complex. The efficient energy randomization results in rapid vibrational relaxation at low temperatures, compared to other molecular systems with a purely repulsive potential. The vibrational relaxation time, computed by means of master equation studies, is nearly an order of magnitude lower than the relaxation time in N2-O collisions. The rotational nonequilibrium starts to play a significant effect at translational temperatures above 8000 K. The present work provides convenient relations for the vibrational and rotational relaxation times as well as for the quasi-steady dissociation rate coefficient and thus fills a gap in data due to a lack of experimental measurements for this system.

  1. Fundamentals of Protein NMR Spectroscopy

    CERN Document Server

    Rule, Gordon S

    2006-01-01

    NMR spectroscopy has proven to be a powerful technique to study the structure and dynamics of biological macromolecules. Fundamentals of Protein NMR Spectroscopy is a comprehensive textbook that guides the reader from a basic understanding of the phenomenological properties of magnetic resonance to the application and interpretation of modern multi-dimensional NMR experiments on 15N/13C-labeled proteins. Beginning with elementary quantum mechanics, a set of practical rules is presented and used to describe many commonly employed multi-dimensional, multi-nuclear NMR pulse sequences. A modular analysis of NMR pulse sequence building blocks also provides a basis for understanding and developing novel pulse programs. This text not only covers topics from chemical shift assignment to protein structure refinement, as well as the analysis of protein dynamics and chemical kinetics, but also provides a practical guide to many aspects of modern spectrometer hardware, sample preparation, experimental set-up, and data pr...

  2. Structural Biology: Practical NMR Applications

    CERN Document Server

    Teng, Quincy

    2005-01-01

    This textbook begins with an overview of NMR development and applications in biological systems. It describes recent developments in instrument hardware and methodology. Chapters highlight the scope and limitation of NMR methods. While detailed math and quantum mechanics dealing with NMR theory have been addressed in several well-known NMR volumes, chapter two of this volume illustrates the fundamental principles and concepts of NMR spectroscopy in a more descriptive manner. Topics such as instrument setup, data acquisition, and data processing using a variety of offline software are discussed. Chapters further discuss several routine stategies for preparing samples, especially for macromolecules and complexes. The target market for such a volume includes researchers in the field of biochemistry, chemistry, structural biology and biophysics.

  3. Relaxation schemes for Chebyshev spectral multigrid methods

    Science.gov (United States)

    Kang, Yimin; Fulton, Scott R.

    1993-01-01

    Two relaxation schemes for Chebyshev spectral multigrid methods are presented for elliptic equations with Dirichlet boundary conditions. The first scheme is a pointwise-preconditioned Richardson relaxation scheme and the second is a line relaxation scheme. The line relaxation scheme provides an efficient and relatively simple approach for solving two-dimensional spectral equations. Numerical examples and comparisons with other methods are given.

  4. Managing the solvent water polarization to obtain improved NMR spectra of large molecular structures

    International Nuclear Information System (INIS)

    Hiller, Sebastian; Wider, Gerhard; Etezady-Esfarjani, Touraj; Horst, Reto; Wuethrich, Kurt

    2005-01-01

    In large molecular structures, the magnetization of all hydrogen atoms in the solute is strongly coupled to the water magnetization through chemical exchange between solvent water and labile protons of macromolecular components, and through dipole-dipole interactions and the associated 'spin diffusion' due to slow molecular tumbling. In NMR experiments with such systems, the extent of the water polarization is thus of utmost importance. This paper presents a formalism that describes the propagation of the water polarization during the course of different NMR experiments, and then compares the results of model calculations for optimized water polarization with experimental data. It thus demonstrates that NMR spectra of large molecular structures can be improved with the use of paramagnetic spin relaxation agents which selectively enhance the relaxation of water protons, so that a substantial gain in signal-to-noise can be achieved. The presently proposed use of a relaxation agent can also replace the water flip-back pulses when working with structures larger than about 30 kDa. This may be a valid alternative in situations where flip-back pulses are difficult to introduce into the overall experimental scheme, or where they would interfere with other requirements of the NMR experiment

  5. Diffusion effects on volume-selective NMR at small length scales; Diffusionseffekte in volumenselektiver NMR auf kleinen Laengenskalen

    Energy Technology Data Exchange (ETDEWEB)

