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Sample records for 2h nmr measurements

  1. Measurement of regional cerebral blood flow in cat brain using intracarotid 2H2O and 2H NMR imaging

    SciTech Connect

    Detre, J.A.; Subramanian, V.H.; Mitchell, M.D.; Smith, D.S.; Kobayashi, A.; Zaman, A.; Leigh, J.S. Jr. )

    1990-05-01

    Cerebral blood flow (CBF) was measured in cat brain in vivo at 2.7 T using 2H NMR to monitor the washout of deuterated saline injected into both carotid arteries via the lingual arteries. In anesthetized cats, global CBF varied directly with PaCO{sub 2} over a range of 20-50 mm Hg, and the corresponding global CBF values ranged from 25 to 125 ml.100 g-1.min-1. Regional CBF was measured in a 1-cm axial section of cat brain using intracarotid deuterated saline and gradient-echo 2H NMR imaging. Blood flow images with a maximum pixel resolution of 0.3 x 0.3 x 1.0 cm were generated from the deuterium signal washout at each pixel. Image derived values for CBF agreed well with other determinations, and decreased significantly with hypocapnia.

  2. 2H NMR studies of supercooled and glassy aspirin

    NASA Astrophysics Data System (ADS)

    Nath, R.; Nowaczyk, A.; Geil, B.; Bohmer, R.

    2007-11-01

    Acetyl salicylic acid, deuterated at the methyl group, was investigated using 2H-NMR in its supercooled and glassy states. Just above the glass transition temperature the molecular reorientations were studied using stimulated-echo spectroscopy and demonstrated a large degree of similarity with other glass formers. Deep in the glassy phase the NMR spectra look similar to those reported for the crystal [A. Detken, P. Focke, H. Zimmermann, U. Haeberlen, Z. Olejniczak, Z. T. Lalowicz, Z. Naturforsch. A 50 (1995) 95] and below 20 K they are indicative for rotational tunneling with a relatively large tunneling frequency. Measurements of the spin-lattice relaxation times for temperatures below 150 K reveal a broad distribution of correlation times in the glass. The dominant energy barrier characterizing the slow-down of the methyl group is significantly smaller than the well defined barrier in the crystal.

  3. Natural-abundance solid-state 2H NMR spectroscopy at high magnetic field.

    PubMed

    Aliev, Abil E; Mann, Sam E; Iuga, Dinu; Hughes, Colan E; Harris, Kenneth D M

    2011-06-01

    High-resolution solid-state (2)H NMR spectroscopy provides a method for measuring (1)H NMR chemical shifts in solids and is advantageous over the direct measurement of high-resolution solid-state (1)H NMR spectra, as it requires only the application of routine magic angle sample spinning (MAS) and routine (1)H decoupling methods, in contrast to the requirement for complex pulse sequences for homonuclear (1)H decoupling and ultrafast MAS in the case of high-resolution solid-state (1)H NMR. However, a significant obstacle to the routine application of high-resolution solid-state (2)H NMR is the very low natural abundance of (2)H, with the consequent problem of inherently low sensitivity. Here, we explore the feasibility of measuring (2)H MAS NMR spectra of various solids with natural isotopic abundances at high magnetic field (850 MHz), focusing on samples of amino acids, peptides, collagen, and various organic solids. The results show that high-resolution solid-state (2)H NMR can be used successfully to measure isotropic (1)H chemical shifts in favorable cases, particularly for mobile functional groups, such as methyl and -N(+)H(3) groups, and in some cases phenyl groups. Furthermore, we demonstrate that routine (2)H MAS NMR measurements can be exploited for assessing the relative dynamics of different functional groups in a molecule and for assessing whole-molecule motions in the solid state. The magnitude and field-dependence of second-order shifts due to the (2)H quadrupole interaction are also investigated, on the basis of analysis of simulated and experimental (1)H and (2)H MAS NMR spectra of fully deuterated and selectively deuterated samples of the α polymorph of glycine at two different magnetic field strengths.

  4. High-resolution solid-state 2H NMR spectroscopy of polymorphs of glycine.

    PubMed

    Aliev, Abil E; Mann, Sam E; Rahman, Aisha S; McMillan, Paul F; Corà, Furio; Iuga, Dinu; Hughes, Colan E; Harris, Kenneth D M

    2011-11-10

    High-resolution solid-state (2)H MAS NMR studies of the α and γ polymorphs of fully deuterated glycine (glycine-d(5)) are reported. Analysis of spinning sideband patterns is used to determine the (2)H quadrupole interaction parameters, and is shown to yield good agreement with the corresponding parameters determined from single-crystal (2)H NMR measurements (the maximum deviation in quadrupole coupling constants determined from these two approaches is only 1%). From analysis of simulated (2)H MAS NMR sideband patterns as a function of reorientational jump frequency (κ) for the -N(+)D(3) group in glycine-d(5), the experimentally observed differences in the (2)H MAS NMR spectrum for the -N(+)D(3) deutrons in the α and γ polymorphs is attributed to differences in the rate of reorientation of the -N(+)D(3) group. These simulations show severe broadening of the (2)H MAS NMR signal in the intermediate motion regime, suggesting that deuterons undergoing reorientational motions at rates in the range κ ≈ 10(4)-10(6) s(-1) are likely to be undetectable in (2)H MAS NMR measurements for materials with natural isotopic abundances. The (1)H NMR chemical shifts for the α and γ polymorphs of glycine have been determined from the (2)H MAS NMR results, taking into account the known second-order shift. Further quantum mechanical calculations of (2)H quadrupole interaction parameters and (1)H chemical shifts reveal the structural dependence of these parameters in the two polymorphs and suggest that the existence of two short intermolecular C-H···O contacts for one of the H atoms of the >CH(2) group in the α polymorph have a significant influence on the (2)H quadrupole coupling and (1)H chemical shift for this site. PMID:21939265

  5. 2H NMR studies of glycerol dynamics in protein matrices.

    PubMed

    Herbers, C R; Sauer, D; Vogel, M

    2012-03-28

    We use (2)H NMR spectroscopy to investigate the rotational motion of glycerol molecules in matrices provided by the connective tissue proteins elastin and collagen. Analyzing spin-lattice relaxation, line-shape properties, and stimulated-echo decays, we determine the rates and geometries of the motion as a function of temperature and composition. It is found that embedding glycerol in an elastin matrix leads to a mild slowdown of glycerol reorientation at low temperatures and glycerol concentrations, while the effect vanishes at ambient temperatures or high solvent content. Furthermore, it is observed that the nonexponential character of the rotational correlation functions is much more prominent in the elastin matrix than in the bulk liquid. Results from spin-lattice relaxation and line shape measurements indicate that, in the mixed systems, the strong nonexponentiality is in large part due to the existence of distributions of correlation times, which are broader on the long-time flank and, hence, more symmetric than in the neat system. Stimulated-echo analysis of slow glycerol dynamics reveals that, when elastin is added, the mechanism for the reorientation crosses over from small-angle jump dynamics to large-angle jump dynamics and the geometry of the motion changes from isotropic to anisotropic. The results are discussed against the background of present and previous findings for glycerol and water dynamics in various protein matrices and compared with observations for other dynamically highly asymmetric mixtures so as to ascertain in which way the viscous freezing of a fast component in the matrix of a slow component differs from the glassy slowdown in neat supercooled liquids. PMID:22462878

  6. 2H NMR studies of glycerol dynamics in protein matrices

    NASA Astrophysics Data System (ADS)

    Herbers, C. R.; Sauer, D.; Vogel, M.

    2012-03-01

    We use 2H NMR spectroscopy to investigate the rotational motion of glycerol molecules in matrices provided by the connective tissue proteins elastin and collagen. Analyzing spin-lattice relaxation, line-shape properties, and stimulated-echo decays, we determine the rates and geometries of the motion as a function of temperature and composition. It is found that embedding glycerol in an elastin matrix leads to a mild slowdown of glycerol reorientation at low temperatures and glycerol concentrations, while the effect vanishes at ambient temperatures or high solvent content. Furthermore, it is observed that the nonexponential character of the rotational correlation functions is much more prominent in the elastin matrix than in the bulk liquid. Results from spin-lattice relaxation and line shape measurements indicate that, in the mixed systems, the strong nonexponentiality is in large part due to the existence of distributions of correlation times, which are broader on the long-time flank and, hence, more symmetric than in the neat system. Stimulated-echo analysis of slow glycerol dynamics reveals that, when elastin is added, the mechanism for the reorientation crosses over from small-angle jump dynamics to large-angle jump dynamics and the geometry of the motion changes from isotropic to anisotropic. The results are discussed against the background of present and previous findings for glycerol and water dynamics in various protein matrices and compared with observations for other dynamically highly asymmetric mixtures so as to ascertain in which way the viscous freezing of a fast component in the matrix of a slow component differs from the glassy slowdown in neat supercooled liquids.

  7. Elucidating proline dynamics in spider dragline silk fibre using 2H-13C HETCOR MAS NMR.

    PubMed

    Shi, Xiangyan; Yarger, Jeffery L; Holland, Gregory P

    2014-05-14

    (2)H-(13)C HETCOR MAS NMR is performed on (2)H/(13)C/(15)N-Pro enriched A. aurantia dragline silk. Proline dynamics are extracted from (2)H NMR line shapes and T1 in a site-specific manner to elucidate the backbone and side chain molecular dynamics for the MaSp2 GPGXX β-turn regions for spider dragline silk in the dry and wet, supercontracted states.

  8. Natural abundance 2H-ERETIC-NMR authentication of the origin of methyl salicylate.

    PubMed

    Le Grand, Flore; George, Gerard; Akoka, Serge

    2005-06-29

    Methyl salicylate is a compound currently used in the creation of many flavors. It can be obtained by synthesis or from two natural sources: essential oil of wintergreen and essential oil of sweet birch bark. Deuterium site-specific natural isotope abundance (A(i)) determination by NMR spectroscopy with the method of reference ERETIC ((2)H-ERETIC-NMR) has been applied to this compound. A(i) measurements have been performed on 19 samples of methyl salicylate from different origins, natural/synthetic and commercial/extracted. This study demonstrates that appropriate treatment performed on the data allows discrimination between synthetic and natural samples. Moreover, the representation of intramolecular ratios R(6/5) as a function of R(3/2) distinguishes between synthetics, wintergreen oils, and sweet birch bark oils.

  9. Revisiting NMR composite pulses for broadband 2H excitation

    PubMed Central

    Shen, Ming; Roopchand, Rabia; Mananga, Eugene S.; Amoureux, Jean-Paul; Chen, Qun; Boutis, Gregory S.; Hu, Bingwen

    2014-01-01

    Quadrupolar echo NMR spectroscopy of static solids often requires RF excitation that covers spectral widths exceeding 100 kHz, which is difficult to obtain due to instrumental limitations. In this work we revisit four well-known composite pulses (COM-I, II, III and IV) for broadband excitation in deuterium quadrupolar echo spectroscopy. These composite pulses are combined with several phase cycling schemes that were previously shown to decrease finite pulse width distortions in deuterium solid-echo experiments performed with two single pulses. The simulations and experiments show that COM-II and IV composite pulses combined with an 8-step phase cycling aid in achieving broadband excitation with limited pulse width distortions. PMID:25583576

  10. 2Q NMR of 2H2O ordering at solid interfaces

    NASA Astrophysics Data System (ADS)

    Krivokhizhina, Tatiana V.; Wittebort, R. J.

    2014-06-01

    Solvent ordering at an interface can be studied by multiple-quantum NMR. Quantitative studies of 2H2O ordering require clean double-quantum (2Q) filtration and an analysis of 2Q buildup curves that accounts for relaxation and, if randomly oriented samples are used, the distribution of residual couplings. A pulse sequence with absorption mode detection is extended for separating coherences by order and measuring relaxation times such as the 2Q filtered T2. Coherence separation is used to verify 2Q filtration and the 2Q filtered T2 is required to extract the coupling from the 2Q buildup curve when it is unresolved. With our analysis, the coupling extracted from the buildup curve in 2H2O hydrated collagen was equivalent to the resolved coupling measured in the usual 1D experiment and the 2Q to 1Q signal ratio was in accord with theory. Application to buildup curves from 2H2O hydrated elastin, which has an unresolved coupling, revealed a large increase in the 2Q signal upon mechanical stretch that is due to an increase in the ordered water fraction while changes in the residual coupling and T2 are small.

  11. (2) H and (139) La NMR Spectroscopy in Aqueous Solutions at Geochemical Pressures.

    PubMed

    Ochoa, Gerardo; Pilgrim, Corey D; Martin, Michele N; Colla, Christopher A; Klavins, Peter; Augustine, Matthew P; Casey, William H

    2015-12-14

    Nuclear spin relaxation rates of (2) H and (139) La in LaCl3 +(2) H2 O and La(ClO4 )3 +(2) H2 O solutions were determined as a function of pressure in order to demonstrate a new NMR probe designed for solution spectroscopy at geochemical pressures. The (2) H longitudinal relaxation rates (T1 ) vary linearly to 1.6 GPa, consistent with previous work at lower pressures. The (139) La T1 values vary both with solution chemistry and pressure, but converge with pressure, suggesting that the combined effects of increased viscosity and enhanced rates of ligand exchange control relaxation. This simple NMR probe design allows experiments on aqueous solutions to pressures corresponding roughly to those at the base of the Earth's continental crust. PMID:26404025

  12. Probing perturbation of bovine lung surfactant extracts by albumin using DSC and 2H-NMR.

    PubMed

    Nag, Kaushik; Keough, Kevin M W; Morrow, Michael R

    2006-05-15

    Lung surfactant (LS), a lipid-protein mixture, forms films at the lung air-water interface and prevents alveolar collapse at end expiration. In lung disease and injury, the surface activity of LS is inhibited by leakage of serum proteins such as albumin into the alveolar hypophase. Multilamellar vesicular dispersions of a clinically used replacement, bovine lipid extract surfactant (BLES), to which (2% by weight) chain-perdeuterated dipalmitoylphosphatidycholine (DPPG mixtures-d(62)) had been added, were studied using deuterium-NMR spectroscopy ((2)H-NMR) and differential scanning calorimetry (DSC). DSC scans of BLES showed a broad gel to liquid-crystalline phase transition between 10-35 degrees C, with a temperature of maximum heat flow (T(max)) around 27 degrees C. Incorporation of the DPPC-d(62) into BLES-reconstituted vesicles did not alter the T(max) or the transition range as observed by DSC or the hydrocarbon stretching modes of the lipids observed using infrared spectroscopy. Transition enthalpy change and (2)H-NMR order parameter profiles were not significantly altered by addition of calcium and cholesterol to BLES. (2)H-NMR spectra of the DPPC-d(62) probes in these samples were characteristic of a single average lipid environment at all temperatures. This suggested either continuous ordering of the bilayer through the transition during cooling or averaging of the DPPC-d(62) environment by rapid diffusion between small domains on a short timescale relative to that characteristic of the (2)H-NMR experiment. Addition of 10% by weight of soluble bovine serum albumin (1:0.1, BLES/albumin, dry wt/wt) broadened the transition slightly and resulted in the superposition of (2)H-NMR spectral features characteristic of coexisting fluid and ordered phases. This suggests the persistence of phase-separated domains throughout the transition regime (5-35 degrees C) of BLES with albumin. The study suggests albumin can cause segregation of protein bound-lipid domains in

  13. Probing Perturbation of Bovine Lung Surfactant Extracts by Albumin using DSC and 2H-NMR

    PubMed Central

    Nag, Kaushik; Keough, Kevin M. W.; Morrow, Michael R.

    2006-01-01

    Lung surfactant (LS), a lipid-protein mixture, forms films at the lung air-water interface and prevents alveolar collapse at end expiration. In lung disease and injury, the surface activity of LS is inhibited by leakage of serum proteins such as albumin into the alveolar hypophase. Multilamellar vesicular dispersions of a clinically used replacement, bovine lipid extract surfactant (BLES), to which (2% by weight) chain-perdeuterated dipalmitoylphosphatidycholine (DPPG mixtures-d62) had been added, were studied using deuterium-NMR spectroscopy (2H-NMR) and differential scanning calorimetry (DSC). DSC scans of BLES showed a broad gel to liquid-crystalline phase transition between 10–35°C, with a temperature of maximum heat flow (Tmax) around 27°C. Incorporation of the DPPC-d62 into BLES-reconstituted vesicles did not alter the Tmax or the transition range as observed by DSC or the hydrocarbon stretching modes of the lipids observed using infrared spectroscopy. Transition enthalpy change and 2H-NMR order parameter profiles were not significantly altered by addition of calcium and cholesterol to BLES. 2H-NMR spectra of the DPPC-d62 probes in these samples were characteristic of a single average lipid environment at all temperatures. This suggested either continuous ordering of the bilayer through the transition during cooling or averaging of the DPPC-d62 environment by rapid diffusion between small domains on a short timescale relative to that characteristic of the 2H-NMR experiment. Addition of 10% by weight of soluble bovine serum albumin (1:0.1, BLES/albumin, dry wt/wt) broadened the transition slightly and resulted in the superposition of 2H-NMR spectral features characteristic of coexisting fluid and ordered phases. This suggests the persistence of phase-separated domains throughout the transition regime (5–35°C) of BLES with albumin. The study suggests albumin can cause segregation of protein bound-lipid domains in surfactant at NMR timescales (10−5 s

  14. Water interactions with varying molecular states of bovine casein: 2H NMR relaxation studies

    SciTech Connect

    Kumosinski, T.F.; Pessen, H.; Prestrelski, S.J.; Farrell, H.M. Jr.

    1987-09-01

    The caseins occur in milk as spherical colloidal complexes of protein and salts with an average diameter of 1200 A, the casein micelles. Removal of Ca2+ is thought to result in their dissociation into smaller protein complexes stabilized by hydrophobic interactions and called submicelles. Whether these submicelles actually occur within the micelles as discrete particles interconnected by calcium phosphate salt bridges has been the subject of much controversy. A variety of physical measurements have shown that casein micelles contain an inordinately high amount of trapped water (2 to 7 g H/sub 2/O/g protein). With this in mind it was of interest to determine if NMR relaxation measurements could detect the presence of this trapped water within the micelles, and to evaluate whether it is a continuum with picosecond correlation times or is associated in part with discrete submicellar structures with nanosecond motions. For this purpose the variations in /sup 2/H NMR longitudinal and transverse relaxation rates of water with protein concentration were determined for bovine casein at various temperatures, under both submicellar and micellar conditions. D/sub 2/O was used instead of H/sub 2/O to eliminate cross-relaxation effects. From the protein concentration dependence of the relaxation rates, the second virial coefficient of the protein was obtained by nonlinear regression analysis. Using either an isotropic tumbling or an intermediate asymmetry model, degrees of hydration, v, and correlation times, tau c, were calculated for the caseins; from the latter parameter the Stokes radius, r, was obtained. Next, estimates of molecular weights were obtained from r and the partial specific volume. Values were in the range of those published from other methodologies for the submicelles.

  15. Backbone motions in a crystalline protein from field-dependent 2H-NMR relaxation and line-shape analysis.

    PubMed

    Mack, J W; Usha, M G; Long, J; Griffin, R G; Wittebort, R J

    2000-01-01

    We have used 2H-nmr to study backbone dynamics of the 2H-labeled, slowly exchanging amide sites of fully hydrated, crystalline hen egg white lysozyme. Order parameters are determined from the residual quadrupole coupling and values increase from S2 = 0.85 at 290 K to S2 = 0.94 at 200 K. Dynamical rates are determined from spin-lattice relaxation at three nmr frequencies (38.8, 61.5, and 76.7 MHz). The approach used here is thus distinct from solution nmr studies where dynamical amplitudes and rates are both determined from relaxation measurements. At temperatures below 250 K, relaxation is independent of the nmr frequency indicating that backbone motions are fast compared to the nmr frequencies. However, as the temperature is increased above 250 K, relaxation is significantly more efficient at the lowest frequency, which shows, in addition, the presence of motions that are slow compared to the nmr frequencies. Using the values of S2 determined from the residual quadrupole coupling and a model-free relaxation formalism that allows for fast and slow internal motions, we conclude that these slow motions have correlation times in the range of 0.1 to 1.0 microsecond and are effectively frozen out at 250 K where fast motions of the amide planes with approximately 15 ps effective correlation times and 9 degrees rms amplitudes dominate relaxation. The fast internal motions increase slightly in amplitude as the temperature rises toward 290 K, but the correlation time, as is also observed in solution nmr studies of RNase H, is approximately constant. These findings are consistent with hypotheses of dynamic glass transitions in hydrated proteins arising from temperature-dependent damping of harmonic modes of motion above the transition point.

  16. NMR resonance splitting of urea in stretched hydrogels: proton exchange and (1)H/(2)H isotopologues.

    PubMed

    Kuchel, Philip W; Naumann, Christoph; Chapman, Bogdan E; Shishmarev, Dmitry; Håkansson, Pär; Bacskay, George; Hush, Noel S

    2014-10-01

    Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively.

  17. NMR resonance splitting of urea in stretched hydrogels: proton exchange and (1)H/(2)H isotopologues.

    PubMed

    Kuchel, Philip W; Naumann, Christoph; Chapman, Bogdan E; Shishmarev, Dmitry; Håkansson, Pär; Bacskay, George; Hush, Noel S

    2014-10-01

    Urea at ∼12 M in concentrated gelatin gel, that was stretched, gave (1)H and (2)H NMR spectral splitting patterns that varied in a predictable way with changes in the relative proportions of (1)H2O and (2)H2O in the medium. This required consideration of the combinatorics of the two amide groups in urea that have a total of four protonation/deuteration sites giving rise to 16 different isotopologues, if all the atoms were separately identifiable. The rate constant that characterized the exchange of the protons with water was estimated by back-transformation analysis of 2D-EXSY spectra. There was no (1)H NMR spectral evidence that the chiral gelatin medium had caused in-equivalence in the protons bonded to each amide nitrogen atom. The spectral splitting patterns in (1)H and (2)H NMR spectra were accounted for by intra-molecular scalar and dipolar interactions, and quadrupolar interactions with the electric field gradients of the gelatin matrix, respectively. PMID:25241007

  18. Slow recrystallization of tripalmitoylglycerol from MCT oil observed by 2H NMR.

    PubMed

    Smith, Kevin W; Smith, Paul R; Furó, István; Pettersson, Erik Thyboll; Cain, Fred W; Favre, Loek; Talbot, Geoff

    2007-10-17

    The crystallization and recrystallization of fats have a significant impact on the properties and quality of many food products. While crystallization has been the subject of a number of studies using pure triacylglycerols (TAG), recrystallization in similarly pure systems is rarely studied. In this work, perdeuterated tripalmitoylglycerol ( (2)H-PPP) was dissolved in medium chain triacylglycerol oil (MCT) to yield a saturated solution. The solution was heated to cause partial melting of the solid and dissolution of the molten fraction of (2)H-PPP in MCT and was then cooled to the original temperature to induce recrystallization from the supersaturated solution. (2)H NMR was used to monitor the disappearance of (2)H-PPP from the solution and showed that recrystallization occurred in two steps. The first step was rapid, taking place over a few minutes, and accounted for more than two-thirds of the total recrystallization. The second step was much slower, taking place over a remarkably long timescale of hours to days. It is proposed that dissolution occurs from all parts of the crystals, leaving an etched and pitted surface. The first step of crystallization is the infilling of these pits, while the second step is the continued growth on the smoothed crystal faces.

  19. Double and zero quantum filtered 2H NMR analysis of D2O in intervertebral disc tissue

    NASA Astrophysics Data System (ADS)

    Ooms, Kristopher J.; Vega, Alexander J.; Polenova, Tatyana; Cannella, Marco; Marcolongo, Michele

    2015-09-01

    The analysis of double and zero quantum filtered 2H NMR spectra obtained from D2O perfused in the nucleus pulposus of human intervertebral disc tissue samples is reported. Fitting the spectra with a three-site model allows for residual quadrupolar couplings and T2 relaxation times to be measured. The analysis reveals changes in both the couplings and relaxation times as the tissue begins to show signs of degradation. The full analysis demonstrates that information about tissue hydration, water collagen interactions, and sample heterogeneity can be obtained and used to better understand the biochemical differences between healthy and degraded tissue.

  20. Investigation of multiaxial molecular dynamics by 2H MAS NMR spectroscopy.

    PubMed

    Kristensen, J H; Hoatson, G L; Vold, R L

    1998-11-01

    The technique of 2H MAS NMR spectroscopy is presented for the investigation of multiaxial molecular dynamics. To evaluate the effects of discrete random reorientation a Lie algebraic formalism based on the stochastic Liouville-von Neumann equation is developed. The solution to the stochastic Liouville-von Neumann equation is obtained both in the presence and absence of rf irradiation. This allows effects of molecular dynamics to be evaluated during rf pulses and extends the applicability of the formalism to arbitrary multiple pulse experiments. Theoretical methods are presented for the description of multiaxial dynamics with particular emphasis on the application of vector parameters to represent molecular rotations. Numerical time and powder integration algorithms are presented that are both efficient and easy to implement computationally. The applicability of 2H MAS NMR spectroscopy for investigating molecular dynamics is evaluated from theoretical spectra. To demonstrate the potential of the technique the dynamics of thiourea-2H4 is investigated experimentally. From a series of variable temperature MAS and quadrupole echo spectra it has been found that the dynamics can be described by composite rotation about the CS and CN bonds. Both experiments are sensitive to the fast CS rotation which is shown to be described by the Arrhenius parameters E(CS) = 46.4 +/- 2.3 kJ mol(-1) and ln(A(CS))= 32.6 +/- 0.9. The MAS experiment represents a significant improvement by simultaneously allowing the dynamics of the slow CN rotation to be fully characterized in terms of E(CN) = 56.3 +/- 3.4 kJ mol(-1) and ln(A(CN)) = 25.3 +/- 1.1. PMID:9875600

  1. Determination of orientational order parameters from 2H NMR spectra of magnetically partially oriented lipid bilayers.

    PubMed Central

    Schäfer, H; Mädler, B; Sternin, E

    1998-01-01

    The partial orientation of multilamellar vesicles (MLVs) in high magnetic fields is known to affect the shape of 2H NMR spectra. There are numerical methods for extracting either the orientational order parameters of lipid molecules for a random distribution of domain orientations in the sample, or the distribution of orientations for a known set of spectral anisotropies. A first attempt at determining the orientational order parameters in the presence of an unknown nonrandom distribution of orientations is presented. The numerical method is based on the Tikhonov regularization algorithm. It is tested using simulated partially oriented spectra. An experimental spectrum of a phospholipid-ether mixture in water is analyzed as an example. The experimental spectrum is consistent with an ellipsoidal shape of MLVs with a ratio of semiaxes of approximately 3.4. PMID:9533713

  2. Local structure and molecular motions in imidazolium hydrogen malonate crystal as studied by 2H and 13C NMR

    NASA Astrophysics Data System (ADS)

    Mizuno, M.; Chizuwa, M.; Umiyama, T.; Kumagai, Y.; Miyatou, T.; Ohashi, R.; Ida, T.; Tansho, M.; Shimizu, T.

    2015-04-01

    The local structure and molecular motion of the imidazolium hydrogen malonate crystal were investigated using solid-state 2H and 13C NMR. The imidazolium ion undergoes isotropic rotation, which is correlated with a defect in the crystal, as observed by 2H NMR broadline spectra above 263 K. A 180∘ flip of the imidazolium ion in the regular site was observed from 2H NMR quadrupole Carr-Purcell-Meiboom-Gill (QCPMG) spectra. The Grotthuss mechanism was accompanied by a 180∘ flip of the imidazolium ion in regular sites. Moreover, the proton transfer associated with the imidazolium ion of the defective crystal is important for proton conductivity of the imidazolium hydrogen malonate crystal.

  3. Interaction of antiaggregant molecule ajoene with membranes. An ESR and 1H, 2H, 31P-NMR study.

    PubMed

    Debouzy, J C; Neumann, J M; Hervé, M; Daveloose, D; Viret, J; Apitz-Castro, R

    1989-01-01

    The structure of ajoene, a molecule extracted from garlic, has been studied by 1H-NMR and its interaction with model membranes by 1H-, 2H-, 31-P-NMR and ESR experiments. This study clearly shows that the ajoene molecule is located deep in the layer and is close to the interlayer medium. Moreover while NMR experiments show that the membrane structure is only slightly affected by the presence of ajoene, ESR experiments reveal significant modifications in phospholipid dynamics. This interaction, observed before with the phenothiazine derivative, promazine, results in an increase of the membrane fluidity in its hydrophobic part and could be related to clinical properties of ajoene.

  4. Deuterium NMR of Val1. (2-2H)Ala3. gramicidin A in oriented DMPC bilayers

    SciTech Connect

    Hing, A.W.; Adams, S.P.; Silbert, D.F.; Norberg, R.E. )

    1990-05-01

    Deuterium NMR is used to study the selectively labeled Val1...(2-2H)Ala3...gramicidin A molecule to investigate the structure and dynamics of the C alpha-2H bond in the Ala3 residue of gramicidin. Val1...(2-2H)Ala3...gramicidin A is synthesized, purified, and characterized and then incorporated into oriented bilayers of dimyristoylphosphatidylcholine sandwiched between glass coverslips. Phosphorus NMR line shapes obtained from this sample are consistent with the presence of the bilayer phase and indicate that no nonbilayer phases are present in significant amounts. Deuterium NMR line shapes obtained from this sample indicate that the motional axis of the gramicidin Ala3 residue is parallel to the coverslip normal, that the distribution of motional axis orientations has a width of 2 degrees, and that only one major conformational and dynamical state of the Ala3 C alpha-2H bond is observed on the NMR time scale. Furthermore, the Ala3 C alpha-2H bond angle relative to the motional axis is 19-20 degrees if fast axial rotation is assumed to be the only motion present but is less than or equal to 19-20 degrees in the absence of such an assumption. This result indicates that various double-stranded, helical dimer models are very unlikely to represent the structure of gramicidin in the sample studied but that the single-stranded, beta 6.3 helical dimer models are consistent with the experimental data. However, a definitive distinction between the left-handed, single-stranded, beta 6.3 helical dimer model and the right-handed, single-stranded, beta 6.3 helical dimer model cannot be made on the basis of the experimental data obtained in this study.

  5. Site-resolved 2H relaxation experiments in solid materials by global line-shape analysis of MAS NMR spectra

    NASA Astrophysics Data System (ADS)

    Lindh, E. L.; Stilbs, P.; Furó, I.

    2016-07-01

    We investigate a way one can achieve good spectral resolution in 2H MAS NMR experiments. The goal is to be able to distinguish between and study sites in various deuterated materials with small chemical shift dispersion. We show that the 2H MAS NMR spectra recorded during a spin-relaxation experiment are amenable to spectral decomposition because of the different evolution of spectral components during the relaxation delay. We verify that the results are robust by global least-square fitting of the spectral series both under the assumption of specific line shapes and without such assumptions (COmponent-REsolved spectroscopy, CORE). In addition, we investigate the reliability of the developed protocol by analyzing spectra simulated with different combinations of spectral parameters. The performance is demonstrated in a model material of deuterated poly(methacrylic acid) that contains two 2H spin populations with similar chemical shifts but different quadrupole splittings. In 2H-exchanged cellulose containing two 2H spin populations with very similar chemical shifts and quadrupole splittings, the method provides new site-selective information about the molecular dynamics.

  6. /sup 2/H-NMR studies of hypocotyl cell walls of germinating beams supplied with perdeuterated myo-inositol

    SciTech Connect

    Sasaki, K.; Wallace, J.C.; MacKay, A.L.; Balza, F.; Taylor, I.E.P.

    1987-04-01

    When myo-(2-/sup 3/H) inositol (MI) was supplied to bean seeds by imbibition, only uronic acid, arabinose and xylose residues of cell wall polysaccharides were labeled. To study the structural mobility of the uronic acid- and/or pentose-rich polysaccharides in cell wall using /sup 2/H-NMR, the authors supplied perdeuterated MI with (2-/sup 3/H) MI to germinating bean seeds. Perdeuterated MI was prepared by the /sup 1/H-/sup 2/H exchange reaction of MI in deuterium oxide with Raney nickel. During the exchange reaction, extensive epimerization occurred and at least 6 inositol epimers in addition to MI were identified in the reaction mixture of GC/MS. The perdeuterated MI was completely resolved from other inositol epimers and purified by anion-exchange chromatography using Dowex 1 (borate form) and by crystallization. The /sup 2/H-NMR analysis resolved the /sup 2/H-labeled hypocotyl cell walls into two components (rigid and mobile components). They also report the distribution of /sup 2/H and /sup 3/H from perdeuterated and (2-/sup 3/H) MI in the cell wall sugar residues.

  7. Detection of Anisotropy in Cartilage Using 2H Double-Quantum-Filtered NMR-Spectroscopy

    NASA Astrophysics Data System (ADS)

    Sharf, Y.; Eliav, U.; Shinar, H.; Navon, G.

    Double-quantum-filtered (DQF) NMR spectroscopy of I = 1 spin systems is a diagnostic tool for the detection of anisotropy in macroscopically disordered systems. For deuterium, this method reveals the presence of a residual quadrupolar interaction for D 2O in bovine nasal cartilage. This tissue is not macroscopically ordered and the quadrupolar splitting is not resolved. Fitting the calculated spectral lineshapes to the experimental results was possible only when a distribution of the residual quadrupolar interaction, omega(q), was assumed. The series of DQF lineshapes obtained for different creation times in the DQF experiment could be fitted using a single set of three parameters: the average residual quadrupolar interaction overlineω q/2π = 110 Hz, its standard deviation Δω q/2π = 73 Hz, and the transverse relaxation rate of 63 s -1. Separate deuterium DQF measurements for the constituents of the cartilage, collagen, and chondroitin sulfate indicated that the DQF spectra of cartilage are the result of anisotropic motion of D 2O due to binding to the fibrous collagen in the tissue.

  8. 1H and 2H NMR studies of water in work-free wheat flour doughs.

    PubMed

    d'Avignon, D A; Hung, C C; Pagel, M T; Hart, B; Bretthorst, G L; Ackerman, J J

    1991-01-01

    Proton and deuterium NMR relaxation methods were used to characterize water compartmentalization and hydration in work-free wheat flour doughs. Transverse (spin-spin) relaxation measurements define three motionally unique water compartments in the work-free dough preparations. The apparent occupancy fraction and relative mobility of each water domain are found to be functions of moisture content, temperature, and flour type. Additionally, the number of relaxation-resolved water compartments and their characteristic relaxation rate constants are found to depend critically on both moisture content and the interpulse-delay employed for the multi-pulse relaxation experiments. Under controlled experimental conditions, dynamics between the three water compartments can be observed to be consistent with the onset of flour hydration. The most notable observation during the initial period of hydration is a loss of "free" or "loosely bound" water to environments characterized by less mobility. Freezing studies show that hard wheat doughs have slightly less amorphous, non-freezable water than do soft wheat flour doughs prepared under similar conditions. PMID:1746346

  9. 2H NMR study of phase transition and hydrogen dynamics in hydrogen bonded organic antiferroelectric 55DMBP-H2ca

    NASA Astrophysics Data System (ADS)

    Asaji, Tetsuo; Hara, Masamichi; Fujimori, Hiroki; Hagiwara, Shoko

    2016-12-01

    Hydrogen dynamics in one-dimensional hydrogen bonded organic antiferroelectric, co-crystal of 5,5'-dimethyl-2,2'-bipyridine (55DMBP) and chloranilic acid (H2ca), was investigated by use of 2H high resolution solid-state NMR. The two types of hydrogen bonds O-H …N and N+-H … O - in the antiferroelectric phase were clearly observed as the splitting of the side band of the 2H MAS NMR spectra of the acid-proton deuterated compound 55DMBP-D 2ca. The temperature dependence of the spin-lattice relaxation time was measured of the N+-H and O-H deuterons, respectively. It was suggested that the motion of the O-H deuteron is already in the antiferroelectric phase in the fast-motion regime in the NMR time scale, while that of the N+-H deuteron is a slow motion. In the high-temperature paraelectric phase, the both deuterons become equivalent and the fast motion of the deuterons in the NMR time scale is taking place with the activation energy of 7.9 kJ mol-1.

  10. Selective photochemistry at stereogenic metal and ligand centers of cis-[Ru(diphosphine)2(H)2]: preparative, NMR, solid state, and laser flash studies.

    PubMed

    Câmpian, Marius V; Perutz, Robin N; Procacci, Barbara; Thatcher, Robert J; Torres, Olga; Whitwood, Adrian C

    2012-02-22

    Three ruthenium complexes Λ-[cis-Ru((R,R)-Me-BPE)(2)(H)(2)] Λ-R,R-Ru1H(2), Δ-[cis-Ru((S,S)-Me-DuPHOS)(2)(H)(2)] Δ-S,S-Ru2H(2), and Λ-[cis-Ru((R,R)-Me-DuPHOS)(2)(H)(2)] Λ-R,R-Ru2H(2) (1 = (Me-BPE)(2), 2 = (Me-DuPHOS)(2)) were characterized by multinuclear NMR and CD spectroscopy in solution and by X-ray crystallography. The chiral ligands allow the full control of stereochemistry and enable mechanistic studies not otherwise available. Oxidative addition of E-H bonds (E = H, B, Si, C) was studied by steady state and laser flash photolysis in the presence of substrates. Steady state photolysis shows formation of single products with one stereoisomer. Solid state structures and circular dichroism spectra reveal a change in configuration at ruthenium for some Δ-S,S-Ru2H(2)/Λ-R,R-Ru2H(2) photoproducts from Λ to Δ (or vice versa) while the configuration for Λ-R,R-Ru1H(2) products remains unchanged as Λ. The X-ray structure of silyl hydride photoproducts suggests a residual H(1)···Si(1) interaction for Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(Et(2)SiH)(H)] and Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(PhSiH(2))(H)] but not for their Ru(R,R-BPE)(2) analogues. Molecular structures were also determined for Λ-[cis-Ru((R,R)-Me-BPE)(2)(Bpin)(H)], Λ-[Ru((S,S)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], Δ-[Ru((R,R)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], and trans-[Ru((R,R)-Me-DuPHOS)(2)(C(6)F(5))(H)]. In situ laser photolysis in the presence of p-H(2) generates hyperpolarized NMR spectra because of magnetically inequivalent hydrides; these experiments and low temperature photolysis with D(2) reveal that the loss of hydride ligands is concerted. The reaction intermediates [Ru(DuPHOS)(2)] and [Ru(BPE)(2)] were detected by laser flash photolysis and have spectra consistent with approximate square-planar Ru(0) structures. The rates of their reactions with H(2), D(2), HBpin, and PhSiH(3) were measured by transient kinetics. Rate constants are significantly faster for [Ru(BPE)(2)] than for [Ru(DuPHOS)(2

  11. Grasping hydrogen adsorption and dynamics in metal-organic frameworks using (2)H solid-state NMR.

    PubMed

    Lucier, Bryan E G; Zhang, Yue; Lee, Kelly J; Lu, Yuanjun; Huang, Yining

    2016-06-18

    Record greenhouse gas emissions have spurred the search for clean energy sources such as hydrogen (H2) fuel cells. Metal-organic frameworks (MOFs) are promising H2 adsorption and storage media, but knowledge of H2 dynamics and adsorption strengths in these materials is lacking. Variable-temperature (VT) (2)H solid-state NMR (SSNMR) experiments targeting (2)H2 gas (i.e., D2) shed light on D2 adsorption and dynamics within six representative MOFs: UiO-66, M-MOF-74 (M = Zn, Mg, Ni), and α-M3(COOH)6 (M = Mg, Zn). D2 binding is relatively strong in Mg-MOF-74, Ni-MOF-74, α-Mg3(COOH)6, and α-Zn3(COOH)6, giving rise to broad (2)H SSNMR powder patterns. In contrast, D2 adsorption is weaker in UiO-66 and Zn-MOF-74, as evidenced by the narrow (2)H resonances that correspond to rapid reorientation of the D2 molecules. Employing (2)H SSNMR experiments in this fashion holds great promise for the correlation of MOF structural features and functional groups/metal centers to H2 dynamics and host-guest interactions. PMID:27181834

  12. sup 2 H NMR study of molecular dynamics and organization in the system C sub 12 E sub 4 -water

    SciTech Connect

    Henriksson, U. ); Jonstroemer, M.; Olsson, U.; Soederman, O. ); Klose, G. )

    1991-05-02

    A sample containing 20 wt % of the nonionic surfactant tetraethylene glycol dodecyl ether (C{sub 12}E{sub 4}), specifically deuterated in the {alpha}-position, was investigated with {sup 2}H NMR relaxation in H{sub 2}O. From the frequency dependence of the longitudinal relaxation rate in the Larmor frequency range 2-55 MHz, it was concluded that the solution contains rodlike micelles. A slow motion in the microsecond time scale, as determined from the transverse relaxation rate, was interpreted taking the flexibility of the rodlike micelles explicitly into account.

  13. 2H NMR study of 2D melting and dynamic behaviour of CDCl3 confined in ACF nanospace.

    PubMed

    Ueda, Takahiro; Omichi, Hiroaki; Chen, Yu; Kobayashi, Hirokazu; Kubota, Osamu; Miyakubo, Keisuke; Eguchi, Taro

    2010-08-28

    Two-dimensional melting of trichloromethane (chloroform) confined in activated carbon fibre was investigated using differential thermal analysis and (2)H NMR techniques. Differential thermal analysis revealed a thermal anomaly with an endothermic peak at 269 K, which was distributed from 250 K to 287 K on the heating direction. This anomaly was also observed upon cooling at the same temperature. Furthermore, (2)H NMR revealed that slow motion such as molecular hopping and/or diffusion of CDCl(3) in ACF affected the spectral line width. The temperature dependence (Arrhenius plot) of the spectral line width showed an inflection point at 227 K. The activation energy of molecular motion of CDCl(3) in ACF was 4 kJ mol(-1) at temperatures greater than 227 K and 7.7 kJ mol(-1) at temperatures less than 227 K. Reduction of the activation energy suggests that the average intermolecular distance between CDCl(3) molecules enlarges above the inflection point. The difference of activation energy (3.7 kJ mol(-1)) is close to the enthalpy of fusion in typical plastic crystals. These results reveal that the thermal anomaly and the transition of dynamic process correspond respectively to melting of CHCl(3) in ACF and the pre-melting phenomenon.

  14. Hydration properties of regioselectively etherified celluloses monitored by 2H and 13C solid-state MAS NMR spectroscopy.

    PubMed

    Larsen, Flemming H; Schöbitz, Michael; Schaller, Jens

    2012-06-20

    The hydration properties of 2,3-O-hydroxypropylcellulose (HPC) and 2,3-O-hydroxyethylcellulose (HEC) were analyzed by multi-nuclear solid-state MAS NMR spectroscopy. By 13C single-pulse (SP) MAS and cross-polarization (CP) MAS NMR, differences between the immobile regions and all parts of the polysaccharides were detected as a function of hydration. Complementary information about the water environments was observed by 2H MAS NMR. By this approach it was demonstrated that side chains in 2,3-O-HPC and 2,3-O-HEC were easier to hydrate than the cellulose backbone. Furthermore the motion of water was more restricted (slower) in 2,3-O-HPC than in 2,3-O-HEC. For both polysaccharides the hydration could be explained by a two-step process: in step one increased ordering of the immobile regions occurs after which the entire polymer is hydrated in step two.

  15. Metabolism of excess methionine in the liver of intact rat: an in vivo /sup 2/H NMR study

    SciTech Connect

    London, R.E.; Gabel, S.A.; Funk, A.

    1987-11-03

    L-Methionine is the most toxic amino acid if supplied in excess, and the metabolic basis for this toxicity has been extensively studied, with varying conclusions. It is demonstrated here that in vivo /sup 2/H NMR spectroscopy provides a useful approach to the study of the hepatic metabolism of methionine in the anesthetized rat. Resonances corresponding to administered L-(methyl-/sup 2/H/sub 3/)methionine, and to the transmethylation product sarcosine, are observed during the first 10-min period after an intravenous injection of the labeled methionine, and the time dependence has been followed for a period of 5 h. A third resonance, assigned to the N-trimethyl groups of carnitine, phosphorylcholine, and other metabolites, becomes observable several hours after administration of the deuteriated methionine. In addition, there is a small increase in the intensity of the HDO resonance over the period of the study, which is interpreted to reflect the ultimate oxidation of the labeled sarcosine methyl group via mitochondrial sarcosine dehydrogenase. Additional small /sup 2/H resonances assigned to N/sup 1/-methylhistidine and creatine could be observed in perchloric acid extracts of the livers of rats treated with the deuteriated methionine. Inhibition of the flux through the transmethylation pathway is observed in the rat pretreated with the S-ethyl analogue of methionine, ethionine. These data provide strong support for the importance of glycine transmethylation in the catabolism of excess methionine.

  16. Proton zero-quantum 2D NMR of 2-propenenitrile aligned by an electric field. Determination of the 2H and 14N quadrupole coupling constants

    NASA Astrophysics Data System (ADS)

    Ruessink, B. H.; De Kanter, F. J. J.; MaClean, C.

    Zero-quantum NMR, selectively detected by 2D NMR, is applied to observe small 1H- 1H dipolar couplings in a polar liquid partially oriented by a strong electric field. The normal (single-quantum) 1H spectrum is severely broadened, which prevents the observation of small couplings. The results from the zero-quantum proton spectrum are used to calculate the 2H and 14N quadrupole coupling constants of 2-deutero-2-propenenitrile from the 2H and 14N NMR spectra.

  17. Selective {sup 2}H and {sup 13}C labeling in NMR analysis of solution protein structure and dynamics

    SciTech Connect

    LeMaster, D.M.

    1994-12-01

    Preparation of samples bearing combined isotope enrichment patterns has played a central role in the recent advances in NMR analysis of proteins in solution. In particular, uniform {sup 13}C, {sup 15}N enrichment has made it possible to apply heteronuclear multidimensional correlation experiments for the mainchain assignments of proteins larger than 30 KDa. In contrast, selective labeling approaches can offer advantages in terms of the directedness of the information provided, such as chirality and residue type assignments, as well as through enhancements in resolution and sensitivity that result from editing the spectral complexity, the relaxation pathways and the scalar coupling networks. In addition, the combination of selective {sup 13}C and {sup 2}H enrichment can greatly facilitate the determination of heteronuclear relaxation behavior.

  18. Differential scanning calorimetry and /sup 2/H NMR studies of the phase behavior of gramicidin-phosphatidylcholine mixtures

    SciTech Connect

    Morrow, M.R.; Davis, J.H.

    1988-03-22

    The extents of two-phase coexistence in the phase diagrams of mixtures of gramicidin with 1,2-bis(perdeuteriopalmitoyl)-sn-glycero-3-phosphocholine (DPPC-d62) and with 1,2-bis(perdeuteriomyristoyl)-sn-glycero-3-phosphocholine (DMPC-d54) mixtures have been explored with differential scanning calorimetry (DSC) and deuterium nuclear magnetic resonance (/sup 2/H NMR). For both systems, increased gramicidin content causes a decrease in transition enthalpy and a broadening of the peak in excess heat capacity at the transition. In DMPC-d54-based mixtures, the broadening is roughly symmetric about the pure lipid transition temperature. Addition of gramicidin to DPPC-d62 extends the excess heat capacity peak on the low-temperature side, resulting in a slightly asymmetric scan. Deuterium NMR spectra showing a superposition of gel and liquid-crystalline components, observed for both mixtures, indicate the presence of two-phase coexistence. For the DPPC-d62-based mixtures, two-phase coexistence is restricted to an approximately 2 degrees C temperature range below the pure transition temperature. For DMPC-d54-based mixtures, the region of two-phase coexistence is even narrower. For both mixtures, beyond a gramicidin mole fraction of 2%, distinct gel and liquid-crystal contributions to the spectra cannot be distinguished. Along with the broad featureless nature of the DSC scan in this region, this is taken to indicate that the transition has been replaced by a continuous phase change. These results are consistent with the existence of a closed two-phase region having a critical concentration of gramicidin below 2 mol%.

  19. NMR Measures of Heterogeneity Length

    NASA Astrophysics Data System (ADS)

    Spiess, Hans W.

    2002-03-01

    Advanced solid state NMR spectroscopy provides a wealth of information about structure and dynamics of complex systems. On a local scale, multidimensional solid state NMR has elucidated the geometry and the time scale of segmental motions at the glass transition. The higher order correlation functions which are provided by this technique led to the notion of dynamic heterogeneities, which have been characterized in detail with respect to their rate memory and length scale. In polymeric and low molar mass glass formers of different fragility, length scales in the range 2 to 4 nm are observed. In polymeric systems, incompatibility of backbone and side groups as in polyalkylmethacrylates leads to heteogeneities on the nm scale, which manifest themselves in unusual chain dynamics at the glass transition involving extended chain conformations. References: K. Schmidt-Rohr and H.W. Spiess, Multidimensional Solid-State NMR and Polymers,Academic Press, London (1994). U. Tracht, M. Wilhelm, A. Heuer, H. Feng, K. Schmidt-Rohr, H.W. Spiess, Phys. Rev. Lett. 81, 2727 (1998). S.A. Reinsberg, X.H. Qiu, M. Wilhelm, M.D. Ediger, H.W. Spiess, J.Chem.Phys. 114, 7299 (2001). S.A. Reinsberg, A. Heuer, B. Doliwa, H. Zimmermann, H.W. Spiess, J. Non-Crystal. Solids, in press (2002)

  20. Effect of divalent cations on the structure of dipalmitoylphosphatidylcholine and phosphatidylcholine/phosphatidylglycerol bilayers: An 2H-NMR study

    SciTech Connect

    Zidovetzki, R.; Atiya, A.W.; De Boeck, H. )

    1989-01-01

    The interactions of CaCl2 or MgCl2 with multilamellar phospholipid bilayers were studied by 2H-NMR. Two model membrane systems were used: (1) dipalmitoylphosphatidylcholine (DPPC) bilayers and (2) bilayers composed of a mixture of phosphatidylcholine and phosphatidylglycerol at a molar ratio of 5:1. Addition of 0.25 M CaCl2 to DPPC bilayers resulted in significant uniform increase of the order parameters of the lipid side chains; the effect of 0.25 M MgCl2 was insignificant. Both phosphatidylcholine and phosphatidylglycerol components of the mixed bilayers were affected by the presence of 0.25 M CaCl2 and, to a much smaller degree, by MgCl2. The addition of Ca2+ induced significantly larger increase of the order parameters of the phosphatidylcholine component. The results are consistent with the long-range effects of Ca2+ binding on the packing of the lipid membranes.

  1. 13C, 2h NMR studies of structural and dynamical modifications of glucose-exposed porcine aortic elastin.

    PubMed

    Silverstein, Moshe C; Bilici, Kübra; Morgan, Steven W; Wang, Yunjie; Zhang, Yanhang; Boutis, Gregory S

    2015-04-01

    Elastin, the principal component of the elastic fiber of the extracellular matrix, imparts to vertebrate tissues remarkable resilience and longevity. This work focuses on elucidating dynamical and structural modifications of porcine aortic elastin exposed to glucose by solid-state NMR spectroscopic and relaxation methodologies. Results from macroscopic stress-strain tests are also presented and indicate that glucose-treated elastin is mechanically stiffer than the same tissue without glucose treatment. These measurements show a large hysteresis in the stress-strain behavior of glucose-treated elastin-a well-known signature of viscoelasticity. Two-dimensional relaxation NMR methods were used to investigate the correlation time, distribution, and population of water in these samples. Differences are observed between the relative populations of water, whereas the measured correlation times of tumbling motion of water across the samples were similar. (13)C magic-angle-spinning NMR methods were applied to investigate structural and dynamical modifications after glucose treatment. Although some overall structure is preserved, the process of glucose exposure results in more heterogeneous structures and slower mobility. The correlation times of tumbling motion of the (13)C-(1)H internuclear vectors in the glucose-treated sample are larger than in untreated samples, pointing to their more rigid structure. The (13)C cross-polarization spectra reveal a notably increased α-helical character in the alanine motifs after glucose exposure. Results from molecular dynamics simulations are provided that add further insight into dynamical and structural changes of a short repeat, [VPGVG]5, an alanine pentamer, desmosine, and isodesmosine sites with and without glucose. The simulations point to changes in the entropic and energetic contributions in the retractive forces of VPGVG and AAAAA motifs. The most notable change is the increase of the energetic contribution in the retractive

  2. 13C, 2H NMR Studies of Structural and Dynamical Modifications of Glucose-Exposed Porcine Aortic Elastin

    PubMed Central

    Silverstein, Moshe C.; Bilici, Kübra; Morgan, Steven W.; Wang, Yunjie; Zhang, Yanhang; Boutis, Gregory S.

    2015-01-01

    Elastin, the principal component of the elastic fiber of the extracellular matrix, imparts to vertebrate tissues remarkable resilience and longevity. This work focuses on elucidating dynamical and structural modifications of porcine aortic elastin exposed to glucose by solid-state NMR spectroscopic and relaxation methodologies. Results from macroscopic stress-strain tests are also presented and indicate that glucose-treated elastin is mechanically stiffer than the same tissue without glucose treatment. These measurements show a large hysteresis in the stress-strain behavior of glucose-treated elastin—a well-known signature of viscoelasticity. Two-dimensional relaxation NMR methods were used to investigate the correlation time, distribution, and population of water in these samples. Differences are observed between the relative populations of water, whereas the measured correlation times of tumbling motion of water across the samples were similar. 13C magic-angle-spinning NMR methods were applied to investigate structural and dynamical modifications after glucose treatment. Although some overall structure is preserved, the process of glucose exposure results in more heterogeneous structures and slower mobility. The correlation times of tumbling motion of the 13C-1H internuclear vectors in the glucose-treated sample are larger than in untreated samples, pointing to their more rigid structure. The 13C cross-polarization spectra reveal a notably increased α-helical character in the alanine motifs after glucose exposure. Results from molecular dynamics simulations are provided that add further insight into dynamical and structural changes of a short repeat, [VPGVG]5, an alanine pentamer, desmosine, and isodesmosine sites with and without glucose. The simulations point to changes in the entropic and energetic contributions in the retractive forces of VPGVG and AAAAA motifs. The most notable change is the increase of the energetic contribution in the retractive force

  3. Global distributions of C2H6, C2H2, HCN, and PAN retrieved from MIPAS reduced spectral resolution measurements

    NASA Astrophysics Data System (ADS)

    Wiegele, A.; Glatthor, N.; Höpfner, M.; Grabowski, U.; Kellmann, S.; Linden, A.; Stiller, G.; von Clarmann, T.

    2011-08-01

    Vertical profiles of mixing ratios of C2H6, C2H2, HCN, and PAN were retrieved from MIPAS reduced spectral resolution nominal mode limb emission measurements. The retrieval strategy followed that of the analysis of MIPAS high resolution measurements, with occasional adjustments to cope with the reduced spectral resolution under which MIPAS is operated since 2005. Largest mixing ratios are found in the troposphere, and reach 1.2 ppbv for C2H6, 1 ppbv for HCN, 600 pptv for PAN, and 450 pptv for C2H2. The estimated precision in case of significantly enhanced mixing ratios (including measurement noise and propagation of uncertain parameters randomly varying in the time domain) and altitude resolution are typically 10 %, 3-4.5 km for C2H6, 15 %, 4-6 km for HCN, 6 %, 2.5-3.5 km for PAN, and 7 %, 2.5-4 km for C2H2.

  4. Orientational ordering of a banana-shaped solute molecule in a nematic calamitic solvent by {sup 2}H-NMR spectroscopy: An indication of glasslike behavior

    SciTech Connect

    Cinacchi, Giorgio; Domenici, Valentina

    2006-09-15

    The Saupe ordering matrix of a banana-shaped mesogenic molecule as a solute in a common nematic calamitic solvent has been determined by {sup 2}H-NMR spectroscopy as a function of temperature. The temperature dependence of the Saupe ordering matrix element associated with the principal molecular axis is consistent with a glassy behavior in the reorientational motion of this particular solute molecule. The Haller expression, appropriately modified, provides a good fit to the experimental data.

  5. Effects of pH and cholesterol on DMPA membranes: a solid state 2H- and 31P-NMR study.

    PubMed Central

    Pott, T; Maillet, J C; Dufourc, E J

    1995-01-01

    The effect of pH and cholesterol on the dimyristoylphosphatidic acid (DMPA) model membrane system has been investigated by solid state 2H- and 31P-NMR. It has been shown that each of the three protonation states of the DMPA molecule corresponds to a 31P-NMR powder pattern with characteristic delta sigma values; this implies additionally that the proton exchange on the membrane surface is slow on the NMR time scale (millisecond range). Under these conditions, the 2H-labeled lipid chains sense only one magnetic environment, indicating that the three spectra detected by 31P-NMR are related to charge-dependent local dynamics or orientations of the phosphate headgroup or both. Chain ordering in the fluid phase is also found to depend weakly on the charge at the interface. In addition, it has also been found that the first pK of the DMPA membrane is modified by changes in the lipid lateral packing (gel or fluid phases or in the presence of cholesterol) in contrast to the second pK. The incorporation of 30 mol% cholesterol affects the phosphatidic acid bilayer in a way similar to what has been reported for phosphatidylcholine/cholesterol membranes, but to an extent comparable to 10-20 mol % sterol in phosphatidylcholines. However, the orientation and molecular order parameter of cholesterol in DMPA are similar to those found in dimyristoylphosphatidylcholine. PMID:8580333

  6. Measurement of vorticity diffusion by NMR microscopy.

    PubMed

    Brown, Jennifer R; Callaghan, Paul T

    2010-05-01

    In a Newtonian fluid, vorticity diffuses at a rate determined by the kinematic viscosity. Here we use rapid NMR velocimetry, based on a RARE sequence, to image the time-dependent velocity field on startup of a fluid-filled cylinder and therefore measure the diffusion of vorticity. The results are consistent with the solution to the vorticity diffusion equation where the angular velocity on the outside surface of the fluid, at the cylinder's rotating wall, is fixed. This method is a means of measuring kinematic viscosity for low viscosity fluids without the need to measure stress. PMID:20189854

  7. The interaction of cannabinoid receptor agonists, CP55940 and WIN55212-2 with membranes using solid state 2H NMR

    PubMed Central

    Tian, Xiaoyu; Pavlopoulos, Spiro; Yang, De-Ping; Makriyannis, Alexandros

    2013-01-01

    Two key commonly used cannabinergic agonists, CP55940 and WIN55212-2, are investigated for their effects on the lipid membrane bilayer using 2H solid state NMR, and the results are compared with our earlier work with delta-9-tetrahydrocannabinol (Δ9-THC). To study the effects of these ligands we used hydrated bilayers of dipalmitoylphosphatidylcholine (DPPC) deuterated at the 2′ and 16′ positions of both acyl chains with deuterium atoms serving as probes for the dynamic and phase changes at the membrane interface and at the bilayer center respectively. All three cannabinergic ligands lower the phospholipid membrane phase transition temperature, increase the lipid sn-2 chain order parameter at the membrane interface and decrease the order at the center of the bilayer. Our studies show that the cannabinoid ligands induce lateral phase separation in the lipid membrane at physiological temperatures. During the lipid membrane phase transition, the cooperative dynamic process whereby the C-2H segments at the interface and center of the bilayer spontaneously reach the fast exchange regime (2H NMR timescale) is distinctively modulated by the two cannabinoids. Specifically, CP55940 is slightly more efficient at inducing liquid crystalline-type 2H NMR spectral features at the membrane interface compared to WIN55212-2. In contrast, WIN55212-2 has a far superior ability to induce liquid crystalline-type spectral features at the center of the bilayer, and it increases the order parameter of the sn-1 chain in addition to the sn-2 chain of the lipids. These observations suggest the cannabinoid ligands may influence lipid membrane domain formations and there may be contributions to their cannabinergic activities through lipid membrane microdomain related mechanisms. Our work demonstrates that experimental design strategies utilizing specifically deuterium labeled lipids yield more detailed insights concerning the properties of lipid bilayers. PMID:21129361

  8. Synthesis, structure and NMR characterization of a new monomeric aluminophosphate [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4 containing four different types of monophosphates

    NASA Astrophysics Data System (ADS)

    Chen, Peng; Li, Jiyang; Xu, Jun; Duan, Fangzheng; Deng, Feng; Xu, Ruren

    2009-03-01

    A new zero-dimensional (0D) aluminophosphate monomer [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4 (designated AlPO-CJ38) with Al/P ratio of 1/6 has been solvothermally prepared by using racemic cobalt complex dl-Co(en) 3Cl 3 as the template. The Al atom is octahedrally linked to six P atoms via bridging oxygen atoms, forming a unique [Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2] 6- monomer. Notably, there exists intramolecular symmetrical O⋯H⋯O bonds, which results in pseudo-4-rings stabilized by the strong H-bonding interactions. The structure is also featured by the existence of four different types of monophosphates that have been confirmed by 31P NMR and 1H NMR spectra. The crystal data are as follows: AlPO-CJ38, [ dl-Co(en) 3] 2[Al(HPO 4) 2(H 1.5PO 4) 2(H 2PO 4) 2](H 3PO 4) 4, M = 1476.33, monoclinic, C2/ c (No. 15), a = 36.028(7) Å, b = 8.9877(18) Å, c = 16.006(3) Å, β = 100.68(3)°, U = 5093.2(18) Å 3,Z = 4, R1 = 0.0509 ( I > 2 σ( I)) and wR2 = 0.1074 (all data). CCDC number 689491.