    Gaedke, Achim

    2009-01-21

    In this thesis, the interplay between diffusion and relaxation effects in spatially selective NMR experiments at short length scales is explored. This is especially relevant in the context of both conventional and mechanically detected MRI at (sub)micron resolution in biological specimens. Recent results on selectively excited very thin slices showed an in-slice-magnetization recovery orders of magnitude faster than the longitudinal relaxation time T1. However, those experiments were run on fully relaxed samples while MRI and especially mechanically detected NMR experiments are typically run in a periodic fashion with repetition times far below T1. The main purpose of this work therefore was to extend the study of the interplay between diffusion and longitudinal relaxation to periodic excitations. In some way, this is inverse phenomenon to the DESIRE (Diffusive Enhancement of SIgnal and REsolution) approach, proposed 1992 by Lauterbur. Experiments on periodically excited thin slices were carried out at a dedicated static field gradient cryomagnet with magnetic field gradients up to 180 T/m. In order to obtain plane slices, an appropriate isosurface of the gradient magnet had to be identified. It was found at a field of 3.8 T with a gradient of 73 T/m. In this field, slices down to a thickness of 3.2 {mu}m could be excited. The detection of the NMR signal was done using FIDs instead of echoes as the excitation bandwidth of those thin slices is sufficiently small to observe FIDs which are usually considered to be elusive to detection in such strong static field gradients. A simulation toolbox based on the full Bloch-Torrey-equation was developed to describe the excitation and the formation of NMR signals under those unusual conditions as well as the interplay of diffusion and magnetization recovery. Both the experiments and the simulations indicate that diffusion effects lead to a strongly enhanced magnetization modulation signal also under periodic excitation

  6. Calorimetric and relaxation properties of xylitol-water mixtures

    Science.gov (United States)

    Elamin, Khalid; Sjöström, Johan; Jansson, Helén; Swenson, Jan

    2012-03-01

    considerably stronger water (w) relaxation at about the same frequency. However, the similarities in time scale and activation energy between the w-relaxation and the β-relaxation of xylitol at water contents below 13 wt. % suggest that the w-relaxation is governed, in some way, by the β-relaxation of xylitol, since clusters of water molecules are rare at these water concentrations. At higher water concentrations the intensity and relaxation rate of the w-relaxation increase rapidly with increasing water content (up to the concentration where ice starts to form), most likely due to a rapid increase of small water clusters where an increasing number of water molecules interacting with other water molecules.

  7. Towards Using NMR to Screen for Spoiled Tomatoes Stored in 1,000 L, Aseptically Sealed, Metal-Lined Totes

    Directory of Open Access Journals (Sweden)

    Michael D. Pinter

    2014-03-01

    Full Text Available Nuclear magnetic resonance (NMR spectroscopy is used to track factory relevant tomato paste spoilage. It was found that spoilage in tomato paste test samples leads to longer spin lattice relaxation times T1 using a conventional low magnetic field NMR system. The increase in T1 value for contaminated samples over a five day room temperature exposure period prompted the work to be extended to the study of industry standard, 1,000 L, non-ferrous, metal-lined totes. NMR signals and T1 values were recovered from a large format container with a single-sided NMR sensor. The results of this work suggest that a handheld NMR device can be used to study tomato paste spoilage in factory process environments.

  8. Influence of water-insoluble nonionic copolymer E(6)P(39)E(6) on the microstructure and self-aggregation dynamics of aqueous SDS solution-NMR and SANS investigations.

    Science.gov (United States)

    Prameela, G K S; Phani Kumar, B V N; Aswal, V K; Mandal, Asit Baran

    2013-10-28

    The influence of water-insoluble nonionic triblock copolymer PEO-PPO-PEO [poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)] i.e., E6P39E6 with molecular weight 2800, on the microstructure and self-aggregation dynamics of anionic surfactant sodium dodecylsulfate (SDS) in aqueous solution (D2O) were investigated using high resolution nuclear magnetic resonance (NMR) and small-angle neutron scattering (SANS) measurements. Variable concentration and temperature proton ((1)H), carbon ((13)C) NMR chemical shifts, (1)H self-diffusion coefficients, (1)H spin-lattice and spin-spin relaxation rates data indicate that the higher hydrophobic nature of copolymer significantly influenced aggregation characteristics of SDS. The salient features of the NMR investigations include (i) the onset of mixed micelles at lower SDS concentrations (SDS free micelles at higher SDS concentrations (~30 mM), (ii) disintegration of copolymer-SDS mixed aggregate at moderate SDS concentrations (~10 mM) and still binding of a copolymer with SDS and (iii) preferential localization of the copolymer occurred at the SDS micelle surface. SANS investigations indicate prolate ellipsoidal shaped mixed aggregates with an increase in SDS aggregation number, while a contrasting behavior in the copolymer aggregation is observed. The aggregation features of SDS and the copolymer, the sizes of mixed aggregates and the degree of counterion dissociation (α) extracted from SANS data analysis corroborate reasonably well with those of (1)H NMR self-diffusion and sodium ((23)Na) spin-lattice relaxation data.