  9. Short hydrogen bonds in salts of dicarboxylic acids; structural correlations from solid-state 13C and 2H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Kalsbeek, Nicoline; Schaumburg, Kjeld; Larsen, Sine

    1993-10-01

    Solid-state 13C and 2H NMR spectra are found to very suitable for characterizing the short Osbnd H...O hydrogen bonds observed in acid salts of dicarboxylic acids. The majority of the investigated compounds are acid salts of malonic, succinic and tartaric acid with monovalent cations derived from alkali metals and small aliphatic amines. They include systems with symmetric and asymmetric hydrogen bonds. Accurate structural information about their geometry is available from low-temperature X-ray diffraction data. The 13C chemical shifts of the C atoms in the different carboxy groups display a linear variation with the absolute difference between the two Csbnd O bond lengths. Theoretical ab initio calculations for model systems showed that the nuclear quadrupole coupling constant NQCC for 2H increases with increasing asymmetry of the hydrogen-bonded system. NQCC values for 2H in the short symmetric hydrogen-bonded systems are in the range 53-59 kHz compared with the larger values of up to 166kHz found in systems with longer asymmetric hydrogen bonds. The 2H NQCC values display a perfect linear dependence on the asymmetry of the hydrogen bond. 2H NQCC decreases with decreasing temperature in the symmetric hydrogen bonds showing that the corresponding potential has a single well.

  10. 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

    PubMed

    Thomas, Freddy; Jamin, Eric

    2009-09-01

    An international collaborative study of isotopic methods applied to control the authenticity of vinegar was organized in order to support the recognition of these procedures as official methods. The determination of the 2H/1H ratio of the methyl site of acetic acid by SNIF-NMR (site-specific natural isotopic fractionation-nuclear magnetic resonance) and the determination of the 13C/12C ratio, by IRMS (isotope ratio mass spectrometry) provide complementary information to characterize the botanical origin of acetic acid and to detect adulterations of vinegar using synthetic acetic acid. Both methods use the same initial steps to recover pure acetic acid from vinegar. In the case of wine vinegar, the determination of the 18O/16O ratio of water by IRMS allows to differentiate wine vinegar from vinegars made from dried grapes. The same set of vinegar samples was used to validate these three determinations. The precision parameters of the method for measuring delta13C (carbon isotopic deviation) were found to be similar to the values previously obtained for similar methods applied to wine ethanol or sugars extracted from fruit juices: the average repeatability (r) was 0.45 per thousand, and the average reproducibility (R) was 0.91 per thousand. As expected from previous in-house study of the uncertainties, the precision parameters of the method for measuring the 2H/1H ratio of the methyl site were found to be slightly higher than the values previously obtained for similar methods applied to wine ethanol or fermentation ethanol in fruit juices: the average repeatability was 1.34 ppm, and the average reproducibility was 1.62 ppm. This precision is still significantly smaller than the differences between various acetic acid sources (delta13C and delta18O) and allows a satisfactory discrimination of vinegar types. The precision parameters of the method for measuring delta18O were found to be similar to the values previously obtained for other methods applied to wine and

  11. Orientational order, molecular organization, and dynamics in mixtures of bent-core and rod-shaped mesogens: a 2H NMR study.

    PubMed

    Calucci, Lucia; Fodor-Csorba, Katalin; Forte, Claudia; Geppi, Marco

    2011-01-27

    Mixtures of a bent-core mesogen (ClPbis10BB) and a calamitic mesogen (6OO8), showing a nematic phase over the entire compositional range and one or two smectic phases (namely, SmA, SmC, or SmC(A)) below the nematic one over a wide concentration range, were investigated by means of (2)H NMR spectroscopy, exploiting selectively deuterated isotopomers of both mesogens. The analysis of (2)H NMR spectra recorded in the liquid crystalline phases on several representative mixtures gave information on the orientational order properties and the molecular organization within the phases as well as on the alignment properties upon application of a magnetic field. On the other hand, the analysis of (2)H longitudinal relaxation times (T(1Z) and T(1Q)) in 6OO8-d(2)/ClPbis10BB mixtures and pure 6OO8-d(2) allowed the influence of the bent-core mesogen on the dynamics of the calamitic one to be highlighted.

  12. Rotational jumps of the tyrosine side chain in crystalline enkephalin. /sup 2/H NMR line shapes for aromatic ring motion in solids

    SciTech Connect

    Rice, D.N.; Wittebort, R.J.; Griffin, R.G.; Meirovitch, E.; Stimson, E.R.; Meinwald, Y.C.; Freed, J.H.; Scheraga, H.A.

    1981-12-30

    Deuterium NMR spectra of polycrystalline (tyrosine-3,5-/sup 2/H/sub 2/)(Leu/sup 5/)enkephalin show that the aromatic tyrosyl ring of this pentapeptide is executing 180/sup 0/ flips about the C/sup ..beta../-C/sup ..gamma../ axis in the solid state. Specifically, the axially symmetric powder pattern observed at low temperature collapses to an axially asymmetric pattern with eta approx. = 0.6 at high temperature. Computer simulation of the NMR line shapes, which account for spectral distortions induced by the quadrupole echo technique, indicate that at room temperature the flipping rate is approximately 5 x 10/sup 4/ s/sup -1/ and that it increases to about 10/sup 6/ s/sup -1/ at 101 /sup 0/C.

  13. NMR measurements of intracellular ions in hypertension

    NASA Astrophysics Data System (ADS)

    Veniero, Joseph C.; Gupta, R. K.

    1993-08-01

    The NMR methods for the measurement of intracellular free Na+, K+, Mg2+, Ca2+, and H+ are introduced. The recent literature is then presented showing applications of these methods to cells and tissues from hypertensive animal model systems, and humans with essential hypertension. The results support the hypothesis of consistent derangement of the intracellular ionic environment in hypertension. The theory that this derangement may be a common link in the disease states of high blood pressure and abnormal insulin and glucose metabolism, which are often associated clinically, is discussed.

  14. Crystal structure, NMR study, dielectric relaxation and AC conductivity of a new compound [Cd3(SCN)2Br6(C2H9N2)2]n

    NASA Astrophysics Data System (ADS)

    Saidi, K.; Kamoun, S.; Ayedi, H. Ferid; Arous, M.

    2013-11-01

    The crystal structure, the 13C NMR spectroscopy and the complex impedance have been carried out on [Cd3(SCN)2Br6(C2H9N2)2]n. Crystal structure shows a 2D polymeric network built up of two crystallographically independent cadmium atoms with two different octahedral coordinations. This compound exhibits a phase transition at (T=355±2 K) which has been characterized by differential scanning calorimetry (DSC), X-rays powder diffraction, AC conductivity and dielectric measurements. Examination of 13C CP/MAS line shapes shows indirect spin-spin coupling (14N and 13C) with a dipolar coupling constant of 1339 Hz. The AC conductivity of this compound has been carried out in the temperature range 325-376 K and the frequency range from 10-2 Hz to 10 MHz. The impedance data were well fitted to two equivalent electrical circuits. The results of the modulus study reveal the presence of two distinct relaxation processes. One, at low frequency side, is thermally activated due to the ionic conduction of the crystal and the other, at higher frequency side, gradually disappears when temperature reaches 355 K which is attributed to the localized dipoles in the crystal. Moreover, the temperature dependence of DC-conductivity in both phases follows the Arrhenius law and the frequency dependence of σ(ω,T) follows Jonscher's universal law. The near values of activation energies obtained from the conductivity data and impedance confirm that the transport is through the ion hopping mechanism.

  15. 2H 2O quadrupolar splitting used to measure water exchange in erythrocytes

    NASA Astrophysics Data System (ADS)

    Kuchel, Philip W.; Naumann, Christoph

    2008-05-01

    The 2H NMR resonance from HDO (D = 2H) in human red blood cells (RBCs) suspended in gelatin that was held stretched in a special apparatus was distinct from the two signals that were symmetrically arranged on either side of it, which were assigned to extracellular HDO. The large extracellular splitting is due to the interaction of the electric quadrupole moment of the 2H nuclei with the electric field gradient tensor of the stretched, partially aligned gelatin. Lack of resolved splitting of the intracellular resonance indicated greatly diminished or absent ordering of the HDO inside RBCs. The separate resonances enabled the application of a saturation transfer method to estimate the rate constants of transmembrane exchange of water in RBCs. However both the theory and the practical applications needed modifications because even in the absence of RBCs the HDO resonances were maximally suppressed when the saturating radio-frequency radiation was applied exactly at the central frequency between the two resonances of the quadrupolar HDO doublet. More statistically robust estimates of the exchange rate constants were obtained by applying two-dimensional exchange spectroscopy (2D EXSY), with back-transformation analysis. A monotonic dependence of the estimates of the efflux rate constants on the mixing time, tmix, used in the 2D EXSY experiment were seen. Extrapolation to tmix = 0, gave an estimate of the efflux rate constant at 15 °C of 31.5 ± 2.2 s -1 while at 25 °C it was ˜50 s -1. These values are close to, but less than, those estimated by an NMR relaxation-enhancement method that uses Mn 2+ doping of the extracellular medium. The basis for this difference is thought to include the high viscosity of the extracellular gel. At the abstract level of quantum mechanics we have used the quadrupolar Hamiltonian to provide chemical shift separation between signals from spin populations across cell membranes; this is the first time, to our knowledge, that this has been

  16. Calibration of NMR well logs from carbonate reservoirs with laboratory NMR measurements and μXRCT

    SciTech Connect

    Mason, Harris E.; Smith, Megan M.; Hao, Yue; Carroll, Susan A.

    2014-12-31

    The use of nuclear magnetic resonance (NMR) well log data has the potential to provide in-situ porosity, pore size distributions, and permeability of target carbonate CO₂ storage reservoirs. However, these methods which have been successfully applied to sandstones have yet to be completely validated for carbonate reservoirs. Here, we have taken an approach to validate NMR measurements of carbonate rock cores with independent measurements of permeability and pore surface area to volume (S/V) distributions using differential pressure measurements and micro X-ray computed tomography (μXRCT) imaging methods, respectively. We observe that using standard methods for determining permeability from NMR data incorrectly predicts these values by orders of magnitude. However, we do observe promise that NMR measurements provide reasonable estimates of pore S/V distributions, and with further independent measurements of the carbonate rock properties that universally applicable relationships between NMR measured properties may be developed for in-situ well logging applications of carbonate reservoirs.

  17. H2O and Cation Structure and Dynamics in Expandable Clays: 2H and 39K NMR Investigations of Hectorite

    SciTech Connect

    Bowers, Geoffrey M.; Bish, David L.; Kirkpatrick, Robert J.

    2008-04-24

    The dynamic behavior of H2O and ionic species in two- and three-dimensional confinement plays a variety of important roles in processes such as ion transport and adsorption, water storage in hostile environments, dissolution/precipitation reactions in aqueous environments, and the swelling of smectite clays (low charge 2:1 type phyllosilicates with expandable interlayers). Historically, the structure and dynamics of ions and water in confined spaces and at solid-fluid interfaces have been difficult to characterize on the molecular scale, but the continued evolution of molecular modeling, neutron scattering, and nuclear magnetic resonance (NMR) spectroscopy has permitted ever more detailed theoretical and experimental investigations, particularly regarding the special case of H2O in the two-dimensional, nanometer-scale interlayer space of phyllosilicates.

  18. NMR Measurements of Granular Flow and Compaction

    NASA Astrophysics Data System (ADS)

    Fukushima, Eiichi

    1998-03-01

    Nuclear magnetic resonance (NMR) can be used to measure statistical distributions of granular flow velocity and fluctuations of velocity, as well as spatial distributions of particulate concentration, flow velocity, its fluctuations, and other parameters that may be derived from these. All measurements have been of protons in liquid-containing particles such as mustard seeds or pharmaceutical pills. Our favorite geometry has been the slowly rotating partially filled rotating drum with granular flow taking place along the free surface of the particles. All the above-mentioned parameters have been studied as well as a spatial distribution of particulate diffusion coefficients, energy dissipation due to collisions, as well as segregation of non-uniform mixtures of granular material. Finally, we describe some motions of granular material under periodic vibrations.

  19. NMR measurements in solutions of dialkylimidazolium haloaluminates

    SciTech Connect

    Takahashi, S.; Saboungi, M.L.; Klingler, R.J.; Chen, M.J.; Rathke, J.W.

    1992-06-01

    {sup 27}Al and {sup 35}Cl NMR spectra of AlCl{sub 3}-1-ethyl-3-methyl imidazolium chloride (EMIC) melts were measured for initial compositions ranging from 50 to 67 mol % AlCl{sub 3} at various temperatures. It was shown by changing the preaquisition delay time (DE value) that the dominant aluminum species are AlCl{sub 4}{sup {minus}} in the melt formed by mixing 50 mol % with EMIC and Al{sub 2}Cl{sub 7}{sup {minus}} in the 67 mol % AlCl{sub 3} melt. In the equimolar mixture, the chemical shift of {sup 27}Al NMR spectrum is 103.28 ppm and the line width is 22.83Hz. In the 67 mol % AlCl{sub 3} mixture, the chemical shift is 103.41 ppm and the line width is 2624Hz. A third species observed at 97 ppm in the {sup 27}Al spectra for the 55 and 60 mol % AlCl{sub 3} mixtures is identified to be a product of the reaction with residual water. The relaxation rates for each species in the melts were determined.

  20. Capturing Guest Dynamics in Metal-Organic Framework CPO-27-M (M = Mg, Zn) by (2)H Solid-State NMR Spectroscopy.

    PubMed

    Xu, Jun; Sinelnikov, Regina; Huang, Yining

    2016-06-01

    Metal-organic frameworks (MOFs) are promising porous materials for gas separation and storage as well as sensing. In particular, a series of isostructural MOFs with coordinately unsaturated metal centers, namely, CPO-27-M or M-MOF-74 (M = Mg, Zn, Mn, Fe, Ni, Co, Cu), have shown exceptional adsorption capacity and selectivity compared to those of classical MOFs that contain only fully coordinated metal sites. Although it is widely accepted that the interaction between guest molecules and exposed metal centers is responsible for good selectivity and large maximum uptake, the investigation of such guest-metal interaction is very challenging because adsorbed molecules are usually disordered in the pores and undergo rapid thermal motions. (2)H solid-state NMR (SSNMR) spectroscopy is one of the most extensively used techniques for capturing guest dynamics in porous materials. In this work, variable-temperature (2)H wide-line SSNMR experiments were performed on CPO-27-M (M = Mg, Zn) loaded with four prototypical guest molecules: D2O, CD3CN, acetone-d6, and C6D6. The results indicate that different guest molecules possess distinct dynamic behaviors inside the channel of CPO-27-M. For a given guest molecule, its dynamic behavior also depends on the nature of the metal centers. The binding strength of guest molecules is discussed on the basis of the (2)H SSNMR data.

  1. Tracing bacterial metabolism using multi-nuclear (1H, 2H, and 13C) Solid State NMR: Realizing an Idea Initiated by James Scott

    NASA Astrophysics Data System (ADS)

    Cody, G.; Fogel, M. L.; Jin, K.; Griffen, P.; Steele, A.; Wang, Y.

    2011-12-01

    Approximately 6 years ago, while at the Geophysical Laboratory, James Scott became interested in the application of Solid State Nuclear Magnetic Resonance Spectroscopy to study bacterial metabolism. As often happens, other experiments intervened and the NMR experiments were not pursued. We have revisited Jame's question and find that using a multi-nuclear approach (1H, 2H, and 13C Solid State NMR) on laboratory cell culture has some distinct advantages. Our experiments involved batch cultures of E. coli (MG1655) harvested at stationary phase. In all experiments the growth medium consisted of MOPS medium for enterobacteria, where the substrate is glucose. In one set of experiments, 10 % of the water was D2O; in another 10 % of the glucose was per-deuterated. The control experiment used both water and glucose at natural isotopic abundance. A kill control of dead E. coli immersed in pure D2O for an extended period exhibited no deuterium incorporation. In both deuterium enriched experiments, considerable incorporation of deuterium into E. coli's biomolecular constituents was detected via 2H Solid State NMR. In the case of the D2O enriched experiment, 58 % of the incorporated deuterium is observed in a sharp peak at a frequency of 0.31 ppm, consistent with D incorporation in the cell membrane lipids, the remainder is observed in a broad peak at a higher frequency (centered at 5.4 ppm, but spanning out to beyond 10 ppm) that is consistent with D incorporation into predominantly DNA and RNA. In the case of the D-glucose experiments, 61 % of the deuterium is observed in a sharp resonance peak at 0.34 ppm, also consistent with D incorporation into membrane lipids, the remainder of the D is observed at a broad resonance peak centered at 4.3 ppm, consistent with D enrichment in glycogen. Deuterium abundance in the E. coli cells grown in 10 % D2O is nearly 2X greater than that grown with 10 % D-glucose. Very subtle differences are observed in both the 1H and 13C solid

  2. Orientation and dynamics of benzyl alcohol and benzyl alkyl ethers dissolved in nematic lyotropic liquid crystals. 2H NMR and molecular dynamics simulations.

    PubMed

    Ahumada, H; Montecinos, R; Tieleman, D P; Weiss-López, B E

    2005-08-01

    Most drugs have to cross cell membranes to reach their final target. A better understanding of the distribution, interactions, and dynamics of biologically active molecules in model bilayers is of fundamental importance in understanding drug functioning and design. 2H NMR quadrupole splittings (delta nu(Q)) and longitudinal relaxation times (T1) from the aromatic ring of benzyl alcohol-d5 (C0), a commonly used anesthetic, and a series of linear alkyl benzyl-d5 ethers with chain lengths from 1 to 12 carbon atoms (C1-C12), were measured. The molecules were dissolved in a nematic discotic lyotropic liquid crystal solution made of tetradecyltrimethylammonium chloride (TTAC)/decanol (DeOH)/NaCl/H2O. Values of delta nu(Q) and T1 from 1,1-dideuteriodecanol (15% enriched) and DHO (H2O with 0.2% D2O) were also measured. Delta nu(Q) of DeOH and DHO remained constant throughout the series. The value of delta nu(Q) of the para position of the ring (delta nu(p)) in C1 is 30% smaller than the delta nu(p) of C0. This is attributed to the existence of an H-bond between the alcohol hydroxyl proton and the solvent, which influences the average orientation of the ring. The relaxation data show that T1o,m is always longer than T1p and both decrease with the increase in alkyl chain length. Molecular dynamics simulations of the experimentally studied systems were performed. The aggregate was represented as a bilayer. The distribution, average orientation, and order parameters of the aromatic ring of the guest molecules in the bilayer were examined. Rotational correlation functions of all the C-D bonds and the OH bond from H2O were evaluated, allowing an estimate of the correlation times and T1. According to these results all spins relax in extreme narrowing conditions, except DeOH. Experimental and calculated T1 values differ at most by a factor of 3. However, the order of magnitude and the observed trends are well reproduced by the calculations. The aromatic ring of C0 possesses a

  3. Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane: A dielectric, 2H NMR, and calorimetric study

    NASA Astrophysics Data System (ADS)

    Robles-Hernández, Beatriz; Sebastián, Nerea; de la Fuente, M. Rosario; López, David O.; Diez-Berart, Sergio; Salud, Josep; Ros, M. Blanca; Dunmur, David A.; Luckhurst, Geoffrey R.; Timimi, Bakir A.

    2015-12-01

    The nature of the nematic-nematic phase transition in the liquid crystal dimer 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and 2H NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (NTB), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the NTB-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and 2H magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the NTB phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. 2H NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director.

  4. Twist, tilt, and orientational order at the nematic to twist-bend nematic phase transition of 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane: A dielectric, (2)H NMR, and calorimetric study.

    PubMed

    Robles-Hernández, Beatriz; Sebastián, Nerea; de la Fuente, M Rosario; López, David O; Diez-Berart, Sergio; Salud, Josep; Ros, M Blanca; Dunmur, David A; Luckhurst, Geoffrey R; Timimi, Bakir A

    2015-12-01

    The nature of the nematic-nematic phase transition in the liquid crystal dimer 1″,9″-bis(4-cyanobiphenyl-4'-yl) nonane (CB9CB) has been investigated using techniques of calorimetry, dynamic dielectric response measurements, and (2)H NMR spectroscopy. The experimental results for CB9CB show that, like the shorter homologue CB7CB, the studied material exhibits a normal nematic phase, which on cooling undergoes a transition to the twist-bend nematic phase (N(TB)), a uniaxial nematic phase, promoted by the average bent molecular shape, in which the director tilts and precesses describing a conical helix. Modulated differential scanning calorimetry has been used to analyze the nature of the N(TB)-N phase transition, which is found to be weakly first order, but close to tricritical. Additionally broadband dielectric spectroscopy and (2)H magnetic resonance studies have revealed information on the structural characteristics of the recently discovered twist-bend nematic phase. Analysis of the dynamic dielectric response in both nematic phases has provided an estimate of the conical angle of the heliconical structure for the N(TB) phase. Capacitance measurements of the electric-field realignment of the director in initially planar aligned cells have yielded values for the splay and bend elastic constants in the high temperature nematic phase. The bend elastic constant is small and decreases with decreasing temperature as the twist-bend phase is approached. This behavior is expected theoretically and has been observed in materials that form the twist-bend nematic phase. (2)H NMR measurements characterize the chiral helical twist identified in the twist-bend nematic phase and also allow the determination of the temperature dependence of the conical angle and the orientational order parameter with respect to the director.

  5. Frequency Comb Assisted IR Measurements of H_3^+, H_2D^+ and D_2H^+ Transitions

    NASA Astrophysics Data System (ADS)

    Jusko, Pavol; Asvany, Oskar; Schlemmer, Stephan

    2016-06-01

    We present recent measurements of the fundamental transitions of H_3^+, H_2D^+ and D_2H^+ in a 4 K 22-pole trap by action spectroscopic techniques. Either Laser Induced Inhibition of Cluster Growth (He attachment at T≈4 K), endothermic reaction of H_3^+ with O_2, or deuterium exchange has been used as measurement scheme. We used a 3 μm optical parametric oscillator coupled to a frequency comb in order to achieve accuracy generally below 1 MHz. Five transitions of H_3^+, eleven of H_2D^+ and ten of D_2H^+ were recorder in our spectral range. We compare our H_3^+ results with two previous frequency comb assisted works. Moreover, accurate determination of the frequency allows us to predict pure rotational transitions for H_2D^+ and D_2H^+ in the THz range. P. Jusko, C. Konietzko, S. Schlemmer, O. Asvany, J. Mol. Spec. 319 (2016) 55 O. Asvany, S. Brünken, L. Kluge, S. Schlemmer, Appl. Phys. B 114 (2014) 203 O. Asvany, J. Krieg, S. Schlemmer, Rev. Sci. Instr. 83 (2012) 093110 J.N. Hodges, A.J. Perry, P.A. Jenkins, B.M. Siller, B.J. McCall, J. Chem. Phys. 139 (2013) 164201 H.-C. Chen, C.-Y. Hsiao, J.-L. Peng, T. Amano, J.-T. Shy, Phys. Rev. Lett. 109 (2012) 263002

  6. Effect of Saturated Very Long-Chain Fatty Acids on the Organization of Lipid Membranes: A Study Combining (2)H NMR Spectroscopy and Molecular Dynamics Simulations.

    PubMed

    Paz Ramos, Adrian; Lagüe, Patrick; Lamoureux, Guillaume; Lafleur, Michel

    2016-07-21

    Little is known about the interaction of very long-chain saturated fatty acids (VLCFAs) with biological membranes. However, this could play an important role on interleaflet interactions and signal transduction mechanisms in cells. The aim of this work is to determine how VLCFA structurally adapts in fluid phospholipid bilayers, since both species must exhibit a significant hydrophobic mismatch. The membrane organization has been described by means of (2)H NMR and molecular dynamics simulations. Our results show that the protonation state affects the position and order of free fatty acids (FFAs) in phospholipid membranes. It was shown that the protonated FFA-C24 carboxyl group is located slightly under the POPC head group and therefore its acyl chain can interact with the lipids of the opposite leaflet. This interdigitation of the end of the acyl chain causes a second plateau observed in SC-D profiles, a very unusual feature in lipid systems. PMID:27351151

  7. Formation of Al2H7- anions--indirect evidence of volatile AlH3 on sodium alanate using solid-state NMR spectroscopy.

    PubMed

    Felderhoff, Michael; Zibrowius, Bodo

    2011-10-14

    After more than a decade of intense research on NaAlH(4) doped with transition metals as hydrogen storage material, the actual mechanism of the decomposition and rehydrogenation reaction is still unclear. Early on, monomeric AlH(3) was named as a possible transport shuttle for aluminium, but never observed experimentally. Here we report for the first time the trapping of volatile AlH(3) produced during the decomposition of undoped NaAlH(4) by an adduct of sodium alanate and crown ether. The resulting Al(2)H(7)(-) anion was identified by solid-state (27)Al NMR spectroscopy. Based on this indirect evidence of volatile alane, we present a simple description of the processes occurring during the reversible dehydrogenation of NaAlH(4). PMID:21879065

  8. The investigation of membrane binding by amphibian peptide agonists of CCK2R using (31)P and (2)H solid-state NMR.

    PubMed

    Sherman, Patrick J; Separovic, Frances; Bowie, John H

    2014-05-01

    It has been proposed that some neuropeptides may be anchored to the cell membranes prior to attaching to the adjacent active sites of transmembrane receptors. The three amphibian skin neuropeptides signiferin 1 [RLCIPYIIPC(OH)] (smooth muscle active and immunomodulator), riparin 1.1 [[RLCIPVIFPC(OH)] (immunomodulator) and rothein 1 [SVSNIPESIGF(OH)] (immunomodulator) act via CCK2 transmembrane receptors. A combination of (31)P and (2)H solid state NMR studies of each of these three peptides in eukaryotic phospholipid models at 25°C shows that rothein 1 does not interact with the membrane at all. In contrast, both of the cyclic disulfides signiferin 1 and riparin 1.1 interact with phospholipid head groups and partially penetrate into the upper leaflet of the model bilayer, but to different extents. These interactions are not sufficiently effective to cause disruption of the lipid bilayer since the peptides are not antimicrobial, anticancer, antifungal nor active against enveloped viruses. PMID:24582625

  9. Effect of Sterol Structure on Chain Ordering of an Unsaturated Phospholipid: A 2H-NMR Study of POPC/Sterol Membranes

    NASA Astrophysics Data System (ADS)

    Shaghaghi, Mehran; Thewalt, Jenifer; Zuckermann, Martin

    2012-10-01

    The physical properties of biological membranes are considerably altered by the presence of sterols. In particular, sterols help to maintain the integrity of the cell by adjusting the fluidity of the plasma membrane. Cholesterol is in addition an important component of lipid rafts which are hypothesized to compartmentalize the cell membrane surface thereby making it possible for certain proteins to function. Using 2H-NMR spectroscopy, we studied the effect of a series of different sterols on the chain ordering of POPC, an unsaturated phospholipid present in eukaryotic cell membranes. We were able to assigned specific roles to the structural differences between the sterols by comparing the manner in which they affect the average lipid chain conformation of POPC.

  10. Study of the ferroelastic phase transition in the tetraethylammonium compound [N(C2H5)4]2ZnBr4 by magic-angle spinning and static NMR

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran

    2016-03-01

    The ferroelastic phase transition of tetraethylammonium compound [N(C2H5)4]2ZnBr4 at the phase transition temperature (TC) = 283 K was characterized by magic-angle spinning (MAS) and static nuclear magnetic resonance (NMR), and confirmed by optical polarizing spectroscopy. The structural geometry near TC was studied in terms of the chemical shifts and the spin-lattice relaxation times T1ρ in the rotating frame for 1H MAS NMR and 13C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups were distinguishable in the 13C NMR spectrum, and the T1ρ results indicate that they undergo tumbling motion above TC in a coupled manner. From the 14N NMR results, the two nitrogen nuclei in the N(C2H5)4+ ions were distinguishable above TC, and the splitting in the spectra below TC was related to the ferroelastic domains with different orientations.

  11. Structure and dynamics of the aliphatic cholesterol side chain in membranes as studied by (2)H NMR spectroscopy and molecular dynamics simulation.

    PubMed

    Vogel, Alexander; Scheidt, Holger A; Baek, Dong Jae; Bittman, Robert; Huster, Daniel

    2016-02-01

    Cholesterol is an evolutionarily highly optimized molecule particularly known for its ability to condense the phospholipids in cellular membranes. Until recently, the accompanying increase in the chain order of the surrounding phospholipids was attributed to the planar and rigid tetracyclic ring structure of cholesterol. However, detailed investigations of cholesterol's aliphatic side chain demonstrated that this side chain is responsible for approximately half of the condensation effect. Therefore, we investigated the structure and dynamics of the aliphatic side chain of cholesterol using (2)H solid-state nuclear magnetic resonance (NMR) spectroscopy and microsecond timescale all-atom molecular dynamics (MD) simulations in four different model membranes: POPC, DPPC, PSM, and POPC/PSM (1 : 1 mol/mol) and at three different temperatures: 5 °C, 37 °C, and 50 °C. A cholesterol variant, in which 11 hydrogens of the aliphatic side chain were exchanged for deuterium, was used and the respective (2)H NMR spectra confirmed the axially asymmetric rotational diffusion of cholesterol in DPPC and PSM. Furthermore, NMR spectra indicated that some hydrogens showed an unexpected magnetic inequivalency. This finding was confirmed by all-atom molecular dynamics simulations and detailed analysis revealed that the hydrogens of the methylene groups at C22, C23, and C24 are magnetically inequivalent. This inequivalency is caused by steric clashes of the aliphatic side chain with the ring structure of cholesterol as well as the branched C21 methyl group. These excluded volume effects result in reduced conformational flexibility of the aliphatic side chain of cholesterol and explain its high order (order parameter of 0.78 for chain motions) and large contribution to the condensation effect. Additionally, the motional pattern of the side chain becomes highly anisotropic such that it shows larger fluctuations perpendicular to the ring plane of cholesterol with a biaxiality of the

  12. Fluxionality and Isomerism of the Bis(dihydrogen) Complex RuH(2)(H(2))(2)(PCy(3))(2): INS, NMR, and Theoretical Studies.

    PubMed

    Rodriguez, Venancio; Sabo-Etienne, Sylviane; Chaudret, Bruno; Thoburn, John; Ulrich, Stefan; Limbach, Hans-Heinrich; Eckert, Juergen; Barthelat, Jean-Claude; Hussein, Khansaa; Marsden, Colin J.

    1998-07-13

    To study the fluxionality of the bis(dihydrogen) complex RuH(2)(H(2))(2)(PCy(3))(2) (1), NMR spectra were recorded in Freons (mixture of CDCl(3), CDFCl(2), and CDF(2)Cl). 1 was found to remain fluxional at all temperatures, but the presence of CDCl(3) necessary for its solubilization induces its transformation into, first, RuHCl(H(2))(2)(PCy(3))(2) (3) and the new ruthenium(IV) dihydride RuH(2)Cl(2)(PCy(3))(2) (4). 4 is produced selectively in pure CDCl(3) but reacts further to give a mixture of chloro complexes. 4 was isolated from the reaction of 1 with aqueous HCl in Et(2)O and shows a fluxional process attributed to the interconversion between two symmetrical isomers. The activation parameters of this process were obtained by (1)H NMR line shape analysis, as well as those corresponding to the exchange between 3 and free dihydrogen. The fluxionality of the dihydrogen-hydride system is also evident at a much faster time scale than that of NMR studies in the inelastic neutron scattering observations of the rotation of the dihydrogen ligands. The geometries and relative energies of several isomers of complexes 1, 3, and 4 were studied using density functional theory (DFT) and MP2 methods, together with a few coupled-cluster (CCSD(T)) calculations. In contrast to what might have been expected, the two hydrides and the two H(2) units of 1 lie in the same plane, due to the attractive "cis effect" created by the hydrides. The two H(2) ligands adopt cis positions in the lowest-energy isomer. Rotation of the two dihydrogen ligands has been analyzed using DFT calculations. A slight preference for a C(2) conrotatory pathway has been found with a calculated barrier in good agreement with the experimental INS value. Two low-energy isomers of 4 have been characterized computationally, both of which have C(2)(v)() symmetry, consistent with the solution NMR spectra. PMID:11670430

  13. Biosynthesis of a specifically deuteriated diunsaturated fatty acid (18:2/sub. delta. 6,9/) for /sup 2/H NMR membrane studies

    SciTech Connect

    Baenziger, J.E.; Smith, I.C.P.; Hill, R.J.

    1987-12-15

    A unique procedure for the biosynthesis and subsequent isolation of a series of specifically deuteriated cis,cis-octadeca-6,9-dienoic acids has been developed. An auxotroph of Tetrahymena, which lacks ..delta..9 and ..delta..12 desaturase activity, is supplemented with specifically deuteriated oleic acid and converts it to the corresponding deuteriated cis,cis-octadeca-6,9-dienoic acid, 18:2/sup ..delta..6,9/. The deuteriated fatty acid is subsequently isolated by argentation chromatography and HPLC. To demonstrate the utility of the procedure, we describe here the biosynthesis of cis,cis-octadeca-6,9-dienoic acid deuteriated at positions 9 and 10. Gas and thin-layer chromatography of the isolated fatty acid showed that it was greater than 99% pure while /sup 13/C NMR and mass spectrometry of the O-(trimethylsilyl) derivative confirmed that the 18-carbon fatty acid contains two double bonds located at positions 6 and 9. The yield, from an 11-L culture, was typically 100 mg of which 35% was found to be deuteriated at both the 9- and 10-positions. The deuteriated fatty acid was esterified to 1-hexadecanoyl-sn-glycero-3-phosphocholine, and aqueous, multilamellar dispersions of the lipid were studied by /sup 2/H NMR. Each spectrum consists of two overlapping powder patterns and therefore yields two quadrupolar splittings. Over a temperature range of 0 to 40/sup 0/C, one splitting decreases from 6.6 to 1.8 kHz while other increases from 4.5 to 5.3 kHz. The magnitudes of the two splittings are equivalent between 10 and 15/sup 0/ C. The values of the splittings, and their response to temperature, differ significantly from those of the corresponding deuteriated oleic acid in microbial membranes and in bilayers of 1-hexadecanoyl-2-cis-octadec-9-enoyl-sn-glycero-3-phosphocholine (POPC).

  14. Increasing the quantitative bandwidth of NMR measurements.

    PubMed

    Power, J E; Foroozandeh, M; Adams, R W; Nilsson, M; Coombes, S R; Phillips, A R; Morris, G A

    2016-02-18

    The frequency range of quantitative NMR is increased from tens to hundreds of kHz by a new pulse sequence, CHORUS. It uses chirp pulses to excite uniformly over very large bandwidths, yielding accurate integrals even for nuclei such as (19)F that have very wide spectra. PMID:26789115

  15. Increasing the quantitative bandwidth of NMR measurements.

    PubMed

    Power, J E; Foroozandeh, M; Adams, R W; Nilsson, M; Coombes, S R; Phillips, A R; Morris, G A

    2016-02-18

    The frequency range of quantitative NMR is increased from tens to hundreds of kHz by a new pulse sequence, CHORUS. It uses chirp pulses to excite uniformly over very large bandwidths, yielding accurate integrals even for nuclei such as (19)F that have very wide spectra.

  16. Calibration of NMR well logs from carbonate reservoirs with laboratory NMR measurements and μXRCT

    DOE PAGES

    Mason, Harris E.; Smith, Megan M.; Hao, Yue; Carroll, Susan A.

    2014-12-31

    The use of nuclear magnetic resonance (NMR) well log data has the potential to provide in-situ porosity, pore size distributions, and permeability of target carbonate CO₂ storage reservoirs. However, these methods which have been successfully applied to sandstones have yet to be completely validated for carbonate reservoirs. Here, we have taken an approach to validate NMR measurements of carbonate rock cores with independent measurements of permeability and pore surface area to volume (S/V) distributions using differential pressure measurements and micro X-ray computed tomography (μXRCT) imaging methods, respectively. We observe that using standard methods for determining permeability from NMR data incorrectlymore » predicts these values by orders of magnitude. However, we do observe promise that NMR measurements provide reasonable estimates of pore S/V distributions, and with further independent measurements of the carbonate rock properties that universally applicable relationships between NMR measured properties may be developed for in-situ well logging applications of carbonate reservoirs.« less

  17. Spin-spin coupling in the HD molecule determined from 1H and 2H NMR experiments in the gas-phase

    NASA Astrophysics Data System (ADS)

    Garbacz, Piotr

    2014-10-01

    The indirect spin-spin coupling of hydrogen deuteride, J(D, H), was determined from a series of 1H and 2H NMR spectra acquired at various densities of gaseous solvents (He, Ar, CO2, and N2O). The analysis of these spectra shows that accurate determination of J(D, H) from this experimental data requires careful examination of the effects of nuclear relaxation and of HD-solvent gas interactions on hydrogen deuteride line shapes. Particularly, it was found that the first-order corrections of the peak-to-peak separations between HD multiplet peaks due to weak van der Waals interactions are proportional to solvent gas density, while these corrections for nuclear relaxation of the proton and the deuteron are proportional to the second power of the inverse of the gas density. Analysis of the data indicates that J(D, H), obtained by correcting for the effects of nuclear relaxation and intermolecular interactions, is 43.136(7) Hz at 300 K.

  18. Interpretation of combined 2H SNIF/NMR and 13C SIRA/MS analyses of fruit juices to detect added sugar.

    PubMed

    Martin, G G; Hanote, V; Lees, M; Martin, Y L

    1996-01-01

    The site-specific natural isotopic fractionation studied by nuclear magnetic resonance (SNIF/NMR) method measures site-specific isotope contents in a variety of organic compounds by deuterium nuclear magnetic resonance spectroscopy. This technique, together with SIRA/MS (stable isotope ratio analysis/mass spectrometry) provides a powerful tool for food authentication and characterization. By using the ethanol resulting from sugar fermentation as a molecular probe, SNIF/NMR (deuterium) and SIRA/MS (13C) have been used together for authentication of fruit juices. The influence of deuterium content of the fermentation water on the isotopic parameters is shown and a means for normalizing the results is proposed. A large number of authentic juices have been analyzed to define the variation of isotopic ratios in natural juices. On the basis of these data, a set of rules was designed to enable interpretation of isotopic parameters in terms of possible adulteration of fruit juices by sugar addition. Results of analyses of Florida orange juice are presented. Orange juice samples from Brazil and Israel are included as 2 extreme cases. Assignment limits for a sample of orange juice of unknown origin also are given. These assignment limits are also provided for apple and grapefruit juices.

  19. Spectroscopic measurement of HO2, H2O2, and OH in the stratosphere

    NASA Technical Reports Server (NTRS)

    Park, J. H.; Carli, B.

    1991-01-01

    Stratospheric concentrations of HO2, H2O2, and OH have been retrieved simultaneously from the far-infrared emission spectra obtained with a balloon-borne Fourier transform spectrometer in June 1983 at 32 deg N latitude. Retrieved concentrations of HO2 and H2O2 are reported, along with vertical distributions of OH which were reported in an earlier paper for the afternoon, sunset, and nighttime periods for altitudes from 26 to 38 km. HO2 distributions are obtained with uncertainties that are about the same as OH for the same vertical range and for the afternoon and sunset periods. H2O2 concentration is obtained at an altitude of 30 km for the period that covers afternoon and sunset hours. The retrieved concentrations of these HO(x) species agree well with other individually measured results and the steady state photochemical predictions. The ratio HO2/OH at around 32 km seems to increase from the afternoon period to the sunset period.

  20. Direct measurements of collisional Raman line broadening in the S-branch transitions of acetylene (C2H2)

    NASA Astrophysics Data System (ADS)

    Hsu, Paul S.; Stauffer, Hans U.; Jiang, Naibo; Gord, James R.; Roy, Sukesh

    2013-10-01

    We report direct measurements of the self- and N2-broadened Raman S-branch linewidths of acetylene (C2H2), obtained by employing time-resolved picosecond rotational coherent anti-Stokes Raman scattering spectroscopy. Using broadband 115-ps pump and Stokes pulses (˜135 cm-1 bandwidth) and a spectrally narrowed 90-ps probe pulse (˜0.2 cm-1 bandwidth), Raman-coherence lifetimes are measured at room temperature for the S-branch (ΔJ = +2) transitions associated with rotational quantum number J = 3-25. These directly measured Raman-coherence lifetimes, when converted to collisional linewidth broadening coefficients, differ from the previously reported broadening coefficients extracted from theoretical calculations by 6%-35% for self-broadening for C2H2 and by up to 60% for N2-broadened C2H2.

  1. Single-crystal XRD and solid-state NMR structural resolution of a layered fluorinated gallium phosphate: RbGa3(PO4)(2)(HPO4)F4·C5N2H16·2H2O (MIL-145).

    PubMed

    Martineau, Charlotte; Loiseau, Thierry; Beitone, Lionel; Férey, Gérard; Bouchevreau, Boris; Taulelle, Francis

    2013-01-14

    A new two-dimensional fluorinated gallium phosphate RbGa(3)(PO(4))(2)(HPO(4))F(4)·C(5)N(2)H(16)·2H(2)O (MIL-145) has been hydrothermally synthesized (180 °C for 36 h) in the presence of 1,5-diaminopentane and rubidium fluoride. Its structural model has been determined by means of single-crystal X-ray diffraction analysis. The structure contains corrugated infinite ribbons of GaO(3)F(3) and GaO(4)F(2) octahedra linked through edge- and corner-sharing mode via fluoride anions. These chains are then connected to each other via phosphate groups to create a layered network delimiting 6-ring channels trapping rubidium cations. The inorganic sheets are intercalated by diprotonated 1,5-diaminopentane and water molecules, ensuring the three-dimensional cohesion via hydrogen bond scheme. (1)H, (13)C, (15)N and (87)Rb solid-state NMR spectra show the presence of two inequivalent amines as well as two Rb cations, confirming the choice of the space group, which was ambiguous from the diffraction data. (71)Ga NMR spectra, acquired at several magnetic fields, contain two different sets of Ga signals, corresponding to the two types of gallium environments in the structure. One-dimensional (19)F and (31)P and (19)F-(31)P two-dimensional NMR experiments have been recorded, which are in full agreement with the proposed structural model. Finally, possible assignments of the (19)F and (31)P resonances to the crystallographic sites in RbGa(3)(PO(4))(2)(HPO(4))F(4)·C(5)N(2)H(16)·2H(2)O have been determined by comparing adjacency matrices build-up from 2D NMR correlation spectra and from the structural data. PMID:23069866

  2. Improvements in Technique of NMR Imaging and NMR Diffusion Measurements in the Presence of Background Gradients.

    NASA Astrophysics Data System (ADS)

    Lian, Jianyu

    In this work, modification of the cosine current distribution rf coil, PCOS, has been introduced and tested. The coil produces a very homogeneous rf magnetic field, and it is inexpensive to build and easy to tune for multiple resonance frequency. The geometrical parameters of the coil are optimized to produce the most homogeneous rf field over a large volume. To avoid rf field distortion when the coil length is comparable to a quarter wavelength, a parallel PCOS coil is proposed and discussed. For testing rf coils and correcting B _1 in NMR experiments, a simple, rugged and accurate NMR rf field mapping technique has been developed. The method has been tested and used in 1D, 2D, 3D and in vivo rf mapping experiments. The method has been proven to be very useful in the design of rf coils. To preserve the linear relation between rf output applied on an rf coil and modulating input for an rf modulating -amplifying system of NMR imaging spectrometer, a quadrature feedback loop is employed in an rf modulator with two orthogonal rf channels to correct the amplitude and phase non-linearities caused by the rf components in the rf system. The modulator is very linear over a large range and it can generate an arbitrary rf shape. A diffusion imaging sequence has been developed for measuring and imaging diffusion in the presence of background gradients. Cross terms between the diffusion sensitizing gradients and background gradients or imaging gradients can complicate diffusion measurement and make the interpretation of NMR diffusion data ambiguous, but these have been eliminated in this method. Further, the background gradients has been measured and imaged. A dipole random distribution model has been established to study background magnetic fields Delta B and background magnetic gradients G_0 produced by small particles in a sample when it is in a B_0 field. From this model, the minimum distance that a spin can approach a particle can be determined by measuring

  3. Isotopic Water Analyzer for Highly Precise Measurements of δ2H, δ18O, and δ17O

    NASA Astrophysics Data System (ADS)

    Berman, E. S.; Fortson, S.; Snaith, S.; Gupta, M.

    2012-12-01

    Measurements of the stable isotope ratios (δ2H, δ18O and δ17O) of both liquid water and water vapor are widely used in hydrology, atmospheric sciences, and biogeochemistry to determine the migration of water through an ecosystem. Previously, discrete samples were collected (or condensed) and transported to an isotope ratio mass spectrometer for characterization. Due to the expense and labor associated with such sampling, isotope studies were generally limited in scope and in temporal resolution. We report on the continued development of a field-portable Isotopic Water Analyzer that exploits cavity-enhanced absorption spectrometry (e.g. Off-Axis ICOS) to accurately and rapidly quantify δ2H, δ18O and δ17O of both liquid water and water vapor. The instrument is thermally-controlled to better than ±8 mK and is capable of measuring over 90 liquid samples/day with δ2H, δ18O and δ17O precisions exceeding ±0.2 ‰, ±0.05 ‰, and ±0.06 ‰ respectively. Subsequent averaging yields δ2H, δ18O and δ17O precisions exceeding ±0.077 ‰, ±0.023 ‰, and ±0.03 ‰ respectively with over 22 samples/day. The accuracy of the liquid analyzer was confirmed over a very wide dynamic range (δ2H = -455 to +671 ‰ with comparable δ18O and δ17O values) by direct comparison to isotope ratio mass spectrometry. Moreover, the ability to directly measure 17O-excess, vapor samples, and unnatural waters (e.g. plant water, soil water, urine, blood, saliva…) will also be presented.

  4. An experiment to measure cosmic ray 2H and 3He in the 4-10 GV range

    NASA Technical Reports Server (NTRS)

    Badhwar, G. D.; Golden, R. L.; Stephens, S. A.

    1975-01-01

    It is known that the mean matter traversed by cosmic rays, X, can be obtained from the observed ratio of the flux of daughter nuclei to that of the parent nuclei provided X is much less than the attenuation mean free of the daughter nuclei. This condition is well satisfied in the case of 2H and 3He. We propose to measure the 2H/1H and 3He/4He ratios, using a multiwire proportional counter array and a superconducting magnet to measure the rigidity, and a set of aerogel Cerenkov counters to measure the velocity, thus yielding the mass of the particle. Results of a Monte-Carlo calculation based on actual experimental conditions are presented to show the resolution of the instrument. The area solid angle of the telescope is 90 sq cm sr with an average maximum detectable momentum of 140 GV.

  5. Experimental ion mobility measurements in Ar-C2H6 mixtures

    NASA Astrophysics Data System (ADS)

    Cortez, A. F. V.; Garcia, A. N. C.; Neves, P. N. B.; Santos, F. P.; Borges, F. I. G. M.; Barata, J. A. S.; Conde, C. A. N.

    2013-12-01

    In this paper we present the experimental results for the mobility of ions in argon-ethane gaseous mixtures (Ar-C2H6) for pressures ranging from 6 to 10 Torr and for reduced electric fields in the 10 Td to 25 Td range, at room temperature. For Ar concentrations below 80% two peaks were observed in the time of arrival spectra which were attributed to ion species with 3-carbons (C3H7+, C3H8+ and C3H9+) and with 4-carbons (which includes C4H7+, C4H9+, C4H10+ and C4H12+ ions). For Ar concentrations above 80% a third peak appears, which may belong to C5H11+. The time of arrival spectra for Ar concentrations of 80%, 85%, 90% and 95% are displayed in the present paper as well as the reduced mobilities determined from the peaks observed for a typical reduced electric field used in gaseous detectors (E/N = 15 Td).

  6. Interaction Study of an Amorphous Solid Dispersion of Cyclosporin A in Poly-Alpha-Cyclodextrin with Model Membranes by 1H-, 2H-, 31P-NMR and Electron Spin Resonance

    PubMed Central

    Debouzy, Jean-Claude; Bourbon, Fréderic; Lahiani-Skiba, Malika; Skiba, Mohamed

    2014-01-01

    The properties of an amorphous solid dispersion of cyclosporine A (ASD) prepared with the copolymer alpha cyclodextrin (POLYA) and cyclosporine A (CYSP) were investigated by 1H-NMR in solution and its membrane interactions were studied by 1H-NMR in small unilamellar vesicles and by 31P 2H NMR in phospholipidic dispersions of DMPC (dimyristoylphosphatidylcholine) in comparison with those of POLYA and CYSP alone. 1H-NMR chemical shift variations showed that CYSP really interacts with POLYA, with possible adduct formation, dispersion in the solid matrix of the POLYA, and also complex formation. A coarse approach to the latter mechanism was tested using the continuous variations method, indicating an apparent 1 : 1 stoichiometry. Calculations gave an apparent association constant of log Ka = 4.5. A study of the interactions with phospholipidic dispersions of DMPC showed that only limited interactions occurred at the polar head group level (31P). Conversely, by comparison with the expected chain rigidification induced by CYSP, POLYA induced an increase in the fluidity of the layer while ASD formation led to these effects almost being overcome at 298 K. At higher temperature, while the effect of CYSP seems to vanish, a resulting global increase in chain fluidity was found in the presence of ASD. PMID:24883210

  7. Development and Characterization of NMR Measurements for Polymer Gel Dosimetry

    NASA Astrophysics Data System (ADS)

    Kwong, Zachary; Whitney, Heather

    2012-03-01

    Polymer gel dosimeters are systems of water, gelatin, and monomers which form polymers upon irradiation. The gelatin matrix retains dose distribution in 3D form, facilitating truly integrated measurements of complex dose plans for radiation therapy. Polymer gels have two proton pools coupled by exchange: free solvent protons and bound polymerized macromolecular protons. Measuring magnetization transfer (MT) and relaxation affords useful insights into particle rigidity and chemical exchange effects on relaxation in polymer gels. Polymer gel dose response has been previously quantified with several techniques, most often in terms of MRI parameters, usually at field strengths of 1.5 T and below. The research described here investigates the dose response of a revised MAGIC gel dosimeter via both high-field imaging and simpler nuclear magnetic resonance (NMR) spectroscopy. This includes both transverse and longitudinal relaxation rates (R2 and R1) and quantitative MT parameters. We investigated estimating polymer molecular weight for a given applied dose using the Rouse model and R2 data from the imaging study. Finally, we began development of NMR methods for studying dose response, requiring adaption of NMR experiments to accommodate for radiation damping.

  8. Pressure-Distribution Measurements on O-2H Airplane in Flight

    NASA Technical Reports Server (NTRS)

    Pearson, H A

    1937-01-01

    Results are given of pressure-distribution measurements made over two different horizontal tail surfaces and the right wing cellule, including the slipstream area, of an observation-type biplane. Measurements were also taken of air speed, control-surface positions, control-stick forces, angular velocities, and accelerations during various abrupt maneuvers. These maneuvers consisted of push-downs and pull-ups from level flight, dive pull-outs, and aileron rolls with various thrust conditions. The results from the pressure-distribution measurements over the wing cellule are given on charts showing the variation of individual rib coefficients with wing coefficients; the data from the tail-surface pressure-distribution measurements are given mainly as total loads and moments. These data are supplemented by time histories of the measured quantities and isometric views of the rib pressure distributions occurring in abrupt maneuvers.

  9. Rheo-NMR Measurements of Cocoa Butter Crystallized Under

    SciTech Connect

    Mudge, E.; Mazzanti, G

    2009-01-01

    Modifications of a benchtop NMR instrument were made to apply temperature control to a shearing NMR cell. This has enabled the determination in situ of the solid fat content (SFC) of cocoa butter under shearing conditions. The cocoa butter was cooled at 3 C/min to three final temperatures of 17.5, 20.0, and 22.5 C with applied shear rates between 45 and 720 s-1. Polymorphic transitions of the cocoa butter were determined using synchrotron X-ray diffraction with an identical shearing system constructed of Lexan. Sheared samples were shown to have accelerated phase transitions compared to static experiments. In experiments where form V was confirmed to be the dominant polymorph, the final SFC averaged around 50%. However, when other polymorphic forms were formed, a lower SFC was measured because the final temperature was within the melting range of that polymorph and only partial crystallization happened. A shear rate of 720 s-1 delayed phase transitions, likely due to viscous heating of the sample. Pulsed NMR is an invaluable tool for determining the crystalline fraction in hydrogen containing materials, yet its use for fundamental and industrial research on fat or alkanes crystallization under shear has only recently been developed.

  10. Peroxy Radical Measurements during the IRRONIC Field Project by C2H6 - NO Chemical Amplification

    NASA Astrophysics Data System (ADS)

    Wood, E. C. D.; Kundu, S.; Deming, B.; Lew, M.; Stevens, P. S.; Sklaveniti, S.; Dusanter, S.

    2015-12-01

    We present measurements of total peroxy radicals (HO2 + RO2) during the Indiana Radical, Reactivity and Ozone Production Intercomparison (IRRONIC) field project in Bloomington, Indiana during July 2015. Peroxy radicals were measured by chemical amplification using ethane and nitric oxide in dual PFA reaction chambers, and the amplification product NO2 was quantified by cavity attenuated phase shift spectroscopy. On sunny days mid-day peroxy radical mixing ratios were typically between 20 and 70 ppt and were well correlated with "HO2*" measured by the Indiana University Laser-Induced Fluorescence with Fluorescence Assay by Gas Expansion (IU-FAGE) instrument. The ratio of total peroxy radicals (UMass) to the IU-FAGE HO2* measurements was greater than two. We also describe results from an informal intercomparison of the two instruments' calibration sources, which are based on acetone photolysis (UMass) and water photolysis (IU). In addition to sampling the IU calibration source in "amplification" mode, the UMass instrument also separately quantified the HO2 mixing ratio in the IU calibration gas by reaction with excess NO and subsequent quantification of the NO2 produced.

  11. Mobile Column Measurements of HCHO, NO2, NH3, and C2H6 in Colorado during FRAPPE

    NASA Astrophysics Data System (ADS)

    Kille, N.; Volkamer, R. M.; Baidar, S.; Ortega, I.; Sinreich, R.; Hannigan, J. W.; Cooper, O. R.; Nussbaumer, E.; Pfister, G.

    2015-12-01

    Gases from anthropogenic sources have the potential to have a profound impact on air quality. Emissions from large cattle feedlots and ONG (Oil and Natural Gas) sites are comprised of NH3 (ammonia) and C2H6 (ethane) as pollutants. C2H6 contributes to photochemical ozone (O3) production and oxidation production of HCHO (formaldehyde). NH3 is a major source for reactive nitrogen to form particulate matter 2.5, which negatively affects human health. NO2 (nitrogen dioxide), emitted during combustion, is considered a large-scale pollutant and contributes to the formation of O3. Deploying an innovative suite of remote sensing instruments in a mobile laboratory, a Multi Axis Differential Optical Absorption Spectrometer (MAX-DOAS), a UV-Vis Spectrometer, and a Fourier Transform Infrared Spectrometer, we obtain mobile column measurements at high spatial and temporal resolution, 2 seconds for the UV-Vis and IR spectrometers and 20 seconds for the MAX-DOAS. Within the scope of the Front Range Air Pollution and Photochemistry Experiment (FRAPPE) we measure total columns of HCHO, NO2, NH3, and C2H6 using the University of Colorado mobile laboratory. Emissions of urban areas, agriculture, and ONG sites were studied. For the measurement of total columns the solar occultation flux method has been applied. We measured significant variability in the columns. The measurement of total columns allows one to determine the emission flux and source strength when driving a closed box around or upwind and downwind of a source with the mobile laboratory. We present results from select research drives.

  12. Measurement of the 2H(d ,p ) 3H reaction at astrophysical energies via the Trojan-horse method

    NASA Astrophysics Data System (ADS)

    Li, Chengbo; Wen, Qungang; Fu, Yuanyong; Zhou, Jing; Zhou, Shuhua; Meng, Qiuying; Spitaleri, C.; Tumino, A.; Pizzone, R. G.; Lamia, L.

    2015-08-01

    The study of the 2H(d ,p ) 3H reaction is very important for the nucleosynthesis in both the standard Big Bang and stellar evolution, as well as for the future fusion reactor's planning of energy production. The 2H(d ,p ) 3H bare nucleus astrophysical S (E ) factor has been measured indirectly at energies from about 400 keV down to several keV by means of the Trojan-horse method applied to the quasifree process 2H(6Li ,p t ) 4He induced at a lithium beam energy of 9.5 MeV, which is closer to the zero-quasifree-energy point. An accurate analysis leads to the determination of the Sbare(0 ) =56.7 ±2.0 keV b and of the corresponding electron screening potential Ue=13.2 ±4.3 eV. In addition, this work gives an updated test for the Trojan-horse nucleus invariance by comparing with previous indirect investigations using the 3He=(d +p ) breakup.

  13. 2H2O incorporation into hepatic acetyl-CoA and de novo lipogenesis as measured by Krebs cycle-mediated 2H-enrichment of glutamate and glutamine.

    PubMed

    Silva, Ana Maria; Martins, Fatima; Jones, John G; Carvalho, Rui

    2011-12-01

    Deuterated water is widely used for measuring de novo lipogenesis on the basis of quantifying lipid (2)H-enrichment relative to that of body water. However, incorporation of (2)H-enrichment from body water into newly synthesized lipid molecules is incomplete therefore the true lipid precursor enrichment differs from that of body water. We describe a novel measurement of de novo lipogenesis that is based on a true precursor-product analysis of hepatic acetyl-CoA and triglyceride methyl enrichments from deuterated water. After deuterated water administration to seven in situ and seven perfused livers, acetyl-CoA methyl enrichment was inferred from (2)H nuclear magnetic resonance analysis of hepatic glutamate/glutamine (Glx) enrichment and triglyceride methyl enrichment was directly determined by (2)H nuclear magnetic resonance of triglycerides. Acetyl-CoA (2) H-enrichment was 71% ± 1% that of body water for in situ livers and 53% ± 2% of perfusate water for perfused livers. From the ratio of triglyceride-methyl/acetyl-CoA enrichments, fractional de novo lipogenesis rates of 0.97% ± 0.09%/2 hr and 7.92% ± 1.47%/48 hr were obtained for perfused and in situ liver triglycerides, respectively. Our method reveals that acetyl-CoA enrichment is significantly less than body water both for in situ and perfused livers. Furthermore, the difference between acetyl-CoA and body water enrichments is sensitive to the experimental setting.

  14. A new NMR method for determining the particle thickness in nanocomposites, using T2,H-selective X{1H} recoupling.

    PubMed

    Schmidt-Rohr, K; Rawal, A; Fang, X-W

    2007-02-01

    A new nuclear magnetic resonance approach for characterizing the thickness of phosphate, silicate, carbonate, and other nanoparticles in organic-inorganic nanocomposites is presented. The particle thickness is probed using the strongly distant-dependent dipolar couplings between the abundant protons in the organic phase and X nuclei (31P, 29Si, 13C, 27Al, 23Na, etc.) in the inorganic phase. This approach requires pulse sequences with heteronuclear dephasing only by the polymer or surface protons that experience strong homonuclear interactions, but not by dispersed OH or water protons in the inorganic phase, which have long transverse relaxation times T2,H. This goal is achieved by heteronuclear recoupling with dephasing by strong homonuclear interactions of protons (HARDSHIP). The pulse sequence alternates heteronuclear recoupling for approximately 0.15 ms with periods of homonuclear dipolar dephasing that are flanked by canceling 90 degrees pulses. The heteronuclear evolution of the long-T2,H protons is refocused within two recoupling periods, so that 1H spin diffusion cannot significantly dephase these coherences. For the short-T2,H protons of a relatively immobile organic matrix, the heteronuclear dephasing rate depends simply on the heteronuclear second moment. Homonuclear interactions do not affect the dephasing, even though no homonuclear decoupling is applied, because long-range 1H-X dipolar couplings approximately commute with short-range 1H-1H couplings, and heteronuclear recoupling periods are relatively short. This is shown in a detailed analysis based on interaction representations. The algorithm for simulating the dephasing data is described. The new method is demonstrated on a clay-polymer nanocomposite, diamond nanocrystals with protonated surfaces, and the bioapatite-collagen nanocomposite in bone, as well as pure clay and hydroxyapatite. The diameters of the nanoparticles in these materials range between 1 and 5 nm. Simulations show that spherical

  15. Improved water δ2H and δ18O calibration and calculation of measurement uncertainty using a simple software tool.

    PubMed

    Gröning, Manfred

    2011-10-15

    The calibration of all δ(2)H and δ(18)O measurements on the VSMOW/SLAP scale should be performed consistently, based on similar principles, independent of the instrumentation used. The basic principles of a comprehensive calibration strategy are discussed taking water as example. The most common raw data corrections for memory and drift effects are described. Those corrections result in a considerable improvement in data consistency, especially in laboratories analyzing samples of quite variable isotopic composition (e.g. doubly labelled water). The need for a reliable uncertainty assessment for all measurements is discussed and an easy implementation method proposed. A versatile evaluation method based on Excel macros and spreadsheets is presented. It corrects measured raw data for memory and drift effects, performs the calibration and calculates the combined standard uncertainty for each measurement. It allows the easy implementation of the discussed principles in any user laboratory. Following these principles will improve the comparability of data among laboratories. PMID:21913248

  16. Structural, vibrational, electronic, NMR, NLO and reactivity analyses of (3Z)-3-(2-oxo-2-phenylethylidene)-1,3-dihydro-2H-indol-2-one (OPEDI) by ab initio HF and DFT calculations.

    PubMed

    Sridevi, C; Velraj, G

    2013-04-15

    This study represents the vibrational, electronic, NMR, NLO, reactivity and structural aspects of (3Z)-3-(2-oxo-2-phenylethylidene)-1,3-dihydro-2H-indol-2-one (OPEDI). A detailed interpretation of the FT-IR, FT-Raman, UV and NMR spectra were reported. Theoretical calculations were performed by ab initio HF and density functional theory (DFT)/B3LYP method using 6-311++G(d,p) basis sets. The most preferred Z isomer (cis-configuration) was confirmed through PES scan studies. The vibrational wavenumbers and potential energy distribution (PED) of various normal modes were calculated. The lower frontier orbital energy gap and high dipole moment of OPEDI illustrates the high reactivity. The stability and charge delocalization of the molecule was studied by natural bond orbital (NBO) analysis. OPEDI exhibited good nonlinear optical activity and was 13 times greater than that of urea. Molecular electrostatic potential (MEP) was carried out for predicting the reactive sites. The NMR results indicated that the observed chemical shifts depend not only on the structure of the molecule being studied, but also on the solvent used.

  17. Two Phase Flow Measurements by Nuclear Magnetic Resonance (NMR)

    SciTech Connect

    Altobelli, Stephen A; Fukushima, Eiichi

    2006-08-14

    In concentrated suspensions, there is a tendency for the solid phase to migrate from regions of high shear rate to regions of low shear (Leighton & Acrivos, 1987). In the early years that our effort was funded by the DOE Division of Basic Energy Science, quantitative measurement of this process in neutrally buoyant suspensions was a major focus (Abbott, et al., 1991; Altobelli, et al., 1991). Much of this work was used to improve multi-phase numerical models at Sandia National Laboratories. Later, our collaborators at Sandia and the University of New Mexico incorporated body forces into their numerical models of suspension flow (Rao, Mondy, Sun, et al., 2002). We developed experiments that allow us to study flows driven by buoyancy, to characterize these flows in well-known and useful engineering terms (Altobelli and Mondy, 2002) and to begin to explore the less well-understood area of flows with multiple solid phases (Beyea, Altobelli, et al., 2003). We also studied flows that combine the effects of shear and buoyancy, and flows of suspensions made from non-Newtonian liquids (Rao, Mondy, Baer, et al, 2002). We were able to demonstrate the usefulness of proton NMR imaging of liquid phase concentration and velocity and produced quantitative data not obtainable by other methods. Fluids flowing through porous solids are important in geophysics and in chemical processing. NMR techniques have been widely used to study liquid flow in porous media. We pioneered the extension of these studies to gas flows (Koptyug, et al, 2000, 2000, 2001, 2002). This extension allows us to investigate a wider range of Peclet numbers, and to gather data on problems of interest in catalysis. We devised two kinds of NMR experiments for three-phase systems. Both experiments employ two NMR visible phases and one phase that gives no NMR signal. The earlier method depends on the two visible phases differing in a NMR relaxation property. The second method (Beyea, Altobelli, et al., 2003) uses two

  18. Hydration of DNA by tritiated water and isotope distribution: a study by /sup 1/H, /sup 2/H, and /sup 3/H NMR spectroscopy

    SciTech Connect

    Mathur-De Vre, R.; Grimee-Declerck, R.; Lejeune, P.; Bertinchamps, A.J.

    1982-06-01

    The hydration layer of DNA (0.75%) in tritiated water represents 3.5% of solvent /sup 3/HHO. The combined effects of temperature (-6 to -40/sup 0/C) and H/sub 2/O//sup 2/H/sub 2/O solvent composition on the spin-lattice relaxation times of water protons and deuterons suggest selective distribution of isotopes in the hydration layer. The ''hydration isotope'' effect and the localization of tritiated water molecules in the hydration layer of DNA have important implications in describing the radiobiological effects of tritiated water because the initial molecular damage caused by /sup 3/HHO (internal radiation source) localizes close to /sup 3/H due to the short range and low energy of /sup 3/H ..beta.. rays.

  19. Xenon NMR measurements of permeability and tortuosity in reservoir rocks.

    PubMed

    Wang, Ruopeng; Pavlin, Tina; Rosen, Matthew Scott; Mair, Ross William; Cory, David G; Walsworth, Ronald Lee

    2005-02-01

    In this work we present measurements of permeability, effective porosity and tortuosity on a variety of rock samples using NMR/MRI of thermal and laser-polarized gas. Permeability and effective porosity are measured simultaneously using MRI to monitor the inflow of laser-polarized xenon into the rock core. Tortuosity is determined from measurements of the time-dependent diffusion coefficient using thermal xenon in sealed samples. The initial results from a limited number of rocks indicate inverse correlations between tortuosity and both effective porosity and permeability. Further studies to widen the number of types of rocks studied may eventually aid in explaining the poorly understood connection between permeability and tortuosity of rock cores. PMID:15833638

  20. Measurement of fibrin concentration by fast field-cycling NMR.

    PubMed

    Broche, Lionel M; Ismail, Saadiya R; Booth, Nuala A; Lurie, David J

    2012-05-01

    The relaxation of (1)H nuclei due to their interaction with quadrupolar (14)N nuclei in gel structures is measured using fast field-cycling NMR. This phenomenon called quadrupolar dips has been reported in different (1)H-(14)N bond-rich species. In this study, we have studied quadrupolar dips in fibrin, an insoluble protein that is the core matrix of thrombi. Fibrin was formed by the addition of thrombin to fibrinogen in 0.2% agarose gel. T(1)-dispersion curves were measured using fast field-cycling NMR relaxometry, over the field range of 1.5-3.5 MHz (proton Larmor frequency), and were analyzed using a curve-fitting algorithm. A linear increase of signal amplitude with increasing fibrin concentration was observed. This agrees with the current theory that predicts a linear relationship of signal amplitude with the concentration of contributing (14)N spins in the sample. Interestingly, fibrin formation gave rise to the signal, regardless of crosslinking induced by the transglutaminase factor XIIIa. To investigate the effect of proteins that might be trapped in the thrombi in vivo, the plasma protein albumin was added to the fibrin gel, and an increase in the quadrupolar signal amplitude was observed. This study can potentially be useful for thrombi classification by fast field-cycling MRI techniques.

  1. Action of melittin on the DPPC-cholesterol liquid-ordered phase: a solid state 2H-and 31P-NMR study.

    PubMed Central

    Pott, T; Dufourc, E J

    1995-01-01

    Solid-state deuterium and phosphorus-31 nuclear magnetic resonance studies of deuterium-labeled beta--[2,2',3,4,4',6-2H6]-cholesterol and 1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine have been undertaken to monitor the action of melittin on model membranes containing 30 mol% cholesterol, both at the molecular and macroscopic level. Cholesterol totally inhibits the toxin-triggered formation of large unilamellar vesicles and strongly restricts the appearance of small discs. The latter remain stable over a wide temperature range (20-60 degrees C) because of an increase in their cholesterol content as the temperature increases. This process is related to a constant disc hydrophobic thickness of approximately 29 A. The system, when not in the form of discs, appears to be composed of very large vesicles on which melittin promotes magnetically induced ellipsoidal deformation. This deformation is the greatest when the maximum of discs is observed. A model to describe both the disc formation and stability is proposed. PMID:7756559

  2. Coupled changes between lipid order and polypeptide conformation at the membrane surface. A sup 2 H NMR and Raman study of polylysine-phosphatidic acid systems

    SciTech Connect

    Laroche, G.; Pezolet, M. ); Dufourc, E.J.; Dufourcq, J. )

    1990-07-10

    Thermotropism and segmental chain order parameters of sn-2-perdeuteriated dimyristoylphosphatidic acid (DMPA)-water dispersions, with and without poly(L-lysine) (PLL) of different molecular weights, have been investigated by solid-state deuterium NMR spectroscopy. The segmental chain order parameter profile of this negatively charged lipid is similar to that already found for other lipids. Addition of long PLL increases the temperature, {Tc}, of the lipid gel-to-fluid phase transition, whereas short PLL has practically no effect on {Tc}. In the fluid phase both varieties of PLL increase the plateau character of segmental order parameters up to carbon position 10. At the same reduced temperature, long PLL more significantly increases the segmental ordering, especially at the methyl terminal position. This leads to the conclusion that polar head-group capping and charge neutralization by PLL induce severe changes in lipid chain ordering, even down to the bilayer core. The structure of PLL bound to the lipid bilayer surface was monitored by Raman spectroscopy, following the amide I bands. Results show that the lipid gel-to-fluid phase transition triggers a conformational transition from ordered {beta}-sheet to random structure of short PLL, while it does not affect the strongly stabilized {beta}-sheet structure of long PLL. It is concluded that both short and long PLL can efficiently cap and neutralize lipid head groups, whatever their structure, and that peptide length is a key parameter in whether lipids or peptides are the driving force in conformationally coupled changes of both partners in the membrane.

  3. Continuous Arctic Ocean Water Vapor Isotope Ratio (δ18O and δ2H) Measurements During a Summer Icebreaker Expedition

    NASA Astrophysics Data System (ADS)

    Klein, E. S.; Welker, J. M.

    2015-12-01

    Warming in the Arctic is reducing sea ice, which may result in changes to the water cycle through increased atmospheric humidity. Here we present the first continuous record of water vapor isotope ratio (δ18O, δ2H, d-excess) measurements from the sub-Arctic and Arctic Ocean during ship transit through both open water and sea ice. As water vapor isotopes were collected across a spectrum of sea ice conditions, the influence of sea ice and availability of open water moisture sources on Arctic Ocean water vapor isotope values (particularly d-excess) is examined. Isotope values reveal characteristics about water availability at vapor sources, as influenced by presence of sea ice (e.g., ice covered arid or open water humid sources), and air parcel trajectory. Higher d-excess values were generally associated with more northern Arctic, ice covered, and arid vapor sources. Conversely, lower d-excess values were related to more southern, open water, and humid vapor sources. Additionally, water vapor isotopes while sea ice was present were generally characterized by more depleted δ18O and δ2H and higher d-excess values, relative to open water values. These water vapor isotope values also present information about potential shifts in moisture sources in an increasingly ice free Arctic Ocean. Understanding these shifts is important to learning about both modern and past patterns of Arctic atmospheric water movement and distribution.

  4. Balloon-borne and aircraft infrared measurements of ethane (C2H6) in the upper troposphere and lower stratosphere

    NASA Technical Reports Server (NTRS)

    Goldman, A.; Murcray, F. J.; Murcray, D. G.; Rinsland, C. P.; Coffey, M. T.; Mankin, W. G.

    1984-01-01

    Quantitative infrared measurements of ethane (C2H6) in the upper troposphere and lower stratosphere are reported. The results have been obtained from the analysis of absorption features of the nu9 band at 12.2 microns, which have been identified in high-resolution balloon-borne and aircraft solar absorption spectra. The balloon-borne spectral data were recorded at sunset with the 0.02/cm resolution University of Denver interferometer system, from a float altitude of 33.5 km near Alamogordo, New Mexico, on March 23, 1981. The aircraft spectra were recorded at sunset in July 1978 with a 0.06/cm resolution interferometer aboard a jet aircraft at 12 km altitude, near 35 deg N, 96 deg W. The balloon analysis indicates the C2H6 mixing ratio decreased from 3.5 ppbv near 8.8 km to 0.91 ppbv near 12.1 km. The results are consistent with the column value obtained from the aircraft data.

  5. Balloon-borne and aircraft infrared measurements of ethane (C2H6) in the upper troposphere and lower stratosphere

    NASA Astrophysics Data System (ADS)

    Goldman, A.; Murcray, F. J.; Murcray, D. G.; Rinsland, C. P.; Coffey, M. T.; Mankin, W. G.

    Quantitative infrared measurements of ethane (C2H6) in the upper troposphere and lower stratosphere are reported. The results have been obtained from the analysis of absorption features of the nu9 band at 12.2 microns, which have been identified in high-resolution balloon-borne and aircraft solar absorption spectra. The balloon-borne spectral data were recorded at sunset with the 0.02/cm resolution University of Denver interferometer system, from a float altitude of 33.5 km near Alamogordo, New Mexico, on March 23, 1981. The aircraft spectra were recorded at sunset in July 1978 with a 0.06/cm resolution interferometer aboard a jet aircraft at 12 km altitude, near 35 deg N, 96 deg W. The balloon analysis indicates the C2H6 mixing ratio decreased from 3.5 ppbv near 8.8 km to 0.91 ppbv near 12.1 km. The results are consistent with the column value obtained from the aircraft data.

  6. Five years of CO, HCN, C2H6, C2H2, CH3OH, HCOOH, and H2CO total columns measured in the Canadian High Arctic

    NASA Astrophysics Data System (ADS)

    Viatte, C.; Strong, K.; Walker, K. A.; Drummond, J. R.

    2013-12-01

    We present a five-year timeseries of seven tropospheric species measured using a ground-based Fourier Transform InfraRed (FTIR) spectrometer at the Polar Environment Atmospheric Research Laboratory (PEARL, Eureka, Nunavut, Canada, 80°05' N, 86°42' W) from 2007 to 2011. Total columns and temporal variabilities of carbon monoxide (CO), hydrogen cyanide (HCN), and ethane (C2H6), as well as the first derived total columns at Eureka of acetylene (C2H2), methanol (CH3OH), formic acid (HCOOH), and formaldehyde (H2CO) are investigated, providing a new dataset in the sparsely sampled high latitudes. Total columns are obtained using the SFIT2 retrieval algorithm based on the Optimal Estimation Method. The microwindows, as well as the a priori profiles and variabilities are selected to optimize the information content of the retrievals, and error analyses are performed for all seven species. Our retrievals show good sensitivities in the troposphere. The seasonal amplitudes of the timeseries, ranging from 34 to 104%, are captured while using a single a priori profile for each species. The timeseries of the CO, C2H6 and C2H2 total columns at PEARL exhibit strong seasonal cycles with maxima in winter and minima in summer, in opposite phase to the HCN, CH3OH, HCOOH and H2CO timeseries. These cycles result from the relative contributions of the photochemistry, oxidation, and transport, as well as biogenic and biomass burning emissions. Comparisons of the FTIR partial columns with coincident satellite measurements by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) show good agreement. The correlation coefficients and the slopes range from 0.56 to 0.97, and 0.50 to 3.35, respectively, for the seven target species. Our new dataset is compared with previous measurements found in the literature to assess atmospheric budgets of these tropospheric species in the high Arctic. The CO and C2H6 concentrations are consistent with negative trends observed over

  7. Five years of CO, HCN, C2H6, C2H2, CH3OH, HCOOH and H2CO total columns measured in the Canadian high Arctic

    NASA Astrophysics Data System (ADS)

    Viatte, C.; Strong, K.; Walker, K. A.; Drummond, J. R.

    2014-06-01

    We present a five-year time series of seven tropospheric species measured using a ground-based Fourier transform infrared (FTIR) spectrometer at the Polar Environment Atmospheric Research Laboratory (PEARL; Eureka, Nunavut, Canada; 80°05' N, 86°42' W) from 2007 to 2011. Total columns and temporal variabilities of carbon monoxide (CO), hydrogen cyanide (HCN) and ethane (C2H6) as well as the first derived total columns at Eureka of acetylene (C2H2), methanol (CH3OH), formic acid (HCOOH) and formaldehyde (H2CO) are investigated, providing a new data set in the sparsely sampled high latitudes. Total columns are obtained using the SFIT2 retrieval algorithm based on the optimal estimation method. The microwindows as well as the a priori profiles and variabilities are selected to optimize the information content of the retrievals, and error analyses are performed for all seven species. Our retrievals show good sensitivities in the troposphere. The seasonal amplitudes of the time series, ranging from 34 to 104%, are captured while using a single a priori profile for each species. The time series of the CO, C2H6 and C2H2 total columns at PEARL exhibit strong seasonal cycles with maxima in winter and minima in summer, in opposite phase to the HCN, CH3OH, HCOOH and H2CO time series. These cycles result from the relative contributions of the photochemistry, oxidation and transport as well as biogenic and biomass burning emissions. Comparisons of the FTIR partial columns with coincident satellite measurements by the Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE-FTS) show good agreement. The correlation coefficients and the slopes range from 0.56 to 0.97 and 0.50 to 3.35, respectively, for the seven target species. Our new data set is compared to previous measurements found in the literature to assess atmospheric budgets of these tropospheric species in the high Arctic. The CO and C2H6concentrations are consistent with negative trends observed over the

  8. Measurements of Flow Distortion within the IRGASON Integrated Sonic Anemometer and CO_2/H_2O Gas Analyzer

    NASA Astrophysics Data System (ADS)

    Horst, T. W.; Vogt, R.; Oncley, S. P.

    2016-07-01

    Wind-tunnel and field measurements are analyzed to investigate flow distortion within the IRGASON integrated sonic anemometer and CO_2/H_2O gas analyzer as a function of wind speed, wind direction and attack angle. The wind-tunnel measurements are complimentary to the field measurements, and the dependence of the wind-tunnel mean-wind-component flow-distortion errors on wind direction agrees well with that of the field measurements. The field measurements exhibit significant overestimation of the crosswind variance and underestimation of the momentum flux with respect to an adjacent CSAT3 sonic, as well as a transfer of turbulent kinetic energy from the streamwise wind component to the cross-stream wind components. In contrast, we find attenuation of only a few percent in the vertical velocity variance and the vertical flux of sonic temperature. The attenuation of the fluxes appears to be caused to a large extent by decorrelation between the horizontal and vertical-velocity components and between the vertical velocity and sonic temperature. Additional flow distortion due to transducer shadowing reduces to some extent the overestimation, but also increases the underestimation of the IRGASON turbulence statistics.

  9. Measurement of /sup 2/H/sub 2/O by IR absorbance in doubly labeled H/sub 2/O studies of energy expenditure

    SciTech Connect

    Karasov, W.H.; Han, L.R.; Munger, J.C.

    1988-07-01

    The energy expenditure of animals in their natural surroundings can be determined by measuring the turnover in body water of isotopes of oxygen and hydrogen. We evaluated the use of infrared spectrophotometry for measuring /sup 2/H/sub 2/O in small (20-microliters) water samples also labeled with 18O. For /sup 2/H/sub 2/O over the enrichment range of 0.1-1 atom%, there was a linear relationship between infrared absorbance and /sup 2/H/sub 2/O enrichment. /sup 2/H/sub 2/O enrichments could be measured with a precision and accuracy of less than or equal to 1%, using this relationship. The presence of /sup 18/O in water samples in enrichments of up to 1 atom% had no significant effect on measurement of /sup 2/H/sub 2/O by infrared absorbance. We measured the simultaneous turnover rates of /sup 2/H/sub 2/O and /sup 3/H in mice and turtles also labeled with 18O. Our results validated the use of infrared absorbance in doubly labeled water measures of energy expenditure and indicated that the fractionation factors in vivo for /sup 2/H/sub 2/O and /sup 3/H do not differ.

  10. Measurements of the {sup 2}H(p-vector,2p)n breakup reaction at 250 MeV

    SciTech Connect

    Maeda, Y.; Dozono, M.; Ihara, E.; Sagara, K.; Wakasa, T.; Hatanaka, K.; Matsubara, H.; Suda, K.; Tameshige, Y.; Tamii, A.; Kawabata, T.; Sakaguchi, S.; Sasamoto, Y.; Shimizu, Y.; Uesaka, T.; Noji, S.; Sakai, H.; Sasano, M.; Yako, K.; Sekiguchi, K.

    2008-04-29

    Recently it was found that the differential cross sections of elastic Nd scattering below 150 MeV can be well reproduced by incorporating a 3NF in Faddeev calculations based on modern nucleon-nucleon (NN) interactions. On the other hand, the differential cross sections for nd and pd at 250 MeV show large discrepancies between the data and the Faddeev calculations with a 3NF. This indicates the existence of the missing features of the three nucleon force in this energy region. For the next step in the 3NF study, we have measured the vector analyzing power A{sub y} and the differential cross sections for the {sup 2}H(p-vector,pp)n breakup reaction at 250 MeV. The experiment was carried out by detecting two protons in the final state with using the double-armed spectrometer Grand Raiden (GR) and the Large Acceptance Spectrometer (LAS) at the Research Center for Nuclear Physics (RCNP). The data was compared with the results of Faddeev calculations with and without a 3NF.

  11. Systematic bias in NMR diffusion measurements on polydisperse systems

    NASA Astrophysics Data System (ADS)

    Zhou, Xiaoyue; Xu, Kaipin; Zhang, Shanmin

    2015-03-01

    Least-squares fitting of the Stejskal-Tanner equation is a routine process in the measurement of molecular diffusion coefficient (MDC) using Nuclear Magnetic Resonance (NMR) Spectroscopy. It is simple and elegant. However, a bias of the MDC is noticed when the system is polydispersed. This is due to improper accounts of the diffusion coefficient distribution. Eventually, it leads to a discrepancy between the observed MDC and the statistical mean value of the distribution. To reveal the discrepancy, an analytical solution is derived when the diffusion data is taken a logarithmic linearization. Computer simulation is also applied to obtain a non-linear regression result. For a Gaussian distribution of the MDCs, the bias is proportional to the square of the distribution width (linear regression), but it is also inversely proportional to the statistical mean value of the distribution (non-linear regression). This indicates that the MDC derived from Stejskal-Tanner equation only holds well for narrow distribution of MDCs. Otherwise, molecular radius derived from the Stokes-Einstein equation needs to be reconsidered due to the incorrect estimation of the MDC.

  12. Systematic bias in NMR diffusion measurements on polydisperse systems.

    PubMed

    Zhou, Xiaoyue; Xu, Kaipin; Zhang, Shanmin

    2015-03-01

    Least-squares fitting of the Stejskal-Tanner equation is a routine process in the measurement of molecular diffusion coefficient (MDC) using Nuclear Magnetic Resonance (NMR) Spectroscopy. It is simple and elegant. However, a bias of the MDC is noticed when the system is polydispersed. This is due to improper accounts of the diffusion coefficient distribution. Eventually, it leads to a discrepancy between the observed MDC and the statistical mean value of the distribution. To reveal the discrepancy, an analytical solution is derived when the diffusion data is taken a logarithmic linearization. Computer simulation is also applied to obtain a non-linear regression result. For a Gaussian distribution of the MDCs, the bias is proportional to the square of the distribution width (linear regression), but it is also inversely proportional to the statistical mean value of the distribution (non-linear regression). This indicates that the MDC derived from Stejskal-Tanner equation only holds well for narrow distribution of MDCs. Otherwise, molecular radius derived from the Stokes-Einstein equation needs to be reconsidered due to the incorrect estimation of the MDC.

  13. Precision measurements of {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He total cross sections at Big Bang nucleosynthesis energies

    SciTech Connect

    Leonard, D.S.; Karwowski, H.J.; Brune, C.R.; Fisher, B.M.; Ludwig, E.J.

    2006-04-15

    Recent Wilkinson Microwave Anisotropy Probe (WMAP) measurements have determined the baryon density of the Universe {omega}{sub b} with a precision of about 4%. With {omega}{sub b} tightly constrained, comparisons of Big Bang nucleosynthesis (BBN) abundance predictions to primordial abundance observations can be made and used to test BBN models and/or to further constrain abundances of isotopes with weak observational limits. To push the limits and improve constraints on BBN models, uncertainties in key nuclear reaction rates must be minimized. To this end, we made new precise measurements of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He total cross sections at lab energies from 110 to 650 keV. A complete fit was performed in energy and angle to both angular distribution and normalization data for both reactions simultaneously. By including parameters for experimental variables in the fit, error correlations between detectors, reactions, and reaction energies were accurately tabulated by computational methods. With uncertainties around 2%{+-}1% scale error, these new measurements significantly improve on the existing data set. At relevant temperatures, by using the data of the present work, both reaction rates are found to be about 7% higher than those in the widely used NACRE (nuclear astrophysics compilation of reaction rates) database. These data will thus lead not only to reduced uncertainties, but also to modifications in the BBN abundance predictions.

  14. NUCLEAR AND HEAVY ION PHYSICS: Measurement of the astrophysical S factor for the low energy 2H(d,γ)4He reaction

    NASA Astrophysics Data System (ADS)

    Zhou, Jing; Fu, Yuan-Yong; Zhou, Shu-Hua; Xia, Hai-Hong; Li, Cheng-Bo; Meng, Qiu-Ying

    2009-05-01

    The γ-rays and protons from an Ed = 20 keV deuteron beam incident on a D—Ti target were measured. A branching ratio of the 2H(d,γ)4 He reaction versus the 2H(d,p) 3H reaction of Γγ/Γp = (1.06 ± 0.34) × 10-7 has been obtained, and the astrophysical S factor of the 2H(d,γ)4 He reaction at the center of mass energy Ecm approx 7 keV of (6.0 ± 2.4) × 10-6 keV·b was deduced.

  15. Method and sample spinning apparatus for measuring the NMR spectrum of an orientationally disordered sample

    DOEpatents

    Pines, Alexander; Samoson, Ago

    1990-01-01

    An improved NMR apparatus and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise orientationally disordered samples. The apparatus spins the sample about an axis. The angle of the axis is mechanically varied such that the time average of two or more Legendre polynomials are zero.

  16. Method and apparatus for measuring the NMR spectrum of an orientationally disordered sample

    DOEpatents

    Pines, Alexander; Samoson, Ago

    1990-01-01

    An improved NMR probe and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise oreintationally disordered samples. The apparatus mechanically varies the orientation of the sample such that the time average of two or more sets of spherical harmonic functions is zero.

  17. Two-dimensional NMR measurement and point dipole model prediction of paramagnetic shift tensors in solids

    SciTech Connect

    Walder, Brennan J.; Davis, Michael C.; Grandinetti, Philip J.; Dey, Krishna K.; Baltisberger, Jay H.

    2015-01-07

    A new two-dimensional Nuclear Magnetic Resonance (NMR) experiment to separate and correlate the first-order quadrupolar and chemical/paramagnetic shift interactions is described. This experiment, which we call the shifting-d echo experiment, allows a more precise determination of tensor principal components values and their relative orientation. It is designed using the recently introduced symmetry pathway concept. A comparison of the shifting-d experiment with earlier proposed methods is presented and experimentally illustrated in the case of {sup 2}H (I = 1) paramagnetic shift and quadrupolar tensors of CuCl{sub 2}⋅2D{sub 2}O. The benefits of the shifting-d echo experiment over other methods are a factor of two improvement in sensitivity and the suppression of major artifacts. From the 2D lineshape analysis of the shifting-d spectrum, the {sup 2}H quadrupolar coupling parameters are 〈C{sub q}〉 = 118.1 kHz and 〈η{sub q}〉 = 0.88, and the {sup 2}H paramagnetic shift tensor anisotropy parameters are 〈ζ{sub P}〉 = − 152.5 ppm and 〈η{sub P}〉 = 0.91. The orientation of the quadrupolar coupling principal axis system (PAS) relative to the paramagnetic shift anisotropy principal axis system is given by (α,β,γ)=((π)/2 ,(π)/2 ,0). Using a simple ligand hopping model, the tensor parameters in the absence of exchange are estimated. On the basis of this analysis, the instantaneous principal components and orientation of the quadrupolar coupling are found to be in excellent agreement with previous measurements. A new point dipole model for predicting the paramagnetic shift tensor is proposed yielding significantly better agreement than previously used models. In the new model, the dipoles are displaced from nuclei at positions associated with high electron density in the singly occupied molecular orbital predicted from ligand field theory.

  18. Measurement of longitudinal relaxation times in crowded 1H NMR spectra using one- and two-dimensional maximum quantum (MAXY) NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Liu, Maili; Ye, Chaohui; Farrant, R. Duncan; Nicholson, Jeremy K.; Lindon, John C.

    Methods for measuring longitudinal relaxation times of protons in heavily overlapped 1H NMR spectra are introduced and exemplified using a solution of cholesteryl acetate. The methods are based on 1-dimensional and 2-dimensional maximum quantum NMR spectroscopy (MAXY), which makes possible the selective detection of CH, CH2 and CH31H NMR resonances. A modification of the BIRD pulse sequence to achieve selective inversion of protons bonded to either 12C or 13C is given. The approach should find application in studies of molecular dynamics where isotopic enrichment is not possible and the level of available sample dictates the use of 1H NMR spectroscopy.

  19. Cerebral blood flow measured by NMR indicator dilution in cats.

    PubMed

    Ewing, J R; Branch, C A; Helpern, J A; Smith, M B; Butt, S M; Welch, K M

    1989-02-01

    We developed techniques to assess the utility of a nuclear magnetic resonance (NMR) indicator for cerebral blood flow studies in cats, using Freon-22 for the first candidate. A PIN-diode-switched NMR experiment allowed the acquisition of an arterial as well as a cerebral fluorine-19 signal proportional to concentration vs. time in a 1.89 T magnet. Mean +/- SD blood:brain partition coefficients for Freon-22 were estimated at 0.93 +/- 0.08 for gray matter and 0.77 +/- 0.12 for white matter. Using maximum-likelihood curve fitting, estimates of mean +/- SD resting cerebral blood flow were 50 +/- 19 ml/100 g-min for gray matter and 5.0 +/- 2.0 ml/100 g-min for white matter. Hypercapnia produced the expected increases in gray and white matter blood flow. The physiologic effects of Freon-22, including an increase in cerebral blood flow itself with administration of 40% by volume, may limit its use as an indicator. Nevertheless, the NMR techniques described demonstrate the feasibility of fluorine-19-labeled compounds as cerebral blood flow indicators and the promise for their use in humans.

  20. Cerebral blood flow measured by NMR indicator dilution in cats

    SciTech Connect

    Ewing, J.R.; Branch, C.A.; Helpern, J.A.; Smith, M.B.; Butt, S.M.; Welch, K.M.

    1989-02-01

    We developed techniques to assess the utility of a nuclear magnetic resonance (NMR) indicator for cerebral blood flow studies in cats, using Freon-22 for the first candidate. A PIN-diode-switched NMR experiment allowed the acquisition of an arterial as well as a cerebral fluorine-19 signal proportional to concentration vs. time in a 1.89 T magnet. Mean +/- SD blood:brain partition coefficients for Freon-22 were estimated at 0.93 +/- 0.08 for gray matter and 0.77 +/- 0.12 for white matter. Using maximum-likelihood curve fitting, estimates of mean +/- SD resting cerebral blood flow were 50 +/- 19 ml/100 g-min for gray matter and 5.0 +/- 2.0 ml/100 g-min for white matter. Hypercapnia produced the expected increases in gray and white matter blood flow. The physiologic effects of Freon-22, including an increase in cerebral blood flow itself with administration of 40% by volume, may limit its use as an indicator. Nevertheless, the NMR techniques described demonstrate the feasibility of fluorine-19-labeled compounds as cerebral blood flow indicators and the promise for their use in humans.

  1. Cerebral blood flow measured by NMR indicator dilution in cats.

    PubMed

    Ewing, J R; Branch, C A; Helpern, J A; Smith, M B; Butt, S M; Welch, K M

    1989-02-01

    We developed techniques to assess the utility of a nuclear magnetic resonance (NMR) indicator for cerebral blood flow studies in cats, using Freon-22 for the first candidate. A PIN-diode-switched NMR experiment allowed the acquisition of an arterial as well as a cerebral fluorine-19 signal proportional to concentration vs. time in a 1.89 T magnet. Mean +/- SD blood:brain partition coefficients for Freon-22 were estimated at 0.93 +/- 0.08 for gray matter and 0.77 +/- 0.12 for white matter. Using maximum-likelihood curve fitting, estimates of mean +/- SD resting cerebral blood flow were 50 +/- 19 ml/100 g-min for gray matter and 5.0 +/- 2.0 ml/100 g-min for white matter. Hypercapnia produced the expected increases in gray and white matter blood flow. The physiologic effects of Freon-22, including an increase in cerebral blood flow itself with administration of 40% by volume, may limit its use as an indicator. Nevertheless, the NMR techniques described demonstrate the feasibility of fluorine-19-labeled compounds as cerebral blood flow indicators and the promise for their use in humans. PMID:2645693

  2. Measuring Level Alignment at the Metal–Molecule Interface by In Situ Electrochemical 13C NMR

    SciTech Connect

    Li, Ying; Zelakiewicz, Brian S.; Allison, Thomas C.; Tong, Yu ye J.

    2015-03-16

    A new technique to measure energy-level alignment at a metal–molecule interface between the Fermi level of the metal and the frontier orbitals of the molecule is proposed and experimentally demonstrated. The method, which combines the electrochemistry of organo-ligand-stabilized Au nanoparticles with 13C NMR spectroscopy (i.e. in situ electrochemical NMR), enables measuring both occupied and unoccupied states.

  3. Ultra-low-field NMR relaxation and diffusion measurements using an optical magnetometer.

    PubMed

    Ganssle, Paul J; Shin, Hyun D; Seltzer, Scott J; Bajaj, Vikram S; Ledbetter, Micah P; Budker, Dmitry; Knappe, Svenja; Kitching, John; Pines, Alexander

    2014-09-01

    Nuclear magnetic resonance (NMR) relaxometry and diffusometry are important tools for the characterization of heterogeneous materials and porous media, with applications including medical imaging, food characterization and oil-well logging. These methods can be extremely effective in applications where high-resolution NMR is either unnecessary, impractical, or both, as is the case in the emerging field of portable chemical characterization. Here, we present a proof-of-concept experiment demonstrating the use of high-sensitivity optical magnetometers as detectors for ultra-low-field NMR relaxation and diffusion measurements.

  4. NMR measurements in a hydrogen/helium slush at 4.2 K

    NASA Astrophysics Data System (ADS)

    Matusiak, Marcin; Hamida, Jaha; Ihas, Gary G.; Sullivan, Neil

    2003-03-01

    Matrix isolation of various atoms in solid hydrogen presents both pure and applied research possibilities. When single atom properties are measured with NMR in the background of a quantum solid, insight into electronic interactions and quantum diffusion may be obtained. A cell has been constructed which, when filled with liquid helium, may have various gases injected into it. If this gas is a mixture of hydrogen and, say, boron, NMR may be performed on both the H and the B nuclei. Crystal or amorphous structures and atomic diffusion may be investigated. Design and construction of the apparatus will be presented. The first pulsed NMR data on H will be presented and interpreted.

  5. J-GFT NMR for precise measurement of mutually correlated nuclear spin-spin couplings.

    PubMed

    Atreya, Hanudatta S; Garcia, Erwin; Shen, Yang; Szyperski, Thomas

    2007-01-24

    G-matrix Fourier transform (GFT) NMR spectroscopy is presented for accurate and precise measurement of chemical shifts and nuclear spin-spin couplings correlated according to spin system. The new approach, named "J-GFT NMR", is based on a largely extended GFT NMR formalism and promises to have a broad impact on projection NMR spectroscopy. Specifically, constant-time J-GFT (6,2)D (HA-CA-CO)-N-HN was implemented for simultaneous measurement of five mutually correlated NMR parameters, that is, 15N backbone chemical shifts and the four one-bond spin-spin couplings 13Calpha-1Halpha, 13Calpha-13C', 15N-13C', and 15N-1HNu. The experiment was applied for measuring residual dipolar couplings (RDCs) in an 8 kDa protein Z-domain aligned with Pf1 phages. Comparison with RDC values extracted from conventional NMR experiments reveals that RDCs are measured with high precision and accuracy, which is attributable to the facts that (i) the use of constant time evolution ensures that signals do not broaden whenever multiple RDCs are jointly measured in a single dimension and (ii) RDCs are multiply encoded in the multiplets arising from the joint sampling. This corresponds to measuring the couplings multiple times in a statistically independent manner. A key feature of J-GFT NMR, i.e., the correlation of couplings according to spin systems without reference to sequential resonance assignments, promises to be particularly valuable for rapid identification of backbone conformation and classification of protein fold families on the basis of statistical analysis of dipolar couplings.

  6. NMR measurement of hydrodynamic dispersion in porous media subject to biofilm mediated precipitation reactions.

    PubMed

    Fridjonsson, Einar O; Seymour, Joseph D; Schultz, Logan N; Gerlach, Robin; Cunningham, Alfred B; Codd, Sarah L

    2011-03-01

    Noninvasive measurements of hydrodynamic dispersion by nuclear magnetic resonance (NMR) are made in a model porous system before and after a biologically mediated precipitation reaction. Traditional magnetic resonance imaging (MRI) was unable to detect the small scale changes in pore structure visualized during light microscopy analysis after destructive sampling of the porous medium. However, pulse gradient spin echo nuclear magnetic resonance (PGSE NMR) measurements clearly indicated a change in hydrodynamics including increased pore scale mixing. These changes were detected through time-dependent measurement of the propagator by PGSE NMR. The dynamics indicate an increased pore scale mixing which alters the preasymptotic approach to asymptotic Gaussian dynamics governed by the advection diffusion equation. The methods described here can be used in the future to directly measure the transport of solutes in biomineral-affected porous media and contribute towards reactive transport models, which take into account the influence of pore scale changes in hydrodynamics.

  7. Achievement of 1020MHz NMR.

    PubMed

    Hashi, Kenjiro; Ohki, Shinobu; Matsumoto, Shinji; Nishijima, Gen; Goto, Atsushi; Deguchi, Kenzo; Yamada, Kazuhiko; Noguchi, Takashi; Sakai, Shuji; Takahashi, Masato; Yanagisawa, Yoshinori; Iguchi, Seiya; Yamazaki, Toshio; Maeda, Hideaki; Tanaka, Ryoji; Nemoto, Takahiro; Suematsu, Hiroto; Miki, Takashi; Saito, Kazuyoshi; Shimizu, Tadashi

    2015-07-01

    We have successfully developed a 1020MHz (24.0T) NMR magnet, establishing the world's highest magnetic field in high resolution NMR superconducting magnets. The magnet is a series connection of LTS (low-Tc superconductors NbTi and Nb3Sn) outer coils and an HTS (high-Tc superconductor, Bi-2223) innermost coil, being operated at superfluid liquid helium temperature such as around 1.8K and in a driven-mode by an external DC power supply. The drift of the magnetic field was initially ±0.8ppm/10h without the (2)H lock operation; it was then stabilized to be less than 1ppb/10h by using an NMR internal lock operation. The full-width at half maximum of a (1)H spectrum taken for 1% CHCl3 in acetone-d6 was as low as 0.7Hz (0.7ppb), which was sufficient for solution NMR. On the contrary, the temporal field stability under the external lock operation for solid-state NMR was 170ppb/10h, sufficient for NMR measurements for quadrupolar nuclei such as (17)O; a (17)O NMR measurement for labeled tri-peptide clearly demonstrated the effect of high magnetic field on solid-state NMR spectra. PMID:25978708

  8. Dissolution Dynamic Nuclear Polarization Instrumentation for Real-time Enzymatic Reaction Rate Measurements by NMR.

    PubMed

    Balzan, Riccardo; Fernandes, Laetitia; Comment, Arnaud; Pidial, Laetitia; Tavitian, Bertrand; Vasos, Paul R

    2016-01-01

    The main limitation of NMR-based investigations is low sensitivity. This prompts for long acquisition times, thus preventing real-time NMR measurements of metabolic transformations. Hyperpolarization via dissolution DNP circumvents part of the sensitivity issues thanks to the large out-of-equilibrium nuclear magnetization stemming from the electron-to-nucleus spin polarization transfer. The high NMR signal obtained can be used to monitor chemical reactions in real time. The downside of hyperpolarized NMR resides in the limited time window available for signal acquisition, which is usually on the order of the nuclear spin longitudinal relaxation time constant, T1, or, in favorable cases, on the order of the relaxation time constant associated with the singlet-state of coupled nuclei, TLLS. Cellular uptake of endogenous molecules and metabolic rates can provide essential information on tumor development and drug response. Numerous previous hyperpolarized NMR studies have demonstrated the relevancy of pyruvate as a metabolic substrate for monitoring enzymatic activity in vivo. This work provides a detailed description of the experimental setup and methods required for the study of enzymatic reactions, in particular the pyruvate-to-lactate conversion rate in presence of lactate dehydrogenase (LDH), by hyperpolarized NMR. PMID:26967906

  9. Identification and correction of spectral contamination in 2H/1H and 18O/16O measured in leaf, stem, and soil water.

    PubMed

    Schultz, Natalie M; Griffis, Timothy J; Lee, Xuhui; Baker, John M

    2011-11-15

    Plant water extracts typically contain organic materials that may cause spectral interference when using isotope ratio infrared spectroscopy (IRIS), resulting in errors in the measured isotope ratios. Manufacturers of IRIS instruments have developed post-processing software to identify the degree of contamination in water samples, and potentially correct the isotope ratios of water with known contaminants. Here, the correction method proposed by an IRIS manufacturer, Los Gatos Research, Inc., was employed and the results were compared with those obtained from isotope ratio mass spectrometry (IRMS). Deionized water was spiked with methanol and ethanol to create correction curves for δ(18)O and δ(2)H. The contamination effects of different sample types (leaf, stem, soil) and different species from agricultural fields, grasslands, and forests were compared. The average corrections in leaf samples ranged from 0.35 to 15.73‰ for δ(2)H and 0.28 to 9.27‰ for δ(18)O. The average corrections in stem samples ranged from 1.17 to 13.70‰ for δ(2)H and 0.47 to 7.97‰ for δ(18)O. There was no contamination observed in soil water. Cleaning plant samples with activated charcoal had minimal effects on the degree of spectral contamination, reducing the corrections, by on average, 0.44‰ for δ(2)H and 0.25‰ for δ(18)O. The correction method eliminated the discrepancies between IRMS and IRIS for δ(18)O, and greatly reduced the discrepancies for δ(2)H. The mean differences in isotope ratios between IRMS and the corrected IRIS method were 0.18‰ for δ(18)O, and -3.39‰ for δ(2)H. The inability to create an ethanol correction curve for δ(2)H probably caused the larger discrepancies. We conclude that ethanol and methanol are the primary compounds causing interference in IRIS analyzers, and that each individual analyzer will probably require customized correction curves. PMID:22006400

  10. First direct measurement of the 2H(α,γ)6Li cross section at big bang energies and the primordial lithium problem.

    PubMed

    Anders, M; Trezzi, D; Menegazzo, R; Aliotta, M; Bellini, A; Bemmerer, D; Broggini, C; Caciolli, A; Corvisiero, P; Costantini, H; Davinson, T; Elekes, Z; Erhard, M; Formicola, A; Fülöp, Zs; Gervino, G; Guglielmetti, A; Gustavino, C; Gyürky, Gy; Junker, M; Lemut, A; Marta, M; Mazzocchi, C; Prati, P; Rossi Alvarez, C; Scott, D A; Somorjai, E; Straniero, O; Szücs, T

    2014-07-25

    Recent observations of (6)Li in metal poor stars suggest a large production of this isotope during big bang nucleosynthesis (BBN). In standard BBN calculations, the (2)H(α,γ)(6)Li reaction dominates (6)Li production. This reaction has never been measured inside the BBN energy region because its cross section drops exponentially at low energy and because the electric dipole transition is strongly suppressed for the isoscalar particles (2)H and α at energies below the Coulomb barrier. Indirect measurements using the Coulomb dissociation of (6)Li only give upper limits owing to the dominance of nuclear breakup processes. Here, we report on the results of the first measurement of the (2)H(α,γ)(6)Li cross section at big bang energies. The experiment was performed deep underground at the LUNA 400 kV accelerator in Gran Sasso, Italy. The primordial (6)Li/(7)Li isotopic abundance ratio has been determined to be (1.5 ± 0.3) × 10(-5), from our experimental data and standard BBN theory. The much higher (6)Li/(7)Li values reported for halo stars will likely require a nonstandard physics explanation, as discussed in the literature.

  11. First direct measurement of the 2H(α,γ)6Li cross section at big bang energies and the primordial lithium problem.

    PubMed

    Anders, M; Trezzi, D; Menegazzo, R; Aliotta, M; Bellini, A; Bemmerer, D; Broggini, C; Caciolli, A; Corvisiero, P; Costantini, H; Davinson, T; Elekes, Z; Erhard, M; Formicola, A; Fülöp, Zs; Gervino, G; Guglielmetti, A; Gustavino, C; Gyürky, Gy; Junker, M; Lemut, A; Marta, M; Mazzocchi, C; Prati, P; Rossi Alvarez, C; Scott, D A; Somorjai, E; Straniero, O; Szücs, T

    2014-07-25

    Recent observations of (6)Li in metal poor stars suggest a large production of this isotope during big bang nucleosynthesis (BBN). In standard BBN calculations, the (2)H(α,γ)(6)Li reaction dominates (6)Li production. This reaction has never been measured inside the BBN energy region because its cross section drops exponentially at low energy and because the electric dipole transition is strongly suppressed for the isoscalar particles (2)H and α at energies below the Coulomb barrier. Indirect measurements using the Coulomb dissociation of (6)Li only give upper limits owing to the dominance of nuclear breakup processes. Here, we report on the results of the first measurement of the (2)H(α,γ)(6)Li cross section at big bang energies. The experiment was performed deep underground at the LUNA 400 kV accelerator in Gran Sasso, Italy. The primordial (6)Li/(7)Li isotopic abundance ratio has been determined to be (1.5 ± 0.3) × 10(-5), from our experimental data and standard BBN theory. The much higher (6)Li/(7)Li values reported for halo stars will likely require a nonstandard physics explanation, as discussed in the literature. PMID:25105610

  12. A Reestimate of the Protosolar (^2^H/^1^H)_p_ ratio from (^3^He/^4^He)_SW_ solar wind measurements.

    NASA Astrophysics Data System (ADS)

    Gautier, D.; Morel, P.

    1997-07-01

    We reanalyze the inference of the protosolar abundance of deuterium made by Geiss (1993, in Origin and Evolution of the Elements, Eds., N. Prantzos, E. Vangioni-Flam, M. Casse, Cambridge University Press, p. 90) from measurements of (^3^He/^4^He)_SW_ in the solar wind. We use an evolutionary solar model with microscopic diffusion, constrained to fit the present age, radius and luminosity, as well as the observed ratio of heavy elements to hydrogen. The protosolar (^2^H/^1^H)_p_ is obtained from the best fit of (^3^He/^4^He)_SW_. Taking for the protosolar (^3^He/^4^He)_p_ the value measured in Jupiter by the Galileo probe (Niemann et al., 1996Sci...272..846N), we derive (^2^H/^1^H)_p_=(3.01+/-0.17)x10^-5^. Compared to the present interstellar medium value (Linsky et al., 1993ApJ...402..694L), this result is compatible with models of the chemical evolution of the Galaxy in the solar neighborhood; it is also marginally compatible with the Jovian (^2^H/^1^H)_J_=(5+/-2)x10^-5^ ratio measured by Galileo.

  13. Satellite Boreal Measurements over Alaska and Canada During June-July 2004: Simultaneous Measurements of Upper Tropospheric CO, C2H6, HCN, CH3Cl, CH4, C2H2, CH2OH, HCOOH, OCS, and SF6 Mixing Ratios

    NASA Technical Reports Server (NTRS)

    Rinsland, Curtis P.; Dufour, Gaelle; Boone, Chris D.; Bernath, Peter F.; Chiou, Linda; Coheur, Pierre-Francois; Turquety, Solene; Clerbaux, Cathy

    2007-01-01

    Simultaneous ACE (Atmospheric Chemistry Experiment) upper tropospheric CO, C2H6, HCN, CH3Cl, CH4 , C2H2 , CH30H, HCOOH, and OCS measurements show plumes up to 185 ppbv (10 (exp -9) per unit volume) for CO, 1.36 ppbv for C2H6, 755 pptv (10(exp -12) per unit volume) for HCN, 1.12 ppbv for CH3C1, 1.82 ppmv, (10(exp -6) per unit volume) for CH4, 0.178 ppbv for C2H2, 3.89 ppbv for CH30H, 0.843 ppbv for HCOOH, and 0.48 ppbv for OCS in western Canada and Alaska at 50 deg N-68 deg N latitude between 29 June and 23 July 2004. Enhancement ratios and emission factors for HCOOH, CH30H, HCN, C2H6, and OCS relative to CO at 250-350 hPa are inferred from measurements of young plumes compared with lower mixing ratios assumed to represent background conditions based on a CO emission factor derived from boreal measurements. Results are generally consistent with the limited data reported for various vegetative types and emission phases measured in extratropical forests including boreal forests. The low correlation between fire product emission mixing ratios and the S176 mixing ratio is consistent with no significant SF6 emissions from the biomass fires.

  14. FIRST MEASUREMENTS OF {sup 15}N FRACTIONATION IN N{sub 2}H{sup +} TOWARD HIGH-MASS STAR-FORMING CORES

    SciTech Connect

    Fontani, F.; Caselli, P.; Bizzocchi, L.; Palau, A.; Ceccarelli, C.

    2015-08-01

    We report on the first measurements of the isotopic ratio {sup 14}N/{sup 15}N in N{sub 2}H{sup +} toward a statistically significant sample of high-mass star-forming cores. The sources belong to the three main evolutionary categories of the high-mass star formation process: high-mass starless cores, high-mass protostellar objects, and ultracompact H ii regions. Simultaneous measurements of the {sup 14}N/{sup 15}N ratio in CN have been made. The {sup 14}N/{sup 15}N ratios derived from N{sub 2}H{sup +} show a large spread (from ∼180 up to ∼1300), while those derived from CN are in between the value measured in the terrestrial atmosphere (∼270) and that of the proto-solar nebula (∼440) for the large majority of the sources within the errors. However, this different spread might be due to the fact that the sources detected in the N{sub 2}H{sup +} isotopologues are more than those detected in the CN ones. The {sup 14}N/{sup 15}N ratio does not change significantly with the source evolutionary stage, which indicates that time seems to be irrelevant for the fractionation of nitrogen. We also find a possible anticorrelation between the {sup 14}N/{sup 15}N (as derived from N{sub 2}H{sup +}) and the H/D isotopic ratios. This suggests that {sup 15}N enrichment could not be linked to the parameters that cause D enrichment, in agreement with the prediction by recent chemical models. These models, however, are not able to reproduce the observed large spread in {sup 14}N/{sup 15}N, pointing out that some important routes of nitrogen fractionation could be still missing in the models.

  15. Measurement of pH by NMR Spectroscopy in Concentrated Aqueous Fluoride Buffers

    PubMed Central

    Gerken, James B.

    2010-01-01

    An NMR spectroscopic technique has been developed to give rapid, accurate pH measurements on tenth-milliliter samples of concentrated acidic aqueous solutions buffered by fluoride ion in the pH 1.5 – 4.5 range. The fluoride 19F chemical shift has been calibrated as a function of pH at 0.1 and 1.0 M concentration by reference to an internal 3-fluoropyridine standard. Subsequent measurements of fluoride buffer pH required no additives and only two NMR spectra in the presence of an external reference standard. PMID:21278857

  16. On the calibration of continuous, high-precision delta18O and delta2H measurements using an off-axis integrated cavity output spectrometer.

    PubMed

    Wang, Lixin; Caylor, Kelly K; Dragoni, Danilo

    2009-02-01

    The (18)O and (2)H of water vapor serve as powerful tracers of hydrological processes. The typical method for determining water vapor delta(18)O and delta(2)H involves cryogenic trapping and isotope ratio mass spectrometry. Even with recent technical advances, these methods cannot resolve vapor composition at high temporal resolutions. In recent years, a few groups have developed continuous laser absorption spectroscopy (LAS) approaches for measuring delta(18)O and delta(2)H which achieve accuracy levels similar to those of lab-based mass spectrometry methods. Unfortunately, most LAS systems need cryogenic cooling and constant calibration to a reference gas, and have substantial power requirements, making them unsuitable for long-term field deployment at remote field sites. A new method called Off-Axis Integrated Cavity Output Spectroscopy (OA-ICOS) has been developed which requires extremely low-energy consumption and neither reference gas nor cryogenic cooling. In this report, we develop a relatively simple pumping system coupled to a dew point generator to calibrate an ICOS-based instrument (Los Gatos Research Water Vapor Isotope Analyzer (WVIA) DLT-100) under various pressures using liquid water with known isotopic signatures. Results show that the WVIA can be successfully calibrated using this customized system for different pressure settings, which ensure that this instrument can be combined with other gas-sampling systems. The precisions of this instrument and the associated calibration method can reach approximately 0.08 per thousand for delta(18)O and approximately 0.4 per thousand for delta(2)H. Compared with conventional mass spectrometry and other LAS-based methods, the OA-ICOS technique provides a promising alternative tool for continuous water vapor isotopic measurements in field deployments. PMID:19142848

  17. Estimation and measurement of flat or solenoidal coil inductance for radiofrequency NMR coil design.

    PubMed

    Rainey, Jan K; DeVries, Jeffrey S; Sykes, Brian D

    2007-07-01

    The inductance of a radiofrequency coil determines its compatibility with a given NMR probe circuit. However, calculation (or estimation) of inductance for radiofrequency coils of dimensions suitable for use in an NMR probe is not trivial, particularly for flat-coils. A comparison of a number of formulae for calculation of inductance is presented through the use of a straightforward inductance measurement circuit. This technique relies upon instrumentation available in many NMR laboratories rather than upon more expensive and specialized instrumentation often utilized in the literature. Inductance estimation methods are suggested and validated for both flat-coils and solenoids. These have proven very useful for fabrication of a number of new coils in our laboratory for use in static solid-state NMR probes operating at (1)H frequencies of 300 and 600MHz. Solenoidal coils with very similar measured and estimated inductances having inner diameters from 1 to 5mm are directly compared as an example of the practical application of inductance estimation for interchange of coils within an existing solid-state NMR probe.

  18. New measurements of the proton migration tunneling splitting in the rotational spectrum of C{sub 2}H{sup +}{sub 3}

    SciTech Connect

    Cordonnier, M.; Coudert, L.H.

    1996-12-31

    New measurements have been carried out in the rotational spectrum of C{sub 2}H{sub 3}{sup +} using a negative glow discharge. Improved resolution made it possible to determine the value of the tunneling splitting for one more line than in previous studies. Microwave data have been analyzed with a formalism based on the Internal-Axis-Method-like approach set-up to treat the water dimer. The three experimentally resolved splittings were predicted within the experimental resolution around the measured values. Calculations also provided more information about the tunneling path along which the three protons migrate.

  19. Local- and regional-scale measurements of CH4, δ13CH4, and C2H6 in the Uintah Basin using a mobile stable isotope analyzer

    NASA Astrophysics Data System (ADS)

    Rella, C. W.; Hoffnagle, J.; He, Y.; Tajima, S.

    2015-10-01

    In this paper, we present an innovative CH4, δ13CH4, and C2H6 instrument based on cavity ring-down spectroscopy (CRDS). The design and performance of the analyzer is presented in detail. The instrument is capable of precision of less than 1 ‰ on δ13CH4 with 1 in. of averaging and about 0.1 ‰ in an hour. Using this instrument, we present a comprehensive approach to atmospheric methane emissions attribution. Field measurements were performed in the Uintah Basin (Utah, USA) in the winter of 2013, using a mobile lab equipped with the CRDS analyzer, a high-accuracy GPS, a sonic anemometer, and an onboard gas storage and playback system. With a small population and almost no other sources of methane and ethane other than oil and gas extraction activities, the Uintah Basin represents an ideal location to investigate and validate new measurement methods of atmospheric methane and ethane. We present the results of measurements of the individual fugitive emissions from 23 natural gas wells and six oil wells in the region. The δ13CH4 and C2H6 signatures that we observe are consistent with the signatures of the gases found in the wells. Furthermore, regional measurements of the atmospheric CH4, δ13CH4, and C2H6 signatures throughout the basin have been made, using continuous sampling into a 450 m long tube and laboratory reanalysis with the CRDS instrument. These measurements suggest that 85 ± 7 % of the total emissions in the basin are from natural gas production.

  20. USGS46 Greenland ice core water – A new isotopic reference material for δ2H and δ18O measurements of water

    USGS Publications Warehouse

    Coplen, Tyler B.; Qi, Haiping; Tarbox, Lauren V.; Lorenz, Jennifer M.; Buck, Bryan

    2015-01-01

    Ice core from Greenland was melted, filtered, homogenised, loaded into glass ampoules, sealed, autoclaved to eliminate biological activity, and calibrated by dual-inlet isotope-ratio mass spectrometry. This isotopic reference material (RM), USGS46, is intended as one of two secondary isotopic reference waters for daily normalisation of stable hydrogen (δ2H) and stable oxygen (δ18O) isotopic analysis of water with a mass spectrometer or a laser absorption spectrometer. The measured δ2H and δ18O values of this reference water were −235.8 ± 0.7‰ and −29.80 ± 0.03‰, respectively, relative to VSMOW on scales normalised such that the δ2H and δ18O values of SLAP reference water are, respectively, −428 and −55.5‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95-percent probability of encompassing the true value. This reference water is available in cases containing 144 glass ampoules that are filled with either 4 ml or 5 ml of water per ampoule.

  1. Combining SIP and NMR Measurements to Develop Improved Estimates of Permeability in Sandstone Cores

    NASA Astrophysics Data System (ADS)

    Keating, K.; Binley, A. M.

    2013-12-01

    Permeability is traditionally measured in-situ by inducing groundwater flow using pumping, slug, or packer tests; however, these methods require the existence of wells, can be labor intensive and can be constrained by measurement support volumes. Indirect estimates of permeability based on geophysical techniques benefit from relatively short measurement times, do not require fluid extraction, and are non-invasive when made from the surface (or minimally invasive when made in a borehole). However, estimates of permeability based on a single geophysical method often require calibration for rock type, and cannot be used to uniquely determine all of the physical properties required to accurately determine permeability. In this laboratory study we present the first critical step towards developing a method for estimating permeability based on the synergistic coupling of two complementary geophysical methods: spectral induced polarization (SIP) and nuclear magnetic resonance (NMR). To develop an improved model for estimating permeability, laboratory SIP and NMR measurements were collected on a series of sandstone cores, covering a wide range of permeabilities. Current models for estimating permeability from each individual geophysical measurement were compared to independently obtained estimates of permeability. The comparison confirmed previous research showing that estimates from SIP or NMR alone only yield the permeability within order of magnitude accuracy and must be calibrated for rock type. Next, the geophysical parameters determined from SIP and NMR were compared to independent measurements the physical properties of the sandstone cores including gravimetric porosity and pores-size distributions (obtained from mercury injection porosimetry); this comparison was used to evaluate which geophysical parameter more consistently and accurately predicted each physical property. Finally, we present an improved method for estimating permeability in sandstone cores based

  2. An introduction to NMR-based approaches for measuring protein dynamics

    PubMed Central

    Kleckner, Ian R; Foster, Mark P

    2010-01-01

    Proteins are inherently flexible at ambient temperature. At equilibrium, they are characterized by a set of conformations that undergo continuous exchange within a hierarchy of spatial and temporal scales ranging from nanometers to micrometers and femtoseconds to hours. Dynamic properties of proteins are essential for describing the structural bases of their biological functions including catalysis, binding, regulation and cellular structure. Nuclear magnetic resonance (NMR) spectroscopy represents a powerful technique for measuring these essential features of proteins. Here we provide an introduction to NMR-based approaches for studying protein dynamics, highlighting eight distinct methods with recent examples, contextualized within a common experimental and analytical framework. The selected methods are (1) Real-time NMR, (2) Exchange spectroscopy, (3) Lineshape analysis, (4) CPMG relaxation dispersion, (5) Rotating frame relaxation dispersion, (6) Nuclear spin relaxation, (7) Residual dipolar coupling, (8) Paramagnetic relaxation enhancement. PMID:21059410

  3. Autonomous Instrumentation for Fast, Continuous and Accurate Isotopic Measurements of Water Vapor (δ18O, δ 2H, H2O) in the Field

    NASA Astrophysics Data System (ADS)

    Liem, J. S.; Dong, F.; Owano, T. G.; Baer, D. S.

    2010-12-01

    Stable isotopes of water vapor are powerful tracers to investigate the hydrological cycle and ecological processes. Therefore, continuous, in-situ and accurate measurements of δ18O and δ2H are critical to advance the understanding of water-cycle dynamics worldwide. Furthermore, the combination of meteorological techniques and high-frequency isotopic water measurements can provide detailed time-resolved information on the eco-physiological performance of plants and enable improved understanding of water fluxes at ecosystem scales. In this work, we present recent development and field deployment of a novel Water Vapor Isotope Measurement System (WVIMS) capable of simultaneous in situ measurements of δ18O and δ2H and water mixing ratio (H2O) with high precision, accuracy and speed (up to 10 Hz measurement rate). The WVIMS consists of an Analyzer (Water Vapor Isotope Analyzer), based on cavity enhanced laser absorption spectroscopy, and a Standard Source (Water Vapor Isotope Standard Source), based on quantitative evaporation of a liquid water standard (with known isotopic content), and operates in a dual-inlet configuration. The WVIMS automatically controls the entire sample and data collection, data analysis and calibration process to allow for continuous, autonomous unattended long-term operation. The WVIMS has been demonstrated for accurate (i.e. fully calibrated) measurements ranging from 500 ppmv (typical of arctic environments) to over 30,000 ppmv (typical of tropical environments) in air. Dual-inlet operation, which involves regular calibration with isotopic water vapor reference standards, essentially eliminates measurement drift, ensures data reliability, and allows operation over an extremely wide ambient temperature range (5-45C). This presentation will include recent measurements recorded using the WVIMS in plant growth chambers and in arctic environments. The availability of this new instrumentation provides new opportunities for detailed continuous

  4. Bandgap measurements and the peculiar splitting of E2H phonon modes of InxAl1-xN nanowires grown by plasma assisted molecular beam epitaxy

    NASA Astrophysics Data System (ADS)

    Tangi, Malleswararao; Mishra, Pawan; Janjua, Bilal; Ng, Tien Khee; Anjum, Dalaver H.; Prabaswara, Aditya; Yang, Yang; Albadri, Abdulrahman M.; Alyamani, Ahmed Y.; El-Desouki, Munir M.; Ooi, Boon S.

    2016-07-01

    The dislocation free InxAl1-xN nanowires (NWs) are grown on Si(111) by nitrogen plasma assisted molecular beam epitaxy in the temperature regime of 490 °C-610 °C yielding In composition ranges over 0.50 ≤ x ≤ 0.17. We study the optical properties of these NWs by spectroscopic ellipsometry (SE), photoluminescence, and Raman spectroscopies since they possesses minimal strain with reduced defects comparative to the planar films. The optical bandgap measurements of InxAl1-xN NWs are demonstrated by SE where the absorption edges of the NW samples are evaluated irrespective of substrate transparency. A systematic Stoke shift of 0.04-0.27 eV with increasing x was observed when comparing the micro-photoluminescence spectra with the Tauc plot derived from SE. The micro-Raman spectra in the NWs with x = 0.5 showed two-mode behavior for A1(LO) phonons and single mode behavior for E2H phonons. As for x = 0.17, i.e., high Al content, we observed a peculiar E2H phonon mode splitting. Further, we observe composition dependent frequency shifts. The 77 to 600 K micro-Raman spectroscopy measurements show that both AlN- and InN-like modes of A1(LO) and E2H phonons in InxAl1-xN NWs are redshifted with increasing temperature, similar to that of the binary III group nitride semiconductors. These studies of the optical properties of the technologically important InxAl1-xN nanowires will path the way towards lasers and light-emitting diodes in the wavelength of the ultra-violet and visible range.