  9. A high-pressure NMR probe for aqueous geochemistry.

    Science.gov (United States)

    Pautler, Brent G; Colla, Christopher A; Johnson, Rene L; Klavins, Peter; Harley, Stephen J; Ohlin, C André; Sverjensky, Dimitri A; Walton, Jeffrey H; Casey, William H

    2014-09-08

    A non-magnetic piston-cylinder pressure cell is presented for solution-state NMR spectroscopy at geochemical pressures. The probe has been calibrated up to 20 kbar using in situ ruby fluorescence and allows for the measurement of pressure dependencies of a wide variety of NMR-active nuclei with as little as 10 μL of sample in a microcoil. Initial (11)B NMR spectroscopy of the H3BO3-catechol equilibria reveals a large pressure-driven exchange rate and a negative pressure-dependent activation volume, reflecting increased solvation and electrostriction upon boron-catecholate formation. The inexpensive probe design doubles the current pressure range available for solution NMR spectroscopy and is particularly important to advance the field of aqueous geochemistry. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  10. Revisiting 63Cu NMR evidence for charge order in superconducting La1.885Sr0.115CuO4

    Science.gov (United States)

    Imai, T.; Takahashi, S. K.; Arsenault, A.; Acton, A. W.; Lee, D.; He, W.; Lee, Y. S.; Fujita, M.

    2017-12-01

    The presence of charge and spin stripe order in the La2CuO4 -based family of superconductors continues to lead to new insight on the unusual ground-state properties of high-Tc cuprates. Soon after the discovery of charge stripe order at Tcharge≃65 K in Nd3 + co-doped La1.48Nd0.4Sr0.12CuO4 (Tc≃6 K) [Tranquada et al., Nature (London) 375, 561 (1995), 10.1038/375561a0], Hunt et al. demonstrated that La1.48Nd0.4Sr0.12CuO4 and superconducting La2 -xSrxCuO4 with x ˜1 /8 (Tc≃30 K) share nearly identical NMR anomalies near Tcharge of the former [Phys. Rev. Lett. 82, 4300 (1999), 10.1103/PhysRevLett.82.4300]. Their inevitable conclusion that La1.885Sr0.115CuO4 also undergoes charge order at a comparable temperature became controversial, because diffraction measurements at the time were unable to detect Bragg peaks associated with charge order. Recent advances in x-ray diffraction techniques finally led to definitive confirmations of the charge order Bragg peaks in La1.885Sr0.115CuO4 with an onset at as high as Tcharge≃80 K. Meanwhile, improved instrumental technology has enabled routine NMR measurements that were not feasible two decades ago. Motivated by these new developments, we revisit the charge order transition of a La1.885Sr0.115CuO4 single crystal based on 63Cu NMR techniques. We demonstrate that 63Cu NMR properties of the nuclear spin Iz=-1/2 to +1/2 central transition below Tcharge exhibit unprecedentedly strong dependence on the measurement time scale set by the separation time τ between the 90∘ and 180∘ radio-frequency pulses; a new kind of anomalous, very broad winglike 63Cu NMR signals gradually emerge below Tcharge only for extremely short τ ≲4 μ s , while the spectral weight INormal of the normal NMR signals is progressively wiped out. The NMR linewidth and relaxation rates depend strongly on τ below Tcharge, and their enhancement in the charge ordered state indicates that charge order turns on strong but inhomogeneous growth of Cu spin

  11. Effects of water on the primary and secondary relaxation of xylitol and sorbitol: Implication on the origin of the Johari-Goldstein relaxation

    Science.gov (United States)

    Psurek, T.; Maslanka, S.; Paluch, M.; Nozaki, R.; Ngai, K. L.

    2004-07-01

    Dielectric spectroscopy was employed to study the effects of water on the primary α -relaxation and the secondary β -relaxation of xylitol. The measurements were made on anhydrous xylitol and mixtures of xylitol with water with three different water concentrations over a temperature range from 173K to 293K . The α -relaxation speeds up with increasing concentration of water in xylitol, whereas the rate of the β -relaxation is essentially unchanged. Some systematic differences in the behavior of α -relaxation for anhydrous xylitol and the mixtures were observed. Our findings confirm all the observations of Nozaki [R. Nozaki, H. Zenitani, A. Minoguchi, and K. Kitai, J. Non-Cryst. Solids 307, 349 (2002)] in sorbitol/water mixtures. Effects of water on both the α - and β -relaxation dynamics in xylitol and sorbitol are explained by using the coupling model.