  5. 1H NMR and calorimetric measurements on rabbit eye lenses.

    PubMed

    Gutsze, A; Bodurka, J; Olechnowicz, R; Buntkowsky, G; Limbach, H H

    1995-01-01

    The dynamic properties of water molecules in the rabbit lens were studied by proton nuclear magnetic resonance line shape analysis, measurements of relaxation times as a function of temperature and calorimetric measurements. The experiments prove, as already suggested by other authors, that there are two types of water in the lens of rabbit eyes, namely bound unfreezable hydration water and bulk freezable water. Line shape analysis and relaxometry showed, that this two types of water exist in two different environments, which may be identified as the nucleus and the cortex of the lens. The line shape analysis showed furthermore that water molecules in the rabbit lens has a common spin lattice relaxation time (T1), but two different transverse relaxation times (T2A and T2B). The tentative model of fast water exchange on the T1 time scale and slow water exchange on the T2 time scale, was used to explain experimental proton relaxation data of the rabbit lens. An estimation for this exchange rate kex by comparing it to the relaxation times is given (T1(-1) < kex < T1(-1)). It has also been shown by a calorimetric measurements, that the lenses can be easily under-cooled to temperatures well below the freezing point of water. The achievable maximum undercooling temperature of the lens is a function of the cooling rate KC, therefore it has to be considered as an experimentally adjustable parameter which is not characteristic for the investigated sample. Thus it must be noted that any previous discussions about the specific value of the temperature of water crystallisation in biological systems need to be carefully reconsidered.

  6. Equilibrium exchange of dimethyl methylphosphonate across the human red cell membrane measured using NMR spin transfer

    NASA Astrophysics Data System (ADS)

    Kirk, Kiaran; Kuchel, Philip W.

    The 31P NMR spectrum of dimethyl methylphosphonate, in a suspension of human erythrocytes in a hypertonic medium, is characterized by separate intra- and extracellular resonances. The compound crosses the red cell membrane too rapidly for its transport to be monitored using conventional NMR time-course techniques. In the present work we adapted the saturation transfer method to measure the unidirectional flux of dimethyl methylphosphonate into the cell at equilibrium and thereby gained an estimate of its permeability coefficient. Repeated measurements on low hematocrit cell suspensions showed no significant variation in the permeability coefficients for cells from five different donors. Saturation transfer measurements conducted over a range of hematocrits demonstrated the hematocrit dependence of the unidirectional rate constant for dimethyl methylphosphonate influx. The calculated permeability coefficient was independent of hematocrit.

  7. Measurement and Imaging of Planar Electromagnetic Phantoms Based on NMR Imaging Methods

    NASA Astrophysics Data System (ADS)

    Frollo, I.; Andris, P.; Přibil, J.; Vojtíšek, L.; Dermek, T.; Valkovič, L.

    2010-01-01

    Planar electromagnetic phantom design for measurement and imaging using NMR has been performed. Electromagnetic phantom computation and testing on a NMR 0.178 Tesla Esaote Opera imager were accomplished. The classical geometrical and chemical phantoms are generally used for testing of NMR imaging systems. They are simple cylindrical or rectangular objects with different dimensions and shapes with holes filled with specially prepared water solutions. In our experiments a homogeneous phantom (reference medium) - a container filled with water - was used. The resultant image represents the magnetic field distribution in the homogeneous phantom. An image acquired by this method is actually a projection of the sample properties onto the homogeneous phantom. The goal of the paper is to map and image the magnetic field deformation using NMR imaging methods. We are using a double slender rectangular vessel with constant thickness filled with specially prepared water solution in our experiments. For detection a carefully tailored gradient-echo imaging method, susceptible to magnetic field homogeneity, was used.

  8. Are Protein Force Fields Getting Better? A Systematic Benchmark on 524 Diverse NMR Measurements.

    PubMed

    Beauchamp, Kyle A; Lin, Yu-Shan; Das, Rhiju; Pande, Vijay S

    2012-04-10

    Recent hardware and software advances have enabled simulation studies of protein systems on biophysically-relevant timescales, often revealing the need for improved force fields. Although early force field development was limited by the lack of direct comparisons between simulation and experiment, recent work from several labs has demonstrated direct calculation of NMR observables from protein simulations. Here we quantitatively evaluate recent molecular dynamics force fields against a suite of 524 chemical shift and J coupling ((3)JH(N)H(α), (3)JH(N)C(β), (3)JH(α)C', (3)JH(N)C', and (3)JH(α)N) measurements on dipeptides, tripeptides, tetra-alanine, and ubiquitin. Of the force fields examined (ff96, ff99, ff03, ff03*, ff03w, ff99sb*, ff99sb-ildn, ff99sb-ildn-phi, ff99sb-ildn-nmr, CHARMM27, OPLS-AA), two force fields (ff99sb-ildn-phi, ff99sb-ildn-nmr) combining recent side chain and backbone torsion modifications achieve high accuracy in our benchmark. For the two optimal force fields, the calculation error is comparable to the uncertainty in the experimental comparison. This observation suggests that extracting additional force field improvements from NMR data may require increased accuracy in J coupling and chemical shift prediction. To further investigate the limitations of current force fields, we also consider conformational populations of dipeptides, which were recently estimated using vibrational spectroscopy.

  9. Measuring chirality in NMR in the presence of a time-dependent electric field

    SciTech Connect

    Walls, Jamie D.; Harris, Robert A.

    2014-06-21

    Traditional nuclear magnetic resonance (NMR) experiments are “blind” to chirality since the spectra for left and right handed enantiomers are identical in an achiral medium. However, theoretical arguments have suggested that the effective Hamiltonian for spin-1/2 nuclei in the presence of electric and magnetic fields can be different for left and right handed enantiomers, thereby enabling NMR to be used to spectroscopically detect chirality even in an achiral medium. However, most proposals to detect the chiral NMR signature require measuring signals that are equivalent to picomolar concentrations for {sup 1}H nuclei, which are outside current NMR detection limits. In this work, we propose to use an AC electric field that is resonantly modulated at the Larmor frequency, thereby enhancing the effect of the chiral term by four to six orders of magnitude. We predict that a steady-state transverse magnetization, whose direction will be opposite for different enantiomers, will build up during application of an AC electric field. We also propose an experimental setup that uses a solenoid coil with an AC current to generate the necessary periodic electric fields that can be used to generate chiral signals which are equivalent to the signal from a {sup 1}H submicromolar concentration.

  10. Biscayne aquifer drinking water (USGS45): a new isotopic reference material for δ2H and δ18O measurements of water

    USGS Publications Warehouse

    Lorenz, Jennifer M.; Tarbox, Lauren V.; Buck, Bryan; Qi, Haiping; Coplen, Tyler B.

    2014-01-01

    RATIONALE As a result of the scarcity of isotopic reference waters for daily use, a new secondary isotopic reference material for international distribution has been prepared from drinking water collected from the Biscayne aquifer in Ft. Lauderdale, Florida. METHODS This isotopic reference water was filtered, homogenized, loaded into glass ampoules, sealed with a torch, autoclaved to eliminate biological activity, and measured by dual-inlet isotope-ratio mass spectrometry. This reference material is available by the case of 144 glass ampoules containing either 4 mL or 5 mL of water in each ampoule. RESULTS The δ2H and δ18O values of this reference material are –10.3 ± 0.4 ‰ and –2.238 ± 0.011 ‰, respectively, relative to VSMOW, on scales normalized such that the δ2H and δ18O values of SLAP reference water are, respectively, –428 and –55.5 ‰. Each uncertainty is an estimated expanded uncertainty (U = 2uc) about the reference value that provides an interval that has about a 95 % probability of encompassing the true value. CONCLUSIONS This isotopic reference material, designated as USGS45, is intended as one of two isotopic reference waters for daily normalization of stable hydrogen and oxygen isotopic analysis of water with an isotope-ratio mass spectrometer or a laser absorption spectrometer. 

  11. PRECISE THz MEASUREMENTS OF HCO{sup +}, N{sub 2}H{sup +}, AND CF{sup +} FOR ASTROPHYSICAL OBSERVATIONS

    SciTech Connect

    Cazzoli, Gabriele; Cludi, Lino; Puzzarini, Cristina; Buffa, Giovanni

    2012-11-15

    Ground-state rotational spectra of HCO{sup +}, N{sub 2}H{sup +}, and CF{sup +} (both {sup 12}C- and {sup 13}C-containing isotopologues) have been recorded in the 1.0-1.6 THz frequency range. Present measurements allowed us to improve the spectroscopic parameters, which in turn enabled the prediction of rotational transitions up to 2.0-2.5 THz with good accuracy. We therefore consider the present results to be of great value in view of the extended spectral coverage made available by the Herschel Space Observatory, Stratospheric Observatory for Infrared Astronomy, and the Atacama Large Millimeter Array. Furthermore, we re-investigated the ground-state rotational spectrum of N{sub 2}H{sup +} in the 93-750 GHz frequency range, thus addressing the open issue of the frequency of the J = 1 <- 0 transition as well as resolving the hyperfine structure of the J + 1 <- J transitions with J = 1, 2, and 3 for the first time.

  12. Measuring variations of δ18O and δ2H in atmospheric water vapour using two commercial laser-based spectrometers: an instrument characterisation study

    NASA Astrophysics Data System (ADS)

    Aemisegger, F.; Sturm, P.; Graf, P.; Sodemann, H.; Pfahl, S.; Knohl, A.; Wernli, H.

    2012-07-01

    Variations of stable water isotopes in water vapour have become measurable at a measurement frequency of about 1 Hz in recent years using novel laser spectroscopic techniques. This enables us to perform continuous measurements for process-based investigations of the atmospheric water cycle at the time scales relevant for synoptic and mesoscale meteorology. An important prerequisite for the interpretation of data from automated field measurements lasting for several weeks or months is a detailed knowledge about instrument properties and the sources of measurement uncertainty. We present here a comprehensive characterisation and comparison study of two commercial laser spectroscopic systems based on cavity ring-down spectroscopy (Picarro) and off-axis integrated cavity output spectroscopy (Los Gatos Research). The uncertainty components of the measurements were first assessed in laboratory experiments, focussing on the effects of (i) water vapour mixing ratio, (ii) measurement stability, (iii) uncertainties due to calibration and (iv) response times of the isotope measurements due to adsorption-desorption processes on the tubing and measurement cavity walls. Based on the experience from our laboratory experiments, we set up a one-week field campaign for comparing measurements of the ambient isotope signals from the two laser spectroscopic systems. The optimal calibration strategy determined for both instruments was applied as well as the correction functions for water vapour mixing ratio effects. The root mean square difference between the isotope signals from the two instruments during the field deployment was 2.3‰ for δ2H, 0.5‰ for δ18O and 3.1‰ for deuterium excess. These uncertainty estimates from field measurements compare well to those found in the laboratory experiments. The present quality of measurements from laser spectroscopic instruments combined with a calibration system opens new possibilities for investigating the atmospheric water cycle and

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

    USGS Publications Warehouse

    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.

  14. Discriminating between Lüders and von Neumann measuring devices: An NMR investigation

    NASA Astrophysics Data System (ADS)

    Sudheer Kumar, C. S.; Shukla, Abhishek; Mahesh, T. S.

    2016-10-01

    Quantum state after measuring a degenerate observable is given by Lüders and von Neumann state update rules. While the former preserves superpositions, the latter does not. Even though both rules are valid and realizable, which rule a given measuring device ("Black Box") obeys, depends on its internal details. Recently Hegerfeldt and Mayato (2012) [5] had formulated a protocol to discriminate between the two kinds of measuring devices. Here we have reformulated this protocol for system and measuring qubits. We then experimentally investigated this protocol on an NMR spectrometer, and found that Lüders rule is favoured.

  15. Measuring fast variations of δ^{18}O and δ^2H in atmospheric water vapour using laser spectroscopy: an instrument inter-comparison and characterisation study

    NASA Astrophysics Data System (ADS)

    Aemisegger, F.; Sturm, P.; Graf, P.; Sodemann, H.; Pfahl, S.; Knohl, A.; Wernli, H.

    2012-04-01

    Fast variations of stable water isotopes in water vapour have become measurable lately using novel laser spectroscopic techniques. This allows us to perform process-based investigations of the atmospheric water cycle at the time scales of significant weather events. An important prerequisite for such studies implying automatic field measurements lasting for several weeks or even months is a detailed knowledge about sources of uncertainty and instrument properties. We present a comprehensive characterisation and comparison study of two commercial laser spectroscopic systems based on cavity ring-down spectroscopy (Picarro) and off-axis integrated cavity output spectroscopy (Los Gatos Resarch). The old versions (L1115-i, WVIA) and the new versions (L2130-i, WVIA-EP) of both systems were tested. The uncertainty components of the measurements were assessed in laboratory experiments, focussing on effects of (i) water vapour mixing ratio, (ii) measurement stability, (iii) uncertainties due to calibration and (iv) response times of the isotope measurements due to adsorption-desorption processes on the tubing and measurement cavity walls. Knowledge from our laboratory experiments was used to setup a one-week field campaign for comparing measurements of the ambient isotope signals from the L1115-i and WVIA systems. The optimal calibration strategy determined for both instruments was applied as well as the correction functions for water vapour mixing ratio effects. Using this field measurement data we address the question of how well the deuterium excess (d=δ2H-8δ18O) of atmospheric water vapour can be determined with laser spectroscopy. The deuterium excess is an interesting parameter for process-based atmospheric water cycle studies, which depends on humidity and temperature conditions at source location of water vapour. Up to now only very few high-time-resolution measurements of deuterium excess exist. Our concurrent measurements of atmospheric isotopes in water vapour

  16. Measurements of heavy-atom isotope effects using 1H NMR spectroscopy.

    PubMed

    Pabis, Anna; Kamiński, Rafał; Ciepielowski, Grzegorz; Jankowski, Stefan; Paneth, Piotr

    2011-10-01

    A novel method for measuring heavy-atom KIEs for magnetically active isotopes using (1)H NMR is presented. It takes advantage of the resonance split of the protons coupled with the heavy atom in the (1)H spectrum. The method is validated by the example of the (13)C-KIE on the hydroamination of styrene with aniline, catalyzed by phosphine-ligated palladium triflates.

  17. An improved technique for computing permeability from NMR measurements in mudstones

    NASA Astrophysics Data System (ADS)

    Daigle, Hugh; Dugan, Brandon

    2011-08-01

    We develop a technique for extending nuclear magnetic resonance (NMR) permeability estimation to clay-rich sediments. Our technique builds on the Schlumberger-Doll Research (SDR) equation by using porosity, grain size, specific surface, and magnetic susceptibility data to yield more accurate permeability estimation in mudstones with large pore surface areas and complex mineralogies. Based on measurements of natural sediments as well as resedimented laboratory mixtures of silica, bentonite, and kaolinite powders, we find that our method predicts permeability values that match measured values over four orders of magnitude and among lithologies that vary widely in grain size, mineralogy, and surface area. Our results show that the relationship between NMR data and permeability is a function of mineralogy and grain geometry, and that permeability predictions in clay-rich sediments can be improved with insights regarding the nature of the pore system made by the Kozeny theory. This technique extends the utility of NMR measurements beyond typical reservoir-quality rocks to a wide range of lithologies.

  18. Using NMR, SIP, and MS measurements for monitoring subsurface biogeochemical reactions at the Rifle IFRC site

    NASA Astrophysics Data System (ADS)

    Rosier, C. L.; Keating, K.; Williams, K. H.; Robbins, M.; Ntarlagiannis, D.; Grunewald, E.; Walsh, D. O.

    2013-12-01

    The Rifle Integrated Field Research Challenge (IFRC) site is located on a former uranium ore-processing facility in Rifle, Colorado (USA). Although removal of tailings and contaminated surface materials was completed in 1996, residual uranium contamination of groundwater and subsurface sediments remains. Since 2002, research at the site has primarily focused on quantifying uranium mobility associated with stimulated and natural biogeochemical processes. Uranium mobility at the Rifle IFRC site is typically quantified through direct sampling of groundwater; however, direct sampling does not provide information about the solid phase material outside of the borehole and continuous measurements are not always possible due to multiple constraints. Geophysical methods have been suggested as a minimally invasive alternative approach for long term monitoring of biogeochemical reactions associated with uranium remediation. In this study, nuclear magnetic resonance (NMR), spectral induced polarization (SIP), and magnetic susceptibility (MS) are considered as potential geophysical methods for monitoring the biogeochemical reactions occurring at the Rifle IFRC site. Additionally, a pilot field study using an NMR borehole-logging tool was carried out at the Rifle IFRC site. These methods are sensitive to changes in the chemical and physical subsurface properties that occur as a result of bioremediation efforts; specifically, changes in the redox state and chemical form of iron, production of iron sulfide minerals, production of the magnetic mineral magnetite, and associated changes in the pore geometry. Laboratory experiments consisted of monitoring changes in the NMR, SIP and MS response of an acetate-amended columns packed with sediments from the Rifle IFRC site over the course of two months. The MS values remained relatively stable throughout the course of the experiment suggesting negligible production of magnetic phases (e.g. magnetite, pyrrhotite) as a result of enhanced

  19. FieldSpec: A field portable mass spectrometer prototype for high frequency measurements of δ (2) H and δ (18) O ratios in water

    NASA Astrophysics Data System (ADS)

    López Días, Veneranda; Quang Hoang, Hung; Martínez-Carreras, Núria; Barnich, François; Wirtz, Tom; Pfister, Laurent; McDonnell, Jeffrey

    2016-04-01

    Hydrological studies relying on stable water isotopes to better understand water sources, flowpaths and transit times are currently limited by the coarse temporal resolution of sampling and analysis protocols. At present, two kinds of lab-based instruments are used : (i) the standard isotope ratio mass spectrometers (IRMS) [1] and (ii) the laser-based instruments [2, 3]. In both cases, samples need to be collected in the field and then transferred to the laboratory for the water isotopic ratio measurements (even further complex sample preparation is required for the IRMS). Hence, past and ongoing research targets the development of field deployable instruments for measuring stable water isotopes at high temporal frequencies. While recent studies have demonstrated that laser-based instruments may be taken to the field [4, 5], their size and power consumption still restrict their use to sites equipped with mains power or generators. Here, we present progress on the development of a field portable mass spectrometer (FieldSpec) for direct high frequency measurements of δ2H and δ18O ratios in water. The FieldSpec instrument is based upon the use of a double focusing magnetic sector mass spectrometer in combination with an electron impact ion source and a membrane dual inlet system. The instrument directly collects liquid water samples in the field, which are then converted into water vapour before being injected into the mass spectrometer for the stable isotope analysis. δ2H and δ18O are derived from the measured mass spectra. All the components are arranged in a vacuum case having a suit case type dimension with portable electronics and battery. Proof-of-concept experiments have been carried out to characterize the instrument. The results show that the FieldSpec instrument has good linearity (R2 = 0.99). The reproducibility of the instrument ranges between 1 and 4 ‰ for δ2H and between 0.1 and 0.4 ‰ for δ18O isotopic ratio measurements. A measurement

  20. A portable single-sided magnet system for remote NMR measurements of pulmonary function

    PubMed Central

    Mikayel, Dabaghyan; Iga, Muradyan; James, Butler; Eric, Frederick; Feng, Zhou; Angelos, Kyriazis; Charles, Hardin; Samuel, Patz; Mirko, Hrovat

    2014-01-01

    In this work, we report initial results from a light-weight, low field magnetic resonance device designed to make relative pulmonary density measurements at the bedside. The development of this device necessarily involves special considerations for the magnet, RF and data acquisition schemes as well as a careful analysis of what is needed to provide useful information in the ICU. A homogeneous field region is created remotely from the surface of the magnet such that when the magnet is placed against the chest, an NMR signal is measured from a small volume in the lung. In order to achieve portability, one must trade off field strength and therefore spatial resolution. We report initial measurements from a ping-pong ball size region in the lung as a function of lung volume. As expected, we measured decreased signal at larger lung volumes since lung density decreases with increasing lung volume. Using a CPMG sequence with ΔTE=3.5 ms and a 20 echo train, a signal to noise ratio ~1100 was obtained from an 8.8mT planar magnet after signal averaging for 43 s. This is the first demonstration of NMR measurements made on a human lung with a light-weight planar NMR device. We argue that very low spatial resolution measurements of different lobar lung regions will provide useful diagnostic information for clinicians treating Acute Respiratory Distress Syndrome as clinicians want to avoid ventilator pressures that cause either lung over distension (too much pressure) or lung collapse (too little pressure). PMID:24953556

  1. Fractional order analysis of Sephadex gel structures: NMR measurements reflecting anomalous diffusion

    NASA Astrophysics Data System (ADS)

    Magin, Richard L.; Akpa, Belinda S.; Neuberger, Thomas; Webb, Andrew G.

    2011-12-01

    We report the appearance of anomalous water diffusion in hydrophilic Sephadex gels observed using pulse field gradient (PFG) nuclear magnetic resonance (NMR). The NMR diffusion data was collected using a Varian 14.1 Tesla imaging system with a home-built RF saddle coil. A fractional order analysis of the data was used to characterize heterogeneity in the gels for the dynamics of water diffusion in this restricted environment. Several recent studies of anomalous diffusion have used the stretched exponential function to model the decay of the NMR signal, i.e., exp[-( bD) α], where D is the apparent diffusion constant, b is determined the experimental conditions (gradient pulse separation, durations and strength), and α is a measure of structural complexity. In this work, we consider a different case where the spatial Laplacian in the Bloch-Torrey equation is generalized to a fractional order model of diffusivity via a complexity parameter, β, a space constant, μ, and a diffusion coefficient, D. This treatment reverts to the classical result for the integer order case. The fractional order decay model was fit to the diffusion-weighted signal attenuation for a range of b-values (0 < b < 4000 s mm -2). Throughout this range of b values, the parameters β, μ and D, were found to correlate with the porosity and tortuosity of the gel structure.

  2. Mechanism of decreased NMR-measured free magnesium in stored erythrocytes

    SciTech Connect

    Bock, J.L.; Wenz, B.; Gupta, R.K.

    1986-05-01

    P-31 NMR spectra of ebythrocytes stored with standard preservation media (ACD or CPDA-1) show a progressive upfield shift of the ..beta..P resonance of ATP. This would seem to indicate lower Mg-saturation of ATP and hence lower intracellular free magnesium (Mg/sub i/), but total intracellular Mg measured by AAS does not change. The authors have now observed similar spectral changes in erythrocytes stored in citrate-free media, hence the shifts are not an effect of citrate. Acidifying fresh blood to mimic the pH changes that occur with storage did not induce comparable shifts, nor did treatment of fresh blood with gramicidin, which causes Na/K redistribution across the erythrocyte membrane similar to that occurring with storage. The shifts were largely reversed when stored cells were incubated at 37/sup 0/C for 1 hr with fresh citrated or heparinized plasma. Such incubation also increased ATP levels but did not increased 2,3-DPG, hence the shifts do not depend on disappearance of 2,3-DPG. P-31 NMR of acid extracts of stored cells show accumulation of some pyrophosphate, but probably not enough to account for the large apparent decreased in Mg/sub i/. The NMR estimation of decreased Mg/sub i/ in stored blood does not appear to be an artifact related to alterations in monovalent cations or in binding of ligands to hemoglobin. A possible mechanism is increased binding of Mg to the cell membrane.

  3. Noninvasive measurements of glycogen in perfused mouse livers using chemical exchange saturation transfer NMR and comparison to (13)C NMR spectroscopy.

    PubMed

    Miller, Corin O; Cao, Jin; Chekmenev, Eduard Y; Damon, Bruce M; Cherrington, Alan D; Gore, John C

    2015-06-01

    Liver glycogen represents an important physiological form of energy storage. It plays a key role in the regulation of blood glucose concentrations, and dysregulations in hepatic glycogen metabolism are linked to many diseases including diabetes and insulin resistance. In this work, we develop, optimize, and validate a noninvasive protocol to measure glycogen levels in isolated perfused mouse livers using chemical exchange saturation transfer (CEST) NMR spectroscopy. Model glycogen solutions were used to determine optimal saturation pulse parameters which were then applied to intact perfused mouse livers of varying glycogen content. Glycogen measurements from serially acquired CEST Z-spectra of livers were compared with measurements from interleaved natural abundance (13)C NMR spectra. Experimental data revealed that CEST-based glycogen measurements were highly correlated with (13)C NMR glycogen spectra. Monte Carlo simulations were then used to investigate the inherent (i.e., signal-to-noise-based) errors in the quantification of glycogen with each technique. This revealed that CEST was intrinsically more precise than (13)C NMR, although in practice may be prone to other errors induced by variations in experimental conditions. We also observed that the CEST signal from glycogen in liver was significantly less than that observed from identical amounts in solution. Our results demonstrate that CEST provides an accurate, precise, and readily accessible method to noninvasively measure liver glycogen levels and their changes. Furthermore, this technique can be used to map glycogen distributions via conventional proton magnetic resonance imaging, a capability universally available on clinical and preclinical magnetic resonance imaging (MRI) scanners vs (13)C detection, which is limited to a small fraction of clinical-scale MRI scanners. PMID:25946616

  4. Noninvasive measurements of glycogen in perfused mouse livers using chemical exchange saturation transfer NMR and comparison to (13)C NMR spectroscopy.

    PubMed

    Miller, Corin O; Cao, Jin; Chekmenev, Eduard Y; Damon, Bruce M; Cherrington, Alan D; Gore, John C

    2015-06-01

    Liver glycogen represents an important physiological form of energy storage. It plays a key role in the regulation of blood glucose concentrations, and dysregulations in hepatic glycogen metabolism are linked to many diseases including diabetes and insulin resistance. In this work, we develop, optimize, and validate a noninvasive protocol to measure glycogen levels in isolated perfused mouse livers using chemical exchange saturation transfer (CEST) NMR spectroscopy. Model glycogen solutions were used to determine optimal saturation pulse parameters which were then applied to intact perfused mouse livers of varying glycogen content. Glycogen measurements from serially acquired CEST Z-spectra of livers were compared with measurements from interleaved natural abundance (13)C NMR spectra. Experimental data revealed that CEST-based glycogen measurements were highly correlated with (13)C NMR glycogen spectra. Monte Carlo simulations were then used to investigate the inherent (i.e., signal-to-noise-based) errors in the quantification of glycogen with each technique. This revealed that CEST was intrinsically more precise than (13)C NMR, although in practice may be prone to other errors induced by variations in experimental conditions. We also observed that the CEST signal from glycogen in liver was significantly less than that observed from identical amounts in solution. Our results demonstrate that CEST provides an accurate, precise, and readily accessible method to noninvasively measure liver glycogen levels and their changes. Furthermore, this technique can be used to map glycogen distributions via conventional proton magnetic resonance imaging, a capability universally available on clinical and preclinical magnetic resonance imaging (MRI) scanners vs (13)C detection, which is limited to a small fraction of clinical-scale MRI scanners.

  5. Measurement of Whole-Body CO2 Production in Birds Using Real-Time Laser-Derived Measurements of Hydrogen (δ(2)H) and Oxygen (δ(18)O) Isotope Concentrations in Water Vapor from Breath.

    PubMed

    Mitchell, G W; Guglielmo, C G; Hobson, K A

    2015-01-01

    The doubly labeled water (DLW) method is commonly used to measure energy expenditure in free-living wildlife and humans. However, DLW studies involving animals typically require three blood samples, which can affect behavior and well-being. Moreover, measurement of H (δ(2)H) and O (δ(18)O) isotope concentrations in H2O derived from blood using conventional isotope ratio mass spectrometry is technically demanding, time-consuming, and often expensive. A novel technique that would avoid these constraints is the real-time measurement of δ(2)H and δ(18)O in the H2O vapor of exhaled breath using cavity ring-down (CRD) spectrometry, provided that δ(2)H and δ(18)O from body H2O and breath were well correlated. Here, we conducted a validation study with CRD spectrometry involving five zebra finches (Taeniopygia guttata), five brown-headed cowbirds (Molothrus ater), and five European starlings (Sturnus vulgaris), where we compared δ(2)H, δ(18)O, and rCO2 (rate of CO2 production) estimates from breath with those from blood. Isotope concentrations from blood were validated by comparing dilution-space estimates with measurements of total body water (TBW) obtained from quantitative magnetic resonance. Isotope dilution-space estimates from δ(2)H and δ(18)O values in the blood were similar to and strongly correlated with TBW measurements (R(2) = 0.99). The (2)H and (18)O (ppm) in breath and blood were also highly correlated (R(2) = 0.99 and 0.98, respectively); however, isotope concentrations in breath were always less enriched than those in blood and slightly higher than expected, given assumed fractionation values between blood and breath. Overall, rCO2 measurements from breath were strongly correlated with those from the blood (R(2) = 0.90). We suggest that this technique will find wide application in studies of animal and human energetics in the field and laboratory. We also provide suggestions for ways this technique could be further improved.

  6. Measurement and Quantification of Heterogeneity, Flow, and Mass Transfer in Porous Media Using NMR Low-Field Techiques

    NASA Astrophysics Data System (ADS)

    Paciok, E.; Olaru, A. M.; Haber, A.; van Landeghem, M.; Haber-Pohlmeier, S.; Sucre, O. E.; Perlo, J.; Casanova, F.; Blümich, B.; RWTH Aachen Mobile Low-Field NMR

    2011-12-01

    Nuclear magnetic resonance (NMR) is renowned for its unique potential to both reveal and correlate spectroscopic, relaxometric, spatial and dynamic properties in a large variety of organic and inorganic systems. NMR has no restrictions regarding sample opacity and is an entirely non-invasive method, which makes it the ideal tool for the investigation of porous media. However, for years NMR research of soils was limited by the use of high-field NMR devices, which necessitated elaborate NMR experiments and were not applicable to bulky samples or on-site field measurements. The evolution of low-field NMR devices during the past 20 years has brought forth portable, small-scale NMR systems with open and closed magnet arrangements specialized to specific NMR applications. In combination with recent advances in 2D-NMR Laplace methodology [1], low-field NMR has opened up the possibility to study real-life microporous systems ranging from granular media to natural soils and oil well boreholes. Thus, information becomes available, which before has not been accessible with high-field NMR. In this work, we present our recent progress in mobile low-field NMR probe design for field measurements of natural soils: a slim-line logging tool, which can be rammed into the soil of interest on-site. The performance of the device is demonstrated in measurements of moisture profiles of model soils [2] and field measurements of relaxometric properties and moisture profiles of natural soils [3]. Moreover, an improved concept of the slim-line logging tool is shown, with a higher excitation volume and a better signal-to-noise due to an improved coil design. Furthermore, we present our recent results in 2D exchange relaxometry and simulation. These include relaxation-relaxation experiments on natural soils with varying degree of moisture saturation, where we could draw a connection between the relaxometric properties of the soil to its pore size-related diffusivity and to its clay content

  7. Optimized slim-line logging NMR tool to measure soil moisture in situ

    NASA Astrophysics Data System (ADS)

    Perlo, Josefina; Danieli, Ernesto; Perlo, Juan; Blümich, Bernhard; Casanova, Federico

    2013-08-01

    We report the optimization of a slim-line logging NMR tool carried out by maximizing the signal-to-noise ratio of the NMR measurements. The tool, based on cylindrical permanent magnets of 20 cm length and 5 cm diameter, has a penetration depth of about 2 cm measured from its surface. This is obtained thanks to a large radio frequency coil whose dimensions are comparable to the sensor size. An analytical expression of the SNR as a function of parameters which take into account the interaction between the radio frequency coil and the magnet shielding is developed. In view of the external constrains such as the one imposed by the excavation hole, a proper tool size is determined in the optimization process. Due to its size and properties, the sensor is suitable to measure water content in the vadose zone, which is the zone comprised within the first meters of the Earth surface and whose study is important for improving water management in agriculture and for refining climate models.

  8. Optimized slim-line logging NMR tool to measure soil moisture in situ.

    PubMed

    Perlo, Josefina; Danieli, Ernesto; Perlo, Juan; Blümich, Bernhard; Casanova, Federico

    2013-08-01

    We report the optimization of a slim-line logging NMR tool carried out by maximizing the signal-to-noise ratio of the NMR measurements. The tool, based on cylindrical permanent magnets of 20 cm length and 5 cm diameter, has a penetration depth of about 2 cm measured from its surface. This is obtained thanks to a large radio frequency coil whose dimensions are comparable to the sensor size. An analytical expression of the SNR as a function of parameters which take into account the interaction between the radio frequency coil and the magnet shielding is developed. In view of the external constrains such as the one imposed by the excavation hole, a proper tool size is determined in the optimization process. Due to its size and properties, the sensor is suitable to measure water content in the vadose zone, which is the zone comprised within the first meters of the Earth surface and whose study is important for improving water management in agriculture and for refining climate models.

  9. Magnetism in CeRhIn5 at high fields measured by NMR

    NASA Astrophysics Data System (ADS)

    Mounce, A. M.; Ronning, F.; Bauer, E. D.; Thompson, J. D.; Reyes, A. P.; Kuhns, P. L.

    2015-03-01

    De Haas-van Alphen measurements of CeRhIn5 at ambient pressure show an abrupt change in the Fermi surface volume at high fields, H* ~ 30 T, and low temperatures resulting in antiferromagnetic phases with a small Fermi surface at fields below H* and a large Fermi surface at fields H such that H* < H < 50 T. Nuclear magnetic resonance (NMR) is the ideal probe for these magnetic states as the microscopic details are still lacking. Our preliminary NMR measurements find the magnetic order for H ∥ c is incommensurate up to 30 T as opposed to H ⊥ c which transitions from incommensurate to commensurate at H ~ 2 T. Furthermore, we find that the magnetic moment decreases near 17 T for H ∥ c . These measurements provide an insight into the magnetic anisotropy of CeRhIn5 and are a crucial step to studying its high field phases. Work at Los Alamos was performed under the auspices of the U.S. DOE, Office of Basic Energy Science, Division of Materials and Engineering.

  10. High-resolution 2D NMR spectroscopy of bicelles to measure the membrane interaction of ligands.

    PubMed

    Dvinskikh, Sergey V; Dürr, Ulrich H N; Yamamoto, Kazutoshi; Ramamoorthy, Ayyalusamy

    2007-01-31

    Magnetically aligned bicelles are increasingly being used as model membranes in solution- and solid-state NMR studies of the structure, dynamics, topology, and interaction of membrane-associated peptides and proteins. These studies commonly utilize the PISEMA pulse sequence to measure dipolar coupling and chemical shift, the two key parameters used in subsequent structural analysis. In the present study, we demonstrate that the PISEMA and other rotating-frame pulse sequences are not suitable for the measurement of long-range heteronuclear dipolar couplings, and that they provide inaccurate values when multiple protons are coupled to a 13C nucleus. Furthermore, we demonstrate that a laboratory-frame separated-local-field experiment is capable of overcoming these difficulties in magnetically aligned bicelles. An extension of this approach to accurately measure 13C-31P and 1H-31P couplings from phospholipids, which are useful to understand the interaction of molecules with the membrane, is also described. In these 2D experiments, natural abundance 13C was observed from bicelles containing DMPC and DHPC lipid molecules. As a first application, these solid-state NMR approaches were utilized to probe the membrane interaction of an antidepressant molecule, desipramine, and its location in the membrane.

  11. Solid-State NMR Study of Paramagnetic Bis(alaninato-κ(2)N,O)copper(II) and Bis(1-amino(cyclo)alkane-1-carboxylato-κ(2)N,O)copper(II) Complexes: Reflection of Stereoisomerism and Molecular Mobility in (13)C and (2)H Fast Magic Angle Spinning Spectra.

    PubMed

    Szalontai, Gábor; Csonka, Róbert; Speier, Gábor; Kaizer, József; Sabolović, Jasmina

    2015-05-18

    Solid-state stereochemistry and mobility of paramagnetic copper(II) complexes formed by aliphatic amino acids (l-alanine, d,l-alanine, 1-amino-2-methyl-alanine) and 1-amino(cyclo)alkane-1-carboxylic acids (alkane = propane, butane, pentane, hexane) as bidentate ligands has been studied by (13)C and (2)H solid-state fast magic angle spinning (MAS) NMR spectroscopy. We examined the prospective method to characterize solid-state paramagnetic compounds in a routine way. Both (13)C and (2)H MAS spectra can distinguish d,l and l,l diastereomers of natural and polydeuterated bis([Dn]alaninato)copper(II) (n = 0, 2, 8) complexes with axial and/or equatorial methyl positions (conformations) primarily due to different Fermi-contact (FC) contributions. The three-bond hyperfine couplings clearly show Karplus-like dependence on the torsional angles which turned out to be a useful assignment aid. Density functional theory calculations of the FC term and crystal structures were also used to aid the final assignments. The correlations obtained for bis(alaninato-κ(2)N,O)copper(II) complexes were successfully used to characterize other complexes. The usefulness of the (2)H MAS spectra of the deuterated complexes was underlined. Even the spectra of the easily exchangeable amine protons contained essential stereochemical information. In the case of a dimer structure of bis(1-aminohexane-1-carboxylato-κ(2)N,O)copper(II) both the (13)C and (2)H resolutions were good enough to confirm the presence of the cis and trans forms in the asymmetric unit. With regard to the internal solid-state motions in the crystal lattice, the obtained quadrupolar tensor parameters were similar for the d,l- and l,l-alaninato isomers and also for the cis-trans forms suggesting similar crystal packing effects, static amine deuterons involved in hydrogen bonding, and fast rotating methyl groups.

  12. Deuterium incorporation in biomass cell wall components by NMR analysis

    SciTech Connect

    Foston, Marcus B; McGaughey, Joseph; O'Neill, Hugh Michael; Evans, Barbara R; Ragauskas, Arthur J

    2012-01-01

    A commercially available deuterated kale sample was analyzed for deuterium incorporation by ionic liquid solution 2H and 1H nuclear magnetic resonance (NMR). This protocol was found to effectively measure the percent deuterium incorporation at 33%, comparable to the 31% value determined by combustion. The solution NMR technique also suggested by a qualitative analysis that deuterium is preferentially incorporated into the carbohydrate components of the kale sample.

  13. Accurate absolute reference frequencies from 1511 to 1545 nm of the {nu}{sub 1}+{nu}{sub 3} band of {sup 12}C{sub 2}H{sub 2} determined with laser frequency comb interval measurements

    SciTech Connect

    Madej, Alan A.; Alcock, A. John; Czajkowski, Andrzej; Bernard, John E.; Chepurov, Sergei

    2006-10-15

    Absolute frequency measurements, with uncertainties as low as 2 kHz (1x10{sup -11}), are presented for the {nu}{sub 1}+{nu}{sub 3} band of {sup 12}C{sub 2}H{sub 2} at 1.5 {mu}m (194-198 THz). The measurements were made using cavity-enhanced, diode-laser-based saturation spectroscopy. With one laser system stabilized to the P(16) line of {sup 13}C{sub 2}H{sub 2} and a system stabilized to the line in {sup 12}C{sub 2}H{sub 2} whose frequency was to be determined, a Cr:YAG laser-based frequency comb was employed to measure the frequency intervals. The systematic uncertainty is notably reduced relative to that of previous studies, and the region of measured lines has been extended. Improved molecular constants are obtained.

  14. Measuring JHH values with a selective constant-time 2D NMR protocol

    NASA Astrophysics Data System (ADS)

    Lin, Liangjie; Wei, Zhiliang; Lin, Yanqin; Chen, Zhong

    2016-11-01

    Proton-proton scalar couplings play important roles in molecule structure elucidation. However, measurements of JHH values in complex coupled spin systems remain challenging. In this study, we develop a selective constant-time (SECT) 2D NMR protocol with which scalar coupling networks involving chosen protons can be revealed, and corresponding JHH values can be measured through doublets along the F1 dimension. All JHH values within a network of n fully coupled protons can be separately determined with (n - 1) SECT experiments. Additionally, the proposed pulse sequence possesses satisfactory sensitivity and handy implementation. Therefore, it will interest scientists who intend to address structural analyzes of molecules with overcrowded spectra, and may greatly facilitate the applications of scalar-coupling constants in molecule structure studies.

  15. On the noninvasive measurement of intracellular free magnesium by 31P NMR spectroscopy.

    PubMed

    Gupta, R K; Gupta, P; Yushok, W D; Rose, Z B

    1983-01-01

    We previously introduced a noninvasive measurement of the concentration of free Mg2+ in intact cells and tissues using 31P NMR. To resolve a controversy in the literature concerning the affinity of Mg2+ for ATP used in our procedure, the apparent dissociation constant of MgATP under simulated intracellular conditions has been determined by three independent magnetic resonance methods, including a newly developed combination procedure for determining this value at intracellular ATP levels. The new combination method, which utilizes 31P NMR to determine the degree of Mg2+ chelation of ATP and the dye antipyrylazo III for optical determination of free Mg2+, yielded a value of (50 +/- 10) microM for this apparent dissociation constant at pH 7.2 in the presence of 0.15 M K+ and 25 degrees C. We further show that hydroxyquinolines are not satisfactory indicators for optical determination of the Mg2+-nucleotide dissociation constant. From our determinations a low value of free Mg2+ (less than 1 mM) is established for all of the tissues studied, including perfused heart muscle, contrary to a recent report in the literature. Saturating human erythrocytes with Mg2+ results in an alpha- and beta-phosphorus resonance separation for intracellular ATP that is indistinguishable from that observed in a noncellular MgATP control under similar conditions, showing that MgATP resonances in this cell are unaffected by the cellular environment.

  16. 1H-NMR measurements of proton mobility in nano-crystalline YSZ.

    PubMed

    Hinterberg, Judith; Adams, Alina; Blümich, Bernhard; Heitjans, Paul; Kim, Sangtae; Munir, Zuhair A; Martin, Manfred

    2013-12-01

    We report nuclear magnetic resonance (NMR) results on water saturated, dense, nano-crystalline YSZ samples (9.5 mol% yttria doped zirconia) which exhibit proton conductivity at temperatures as low as room temperature. (1)H-NMR spectra recorded under static and magic angle spinning conditions show two distinct signals. Their temperature-dependent behavior and their linewidths suggest that one can be attributed to (free) water adsorbed on the surface of the sample and the other one to mobile protons within the sample. This interpretation is supported by comparison with measurements on a single-crystalline sample. For the nano-crystalline samples motional narrowing is observed for the signal originating from protons in the sample interior. For these protons, the analysis of temperature and field dependent spin-lattice relaxation time T1 points towards diffusion in a confined two-dimensional geometry. We attribute this quasi two-dimensional motion to protons that are mobile along internal interfaces or nanopores of nano-crystalline YSZ.

  17. O-tert-Butyltyrosine, an NMR tag for high-molecular-weight systems and measurements of submicromolar ligand binding affinities.

    PubMed

    Chen, Wan-Na; Kuppan, Kekini Vahini; Lee, Michael David; Jaudzems, Kristaps; Huber, Thomas; Otting, Gottfried

    2015-04-01

    O-tert-Butyltyrosine (Tby) is an unnatural amino acid that can be site-specifically incorporated into proteins using established orthogonal aminoacyl-tRNA synthetase/tRNA systems. Here we show that the tert-butyl group presents an outstanding NMR tag that can readily be observed in one-dimensional (1)H NMR spectra without any isotope labeling. Owing to rapid bond rotations and the chemical equivalence of the protons of a solvent-exposed tert-butyl group from Tby, the singlet resonance from the tert-butyl group generates an easily detectable narrow signal in a spectral region with limited overlap with other methyl resonances. The potential of the tert-butyl (1)H NMR signal in protein research is illustrated by the observation and assignment of two resonances in the Bacillus stearothermophilus DnaB hexamer (320 kDa), demonstrating that this protein preferentially assumes a 3-fold rather than 6-fold symmetry in solution, and by the quantitative measurement of the submicromolar dissociation constant Kd (0.2 μM) of the complex between glutamate and the Escherichia coli aspartate/glutamate binding protein (DEBP, 32 kDa). The outstanding signal height of the (1)H NMR signal of the Tby tert-butyl group allows Kd measurements using less concentrated protein solutions than usual, providing access to Kd values 1 order of magnitude lower than established NMR methods that employ direct protein detection for Kd measurements. PMID:25789794

  18. Measuring Residual Dipolar Couplings in Excited Conformational States of Nucleic Acids by CEST NMR Spectroscopy.

    PubMed

    Zhao, Bo; Zhang, Qi

    2015-10-28

    Nucleic acids undergo structural transitions to access sparsely populated and transiently lived conformational states--or excited conformational states--that play important roles in diverse biological processes. Despite ever-increasing detection of these functionally essential states, 3D structure determination of excited states (ESs) of RNA remains elusive. This is largely due to challenges in obtaining high-resolution structural constraints in these ESs by conventional structural biology approaches. Here, we present nucleic-acid-optimized chemical exchange saturation transfer (CEST) NMR spectroscopy for measuring residual dipolar couplings (RDCs), which provide unique long-range angular constraints in ESs of nucleic acids. We demonstrate these approaches on a fluoride riboswitch, where one-bond (13)C-(1)H RDCs from both base and sugar moieties provide direct structural probes into an ES of the ligand-free riboswitch.

  19. Direct measurement of brain glucose concentrations in humans by sup 13 C NMR spectroscopy

    SciTech Connect

    Gruetter, R.; Novotny, E.J.; Boulware, S.D.; Rothman, D.L.; Mason, G.F.; Shulman, G.I.; Shulan, R.G.; Tamborlane, W.V. )

    1992-02-01

    Glucose is the main fuel for energy metabolism in the normal human brain. It is generally assumed that glucose transport into the brain is not rate-limiting for metabolism. Since brain glucose concentrations cannot be determined directly by radiotracer techniques, the authors used {sup 13}C NMR spectroscopy after infusing enriched D-(1-{sup 13}C)glucose to measure brain glucose concentrations at euglycemia and at hyperglycemia in six healthy children. Brain glucose concentrations averaged 1.0 {plus minus} 0.1 {mu}mol/ml at euglycemia and 1.8-2.7 {mu}mol/ml at hyperglycemia. Michaelis-Menten parameters of transport were calculated from the relationship between plasma and brain glucose concentrations. The brain glucose concentrations and transport constants are consistent with transport not being rate-limiting for resting brain metabolism at plasma levels >3 mM.

  20. Dynamical theory of spin noise and relaxation: Prospects for real-time NMR measurements.

    PubMed

    Field, Timothy R

    2014-11-01

    Recent developments in theoretical aspects of spin noise and relaxation and their interrelationship reveal a modified spin density, distinct from the density matrix, as the necessary object to describe fluctuations in spin systems. These fluctuations are to be viewed as an intrinsic quantum mechanical property of such systems immersed in random magnetic environments and are observed as "spin noise" in the absence of any radio frequency excitation. With the prospect of ultrafast digitization, the role of spin noise in real-time parameter extraction for (NMR) spin systems, and the advantage over standard techniques, is of essential importance, especially for systems containing a small number of spins. In this article we outline prospects for harnessing the recent dynamical theory in terms of spin-noise measurement, with attention to real-time properties.

  1. The Effect of Inhomogeneous Sample Susceptibility on Measured Diffusion Anisotropy Using NMR Imaging

    NASA Astrophysics Data System (ADS)

    Trudeau, J. D.; Dixon, W. T.; Hawkins, J.

    1995-07-01

    Water diffusion measurements in white matter of freshly excised pig spinal cord and in parenchyma of fresh celery (excluding the fibers along the edge of the stalk) were performed using NMR at 200 MHz. In white matter of pig spinal cord, the measured diffusion coefficient is anisotropic and independent of sample orientation with respect to the magnetic field, In celery parenchyma, diffusion is isotropic and independent of orientation in the magnetic field when using a diffusion sequence that gives results independent of self-induced magnetic-held gradients. However, when the standard diffusion pulse sequence that gives results dependent upon self-induced magnetic-field gradients is used, diffusion in celery appears isotropic when the stalk is oriented parallel to the magnetic field but anisotropic when oriented perpendicular. Susceptibility variations leading to anisotropic self-induced magnetic-field gradients approximately 3 kHz/cm in magnitude when the celery is oriented perpendicular to the magnetic field can explain this apparent anisotropic diffusion. A study of the apparent diffusion coefficient (ADC) in celery as a function of diffusion times ranging from 8 to 22 ms indicates that the motion is at most only slightly restricted. Therefore, although the effect is not seen in all types of samples, one must be aware that self-induced gradients may affect the ADC and may cause isotropic diffusion to appear anisotropic. In addition, NMR experiments that change diffusion-sensitizing gradient timings to study restricted diffusion change the effects of the self-induced gradients as well as the effect of barriers on the ADC, complicating interpretation.

  2. Binding of phenol and differently halogenated phenols to dissolved humic matter as measured by NMR spectroscopy.

    PubMed

    Smejkalová, Daniela; Spaccini, Riccardo; Fontaine, Barbara; Piccolo, Alessandro

    2009-07-15

    1H- and 19F-NMR measurements of spin-lattice (T1) and spin-spin (T2) relaxationtimes and diffusion ordered spectroscopy (DOSY) were applied to investigate the association of nonsubstituted (phenol (P)) and halogen-substituted (2,4-dichlorophenol (DCP); 2,4,6-trichlorophenol (TCP), and 2,4,6-trifluorophenol (TFP) phenols with a dissolved humic acid (HA). T1 and T2 values for both 1H and 19F in phenols decreased with enhancing HA concentration, indicating reduction in molecular mobility due to formation of noncovalent interactions. Moreover, correlation times (tau c) for different hydrogen and fluorine atoms in phenols showed that anisotropic mobility turned into isotropic motion with HA additions. Changes in relaxation times suggested that DCP and TCP were more extensively bound to HA than P and TFP. This was confirmed by diffusion measurements which showed full association of DCP and TCP to a less amount of HA than that required for entire complexation of P and TFP. Calculated values of binding constants (Ka) reflected the overall NMR behavior, being significantly larger for DCP- and TCP-HA (10.04 +/- 1.32 and 4.47 +/- 0.35 M(-1), respectively) than for P- and TFP-HA complexes (0.57 +/- 0.03 and 0.28 +/- 0.01 M(-1), respectively). Binding increased with decreasing solution pH, thus indicating a dependence on the fraction of protonated form (alpha) of phenols in solution. However, it was found that the hydrophobicity conferred to phenols by chlorine atoms on aromatic rings is a stronger drive than alpha for the phenols repartition within the HA hydrophobic domains.

  3. Lithium ion diffusion in Li β-alumina single crystals measured by pulsed field gradient NMR spectroscopy

    SciTech Connect

    Chowdhury, Mohammed Tareque Takekawa, Reiji; Iwai, Yoshiki; Kuwata, Naoaki; Kawamura, Junichi

    2014-03-28

    The lithium ion diffusion coefficient of a 93% Li β-alumina single crystal was measured for the first time using pulsed field gradient (PFG) NMR spectroscopy with two different crystal orientations. The diffusion coefficient was found to be 1.2 × 10{sup −11} m{sup 2}/s in the direction perpendicular to the c axis at room temperature. The Li ion diffusion coefficient along the c axis direction was found to be very small (6.4 × 10{sup −13} m{sup 2}/s at 333 K), which suggests that the macroscopic diffusion of the Li ion in the β-alumina crystal is mainly two-dimensional. The diffusion coefficient for the same sample was also estimated using NMR line narrowing data and impedance measurements. The impedance data show reasonable agreement with PFG-NMR data, while the line narrowing measurements provided a lower value for the diffusion coefficient. Line narrowing measurements also provided a relatively low value for the activation energy and pre-exponential factor. The temperature dependent diffusion coefficient was obtained in the temperature range 297–333 K by PFG-NMR, from which the activation energy for diffusion of the Li ion was estimated. The activation energy obtained by PFG-NMR was smaller than that obtained by impedance measurements, which suggests that thermally activated defect formation energy exists for 93% Li β-alumina single crystals. The diffusion time dependence of the diffusion coefficient was observed for the Li ion in the 93% Li β-alumina single crystal by means of PFG-NMR experiments. Motion of Li ion in fractal dimension might be a possible explanation for the observed diffusion time dependence of the diffusion coefficient in the 93% Li β–alumina system.

  4. Ultrafast NMR T1 Relaxation Measurements: Probing Molecular Properties in Real Time

    PubMed Central

    Smith, Pieter E. S.; Donovan, Kevin J.; Szekely, Or; Baias, Maria; Frydman, Lucio

    2016-01-01

    The longitudinal relaxation properties of NMR active nuclei carry useful information about the site-specific chemical environments and about the mobility of molecular fragments. Molecular mobility is in turn a key parameter reporting both on stable properties like size, as well as on dynamic ones such as transient interactions and irreversible aggregation. In order to fully investigate the latter, a fast sampling of the relaxation parameters of transiently formed molecular species may be needed. Nevertheless, the acquisition of longitudinal relaxation data is typically slow, being limited by the requirement that the time for which the nucleus relaxes be varied incrementally until a complete build-up curve is generated. Recently a number of single-shot inversion recovery methods have been developed capable of alleviating this need; still, these may be challenged by either spectral resolution restrictions or when coping with very fast relaxing nuclei. Here we present a new experiment to measure the T1s of multiple nuclear spins that experience fast longitudinal relaxation, while retaining full high-resolution chemical shift information. Good agreement is observed between T1s measured with conventional means and T1s measured using the new technique. The method is applied to the real time investigation of the reaction between D-xylose and sodium borate, which is in turn elucidated with the aid of ancillary ultrafast and conventional 2D TOCSY measurements. PMID:23878001

  5. Measurement of Solution Viscosity via Diffusion-Ordered NMR Spectroscopy (DOSY)

    ERIC Educational Resources Information Center

    Li, Weibin; Kagan, Gerald; Hopson, Russell; Williard, Paul G.

    2011-01-01

    Increasingly, the undergraduate chemistry curriculum includes nuclear magnetic resonance (NMR) spectroscopy. Advanced NMR techniques are often taught including two-dimensional gradient-based experiments. An investigation of intermolecular forces including viscosity, by a variety of methods, is often integrated in the undergraduate physical and…

  6. A portable NMR sensor to measure dynamic changes in the amount of water in living stems or fruit and its potential to measure sap flow.

    PubMed

    Windt, Carel W; Blümler, Peter

    2015-04-01

    Nuclear magnetic resonance (NMR) and NMR imaging (magnetic resonance imaging) offer the possibility to quantitatively and non-invasively measure the presence and movement of water. Unfortunately, traditional NMR hardware is expensive, poorly suited for plants, and because of its bulk and complexity, not suitable for use in the field. But does it need to be? We here explore how novel, small-scale portable NMR devices can be used as a flow sensor to directly measure xylem sap flow in a poplar tree (Populus nigra L.), or in a dendrometer-like fashion to measure dynamic changes in the absolute water content of fruit or stems. For the latter purpose we monitored the diurnal pattern of growth, expansion and shrinkage in a model fruit (bean pod, Phaseolus vulgaris L.) and in the stem of an oak tree (Quercus robur L.). We compared changes in absolute stem water content, as measured by the NMR sensor, against stem diameter variations as measured by a set of conventional point dendrometers, to test how well the sensitivities of the two methods compare and to investigate how well diurnal changes in trunk absolute water content correlate with the concomitant diurnal variations in stem diameter. Our results confirm the existence of a strong correlation between the two parameters, but also suggest that dynamic changes in oak stem water content could be larger than is apparent on the basis of the stem diameter variation alone.

  7. A portable NMR sensor to measure dynamic changes in the amount of water in living stems or fruit and its potential to measure sap flow.

    PubMed

    Windt, Carel W; Blümler, Peter

    2015-04-01

    Nuclear magnetic resonance (NMR) and NMR imaging (magnetic resonance imaging) offer the possibility to quantitatively and non-invasively measure the presence and movement of water. Unfortunately, traditional NMR hardware is expensive, poorly suited for plants, and because of its bulk and complexity, not suitable for use in the field. But does it need to be? We here explore how novel, small-scale portable NMR devices can be used as a flow sensor to directly measure xylem sap flow in a poplar tree (Populus nigra L.), or in a dendrometer-like fashion to measure dynamic changes in the absolute water content of fruit or stems. For the latter purpose we monitored the diurnal pattern of growth, expansion and shrinkage in a model fruit (bean pod, Phaseolus vulgaris L.) and in the stem of an oak tree (Quercus robur L.). We compared changes in absolute stem water content, as measured by the NMR sensor, against stem diameter variations as measured by a set of conventional point dendrometers, to test how well the sensitivities of the two methods compare and to investigate how well diurnal changes in trunk absolute water content correlate with the concomitant diurnal variations in stem diameter. Our results confirm the existence of a strong correlation between the two parameters, but also suggest that dynamic changes in oak stem water content could be larger than is apparent on the basis of the stem diameter variation alone. PMID:25595754

  8. General order parameter based correlation analysis of protein backbone motions between experimental NMR relaxation measurements and molecular dynamics simulations.

    PubMed

    Liu, Qing; Shi, Chaowei; Yu, Lu; Zhang, Longhua; Xiong, Ying; Tian, Changlin

    2015-02-13

    Internal backbone dynamic motions are essential for different protein functions and occur on a wide range of time scales, from femtoseconds to seconds. Molecular dynamic (MD) simulations and nuclear magnetic resonance (NMR) spin relaxation measurements are valuable tools to gain access to fast (nanosecond) internal motions. However, there exist few reports on correlation analysis between MD and NMR relaxation data. Here, backbone relaxation measurements of (15)N-labeled SH3 (Src homology 3) domain proteins in aqueous buffer were used to generate general order parameters (S(2)) using a model-free approach. Simultaneously, 80 ns MD simulations of SH3 domain proteins in a defined hydrated box at neutral pH were conducted and the general order parameters (S(2)) were derived from the MD trajectory. Correlation analysis using the Gromos force field indicated that S(2) values from NMR relaxation measurements and MD simulations were significantly different. MD simulations were performed on models with different charge states for three histidine residues, and with different water models, which were SPC (simple point charge) water model and SPC/E (extended simple point charge) water model. S(2) parameters from MD simulations with charges for all three histidines and with the SPC/E water model correlated well with S(2) calculated from the experimental NMR relaxation measurements, in a site-specific manner.

  9. Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C2H6, and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Tropical Fires of 1997-1998

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Stephen, T. M.; Pougatchev, N. S.; Fishman, J.; David, S. J.; Blatherwick, R. D.; Novelli, P. C.; Jones, N. B.

    1999-01-01

    High spectral resolution (0.003 per cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5N, 155.6W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the 3.4-16 km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first 2 years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO 3.4-16 km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32'N and 45'S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average 3.4-16 km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during the strong El Nino warm phase of 1997- 1998 are the likely source of the elevated emission products.

  10. Determination of the biogenic secondary organic aerosol fraction in the boreal forest by AMS and NMR measurements

    NASA Astrophysics Data System (ADS)

    Finessi, E.; Decesari, S.; Paglione, M.; Giulianelli, L.; Carbone, C.; Gilardoni, S.; Fuzzi, S.; Saarikoski, S.; Raatikainen, T.; Hillamo, R.; Allan, J.; Mentel, Th. F.; Tiitta, P.; Laaksonen, A.; Petäjä, T.; Kulmala, M.; Worsnop, D. R.; Facchini, M. C.

    2011-08-01

    The study investigates the sources of fine organic aerosol (OA) in the boreal forest, based on measurements including both filter sampling (PM1) and online methods and carried out during a one-month campaign held in Hyytiälä, Finland, in spring 2007. Two aerosol mass spectrometers (Q-AMS, ToF-AMS) were employed to measure on-line air mass concentrations of major non-refractory aerosol species, while the water extracts of the filter samples were analyzed by nuclear magnetic resonance (NMR) spectroscopy for organic functional group characterization of the polar organic fraction of the aerosol. AMS and NMR spectra were processed separately by non-negative factorization algorithms, in order to apportion the main components underlying the submicrometer organic aerosol composition and depict them in terms of both mass fragmentation patterns and functional group compositions. The NMR results supported the AMS speciation of oxidized organic aerosol (OOA) into two main fractions, which could be generally labelled as more and less oxidized organics. The more oxidized component was characterized by a mass spectrum dominated by the m/z 44 peak, and in parallel by a NMR spectrum showing aromatic and aliphatic backbones highly substituted with oxygenated functional groups (carbonyls/carboxyls and hydroxyls). Such component, contributing on average 50 % of the OA mass throughout the observing period, was associated with pollution outbreaks from the Central Europe. The less oxidized component showed features consistent with less oxygenated aerosols and was enhanced in concomitance with air masses originating from the North-to-West sector, in agreement with previous investigations conducted at this site. NMR factor analysis was able to separate two distinct components under the less oxidized fraction of OA. One of these NMR-factors was associated to the formation of terrestrial biogenic secondary organic aerosol (BSOA), based on the comparison with spectral profiles obtained from

  11. Study on ethyl groups with two different orientations in [N(C2H5)4]2CuBr4

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran

    2016-06-01

    The crystal structure and phase transition temperature of [N(C2H5)4]2CuBr4 are studied using X-ray diffraction and differential scanning calorimetry (DSC); measurements revealed a tetragonal structure and the two phase transition temperatures TC of 204 K and 255.5 K. The structural geometry near TC is discussed in terms of the chemical shifts for 1H magic angle spinning (MAS) nuclear magnetic resonance (NMR) and 13C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups are distinguishable by the 13C NMR spectrum. The molecular motions are discussed in terms of the spin-lattice relaxation times T1ρ in the rotating frame for 1H MAS NMR and 13C CP/MAS NMR. The T1ρ results reveal that the ethyl groups undergo tumbling motion, and furthermore that the ethyl groups are highly mobile.