  12. Nuclear magnetic relaxation and origins of RMN signals from GdAl2

    International Nuclear Information System (INIS)

    Santos Oliveira Junior, I. dos.

    1988-12-01

    The intermetallic compound GdAl 2 crystallizes in the cubic Laves phase C15. It is a simple ferromagnet below 176K. The easy direction of magnetization in this compound is such that the Al ions are distributed among two magnetically inequivalent sites. The pulsed NMR technique was used to study the origin of the signals from these two sites and the nuclear magnetic relaxation. (author) [pt

  13. Effect of carrier relaxation lifetime on the performance of InAs/InP quantum-dash lasers

    KAUST Repository

    Khan, Mohammed Zahed Mustafa

    2011-12-01

    The effect of carrier relaxation process into the quantum dash (Qdash) ground state (GS) is examined theoretically by carrier-photon rate equation model incorporating the inhomogeneous broadening. Increase in the relaxation time and the inhomogeneous broadening degrades the threshold current density. Moreover, our results show that a relaxation time of less than 2 ps gives optimum laser performance. © 2011 IEEE.

  14. Psychomotricity and Relaxation in Psychiatry

    Directory of Open Access Journals (Sweden)

    Janete Maximiano

    2014-10-01

    Full Text Available The author pretends to present with this article, the therapeutic contributions of Psychomotricity and Relaxation in Mental Health context, making only reference to adults intervention. A brief description of the body, as a biopsychosocial unity, is found in the introduction, which is followed by the explanation of conceptual and interventional models in Clinical Psychomotricity. The author makes reference to psychotherapeutic values of relaxation, giving some examples of techniques and exposing a clinical case. Finally, the author briefly describes her recent experience of Psychomotor intervention in Psychiatric Service of Hospital Fernando Fonseca.

  15. Relaxation Oscillation and Canard Explosion

    Science.gov (United States)

    Krupa, M.; Szmolyan, P.

    2001-08-01

    We give a geometric analysis of relaxation oscillations and canard cycles in singularly perturbed planar vector fields. The transition from small Hopf-type cycles to large relaxation cycles, which occurs in an exponentially thin parameter interval, is described as a perturbation of a family of singular cycles. The results are obtained by means of two blow-up transformations combined with standard tools of dynamical systems theory. The efficient use of various charts is emphasized. The results are applied to the van der Pol equation.

  16. The Interplay of Preference, Familiarity and Psychophysical Properties in Defining Relaxation Music.

    Science.gov (United States)

    Tan, Xueli; Yowler, Charles J; Super, Dennis M; Fratianne, Richard B

    2012-01-01

    The stress response has been well documented in past music therapy literature. However, hypometabolism, or the relaxation response, has received much less attention. Music therapists have long utilized various music-assisted relaxation techniques with both live and recorded music to elicit such a response. The ongoing proliferations of relaxation music through commercial media and the dire lack of evidence to support such claims warrant attention from healthcare professionals and music therapists. The purpose of these 3 studies was to investigate the correlational relationships between 12 psychophysical properties of music, preference, familiarity, and degree of perceived relaxation in music. Fourteen music therapists recommended and analyzed 30 selections of relaxation music. A group of 80 healthy adults then rated their familiarity, preference, and degree of perceived relaxation in the music. The analysis provided a detailed description of the intrinsic properties in music that were perceived to be relaxing by listeners. These properties included tempo, mode, harmonic, rhythmic, instrumental, and melodic complexities, timbre, vocalization/lyrics, pitch range, dynamic variations, and contour. In addition, music preference was highly correlated with listeners' perception of relaxation in music for both music therapists and healthy adults. The correlation between familiarity and degree of relaxation reached significance in the healthy adult group. Results from this study provided an in-depth operational definition of the intrinsic parameters in relaxation music and also highlighted the importance of preference and familiarity in eliciting the relaxation response.

  17. Magnetic fluctuations and superconducting properties of CaKFe4As4 studied by 75As NMR

    Science.gov (United States)

    Cui, J.; Ding, Q.-P.; Meier, W. R.; Böhmer, A. E.; Kong, T.; Borisov, V.; Lee, Y.; Bud'ko, S. L.; Valentí, R.; Canfield, P. C.; Furukawa, Y.

    2017-09-01

    We report 75As nuclear magnetic resonance (NMR) studies on a new iron-based superconductor, CaKFe4As4 , with Tc=35 K. 75As NMR spectra show two distinct lines corresponding to the As(1) and As(2) sites close to the K and Ca layers, respectively, revealing that K and Ca layers are well ordered without site inversions. We found that nuclear quadrupole frequencies νQ of the As(1) and As(2) sites show an opposite temperature T dependence. Nearly T independent behavior of the Knight shifts K is observed in the normal state, and a sudden decrease in K in the superconducting (SC) state suggests spin-singlet Cooper pairs. 75As spin-lattice relaxation rates 1 /T1 show a power-law T dependence with different exponents for the two As sites. The isotropic antiferromagnetic spin fluctuations characterized by the wave vector q =(π ,0 ) or (0 ,π ) in the single-iron Brillouin zone notation are revealed by 1 /T1T and K measurements. Such magnetic fluctuations are necessary to explain the observed temperature dependence of the 75As quadrupole frequencies, as evidenced by our first-principles calculations. In the SC state, 1 /T1 shows a rapid decrease below Tc without a Hebel-Slichter peak and decreases exponentially at low T , consistent with an s± nodeless two-gap superconductor.

  18. Single ferromagnetic fluctuations in UCoGe revealed by 73Ge- and 59Co-NMR studies

    Science.gov (United States)

    Manago, Masahiro; Ishida, Kenji; Aoki, Dai

    2018-02-01

    73Ge and 59Co nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements have been performed on a 73Ge-enriched single-crystalline sample of the ferromagnetic superconductor UCoGe in the paramagnetic state. The 73Ge NQR parameters deduced from NQR and NMR are close to those of another isostructural ferromagnetic superconductor URhGe. The Knight shifts of the Ge and Co sites are well scaled to each other when the magnetic field is parallel to the b or c axis. The hyperfine coupling constants of Ge are estimated to be close to those of Co. The large difference of spin susceptibilities between the a and b axes could lead to the different response of the superconductivity and ferromagnetism with the field parallel to these directions. The temperature dependence of the nuclear spin-lattice relaxation rates 1 /T1 at the two sites is similar to each other above 5 K. These results indicate that the itinerant U-5 f electrons are responsible for the ferromagnetism in this compound, consistent with previous studies. The similarities and differences in the three ferromagnetic superconductors are discussed.

  19. Fetal response to abbreviated relaxation techniques. A randomized controlled study.

    Science.gov (United States)

    Fink, Nadine S; Urech, Corinne; Isabel, Fornaro; Meyer, Andrea; Hoesli, Irène; Bitzer, Johannes; Alder, Judith

    2011-02-01

    stress during pregnancy can have adverse effects on the course of pregnancy and on fetal development. There are few studies investigating the outcome of stress reduction interventions on maternal well-being and obstetric outcome. this study aims (1) to obtain fetal behavioral states (quiet/active sleep, quiet/active wakefulness), (2) to investigate the effects of maternal relaxation on fetal behavior as well as on uterine activity, and (3) to investigate maternal physiological and endocrine parameters as potential underlying mechanisms for maternal-fetal relaxation-transferral. the behavior of 33 fetuses was analyzed during laboratory relaxation/quiet rest (control group, CG) and controlled for baseline fetal behavior. Potential associations between relaxation/quiet rest and fetal behavior (fetal heart rate (FHR), FHR variation, FHR acceleration, and body movements) and uterine activity were studied, using a computerized cardiotocogram (CTG) system. Maternal heart rate, blood pressure, cortisol, and norepinephrine were measured. intervention (progressive muscle relaxation, PMR, and guided imagery, GI) showed changes in fetal behavior. The intervention groups had higher long-term variation during and after relaxation compared to the CG (p=.039). CG fetuses had more FHR acceleration, especially during and after quiet rest (p=.027). Women in the PMR group had significantly more uterine activity than women in the GI group (p=.011) and than CG women. Maternal heart rate, blood pressure, and stress hormones were not associated with fetal behavior. this study indicates that the fetus might participate in maternal relaxation and suggests that GI is superior to PMR. This could especially be true for women who tend to direct their attention to body sensations such as abdominal activity. 2010 Elsevier Ltd. All rights reserved.

  20. Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

    Science.gov (United States)

    Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

    2018-04-01

    Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high