  12. General order parameter based correlation analysis of protein backbone motions between experimental NMR relaxation measurements and molecular dynamics simulations

    SciTech Connect

    Liu, Qing; Shi, Chaowei; Yu, Lu; Zhang, Longhua; Xiong, Ying; Tian, Changlin

    2015-02-13

    Internal backbone dynamic motions are essential for different protein functions and occur on a wide range of time scales, from femtoseconds to seconds. Molecular dynamic (MD) simulations and nuclear magnetic resonance (NMR) spin relaxation measurements are valuable tools to gain access to fast (nanosecond) internal motions. However, there exist few reports on correlation analysis between MD and NMR relaxation data. Here, backbone relaxation measurements of {sup 15}N-labeled SH3 (Src homology 3) domain proteins in aqueous buffer were used to generate general order parameters (S{sup 2}) using a model-free approach. Simultaneously, 80 ns MD simulations of SH3 domain proteins in a defined hydrated box at neutral pH were conducted and the general order parameters (S{sup 2}) were derived from the MD trajectory. Correlation analysis using the Gromos force field indicated that S{sup 2} values from NMR relaxation measurements and MD simulations were significantly different. MD simulations were performed on models with different charge states for three histidine residues, and with different water models, which were SPC (simple point charge) water model and SPC/E (extended simple point charge) water model. S{sup 2} parameters from MD simulations with charges for all three histidines and with the SPC/E water model correlated well with S{sup 2} calculated from the experimental NMR relaxation measurements, in a site-specific manner. - Highlights: • Correlation analysis between NMR relaxation measurements and MD simulations. • General order parameter (S{sup 2}) as common reference between the two methods. • Different protein dynamics with different Histidine charge states in neutral pH. • Different protein dynamics with different water models.

  13. Quantitative Measurements of HO2 and other products of n-butane oxidation (H2O2, H2O, CH2O, and C2H4) at elevated temperatures by direct coupling of a jet-stirred reactor with sampling nozzle and cavity ring-down spectroscopy (cw-CRDS).

    PubMed

    Djehiche, Mokhtar; Le Tan, Ngoc Linh; Jain, Chaithanya D; Dayma, Guillaume; Dagaut, Philippe; Chauveau, Christian; Pillier, Laure; Tomas, Alexandre

    2014-11-26

    For the first time quantitative measurements of the hydroperoxyl radical (HO2) in a jet-stirred reactor were performed thanks to a new experimental setup involving fast sampling and near-infrared cavity ring-down spectroscopy at low pressure. The experiments were performed at atmospheric pressure and over a range of temperatures (550-900 K) with n-butane, the simplest hydrocarbon fuel exhibiting cool flame oxidation chemistry which represents a key process for the auto-ignition in internal combustion engines. The same technique was also used to measure H2O2, H2O, CH2O, and C2H4 under the same conditions. This new setup brings new scientific horizons for characterizing complex reactive systems at elevated temperatures. Measuring HO2 formation from hydrocarbon oxidation is extremely important in determining the propensity of a fuel to follow chain-termination pathways from R + O2 compared to chain branching (leading to OH), helping to constrain and better validate detailed chemical kinetics models. PMID:25381864

  14. NMR methods for in-situ biofilm metabolism studies: spatial and temporal resolved measurements

    SciTech Connect

    Majors, Paul D.; Mclean, Jeffrey S.; Fredrickson, Jim K.; Wind, Robert A.

    2005-11-01

    We are developing nuclear magnetic resonance (NMR) microscopy, spectroscopy and combined NMR/optical techniques to the study of biofilms. Objectives include: time and depth-resolved metabolite concentrations with isotropic spatial resolution on the order of 10 microns, metabolic pathways and flux rates, mass transport and ultimately their correlation with gene expression by optical microscopy in biofilms. These methods are being developed with Shewanella oneidensis MR-1 as a model system, but are equally applicable to other biofilm systems of interest. Thus, spatially resolved NMR of biofilms is expected to contribute significantly to the understanding of adherent cell metabolism.

  15. Measurements of excess O3, CO2, CH4, C2H4, C2H2, HCN, NO, NH3, HCOOH, CH3COOH, HCHO, and CH3H in 1997 Alaskan biomass burning plumes by airborne Fourier transform infrared spectroscopy (AFTIR) [O3 CO2 CH4 C2H4 C2H2 NH3 CH3COOH CH3H

    NASA Astrophysics Data System (ADS)

    Goode, Jon G.; Yokelson, Robert J.; Ward, Darold E.; Susott, Ronald A.; Babbitt, Ronald E.; Davies, Mary Ann; Hao, Wei Min

    2000-09-01

    We used an airborne Fourier transform infrared spectrometer (AFTIR), coupled to a flow-through, air-sampling cell, on a King Air B-90 to make in situ trace gas measurements in isolated smoke plumes from four, large, boreal zone wildfires in interior Alaska during June 1997. AFTIR spectra acquired near the source of the smoke plumes yielded excess mixing ratios for 13 of the most common trace gases: water, carbon dioxide, carbon monoxide, methane, nitric oxide, formaldehyde, acetic acid, formic acid, methanol, ethylene, acetylene, ammonia and hydrogen cyanide. Emission ratios to carbon monoxide for formaldehyde, acetic acid, and methanol were 2.2±0.4%, 1.3±0.4%, and 1.4±0.1%, respectively. For each oxygenated organic compound, a single linear equation fits our emission factors from Alaska, North Carolina, and laboratory fires as a function of modified combustion efficiency (MCE). A linear equation for predicting the NH3/NOx emission ratio as a function of MCE fits our Alaskan AFTIR results and those from many other studies. AFTIR spectra collected in downwind smoke that had aged 2.2±1 hours in the upper, early plume yielded ΔO3/ΔCO ratios of 7.9±2.4% resulting from O3 production rates of ˜50 ppbv h-1. The ΔNH3/ΔCO ratio in another plume decreased to 1/e of its initial value in ˜2.5 hours. A set of average emission ratios and emission factors for fires in Alaskan boreal forests is derived. We estimate that the 1997 Alaskan fires emitted 46±11 Tg of CO2.

  16. The use of dielectric and NMR measurements to determine the pore-scale location of organic. 1998 annual progress report

    SciTech Connect

    Knight, R.

    1998-06-01

    'The objective of the three-year research project is to investigate the effect of adsorbed organics on the dielectric and nuclear magnetic resonance (NMR) response of porous geological materials. This will allow the author to assess the use of dielectric and NMR measurements at a site to determine whether organic contaminants are present in the central volume of the pore space or are adsorbed to the solid surfaces. In addition, she proposes to use laboratory dielectric and NMR measurements to study the kinetics of the adsorption and desorption of organics. This report summarizes work completed after 20 months of a three-year project. The research involves the study of the NMR and dielectric behavior of sands with three types of solid surfaces: water-wet, where water spontaneously coats and adsorbs to the solid surfaces; hydrophobic, where water is repelled from the solid surfaces by an organosilane coating; and oil-wet, where oil coats the solid surfaces. The oil-wet case is representative of a contaminated soil, in which oil has become adsorbed to the solid surfaces.'

  17. Diffusion anisotropy in excised normal rat spinal cord measured by NMR microscopy.

    PubMed

    Inglis, B A; Yang, L; Wirth, E D; Plant, D; Mareci, T H

    1997-01-01

    A conventional spin-echo NMR imaging pulse sequence was used to obtain high-resolution images of excised normal rat spinal cord at 7 and 14 T. It was observed that the large pulsed-field gradients necessary for high-resolution imaging caused a diffusion weighting that dominated the image contrast and that could be used to infer microscopic structural organization beyond that defined by the resolution of the image matrix (i.e., fiber orientation could be assigned based on diffusion anisotropy). Anisotropic diffusion coefficients were therefore measured using apparent diffusion tensor (ADT) imaging to assess more accurately fiber orientations in the spinal cord; structural anisotropy information is portrayed in the six unique images of the complete ADT. To reduce the dimensionality of the data, a trace image was generated using a separate color scale for each of the three diagonal element images of the ADT. This new image retains much of the invariance of the trace to the relative orientations of laboratory and sample axes (inherent to a greyscale trace image) but provides, by the use of color, contrast reflecting diffusion anisotropy. The colored trace image yields a pseudo-three-dimensional view of the rat spinal cord, from which it is possible to deduce fiber orientations.

  18. Carbon monoxide (CO) and ethane (C2H6) trends from ground-based solar FTIR measurements at six European stations, comparison and sensitivity analysis with the EMEP model

    NASA Astrophysics Data System (ADS)

    Angelbratt, J.; Mellqvist, J.; Simpson, D.; Jonson, J. E.; Blumenstock, T.; Borsdorff, T.; Duchatelet, P.; Forster, F.; Hase, F.; Mahieu, E.; de Mazière, M.; Notholt, J.; Petersen, A. K.; Raffalski, U.; Servais, C.; Sussmann, R.; Warneke, T.; Vigouroux, C.

    2011-09-01

    Trends in the CO andC2H6 partial columns ~0-15 km) have been estimated from four European ground-based solar FTIR (Fourier Transform InfraRed) stations for the 1996-2006 time period. The CO trends from the four stations Jungfraujoch, Zugspitze, Harestua and Kiruna have been estimated to -0.45 ± 0.16% yr-1, -1.00 ± 0.24% yr-1, -0.62 ± 0.19 % yr-1 and -0.61 ± 0.16% yr-1, respectively. The corresponding trends for C2H6 are -1.51 ± 0.23% yr-1, -2.11 ± 0.30% yr-1, -1.09 ± 0.25% yr-1 and -1.14 ± 0.18% yr-1. All trends are presented with their 2-σ confidence intervals. To find possible reasons for the CO trends, the global-scale EMEP MSC-W chemical transport model has been used in a series of sensitivity scenarios. It is shown that the trends are consistent with the combination of a 20% decrease in the anthropogenic CO emissions seen in Europe and North America during the 1996-2006 period and a 20% increase in the anthropogenic CO emissions in East Asia, during the same time period. The possible impacts of CH4 and biogenic volatile organic compounds (BVOCs) are also considered. The European and global-scale EMEP models have been evaluated against the measured CO and C2H6 partial columns from Jungfraujoch, Zugspitze, Bremen, Harestua, Kiruna and Ny-Ålesund. The European model reproduces, on average the measurements at the different sites fairly well and within 10-22% deviation for CO and 14-31% deviation for C2H6. Their seasonal amplitude is captured within 6-35% and 9-124% for CO and C2H6, respectively. However, 61-98% of the CO and C2H6 partial columns in the European model are shown to arise from the boundary conditions, making the global-scale model a more suitable alternative when modeling these two species. In the evaluation of the global model the average partial columns for 2006 are shown to be within 1-9% and 37-50% of the measurements for CO and C2H6, respectively. The global model sensitivity for assumptions made in this paper is also analyzed.

  19. Diffusion of small solutes in cartilage as measured by nuclear magnetic resonance (NMR) spectroscopy and imaging.

    PubMed

    Burstein, D; Gray, M L; Hartman, A L; Gipe, R; Foy, B D

    1993-07-01

    The ability of water and solutes to move through the cartilage matrix is important to the normal function of cartilage and is presumed to be altered in degenerative diseases of cartilage such as osteoarthritis and rheumatoid arthritis. Nuclear magnetic resonance (NMR) spectroscopy and magnetic resonance imaging (MRI) techniques were used to measure a self diffusion coefficient (D) for small solutes in samples of explanted cartilage for diffusion times ranging from 13 ms to 2 s. With a diffusion time of 13 ms, the intratissue diffusivity of several small solutes (water, Na+, Li+, and CF3CO2-) was found consistently to be about 60% of the diffusivity of the same species in free solution. Equilibration of the samples at low pH (which titrates the charge groups so that the net matrix charge of -300 mM at pH 8 becomes approximately -50 mM at pH 2) did not affect the diffusivity of water or Na+. These data, and the similarity between the D in cartilage relative to free solution for water, anions, and cations, are consistent with the view that charge is not an important determinant of the intratissue diffusivity of small solutes in cartilage. With 35% compression, the diffusivity of water and Li+ dropped by 19 and 39%, respectively. In contrast, the diffusivity of water increased by 20% after treatment with trypsin (to remove the proteoglycans and noncollagenous proteins). These data and the lack of an effect of charge on diffusivity are consistent with D being dependent on the composition and density of the solid tissue matrix. A series of diffusion-weighted proton images demonstrated that D could be measured on a localized basis and that changes in D associated with an enzymatically depleted matrix could be clearly observed. Finally, evidence of restriction to diffusion within the tissue was found with studies in which D was measured as a function of diffusion time. The measured D for water in cartilage decreased with diffusion times ranging from 25 ms to 2 s, at which

  20. Studies of 3He polarization losses during NMR and EPR measurment and Polarized 3He target cell lifetime

    NASA Astrophysics Data System (ADS)

    An, Peibo

    2014-09-01

    The 3He target cell polarized by spin-exchange optical pumping(SEOP) is used as a neutron substitute to study the inner structure of the neutron. In our lab, nuclear-magnetic-resonance(NMR) is used to measure the relative polarization and electron-paramagnetic-resonance(EPR) is used to measure the spin exchange EPR frequency shift parameter of potassium and rubidium in our target cell presented in magnetic fields. The alkali in the cell is used to facilitate the polarization of 3He. The first part of my work presents the study of the polarization losses of the cell during both NMR and EPR. With the help of improved RF coils, we keep the background noise received by pickup coils reasonably low, but three other kinds of losses are inevitable: losses during Adiabatic Fast Passage (AFP) sweep, losses due to flux change caused by different cell orientation with respect to RF fields and physical losses. Fortunately there is only flux change in NMR measurements. The second part of my work presents the study of cell lifetime improvement. The polarization decreases in a process called relaxation exponentially. The lifetime of a cell is how long it can keep its polarization. The typical lifetime of cells produced in our lab is about 22 hours. With a newly designed vacuum system. The 3He target cell polarized by spin-exchange optical pumping(SEOP) is used as a neutron substitute to study the inner structure of the neutron. In our lab, nuclear-magnetic-resonance(NMR) is used to measure the relative polarization and electron-paramagnetic-resonance(EPR) is used to measure the spin exchange EPR frequency shift parameter of potassium and rubidium in our target cell presented in magnetic fields. The alkali in the cell is used to facilitate the polarization of 3He. The first part of my work presents the study of the polarization losses of the cell during both NMR and EPR. With the help of improved RF coils, we keep the background noise received by pickup coils reasonably low, but

  1. Results from Boiling Temperature Measurements for Saturated Solutions in the Systems NaCl + Ca(NO3)2 + H2O, NaNO3 + KNO3 + H2O, and NaCl + KNO3 + H2O, and Dry Out Temperatures for NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O

    SciTech Connect

    Rard, J A

    2005-11-29

    Boiling temperature measurements have been made for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O and NaNO{sub 3} + KNO{sub 3} + H{sub 2}O at three selected salt ratios and for NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range. The maximum boiling temperature found for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C, and the composition is estimated to occur at x(Ca(NO{sub 3}){sub 2}) {approx} 0.25. Experiments were also performed for the five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures with the molar ratio of NaCl:NaNO{sub 3}:KNO{sub 3} held essentially constant at 1:0.9780:1.1468 as the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}), was varied between 0 and 0.25. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms low melting mixtures and thus boiling temperatures for saturated were not determined. Instead, the temperatures corresponding to the cessation of boiling (i.e., dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge} 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. The investigated mixture compositions correspond to some of the major mineral assemblages that are predicted to control the deliquescence relative humidity of salts formed by leaching dust samples from the proposed nuclear repository at Yucca Mountain, Nevada.

  2. Sensitivity and resolution of two-dimensional NMR diffusion-relaxation measurements.

    PubMed

    Kausik, Ravinath; Hürlimann, Martin D

    2016-09-01

    The performance of 2D NMR diffusion-relaxation measurements for fluid typing applications is analyzed. In particular, we delineate the region in the diffusion - relaxation plane that can be determined with a given gradient strength and homogeneity, and compare the performance of the single and double echo encoding with the stimulated echo diffusion encoding. We show that the diffusion editing based approach is able to determine the diffusion coefficient only if the relaxation time T2 exceeds a cutoff value T2,cutoff, that scales like T2,cutoff∝g(-2/3)D(-1/3). For stimulated echo encoding, the optimal diffusion encoding times (Td and δ), that provide the best diffusion sensitivity, rely only on the T1/T2 ratios and not on the diffusion coefficients of the fluids or the applied gradient strengths. Irrespective of T1, for high enough gradients (i.e. when γ(2)g(2)DT2(3)>10(2)), the Hahn echo based encoding is superior to encoding based on the stimulated echo. For weaker gradients, the stimulated echo is superior only if the T1/T2 ratio is much larger than 1. For single component systems, the diffusion sensitivity is not adversely impacted by the uniformity of the gradients and the diffusion distributions can be well measured. The presence of non-uniform gradients can affect the determination of the diffusion distributions when you have two fluids of comparable T2. In such situations the effective single component diffusion coefficient is always closer to the geometric mean diffusion coefficient of the two fluids. PMID:27389638

  3. Solute diffusion in ionic liquids, NMR measurements and comparisons to conventional solvents.

    PubMed

    Kaintz, Anne; Baker, Gary; Benesi, Alan; Maroncelli, Mark

    2013-10-01

    Diffusion coefficients of a variety of dilute solutes in the series of 1-alkyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imides ([Prn1][Tf2N], n = 3, 4, 6, 8, and 10), trihexyltetracedecylphosphonium bis(trifluoromethanesulfonyl)imide [P14,666][Tf2N], and assorted imidazolium ionic liquids are measured using pulsed field gradient (1)H NMR. These data, combined with available literature data, are used to try to uncover the solute and solvent characteristics most important in determining tracer diffusion rates. Discussion is framed in terms of departures from simple hydrodynamic predictions for translational friction using the ratio ζobs/ζSE, where ζobs is the observed friction, determined from the measured diffusion coefficient D via ζobs = kBT/D, and ζSE = 6πηR is the Stokes friction on a sphere of radius R (determined from the solute van der Waals volume) in a solvent with viscosity η. In the case of neutral solutes, the primary determinant of whether hydrodynamic predictions are accurate is the relative size of solute versus solvent molecules. A single correlation, albeit with considerable scatter, is found between ζobs/ζSE and the ratio of solute-to-solvent van der Waals volumes, ζobs/ζSE = {1 + a(VU/VV)(-p)}, with constants a = 1.93 and p = 1.88. In the case of small solutes, the observed friction is over 100-fold smaller than predictions of hydrodynamic models. The dipole moment of the solute has little effect on the friction, whereas solute charge has a marked effect. For monovalent solutes of size comparable to or smaller than the solvent ions, the observed friction is comparable to or even greater than what is predicted by hydrodynamics. These general trends are shown to be quite similar to what is observed for tracer diffusion in conventional solvents. PMID:23968276

  4. Sensitivity and resolution of two-dimensional NMR diffusion-relaxation measurements

    NASA Astrophysics Data System (ADS)

    Kausik, Ravinath; Hürlimann, Martin D.

    2016-09-01

    The performance of 2D NMR diffusion-relaxation measurements for fluid typing applications is analyzed. In particular, we delineate the region in the diffusion - relaxation plane that can be determined with a given gradient strength and homogeneity, and compare the performance of the single and double echo encoding with the stimulated echo diffusion encoding. We show that the diffusion editing based approach is able to determine the diffusion coefficient only if the relaxation time T2 exceeds a cutoff value T2,cutoff , that scales like T2,cutoff ∝g - 2 / 3D - 1 / 3 . For stimulated echo encoding, the optimal diffusion encoding times (Td and δ), that provide the best diffusion sensitivity, rely only on the T1 /T2 ratios and not on the diffusion coefficients of the fluids or the applied gradient strengths. Irrespective of T1 , for high enough gradients (i.e. when γ2g2 DT23 >102), the Hahn echo based encoding is superior to encoding based on the stimulated echo. For weaker gradients, the stimulated echo is superior only if the T1 /T2 ratio is much larger than 1. For single component systems, the diffusion sensitivity is not adversely impacted by the uniformity of the gradients and the diffusion distributions can be well measured. The presence of non-uniform gradients can affect the determination of the diffusion distributions when you have two fluids of comparable T2 . In such situations the effective single component diffusion coefficient is always closer to the geometric mean diffusion coefficient of the two fluids.

  5. Measurements of the Differential Cross Sections for the Elastic n-{sup 3}H and n-{sup 2}H Scattering at 14.1 MeV by Using an Inertial Confinement Fusion Facility

    SciTech Connect

    Frenje, J. A.; Li, C. K.; Seguin, F. H.; Casey, D. T.; Petrasso, R. D.; McNabb, D. P.; Navratil, P.; Quaglioni, S.; Sangster, T. C.; Glebov, V. Yu; Meyerhofer, D. D.

    2011-09-16

    For the first time the differential cross section for the elastic neutron-triton (n-{sup 3}H) and neutron-deuteron (n-{sup 2}H) scattering at 14.1 MeV has been measured by using an inertial confinement fusion facility. In these experiments, which were carried out by simultaneously measuring elastically scattered {sup 3}H and {sup 2}H ions from a deuterium-tritium gas-filled inertial confinement fusion capsule implosion, the differential cross section for the elastic n-{sup 3}H scattering was obtained with significantly higher accuracy than achieved in previous accelerator experiments. The results compare well with calculations that combine the resonating-group method with an ab initio no-core shell model, which demonstrate that recent advances in ab initio theory can provide an accurate description of light-ion reactions.

  6. A compact high-performance low-field NMR apparatus for measurements on fluids at very high pressures and temperatures

    SciTech Connect

    Freedman, R.; Anand, V. Ganesan, K.; Tabrizi, P.; Torres, R.; Grant, B.; Catina, D.; Ryan, D.; Borman, C.; Krueckl, C.

    2014-02-15

    We discuss an innovative new high-performance apparatus for performing low-field Nuclear Magnetic Resonance (NMR) relaxation times and diffusion measurements on fluids at very high pressures and high temperatures. The apparatus sensor design and electronics specifications allow for dual deployment either in a fluid sampling well logging tool or in a laboratory. The sensor and electronics were designed to function in both environments. This paper discusses the use of the apparatus in a laboratory environment. The operating temperature and pressure limits, and the signal-to-noise ratio (SNR) of the new system exceed by a very wide margin what is currently possible. This major breakthrough was made possible by a revolutionary new sensor design that breaks many of the rules of conventional high pressure NMR sensor design. A metallic sample holder capable of operating at high pressures and temperatures is provided to contain the fluid under study. The sample holder has been successfully tested for operation up to 36 Kpsi. A solenoid coil wound on a slotted titanium frame sits inside the metallic sample holder and serves as an antenna to transmit RF pulses and receive NMR signals. The metal sample holder is sandwiched between a pair of gradient coils which provide a linear field gradient for pulsed field gradient diffusion measurements. The assembly sits in the bore of a low-gradient permanent magnet. The system can operate over a wide frequency range without the need for tuning the antenna to the Larmor frequency. The SNR measured on a water sample at room temperature is more than 15 times greater than that of the commercial low-field system in our laboratory. Thus, the new system provides for data acquisition more than 200 times faster than was previously possible. Laboratory NMR measurements of relaxations times and diffusion coefficients performed at pressures up to 25 Kpsi and at temperatures up to 175 °C with crude oils enlivened with dissolved hydrocarbon gases

  7. A compact high-performance low-field NMR apparatus for measurements on fluids at very high pressures and temperatures.

    PubMed

    Freedman, R; Anand, V; Grant, B; Ganesan, K; Tabrizi, P; Torres, R; Catina, D; Ryan, D; Borman, C; Krueckl, C

    2014-02-01

    We discuss an innovative new high-performance apparatus for performing low-field Nuclear Magnetic Resonance (NMR) relaxation times and diffusion measurements on fluids at very high pressures and high temperatures. The apparatus sensor design and electronics specifications allow for dual deployment either in a fluid sampling well logging tool or in a laboratory. The sensor and electronics were designed to function in both environments. This paper discusses the use of the apparatus in a laboratory environment. The operating temperature and pressure limits, and the signal-to-noise ratio (SNR) of the new system exceed by a very wide margin what is currently possible. This major breakthrough was made possible by a revolutionary new sensor design that breaks many of the rules of conventional high pressure NMR sensor design. A metallic sample holder capable of operating at high pressures and temperatures is provided to contain the fluid under study. The sample holder has been successfully tested for operation up to 36 Kpsi. A solenoid coil wound on a slotted titanium frame sits inside the metallic sample holder and serves as an antenna to transmit RF pulses and receive NMR signals. The metal sample holder is sandwiched between a pair of gradient coils which provide a linear field gradient for pulsed field gradient diffusion measurements. The assembly sits in the bore of a low-gradient permanent magnet. The system can operate over a wide frequency range without the need for tuning the antenna to the Larmor frequency. The SNR measured on a water sample at room temperature is more than 15 times greater than that of the commercial low-field system in our laboratory. Thus, the new system provides for data acquisition more than 200 times faster than was previously possible. Laboratory NMR measurements of relaxations times and diffusion coefficients performed at pressures up to 25 Kpsi and at temperatures up to 175 °C with crude oils enlivened with dissolved hydrocarbon gases

  8. A compact high-performance low-field NMR apparatus for measurements on fluids at very high pressures and temperatures

    NASA Astrophysics Data System (ADS)

    Freedman, R.; Anand, V.; Grant, B.; Ganesan, K.; Tabrizi, P.; Torres, R.; Catina, D.; Ryan, D.; Borman, C.; Krueckl, C.

    2014-02-01

    We discuss an innovative new high-performance apparatus for performing low-field Nuclear Magnetic Resonance (NMR) relaxation times and diffusion measurements on fluids at very high pressures and high temperatures. The apparatus sensor design and electronics specifications allow for dual deployment either in a fluid sampling well logging tool or in a laboratory. The sensor and electronics were designed to function in both environments. This paper discusses the use of the apparatus in a laboratory environment. The operating temperature and pressure limits, and the signal-to-noise ratio (SNR) of the new system exceed by a very wide margin what is currently possible. This major breakthrough was made possible by a revolutionary new sensor design that breaks many of the rules of conventional high pressure NMR sensor design. A metallic sample holder capable of operating at high pressures and temperatures is provided to contain the fluid under study. The sample holder has been successfully tested for operation up to 36 Kpsi. A solenoid coil wound on a slotted titanium frame sits inside the metallic sample holder and serves as an antenna to transmit RF pulses and receive NMR signals. The metal sample holder is sandwiched between a pair of gradient coils which provide a linear field gradient for pulsed field gradient diffusion measurements. The assembly sits in the bore of a low-gradient permanent magnet. The system can operate over a wide frequency range without the need for tuning the antenna to the Larmor frequency. The SNR measured on a water sample at room temperature is more than 15 times greater than that of the commercial low-field system in our laboratory. Thus, the new system provides for data acquisition more than 200 times faster than was previously possible. Laboratory NMR measurements of relaxations times and diffusion coefficients performed at pressures up to 25 Kpsi and at temperatures up to 175 °C with crude oils enlivened with dissolved hydrocarbon gases

  9. Secondary ion emission from CO2-H2O ice irradiated by energetic heavy ions: Part I. Measurement of the mass spectra

    NASA Astrophysics Data System (ADS)

    Farenzena, L. S.; Collado, V. M.; Ponciano, C. R.; da Silveira, E. F.; Wien, K.

    2005-05-01

    Secondary ion mass spectrometry is used to investigate ion emission from a frozen-gas mixture (T = 80-90 K) of CO2 and H2O bombarded by MeV nitrogen ions and by 252Cf fission fragments (FF). The aim of the experiments is to produce organic molecules in the highly excited material around the nuclear track and to detect them in the flux of sputtered particles. Such sputter processes are known to occur at the icy surfaces of planetary or interstellar objects. Time-of-flight (TOF) mass spectrometry is employed to identify the desorbed ions. Mass spectra of positive and negative ions were taken for several molecular H2O/CO2 ratios. In special, positive ions induced by MeV nitrogen beam were analyzed for 9 and 18% H2O concentrations of the CO2-H2O ice and negative ions for ~5% H2O. The ion peaks are separated to generate exclusive the spectra of CO2 specific ions, H2O specific ions and hybrid molecular ions, the latter ones corresponding to ions that contain mostly H and C atoms. In the mass range from 10 to 320 u, the latter exhibits 35 positive and 58 negative ions. The total yield of the positive ions is 0.35 and 0.57 ions/impact, respectively, and of negative ions 0.066 ions/impact. Unexpected effects of secondary ion sputtering yields on H2O/CO2 ratio are attributed to the influence of water molecules concentration on the ionization process.

  10. High resolution NMR measurements using a 400MHz NMR with an (RE)Ba2Cu3O7-x high-temperature superconducting inner coil: Towards a compact super-high-field NMR.

    PubMed

    Piao, R; Iguchi, S; Hamada, M; Matsumoto, S; Suematsu, H; Saito, A T; Li, J; Nakagome, H; Takao, T; Takahashi, M; Maeda, H; Yanagisawa, Y

    2016-02-01

    Use of high-temperature superconducting (HTS) inner coils in combination with conventional low-temperature superconducting (LTS) outer coils for an NMR magnet, i.e. a LTS/HTS NMR magnet, is a suitable option to realize a high-resolution NMR spectrometer with operating frequency >1GHz. From the standpoint of creating a compact magnet, (RE: Rare earth) Ba2Cu3O7-x (REBCO) HTS inner coils which can tolerate a strong hoop stress caused by a Lorentz force are preferred. However, in our previous work on a first-generation 400MHz LTS/REBCO NMR magnet, the NMR resolution and sensitivity were about ten times worse than that of a conventional LTS NMR magnet. The result was caused by a large field inhomogeneity in the REBCO coil itself and the shielding effect of a screening current induced in that coil. In the present paper, we describe the operation of a modified 400MHz LTS/REBCO NMR magnet with an advanced field compensation technology using a combination of novel ferromagnetic shimming and an appropriate procedure for NMR spectrum line shape optimization. We succeeded in obtaining a good NMR line shape and 2D NOESY spectrum for a lysozyme aqueous sample. We believe that this technology is indispensable for the realization of a compact super-high-field high-resolution NMR. PMID:26778351

  11. Dynamic NMR microscopy measurement of the dynamics and flow partitioning of colloidal particles in a bifurcation

    NASA Astrophysics Data System (ADS)

    Fridjonsson, Einar O.; Seymour, Joseph D.; Cokelet, Giles R.; Codd, Sarah L.

    2011-05-01

    The flow and distribution of Newtonian, polymeric and colloid suspension fluids at low Reynolds numbers in bifurcations has importance in a wide range of disciplines, including microvascular physiology and microfluidic devices. A bifurcation consisting of circular capillaries laser etched into a hard polymer with inlet diameter 2.50 ± 0.01 mm, bifurcating to a small diameter outlet of 0.76 ± 0.01 mm and a large diameter outlet of 1.25 ± 0.01 mm is examined. Four distinct fluids (water, 0.25%wt xanthan gum, 8 and 22%vol hard-sphere colloidal suspensions) are flowed at flow rates from 10 to 30 ml/h corresponding to Reynolds numbers based on the entry flow from 0.001 to 8. PGSE NMR techniques are applied to obtain dynamic images of the fluids inside the bifurcation with spatial resolution of 59 × 59 μm/pixel in plane over a 200-μm-thick slice. Velocity in all three spatial directions is examined to determine the impact of secondary flows and characterize the transport in the bifurcation. The velocity data provide direct measurement of the volumetric distribution of the flow between the two channels as a function of flow rate. Water and the 8% colloidal suspension show a constant distribution with increasing flow rate, the xanthan gum shows an increase in fluid going into the larger outlet with higher flow rate, and the 22% colloidal suspension shows a decrease in fluid entering the larger channel with higher flow rate. For the colloidal particle flow, the distribution of colloid particles down the capillary is determined by examining the spectrally resolved propagator for the oil inside the core-shell particles in a direction perpendicular to the axial flow. Using dynamic magnetic resonance microscopy, the potential for using magnetic resonance for "particle counting" in a microscale bifurcation is thus demonstrated.

  12. Comparison of double-quantum NMR normalization schemes to measure homonuclear dipole-dipole interactions

    SciTech Connect

    Saalwächter, Kay

    2014-08-14

    A recent implementation of a double-quantum (DQ) recoupling solid-state NMR experiment, dubbed DQ-DRENAR, provides a quantitative measure of homonuclear dipole-dipole coupling constants in multispin-1/2 systems. It was claimed to be more robust than another, previously known experiment relying on the recording of point-by-point normalized DQ build-up curves. Focusing on the POST-C7 and BaBa-xy16 DQ pulse sequences, I here present an in-depth comparison of both approaches based upon spin-dynamics simulations, stressing that they are based upon very similar principles and that they are largely equivalent when no imperfections are present. With imperfections, it is found that DQ-DRENAR/POST-C7 does not fully compensate for additional signal dephasing related to chemical shifts (CS) and their anisotropy (CSA), which over-compensates the intrinsic CS(A)-related efficiency loss of the DQ Hamiltonian and leads to an apparent cancellation effect. The simulations further show that the CS(A)-related dephasing in DQ-DRENAR can be removed by another phase cycle step or an improved super-cycled wideband version. Only the latter, or the normalized DQ build-up, are unaffected by CS(A)-related signal loss and yield clean pure dipolar-coupling information subject to unavoidable, pulse sequence specific performance reduction related to higher-order corrections of the dipolar DQ Hamiltonian. The intrinsically super-cycled BaBa-xy16 is shown to exhibit virtually no CS(A) related imperfection terms, but its dipolar performance is somewhat more challenged by CS(A) effects than POST-C7, which can however be compensated when applied at very fast MAS (>50 kHz). Practically, DQ-DRENAR uses a clever phase cycle separation to achieve a significantly shorter experimental time, which can also be beneficially employed in normalized DQ build-up experiments.

  13. Comparison of double-quantum NMR normalization schemes to measure homonuclear dipole-dipole interactions

    NASA Astrophysics Data System (ADS)

    Saalwächter, Kay

    2014-08-01

    A recent implementation of a double-quantum (DQ) recoupling solid-state NMR experiment, dubbed DQ-DRENAR, provides a quantitative measure of homonuclear dipole-dipole coupling constants in multispin-1/2 systems. It was claimed to be more robust than another, previously known experiment relying on the recording of point-by-point normalized DQ build-up curves. Focusing on the POST-C7 and BaBa-xy16 DQ pulse sequences, I here present an in-depth comparison of both approaches based upon spin-dynamics simulations, stressing that they are based upon very similar principles and that they are largely equivalent when no imperfections are present. With imperfections, it is found that DQ-DRENAR/POST-C7 does not fully compensate for additional signal dephasing related to chemical shifts (CS) and their anisotropy (CSA), which over-compensates the intrinsic CS(A)-related efficiency loss of the DQ Hamiltonian and leads to an apparent cancellation effect. The simulations further show that the CS(A)-related dephasing in DQ-DRENAR can be removed by another phase cycle step or an improved super-cycled wideband version. Only the latter, or the normalized DQ build-up, are unaffected by CS(A)-related signal loss and yield clean pure dipolar-coupling information subject to unavoidable, pulse sequence specific performance reduction related to higher-order corrections of the dipolar DQ Hamiltonian. The intrinsically super-cycled BaBa-xy16 is shown to exhibit virtually no CS(A) related imperfection terms, but its dipolar performance is somewhat more challenged by CS(A) effects than POST-C7, which can however be compensated when applied at very fast MAS (>50 kHz). Practically, DQ-DRENAR uses a clever phase cycle separation to achieve a significantly shorter experimental time, which can also be beneficially employed in normalized DQ build-up experiments.

  14. Backbone dynamics of the oligomerization domain of p53 determined from 15N NMR relaxation measurements.

    PubMed

    Clubb, R T; Omichinski, J G; Sakaguchi, K; Appella, E; Gronenborn, A M; Clore, G M

    1995-05-01

    The backbone dynamics of the tetrameric p53 oligomerization domain (residues 319-360) have been investigated by two-dimensional inverse detected heteronuclear 1H-15N NMR spectroscopy at 500 and 600 MHz. 15N T1, T2, and heteronuclear NOEs were measured for 39 of 40 non-proline backbone NH vectors at both field strengths. The overall correlation time for the tetramer, calculated from the T1/T2 ratios, was found to be 14.8 ns at 35 degrees C. The correlation times and amplitudes of the internal motions were extracted from the relaxation data using the model-free formalism (Lipari G, Szabo A, 1982, J Am Chem Soc 104:4546-4559). The internal dynamics of the structural core of the p53 oligomerization domain are uniform and fairly rigid, with residues 327-354 exhibiting an average generalized order parameter (S2) of 0.88 +/- 0.08. The N- and C-termini exhibit substantial mobility and are unstructured in the solution structure of p53. Residues located at the N- and C-termini, in the beta-sheet, in the turn between the alpha-helix and beta-sheet, and at the C-terminal end of the alpha-helix display two distinct internal motions that are faster than the overall correlation time. Fast internal motions (< or = 20 ps) are within the extreme narrowing limit and are of uniform amplitude. The slower motions (0.6-2.2 ns) are outside the extreme narrowing limit and vary in amplitude.(ABSTRACT TRUNCATED AT 250 WORDS) PMID:7663341

  15. Increasing the sensitivity of NMR diffusion measurements by paramagnetic longitudinal relaxation enhancement, with application to ribosome–nascent chain complexes

    PubMed Central

    Cassaignau, Anaïs M. E.; Cabrita, Lisa D.

    2016-01-01

    The translational diffusion of macromolecules can be examined non-invasively by stimulated echo (STE) NMR experiments to accurately determine their molecular sizes. These measurements can be important probes of intermolecular interactions and protein folding and unfolding, and are crucial in monitoring the integrity of large macromolecular assemblies such as ribosome–nascent chain complexes (RNCs). However, NMR studies of these complexes can be severely constrained by their slow tumbling, low solubility (with maximum concentrations of up to 10 μM), and short lifetimes resulting in weak signal, and therefore continuing improvements in experimental sensitivity are essential. Here we explore the use of the paramagnetic longitudinal relaxation enhancement (PLRE) agent NiDO2A on the sensitivity of 15N XSTE and SORDID heteronuclear STE experiments, which can be used to monitor the integrity of these unstable complexes. We exploit the dependence of the PLRE effect on the gyromagnetic ratio and electronic relaxation time to accelerate recovery of 1H magnetization without adversely affecting storage on Nz during diffusion delays or introducing significant transverse relaxation line broadening. By applying the longitudinal relaxation-optimized SORDID pulse sequence together with NiDO2A to 70S Escherichia coli ribosomes and RNCs, NMR diffusion sensitivity enhancements of up to 4.5-fold relative to XSTE are achieved, alongside ~1.9-fold improvements in two-dimensional NMR sensitivity, without compromising the sample integrity. We anticipate these results will significantly advance the use of NMR to probe dynamic regions of ribosomes and other large, unstable macromolecular assemblies. PMID:26253948

  16. Infrared Solar Spectroscopic Measurements of Free Tropospheric CO, C2H6, and HCN above Mauna Loa, Hawaii: Seasonal Variations and Evidence for Enhanced Emissions from the Southeast Asian Fires of 1997-1998. Revised

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Goldman, A.; Murcray, F. J.; Stephen, T. M.; Pougatchev, N. S.; Fishman, J.; David, S. J.; Blatherwick, R. D.; Novelli, P. C.; Jones, N. B.; Connor, B. J.

    1999-01-01

    High spectral resolution (0.003/ cm) infrared solar absorption measurements of CO, C2H6, and HCN have been recorded at the Network for the Detection of Stratospheric Change station on Mauna Loa, Hawaii, (19.5 deg N, 155.6 deg W, altitude 3.4 km). The observations were obtained on over 250 days between August 1995 and February 1998. Column measurements are reported for the 3.4 - 16 km altitude region, which corresponds approximately to the free troposphere above the station. Average CO mixing ratios computed for this layer have been compared with flask sampling CO measurements obtained in situ at the station during the same time period. Both show asymmetrical seasonal cycles superimposed on significant variability. The first two years of observations exhibit a broad January-April maximum and a sharper CO minimum during late summer. The C2H6 and CO 3.4 - 16 km columns were highly correlated throughout the observing period with the C2H6/CO slope intermediate between higher and lower values derived from similar infrared spectroscopic measurements at 32 deg N and 45 deg S latitude, respectively. Variable enhancements in CO, C2H6, and particularly HCN were observed beginning in about September 1997. The maximum HCN free tropospheric monthly mean column observed in November 1997 corresponds to an average 3.4 - 16 km mixing ratio of 0.7 ppbv (1 ppbv = 10(exp -9) per unit volume), more than a factor of 3 above the background level. The HCN enhancements continued through the end of the observational series. Back-trajectory calculations suggest that the emissions originated at low northern latitudes in southeast Asia. Surface CO mixing ratios and the C2H6 tropospheric columns measured during the same time also showed anomalous autumn 1997 maxima. The intense and widespread tropical wild fires that burned during 3 the strong El Nino warm phase of 1997-1998 are the likely source of the elevated emission products.

  17. On the role of experimental imperfections in constructing (1)H spin diffusion NMR plots for domain size measurements.

    PubMed

    Nieuwendaal, Ryan C

    2016-01-01

    We discuss the precision of 1D chemical-shift-based (1)H spin diffusion NMR experiments as well as straightforward experimental protocols for reducing errors. The (1)H spin diffusion NMR experiments described herein are useful for samples that contain components with significant spectral overlap in the (1)H NMR spectrum and also for samples of small mass (<1mg). We show that even in samples that display little spectral contrast, domain sizes can be determined to a relatively high degree of certainty if common experimental variability is accounted for and known. In particular, one should (1) measure flip angles to high precision (≈±1° flip angle), (2) establish a metric for phase transients to ensure their repeatability, (3) establish a reliable spectral deconvolution procedure to ascertain the deconvolved spectra of the neat components in the composite or blend spin diffusion spectrum, and (4) when possible, perform 1D chemical-shift-based (1)H spin diffusion experiments with zero total integral to partially correct for errors and uncertainties if these requirements cannot fully be implemented. We show that minimizing the degree of phase transients is not a requirement for reliable domain size measurement, but their repeatability is essential, as is knowing their contribution to the spectral offset (i.e. the J1 coefficient). When performing experiments with zero total integral in the spin diffusion NMR spectrum with carefully measured flip angles and known phase transient effects, the largest contribution to error arises from an uncertainty in the component lineshapes which can be as high as 7%. This uncertainty can be reduced considerably if the component lineshapes deconvolved from the composite or blend spin diffusion spectra adequately match previously acquired pure component spectra. PMID:27039203

  18. In situ measurement of molecular diffusion during catalytic reaction by pulsed-field gradient NMR spectroscopy

    SciTech Connect

    Hong, Y.; Kaerger, J.; Hunger, B. ); Feoktistova, N.N.; Zhdanov, S.P. )

    1992-09-01

    Pulsed-field gradient (PFG) NMR spectroscopy is applied to study the intracrystalline diffusivity of the reactant and product molecules during the conversion of cyclopropane to propene in Zeolite X. The diffusivities are found to be large enough that any influence of intracrystalline diffusion on the overall reaction in flow reactors may be excluded.

  19. The spectroscopic (FT-IR, FT-Raman and NMR), NCA, Fukui function analysis first order hyperpolarizability, TGA of 6-chloro-3,4dihydro-2H-1,2,4-benzothiazine-7-sulphonamide1,1-dioxide by ab initio HF and Density Functional method.

    PubMed

    Elamurugu Porchelvi, E; Muthu, S

    2014-04-01

    The Fourier-Transform Infrared and Fourier-Transform Raman spectra of 6-Chloro-3,4dihydro-2H-1,2,4-benzothiazine-7sulphonamide1,1-dioxide(6CDBSD) was recorded in the region 4000-450cm(-1) and 4000-100cm(-1)respectively. Quantum chemical calculations of energies, geometrical structure and vibrational wave numbers of 6CDBSD were carried out by HF and DFT (B3LYP) method with 6-31G (d,p) basis set. The difference between the observed and scaled wavenumber value of most of the fundamentals is very small. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The linear polariazability (α) and the first order hyperpolarizability (βtot) values of the investigated molecule have been computed using HF and DFT with 6-31G (d,p) basis set. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The (1)H and (13)C Nuclear Magnetic Resonance (NMR) chemical shifts of the molecules were calculated using the Gauge-Invariant Atomic orbital (GIAO) method, confirms with the experimental values. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. Thermal stability of 6CDBSD was studied by thermo gravimetric analysis (TGA). Next Fukui functions was calculated to identify changes in the reactivity of molecule. Finally molecular electrostatic potential (MEP) and other molecular properties were performed.

  20. Longitudinal NMR parameter measurements of Japanese pear fruit during the growing process using a mobile magnetic resonance imaging system

    NASA Astrophysics Data System (ADS)

    Geya, Yuto; Kimura, Takeshi; Fujisaki, Hirotaka; Terada, Yasuhiko; Kose, Katsumi; Haishi, Tomoyuki; Gemma, Hiroshi; Sekozawa, Yoshihiko

    2013-01-01

    Longitudinal nuclear magnetic resonance (NMR) parameter measurements of Japanese pear fruit (Pyrus pyrifolia Nakai, Kosui) were performed using an electrically mobile magnetic resonance imaging (MRI) system with a 0.2 T and 16 cm gap permanent magnet. To measure the relaxation times and apparent diffusion coefficients of the pear fruit in relation to their weight, seven pear fruits were harvested almost every week during the cell enlargement period and measured in a research orchard. To evaluate the in situ relaxation times, six pear fruits were longitudinally measured for about two months during the same period. The measurements for the harvested samples showed good agreement with the in situ measurements. From the measurements of the harvested samples, it is clear that the relaxation rates of the pear fruits linearly change with the inverse of the linear dimension of the fruits, demonstrating that the relaxation mechanism is a surface relaxation. We therefore conclude that the mobile MRI system is a useful device for measuring the NMR parameters of outdoor living plants.

  1. SVD-Based Technique for Interference Cancellation and Noise Reduction in NMR Measurement of Time-Dependent Magnetic Fields.

    PubMed

    Chen, Wenjun; Ma, Hong; Yu, De; Zhang, Hua

    2016-03-04

    A nuclear magnetic resonance (NMR) experiment for measurement of time-dependent magnetic fields was introduced. To improve the signal-to-interference-plus-noise ratio (SINR) of NMR data, a new method for interference cancellation and noise reduction (ICNR) based on singular value decomposition (SVD) was proposed. The singular values corresponding to the radio frequency interference (RFI) signal were identified in terms of the correlation between the FID data and the reference data, and then the RFI and noise were suppressed by setting the corresponding singular values to zero. The validity of the algorithm was verified by processing the measured NMR data. The results indicated that, this method has a significantly suppression of RFI and random noise, and can well preserve the FID signal. At present, the major limitation of the proposed SVD-based ICNR technique is that the threshold value for interference cancellation needs to be manually selected. Finally, the inversion waveform of the applied alternating magnetic field was given by fitting the processed experimental data.

  2. SVD-Based Technique for Interference Cancellation and Noise Reduction in NMR Measurement of Time-Dependent Magnetic Fields

    PubMed Central

    Chen, Wenjun; Ma, Hong; Yu, De; Zhang, Hua

    2016-01-01

    A nuclear magnetic resonance (NMR) experiment for measurement of time-dependent magnetic fields was introduced. To improve the signal-to-interference-plus-noise ratio (SINR) of NMR data, a new method for interference cancellation and noise reduction (ICNR) based on singular value decomposition (SVD) was proposed. The singular values corresponding to the radio frequency interference (RFI) signal were identified in terms of the correlation between the FID data and the reference data, and then the RFI and noise were suppressed by setting the corresponding singular values to zero. The validity of the algorithm was verified by processing the measured NMR data. The results indicated that, this method has a significantly suppression of RFI and random noise, and can well preserve the FID signal. At present, the major limitation of the proposed SVD-based ICNR technique is that the threshold value for interference cancellation needs to be manually selected. Finally, the inversion waveform of the applied alternating magnetic field was given by fitting the processed experimental data. PMID:26959024

  3. Rapid measurement of multidimensional 1H solid-state NMR spectra at ultra-fast MAS frequencies

    NASA Astrophysics Data System (ADS)

    Ye, Yue Qi; Malon, Michal; Martineau, Charlotte; Taulelle, Francis; Nishiyama, Yusuke

    2014-02-01

    A novel method to realize rapid repetition of 1H NMR experiments at ultra-fast MAS frequencies is demonstrated. The ultra-fast MAS at 110 kHz slows the 1H-1H spin diffusion, leading to variations of 1H T1 relaxation times from atom to atom within a molecule. The different relaxation behavior is averaged by applying 1H-1H recoupling during relaxation delay even at ultra-fast MAS, reducing the optimal relaxation delay to maximize the signal to noise ratio. The way to determine optimal relaxation delay for arbitrary relaxation curve is shown. The reduction of optimal relaxation delay by radio-frequency driven recoupling (RFDR) was demonstrated on powder samples of glycine and ethenzamide with one and multi-dimensional NMR measurements.

  4. Charge carrier effective mass and concentration derived from combination of Seebeck coefficient and Te125 NMR measurements in complex tellurides

    DOE PAGES

    Levin, E. M.

    2016-06-27

    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 coefficientmore » 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 AgxSbxGe50–2xTe50, 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. Thus, 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.« less

  5. Effect of small admixtures of N2, H2 or O2 on the electron drift velocity in argon: experimental measurements and calculations

    NASA Astrophysics Data System (ADS)

    Stano, M.; Pinhão, N.; Loffhagen, D.; Kučera, M.; Donkó, Z.; Matejčík, Š.

    2011-12-01

    The electron drift velocity in argon with admixtures of up to 2% of nitrogen, hydrogen or oxygen is measured in a pulsed Townsend system for reduced electric fields ranging from 0.1 Td to 2.5 Td. The results are compared with those obtained by Monte Carlo simulations and from the solution of the electron Boltzmann equation using two different solution techniques: a multiterm method based on Legendre polynomial expansion of the angular dependence of the velocity distribution function and the S n method applied to a density gradient expansion representation of the distribution function. An almost perfect agreement between the results of the three numerical methods and, in general, very good agreement between the experimental and the calculated results is obtained. Measurements in Ar-O2 mixtures were limited by electron attachment to oxygen molecules, which contributes to the measured drift velocity. As a result of this attachment contribution, the bulk drift velocity becomes larger than the flux drift velocity if attachment is more probable for electrons with energy below the mean value and smaller in the opposite case. Attachment also contributes to the negative differential conductivity observed in Ar-O2 mixtures.

  6. Cross Section Measurement of ^2H(n,np)n at 16 MeV in Symmetric Constant Relative Energy Configurations

    NASA Astrophysics Data System (ADS)

    Couture, A.; Clegg, T. B.; Howell, C. R.; Tajima, S.; Crowell, A.; Esterline, J.; Fallin, B.; Cumberbatch, L.; Crowe, B.; Markoff, D.; Pedroni, R.

    2010-11-01

    We have made cross-section measurements of neutron-deuteron breakup at an incident neutron energy of 16 MeV. The scattered proton was detected in coincidence with one of the neutrons and their energies were determined via time-of-flight techniques. Target-beam luminosity is obtained from n-d elastic scattering performed concurrently with the main experiment by detecting the scattered deuteron. Our current measurements are of two special cases of the Symmetric Constant Relative Energy Configuration: the space-star and the coplanar star. Data are compared with theoretical predictions [1] through Monte Carlo calculations which smear point geometry predictions over the finite beam, target, and detectors. Preliminary results for the space star are in agreement with previous experimental measurements [2] and are at least 20% larger than theoretical predictions. [4pt] [1] H Witala and W Glóckle. J. Phys. G: Nucl. Part. Phys. 37 064003 (2010). [0pt] [2] C.R. Howell, Nucl. Phys. A 689, 298c (2001).

  7. Quasiparticle density of states of 2H-NbSe{sub 2} single crystals revealed by low-temperature specific heat measurements according to a two-component model.

    SciTech Connect

    Yan, J.; Shan, L.; Wang, Y.; Xiao, Z. L.; Wen, H. H.

    2008-06-01

    Low-temperature specific heat in a dichalcogenide superconductor 2H-NbSe{sub 2} is measured in various magnetic fields. It is found that the specific heat can be described very well by a simple model concerning two components corresponding to vortex normal core and ambient superconducting region, separately. For calculating the specific heat outside the vortex core region, we use the Bardeen-Cooper-Schrieffer (BCS) formalism under the assumption of a narrow distribution of the superconducting gaps. The field-dependent vortex core size in the mixed state of 2H-NbSe{sub 2}, determined by using this model, can explain the nonlinear field dependence of specific heat coefficient {gamma}(H), which is in good agreement with the previous experimental results and more formal calculations. With the high-temperature specific heat data, we can find that, in the multi-band superconductor 2H-NbSe{sub 2}, the recovered density of states (or Fermi surface) below T{sub c} under a magnetic field seems not to be gapped again by the charge density wave (CDW) gap, which suggests that the superconducting gap and the CDW gap may open on different Fermi surface sheets.

  8. (77)Se chemical shift tensor of L-selenocystine: experimental NMR measurements and quantum chemical investigations of structural effects.

    PubMed

    Struppe, Jochem; Zhang, Yong; Rozovsky, Sharon

    2015-03-01

    The genetically encoded amino acid selenocysteine and its dimeric form, selenocystine, are both utilized by nature. They are found in active sites of selenoproteins, enzymes that facilitate a diverse range of reactions, including the detoxification of reactive oxygen species and regulation of redox pathways. Due to selenocysteine and selenocystine's specialized biological roles, it is of interest to examine their (77)Se NMR properties and how those can in turn be employed to study biological systems. We report the solid-state (77)Se NMR measurements of the L-selenocystine chemical shift tensor, which provides the first experimental chemical shift tensor information on selenocysteine-containing systems. Quantum chemical calculations of L-selenocystine models were performed to help understand various structural effects on (77)Se L-selenocystine's chemical shift tensor. The effects of protonation state, protein environment, and substituent of selenium-bonded carbon on the isotropic chemical shift were found to be in a range of ca. 10-20 ppm. However, the conformational effect was found to be much larger, spanning ca. 600 ppm for the C-Se-Se-C dihedral angle range of -180° to +180°. Our calculations show that around the minimum energy structure with a C-Se-Se-C dihedral angle of ca. -90°, the energy costs to alter the dihedral angle in the range from -120° to -60° are within only 2.5 kcal/mol. This makes it possible to realize these conformations in a protein or crystal environment. (77)Se NMR was found to be a sensitive probe to such changes and has an isotropic chemical shift range of 272 ± 30 ppm for this energetically favorable conformation range. The energy-minimized structures exhibited calculated isotropic shifts that lay within 3-9% of those reported in previous solution NMR studies. The experimental solid-state NMR isotropic chemical shift is near the lower bound of this calculated range for these readily accessible conformations. These results suggest

  9. Gas-phase NMR measurements, absolute shielding scales, and magnetic dipole moments of 29Si and 73Ge nuclei.

    PubMed

    Makulski, W; Jackowski, K; Antusek, A; Jaszuński, M

    2006-10-12

    New gas-phase NMR measurements of the shielding constants of 29Si, 73Ge, and 1H nuclei in SiH4 and GeH4 are reported. The results, extrapolated to zero density, provide accurate isolated molecule values, best suited for comparison with theoretical calculations. Using the recent ab initio results for these molecules and the measured chemical shifts, we determine the absolute shielding scales for 29Si and 73Ge. This allows us to provide new values of the nuclear magnetic dipole moments for these two nuclei; in addition, we examine the dipole moments of 13C and 119Sn.

  10. Biogenic phosphorus in oligotrophic mountain lake sediments: differences in composition measured with NMR spectroscopy.

    PubMed

    Ahlgren, Joakim; Reitzel, Kasper; Danielsson, Rolf; Gogoll, Adolf; Rydin, Emil

    2006-12-01

    Phosphorus (P) composition in alkaline sediment extracts from three Swedish oligotrophic mountain lakes was investigated using 31P-NMR spectroscopy. Surface sediments from one natural lake and two mature reservoirs, one of which has received nutrient additions over the last 3 years, were compared with respect to biogenic P composition. The results show significant differences in the occurrence of labile and biogenic P species in the sediments of the different systems. The P compound groups that varied most between these three systems were pyrophosphate and polyphosphates, compound groups known to play an important role in sediment P recycling. The content of these compound groups was lowest in the reservoirs and may indicate a coupling between anthropogenic disturbances (i.e., impoundment) to a water system and the availability of labile P species in the sediment. A statistical study was also conducted to determine the accuracy and reliability of using 31P-NMR spectroscopy for quantification of sediment P forms. PMID:17070896

  11. Microsolvation and sp2-stereoinversion of monomeric α-(2,6-di-tert-butylphenyl)vinyllithium as measured by NMR

    PubMed Central

    Knittl, Monika; Rossmann, Eva C

    2014-01-01

    Summary The β-unsubstituted title compound dissolves in THF as a uniformly trisolvated monomer, whereas it forms exclusively disolvated monomers in tert-butyl methyl ether, Et2O, TMEDA, or toluene with TMEDA (1.4 equiv). This was established at low temperatures through the observation of separated NMR signals for free and lithium-coordinated ligands and/or through the patterns and magnitudes of 13C,6Li NMR coupling constants. An aggregated form was observed only with Et2O (2 equiv) in toluene as the solvent. The olefinic geminal interproton coupling constants of the H2C= part can be used as a secondary criterion to differentiate between these differently solvated ground-states (3, 2, or <2 coordinated ligands per Li). Due to a kinetic trisolvation privilege of THF, the cis/trans sp2-stereoinversion rates could be measured through analyses of 1H NMR line broadening and coalescence only in THF as the solvent: The pseudomonomolecular (because THF-catalyzed), ionic mechanism is initialized by a C–Li bond heterolysis with the transient immobilization of one additional THF ligand, followed by stereoinversion of the quasi-sp2-hybridized carbanionic center in cooperation with a “conducted tour” migration of Li+(THF)4 along the α-aryl group within the solvent-separated ion pair. PMID:25383123

  12. Aggregation properties and structural studies of anticancer drug Irinotecan in DMSO solution based on NMR measurements

    NASA Astrophysics Data System (ADS)

    D'Amelio, N.; Aroulmoji, V.; Toraldo, A.; Sundaraganesan, N.; Anbarasan, P. M.

    2012-04-01

    Irinotecan is an antitumor drug mostly used in the treatment of colorectal cancer. Its efficacy is influenced by the chemical state of the molecule undergoing chemical equilibria, metabolic changes and photodegradation. In this work, we describe the chemical equilibria of the drug in dimethyl sulfoxide (DMSO). The energetic barrier for hindered rotation around the bond connecting the piperidino—piperidino moiety with the camptothecin-like fragment was evaluated. Furthermore, we showed how the molecule aggregates in DMSO solution forming dimeric species able to prevent its degradation. The equilibrium constant for self-aggregation was determined by NMR based on the assumption of the isodesmic model. The formation of a dimer was highlighted by NMR diffusion ordered spectroscopy (NMR-DOSY) experiments at the concentrations used. Structural features of the complex were inferred by NOE and 13C chemical shift data. Molecular modelling of the complex driven by experimental data, lead to a structure implying the formation of two hydrogen bonds involving the lactone ring whose opening is one of the main causes of drug degradation. This species is probably responsible for the improved stability of the drug at concentrations higher than 1 mM.

  13. Tortuosity measurement and the effects of finite pulse widths on xenon gas diffusion NMR studies of porous media

    NASA Technical Reports Server (NTRS)

    Mair, R. W.; Hurlimann, M. D.; Sen, P. N.; Schwartz, L. M.; Patz, S.; Walsworth, R. L.

    2001-01-01

    We have extended the utility of NMR as a technique to probe porous media structure over length scales of approximately 100-2000 microm by using the spin 1/2 noble gas 129Xe imbibed into the system's pore space. Such length scales are much greater than can be probed with NMR diffusion studies of water-saturated porous media. We utilized Pulsed Gradient Spin Echo NMR measurements of the time-dependent diffusion coefficient, D(t), of the xenon gas filling the pore space to study further the measurements of both the pore surface-area-to-volume ratio, S/V(p), and the tortuosity (pore connectivity) of the medium. In uniform-size glass bead packs, we observed D(t) decreasing with increasing t, reaching an observed asymptote of approximately 0.62-0.65D(0), that could be measured over diffusion distances extending over multiple bead diameters. Measurements of D(t)/D(0) at differing gas pressures showed this tortuosity limit was not affected by changing the characteristic diffusion length of the spins during the diffusion encoding gradient pulse. This was not the case at the short time limit, where D(t)/D(0) was noticeably affected by the gas pressure in the sample. Increasing the gas pressure, and hence reducing D(0) and the diffusion during the gradient pulse served to reduce the previously observed deviation of D(t)/D(0) from the S/V(p) relation. The Pade approximation is used to interpolate between the long and short time limits in D(t). While the short time D(t) points lay above the interpolation line in the case of small beads, due to diffusion during the gradient pulse on the order of the pore size, it was also noted that the experimental D(t) data fell below the Pade line in the case of large beads, most likely due to finite size effects.

  14. Tortuosity measurement and the effects of finite pulse widths on xenon gas diffusion NMR studies of porous media.

    PubMed

    Mair, R W; Hürlimann, M D; Sen, P N; Schwartz, L M; Patz, S; Walsworth, R L

    2001-01-01

    We have extended the utility of NMR as a technique to probe porous media structure over length scales of approximately 100-2000 microm by using the spin 1/2 noble gas 129Xe imbibed into the system's pore space. Such length scales are much greater than can be probed with NMR diffusion studies of water-saturated porous media. We utilized Pulsed Gradient Spin Echo NMR measurements of the time-dependent diffusion coefficient, D(t), of the xenon gas filling the pore space to study further the measurements of both the pore surface-area-to-volume ratio, S/V(p), and the tortuosity (pore connectivity) of the medium. In uniform-size glass bead packs, we observed D(t) decreasing with increasing t, reaching an observed asymptote of approximately 0.62-0.65D(0), that could be measured over diffusion distances extending over multiple bead diameters. Measurements of D(t)/D(0) at differing gas pressures showed this tortuosity limit was not affected by changing the characteristic diffusion length of the spins during the diffusion encoding gradient pulse. This was not the case at the short time limit, where D(t)/D(0) was noticeably affected by the gas pressure in the sample. Increasing the gas pressure, and hence reducing D(0) and the diffusion during the gradient pulse served to reduce the previously observed deviation of D(t)/D(0) from the S/V(p) relation. The Pade approximation is used to interpolate between the long and short time limits in D(t). While the short time D(t) points lay above the interpolation line in the case of small beads, due to diffusion during the gradient pulse on the order of the pore size, it was also noted that the experimental D(t) data fell below the Pade line in the case of large beads, most likely due to finite size effects. PMID:11445310

  15. Measurement of the structure function of the nearly free neutron using spectator tagging in inelastic 2H(e ,e'ps )X scattering with CLAS

    NASA Astrophysics Data System (ADS)

    Tkachenko, S.; Baillie, N.; Kuhn, S. E.; Zhang, J.; Arrington, J.; Bosted, P.; Bültmann, S.; Christy, M. E.; Fenker, H.; Griffioen, K. A.; Kalantarians, N.; Keppel, C. E.; Melnitchouk, W.; Tvaskis, V.; Adhikari, K. P.; Aghasyan, M.; Amaryan, M. J.; Anefalos Pereira, S.; Avakian, H.; Ball, J.; Baltzell, N. A.; Battaglieri, M.; Bedlinskiy, I.; Biselli, A. S.; Briscoe, W. J.; Brooks, W. K.; Burkert, V. D.; Carman, D. S.; Celentano, A.; Chandavar, S.; Charles, G.; Cole, P. L.; Contalbrigo, M.; Cortes, O.; Crede, V.; D'Angelo, A.; Dashyan, N.; De Vita, R.; De Sanctis, E.; Deur, A.; Djalali, C.; Dodge, G. E.; Doughty, D.; Dupre, R.; Egiyan, H.; El Alaoui, A.; El Fassi, L.; Elouadrhiri, L.; Eugenio, P.; Fedotov, G.; Fleming, J. A.; Garillon, B.; Gevorgyan, N.; Ghandilyan, Y.; Gilfoyle, G. P.; Giovanetti, K. L.; Girod, F. X.; Goetz, J. T.; Golovatch, E.; Gothe, R. W.; Guidal, M.; Guo, L.; Hafidi, K.; Hakobyan, H.; Hanretty, C.; Harrison, N.; Hattawy, M.; Hicks, K.; Ho, D.; Holtrop, M.; Hyde, C. E.; Ilieva, Y.; Ireland, D. G.; Ishkhanov, B. S.; Jo, H. S.; Keller, D.; Khandaker, M.; Kim, A.; Kim, W.; King, P. M.; Klein, A.; Klein, F. J.; Koirala, S.; Kubarovsky, V.; Kuleshov, S. V.; Lenisa, P.; Lewis, S.; Livingston, K.; Lu, H.; MacCormick, M.; MacGregor, I. J. D.; Markov, N.; Mayer, M.; McKinnon, B.; Mineeva, T.; Mirazita, M.; Mokeev, V.; Montgomery, R. A.; Moutarde, H.; Munoz Camacho, C.; Nadel-Turonski, P.; Niccolai, S.; Niculescu, G.; Niculescu, I.; Osipenko, M.; Pappalardo, L. L.; Paremuzyan, R.; Park, K.; Pasyuk, E.; Phillips, J. J.; Pisano, S.; Pogorelko, O.; Pozdniakov, S.; Price, J. W.; Procureur, S.; Protopopescu, D.; Puckett, A. J. R.; Rimal, D.; Ripani, M.; Rizzo, A.; Rosner, G.; Rossi, P.; Roy, P.; Sabatié, F.; Schott, D.; Schumacher, R. A.; Seder, E.; Senderovich, I.; Sharabian, Y. G.; Simonyan, A.; Smith, G. D.; Sober, D. I.; Sokhan, D.; Stepanyan, S.; Stepanyan, S. S.; Strauch, S.; Tang, W.; Ungaro, M.; Vlassov, A. V.; Voskanyan, H.; Voutier, E.; Walford, N. K.; Watts, D.; Wei, X.; Weinstein, L. B.; Wood, M. H.; Zana, L.; Zonta, I.; CLAS Collaboration

    2014-04-01

    Background: Much less is known about neutron structure than that of the proton due to the absence of free neutron targets. Neutron information is usually extracted from data on nuclear targets such as deuterium, requiring corrections for nuclear binding and nucleon off-shell effects. These corrections are model dependent and have significant uncertainties, especially for large values of the Bjorken scaling variable x . As a consequence, the same data can lead to different conclusions, for example, about the behavior of the d quark distribution in the proton at large x . Purpose: The Barely Off-shell Nucleon Structure experiment at Jefferson Lab measured the inelastic electron-deuteron scattering cross section, tagging spectator protons in coincidence with the scattered electrons. This method reduces nuclear binding uncertainties significantly and has allowed for the first time a (nearly) model-independent extraction of the neutron structure function F2(x ,Q2) in the resonance and deep-inelastic regions. Method: A novel compact radial time projection chamber was built to detect protons with momentum between 70 and 150 MeV/c and over a nearly 4 π angular range. For the extraction of the free-neutron structure function F2n, spectator protons at backward angles (>100∘ relative to the momentum transfer) and with momenta below 100 MeV/c were selected, ensuring that the scattering took place on a nearly free neutron. The scattered electrons were detected with Jefferson Lab's CLAS spectrometer, with data taken at beam energies near 2, 4, and 5 GeV. Results: The extracted neutron structure function F2n and its ratio to the inclusive deuteron structure function F2d are presented in both the resonance and the deep-inelastic regions for momentum transfer squared Q2 between 0.7 and 5 GeV2/c2 , invariant mass W between 1 and 2.7 GeV/c2 , and Bjorken x between 0.25 and 0.6 (in the deep-inelastic scattering region). The dependence of the semi-inclusive cross section on the

  16. Measurement of lipid accumulation in Chlorella vulgaris via flow cytometry and liquid-state ¹H NMR spectroscopy for development of an NMR-traceable flow cytometry protocol.

    PubMed

    Bono, Michael S; Garcia, Ravi D; Sri-Jayantha, Dylan V; Ahner, Beth A; Kirby, Brian J

    2015-01-01

    In this study, we cultured Chlorella vulgaris cells with a range of lipid contents, induced via nitrogen starvation, and characterized them via flow cytometry, with BODIPY 505/515 as a fluorescent lipid label, and liquid-state 1H NMR spectroscopy. In doing so, we demonstrate the utility of calibrating flow cytometric measurements of algal lipid content using triacylglyceride (TAG, also known as triacylglycerol or triglyceride) content per cell as measured via quantitative 1H NMR. Ensemble-averaged fluorescence of BODIPY-labeled cells was highly correlated with average TAG content per cell measured by bulk NMR, with a linear regression yielding a linear fit with r2 = 0.9974. This correlation compares favorably to previous calibrations of flow cytometry protocols to lipid content measured via extraction, and calibration by NMR avoids the time and complexity that is generally required for lipid quantitation via extraction. Flow cytometry calibrated to a direct measurement of TAG content can be used to investigate the distribution of lipid contents for cells within a culture. Our flow cytometry measurements showed that Chlorella vulgaris cells subjected to nitrogen limitation exhibited higher mean lipid content but a wider distribution of lipid content that overlapped the relatively narrow distribution of lipid content for replete cells, suggesting that nitrogen limitation induces lipid accumulation in only a subset of cells. Calibration of flow cytometry protocols using direct in situ measurement of TAG content via NMR will facilitate rapid development of more precise flow cytometry protocols, enabling investigation of algal lipid accumulation for development of more productive algal biofuel feedstocks and cultivation protocols. PMID:26267664

  17. Measurement of Lipid Accumulation in Chlorella vulgaris via Flow Cytometry and Liquid-State ¹H NMR Spectroscopy for Development of an NMR-Traceable Flow Cytometry Protocol

    PubMed Central

    Bono Jr., Michael S.; Garcia, Ravi D.; Sri-Jayantha, Dylan V.; Ahner, Beth A.; Kirby, Brian J.

    2015-01-01

    In this study, we cultured Chlorella vulgaris cells with a range of lipid contents, induced via nitrogen starvation, and characterized them via flow cytometry, with BODIPY 505/515 as a fluorescent lipid label, and liquid-state 1H NMR spectroscopy. In doing so, we demonstrate the utility of calibrating flow cytometric measurements of algal lipid content using triacylglyceride (TAG, also known as triacylglycerol or triglyceride) content per cell as measured via quantitative 1H NMR. Ensemble-averaged fluorescence of BODIPY-labeled cells was highly correlated with average TAG content per cell measured by bulk NMR, with a linear regression yielding a linear fit with r2 = 0.9974. This correlation compares favorably to previous calibrations of flow cytometry protocols to lipid content measured via extraction, and calibration by NMR avoids the time and complexity that is generally required for lipid quantitation via extraction. Flow cytometry calibrated to a direct measurement of TAG content can be used to investigate the distribution of lipid contents for cells within a culture. Our flow cytometry measurements showed that Chlorella vulgaris cells subjected to nitrogen limitation exhibited higher mean lipid content but a wider distribution of lipid content that overlapped the relatively narrow distribution of lipid content for replete cells, suggesting that nitrogen limitation induces lipid accumulation in only a subset of cells. Calibration of flow cytometry protocols using direct in situ measurement of TAG content via NMR will facilitate rapid development of more precise flow cytometry protocols, enabling investigation of algal lipid accumulation for development of more productive algal biofuel feedstocks and cultivation protocols. PMID:26267664

  18. Local electromagnetic properties of magnetic pnictides: a comparative study probed by NMR measurements.

    PubMed

    Majumder, M; Ghoshray, K; Ghoshray, A; Pal, A; Awana, V P S

    2013-05-15

    (75)As and (31)P NMR studies are performed in PrCoAsO and NdCoPO respectively. The Knight shift data in PrCoAsO indicate the presence of an antiferromagnetic interaction between the 4f moments along the c axis in the ferromagnetic state of Co 3d moments. We propose a possible spin structure in this system. The (75)As quadrupolar coupling constant, νQ, increases continuously with decrease of temperature and is found to vary linearly with the intrinsic spin susceptibility, K(iso). This indicates the possibility of the presence of a coupling between charge density and spin density fluctuations. Further, the (31)P NMR Knight shift and spin-lattice relaxation rate (1/T1) in the paramagnetic state of NdCoPO indicate that the differences of LaCoPO and NdCoPO from SmCoPO are due to the decrement of the interlayer separation and not due to the moments of the 4f electrons. The nuclear spin-lattice relaxation time (T1) in NdCoPO shows weak anisotropy at 300 K. Using the self-consistent renormalization (SCR) theory of itinerant ferromagnets, it is shown that in the ab plane, the spin fluctuations are three-dimensional ferromagnetic in nature. From SCR theory the important spin-fluctuation parameters (T0, TA, F¯1) are evaluated. The similarities and dissimilarities of the NMR results in As and P based systems with different rare earths are also discussed. PMID:23604391

  19. Local electromagnetic properties of magnetic pnictides: a comparative study probed by NMR measurements.

    PubMed

    Majumder, M; Ghoshray, K; Ghoshray, A; Pal, A; Awana, V P S

    2013-05-15

    (75)As and (31)P NMR studies are performed in PrCoAsO and NdCoPO respectively. The Knight shift data in PrCoAsO indicate the presence of an antiferromagnetic interaction between the 4f moments along the c axis in the ferromagnetic state of Co 3d moments. We propose a possible spin structure in this system. The (75)As quadrupolar coupling constant, νQ, increases continuously with decrease of temperature and is found to vary linearly with the intrinsic spin susceptibility, K(iso). This indicates the possibility of the presence of a coupling between charge density and spin density fluctuations. Further, the (31)P NMR Knight shift and spin-lattice relaxation rate (1/T1) in the paramagnetic state of NdCoPO indicate that the differences of LaCoPO and NdCoPO from SmCoPO are due to the decrement of the interlayer separation and not due to the moments of the 4f electrons. The nuclear spin-lattice relaxation time (T1) in NdCoPO shows weak anisotropy at 300 K. Using the self-consistent renormalization (SCR) theory of itinerant ferromagnets, it is shown that in the ab plane, the spin fluctuations are three-dimensional ferromagnetic in nature. From SCR theory the important spin-fluctuation parameters (T0, TA, F¯1) are evaluated. The similarities and dissimilarities of the NMR results in As and P based systems with different rare earths are also discussed.

  20. Cation location in microporous zeolite, SSZ-13, probed with xenon adsorption measurement and 129Xe NMR spectrum.

    PubMed

    Shin, Na Ra; Kim, Su Hyun; Shin, Hye Sun; Jang, Ik Jun; Cho, Sung June

    2013-06-01

    The location of metal ion, Ag2+, Ca2+, Cu2+ and Y3+ in the SSZ-13 has been investigated with xenon adsorption measurement and 129Xe NMR spectrum. It was referred that the location of the metal ion varies depending on the corresponding charge. The ion-exchanged Ag ion was located in the alpha-cage to interact directly with xenon. Others multivalent cation contributed little with xenon because these were present near the six membered rings where xenon cannot access. PMID:23862500

  1. Hunting for hydrogen: random structure searching and prediction of NMR parameters of hydrous wadsleyite† †Electronic supplementary information (ESI) available: Further information on the structures generated by AIRSS, alternative structural models, supercell calculations, total enthalpies of all computed structures and further information on 1H/2H NMR parameters. Example input and all raw output files from AIRSS and CASTEP NMR calculations are also included. See DOI: 10.1039/c6cp01529h Click here for additional data file.

    PubMed Central

    Moran, Robert F.; McKay, David; Pickard, Chris J.; Berry, Andrew J.; Griffin, John M.

    2016-01-01

    The structural chemistry of materials containing low levels of nonstoichiometric hydrogen is difficult to determine, and producing structural models is challenging where hydrogen has no fixed crystallographic site. Here we demonstrate a computational approach employing ab initio random structure searching (AIRSS) to generate a series of candidate structures for hydrous wadsleyite (β-Mg2SiO4 with 1.6 wt% H2O), a high-pressure mineral proposed as a repository for water in the Earth's transition zone. Aligning with previous experimental work, we solely consider models with Mg3 (over Mg1, Mg2 or Si) vacancies. We adapt the AIRSS method by starting with anhydrous wadsleyite, removing a single Mg2+ and randomly placing two H+ in a unit cell model, generating 819 candidate structures. 103 geometries were then subjected to more accurate optimisation under periodic DFT. Using this approach, we find the most favourable hydration mechanism involves protonation of two O1 sites around the Mg3 vacancy. The formation of silanol groups on O3 or O4 sites (with loss of stable O1–H hydroxyls) coincides with an increase in total enthalpy. Importantly, the approach we employ allows observables such as NMR parameters to be computed for each structure. We consider hydrous wadsleyite (∼1.6 wt%) to be dominated by protonated O1 sites, with O3/O4–H silanol groups present as defects, a model that maps well onto experimental studies at higher levels of hydration (J. M. Griffin et al., Chem. Sci., 2013, 4, 1523). The AIRSS approach adopted herein provides the crucial link between atomic-scale structure and experimental studies. PMID:27020937

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

    SciTech Connect

    Koretsky, A.P.

    1984-08-01

    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. Chronically implanted detection coils, employing a balanced matching configuration of capacitors in the tuned circuit, were used to obtain /sup 31/P NMR spectra from heart, kidney, and liver in situ. Gated spectra of heart obtained at systole and diastole and the effects of fructose on kidney and liver were studied. The ability to observe other nuclei using implanted coils is illustrated with /sup 39/K NMR spectra from kidney and muscle. 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 (13 ..mu..mol/min/gm tissue) were compared to whole kidney oxygen consumption and Na/sup +/ reabsorption rates to derive ATP/O (0.8 to 1.7) and Na/sup +//ATP (4 to 10) 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.

  3. Sediment depth attenuation of biogenic phosphorus compounds measured by 31P NMR.

    PubMed

    Ahlgren, Joakim; Tranvik, Lars; Gogoll, Adolf; Waldeback, Monica; Markides, Karin; Rydin, Emil

    2005-02-01

    Being a major cause of eutrophication and subsequent loss of water quality, the turnover of phosphorus (P) in lake sediments is in need of deeper understanding. A major part of the flux of P to eutrophic lake sediments is organically bound or of biogenic origin. This P is incorporated in a poorly described mixture of autochthonous and allochthonous sediment and forms the primary storage of P available for recycling to the water column, thus regulating lake trophic status. To identify and quantify biogenic sediment P and assess its lability, we analyzed sediment cores from Lake Erken, Sweden, using traditional P fractionation, and in parallel, NaOH extracts were analyzed using 31P NMR. The surface sediments contain orthophosphates (ortho-P) and pyrophosphates (pyro-P), as well as phosphate mono- and diesters. The first group of compounds to disappear with increased sediment depth is pyrophosphate, followed by a steady decline of the different ester compounds. Estimated half-life times of these compound groups are about 10 yr for pyrophosphate and 2 decades for mono- and diesters. Probably, these compounds will be mineralized to ortho-P and is thus potentially available for recycling to the water column, supporting further growth of phytoplankton. In conclusion, 31P NMR is a useful tool to asses the bioavailability of certain P compound groups, and the combination with traditional fractionation techniques makes quantification possible. PMID:15757351

  4. Synthesis, structural characterization, and solid-state NMR spectroscopy of [Ga(phen)(H{sub 1.5}PO{sub 4}){sub 2}].H{sub 2}O and [Ga(phen)(HPO{sub 4})(H{sub 2}PO{sub 4})].1.5H{sub 2}O (phen=1, 10-phenanthroline), two organic-inorganic hybrid compounds with 1-D chain structures

    SciTech Connect

    Chang, W.-J.; Chang, P.-C.; Kao, H.-M.; Lii, K.-H. . E-mail: liikh@cc.ncu.edu.tw

    2005-12-15

    Two new organic-inorganic hybrid compounds, [Ga(phen)(H{sub 1.5}PO{sub 4}){sub 2}].H{sub 2}O (1) and [Ga(phen)(HPO{sub 4})(H{sub 2}PO{sub 4})].1.5H{sub 2}O (2) (phen=1,10-phenanthroline), have been synthesized by hydrothermal methods and structurally characterized by single-crystal X-ray diffraction, infrared spectroscopy, thermogravimetric analysis, and solid-state NMR spectroscopy. Their structures consist of 1-D chains of strictly alternating GaO{sub 4}N{sub 2} octahedra and phosphate tetrahedra. The phen ligands in both compounds bind in a bidentate fashion to the gallium atoms and the 1-D structures extend into 3-D supramolecular arrays via {pi}-{pi} stacking interactions of phen ligands and hydrogen bonds. {sup 2}H MAS NMR spectroscopy was applied to study the deuterated sample of 1 which contains very short hydrogen bonds with an O-O distance of 2.406(2) A. Crystal data for 1: monoclinic, space group C2/c (No. 15), a=11.077(1) A, b=21.496(2) A, c=7.9989(7) A, {beta}=127.211(2){sup o}, and Z=4. The crystal symmetry is the same for 2 as for 1 except a=27.555(2) A, b=6.3501(5) A, c=21.327(2) A, {beta}=122.498(1){sup o}, and Z=8.

  5. sup 31 P NMR measurements of the ADP concentration in yeast cells genetically modified to express creatine kinase

    SciTech Connect

    Brindle, K.; Braddock, P.; Fulton, S. )

    1990-04-03

    Rabbit muscle creatine kinase has been introduced into the yeast Saccharomyces cerevisiae by transforming cells with a multicopy plasmid containing the coding sequence for the enzyme under the control of the yeast phosphoglycerate kinase promoter. The transformed cells showed creating kinase activities similar to those found in mammalian heart muscle. {sup 31}P NMR measurements of the near-equilibrium concentrations of phosphocreatine and cellular pH together with measurements of the total extractable concentrations of phosphocreatine and creatine allowed calculation of the free ADP/ATP ratio in the cell. The calculated ratio of approximately 2 was considerably higher than the ratio of between 0.06 and 0.1 measured directly in cell extracts.

  6. Revisiting spin-lattice relaxation time measurements for dilute spins in high-resolution solid-state NMR spectroscopy.

    PubMed

    Fu, Riqiang; Li, Jun; Cui, Jingyu; Peng, Xinhua

    2016-07-01

    Numerous nuclear magnetic resonance (NMR) measurements of spin-lattice relaxation times (T1S) for dilute spins such as (13)C have led to investigations of the motional dynamics of individual functional groups in solid materials. In this work, we revisit the Solomon equations and analyze how the heteronuclear cross relaxation between the dilute S (e.g. (13)C) and abundant I (e.g. (1)H) spins affects the measured T1S values in solid-state NMR in the absence of (1)H saturation during the recovery time. It is found theoretically that at the beginning of the S spin magnetization recovery, the existence of non-equilibrium I magnetization introduces the heteronuclear cross relaxation effect onto the recovery of the S spin magnetization and confirmed experimentally that such a heteronuclear cross relaxation effect results in the recovery overshoot phenomena for the dilute spins when T1S is on the same order of T1H, leading to inaccurate measurements of the T1S values. Even when T1S is ten times larger than T1H, the heteronuclear cross relaxation effect on the measured T1S values is still noticeable. Furthermore, this cross relaxation effect on recovery trajectory of the S spins can be manipulated and even suppressed by preparing the initial I and S magnetization, so as to obtain the accurate T1S values. A sample of natural abundance l-isoleucine powder has been used to demonstrate the T1S measurements and their corresponding measured T1C values under various experimental conditions. PMID:27187211

  7. Revisiting spin-lattice relaxation time measurements for dilute spins in high-resolution solid-state NMR spectroscopy.

    PubMed

    Fu, Riqiang; Li, Jun; Cui, Jingyu; Peng, Xinhua

    2016-07-01

    Numerous nuclear magnetic resonance (NMR) measurements of spin-lattice relaxation times (T1S) for dilute spins such as (13)C have led to investigations of the motional dynamics of individual functional groups in solid materials. In this work, we revisit the Solomon equations and analyze how the heteronuclear cross relaxation between the dilute S (e.g. (13)C) and abundant I (e.g. (1)H) spins affects the measured T1S values in solid-state NMR in the absence of (1)H saturation during the recovery time. It is found theoretically that at the beginning of the S spin magnetization recovery, the existence of non-equilibrium I magnetization introduces the heteronuclear cross relaxation effect onto the recovery of the S spin magnetization and confirmed experimentally that such a heteronuclear cross relaxation effect results in the recovery overshoot phenomena for the dilute spins when T1S is on the same order of T1H, leading to inaccurate measurements of the T1S values. Even when T1S is ten times larger than T1H, the heteronuclear cross relaxation effect on the measured T1S values is still noticeable. Furthermore, this cross relaxation effect on recovery trajectory of the S spins can be manipulated and even suppressed by preparing the initial I and S magnetization, so as to obtain the accurate T1S values. A sample of natural abundance l-isoleucine powder has been used to demonstrate the T1S measurements and their corresponding measured T1C values under various experimental conditions.

  8. Revisiting spin-lattice relaxation time measurements for dilute spins in high-resolution solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Fu, Riqiang; Li, Jun; Cui, Jingyu; Peng, Xinhua

    2016-07-01

    Numerous nuclear magnetic resonance (NMR) measurements of spin-lattice relaxation times (T1S) for dilute spins such as 13C have led to investigations of the motional dynamics of individual functional groups in solid materials. In this work, we revisit the Solomon equations and analyze how the heteronuclear cross relaxation between the dilute S (e.g. 13C) and abundant I (e.g. 1H) spins affects the measured T1S values in solid-state NMR in the absence of 1H saturation during the recovery time. It is found theoretically that at the beginning of the S spin magnetization recovery, the existence of non-equilibrium I magnetization introduces the heteronuclear cross relaxation effect onto the recovery of the S spin magnetization and confirmed experimentally that such a heteronuclear cross relaxation effect results in the recovery overshoot phenomena for the dilute spins when T1S is on the same order of T1H, leading to inaccurate measurements of the T1S values. Even when T1S is ten times larger than T1H, the heteronuclear cross relaxation effect on the measured T1S values is still noticeable. Furthermore, this cross relaxation effect on recovery trajectory of the S spins can be manipulated and even suppressed by preparing the initial I and S magnetization, so as to obtain the accurate T1S values. A sample of natural abundance L-isoleucine powder has been used to demonstrate the T1S measurements and their corresponding measured T1C values under various experimental conditions.

  9. Pulsed NMR Measurements in Superfluid 3He in Aerogel of 97.5 % Porosity

    SciTech Connect

    Ishikawa, Osamu; Kado, Ryusuke; Obara, Ken; Yano, Hideo; Hata, Tohru; Nakagawa, Hisashi; Yokogawa, Hiroshi; Yokoyama, Masaru

    2006-09-07

    Aerogel is made of thin SiO2 strands of a few nanometer diameter. Since the coherence length of superfluid 3He is much longer than the silica strand diameter and is nearly the same as the mean distance between silica strands, aerogel gives us a chance to study the effects of an impurity in superfluid 3He. To investigate what superfluid states are formed in aerogel, we performed a pulsed NMR experiment. Both the A-like and B-like phases show a tipping angle dependent frequency shift in the FID signal after an rf pulse. The dependence in the A-like phase is well explained by an expectation based on the ''robust phase'' introduced by Fomin, while the FID frequencies in the B-like phase behave similarly to those observed in the bulk B phase in a slab geometry with the initial condition of a non-Leggett configuration.

  10. Structure and equilibria of Ca 2+-complexes of glucose and sorbitol from multinuclear ( 1H, 13C and 43Ca) NMR measurements supplemented with molecular modelling calculations

    NASA Astrophysics Data System (ADS)

    Pallagi, A.; Dudás, Cs.; Csendes, Z.; Forgó, P.; Pálinkó, I.; Sipos, P.

    2011-05-01

    Ca 2+-complexation of D-glucose and D-sorbitol have been investigated with the aid of multinuclear ( 1H, 13C and 43Ca) NMR spectroscopy and ab initio quantum chemical calculations. Formation constants of the forming 1:1 complexes have been estimated from one-dimensional 13C NMR spectra obtained at constant ionic strength (1 M NaCl). Binding sites were identified from 2D 1H- 43Ca NMR spectra. 2D NMR measurements and ab initio calculations indicated that Ca 2+ ions were bound in a tridentate manner via the glycosidic OH, the ethereal oxygen in the ring and the OH on the terminal carbon for the α- and β-anomers of glucose and for sorbitol simultaneous binding of four hydroxide moieties (C1, C2, C4 and C6) was suggested.

  11. Dissociative recombination of N2H+

    NASA Astrophysics Data System (ADS)

    dos Santos, S. Fonseca; Ngassam, V.; Orel, A. E.; Larson, Å.

    2016-08-01

    The direct and indirect mechanisms of dissociative recombination of N2H+ are theoretically studied. At low energies, the electron capture is found to be driven by recombination into bound Rydberg states, while at collision energies above 0.1 eV, the direct capture and dissociation along electronic resonant states becomes important. Electron-scattering calculations using the complex Kohn variational method are performed to obtain the scattering matrix as well as energy positions and autoionization widths of resonant states. Potential-energy surfaces of electronic bound states of N2H and N2H+ are computed using structure calculations with the multireference configuration interaction method. The cross section for the indirect mechanism is calculated using a vibrational frame transformation of the elements of the scattering matrix at energies just above the ionization threshold. Here vibrational excitations of the ionic core from v =0 to v =1 and v =2 for all three normal modes are considered and autoionization is neglected. The cross section for the direct dissociation along electronic resonant states is computed with wave-packet calculations using the multiconfiguration time-dependent Hartree method, where all three internal degrees of freedom are considered. The calculated cross sections are compared to measurements.

  12. High-resolution magic angle spinning (1) H NMR measurement of ligand concentration in solvent-saturated chromatographic beads.

    PubMed

    Elwinger, Fredrik; Furó, István

    2016-04-01

    A method based on (1) H high-resolution magic angle spinning NMR has been developed for measuring concentration accurately in heterogeneous materials like that of ligands in chromatography media. Ligand concentration is obtained by relating the peak integrals for a butyl ligand in the spectrum of a water-saturated chromatography medium to the integral of the added internal reference. The method is fast, with capacity of 10 min total sample preparation and analysis time per sample; precise, with a reproducibility expressed as 1.7% relative standard deviation; and accurate, as indicated by the excellent agreement of derived concentration with that obtained previously by (13) C single-pulse excitation MAS NMR. The effects of radiofrequency field inhomogeneity, spin rate, temperature increase due to spinning, and distribution and re-distribution of medium and reference solvent both inside the rotor during spinning and between bulk solvent and pore space are discussed in detail. © 2016 The Authors Magnetic Resonance in Chemistry published by John Wiley & Sons Ltd.

  13. Boiling Temperature and Reversed Deliquescence Relative Humidity Measurements for Mineral Assemblages in the NaCl + NaNO3 + KNO3 + Ca(NO3)2 + H2O System

    SciTech Connect

    Rard, J A; Staggs, K J; Day, S D; Carroll, S A

    2005-12-01

    Boiling temperature measurements have been made at ambient pressure for saturated ternary solutions of NaCl + KNO{sub 3} + H{sub 2}O, NaNO{sub 3} + KNO{sub 3} + H{sub 2}O, and NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O over the full composition range, along with those of the single salt systems. Boiling temperatures were also measured for the four component NaCl + NaNO{sub 3} + KNO{sub 3} + H{sub 2}O and five component NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O mixtures, where the solute mole fraction of Ca(NO{sub 3}){sub 2}, x(Ca(NO{sub 3}){sub 2}), was varied between 0 and 0.25. The maximum boiling temperature found for the NaCl + KNO{sub 3} + H{sub 2}O system is {approx} 134.9 C; for the NaNO{sub 3} + KNO{sub 3} + H{sub 2}O system is {approx} 165.1 C at x(NaNO{sub 3}) {approx} 0.46 and x(KNO{sub 3}) {approx} 0.54; and for the NaCl + Ca(NO{sub 3}){sub 2} + H{sub 2}O system is 164.7 {+-} 0.6 C at x(NaCl) {approx} 0.25 and x(Ca(NO{sub 3}){sub 2}) {approx} 0.75. The NaCl + NaNO{sub 3} + KNO{sub 3} + Ca(NO{sub 3}){sub 2} + H{sub 2}O system forms molten salts below their maximum boiling temperatures, and the temperatures corresponding to the cessation of boiling (dry out temperatures) of these liquid mixtures were determined. These dry out temperatures range from {approx} 300 C when x(Ca(NO{sub 3}){sub 2}) = 0 to {ge} 400 C when x(Ca(NO{sub 3}){sub 2}) = 0.20 and 0.25. Mutual deliquescence/efflorescence relative humidity (MDRH/MERH) measurements were also made for the NaNO{sub 3} + KNO{sub 3} and NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture from 120 to 180 C at ambient pressure. The NaNO{sub 3} and NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture has a MDRH of 26.4% at 120 C and 20.0% at 150 C. This salt mixture also absorbs water at 180 C, which is higher than expected from the boiling temperature experiments. The NaCl + NaNO{sub 3} + KNO{sub 3} salt mixture was found to have a MDRH of 25.9% at 120 C and 10.5% at 180 C. The investigated mixture

  14. Measuring the Longitudinal NMR Relaxation Rates of Fast Relaxing Nuclei Using a Signal Eliminating Relaxation Filter

    NASA Astrophysics Data System (ADS)

    Hansen, D. Flemming; Led, Jens J.

    2001-08-01

    A new experiment for selective determination of the relaxation rates of fast relaxing NMR signals is presented. The experiment is derived from the conventional inversion recovery experiment by substituting the 180° inversion pulse of this experiment with a signal eliminating relaxation filter (SERF) consisting of three 180° pulses separated by two variable delays, Δ1 and Δ2. The SERF experiment allows a selective suppression of signals with relaxation rates below a given limit while monitoring the relaxation of faster relaxing signals. The experiment was tested on a sample of 20% oxidized plastocyanin from Anabaena variabilis, where the fast exchange of an electron between the reduced (diamagnetic) and the oxidized (paramagnetic) form results in a series of average signals with widely different relaxation rates. To ensure an optimum extraction of information from the experimental data, the relaxation rates were obtained from the SERF experiment by a simultaneous analysis of all the FIDs of the experiment using a fast linear prediction model method developed previously. The reliability of the relaxation rates obtained from the SERF experiment was confirmed by a comparison of the rates with the corresponding rates obtained from a conventional inversion recovery experiment.

  15. Measuring the longitudinal NMR relaxation rates of fast relaxing nuclei using a signal eliminating relaxation filter.

    PubMed

    Hansen, D F; Led, J J

    2001-08-01

    A new experiment for selective determination of the relaxation rates of fast relaxing NMR signals is presented. The experiment is derived from the conventional inversion recovery experiment by substituting the 180 degrees inversion pulse of this experiment with a signal eliminating relaxation filter (SERF) consisting of three 180 degrees pulses separated by two variable delays, Delta1 and Delta2. The SERF experiment allows a selective suppression of signals with relaxation rates below a given limit while monitoring the relaxation of faster relaxing signals. The experiment was tested on a sample of 20% oxidized plastocyanin from Anabaena variabilis, where the fast exchange of an electron between the reduced (diamagnetic) and the oxidized (paramagnetic) form results in a series of average signals with widely different relaxation rates. To ensure an optimum extraction of information from the experimental data, the relaxation rates were obtained from the SERF experiment by a simultaneous analysis of all the FIDs of the experiment using a fast linear prediction model method developed previously. The reliability of the relaxation rates obtained from the SERF experiment was confirmed by a comparison of the rates with the corresponding rates obtained from a conventional inversion recovery experiment.

  16. Transport properties of bulk hydrogen and hydrogen-helium slush at 4MHz using NMR measurements.

    NASA Astrophysics Data System (ADS)

    Hamida, J. A.; Sullivan, N. S.

    2004-03-01

    The most promising large-scale advance in rocket propulsion is the use of atomic propellants, stabilized in cryogenic environments. The high energy atomic propellants must be stored in a stabilizing medium to inhibit or delay their combination into molecules. We report studies of a suitable cryogenic matrix for atomic propellants consisting of a slush of small grains of solid hydrogen floating in liquid helium. Using NMR techniques, transport properties for bulk samples of solid hydrogen at 4 MHz have been studied as a function of ortho concentration and temperature. In an earlier experiment we determined the stability, transport and thermal properties of a solid hydrogen-liquid helium stabilizer. The nuclear spin-spin and spin-lattice relaxation times of the stabilizer were observed to be appreciably shorter than that expected for bulk samples. We anticipate that the solid-liquid surface relaxation could be the critical path for relaxation towards equilibrium. To address this question, data on relaxation processes for hydrogen -helium slush prepared by different methods will be compared.

  17. Dynamical structure of paramagnetic [M(H2O)6][SiF6] (M = Fe2+,Ni2+) crystal studied by means of 2H nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Mizuno, M.; Iijima, T.; Suhara, M.

    2000-08-01

    The temperature dependences of the 2H nuclear magnetic resonance (NMR) spectra and the spin-lattice relaxation time T1 were measured for [Ni(H2O)6][SiF6] and [Fe(H2O)6][SiF6]. The motional modes for both compounds were discussed on the basis of the spectral simulation. The temperature variations of the 2H NMR spectra at high temperatures could be explained by three-site jumps of [Ni(H2O)6]2+ about the C3 axis for [Ni(H2O)6][SiF6]. For [Fe(H2O)6][SiF6], however, six-site jumps of [Fe(H2O)6]2+ about the C3 axis were found to be most probable form of motion at high temperatures. At low temperatures, the 2H NMR spectra of both compounds could be explained by 180° flips of the water molecule. The 2H NMR T1 was dominated by the fluctuations of the electric field gradient caused by the molecular motion and of the magnetic interaction between the 2H nucleus and the unpaired electron spin in the metal ion. T1 was analysed in terms of the motional modes predicted from the spectral simulation. The activation energies, the jumping rates at infinite temperature for each form of motion and the quadrupole interaction parameters (e2Qq/h,η) were obtained from the 2H NMR spectra and T1. The conclusions from the spectral simulation are in good agreement with the results for T1. These results suggest that [Fe(H2O)6][SiF6] possesses dynamic disorder structure in the high-temperature phase.

  18. Unraveling the complexity of protein backbone dynamics with combined (13)C and (15)N solid-state NMR relaxation measurements.

    PubMed

    Lamley, Jonathan M; Lougher, Matthew J; Sass, Hans Juergen; Rogowski, Marco; Grzesiek, Stephan; Lewandowski, Józef R

    2015-09-14

    Typically, protein dynamics involve a complex hierarchy of motions occurring on different time scales between conformations separated by a range of different energy barriers. NMR relaxation can in principle provide a site-specific picture of both the time scales and amplitudes of these motions, but independent relaxation rates sensitive to fluctuations in different time scale ranges are required to obtain a faithful representation of the underlying dynamic complexity. This is especially pertinent for relaxation measurements in the solid state, which report on dynamics in a broader window of time scales by more than 3 orders of magnitudes compared to solution NMR relaxation. To aid in unraveling the intricacies of biomolecular dynamics we introduce (13)C spin-lattice relaxation in the rotating frame (R1ρ) as a probe of backbone nanosecond-microsecond motions in proteins in the solid state. We present measurements of (13)C'R1ρ rates in fully protonated crystalline protein GB1 at 600 and 850 MHz (1)H Larmor frequencies and compare them to (13)C'R1, (15)N R1 and R1ρ measured under the same conditions. The addition of carbon relaxation data to the model free analysis of nitrogen relaxation data leads to greatly improved characterization of time scales of protein backbone motions, minimizing the occurrence of fitting artifacts that may be present when (15)N data is used alone. We also discuss how internal motions characterized by different time scales contribute to (15)N and (13)C relaxation rates in the solid state and solution state, leading to fundamental differences between them, as well as phenomena such as underestimation of picosecond-range motions in the solid state and nanosecond-range motions in solution.

  19. /sup 2/H nuclear magnetic resonance of exchange-labeled gramicidin in an oriented lyotropic nematic phase

    SciTech Connect

    Davis, J.H.

    1988-01-12

    Lyotropic nematic liquid-crystalline phases, such as that formed by potassium laurate/decanol/KCl/water, are found to accept readily large amphiphilic solute molecules. Since these phases spontaneously orient in high magnetic fields, it becomes possible to obtain NMR spectra of biologically interesting solutes in an oriented axially symmetric environment. The amide hydrogens of the peptide backbone of gramicidin D (Dubos) were exchanged for deuterium, and the gramicidin was incorporated into a lyotropic nematic phase made with deuteriated buffer in place of water. /sup 2/H NMR spectra of oriented, exchange-labeled gramicidin were then obtained. The strong water signal from the deuteriated buffer was eliminated by using selective excitation and a polynomial subtraction procedure. The /sup 2/H NMR spectra at high temperature consist of twelve major quadrupolar doublets. The splittings observed are largely independent of temperature, suggesting a highly rigid backbone structure. Two of the doublets, which are chemically shifted relative to the others, show stronger temperature dependence. These two probably arise from the exchangeable amino hydrogens on the tryptophan indole moieties of the peptide. While we cannot yet assign all of the doublets, the spectra and nuclear magnetic relaxation data are consistent with a rigid slightly distorted ..beta../sub LD//sup 6.3/ helix undergoing axially symmetric reorientation about the director of the liquid-crystalline phase. The correlation time for the axially symmetric reorientation is determined by relaxation measurements to be about 10/sup -7/s.

  20. NMR logging apparatus

    DOEpatents

    Walsh, David O; Turner, Peter

    2014-05-27

    Technologies including NMR logging apparatus and methods are disclosed. Example NMR logging apparatus may include surface instrumentation and one or more downhole probes configured to fit within an earth borehole. The surface instrumentation may comprise a power amplifier, which may be coupled to the downhole probes via one or more transmission lines, and a controller configured to cause the power amplifier to generate a NMR activating pulse or sequence of pulses. Impedance matching means may be configured to match an output impedance of the power amplifier through a transmission line to a load impedance of a downhole probe. Methods may include deploying the various elements of disclosed NMR logging apparatus and using the apparatus to perform NMR measurements.

  1. Quantitation of methadone enantiomers in humans using stable isotope-labeled (2H3)-, (2H5)-, and (2H8)Methadone

    SciTech Connect

    Nakamura, K.; Hachey, D.L.; Kreek, M.J.; Irving, C.S.; Klein, P.D.

    1982-01-01

    A new technique for simultaneous stereoselective kinetic studies of methadone enantiomers was developed using three deuterium-labeled forms of methadone and GLC-chemical-ionization mass spectrometry. A racemic mixture (1:1) of (R)-(-)-(2H5)methadone (l-form) and (S)-(R)-(2H3)methadone (d-form) was administered orally in place of a single daily dose of unlabeled (+/-)-(2H0)methadone in long-term maintenance patients. Racemic (+/-)-(2H8)methadone was used as an internal standard for the simultaneous quantitation of (2H0)-, (2H3)-, and (2H5)methadone in plasma and urine. A newly developed extraction procedure, using a short, disposable C18 reversed-phase cartridge and improved chemical-ionization procedures employing ammonia gas, resulted in significant reduction of the background impurities contributing to the ions used for isotopic abundance measurements. These improvements enabled the measurement of labeled plasma methadone levels for 120 hr following a single dose. This methodology was applied to the study of methadone kinetics in two patients; in both patients, the analgesically active l-enantiomer of the drug had a longer plasma elimination half-life and a smaller area under the plasma disappearance curve than did the inactive d-form.

  2. NMR evidence of a sharp change in a measure of local order in deeply supercooled confined water

    PubMed Central

    Mallamace, F.; Corsaro, C.; Broccio, M.; Branca, C.; González-Segredo, N.; Spooren, J.; Chen, S.-H.; Stanley, H. E.

    2008-01-01

    Using NMR, we measure the proton chemical shift δ, of supercooled nanoconfined water in the temperature range 195 K < T < 350 K. Because δ is directly connected to the magnetic shielding tensor, we discuss the data in terms of the local hydrogen bond geometry and order. We argue that the derivative −(∂ ln δ/∂T)P should behave roughly as the constant pressure specific heat CP(T), and we confirm this argument by detailed comparisons with literature values of CP(T) in the range 290–370 K. We find that −(∂ ln δ/∂T)P displays a pronounced maximum upon crossing the locus of maximum correlation length at ≈240 K, consistent with the liquid-liquid critical point hypothesis for water, which predicts that CP(T) displays a maximum on crossing the Widom line. PMID:18753633

  3. Thz Spectroscopy of D_2H^+

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Pearson, John; Amano, Takayoshi

    2015-06-01

    Pure rotational transitions of D_2H^+ observed by high-resolution spectroscopy have been limited so far to the J = 110-101 transition at 691.7 GHz, J=220-211 at 1.370 THz, and J=111-000 at 1.477 THz. As this ion is a light asymmetric-top molecule, spectroscopic characterization and prediction of other rotational transition frequencies are not straightforward. In this presentation, we extended the measurements up to 2 THz by using the JPL frequency multiplier chains, and observed three new THz lines and re-measured the three known transitions. D_2H^+ was generated in an extended negative glow discharge cell cooled to liquid nitrogen temperature. Six rotational transition frequencies together with the combination differences derived from three fundamental bands were subject to least square analysis to determine the molecular constants. New THz measurements are definitely useful for better characterization of spectroscopic properties. The improved molecular constants provide better predictions of other unobserved rotational transitions. T. Hirao and T. Amano, Ap. J.,597, L85 (2003) K. M. Evenson et al cited by O. L. Polyansky and A. R. W. McKellar, J. Chem. Phys., 92, 4039 (1990) O. Asvany et al, Phys. Rev. Lett., 100, 233004 (2008)

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

    SciTech Connect

    Koretsky, A.P.

    1984-01-01

    /sup 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/sup +/ 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.

  5. ACE-FTS Observation of a Young Biomass Burning Plume: First Reported Measurements of C2H4, C3H6O, H2CO and PAN by Infrared Occultation from Space

    NASA Technical Reports Server (NTRS)

    Coheur, Pierre-Francois; Herbin, Herve; Clerbaux, Cathy; Hurtmans, Daniel; Wespes, Catherine; Carleer, Michel; Turquety, Solene; Rinsland, Curtis P.; Remedios, John; Hauglustaine, Didier; Boone, Chris D.; Bernath, Peter F.

    2007-01-01

    In the course of our study of the upper tropospheric composition with the infrared 35 Atmospheric Chemistry Experiment Fourier Transform Spectrometer (ACE FTS), we 36 found an occultation sequence that on 8 October 2005, sampled a remarkable plume near the 37 east coast of Tanzania. Model simulations of the CO distribution in the Southern hemisphere 38 are performed for this period and they demonstrate that the emissions for this event originated 39 from a nearby forest fire, after which the plume was transported from the source region to the 40 upper troposphere. Taking advantage of the very high signal-to-noise ratio of the ACE FTS 41 spectra over a wide wavenumber range (750-4400 cm(exp -1), we present in-depth analyses of the 42 chemical composition of this plume in the middle and upper troposphere, focusing on the 43 measurements of weakly absorbing pollutants. For this specific biomass burning event, we 44 report simultaneous observations of an unprecedented number of organic species. 45 Measurements of C2H4 (ethene), C3H4 (propyne), H2CO (formaldehyde), C3H6O (acetone) 46 and CH3COO2NO2 (perxoxyacetylnitrate, abbreviated as PAN) are the first reported 47 detections using infrared occultation spectroscopy from satellites. Based on the lifetime of the 48 emitted species, we discuss the photochemical age of the plume and also report, whenever 49 possible, the enhancement ratios relative to CO.

  6. Reduction of magnetic field fluctuations in powered magnets for NMR using inductive measurements and sampled-data feedback control.

    PubMed

    Li, Mingzhou; Schiano, Jeffrey L; Samra, Jenna E; Shetty, Kiran K; Brey, William W

    2011-10-01

    Resistive and hybrid (resistive/superconducting) magnets provide substantially higher magnetic fields than those available in low-temperature superconducting magnets, but their relatively low spatial homogeneity and temporal field fluctuations are unacceptable for high resolution NMR. While several techniques for reducing temporal fluctuations have demonstrated varying degrees of success, this paper restricts attention to methods that utilize inductive measurements and feedback control to actively cancel the temporal fluctuations. In comparison to earlier studies using analog proportional control, this paper shows that shaping the controller frequency response results in significantly higher reductions in temporal fluctuations. Measurements of temporal fluctuation spectra and the frequency response of the instrumentation that cancels the temporal fluctuations guide the controller design. In particular, we describe a sampled-data phase-lead-lag controller that utilizes the internal model principle to selectively attenuate magnetic field fluctuations caused by the power supply ripple. We present a quantitative comparison of the attenuation in temporal fluctuations afforded by the new design and a proportional control design. Metrics for comparison include measurements of the temporal fluctuations using Faraday induction and observations of the effect that the fluctuations have on nuclear resonance measurements.

  7. Rate Coefficients of C2H with C2H4, C2H6, and H2 from 150 to 359 K

    NASA Technical Reports Server (NTRS)

    Opansky, Brian J.; Leone, Stephen R.

    1996-01-01

    Rate coefficients for the reactions C2H with C2H4, C2H6, and H2 are measured over the temperature range 150-359 K using transient infrared laser absorption spectroscopy. The ethynyl radical is formed by photolysis of C2H2 with a pulsed excimer laser at 193 nm, and its transient absorption is monitored with a color center laser on the Q(sub 11)(9) line of the A(sup 2) Pi-Chi(sup 2) Sigma transition at 3593.68 cm(exp -1). Over the experimental temperature range 150-359 K the rate constants of C2H with C2H4, C2H6, and H2 can be fitted to the Arrhenius expressions k(sub C2H4) = (7.8 +/- 0.6) x 10(exp -11) exp[(134 +/- 44)/T], k(sub C2H6) = (3.5 +/- 0.3) x 10(exp -11) exp[(2.9 +/- 16)/T], and k(sub H2) = (1.2 +/- 0.3) x 10(exp -11) exp[(-998 +/- 57)]/T cm(exp 3) molecule(exp -1) sec(exp -1). The data for C2H with C2H4 and C2H6 indicate a negligible activation energy to product formation shown by the mild negative temperature dependence of both reactions. When the H2 data are plotted together with the most recent high-temperature results from 295 to 854 K, a slight curvature is observed. The H2 data can be fit to the non-Arrhenius form k(sub H2) = 9.2 x 10(exp -18) T(sup 2.17 +/- 0.50) exp[(-478 +/- 165)/T] cm(exp 3) molecules(exp -1) sec(exp -1). The curvature in the Arrhenius plot is discussed in terms of both quantum mechanical tunneling of the H atom from H2 to the C2H radical and bending mode contributions to the partition function.

  8. Reversible unfolding of cytochrome c upon interaction with cardiolipin bilayers. 2. Evidence from phosphorus-31 NMR measurements

    SciTech Connect

    Spooner, P.J.R.; Watts, A. )

    1991-04-23

    {sup 31}P NMR measurements were conducted to determine the structural and chemical environment of beef heart cardiolipin when bound to cytochrome c. {sup 31}P NMR line shapes infer that the majority of lipid remains in the bilayer state and that the average conformation of the lipid phosphate is not greatly affected by binding to the protein. An analysis of the spin-lattice (T{sub 1}) relaxation times of hydrated cardiolipin as a function of temperature describes a T{sub 1} minimum at around 25{degree}C which leads to a correlation time for the phosphates in the lipid headgroup of 0.71 ns. The relaxation behavior of the protein-lipid complex was markedly different, showing a pronounced enhancement in the phosphorus spin-lattice relaxation rate. This effect of the protein increased progressively with increasing temperature, giving no indication of a minimum in T{sub 1} up to 75{degree}C. The enhancement in lipid phosphorus T{sub 1} relaxation was observed with protein in both oxidation states, being somewhat less marked for the reduced form. The characteristics of the T{sub 1} effects and the influence of the protein on other relaxation processes determined for the lipid phosphorus (spin-spin relaxation and longitudinal relaxation in the rotating frame) point to a strong paramagnetic interaction from the protein. A comparison with the relaxation behavior of samples spinning at the magic angle was also consistent with this mechanism. The results suggest that cytochrome c reversibly denatures on complexation with cardiolipin bilayers, such that the electronic ground state prevailing in the native structure of both oxidized and reduced protein can convert to high-spin states with greater magnetic susceptibility.

  9. NMR-Based Amide Hydrogen-Deuterium Exchange Measurements for Complex Membrane Proteins: Development and Critical Evaluation

    NASA Astrophysics Data System (ADS)

    Czerski, Lech; Vinogradova, Olga; Sanders, Charles R.

    2000-01-01

    A method for measuring site-specific amide hydrogen-deuterium exchange rates for membrane proteins in bilayers is reported and evaluated. This method represents an adaptation and extension of the approach of Dempsey and co-workers (Biophys. J. 70, 1777-1788 (1996)) and is based on reconstituting 15N-labeled membrane proteins into phospholipid bilayers, followed by lyophilization and rehydration with D2O or H2O (control). Following incubation for a time t under hydrated conditions, samples are again lyophilized and then solubilized in an organic solvent system, where 1H-15N HSQC spectra are recorded. Comparison of spectra from D2O-exposed samples to spectra from control samples yields the extent of the H-D exchange which occurred in the bilayers during time t. Measurements are site specific if specific 15N labeling is used. The first part of this paper deals with the search for a suitable solvent system in which to solubilize complex membrane proteins in an amide "exchange-trapped" form for NMR quantitation of amide peak intensities. The second portion of the paper documents application of the overall procedure to measuring site-specific amide exchange rates in diacylglycerol kinase, a representative integral membrane protein. Both the potential usefulness and the significant limitations of the new method are documented.

  10. Sensitivity of proton NMR relaxation times in a HTPB based polyurethane elastomer to thermo-oxidative aging.

    SciTech Connect

    Assink, Roger Alan; Mowery, Daniel Michael; Celina, Mathias Christopher

    2004-09-01

    Solid-state {sup 1}H NMR relaxometry studies were conducted on a hydroxy-terminated polybutadiene (HTPB) based polyurethane elastomer thermo-oxidatively aged at 80 C. The {sup 1}H T{sub 1}, T{sub 2}, and T{sub 1{rho}} relaxation times of samples thermally aged for various periods of time were determined as a function of NMR measurement temperature. The response of each measurement was calculated from a best-fit linear function of the relaxation time vs. aging time. It was found that the T{sub 2,H} and T{sub 1{rho},H} relaxation times exhibited the largest response to thermal degradation, whereas T{sub 1,H} showed minimal change. All of the NMR relaxation measurements on solid samples showed significantly less sensitivity to thermal aging than the T{sub 2,H} relaxation times of solvent-swollen samples.

  11. Measurement of the intracrystalline self-diffusion of xenon in zeolites by the NMR pulsed field gradient technique

    SciTech Connect

    Heink, W.; Kaerger, J.; Pfeifer, H.; Stallmach, F. )

    1990-03-14

    With use of {sup 129}Xe NMR, the NMR pulsed field gradient technique is applied to study the self-diffusion of xenon adsorbed on zeolites NaX, NaCaA, and ZSM-5. In their dependence on both the type of adsorbent and the sorbate concentration, the self-diffusion coefficients are found to follow the same patterns as previously determined for methane by {sup 1}H NMR. For NaCaA, the comparison of the present results with literature data reveals large discrepancies, while recent computer simulations of xenon self-diffusion in ZSM-5 are found to be in reasonable agreement.

  12. Sizing of reverse micelles in microemulsions using NMR measurements of diffusion.

    PubMed

    Law, Susan J; Britton, Melanie M

    2012-08-14

    This paper reports the size of reverse micelles (RMs) in AOT/octane/H(2)O and CTAB/hexanol/H(2)O microemulsions using magnetic resonance (MR) pulsed field gradient (PFG) measurements of diffusion. Diffusion data were measured using the pulsed gradient stimulated echo (PGSTE) experiment for surfactant molecules residing in the RM interface. Inverse Laplace transformation of these data generated diffusion coefficients for the RMs, which were converted into hydrodynamic radii using the Stokes-Einstein relation. This technique is complementary to those previously used to size RMs, such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), but also offers several advantages, which are discussed. RM sizes, determined using the PGSTE method, in the AOT (sodium bis(2-ethylhexyl) sulfosuccinate) and CTAB (cetyltrimethylammonium bromide) microemulsions were compared with previous DLS and SAXS data, showing good agreement. Methods for determining number distributions from the PGSTE data, through the use of scaling factors, were investigated. PMID:22794150

  13. Sizing of reverse micelles in microemulsions using NMR measurements of diffusion.

    PubMed

    Law, Susan J; Britton, Melanie M

    2012-08-14

    This paper reports the size of reverse micelles (RMs) in AOT/octane/H(2)O and CTAB/hexanol/H(2)O microemulsions using magnetic resonance (MR) pulsed field gradient (PFG) measurements of diffusion. Diffusion data were measured using the pulsed gradient stimulated echo (PGSTE) experiment for surfactant molecules residing in the RM interface. Inverse Laplace transformation of these data generated diffusion coefficients for the RMs, which were converted into hydrodynamic radii using the Stokes-Einstein relation. This technique is complementary to those previously used to size RMs, such as dynamic light scattering (DLS) and small-angle X-ray scattering (SAXS), but also offers several advantages, which are discussed. RM sizes, determined using the PGSTE method, in the AOT (sodium bis(2-ethylhexyl) sulfosuccinate) and CTAB (cetyltrimethylammonium bromide) microemulsions were compared with previous DLS and SAXS data, showing good agreement. Methods for determining number distributions from the PGSTE data, through the use of scaling factors, were investigated.

  14. 2H nuclear magnetic resonance study of deuterated water dynamics in perfluorosulfonic acid ionomer Nafion

    NASA Astrophysics Data System (ADS)

    Han, Jun Hee; Lee, Kyu Won; Lee, Cheol Eui

    2016-11-01

    We have employed deuteron nuclear magnetic resonance (NMR) spectroscopy in order to study the dynamics of the deuterated water (D2O) molecules introduced into a perfluorosulfonic acid ionomer Nafion (NR-211) film. According to the 2H NMR spectral analysis, the deuterated water molecules at low temperatures occupied either relatively rigid or mobile sites up to the temperature TM=240 K where all the deuterated water molecules became mobile. The temperature-dependent NMR linewidths sensitively reflected the motional narrowing of the rigid and mobile sites, and the NMR chemical shift reflected significant changes in the hydrogen bonds of the deuterated water. While a slow- to fast-limit motional transition was manifested at TM in the laboratory-frame NMR spin-lattice relaxation, the rotating-frame spin-lattice relaxation indicated no bulk liquid water state down to 200 K.

  15. The Inversion of NMR Log Data Sets with Different Measurement Errors

    NASA Astrophysics Data System (ADS)

    Dunn, Keh-Jim; LaTorraca, Gerald A.

    1999-09-01

    We present a composite-data processing method which simultaneously processes two or more data sets with different measurement errors. We examine the role of the noise level of the data in the singular value decomposition inversion process, the criteria for a proper cutoff, and its effect on the uncertainty of the solution. Examples of processed logs using the composite-data processing method are presented and discussed. The possible usefulness of the apparent T1/T2 ratio extracted from the logs is illustrated.

  16. The inversion of NMR log data sets with different measurement errors.

    PubMed

    Dunn, K J; LaTorraca, G A

    1999-09-01

    We present a composite-data processing method which simultaneously processes two or more data sets with different measurement errors. We examine the role of the noise level of the data in the singular value decomposition inversion process, the criteria for a proper cutoff, and its effect on the uncertainty of the solution. Examples of processed logs using the composite-data processing method are presented and discussed. The possible usefulness of the apparent T(1)/T(2) ratio extracted from the logs is illustrated. PMID:10479558

  17. Macromolecular Crowding Studies of Amino Acids Using NMR Diffusion Measurements and Molecular Dynamics Simulations

    NASA Astrophysics Data System (ADS)

    Virk, Amninder; Stait-Gardner, Timothy; Willis, Scott; Torres, Allan; Price, William

    2015-02-01

    Molecular crowding occurs when the total concentration of macromolecular species in a solution is so high that a considerable proportion of the volume is physically occupied and therefore not accessible to other molecules. This results in significant changes in the solution properties of the molecules in such systems. Macromolecular crowding is ubiquitous in biological systems due to the generally high intracellular protein concentrations. The major hindrance to understanding crowding is the lack of direct comparison of experimental data with theoretical or simulated data. Self-diffusion is sensitive to changes in the molecular weight and shape of the diffusing species, and the available diffusion space (i.e., diffusive obstruction). Consequently, diffusion measurements are a direct means for probing crowded systems including the self-association of molecules. In this work, nuclear magnetic resonance measurements of the self-diffusion of four amino acids (glycine, alanine, valine and phenylalanine) up to their solubility limit in water were compared directly with molecular dynamics simulations. The experimental data were then analyzed using various models of aggregation and obstruction. Both experimental and simulated data revealed that the diffusion of both water and the amino acids were sensitive to the amino acid concentration. The direct comparison of the simulated and experimental data afforded greater insights into the aggregation and obstruction properties of each amino acid.

  18. Macroscopic orientation effects in broadline NMR-spectra of model membranes at high magnetic field strength: A method preventing such effects.

    PubMed

    Brumm, T; Möps, A; Dolainsky, C; Brückner, S; Bayerl, T M

    1992-04-01

    The partial orientation of multilamellar vesicles (MLV) in high magnetic fields has been studied and a method to prevent such effects is herewith proposed. The orientation effect was measured with (2)H-, (31)P-NMR and electron microscopy on MLVs of dipalmitoyl phosphatidylcholine with 30 mol% cholesterol. We present the first freeze-etch electron microscopy data obtained from MLV samples that were frozen directly in the NMR magnet at a field strength of 9.4 Tesla. These experiments clearly show that the MLVs adopt an ellipsoidal (but not a cylindrical) shape in the magnetic field. Best fit (31)P-NMR lineshape calculations assuming an ellipsoidal distribution of molecular director axes to the experimentally obtained spectra provide a quantitative measure of the average semiaxis ratio of the ellipsoidal MLVs and its change with temperature. The application of so-called spherical supported vesicles (SSV) is found to prevent any partial orientation effects so that undistorted NMR powder pattern of the bilayer can be measured independently of magnetic field strength and temperature.The usefulness of SSVs is further demonstrated by a direct comparison of spectral data such as (31)P-and (2)H-NMR lineshapes and relaxation times as well as (2)H-NMR dePaked spectra obtained for both model systems. These experiments show that spectral data obtained from partially oriented MLVs are not unambiguous to interpret, in particular, if an external parameter such as temperature is varied.

  19. Autocorrelation spectra of an air-fluidized granular system measured by NMR

    NASA Astrophysics Data System (ADS)

    Lasic, S.; Stepisnik, J.; Mohoric, A.; Sersa, I.; Planinsic, G.

    2006-09-01

    A novel insight into the dynamics of a fluidized granular system is given by a nuclear magnetic resonance method that yields the spin-echo attenuation proportional to the spectrum of the grain positional fluctuation. Measurements of the air-fluidized oil-filled spheres and mustard seeds at different degrees of fluidization and grain volume fractions provide the velocity autocorrelation that differs from the commonly anticipated exponential Enskog decay. An empiric formula, which corresponds to the model of grain caging at collisions with adjacent beads, fits well to the experimental data. Its parameters are the characteristic collision time, the free path between collisions and the cage-breaking rate or the diffusion-like constant, which decreases with increasing grain volume fraction. Mean-squared displacements calculated from the correlation spectrum clearly show transitions from ballistic, through sub-diffusion and into diffusion regimes of grain motion.

  20. Rapid measurement of pseudocontact shifts in metalloproteins by proton-detected solid-state NMR spectroscopy.

    PubMed

    Knight, Michael J; Felli, Isabella C; Pierattelli, Roberta; Bertini, Ivano; Emsley, Lyndon; Herrmann, Torsten; Pintacuda, Guido

    2012-09-12

    Pseudocontact shifts (PCSs) arise in paramagnetic systems in which the susceptibility tensor is anisotropic. PCSs depend upon the distance from the paramagnetic center and the position relative to the susceptibility tensor, and they can be used as structural restraints in protein structure determination. We show that the use of (1)H-detected solid-state correlations provides facile and rapid detection and assignment of site-specific PCSs, including resolved (1)H PCSs, in a large metalloprotein, Co(2+)-substituted superoxide dismutase (Co(2+)-SOD). With only 3 mg of sample and a small set of experiments, several hundred PCSs were measured and assigned, and these PCSs were subsequently used in combination with (1)H-(1)H distance and dihedral angle restraints to determine the protein backbone geometry with a precision paralleling those of state-of-the-art liquid-state determinations of diamagnetic proteins, including a well-defined active site.

  1. Measurement of Heteronuclear Dipolar Coupling by Transferred-Echo Double-Resonance NMR

    NASA Astrophysics Data System (ADS)

    Hing, A. W.; Vega, S.; Schaefer, J.

    A magic-angle spinning experiment called transferred-echo double resonance (TEDOR) has been introduced recently to measure the I-S dipolar coupling of heteronuclear I-S pairs of spin- {1}/{2} nuclei while eliminating unwanted background signals from uncoupled I and S spins via a coherence-transfer process. In this paper, a quantitative description of the TEDOR experiment is given in terms of the evolution of the density matrix for a pair of heteronuclear spins. The resulting equations provide a theoretical basis for evaluating the selectivity and sensitivity of TEDOR and suggest strategies for determining dipolar coupling constants directly from TEDOR data. Experimental examples illustrating these aspects of TEDOR are provided by studies performed on a range of 13C- 15N dipolar couplings found in double-labeled asparagine, alanine, glycine, and the linear peptide antibiotic, gramicidin.

  2. Investigation into the structural composition of hydroalcoholic solutions as basis for the development of multiple suppression pulse sequences for NMR measurement of alcoholic beverages.

    PubMed

    Monakhova, Yulia B; Mushtakova, Svetlana P; Kuballa, Thomas; Lachenmeier, Dirk W

    2014-12-01

    An eight-fold suppression pulse sequence was recently developed to improve sensitivity in (1) H NMR measurements of alcoholic beverages [Magn. Res. Chem. 2011 (49): 734-739]. To ensure that only one combined hydroxyl peak from water and ethanol appears in the spectrum, adjustment to a certain range of ethanol concentrations was required. To explain this observation, the structure of water-ethanol solutions was studied. Hydroalcoholic solutions showed extreme behavior at 25% vol, 46% vol, and 83% vol ethanol according to (1) H NMR experiments. Near-infrared spectroscopy confirmed the occurrence of four significant compounds ('individual' ethanol and water structures as well as two water-ethanol complexes of defined composition - 1 : 1 and 1 : 3). The successful multiple suppression can be achieved for every kind of alcoholic beverage with different alcoholic strengths, when the final ethanol concentration is adjusted to a range between 25% vol and 46% vol (e.g. using dilution or pure ethanol addition). In this optimum region, an individual ethanol peak was not detected, because the 'individual' water structure and the 1 : 1 ethanol-water complex predominate. The nature of molecular association in ethanol-water solutions is essential to elucidate NMR method development for measurement of alcoholic beverages. The presented approach can be used to optimize other NMR suppression protocols for binary water-organic solvent mixtures, where hydrogen bonding plays a dominant role.

  3. Development of an eight-channel NMR system using RF detection coils for measuring spatial distributions of current density and water content in the PEM of a PEFC.

    PubMed

    Ogawa, Kuniyasu; Yokouchi, Yasuo; Haishi, Tomoyuki; Ito, Kohei

    2013-09-01

    The water generation and water transport occurring in a polymer electrolyte fuel cell (PEFC) can be estimated from the current density generated in the PEFC, and the water content in the polymer electrolyte membrane (PEM). In order to measure the spatial distributions and time-dependent changes of current density generated in a PEFC and the water content in a PEM, we have developed an eight-channel nuclear magnetic resonance (NMR) system. To detect a NMR signal from water in a PEM at eight positions, eight small planar RF detection coils of 0.6 mm inside diameter were inserted between the PEM and the gas diffusion layer (GDL) in a PEFC. The local current density generated at the position of the RF detection coil in a PEFC can be calculated from the frequency shift of the obtained NMR signal due to an additional magnetic field induced by the local current density. In addition, the water content in a PEM at the position of the RF detection coil can be calculated by the amplitude of the obtained NMR signal. The time-dependent changes in the spatial distributions were measured at 4 s intervals when the PEFC was operated with supply gas under conditions of fuel gas utilization of 0.67 and relative humidity of the fuel gas of 70%RH. The experimental result showed that the spatial distributions of the local current density and the water content in the PEM within the PEFC both fluctuated with time.

  4. Strategies for diagnosing and alleviating artifactual attenuation associated with large gradient pulses in PGSE NMR diffusion measurements.

    PubMed

    Price, W S; Hayamizu, K; Ide, H; Arata, Y

    1999-08-01

    The generation of phase-based artifacts resulting from mismatch in the effective areas (i.e., the time integrals) of sequential gradient pulses is discussed in the context of large gradient pulsed-gradient spin-echo (PGSE) NMR diffusion measurements. Such effects result in artifactual attenuation and distortion in the spectra which, in the first instance, are similar to (and commonly mistaken for) the effects of eddy currents. Small degrees of mismatch cause "unphysical" concave downward curvature in PGSE attenuation plots of freely diffusing species. However, larger mismatches can result in artifactual diffraction peaks in the plots which could easily be confused for true restricted diffusion effects. Although "rectangular" gradient pulses are preferable from a theoretical viewpoint, we found that shaped gradient (e.g., half-sine) pulses, which due to their slower rise and fall times were more tractable for the current amplifier, were more sequentially reproducible. As well as generating fewer phase-based artifacts such shaped pulses also decrease the likelihood of vibration problems.

  5. Direct measurement of the Mn(II) hydration state in metal complexes and metalloproteins through 17O NMR line widths.

    PubMed

    Gale, Eric M; Zhu, Jiang; Caravan, Peter

    2013-12-11

    Here we describe a simple method to estimate the inner-sphere hydration state of the Mn(II) ion in coordination complexes and metalloproteins. The line width of bulk H2(17)O is measured in the presence and absence of Mn(II) as a function of temperature, and transverse (17)O relaxivities are calculated. It is demonstrated that the maximum (17)O relaxivity is directly proportional to the number of inner-sphere water ligands (q). Using a combination of literature data and experimental data for 12 Mn(II) complexes, we show that this method provides accurate estimates of q with an uncertainty of ±0.2 water molecules. The method can be implemented on commercial NMR spectrometers working at fields of 7 T and higher. The hydration number can be obtained for micromolar Mn(II) concentrations. We show that the technique can be extended to metalloproteins or complex:protein interactions. For example, Mn(II) binds to the multimetal binding site A on human serum albumin with two inner-sphere water ligands that undergo rapid exchange (1.06 × 10(8) s(-1) at 37 °C). The possibility of extending this technique to other metal ions such as Gd(III) is discussed.

  6. A Method for Helical RNA Global Structure Determination in Solution Using Small Angle X-ray Scattering and NMR Measurements

    PubMed Central

    Wang, Jinbu; Zuo, Xiaobing; Yu, Ping; Xu, Huan; Starich, Mary R.; Tiede, David M.; Shapiro, Bruce A.; Schwieters, Charles D.; Wang, Yun-Xing

    2009-01-01

    We report a “top-down” method that uses mainly duplexes' global orientations and overall molecular dimension and shape restraints, which were extracted from experimental NMR and small angle X-ray scattering (SAXS) data respectively, to determine global architectures of RNA molecules consisting of mostly A-form like duplexes. The method is implemented in the G2G (from Global measurement to Global Structure) toolkit of programs. We demonstrate the efficiency and accuracy of the method by determining the global structure of a 71-nucleotide RNA using experimental data. The backbone root-mean-square-deviation (RMSD) of the ensemble of the calculated global structures relative to the X-ray crystal structure using the experimental data is 3.0 ± 0.3 Å, and the RMSD is only 2.5 ± 0.2 Å for the three duplexes that were orientation-restrained during the calculation. The global structure simplifies interpretation of multi-dimensional nuclear Overhauser spectra for high resolution structure determination. The potential general application of the method for RNA structure determination is discussed. PMID:19666030

  7. Structure and dynamics of water in tendon from NMR relaxation measurements.

    PubMed Central

    Peto, S; Gillis, P; Henri, V P

    1990-01-01

    Nuclear magnetic relaxation times were measured in collagen tissue when varying the orientation of the fiber with respect to the static field. T1 was found to be only slightly dependent on theta, the fiber-to-field angle, but T2 was very sensitive to the orientation, with a maximum value at the magic angle. The transverse decay curves were multiexponential. Their deconvolution displayed four components; the ones that decayed most slowly were almost independent of theta, but the two fastest ones showed a strong angular dependence that was interpreted with a cross-relaxation model. Quadrupolar dips were visible in the 1/T1 dispersion curves. These dips were independent of theta, so that the magnetization transfer could also be assumed to be independent of the fiber orientation. Finally, each component was assigned to a fraction of protons localized in the macromolecular structure and characterized by particular dynamics. The model of Woessner was applied to the water molecules tightly bound into the macromolecules, which resulted in a dynamical description of this water fraction. This description is compatible with the two-sites model of Ramachandran based on x-ray diffraction and with the extensive studies of Berendsen. However, the important indications obtained from the deconvolution lead to a less static representation of the tissue. PMID:2297563

  8. Approximation and noise errors of measured T/sub 1/ in NMR imaging

    SciTech Connect

    Persyk, D.E.

    1984-01-01

    Photomultiplier tubes (PMTs) of various types from four manufacturers were measured to determine their gain drift characteristics. This was in turn related to retuning frequency in Anger cameras. A well stabilized light source illuminated sets of thirty-seven PMTs, simulating ideal steady-state conditions in an Anger camera. Anode outputs were sampled at six minute intervals for periods of up to three weeks using a multichannel data logger. Data were analyzed off line. It was found that PMT gains diverged form their initial values at a rate which decreased with time. The standard deviation of the gain changes, called drift, was plotted versus time. Drift was found to generally obey a power law function: D(%) = 0.16 x t/sup 0.6/ where t is the elapsed time in hours. In testing thousands of PMTs the authors occasionally found ''flyers'' with drift rates considerably larger than the average. The authors conclude that with sets of carefully selected PMTs the frequency of tuning would generally decrease as the tubes age. They also conclude that the presence of an occasional ''flyer'' PMT in a camera would undoubtedly necessitate more frequent tuning, in some cases on a weekly basis. These findings support the observed wide variation in tuning frequency among Anger cameras without active PMT gain compensation.

  9. Effect of acute stresses on zebra fish (Danio rerio) metabolome measured by NMR-based metabolomics.

    PubMed

    Mushtaq, Mian Yahya; Marçal, Rosilene Moretti; Champagne, Danielle L; van der Kooy, Frank; Verpoorte, Robert; Choi, Young Hae

    2014-09-01

    We applied an acute stress model to zebra fish in order to measure the changes in the metabolome due to biological stress. This was done by submitting the fish to fifteen minutes of acute confinement (netting) stress, and then five minutes for the open field and light/dark field tests. A polar extract of the zebra fish was then subjected to (1)H nuclear magnetic spectroscopy. Multivariate data analysis of the spectra showed a clear separation associated to a wide range of metabolites between zebra fish that were submitted to open field and light/dark field tests. Alanine, taurine, adenosine, creatine, lactate, and histidine were high in zebra fish to which the light/dark field test was applied, regardless of stress, while acetate and isoleucine/lipids appeared to be higher in zebra fish exposed to the open field test. These results show that any change in the environment, even for a small period of time, has a noticeable physiological impact. This research provides an insight of how different mechanisms are activated under different environments to maintain the homeostasis of the body. It should also contribute to establish zebra fish as a model for metabolomics studies. PMID:25098933

  10. Measurement of State-Specific Association Constants in Allosteric Sensors through Molecular Stapling and NMR.

    PubMed

    Moleschi, Kody J; Akimoto, Madoka; Melacini, Giuseppe

    2015-08-26

    Allostery is a ubiquitous mechanism to control biological function and arises from the coupling of inhibitory and binding equilibria. The extent of coupling reflects the inactive vs active state selectivity of the allosteric effector. Hence, dissecting allosteric determinants requires quantification of state-specific association constants. However, observed association constants are typically population-averages, reporting on overall affinities but not on allosteric coupling. Here we propose a general method to measure state-specific association constants in allosteric sensors based on three key elements, i.e., state-selective molecular stapling through disulfide bridges, competition binding saturation transfer experiments and chemical shift correlation analyses to gauge state populations. The proposed approach was applied to the prototypical cyclic adenosine monophosphate (cAMP)-dependent protein kinase (PKA-RIα), for which the structures of the inactive and active states are available, as needed to design the state-selective disulfide bridges. Surprisingly, the PKA-RIα state-specific association constants are comparable to those of a structurally homologous domain with ∼10(3)-fold lower cAMP-affinity, suggesting that the affinity difference arises primarily from changes in the position of the dynamic apo inhibitory equilibrium.

  11. Water permeability of polyunsaturated lipid membranes measured by 17O NMR.

    PubMed

    Huster, D; Jin, A J; Arnold, K; Gawrisch, K

    1997-08-01

    Diffusion-controlled water permeation across bilayers of polyunsaturated phospholipids was measured by 17O nuclear magnetic resonance. In 100-nm extruded liposomes containing 50 mM MnCl2, water exchange between internal and external solutions was monitored via changes in the linewidth of the 17O water resonance of external water. Liposome size and shape were characterized by light scattering methods and determination of liposome trapped volume. At 25 degrees C, the following water permeability coefficients were determined: 18:0-18:1n-9 PC, 155 +/- 24 microns/s; 18:0-18:3n-3 PC, 330 +/- 88 microns/s; and 18:0-22:6n-3 PC, 412 +/- 91 microns/s. The addition of 1 M ethanol reduced permeability coefficients to 66 +/- 15 microns/s for 18:0-18:1n-9 PC and to 239 +/- 67 microns/s for 18:0-22:6n-3 PC. Furthermore, the addition of 50 mol% 18:1n-9-18:1n-9 PE reduced the water permeability from 122 +/- 21 microns/s for pure 18:1n-9-18:1n-9 PC to 74 +/- 15 microns/s for the mixture. The significant increase in water permeation for membranes with polyunsaturated hydrocarbon chains correlates with looser packing of polyunsaturated lipids at the lipid-water interface and the suggested deeper penetration of water into these bilayers. Ethanol may block water diffusion pathways by occupying points of water entry into bilayers at the interface. The addition of dioleoylphosphatidylethanolamine increases lipid packing density and, consequently, reduces permeation rates.

  12. “CLASSIC NMR”: An In-Situ NMR Strategy for Mapping the Time-Evolution of Crystallization Processes by Combined Liquid-State and Solid-State Measurements**

    PubMed Central

    Hughes, Colan E; Williams, P Andrew; Harris, Kenneth D M

    2014-01-01

    A new in-situ NMR strategy (termed CLASSIC NMR) for mapping the evolution of crystallization processes is reported, involving simultaneous measurement of both liquid-state and solid-state NMR spectra as a function of time. This combined strategy allows complementary information to be obtained on the evolution of both the solid and liquid phases during the crystallization process. In particular, as crystallization proceeds (monitored by solid-state NMR), the solution state becomes more dilute, leading to changes in solution-state speciation and the modes of molecular aggregation in solution, which are monitored by liquid-state NMR. The CLASSIC NMR experiment is applied here to yield new insights into the crystallization of m-aminobenzoic acid. PMID:25044662

  13. Solid State NMR Measurements for Preliminary Lifetime Assessments in gamma-Irradiated and Thermally Aged Siloxane Elastomers

    SciTech Connect

    Chinn, S C; Herberg, J L; Sawvel, A M; Maxwell, R S

    2004-11-29

    Siloxanes have a wide variety of applications throughout the aerospace industry which take advantage of their exceptional insulating and adhesive properties and general resilience. They also offer a wide range of tailorable engineering properties with changes in composition and filler content. They are, however, subject to degradation in radiatively and thermally harsh environments. We are using solid state nuclear magnetic resonance techniques to investigate changes in network and interfacial structure in siloxane elastomers and their correlations to changes in engineering performance in a series of degraded materials. NMR parameters such as transverse ( T{sub 2}) relaxation times, cross relaxation rates, and residual dipolar coupling constants provide excellent probes of changes crosslink density and motional dynamics of the polymers caused by multi-mechanism degradation. The results of NMR studies on aged siloxanes are being used in conjunction with other mechanical tests to provide insight into component failure and degradation kinetics necessary for preliminary lifetime assessments of these materials as well as into the structure-property relationships of the polymers. NMR and MRI results obtained both from high resolution NMR spectrometers as well as low resolution benchtop NMR screening tools will be presented.

  14. Solid State NMR Measurements for Preliminary Lifetime Assessments in (gamma)-Irradiated and Thermally Aged Siloxane Elastomers

    SciTech Connect

    Chinn, S C; Herberg, J L; Sawvel, A M; Maxwell, R S

    2005-02-03

    Siloxanes have a wide variety of applications throughout the aerospace industry which take advantage of their exceptional insulating and adhesive properties and general resilience. They also offer a wide range of tailorable engineering properties with changes in composition and filler content. They are, however, subject to degradation in radiatively and thermally harsh environments. We are using solid state nuclear magnetic resonance techniques to investigate changes in network and interfacial structure in siloxane elastomers and their correlations to changes in engineering performance in a series of degraded materials. Nuclear magnetic resonance (NMR) parameters such as transverse (T{sub 2}) relaxation times, cross relaxation rates, and residual dipolar coupling constants provide excellent probes of changes crosslink density and motional dynamics of the polymers caused by multi-mechanism degradation. The results of NMR studies on aged siloxanes are being used in conjunction with other mechanical tests to provide insight into component failure and degradation kinetics necessary for preliminary lifetime assessments of these materials as well as into the structure-property relationships of the polymers. NMR and magnetic resonance imaging (MRI) results obtained both from high resolution NMR spectrometers as well as low resolution benchtop NMR screening tools will be presented.

  15. The conversion of phenylalanine to tyrosine in man. Direct measurement by continuous intravenous tracer infusions of L-(ring-/sup 2/H5)phenylalanine and L-(1-/sup 13/C) tyrosine in the postabsorptive state

    SciTech Connect

    Clarke, J.T.; Bier, D.M.

    1982-10-01

    Steady state phenylalanine and tyrosine turnover and the rate of conversion of phenylalanine of tyrosine in vivo were determined in 6 healthy postabsorptive adult volunteers. Continuous infusions of tracer amounts of L-(ring-/sup 2/H5)phenylalanine were determined intravenously for 13-14 hr. After 9-10 hr, a priming dose followed by a continuous infusion of L-(1-/sup 13/C)tyrosine was added and maintained, along with the (/sup 2/H5)phenylalanine infusion, for 4 hr. Venous plasma samples were obtained before the initiation of each infusion and every 30 min during the course of the combined (/sup 2/H5)phenylalanine and (/sup 13/C)tyrosine infusion for determination of isotopic enrichments of (/sup 2/H5)phenylalanine, (/sup 13/C)tyrosine, and (/sup 2/H4)tyrosine by gas chromatograph-mass spectrometric analysis of the N-trifluoroacetyl-, methyl ester derivatives of the amino acids. Calculated from the observed enrichments, free phenylalanine and tyrosine turnover rates were 36.1 +/- 5.1 mumole . kg-1 . h-1 and 39.8 +/- 3.5 mumole . kg-1 . h-1, respectively. Phenylalanine was converted to tyrosine at the rate of 5.83 +/- 0.59 mumole . kg-1 . h-1, accounting for approximately 16% of either the phenylalanine or the tyrosine flux. The results indicate that the normal basal steady state phenylalanine hydroxylase activity in vivo in man is lower than that obtained from phenylalanine loading studies. This supports the existence of some type of substance activation of the enzyme as reflected in the previously reported exponential relationship between phenylalanine concentration and phenylalanine hydroxylase activity in vitro. The use of continuous simultaneous infusions of tracer amounts of stable isotope-labeled phenylalanine and tyrosine provides a direct means for studying physiological regulation of phenylalanine hydroxylase activity in vivo.

  16. Measuring small compartment dimensions by probing diffusion dynamics via Non-uniform Oscillating-Gradient Spin-Echo (NOGSE) NMR

    NASA Astrophysics Data System (ADS)

    Shemesh, Noam; Álvarez, Gonzalo A.; Frydman, Lucio

    2013-12-01

    Noninvasive measurements of microstructure in materials, cells, and in biological tissues, constitute a unique capability of gradient-assisted NMR. Diffusion-diffraction MR approaches pioneered by Callaghan demonstrated this ability; Oscillating-Gradient Spin-Echo (OGSE) methodologies tackle the demanding gradient amplitudes required for observing diffraction patterns by utilizing constant-frequency oscillating gradient pairs that probe the diffusion spectrum, D(ω). Here we present a new class of diffusion MR experiments, termed Non-uniform Oscillating-Gradient Spin-Echo (NOGSE), which dynamically probe multiple frequencies of the diffusion spectral density at once, thus affording direct microstructural information on the compartment's dimension. The NOGSE methodology applies N constant-amplitude gradient oscillations; N - 1 of these oscillations are spaced by a characteristic time x, followed by a single gradient oscillation characterized by a time y, such that the diffusion dynamics is probed while keeping (N - 1)x + y ≡ TNOGSE constant. These constant-time, fixed-gradient-amplitude, multi-frequency attributes render NOGSE particularly useful for probing small compartment dimensions with relatively weak gradients - alleviating difficulties associated with probing D(ω) frequency-by-frequency or with varying relaxation weightings, as in other diffusion-monitoring experiments. Analytical descriptions of the NOGSE signal are given, and the sequence's ability to extract small compartment sizes with a sensitivity towards length to the sixth power, is demonstrated using a microstructural phantom. Excellent agreement between theory and experiments was evidenced even upon applying weak gradient amplitudes. An MR imaging version of NOGSE was also implemented in ex vivo pig spinal cords and mouse brains, affording maps based on compartment sizes. The effects of size distributions on NOGSE are also briefly analyzed.

  17. Carbon-deuterium rotational-echo double-resonance NMR spectroscopy of lyophilized aspartame formulations.

    PubMed

    Luthra, Suman A; Utz, Marcel; Gorman, Eric M; Pikal, Michael J; Munson, Eric J; Lubach, Joseph W

    2012-01-01

    In this study, changes in the local conformation of aspartame were observed in annealed lyophilized glasses by monitoring changes in the distance between two labeled sites using C-(2)H rotational-echo double-resonance (REDOR) nuclear magnetic resonance (NMR) spectroscopy. Confirmation that the REDOR experiments were producing accurate distance measurement was ensured by measuring the (13)C-(15)N distance in glycine. The experiment was further verified by measuring the REDOR dephasing curve on (13)C-(2)H methionine. (13)C-(2)H REDOR dephasing curves were then measured on lyophilized aspartame-disaccharide formulations. In aspartame-sucrose formulation, the internuclear distances increased upon annealing, which correlated with decreased chemical reactivity. By contrast, annealing had only a minimal effect on the dephasing curve in aspartame-trehalose formulation. The results show that stability is a function of both mobility and local structure (conformation), even in a small molecule system such as lyophilized aspartame-sucrose. PMID:21935954

  18. Carbon-deuterium rotational-echo double-resonance NMR spectroscopy of lyophilized aspartame formulations.

    PubMed

    Luthra, Suman A; Utz, Marcel; Gorman, Eric M; Pikal, Michael J; Munson, Eric J; Lubach, Joseph W

    2012-01-01

    In this study, changes in the local conformation of aspartame were observed in annealed lyophilized glasses by monitoring changes in the distance between two labeled sites using C-(2)H rotational-echo double-resonance (REDOR) nuclear magnetic resonance (NMR) spectroscopy. Confirmation that the REDOR experiments were producing accurate distance measurement was ensured by measuring the (13)C-(15)N distance in glycine. The experiment was further verified by measuring the REDOR dephasing curve on (13)C-(2)H methionine. (13)C-(2)H REDOR dephasing curves were then measured on lyophilized aspartame-disaccharide formulations. In aspartame-sucrose formulation, the internuclear distances increased upon annealing, which correlated with decreased chemical reactivity. By contrast, annealing had only a minimal effect on the dephasing curve in aspartame-trehalose formulation. The results show that stability is a function of both mobility and local structure (conformation), even in a small molecule system such as lyophilized aspartame-sucrose.

  19. Comparison of surface NMR with non-invasive and in-situ measurements of soil water content at a floodplain field site

    NASA Astrophysics Data System (ADS)

    Dietrich, P.; Werban, U.; Schrön, M.; Walsh, D. O.; Grunewald, E. D.; Pohle, M.; Kathage, S.

    2015-12-01

    Quantification of soil water content is a very relevant issue in soil and environmental studies. There is a broad spectrum of methods applied for measuring soil water content in the field either deployed in situ or non-invasively from the surface. For many reasons the latter is preferred in field studies. Nuclear Magnetic Resonance (NMR) is one of the rare methods that measure the water content directly. Whereas others, e.g. geophysical methods, make use of proximal relationships for determination of soil water content. We applied a new single-sided NMR sensor to non-invasively measure in-situ soil moisture profiles at several points along two transects in a floodplain. The field site exhibits variations in soil water content due to morphology, e.g. flood channels and alluvial fan structures. Furthermore we applied at the same transects (1) in situ methods: soil sampling for gravimetrical analysis and TDR and (2) non-invasive methods: electromagnetical induction, mobile cosmic-ray neutron sensing with a rover and gamma-ray spectrometry. We will present results that confirm agreement of NMR and gravimetrical analysis from soil sampling and discuss issues that arise when using non-unique proxy methods and relationships for determination of soil water content.

  20. Comparison of surface NMR with non-invasive and in-situ measurements of soil water content at a floodplain field site

    NASA Astrophysics Data System (ADS)

    Werban, Ulrike; Schrön, Martin; Dietrich, Peter; Walsh, David; Grunewald, Elliot; Pohle, Marco; Kathage, Susanne

    2016-04-01

    Quantification of soil water content is a very relevant issue in soil and environmental studies. There is a broad spectrum of methods applied for measuring soil water content in the field either deployed in situ or non-invasively from the surface. For many reasons the latter is preferred in field studies. Nuclear Magnetic Resonance (NMR) is one of the rare methods that measure the water content directly. Whereas others, e.g. geophysical methods, make use of proximal relationships for determination of soil water content. We applied a new single-sided NMR sensor to non-invasively measure in-situ soil moisture profiles at several points along two transects in a floodplain. The field site exhibits variations in soil water content due to morphology, e.g. flood channels and alluvial fan structures. Furthermore we applied at the same transects (1) in situ methods: soil sampling for gravimetrical analysis and TDR and (2) non-invasive methods: electromagnetical induction, mobile cosmic-ray neutron sensing with a rover and gamma-ray spectrometry. We will present results that confirm agreement of NMR and gravimetrical analysis from soil sampling and discuss issues that arise when using non-unique proxy methods and relationships for determination of soil water content.

  1. Aircraft measurements of BrO, IO, glyoxal, NO2, H2O, O2-O2 and aerosol extinction profiles in the tropics: comparison with aircraft-/ship-based in situ and lidar measurements

    NASA Astrophysics Data System (ADS)

    Volkamer, R.; Baidar, S.; Campos, T. L.; Coburn, S.; DiGangi, J. P.; Dix, B.; Eloranta, E. W.; Koenig, T. K.; Morley, B.; Ortega, I.; Pierce, B. R.; Reeves, M.; Sinreich, R.; Wang, S.; Zondlo, M. A.; Romashkin, P. A.

    2015-05-01

    Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4) were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAX-DOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity

  2. Aircraft Measurements of BrO, IO, Glyoxal, NO2, H2O, O2-O2 and Aerosol Extinction Profiles in the Tropics: Comparison with Aircraft-/Ship-Based in Situ and Lidar Measurements

    NASA Technical Reports Server (NTRS)

    Volkamer, R.; Baidar, S.; Campos, T. L.; Coburn, S.; DiGangi, J. P.; Dix, B.; Eloranta, E. W.; Koenig, T. K.; Morley, B.; Ortega, I.; Pierce, B. R.; Reeves, M.; Sinreich, R.; Wang, S.; Zondlo, M. A.; Romashkin, P. A.

    2015-01-01

    Tropospheric chemistry of halogens and organic carbon over tropical oceans modifies ozone and atmospheric aerosols, yet atmospheric models remain largely untested for lack of vertically resolved measurements of bromine monoxide (BrO), iodine monoxide (IO) and small oxygenated hydrocarbons like glyoxal (CHOCHO) in the tropical troposphere. BrO, IO, glyoxal, nitrogen dioxide (NO2), water vapor (H2O) and O2-O2 collision complexes (O4/ were measured by the University of Colorado Airborne Multi-AXis Differential Optical Absorption Spectroscopy (CU AMAXDOAS) instrument, aerosol extinction by high spectral resolution lidar (HSRL), in situ aerosol size distributions by an ultra high sensitivity aerosol spectrometer (UHSAS) and in situ H2O by vertical-cavity surface-emitting laser (VCSEL) hygrometer. Data are presented from two research flights (RF12, RF17) aboard the National Science Foundation/ National Center for Atmospheric Research Gulfstream V aircraft over the tropical Eastern Pacific Ocean (tEPO) as part of the "Tropical Ocean tRoposphere Exchange of Reactive halogens and Oxygenated hydrocarbons" (TORERO) project (January/February 2012). We assess the accuracy of O4 slant column density (SCD) measurements in the presence and absence of aerosols. Our O4-inferred aerosol extinction profiles at 477 nm agree within 6% with HSRL in the boundary layer and closely resemble the renormalized profile shape of Mie calculations constrained by UHSAS at low (sub-Rayleigh) aerosol extinction in the free troposphere. CU AMAX-DOAS provides a flexible choice of geometry, which we exploit to minimize the SCD in the reference spectrum (SCDREF, maximize signal-to-noise ratio) and to test the robustness of BrO, IO and glyoxal differential SCDs. The RF12 case study was conducted in pristine marine and free tropospheric air. The RF17 case study was conducted above the NOAA RV Ka'imimoana (TORERO cruise, KA-12-01) and provides independent validation data from ship-based in situ cavity

  3. Synthesis of [2H7]indatraline.

    PubMed

    Allmendinger, L; Wanner, K T

    2014-11-01

    Deuterium-labelled indatraline was synthesized in high efficiency employing a Friedel-Crafts alkylation of [(2)H6]benzene with (E)-3-(3,4-dichlorophenyl)acrylic acid as a key step. The desired labelling of the final compound was ascertained in two ways, by incorporation of [(2)H6]benzene in the target molecule and additionally by deuterium transfer to the non-deuterated aryl moiety of the Friedel-Crafts alkylation product from [(2)H6]benzene, the latter thus serving as reagent and solvent. PMID:25382822

  4. Heterozygous FA2H mutations in autism spectrum disorders

    PubMed Central

    2013-01-01

    Background Widespread abnormalities in white matter development are frequently reported in cases of autism spectrum disorders (ASD) and could be involved in the disconnectivity suggested in these disorders. Homozygous mutations in the gene coding for fatty-acid 2-hydroxylase (FA2H), an enzyme involved in myelin synthesis, are associated with complex leukodystrophies, but little is known about the functional impact of heterozygous FA2H mutations. We hypothesized that rare deleterious heterozygous mutations of FA2H might constitute risk factors for ASD. Methods We searched deleterious mutations affecting FA2H, by genotyping 1256 independent patients with ASD genotyped using Genome Wide SNP arrays, and also by sequencing in independent set of 186 subjects with ASD and 353 controls. We then explored the impact of the identified mutations by measuring FA2H enzymatic activity and expression, in transfected COS7 cells. Results One heterozygous deletion within 16q22.3-q23.1 including FA2H was observed in two siblings who share symptoms of autism and severe cognitive impairment, axial T2-FLAIR weighted MRI posterior periventricular white matter lesions. Also, two rare non-synonymous mutations (R113W and R113Q) were reported. Although predictive models suggested that R113W should be a deleterious, we did not find that FA2H activity was affected by expression of the R113W mutation in cultured COS cells. Conclusions While our results do not support a major role for FA2H coding variants in ASD, a screening of other genes related to myelin synthesis would allow us to better understand the role of non-neuronal elements in ASD susceptibility. PMID:24299421

  5. C2H observations toward the Orion Bar

    NASA Astrophysics Data System (ADS)

    Nagy, Z.; Ossenkopf, V.; Van der Tak, F. F. S.; Faure, A.; Makai, Z.; Bergin, E. A.

    2015-06-01

    Context. The ethynyl radical (C2H) is one of the first radicals to be detected in the interstellar medium. Its higher rotational transitions have recently become available with the Herschel Space Observatory. Aims: We aim to constrain the physical parameters of the C2H emitting gas toward the Orion Bar. Methods: We analyze the C2H line intensities measured toward the Orion Bar CO+ Peak and Herschel/HIFI maps of C2H, CH, and HCO+ and a NANTEN map of [Ci]. We interpret the observed C2H emission using the combination of Herschel/HIFI and NANTEN data with radiative transfer and PDR models. Results: Five rotational transitions of C2H (from N = 6-5 up to N = 10-9) have been detected in the HIFI frequency range toward the CO+ peak of the Orion Bar. Based on the five detected C2H transitions, a single component rotational diagram analysis gives a rotation temperature of ~64 K and a beam-averaged C2H column density of 4 × 1013 cm-2. The rotational diagram is also consistent with a two-component fit, resulting in rotation temperatures of 43 ± 0.2 K and 123 ± 21 K and in beam-averaged column densities of ~8.3 × 1013 cm-2 and ~2.3 × 1013 cm-2 for the three lower-N and for the three higher-N transitions, respectively. The measured five rotational transitions cannot be explained by any single parameter model. According to a non-LTE model, most of the C2H column density produces the lower-N C2H transitions and traces a warm (Tkin ~ 100-150 K) and dense (n(H2) ~ 105-106 cm-3) gas. A small fraction of the C2H column density is required to reproduce the intensity of the highest-N transitions (N = 9-8 and N = 10-9) originating in a high-density (n(H2) ~5 × 106 cm-3) hot (Tkin ~ 400 K) gas. The total beam-averaged C2H column density in the model is 1014 cm-2. A comparison of the spatial distribution of C2H to those of CH, HCO+, and [Ci] shows the best correlation with CH. Conclusions: Both the non-LTE radiative transfer model and a simple PDR model representing the Orion Bar

  6. Acceleration of Natural-Abundance Solid-State MAS NMR Measurements on Bone by Paramagnetic Relaxation from Gadolinium-DTPA

    PubMed Central

    Mroue, Kamal H.; Zhang, Rongchun; Zhu, Peizhi; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

    2014-01-01

    Reducing the data collection time without affecting the signal intensity and spectral resolution is one of the major challenges for the widespread application of multidimensional nuclear magnetic resonance (NMR) spectroscopy, especially in experiments conducted on complex heterogeneous biological systems such as bone. In most of these experiments, the NMR data collection time is ultimately governed by the proton spin-lattice relaxation times (T1). For over two decades, gadolinium(III)-DTPA (Gd-DTPA, DTPA = Diethylenetriamine pentaacetic acid) has been one of the most widely used contrast-enhancement agents in magnetic resonance imaging (MRI). In this study, we demonstrate that Gd-DTPA can also be effectively used to enhance the longitudinal relaxation rates of protons in solid-state NMR experiments conducted on bone without significant line-broadening and chemical-shift-perturbation side effects. Using bovine cortical bone samples incubated in different concentrations of Gd-DTPA complex, the 1H T1 values were calculated from data collected by 1H spin-inversion recovery method detected in natural-abundance 13C cross-polarization magic angle spinning (CPMAS) NMR experiments. Our results reveal that the 1H T1 values can be successfully reduced by a factor of 3.5 using as low as 10 mM Gd-DTPA without reducing the spectral resolution and thus enabling faster data acquisition of the 13C CPMAS spectra. These results obtained from 13C-detected CPMAS experiments were further confirmed using 1H-detected ultrafast MAS experiments on Gd-DTPA doped bone samples. This approach considerably improves the signal-to-noise ratio per unit time of NMR experiments applied to bone samples by reducing the experimental time required to acquire the same number of scans. PMID:24881032

  7. In vivo measurement of the size of oil bodies in plant seeds using a simple and robust pulsed field gradient NMR method.

    PubMed

    Gromova, Marina; Guillermo, Armel; Bayle, Pierre-Alain; Bardet, Michel

    2015-04-01

    An easy to implement and convenient method to measure the mean size of oil bodies (OBs) in plant seeds is proposed using a pulsed field gradient nuclear magnetic resonance (PFGNMR) approach. PFGNMR is a well-known technique used to study either free or restricted diffusion of molecules. As triacylglycerols (TAG) are confined in OBs, analysis of their diffusion properties is a well-suited experimental approach to determine OB sizes. In fact, at long diffusion time, TAG mean squared displacement is limited by the size of the domain where these molecules are confined. In order to access the OB size distribution, strong intensities of magnetic field gradients are generally required. In this work we demonstrate for the first time that a standard liquid-phase NMR probe equipped with a weak-intensity gradient coil can be used to determine the mean size of OBs. Average sizes were measured for several seeds, and OB diameters obtained by PFGNMR were fully consistent with previously published values obtained by microscopy techniques. Moreover, this approach provided evidence of TAG transfer through the network of interconnected OBs, which is dependent on the ability of adjacent membranes to open diffusion routes between OBs. The main advantage of the NMR method is that it does not require any sample preparation and experiments are performed with whole seeds directly introduced in a standard NMR tube.

  8. Suppression of electron correlations in the collapsed tetragonal phase of CaFe2As2 under ambient pressure demonstrated by As75 NMR/NQR measurements

    NASA Astrophysics Data System (ADS)

    Furukawa, Y.; Roy, B.; Ran, S.; Bud'ko, S. L.; Canfield, P. C.

    2014-03-01

    The static and the dynamic spin correlations in the low-temperature collapsed tetragonal and the high-temperature tetragonal phase in CaFe2As2 have been investigated by As75 nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements. Through the temperature (T) dependence of the nuclear spin lattice relaxation rates (1/T1) and the Knight shifts, although stripe-type antiferromagnetic (AFM) spin correlations are realized in the high-temperature tetragonal phase, no trace of the AFM spin correlations can be found in the nonsuperconducting, low-temperature, collapsed tetragonal (cT) phase. Given that there is no magnetic broadening in As75 NMR spectra, together with the T-independent behavior of magnetic susceptibility χ and the T dependence of 1/T1Tχ, we conclude that Fe spin correlations are completely quenched statically and dynamically in the nonsuperconducting cT phase in CaFe2As2.

  9. The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

    NASA Astrophysics Data System (ADS)

    Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

    2016-05-01

    A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

  10. Dual Species NMR Oscillator

    NASA Astrophysics Data System (ADS)

    Weber, Joshua; Korver, Anna; Thrasher, Daniel; Walker, Thad

    2016-05-01

    We present progress towards a dual species nuclear magnetic oscillator using synchronous spin exchange optical pumping. By applying the bias field as a sequence of alkali 2 π pulses, we generate alkali polarization transverse to the bias field. The alkali polarization is then modulated at the noble gas resonance so that through spin exchange collisions the noble gas becomes polarized. This novel method of NMR suppresses the alkali field frequency shift by at least a factor of 2500 as compared to longitudinal NMR. We will present details of the apparatus and measurements of dual species co-magnetometry using this method. Research supported by the NSF and Northrop-Grumman Corp.

  11. Physical properties of single phospholipid bilayers adsorbed to micro glass beads. A new vesicular model system studied by 2H-nuclear magnetic resonance.

    PubMed

    Bayerl, T M; Bloom, M

    1990-08-01

    Spherical supported vesicles (SSVs), a new model system consisting of single dimyristoyl phosphatidylcholine (DMPC) bilayers adsorbed to spherical glass beads with a narrow size distribution, were prepared at two different sizes (0.5 and 1.5 microns) and their physical properties were studied by deuterium nuclear magnetic resonance (2H-NMR). Such SSV samples can be prepared at any desired size between 0.3 and 10 microns. The 2H-NMR measurements provide evidence for a strong dependence of the spectra and the transverse relaxation times on the curvature of the SSVs in a diameter range between 0.5 and 1.5 microns. For larger SSVs (1.5 microns diameter) their powder spectra and their calculated oriented spectra are similar to those obtained for multilamellar dispersions of DMPC-d54. The lineshape of the smaller SSVs exhibits a temperature dependence which is not found in multilamellar samples. The SSVs are stable in the liquid crystalline phase over days but irreversibly change to multilamellar vesicles in the gel state. The average thickness of the water layer between the single bilayer and the glass bead surface was estimated by 1H-NMR to e 17 +/- 5 A.

  12. Physical properties of single phospholipid bilayers adsorbed to micro glass beads. A new vesicular model system studied by 2H-nuclear magnetic resonance.

    PubMed Central

    Bayerl, T M; Bloom, M

    1990-01-01

    Spherical supported vesicles (SSVs), a new model system consisting of single dimyristoyl phosphatidylcholine (DMPC) bilayers adsorbed to spherical glass beads with a narrow size distribution, were prepared at two different sizes (0.5 and 1.5 microns) and their physical properties were studied by deuterium nuclear magnetic resonance (2H-NMR). Such SSV samples can be prepared at any desired size between 0.3 and 10 microns. The 2H-NMR measurements provide evidence for a strong dependence of the spectra and the transverse relaxation times on the curvature of the SSVs in a diameter range between 0.5 and 1.5 microns. For larger SSVs (1.5 microns diameter) their powder spectra and their calculated oriented spectra are similar to those obtained for multilamellar dispersions of DMPC-d54. The lineshape of the smaller SSVs exhibits a temperature dependence which is not found in multilamellar samples. The SSVs are stable in the liquid crystalline phase over days but irreversibly change to multilamellar vesicles in the gel state. The average thickness of the water layer between the single bilayer and the glass bead surface was estimated by 1H-NMR to e 17 +/- 5 A. PMID:2207243

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

    NASA Astrophysics Data System (ADS)

    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.

  14. Transport properties investigation of aqueous protic ionic liquid solutions through conductivity, viscosity, and NMR self-diffusion measurements.

    PubMed

    Anouti, Mérièm; Jacquemin, Johan; Porion, Patrice

    2012-04-12

    We present a study on the transport properties through conductivity (σ), viscosity (η), and self-diffusion coefficient (D) measurements of two pure protic ionic liquids--pyrrolidinium hydrogen sulfate, [Pyrr][HSO(4)], and pyrrolidinium trifluoroacetate, [Pyrr][CF(3)COO]--and their mixtures with water over the whole composition range at 298.15 K and atmospheric pressure. Based on these experimental results, transport mobilities of ions have been then investigated in each case through the Stokes-Einstein equation. From this, the proton conduction in these PILs follows a combination of Grotthuss and vehicle-type mechanisms, which depends also on the water composition in solution. In each case, the displacement of the NMR peak attributed to the labile proton on the pyrrolidinium cation with the PILs concentration in aqueous solution indicates that this proton is located between the cation and the anion for a water weight fraction lower than 8%. In other words, for such compositions, it appears that this labile proton is not solvated by water molecules. However, for higher water content, the labile protons are in solution as H(3)O(+). This water weight fraction appears to be the solvation limit of the H(+) ions by water molecules in these two PILs solutions. However, [Pyrr][HSO(4)] and [Pyrr][CF(3)COO] PILs present opposed comportment in aqueous solution. In the case of [Pyrr][CF(3)COO], η, σ, D, and the attractive potential, E(pot), between ions indicate clearly that the diffusion of each ion is similar. In other words, these ions are tightly bound together as ion pairs, reflecting in fact the importance of the hydrophobicity of the trifluoroacetate anion, whereas, in the case of the [Pyrr][HSO(4)], the strong H-bond between the HSO(4)(-) anion and water promotes a drastic change in the viscosity of the aqueous solution, as well as on the conductivity which is up to 187 mS·cm(-1) for water weight fraction close to 60% at 298 K.

  15. Advanced NMR characterization of zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Welsh, L. B.

    1985-04-01

    The program discussed in this report is a two-year two-phase joint UOP-University of Illinois study of the application of improved high resolution solid state nuclear magnetic resonance (NMR) techniques to the characterization of zeolite catalysts. During the first phase of this program very pure, and in some cases isotopically enriched faujasites will be prepared and studied by magic angle sample spinning NMR (MASS NMR) and variable engine sample spinning NMR (VASS NMR) on 500 and 360 MHz (proton frequency) NMR spectrometers. The NMR techniques that will be emphasized are the measurement and analysis of the (17)O NMR properties, (27)Al NMR intensity quantitation, and (27)Al and (29)Si NMR relaxation rates. During the second phase of this program these NMR techniques will be used to study the effects of impurity concentration, dealumination treatments and cation exchange on the NMR properties of faujasites. The initial emphasis of this program during Phase I is on the preparation and measurement of the NMR properties of (17)O enriched Na-Y faujasties.

  16. Protein structure by solid-state NMR of oriented systems

    SciTech Connect

    Stewart, P.L.

    1987-01-01

    A method for determining protein backbone structure from angular information obtainable by solid state NMR spectroscopy is presented. Various spin interactions including quadrupole, dipole, and chemical shift interactions and nuclei including /sup 14/N, /sup 15/N, /sup 13/C, and /sup 2/H may be observed. Angularly dependent measurements can be made when the sample has at least one direction of order along the externally applied magnetic field. Several NMR parameters are used to determine the orientation of each peptide plane with respect to the magnetic field vector, B/sub O/, to within a few symmetry related possibilities. The computer program Totlink can then be used to perform the necessary coordinate transformations and to evaluate the possible backbone structures and select for the most chemically reasonable. Experimental /sup 14/N NMR structural studies of the model peptides n-acetyl-d,l-valine, n-acetyl-l-valyl-l-leucine, and l-alanyl-glycyl-glycine and preliminary /sup 14/N NMR results on a large single crystal of orthorhombic lysozyme are presented.

  17. TCA Cycle Turnover And Serum Glucose Sources By Automated Bayesian Analysis Of NMR Spectra

    SciTech Connect

    Merritt, Matthew E.; Burgess, Shawn; Jeffrey, F. Mark; Sherry, A. Dean; Malloy, Craig; Bretthorst, G. Larry

    2004-04-21

    Changes in sources of serum glucose are indicative of a variety of pathological metabolic states. It is possible to measure the sources of serum glucose by the administration of deuterated water to a subject followed by analysis of the 2H enrichment levels in glucose extracted from plasma from a single blood draw by 2H NMR. Markov Chain Monte Carlo simulations of the posterior probability densities may then be used to evaluate the contribution of glycogenolysis, glycerol, and the Kreb's cycle to serum glucose. Experiments with simulated NMR spectra show that in spectra with a S/N of 20 to 1, the resulting metabolic information may be evaluated with an accuracy of about 4 percent.

  18. TCA Cycle Turnover And Serum Glucose Sources By Automated Bayesian Analysis Of NMR Spectra

    NASA Astrophysics Data System (ADS)

    Merritt, Matthew E.; Burgess, Shawn; Jeffrey, F. Mark; Sherry, A. Dean; Malloy, Craig; Bretthorst, G. Larry

    2004-04-01

    Changes in sources of serum glucose are indicative of a variety of pathological metabolic states. It is possible to measure the sources of serum glucose by the administration of deuterated water to a subject followed by analysis of the 2H enrichment levels in glucose extracted from plasma from a single blood draw by 2H NMR. Markov Chain Monte Carlo simulations of the posterior probability densities may then be used to evaluate the contribution of glycogenolysis, glycerol, and the Kreb's cycle to serum glucose. Experiments with simulated NMR spectra show that in spectra with a S/N of 20 to 1, the resulting metabolic information may be evaluated with an accuracy of about 4 percent.

  19. Tracer diffusion measurements in solid lithium: a test case for the comparison between NMR in static and pulsed magnetic field gradients after upgrading a standard solid state NMR spectrometer.

    PubMed

    Marion Fischer, D; Duwe, Peter; Indris, Sylvio; Heitjans, Paul

    2004-09-01

    This paper reports on the upgrading of a standard solid state NMR spectrometer, which has been used in combination with a field variable 7 T cryomagnet, to a low-cost combined SFG and PFG NMR spectrometer. Both methods are applied to solid lithium as a simple test case. The results show that under the given conditions SFG NMR and PFG NMR can provide tracer diffusion coefficients for 7 Li diffusion down to about 10(-14) and 10(-13) m2/s, respectively. SFG and PFG NMR are complementary methods. The paper demonstrates advantages and disadvantages of each method with a concrete example and why it is desirable to be able to apply both methods to the same sample.

  20. THz Dynamic Nuclear Polarization NMR

    PubMed Central

    Nanni, Emilio A.; Barnes, Alexander B.; Griffin, Robert G.; Temkin, Richard J.

    2013-01-01

    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. PMID:24639915

  1. Mapping membrane protein backbone dynamics: a comparison of site-directed spin labeling with NMR 15N-relaxation measurements.

    PubMed

    Lo, Ryan H; Kroncke, Brett M; Solomon, Tsega L; Columbus, Linda

    2014-10-01

    The ability to detect nanosecond backbone dynamics with site-directed spin labeling (SDSL) in soluble proteins has been well established. However, for membrane proteins, the nitroxide appears to have more interactions with the protein surface, potentially hindering the sensitivity to backbone motions. To determine whether membrane protein backbone dynamics could be mapped with SDSL, a nitroxide was introduced at 55 independent sites in a model polytopic membrane protein, TM0026. Electron paramagnetic resonance spectral parameters were compared with NMR (15)N-relaxation data. Sequential scans revealed backbone dynamics with the same trends observed for the R1 relaxation rate, suggesting that nitroxide dynamics remain coupled to the backbone on membrane proteins.

  2. Proton clouds to measure long-range contacts between nonexchangeable side chain protons in solid-state NMR.

    PubMed

    Sinnige, Tessa; Daniëls, Mark; Baldus, Marc; Weingarth, Markus

    2014-03-26

    We show that selective labeling of proteins with protonated amino acids embedded in a perdeuterated matrix, dubbed 'proton clouds', provides general access to long-range contacts between nonexchangeable side chain protons in proton-detected solid-state NMR, which is important to study protein tertiary structure. Proton-cloud labeling significantly improves spectral resolution by simultaneously reducing proton line width and spectral crowding despite a high local proton density in clouds. The approach is amenable to almost all canonical amino acids. Our method is demonstrated on ubiquitin and the β-barrel membrane protein BamA.

  3. A multiple pulse zero crossing NMR technique, and its application to F-19 chemical shift measurements in solids

    NASA Technical Reports Server (NTRS)

    Burum, D. P.; Elleman, D. D.; Rhim, W.-K.

    1978-01-01

    A simple multiple-pulse 'zero crossing technique' for accurately determining the first moment of a solid-state NMR spectrum is introduced. This technique was applied to obtain the F-19 chemical shift versus pressure curves up to 5 kbar for single crystals of CaF2 (0.29 + or - 0.02 ppm/kbar) and BaF2 (0.62 + or - 0.05 ppm/kbar). Results at ambient temperature and pressure are also reported for a number of other fluorine compounds. Because of its high data rate, this technique is potentially several orders of magnitude more sensitive than similar CW methods.

  4. Absolute nutrient concentration measurements in cell culture media: (1)H q-NMR spectra and data to compare the efficiency of pH-controlled protein precipitation versus CPMG or post-processing filtering approaches.

    PubMed

    Goldoni, Luca; Beringhelli, Tiziana; Rocchia, Walter; Realini, Natalia; Piomelli, Daniele

    2016-09-01

    The NMR spectra and data reported in this article refer to the research article titled "A simple and accurate protocol for absolute polar metabolite quantification in cell cultures using q-NMR" [1]. We provide the (1)H q-NMR spectra of cell culture media (DMEM) after removal of serum proteins, which show the different efficiency of various precipitating solvents, the solvent/DMEM ratios, and pH of the solution. We compare the data of the absolute nutrient concentrations, measured by PULCON external standard method, before and after precipitation of serum proteins and those obtained using CPMG (Carr-Purcell-Meiboom-Gill) sequence or applying post-processing filtering algorithms to remove, from the (1)H q-NMR spectra, the proteins signal contribution. For each of these approaches, the percent error in the absolute value of every measurement for all the nutrients is also plotted as accuracy assessment. PMID:27331118

  5. Synthesis and Stereochemical Assignment of Crypto-Optically Active (2) H6 -Neopentane.

    PubMed

    Masarwa, Ahmad; Gerbig, Dennis; Oskar, Liron; Loewenstein, Aharon; Reisenauer, Hans Peter; Lesot, Philippe; Schreiner, Peter R; Marek, Ilan

    2015-10-26

    The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of (2) H6 -1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to (2) H6 -1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory. PMID:26480341

  6. Synthesis and Stereochemical Assignment of Crypto-Optically Active (2) H6 -Neopentane.

    PubMed

    Masarwa, Ahmad; Gerbig, Dennis; Oskar, Liron; Loewenstein, Aharon; Reisenauer, Hans Peter; Lesot, Philippe; Schreiner, Peter R; Marek, Ilan

    2015-10-26

    The determination of the absolute configuration of chiral molecules is at the heart of asymmetric synthesis. Here we probe the spectroscopic limits for chiral discrimination with NMR spectroscopy in chiral aligned media and with vibrational circular dichroism spectroscopy of the sixfold-deuterated chiral neopentane. The study of this compound presents formidable challenges since its stereogenicity is only due to small mass differences. For this purpose, we selectively prepared both enantiomers of (2) H6 -1 through a concise synthesis utilizing multifunctional intermediates. While NMR spectroscopy in chiral aligned media could be used to characterize the precursors to (2) H6 -1, the final assignment could only be accomplished with VCD spectroscopy, despite the fleetingly small dichroic properties of 1. Both enantiomers were assigned by matching the VCD spectra with those computed with density functional theory.

  7. The effects of cholera enterotoxin on intestinal tissue water as measured by nuclear magnetic resonance (NMR) spectroscopy.

    PubMed

    Udall, J N; Alvarez, L A; Nichols, B L; Hazlewood, C F

    1975-01-01

    Cholera enterotoxin has been postulated to change the configuration of the intracellular protein-water system, altering the permeability of the cell to water. Using nuclear magnetic resonance (NMR) spectroscopy, this protein-water relationship can be examined. Small intestinal loops in the rat were injected with 0.5 ml of either Schwarz/Mann cholera enterotoxin (40 mug/cc saline solution) or normal saline. Full thickness segments of intestine from each loop were taken and percentage water (using a gravimetric procedure which includes a correction for fat) and NMR relaxation times were determined. The mean value +/- S.D. for tissue water was 79.49 +/- 2.65% in the controls and 84.52 +/- 2.01% in the cholera specimens (p less than .001). T1 (spin-lattice) relaxation times were 521.22 +/- 69.5 msec in the controls and 667.96 +/- 119.25 msec in cholera tissue (p less than .001). T2 (spin-spin) relaxation times were 62.34 +/- 9.59 msec in controls and 80.35 +/- 21.46 msec in cholera tissue (p less than .02). These findings are consistent with the theory that cholera enterotoxin acts to alter intracellular protein-water relationship.

  8. In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

    PubMed

    Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

    2013-01-01

    We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions. PMID:22676479

  9. Achievement of a 920-MHz High Resolution NMR

    NASA Astrophysics Data System (ADS)

    Hashi, Kenjiro; Shimizu, Tadashi; Goto, Atsushi; Kiyoshi, Tsukasa; Matsumoto, Shinji; Wada, Hitoshi; Fujito, Teruaki; Hasegawa, Ken-ichi; Yoshikawa, Masatoshi; Miki, Takashi; Ito, Satoshi; Hamada, Mamoru; Hayashi, Seiji

    2002-06-01

    We have developed a 920-MHz NMR system and performed the proton NMR measurement of H 2O and ethylbenzene using the superconducting magnet operating at 21.6 T (920 MHz for proton), which is the highest field produced by a superconducting NMR magnet in the persistent mode. From the NMR measurements, it is verified that both homogeneity and stability of the magnet have a specification sufficient for a high resolution NMR.

  10. Fully-Automated High-Throughput NMR System for Screening of Haploid Kernels of Maize (Corn) by Measurement of Oil Content.

    PubMed

    Wang, Hongzhi; Liu, Jin; Xu, Xiaoping; Huang, Qingming; Chen, Shanshan; Yang, Peiqiang; Chen, Shaojiang; Song, Yiqiao

    2016-01-01

    One of the modern crop breeding techniques uses doubled haploid plants that contain an identical pair of chromosomes in order to accelerate the breeding process. Rapid haploid identification method is critical for large-scale selections of double haploids. The conventional methods based on the color of the endosperm and embryo seeds are slow, manual and prone to error. On the other hand, there exists a significant difference between diploid and haploid seeds generated by high oil inducer, which makes it possible to use oil content to identify the haploid. This paper describes a fully-automated high-throughput NMR screening system for maize haploid kernel identification. The system is comprised of a sampler unit to select a single kernel to feed for measurement of NMR and weight, and a kernel sorter to distribute the kernel according to the measurement result. Tests of the system show a consistent accuracy of 94% with an average screening time of 4 seconds per kernel. Field test result is described and the directions for future improvement are discussed. PMID:27454427

  11. Quantitative measurement of major secoiridoid derivatives in olive oil using qNMR. Proof of the artificial formation of aldehydic oleuropein and ligstroside aglycon isomers.

    PubMed

    Karkoula, Evangelia; Skantzari, Angeliki; Melliou, Eleni; Magiatis, Prokopios

    2014-01-22

    A previously developed method for measurement of oleocanthal and oleacein in olive oil by quantitative (1)H NMR was expanded to include the measurement of the monoaldehydic forms of oleuropein and ligstroside aglycons. The method was validated and applied to the study of 340 monovarietal Greek and Californian olive oils from 23 varieties and for a 3-year period. A wide variation concerning the concentrations of all four secoiridoids was recorded. The concentration of each one ranged from nondetectable to 711 mg/kg and the sum of the four major secoiridoids (named as D3) ranged from nondetectable to 1534 mg/kg. Examination of the NMR profile of the olive oil extract before and after contact with normal or reversed stationary chromatography phase proved the artificial formation of the 5S,8S,9S aldehydic forms of oleuropein and ligstroside aglycon isomers during chromatography. Finally, methyl elenolate was identified for the first time as a minor constituent of olive oil. PMID:24384036

  12. Fully-Automated High-Throughput NMR System for Screening of Haploid Kernels of Maize (Corn) by Measurement of Oil Content

    PubMed Central

    Xu, Xiaoping; Huang, Qingming; Chen, Shanshan; Yang, Peiqiang; Chen, Shaojiang; Song, Yiqiao

    2016-01-01

    One of the modern crop breeding techniques uses doubled haploid plants that contain an identical pair of chromosomes in order to accelerate the breeding process. Rapid haploid identification method is critical for large-scale selections of double haploids. The conventional methods based on the color of the endosperm and embryo seeds are slow, manual and prone to error. On the other hand, there exists a significant difference between diploid and haploid seeds generated by high oil inducer, which makes it possible to use oil content to identify the haploid. This paper describes a fully-automated high-throughput NMR screening system for maize haploid kernel identification. The system is comprised of a sampler unit to select a single kernel to feed for measurement of NMR and weight, and a kernel sorter to distribute the kernel according to the measurement result. Tests of the system show a consistent accuracy of 94% with an average screening time of 4 seconds per kernel. Field test result is described and the directions for future improvement are discussed. PMID:27454427

  13. Formation of κ-carrageenan-gelatin polyelectrolyte complexes studied by (1)H NMR, UV spectroscopy and kinematic viscosity measurements.

    PubMed

    Voron'ko, Nicolay G; Derkach, Svetlana R; Vovk, Mikhail A; Tolstoy, Peter M

    2016-10-20

    The intermolecular interactions between an anionic polysaccharide from the red algae κ-carrageenan and a gelatin polypeptide, forming stoichiometric polysaccharide-polypeptide (bio)polyelectrolyte complexes in the aqueous phase, were examined. The major method of investigation was high-resolution (1)H NMR spectroscopy. Additional data were obtained by UV absorption spectroscopy, light scattering dispersion and capillary viscometry. Experimental data were interpreted in terms of the changing roles of electrostatic interactions, hydrophobic interactions and hydrogen bonds when κ-carrageenan-gelatin complexes are formed. At high temperatures, when biopolymer macromolecules in solution are in the state of random coil, hydrophobic interactions make a major contribution to complex stabilization. At the temperature of gelatin's coil→helix conformational transition and at lower temperatures, electrostatic interactions and hydrogen bonds play a defining role in complex formation. A proposed model of the κ-carrageenan-gelatin complex is discussed. PMID:27474666

  14. Refractive index and birefringence of 2H silicon carbide

    NASA Technical Reports Server (NTRS)

    Powell, J. A.

    1972-01-01

    The refractive indices of 2H SiC were measured over the wavelength range 435.8 to 650.9 nm by the method of minimum deviation. At the wavelength lambda = 546.1 nm, the ordinary index n sub 0 was 2.6480 and the extraordinary index n sub e was 2.7237. The estimated error (standard deviation) in the measured values is 0.0006 for n sub 0 and 0.0009 for n sub e. The experimental data were curve fitted to the Cauchy equation for the index of refraction as a function of wavelength. The birefringence of 2H SiC was found to vary from 0.0719 at lambda = 650.9 nm to 0.0846 at lambda = 435.8 nm.

  15. Measurement of Internal Acyl Migration Reaction Kinetics Using Directly Coupled HPLC-NMR:  Application for the Positional Isomers of Synthetic (2-Fluorobenzoyl)-d-glucopyranuronic Acid.

    PubMed

    Sidelmann, U G; Hansen, S H; Gavaghan, C; Carless, H A; Lindon, J C; Farrant, R D; Wilson, I D; Nicholson, J K

    1996-08-01

    Ester glucuronides (1-O-acyl-β-d-glucopyranuronates) of many drugs may undergo internal acyl migration reactions, resulting in the formation of new positional isomers with both α- and β-anomers. We illustrate here a novel approach for the direct investigation of the acyl migration kinetics of ester glucuronides and show the application with respect to the isomers of synthetic (2-fluorobenzoyl)-d-glucopyranuronic acid. Individual isomers were separated from an equilibrium mixture containing the β-1-O-acyl, α- and β-2-O-acyl, α- and β-3-O-acyl, and α- and β-4-O-acyl isomers at pH 7.4 in 20 mM phosphate buffer. The interconverting isomers were separated using reversed-phase HPLC and pumped directly into a dedicated on-line NMR flow probe in a 600 MHz NMR spectrometer. The flow was stopped with each isomer in the NMR flow probe, and sequential NMR spectra were collected at 25 °C, allowing direct measurement of the production of positional isomers from each selectively isolated glucuronide isomer. All of the positional isomers and anomers were characterized, and relative quantities determined, and a kinetic model describing the rearrangement reactions was constructed. The acyl migration reaction kinetics were simulated using a theoretical approach using nine first-order rate constants determined for the acyl migration reactions and six first-order rate constants describing the mutarotation each of the 2-, 3-, and 4-positional isomers. The rate constants (in h(-)(1)) for the rearrangement reactions of the 2-fluorobenzoyl glucuronide isomers were as follows:  β-1-O-acyl, 0.29 ± 0.01; α-2-O-acyl, 0.11 ± 0.01; β-2-O-acyl, 0.07 ± 0.01; α-3-O-acyl, 0.10 ± 0.01; β-3-O-acyl, 0.09 ± 0.01; α-4-O-acyl, 0.09 ± 0.01; and β-4-O-acyl, 0.06 ± 0.01. The α- and β-anomerization rates were estimated on the basis of the kinetics model; the anomerization rates of the 4-O-acyl isomers were additionally determined experimentally using directly coupled HPLC-NMR. The

  16. Full-dimensional quantum dynamics study of the H2 + C2H → H + C2H2 reaction on an ab initio potential energy surface.

    PubMed

    Chen, Liuyang; Shao, Kejie; Chen, Jun; Yang, Minghui; Zhang, Dong H

    2016-05-21

    This work performs a time-dependent wavepacket study of the H2 + C2H → H + C2H2 reaction on a new ab initio potential energy surface (PES). The PES is constructed using neural network method based on 68 478 geometries with energies calculated at UCCSD(T)-F12a/aug-cc-pVTZ level and covers H2 + C2H↔H + C2H2, H + C2H2 → HCCH2, and HCCH2 radial isomerization reaction regions. The reaction dynamics of H2 + C2H → H + C2H2 are investigated using full-dimensional quantum dynamics method. The initial-state selected reaction probabilities are calculated for reactants in eight vibrational states. The calculated results showed that the H2 vibrational excitation predominantly enhances the reactivity while the excitation of bending mode of C2H slightly inhibits the reaction. The excitations of two stretching modes of C2H molecule have negligible effect on the reactivity. The integral cross section is calculated with J-shift approximation and the mode selectivity in this reaction is discussed. The rate constants over 200-2000 K are calculated and agree well with the experimental measured values.

  17. Volovik effect and Fermi-liquid behavior in the s-wave superconductor CaPd2As2: As75 NMR-NQR measurements

    DOE PAGES

    Ding, Q. -P.; Wiecki, P.; Anand, V. K.; Sangeetha, N. S.; Lee, Y.; Johnston, D. C.; Furukawa, Y.

    2016-04-07

    The electronic and magnetic properties of the collapsed-tetragonal CaPd2As2 superconductor (SC) with a transition temperature of 1.27 K have been investigated by 75As nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) measurements. The temperature (T) dependence of the nuclear spin lattice relaxation rates (1/T1) and the Knight shifts indicate the absence of magnetic correlations in the normal state. In the SC state, 1/T1 measured by 75As NQR shows a clear Hebel-Slichter (HS) peak just below Tc and decreases exponentially at lower T, confirming a conventional s-wave SC. Additionally, the Volovik effect, also known as the Doppler shift effect, hasmore » been clearly evidenced by the observation of the suppression of the HS peak with applied magnetic field.« less

  18. Copper-catalysed asymmetric allylic alkylation of alkylzirconocenes to racemic 3,6-dihydro-2H-pyrans

    PubMed Central

    Rideau, Emeline

    2015-01-01

    Summary Asymmetric allylic alkylation is a powerful reaction that allows the enantioselective formation of C–C bonds. Here we describe the asymmetric alkylation of alkylzirconium species to racemic 3,6-dihydro-2H-pyrans. Two systems were examined: 3-chloro-3,6-dihydro-2H-pyran using linear optimization (45–93% ee, up to 33% yield, 5 examples) and 3,6-dihydro-2H-pyran-3-yl diethyl phosphate with the assistance of a design of experiments statistical approach (83% ee, 12% yield). 1H NMR spectroscopy was used to gain insight into the reaction mechanisms. PMID:26734091

  19. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  20. Hyphenated low-field NMR techniques: combining NMR with NIR, GPC/SEC and rheometry.

    PubMed

    Räntzsch, Volker; Wilhelm, Manfred; Guthausen, Gisela

    2016-06-01

    Hyphenated low-field NMR techniques are promising characterization methods for online process analytics and comprehensive offline studies of soft materials. By combining different analytical methods with low-field NMR, information on chemical and physical properties can be correlated with molecular dynamics and complementary chemical information. In this review, we present three hyphenated low-field NMR techniques: a combination of near-infrared spectroscopy and time-domain NMR (TD-NMR) relaxometry, online (1) H-NMR spectroscopy measured directly after size exclusion chromatographic (SEC, also known as GPC) separation and a combination of rheometry and TD-NMR relaxometry for highly viscous materials. Case studies are reviewed that underline the possibilities and challenges of the different hyphenated low-field NMR methods. Copyright © 2015 John Wiley & Sons, Ltd.

  1. Synthesis of stereospecifically deuterated desoxypodophyllotoxins and 1H-nmr assignment of desoxypodophyllotoxin

    NASA Technical Reports Server (NTRS)

    Pullockaran, A. J.; Kingston, D. G.; Lewis, N. G.

    1989-01-01

    [4 beta- 2H1]Desoxypodophyllotoxin [3], [4 alpha- 2H1]desoxypodophyllotoxin [4], and [4, 4- 2 H2]desoxypodophyllotoxin [9] were prepared from podophyllotoxin [1] via its chloride [5]. A complete assignment of the 1H-nmr spectrum of desoxypodophyllotoxin [2] was made on the basis of the spectra of the deuterated compounds [3] and [4].

  2. 33S NMR cryogenic probe for taurine detection

    NASA Astrophysics Data System (ADS)

    Hobo, Fumio; Takahashi, Masato; Maeda, Hideaki

    2009-03-01

    With the goal of a S33 nuclear magnetic resonance (NMR) probe applicable to in vivo NMR on taurine-biological samples, we have developed the S33 NMR cryogenic probe, which is applicable to taurine solutions. The NMR sensitivity gain relative to a conventional broadband probe is as large as 3.5. This work suggests that improvements in the preamplifier could allow NMR measurements on 100 μM taurine solutions, which is the level of sensitivity necessary for biological samples.

  3. Analysis of internal motions of interleukin-13 variant associated with severe bronchial asthma using {sup 15}N NMR relaxation measurements

    SciTech Connect

    Yoshida, Yuichiro; Ohkuri, Takatoshi; Takeda, Chika; Kuroki, Ryota; Izuhara, Kenji; Imoto, Taiji; Ueda, Tadashi . E-mail: ueda@phar.kyushu-u.ac.jp

    2007-06-22

    The single nucleotide polymorphism interleukin-13 (IL-13) R110Q is associated with severe bronchial asthma because its lower affinity leads to the augmentation of local IL-13 concentration, resulting in an increase in the signal transduction via IL-13R. Since the mutation site does not directly bind to IL-13R{alpha}2, we carried out NMR relaxation analyses of the wild-type IL-13 and IL-13-R110Q in order to examine whether the R110Q mutation affects the internal motions in IL-13 molecules. The results showed that the internal motion in the micro- to millisecond time scale on helix D, which is suggested to be important for the interaction between IL-13 and IL-13R{alpha}2, is increased in IL-13-R110Q compared with that in the wild-type IL-13. It therefore appears that the difference in the internal motions on helix D between the wild-type IL-13 and IL-13-R110Q may be involved in their affinity differences with IL-13R{alpha}2.

  4. Direct measurement of agonist binding to genetically engineered peptides of the acetylcholine receptor by selective T sub 1 NMR relaxation

    SciTech Connect

    Fraenkel, Y.; Navon, G. ); Aronheim, A.; Gershoni, J.M. )

    1990-03-13

    Interactions of four ligands of the nicotinic acetylcholine receptor with genetically engineered peptides have been studied by NMR. A recombinant cholinergic binding site was prepared as a fusion protein between a truncated form of the bacterial protein trpE and a peptide corresponding to the sequence {alpha}184-200 from the Torpedo californica receptor. This construct binds {alpha}-bungarotoxin while the trpE protein alone does not, and thus serves as a negative control. In this study agonist binding to {alpha}184-200 is demonstrated by monitoring the T{sub 1} relaxation of the ligand's protons in the presence and absence of the recombinant binding site. This binding is specific as it can be competed with {alpha}-bungarotoxin. Quantitative analyses of such competitions yielded the concentration of binding sites, which corresponded to 3.3% and 16.5% of the total protein, for partially purified and affinity-purified {alpha}184-200 constructs, respectively. The K{sub D} values for the binding of acetylcholine, nicotine, d-tubocurarine, and gallamine to the affinity-purified construct were 1.4, 1.4, 0.20, and 0.21 mM, respectively, while K{sub D}'s with the nontoxin binding protein were all above 10 mM. Thus, this is a direct demonstration that the toxin binding domain {alpha}184-200 may comprise a major component of the cholinergic agonist site.

  5. Metastatic Melanoma Induced Metabolic Changes in C57BL/6J Mouse Stomach Measured by 1H NMR Spectroscopy

    SciTech Connect

    Hu, M; Wang, Xiliang

    2014-12-05

    Melanoma is a malignant tumor of melanocytes with high capability of invasion and rapid metastasis to other organs. Malignant melanoma is the most common metastatic malignancy found in gastrointestinal tract (GI). To the best of our knowledge, previous studies of melanoma in gastrointestinal tract are all clinical case reports. In this work, 1H NMR-based metabolomics approach is used to investigate the metabolite profiles differences of stomach tissue extracts of metastatic B16-F10 melanoma in C57BL/6J mouse and search for specific metabolite biomarker candidates. Principal Component Analysis (PCA), an unsupervised multivariate data analysis method, is used to detect possible outliers, while Orthogonal Projection to Latent Structure (OPLS), a supervised multivariate data analysis method, is employed to evaluate important metabolites responsible for discriminating the control and the melanoma groups. Both PCA and OPLS results reveal that the melanoma group can be well separated from its control group. Among the 50 identified metabolites, it is found that the concentrations of 19 metabolites are statistically and significantly changed with the levels of O-phosphocholine and hypoxanthine down-regulated while the levels of isoleucine, leucine, valine, isobutyrate, threonine, cadaverine, alanine, glutamate, glutamine, methionine, citrate, asparagine, tryptophan, glycine, serine, uracil, and formate up-regulated in the melanoma group. These significantly changed metabolites are associated with multiple biological pathways and may be potential biomarkers for metastatic melanoma in stomach.

  6. Metastatic Melanoma Induced Metabolic Changes in C57BL/6J Mouse Stomach Measured by 1H NMR Spectroscopy

    DOE PAGES

    Hu, M; Wang, Xiliang

    2014-12-05

    Melanoma is a malignant tumor of melanocytes with high capability of invasion and rapid metastasis to other organs. Malignant melanoma is the most common metastatic malignancy found in gastrointestinal tract (GI). To the best of our knowledge, previous studies of melanoma in gastrointestinal tract are all clinical case reports. In this work, 1H NMR-based metabolomics approach is used to investigate the metabolite profiles differences of stomach tissue extracts of metastatic B16-F10 melanoma in C57BL/6J mouse and search for specific metabolite biomarker candidates. Principal Component Analysis (PCA), an unsupervised multivariate data analysis method, is used to detect possible outliers, while Orthogonalmore » Projection to Latent Structure (OPLS), a supervised multivariate data analysis method, is employed to evaluate important metabolites responsible for discriminating the control and the melanoma groups. Both PCA and OPLS results reveal that the melanoma group can be well separated from its control group. Among the 50 identified metabolites, it is found that the concentrations of 19 metabolites are statistically and significantly changed with the levels of O-phosphocholine and hypoxanthine down-regulated while the levels of isoleucine, leucine, valine, isobutyrate, threonine, cadaverine, alanine, glutamate, glutamine, methionine, citrate, asparagine, tryptophan, glycine, serine, uracil, and formate up-regulated in the melanoma group. These significantly changed metabolites are associated with multiple biological pathways and may be potential biomarkers for metastatic melanoma in stomach.« less

  7. Lipid-ethanol interaction studied by NMR on bicelles.

    PubMed

    Koenig, Bernd W; Gawrisch, Klaus

    2005-04-21

    The interaction of ethanol with phospholipids was studied in bicelles at a physiologically relevant ethanol concentration of 20 mM and a lipid content of 14 wt % by high-resolution NMR. Transient association of ethanol with magnetically aligned bicelles imparts a small degree of anisotropy to the solute. This anisotropy allows detection of residual (1)H-(1)H and (1)H-(13)C dipolar couplings, which are superimposed on scalar couplings. Residual (2)H NMR quadrupole splittings of isotope-labeled ethanol were measured as well. The analysis of residual tensorial interactions yielded information on the orientation and motions of ethanol in the membrane-bound state. The fraction of phosphatidylcholine-bound ethanol was determined independently by gas chromatography and NMR. About 4% of ethanol is bound to phosphatidylcholine at a bicelle concentration of 14 wt % at 40 degrees C. Free and bound ethanol are in rapid exchange. The lifetime of ethanol association with phosphatidylcholine membranes is of the order of a few nanoseconds.

  8. Efficient design of multituned transmission line NMR probes: the electrical engineering approach.

    PubMed

    Frydel, J A; Krzystyniak, M; Pienkowski, D; Pietrzak, M; de Sousa Amadeu, N; Ratajczyk, T; Idzik, K; Gutmann, T; Tietze, D; Voigt, S; Fenn, A; Limbach, H H; Buntkowsky, G

    2011-01-01

    Transmission line-based multi-channel solid state NMR probes have many advantages regarding the cost of construction, number of RF-channels, and achievable RF-power levels. Nevertheless, these probes are only rarely employed in solid state-NMR-labs, mainly owing to the difficult experimental determination of the necessary RF-parameters. Here, the efficient design of multi-channel solid state MAS-NMR probes employing transmission line theory and modern techniques of electrical engineering is presented. As technical realization a five-channel ((1)H, (31)P, (13)C, (2)H and (15)N) probe for operation at 7 Tesla is described. This very cost efficient design goal is a multi port single coil transmission line probe based on the design developed by Schaefer and McKay. The electrical performance of the probe is determined by measuring of Scattering matrix parameters (S-parameters) in particular input/output ports. These parameters are compared to the calculated parameters of the design employing the S-matrix formalism. It is shown that the S-matrix formalism provides an excellent tool for examination of transmission line probes and thus the tool for a rational design of these probes. On the other hand, the resulting design provides excellent electrical performance. From a point of view of Nuclear Magnetic Resonance (NMR), calibration spectra of particular ports (channels) are of great importance. The estimation of the π/2 pulses length for all five NMR channels is presented.

  9. Dynamic High-Resolution H-1 and P-31 NMR Spectroscopy and H-1 T-2 Measurements in Postmortem Rabbit Muscles Using Slow Magic Angle Spinning

    SciTech Connect

    Bertram, Hanne Christine; Hu, Jian Zhi; Rommereim, Donald N.; Wind, Robert A.; Andersen, Henrik J.

    2004-05-05

    Postmortem changes in rabbit muscle tissue with different glycogen status (normal vs low) were followed continuously from 13 min postmortem until 8 h postmortem and again 20 h postmortem using simultaneous magic angle spinning 1H and 31P NMR spectroscopy together with measurement of the transverse relaxation time, T2, of the muscle water. The 1H metabolite spectra were measured using the phase-altered spinning sidebands (PASS) technique at a spinning rate of 40 Hz. pH values calculated from the 31P NMR spectra using the chemical shifts of the C-6 line of histidine in the 1H spectra and the chemical shifts of inorganic phosphate in the 31P spectra confirmed the different muscle glycogen status in the tissues. High-resolution 1H spectra obtained from the PASS technique revealed the presence of a new resonance line at 6.8 ppm during the postmortem period, which were absent in muscles with low muscle glycogen content. This new resonance line may originate from the aminoprotons in creatine, and its appearance may be a result of a pH effect on the exchange rate between the amino and the water protons and thereby the NMR visibility. Alternatively, the new resonance line may originate from the aromatic protons in tyrosine, and its appearance may be a result of a pH-induced protein unfolding exposing hydrophobic amino acid residues to the aqueous environment. Further studies are needed to evaluate these hypotheses. Finally, distributed analysis of the water T2 relaxation data revealed three relaxation populations and an increase in the population believed to reflect extramyofibrillar water through the postmortem period. This increase was significantly reduced (p < 0.0001) in samples from animals with low muscle glycogen content, indicating that the pH is controlling the extent of postmortem expulsion of water from myofibrillar structures. The significance of the postmortem increase in the amount extramyofibrillar water on the water-holding capacity was verified by

  10. Microwave-assisted synthesis of novel 2H-chromene derivatives bearing phenylthiazolidinones and their biological activity assessment.

    PubMed

    El Azab, Islam H; Youssef, Mohamed M; Amin, Mahmoud A

    2014-01-01

    6-Hydroxy-2-oxo-2H-chromene-4-carbaldehyde (2), 6-chloro-2-oxo-2H-chromene-4-carbaldehyde (3) and 6-hydrazinyl-4-methyl-2H-chromen-2-one (5) were prepared as single-pharmacophore motif key intermediates. Compounds 2, 3 and 5 were incorporated in a series of multicomponent reactions (MCRs), under microwave assistance as well as conventional chemical synthesis processes, to afford a series of three and/or four-pharmacophoric-motif conjugates 8a,b, 11, 13, 16, 17, 19 and 20 in good yields. The newly synthesized compounds were characterized by IR, NMR, 13C-NMR, MS and elemental analyses. Finally the synthesized compounds have been screened for their biological activity whereupon they exhibited remarkable antimicrobial activity on different classes of bacteria and the fungus. PMID:25432014

  11. Solid State 2H NMR Analysis of Furanose Ring Dynamics in DNA Containing Uracil

    PubMed Central

    Kinde-Carson, Monica N.; Ferguson, Crystal; Oyler, Nathan A.; Harbison, Gerard S.; Meints, Gary A.

    2010-01-01

    DNA damage has been implicated in numerous human diseases, particularly cancer, and the aging process. Single-base lesions, such as uracil, in DNA can be cytotoxic or mutagenic and are recognized by a DNA glycosylase during the process of base excision repair. Increased dynamic properties in lesion-containing DNAs have been suggested to assist recognition and specificity. Deuterium solid-state nuclear magnetic resonance (SSNMR) has been used to directly observe local dynamics of the furanose ring within a uracil: adenine (U:A) base pair and compared to a normal thymine:adenine (T:A) base pair. Quadrupole echo lineshapes, ⟨T1Z⟩, and ⟨T2e⟩ relaxation data were collected, and computer modeling was performed. The results indicate that the relaxation times are identical within the experimental error, the solid lineshapes are essentially indistinguishable above the noise level, and our lineshapes are best fit with a model that does not have significant local motions. Therefore, U:A base pair furanose rings appear to have essentially identical dynamic properties as a normal T:A base pair, and the local dynamics of the furanose ring are unlikely to be the sole arbiter for uracil recognition and specificity in U:A base pairs. PMID:20151717

  12. Hydrostatic pressure-induced conformational changes in phosphatidylcholine headgroups: a 2H NMR study.

    PubMed Central

    Bonev, B B; Morrow, M R

    1995-01-01

    The effects of pressure and temperature on 1,2-dipalmitoyl-sn-glycero-3-phosphocholine and 1,2-dimyristoyl-sn-glycero-3-phosphocholine headgroup conformations were examined using deuterium nuclear magnetic resonance. Isothermal compression was found to produce a decrease in the choline alpha deuteron quadrupole splitting and increases in the choline beta and gamma deuteron quadrupole splittings. A similar counterdirectional change, seen in the presence of positive surface charge, has been attributed to tilting of the headgroup away from the bilayer surface in response to the torque exerted on the phosphocholine dipole by positive surface charges. The direction of the change in headgroup deuteron quadrupole splitting is consistent with the pressure-induced reduction in area per lipid in the liquid crystalline phase, which can be inferred from the ordering of phospholipid acyl chains under comparable conditions. The temperature dependences of the headgroup deuteron quadrupole splittings were also examined. It was found that at elevated pressure, the alpha splitting was insensitive to temperature, whereas the beta and gamma splittings decreased. The response of the beta deuteron splitting to temperature was found to be weaker at elevated pressure than at ambient pressure. PMID:8527666

  13. Hydrostatic pressure-induced conformational changes in phosphatidylcholine headgroups: a 2H NMR study.

    PubMed

    Bonev, B B; Morrow, M R

    1995-08-01

    The effects of pressure and temperature on 1,2-dipalmitoyl-sn-glycero-3-phosphocholine and 1,2-dimyristoyl-sn-glycero-3-phosphocholine headgroup conformations were examined using deuterium nuclear magnetic resonance. Isothermal compression was found to produce a decrease in the choline alpha deuteron quadrupole splitting and increases in the choline beta and gamma deuteron quadrupole splittings. A similar counterdirectional change, seen in the presence of positive surface charge, has been attributed to tilting of the headgroup away from the bilayer surface in response to the torque exerted on the phosphocholine dipole by positive surface charges. The direction of the change in headgroup deuteron quadrupole splitting is consistent with the pressure-induced reduction in area per lipid in the liquid crystalline phase, which can be inferred from the ordering of phospholipid acyl chains under comparable conditions. The temperature dependences of the headgroup deuteron quadrupole splittings were also examined. It was found that at elevated pressure, the alpha splitting was insensitive to temperature, whereas the beta and gamma splittings decreased. The response of the beta deuteron splitting to temperature was found to be weaker at elevated pressure than at ambient pressure. PMID:8527666

  14. Soils, Pores, and NMR

    NASA Astrophysics Data System (ADS)

    Pohlmeier, Andreas; Haber-Pohlmeier, Sabina; Haber, Agnes; Sucre, Oscar; Stingaciu, Laura; Stapf, Siegfried; Blümich, Bernhard

    2010-05-01

    Within Cluster A, Partial Project A1, the pore space exploration by means of Nuclear Magnetic Resonance (NMR) plays a central role. NMR is especially convenient since it probes directly the state and dynamics of the substance of interest: water. First, NMR is applied as relaxometry, where the degree of saturation but also the pore geometry controls the NMR signature of natural porous systems. Examples are presented where soil samples from the Selhausen, Merzenhausen (silt loams), and Kaldenkirchen (sandy loam) test sites are investigated by means of Fast Field Cycling Relaxometry at different degrees of saturation. From the change of the relaxation time distributions with decreasing water content and by comparison with conventional water retention curves we conclude that the fraction of immobile water is characterized by T1 < 5 ms. Moreover, the dependence of the relaxation rate on magnetic field strength allows the identification of 2D diffusion at the interfaces as the mechanism which governs the relaxation process (Pohlmeier et al. 2009). T2 relaxation curves are frequently measured for the rapid characterization of soils by means of the CPMG echo train. Basically, they contain the same information about the pore systems like T1 curves, since mostly the overall relaxation is dominated by surface relaxivity and the surface/volume ratio of the pores. However, one must be aware that T2 relaxation is additionally affected by diffusion in internal gradients, and this can be overcome by using sufficiently short echo times and low magnetic fields (Stingaciu et al. 2009). Second, the logic continuation of conventional relaxation measurements is the 2-dimensional experiment, where prior to the final detection of the CPMG echo train an encoding period is applied. This can be T1-encoding by an inversion pulse, or T2 encoding by a sequence of 90 and 180° pulses. During the following evolution time the separately encoded signals can mix and this reveals information about

  15. Solid state {sup 31}P MAS NMR spectroscopy and conductivity measurements on NbOPO{sub 4} and H{sub 3}PO{sub 4} composite materials

    SciTech Connect

    Risskov Sørensen, Daniel; Nielsen, Ulla Gro; Skou, Eivind M.

    2014-11-15

    A systematic study of composite powders of niobium oxide phosphate (NbOPO{sub 4}) and phosphoric acid (H{sub 3}PO{sub 4}) has been performed in order to characterize the material's ability to perform as an electrolyte material in medium temperature fuel cells and electrolyzers. Powders of H{sub 3}PO{sub 4} contents between 13.1 and 74.2 M% were produced and characterized with powder X-ray diffraction, {sup 31}P MAS NMR and impedance spectroscopy. NMR revealed that a significant degree of dehydration and vaporization of H{sub 3}PO{sub 4} takes place above 200 °C, and increases with temperature. At 500 °C the NbOPO{sub 4} and H{sub 3}PO{sub 4} has reacted to form niobium pyrophosphate (Nb{sub 2}P{sub 4}O{sub 15}). Impedance spectroscopy showed an increase in conductivity with increasing acid concentration, whereas the conductivity decreased slightly with increasing temperature. The highest conductivity measured was 2.5·10{sup −3} S/cm for a sample containing 74.2 M% of H{sub 3}PO{sub 4}. Lastly, it was shown that NbOPO{sub 4} has no significant conductivity of its own. - Graphical abstract: Conductivity of NbOPO{sub 4}/H{sub 3}PO{sub 4} composites as a function of equivalent P{sub 2}O{sub 5} content. The conductivity is insignificant for pure NbOPO{sub 4}. - Highlights: • Composites have been made from NbOPO{sub 4} and H{sub 3}PO{sub 4}. • The composites composition has been investigated with solid state NMR. • The composites have shown clear signs of acid dehydration upon heating. • The conductivity of the composites increases for increasing acid content. • NbOPO{sub 4} has no significant conductivity of its own.

  16. Phase behavior and 13C NMR spectroscopic analysis of the mixed methane + ethane + propane hydrates in mesoporous silica gels.

    PubMed

    Lee, Seungmin; Cha, Inuk; Seo, Yongwon

    2010-11-25

    In this study, the phase behavior and quantitative determination of hydrate composition and cage occupancy for the mixed CH(4) + C(2)H(6) + C(3)H(8) hydrates were closely investigated through the experimental measurement of three-phase hydrate (H)-water-rich liquid (L(W))-vapor (V) equilibria and (13)C NMR spectra. To examine the effect of pore size and salinity, we measured hydrate phase equilibria for the quaternary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + water mixtures in silica gel pores of nominal diameters of 6.0, 15.0, and 30.0 nm and for the quinary CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) + NaCl + water mixtures of two different NaCl concentrations (3 and 10 wt %) in silica gel pores of a nominal 30.0 nm diameter. The value of hydrate-water interfacial tension for the CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) hydrate was found to be 47 ± 4 mJ/m(2) from the relation of the dissociation temperature depression with the pore size of silica gels at a given pressure. At a specified temperature, three-phase H-L(W)-V equilibrium curves of pore hydrates were shifted to higher pressure regions depending on pore sizes and NaCl concentrations. From the cage-dependent (13)C NMR chemical shifts of enclathrated guest molecules, the mixed CH(4) (90%) + C(2)H(6) (7%) + C(3)H(8) (3%) gas hydrate was confirmed to be structure II. The cage occupancies of each guest molecule and the hydration number of the mixed gas hydrates were also estimated from the (13)C NMR spectra.

  17. Electron swarm parameters in pure C2H2 and in C2H2-Ar mixtures and electron collision cross sections for the C2H2 molecule

    NASA Astrophysics Data System (ADS)

    Nakamura, Yoshiharu

    2010-09-01

    Electron swarm parameters (the drift velocity and the longitudinal diffusion coefficient) were measured in pure C2H2 and also in C2H2-Ar mixtures containing 0.517% and 5.06% acetylene over wide E/N ranges. These swarm parameters were analysed using a Boltzmann equation analysis and a set of electron collision cross sections for the C2H2 molecule was derived so that it was consistent with the present swarm data and published ionization coefficient. The present result suggested the presence of a Ramsauer-Townsend minimum in the elastic momentum transfer cross section at 0.08 eV and prominent threshold and resonance peaks in the ν4/ν5 vibrational excitation cross section. The present cross section set was also confirmed to be consistent with the published experimental total cross section of C2H2.

  18. Measurement of the Isotopic Ratio of [to the tenth power]B/[to the eleventh power]B in NaBH[subscript 4] by [to the first power]H NMR

    ERIC Educational Resources Information Center

    Zanger, Murray; Moyna, Guillermo

    2005-01-01

    A study uses nuclear magnetic resonance (NMR) spectroscopy in a novel way to determine the isotopic ration between [to the tenth power]B and [to the eleventh power]B in sodium borohydride (NaBH4). The experiment provides an unusual and relatively simple means for undergraduate chemistry students to accurately measure the distribution of the two…

  19. Crystal structure and hydrogen bonding study of (10E)-2,2-dimethyl-3,4-dihydro-2H-benzo[g]chromene-5,10-dione 10-oxime derived from α-lapachone.

    PubMed

    da Silva, Andrea R; Herbst, Marcelo H; Ferreira, Aurelio B B; da Silva, Ari M; Visentin, Lorenzo C

    2011-01-27

    The compound (10E)-2,2-dimethyl-3,4-dihydro-2H-benzo[g]chromene-5,10-dione-10-oxime (1) was synthesized from a-lapachone and hydroxylamine chloride in alkaline medium. Single-crystals suitable for X-ray diffraction measurements were grown from an ethanol solution, and the crystal structure of the title molecule is reported for the first time. The title molecule was also characterized by ¹H- and ¹³C-NMR in CDCl₃ solution, FTIR and MS. The crystal structure of 1 shows an E stereochemistry and dimers formed through classical hydrogen bonds.

  20. An Inversion Recovery NMR Kinetics Experiment

    ERIC Educational Resources Information Center

    Williams, Travis J.; Kershaw, Allan D.; Li, Vincent; Wu, Xinping

    2011-01-01

    A convenient laboratory experiment is described in which NMR magnetization transfer by inversion recovery is used to measure the kinetics and thermochemistry of amide bond rotation. The experiment utilizes Varian spectrometers with the VNMRJ 2.3 software, but can be easily adapted to any NMR platform. The procedures and sample data sets in this…

  1. Uncertainty minimization in NMR measurements of dynamic nuclear polarization of a proton target for nuclear physics experiments

    SciTech Connect

    Keller, Dustin M.

    2013-11-01

    A comprehensive investigation into the measurement uncertainty in polarization produced by Dynamic Nuclear Polarization is outlined. The polarization data taken during Jefferson Lab experiment E08-007 is used to obtain error estimates and to develop an algorithm to minimize uncertainty of the measurement of polarization in irradiated View the ^14NH_3 targets, which is readily applied to other materials. The target polarization and corresponding uncertainties for E08-007 are reported. The resulting relative uncertainty found in the target polarization is determined to be less than or equal to 3.9%.

  2. A 300 MHz and 600 MHz proton NMR study of a 12 base pair restriction fragment: investigation of structure by relaxation measurements.

    PubMed Central

    Early, T A; Kearns, D R; Hillen, W; Wells, R D

    1980-01-01

    The 1H NMR spectrum of a 12 base pair DNA restriction fragment has been measured at 300 and 600 MHz and resonances from over 70 protons are individually resolved. Relaxation rate measurements have been carried out at 300 MHz and compared with the theoretical predictions obtained using an isotropic rigid rotor model with coordinates derived from a Dreiding model of DNA. The model gives results that are in excellent agreement with experiment for most protons when a 7 nsec rotational correlation time is used, although agreement is improved for certain base protons by using a shorter correlation time for the sugar group, or by increasing the sugar-base interproton distances. A comparison of non-selective and selective spin-lattice relaxation rates for carbon bound protons indicates that there is extensive spin diffusion even in this short DNA fragment. Examination of the spin-spin relaxation rates for the same type of proton on different base pairs reveals little sequence effect on conformation. PMID:6258152

  3. Correlating steric hydration forces with water dynamics through surface force and diffusion NMR measurements in a lipid-DMSO-H2O system.

    PubMed

    Schrader, Alex M; Donaldson, Stephen H; Song, Jinsuk; Cheng, Chi-Yuan; Lee, Dong Woog; Han, Songi; Israelachvili, Jacob N

    2015-08-25

    Dimethyl sulfoxide (DMSO) is a common solvent and biological additive possessing well-known utility in cellular cryoprotection and lipid membrane permeabilization, but the governing mechanisms at membrane interfaces remain poorly understood. Many studies have focused on DMSO-lipid interactions and the subsequent effects on membrane-phase behavior, but explanations often rely on qualitative notions of DMSO-induced dehydration of lipid head groups. In this work, surface forces measurements between gel-phase dipalmitoylphosphatidylcholine membranes in DMSO-water mixtures quantify the hydration- and solvation-length scales with angstrom resolution as a function of DMSO concentration from 0 mol% to 20 mol%. DMSO causes a drastic decrease in the range of the steric hydration repulsion, leading to an increase in adhesion at a much-reduced intermembrane distance. Pulsed field gradient NMR of the phosphatidylcholine (PC) head group analogs, dimethyl phosphate and tetramethylammonium ions, shows that the ion hydrodynamic radius decreases with increasing DMSO concentration up to 10 mol% DMSO. The complementary measurements indicate that, at concentrations below 10 mol%, the primary effect of DMSO is to decrease the solvated volume of the PC head group and that, from 10 mol% to 20 mol%, DMSO acts to gradually collapse head groups down onto the surface and suppress their thermal motion. This work shows a connection between surface forces, head group conformation and dynamics, and surface water diffusion, with important implications for soft matter and colloidal systems.

  4. Correlating steric hydration forces with water dynamics through surface force and diffusion NMR measurements in a lipid–DMSO–H2O system

    PubMed Central

    Schrader, Alex M.; Donaldson, Stephen H.; Song, Jinsuk; Cheng, Chi-Yuan; Lee, Dong Woog; Han, Songi; Israelachvili, Jacob N.

    2015-01-01

    Dimethyl sulfoxide (DMSO) is a common solvent and biological additive possessing well-known utility in cellular cryoprotection and lipid membrane permeabilization, but the governing mechanisms at membrane interfaces remain poorly understood. Many studies have focused on DMSO–lipid interactions and the subsequent effects on membrane-phase behavior, but explanations often rely on qualitative notions of DMSO-induced dehydration of lipid head groups. In this work, surface forces measurements between gel-phase dipalmitoylphosphatidylcholine membranes in DMSO–water mixtures quantify the hydration- and solvation-length scales with angstrom resolution as a function of DMSO concentration from 0 mol% to 20 mol%. DMSO causes a drastic decrease in the range of the steric hydration repulsion, leading to an increase in adhesion at a much-reduced intermembrane distance. Pulsed field gradient NMR of the phosphatidylcholine (PC) head group analogs, dimethyl phosphate and tetramethylammonium ions, shows that the ion hydrodynamic radius decreases with increasing DMSO concentration up to 10 mol% DMSO. The complementary measurements indicate that, at concentrations below 10 mol%, the primary effect of DMSO is to decrease the solvated volume of the PC head group and that, from 10 mol% to 20 mol%, DMSO acts to gradually collapse head groups down onto the surface and suppress their thermal motion. This work shows a connection between surface forces, head group conformation and dynamics, and surface water diffusion, with important implications for soft matter and colloidal systems. PMID:26261313

  5. Review of advances in coupling electrochemistry and liquid state NMR.

    PubMed

    Bussy, Ugo; Boujtita, Mohammed

    2015-05-01

    The coupling of electrochemistry and NMR spectroscopy (EC-NMR) may present an interesting approach in the environmental oxidative degradation or metabolism studies. This review presents experimental advances in the field of EC-NMR and highlights the main advantages and drawbacks of in situ and on line of NMR spectroelectrochemistry. The analysis of NMR spectra recorded in situ or on line EC-NMR permits to elucidate the reaction pathway of the electrochemical oxidation reactions and could constitute a fast way for monitoring unstable species as for instance quinone and quinone imine structures without using any coupling agents. The use of 1D and 2D NMR coupled with electrochemistry may leads to the elucidation of the major species produced from the electrochemical oxidation process. The present review gives an overview about the development of the electrochemical cells which can operate on line or in situ with NMR measurements. Future developments and potential applications of EC-NMR are also discussed.

  6. NMR analysis of biodiesel

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biodiesel is usually analyzed by the various methods called for in standards such as ASTM D6751 and EN 14214. Nuclear magnetic resonance (NMR) is not one of these methods. However, NMR, with 1H-NMR commonly applied, can be useful in a variety of applications related to biodiesel. These include monit...

  7. Studies on Effects of Impurity Doping and NMR Measurements of La 1111 and/or Nd 1111 Fe-Pnictide Superconductors

    NASA Astrophysics Data System (ADS)

    Sato, Masatoshi; Kobayashi, Yoshiaki; Lee, Sang Chul; Takahashi, Hidefumi; Satomi, Erika; Miura, Yoko

    2010-01-01

    Measurements of the electrical resistivity ρ, Hall coefficient RH, thermoelectric power S, and the electronic specific heat coefficient γ have been carried out for samples of LnFe1-yMyAsO1-xFx (Ln=La, Nd; M=Co, Mn; x=0.11) obtained by doping M atoms into the superconducting LnFeAsO1-xFx (Ln 1111) system. The NMR longitudinal relaxation rate 1/T1 has also been measured for samples of LaFe1-yCoyAsO1-xFx with various x values. Co atoms doped into the superconducting LnFeAsO1-xFx are nonmagnetic, and the rate of Tc-suppression |dTc/dx| by Co atoms has been found to be too small to be explained by the pair-breaking effect expected for the S± superconducting symmetry proposed as the most probable symmetry for the system. This result throws a serious doubt on whether the symmetry is realized in the system. Instead of the pair breaking, two mechanisms of Tc suppression by the doped impurities have been found: One is the electron localization, which appears when the sheet resistance R\\square exceeds h/4e2=6.45 kΩ, and the other is the disappearance (or reduction in the area) of the hole Fermi surfaces around the Γ point in the reciprocal space. The latter mechanism has been observed when the number of electrons increases with increasing Co doping level and the system changes from an “anomalous metal” to an ordinary one. Regarding the two distinct T dependences of the NMR longitudinal relaxation rate 1/T1 of LaFeAsO1-xFx, (1/T1\\propto T6 reported by our group in the T region from Tc to ˜0.4 Tc for samples with the highest Tc values with varying x, and 1/T1\\propto T2.5--3.0 observed by many groups in almost the entire T region studied below Tc), we discuss the origin of such a difference, and show that, at least, the T2.5--3.0-like dependence of 1/T1 cannot be considered as the experimental evidence for the S± symmetry of Δ.

  8. A combined deuterium NMR and quantum chemical investigation of inequivalent hydrogen bonds in organic solids.

    PubMed

    Webber, Renee; Penner, Glenn H

    2012-01-01

    Deuterium magic angle spinning (MAS) NMR spectroscopy and quantum chemical calculations are used to investigate organic solids in which inequivalent hydrogen bonds are present. The use of (2)H MAS allows one to measure the chemical shift, δ, quadrupolar coupling constant, C(Q), and asymmetry in the quadrupolar interaction, η(Q), for each type of hydrogen bond present in the system. Quantum chemical calculations of the magnetic shielding (σ, which can be related to δ) and the electric field gradient (EFG, which can be related to C(Q)) are compared to the experimental results and are discussed with respect to the relative strengths of the hydrogen bonds within each system.

  9. Quantitative 2D liquid-state NMR.

    PubMed

    Giraudeau, Patrick

    2014-06-01

    Two-dimensional (2D) liquid-state NMR has a very high potential to simultaneously determine the absolute concentration of small molecules in complex mixtures, thanks to its capacity to separate overlapping resonances. However, it suffers from two main drawbacks that probably explain its relatively late development. First, the 2D NMR signal is strongly molecule-dependent and site-dependent; second, the long duration of 2D NMR experiments prevents its general use for high-throughput quantitative applications and affects its quantitative performance. Fortunately, the last 10 years has witnessed an increasing number of contributions where quantitative approaches based on 2D NMR were developed and applied to solve real analytical issues. This review aims at presenting these recent efforts to reach a high trueness and precision in quantitative measurements by 2D NMR. After highlighting the interest of 2D NMR for quantitative analysis, the different strategies to determine the absolute concentrations from 2D NMR spectra are described and illustrated by recent applications. The last part of the manuscript concerns the recent development of fast quantitative 2D NMR approaches, aiming at reducing the experiment duration while preserving - or even increasing - the analytical performance. We hope that this comprehensive review will help readers to apprehend the current landscape of quantitative 2D NMR, as well as the perspectives that may arise from it.

  10. Efficient compensation of low-frequency magnetic field disturbances in NMR with fluxgate sensors.

    PubMed

    Kazimierczuk, Krzysztof; Koźmiński, Wiktor

    2005-06-01

    A simple stabilization scheme of B(0) magnetic field fluctuations is described. The method is based on external measurements of time dependent magnetic field fluctuations by fluxgate sensors and generation of a compensating correction current in a coil mounted directly on an NMR magnet. It is shown that such an approach efficiently eliminates relatively slow magnetic field variations with frequency up to approximately 100 Hz. In combination with a standard (2)H field-frequency lock system, the method enables acquisition of reproducible lineshapes and dramatically improves overall performance of a high resolution NMR spectrometer. The presented solution might substitute for the internal lock system in these case where deuterium lock is not available. PMID:15862246

  11. Pulse Electron Double Resonance Detected Multinuclear NMR Spectra of Distant and Low Sensitivity Nuclei and Its Application to the Structure of Mn(II) Centers in Organisms.

    PubMed

    Bruch, Eduardo M; Warner, Melissa T; Thomine, Sébastien; Tabares, Leandro C; Un, Sun

    2015-10-29

    The ability to characterize the structure of metal centers beyond their primary ligands is important to understanding their chemistry. High-magnetic-field pulsed electron double resonance detected NMR (ELDOR-NMR) is shown to be a very sensitive approach to measuring the multinuclear NMR spectra of the nuclei surrounding Mn(II) ions. Resolved spectra of intact organisms with resonances arising from (55)Mn, (31)P, (1)H, (39)K, (35)Cl, (23)Na, and (14)N nuclei surrounding Mn(2+) centers were obtained. Naturally abundant cellular (13)C could be routinely measured as well. The amplitudes of the (14)N and (2)H ELDOR-NMR spectra were found to be linearly dependent on the number of nuclei in the ligand sphere. The evolution of the Mn(II) ELDOR-NMR spectra as a function of excitation time was found to be best described by a saturation phenomenon rather than a coherently driven process. Mn(II) ELDOR-NMR revealed details about not only the immediate ligands to the Mn(II) ions but also more distant nuclei, providing a view of their extended structures. This will be important for understanding the speciation and chemistry of the manganese complexes as well as other metals found in organisms.

  12. Amplitude Higgs mode in the 2H-NbSe2 superconductor

    NASA Astrophysics Data System (ADS)

    Méasson, M.-A.; Gallais, Y.; Cazayous, M.; Clair, B.; Rodière, P.; Cario, L.; Sacuto, A.

    2014-02-01

    We report experimental evidence for the observation of the superconducting amplitude mode, the so-called ``Higgs" mode, in the charge density wave superconductor 2H-NbSe2 using Raman scattering. By comparing 2H-NbSe2 and its isostructural partner 2H-NbS2 which shows superconductivity but lacks the charge density wave order, we demonstrate that the superconducting mode in 2H-NbSe2 owes its spectral weight to the presence of the coexisting charge density wave order. In addition, temperature dependent measurements in 2H-NbSe2 show a full spectral weight transfer from the charge density wave mode to the superconducting mode upon entering the superconducting phase. Both observations are fully consistent with a superconducting amplitude mode or Higgs mode.

  13. Vibrational and Rotational Spectroscopy of CD_2H^+

    NASA Astrophysics Data System (ADS)

    Asvany, Oskar; Jusko, Pavol; Brünken, Sandra; Schlemmer, Stephan

    2016-06-01

    The lowest rotational levels (J=0-5) of the CD_2H^+ ground state have been probed by high-resolution rovibrational and pure rotational spectroscopy in a cryogenic 22-pole ion trap. For this, the ν_1 rovibrational band has been revisited, detecting 107 transitions, among which 35 are new. The use of a frequency comb system allowed to measure the rovibrational transitions with high precision and accuracy, typically better than 1 MHz. The high precision has been confirmed by comparing combination differences in the ground and vibrationally excited state. For the ground state, this allowed for equally precise predictions of pure rotational transitions, 24 of which have been measured directly by a novel IR - mm-wave double resonance method. M.-F. Jagod et al, J. Molec. Spectrosc. 153, 666, 1992 S. Gartner et al, J. Phys. Chem. A 117, 9975, 2013

  14. Direct measurement of oleocanthal and oleacein levels in olive oil by quantitative (1)H NMR. Establishment of a new index for the characterization of extra virgin olive oils.

    PubMed

    Karkoula, Evangelia; Skantzari, Angeliki; Melliou, Eleni; Magiatis, Prokopios

    2012-11-28

    A new method for direct measurement of the oleocanthal and oleacein levels in olive oil by quantitative (1)H NMR was developed. The method was applied to the study of 175 monovarietal commercial Greek and California olive oil samples. The main findings were as follows: (1) There was a significant variation concerning the concentrations of oleocanthal and oleacein among the studied samples. Their concentrations ranged from nondetectable to 355 mg/kg and their sum (index D1) from 0 to 501 mg/kg. (2) There are olive varieties that independent of geographic origin and harvest time produce oil that contains both compounds in low levels. (3) There is a positive correlation of a high level of oleocanthal and oleacein in olive oils with the early time of harvest. Although there is a need for more extensive study, a new index for the characterization of extra virgin olive oils, which is a combination of D1 = oleocanthal + oleacein level and D2 = oleocanthal/oleacein ratio, seems to be very useful. PMID:23116297

  15. Direct measurement of oleocanthal and oleacein levels in olive oil by quantitative (1)H NMR. Establishment of a new index for the characterization of extra virgin olive oils.

    PubMed

    Karkoula, Evangelia; Skantzari, Angeliki; Melliou, Eleni; Magiatis, Prokopios

    2012-11-28

    A new method for direct measurement of the oleocanthal and oleacein levels in olive oil by quantitative (1)H NMR was developed. The method was applied to the study of 175 monovarietal commercial Greek and California olive oil samples. The main findings were as follows: (1) There was a significant variation concerning the concentrations of oleocanthal and oleacein among the studied samples. Their concentrations ranged from nondetectable to 355 mg/kg and their sum (index D1) from 0 to 501 mg/kg. (2) There are olive varieties that independent of geographic origin and harvest time produce oil that contains both compounds in low levels. (3) There is a positive correlation of a high level of oleocanthal and oleacein in olive oils with the early time of harvest. Although there is a need for more extensive study, a new index for the characterization of extra virgin olive oils, which is a combination of D1 = oleocanthal + oleacein level and D2 = oleocanthal/oleacein ratio, seems to be very useful.

  16. Measuring dynamic and kinetic information in the previously inaccessible supra-τ(c) window of nanoseconds to microseconds by solution NMR spectroscopy.

    PubMed

    Ban, David; Sabo, T Michael; Griesinger, Christian; Lee, Donghan

    2013-09-26

    Nuclear Magnetic Resonance (NMR) spectroscopy is a powerful tool that has enabled experimentalists to characterize molecular dynamics and kinetics spanning a wide range of time-scales from picoseconds to days. This review focuses on addressing the previously inaccessible supra-tc window (defined as τ(c) < supra-τ(c) < 40 μs; in which tc is the overall tumbling time of a molecule) from the perspective of local inter-nuclear vector dynamics extracted from residual dipolar couplings (RDCs) and from the perspective of conformational exchange captured by relaxation dispersion measurements (RD). The goal of the first section is to present a detailed analysis of how to extract protein dynamics encoded in RDCs and how to relate this information to protein functionality within the previously inaccessible supra-τ(c) window. In the second section, the current state of the art for RD is analyzed, as well as the considerable progress toward pushing the sensitivity of RD further into the supra-τ(c) scale by up to a factor of two (motion up to 25 μs). From the data obtained with these techniques and methodology, the importance of the supra-τ(c) scale for protein function and molecular recognition is becoming increasingly clearer as the connection between motion on the supra-τ(c) scale and protein functionality from the experimental side is further strengthened with results from molecular dynamics simulations.

  17. Symmetry of the gradient profile as second experimental dimension in the short-time expansion of the apparent diffusion coefficient as measured with NMR diffusometry.

    PubMed

    Laun, Frederik Bernd; Kuder, Tristan Anselm; Zong, Fangrong; Hertel, Stefan; Galvosas, Petrik

    2015-10-01

    The time-dependent apparent diffusion coefficient as measured by pulsed gradient NMR can be used to estimate parameters of porous structures including the surface-to-volume ratio and the mean curvature of pores. In this work, the short-time diffusion limit and in particular the influence of the temporal profile of diffusion gradients on the expansion as proposed by Mitra et al. (1993) is investigated. It is shown that flow-compensated waveforms, i.e. those whose first moment is zero, are blind to the term linear in observation time, which is the term that is proportional to mean curvature and surface permeability. A gradient waveform that smoothly interpolates between flow-compensated and bipolar waveform is proposed and the degree of flow-compensation is used as a second experimental dimension. This two-dimensional ansatz is shown to yield an improved precision when characterizing the confining domain. This technique is demonstrated with simulations and in experiments performed with cylindrical capillaries of 100 μm radius.

  18. A method for helical RNA global structure determination in solution using small-angle x-ray scattering and NMR measurements.

    PubMed

    Wang, Jinbu; Zuo, Xiaobing; Yu, Ping; Xu, Huan; Starich, Mary R; Tiede, David M; Shapiro, Bruce A; Schwieters, Charles D; Wang, Yun-Xing

    2009-10-30

    We report a "top-down" method that uses mainly duplexes' global orientations and overall molecular dimension and shape restraints, which were extracted from experimental NMR and small-angle X-ray scattering data, respectively, to determine global architectures of RNA molecules consisting of mostly A-form-like duplexes. The method is implemented in the G2G (from global measurement to global structure) toolkit of programs. We demonstrate the efficiency and accuracy of the method by determining the global structure of a 71-nt RNA using experimental data. The backbone root-mean-square deviation of the ensemble of the calculated global structures relative to the X-ray crystal structure is 3.0+/-0.3 A using the experimental data and is only 2.5+/-0.2 A for the three duplexes that were orientation restrained during the calculation. The global structure simplifies interpretation of multidimensional nuclear Overhauser spectra for high-resolution structure determination. The potential general application of the method for RNA structure determination is discussed. PMID:19666030

  19. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    SciTech Connect

    Hou, Guangjin E-mail: tpolenov@udel.edu; Lu, Xingyu E-mail: lexvega@comcast.net; Vega, Alexander J. E-mail: lexvega@comcast.net; Polenova, Tatyana E-mail: tpolenov@udel.edu

    2014-09-14

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear {sup 1}H-X (X = {sup 13}C, {sup 15}N, {sup 31}P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the {sup 1}H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the {sup 1}H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from {sup 1}H chemical shift anisotropy, while keeping the {sup 1}H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [{sup 15}N]-N-acetyl-valine and [U-{sup 13}C,{sup 15}N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate {sup 1}H-{sup 15}N dipolar couplings in the context of 3D experiments is presented on U-{sup 13}C,{sup 15}N-enriched dynein light chain protein LC8.

  20. Accurate measurement of heteronuclear dipolar couplings by phase-alternating R-symmetry (PARS) sequences in magic angle spinning NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Hou, Guangjin; Lu, Xingyu; Vega, Alexander J.; Polenova, Tatyana

    2014-09-01

    We report a Phase-Alternating R-Symmetry (PARS) dipolar recoupling scheme for accurate measurement of heteronuclear 1H-X (X = 13C, 15N, 31P, etc.) dipolar couplings in MAS NMR experiments. It is an improvement of conventional C- and R-symmetry type DIPSHIFT experiments where, in addition to the dipolar interaction, the 1H CSA interaction persists and thereby introduces considerable errors in the dipolar measurements. In PARS, phase-shifted RN symmetry pulse blocks applied on the 1H spins combined with π pulses applied on the X spins at the end of each RN block efficiently suppress the effect from 1H chemical shift anisotropy, while keeping the 1H-X dipolar couplings intact. Another advantage over conventional DIPSHIFT experiments, which require the signal to be detected in the form of a reduced-intensity Hahn echo, is that the series of π pulses refocuses the X chemical shift and avoids the necessity of echo formation. PARS permits determination of accurate dipolar couplings in a single experiment; it is suitable for a wide range of MAS conditions including both slow and fast MAS frequencies; and it assures dipolar truncation from the remote protons. The performance of PARS is tested on two model systems, [15N]-N-acetyl-valine and [U-13C,15N]-N-formyl-Met-Leu-Phe tripeptide. The application of PARS for site-resolved measurement of accurate 1H-15N dipolar couplings in the context of 3D experiments is presented on U-13C,15N-enriched dynein light chain protein LC8.

  1. NMR spectroscopy of some electrolyte solutions to 1.9 GPa

    NASA Astrophysics Data System (ADS)

    Ochoa, Gerardo; Colla, Christopher A.; Klavins, Peter; Augustine, Matthew P.; Casey, William H.

    2016-11-01

    Nuclear-magnetic resonance (NMR) spectra of CsCl and LaCl3 in D2O/H2O solutions were collected up to pressures of 1.9 GPa using a new NMR probe design that considerably extends the pressure range available for geochemical experiments. The longitudinal-relaxation times (T1) for 2H compare well with those reported in the previous studies of Lee et al. (1974), who examined lower pressures, and indicate that the probe functions properly. In some experiments, 133Cs and 1H NMR spectra could be taken on solutions to pressures well beyond the nominal freezing pressure of D2O or H2O to form Ice VI (near 0.9 GPa). Freezing to form the high-pressure ice is kinetically slow on an experimental time scale (minutes to hours). The data indicate that the electrolyte concentrations increase the freezing pressure of the solution. This result means that solution NMR spectra can be collected at pressures that are nearly twice the nominal freezing pressure of pure D2O or H2O. Pulsed-magnetic-field-gradient NMR methods are used to independently measure the self-diffusion coefficient of H2O in these solutions, which yields estimates of solution viscosity via the Stokes-Einstein relation. The increased viscosity accounts for the pressure variation of T1 values as rates of molecular tumbling are affected. Accounting for such changes is essential if NMR spectral line widths are used to infer pressure-enhanced rates of geochemical reactions, such as interconversion of aqueous complexes.

  2. NMR characterization of membrane protein–detergent micelle solutions using microcoil equipment

    PubMed Central

    Stanczak, Pawel; Horst, Reto; Serrano, Pedro; Wüthrich, Kurt

    2010-01-01

    Using microcoil NMR technology, the uniformly 2H,15N-labeled integral membrane protein OmpX and the phosphocholine derivative detergent Fos-10 (n-decylphosphocholine), we investigated solutions of mixed protein–detergent micelles to determine the influence of the detergent concentration on the NMR spectra of the protein. In a first step, we identified key parameters that influence the composition of the micelle solutions, which resulted in a new protocol for the preparation of well-defined concentrated protein solutions. This led to the observation that high-quality 2D [15N,1H]-TROSY spectra of OmpX reconstituted in mixed micelles with Fos-10 were obtained only in a limited range of detergent concentrations. Outside of this range from about 90 mM to 180 mM, we observed a significant decrease of the average peak intensity. Relaxation-optimized NMR measurements of the rotational and translational diffusion coefficients of the OmpX/Fos-10 mixed micelles, Dr and Dt, respectively, then showed that the stoichiometry and the effective hydrodynamic radius of the protein-containing micelles are not significantly affected by high Fos-10 concentrations, and that the deterioration of NMR spectra is due to the increased viscosity at high detergent concentrations. The paper thus provides a basis for refined guidelines on the preparation of integral membrane proteins for structural studies. PMID:19950959

  3. NMR characterization of membrane protein-detergent micelle solutions by use of microcoil equipment.

    PubMed

    Stanczak, Pawel; Horst, Reto; Serrano, Pedro; Wüthrich, Kurt

    2009-12-30

    Using microcoil NMR technology, the uniformly (2)H,(15)N-labeled integral membrane protein OmpX, and the phosphocholine derivative detergent Fos-10 (n-decylphosphocholine), we investigated solutions of mixed protein-detergent micelles to determine the influence of the detergent concentration on the NMR spectra of the protein. In a first step, we identified key parameters that influence the composition of the micelle solutions, which resulted in a new protocol for the preparation of well-defined concentrated protein solutions. This led to the observation that high-quality 2D [(15)N,(1)H]-transverse relaxation-optimized spectroscopy (TROSY) spectra of OmpX reconstituted in mixed micelles with Fos-10 were obtained only in a limited range of detergent concentrations. Outside of this range from about 90-180 mM, we observed a significant decrease of the average peak intensity. Relaxation-optimized NMR measurements of the rotational and translational diffusion coefficients of the OmpX/Fos-10 mixed micelles, D(r) and D(t), respectively, then showed that the stoichiometry and the effective hydrodynamic radius of the protein-containing micelles are not significantly affected by high Fos-10 concentrations and that the deterioration of NMR spectra is due to the increased viscosity at high detergent concentrations. The paper thus provides a basis for refined guidelines on the preparation of integral membrane proteins for structural studies.

  4. Glutamatergic and GABAergic energy metabolism measured in the rat brain by (13) C NMR spectroscopy at 14.1 T.

    PubMed

    Duarte, João M N; Gruetter, Rolf

    2013-09-01

    Energy metabolism supports both inhibitory and excitatory neurotransmission processes. This study investigated the specific contribution of astrocytic metabolism to γ-aminobutyric acid (GABA) synthesis and inhibitory GABAergic neurotransmission that remained to be ilucidated in vivo. Therefore, we measured (13)C incorporation into brain metabolites by dynamic (13)C nuclear magnetic resonance spectroscopy at 14.1 T in rats under α-chloralose anaesthesia during infusion of [1,6-(13)C]glucose. The enhanced sensitivity at 14.1 T allowed to quantify incorporation of (13) C into the three aliphatic carbons of GABA non-invasively. Metabolic fluxes were determined with a mathematical model of brain metabolism comprising glial, glutamatergic and GABAergic compartments. GABA synthesis rate was 0.11 ± 0.01 μmol/g/min. GABA-glutamine cycle was 0.053 ± 0.003 μmol/g/min and accounted for 22 ± 1% of total neurotransmitter cycling between neurons and glia. Cerebral glucose oxidation was 0.47 ± 0.02 μmol/g/min, of which 35 ± 1% and 7 ± 1% was diverted to the glutamatergic and GABAergic tricarboxylic acid cycles, respectively. The remaining fraction of glucose oxidation was in glia, where 12 ± 1% of the TCA cycle flux was dedicated to oxidation of GABA. 16 ± 2% of glutamine synthesis was provided to GABAergic neurons. We conclude that substantial metabolic activity occurs in GABAergic neurons and that glial metabolism supports both glutamatergic and GABAergic neurons in the living rat brain. PMID:23745684

  5. Using NMR to study full intact wine bottles

    NASA Astrophysics Data System (ADS)

    Weekley, A. J.; Bruins, P.; Sisto, M.; Augustine, M. P.

    2003-03-01

    A nuclear magnetic resonance (NMR) probe and spectrometer capable of investigating full intact wine bottles is described and used to study a series of Cabernet Sauvignons with high resolution 1H NMR spectroscopy. Selected examples of full bottle 13C NMR spectra are also provided. The application of this full bottle NMR method to the measurement of acetic acid content, the detection of complex sugars, phenols, and trace elements in wine is discussed.

  6. Microwave Spectra and Geometries of C2H2\\cdots AuI and C2H4\\cdots AuI

    NASA Astrophysics Data System (ADS)

    Stephens, Susanna Louise; Mullaney, John Connor; Sprawling, Matt John; Tew, David Peter; Walker, Nick; Legon, Anthony

    2014-06-01

    A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H2\\cdots AuI and C2H4\\cdots AuI. These complexes are generated via laser ablation at 532 nm of a gold surface in the presence of CF3I and either C2H2 or C2H4 and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ, ΔJK and δJ) of each molecule have been determined as well the nuclear electric quadrupole coupling constants of gold and iodine atoms (χaa(Au}, χbb-χcc(Au), χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H2 or C2H4 subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule.

  7. NMR investigations of molecular dynamics

    NASA Astrophysics Data System (ADS)

    Palmer, Arthur

    2011-03-01

    NMR spectroscopy is a powerful experimental approach for characterizing protein conformational dynamics on multiple time scales. The insights obtained from NMR studies are complemented and by molecular dynamics (MD) simulations, which provide full atomistic details of protein dynamics. Homologous mesophilic (E. coli) and thermophilic (T. thermophilus) ribonuclease H (RNase H) enzymes serve to illustrate how changes in protein sequence and structure that affect conformational dynamic processes can be monitored and characterized by joint analysis of NMR spectroscopy and MD simulations. A Gly residue inserted within a putative hinge between helices B and C is conserved among thermophilic RNases H, but absent in mesophilic RNases H. Experimental spin relaxation measurements show that the dynamic properties of T. thermophilus RNase H are recapitulated in E. coli RNase H by insertion of a Gly residue between helices B and C. Additional specific intramolecular interactions that modulate backbone and sidechain dynamical properties of the Gly-rich loop and of the conserved Trp residue flanking the Gly insertion site have been identified using MD simulations and subsequently confirmed by NMR spin relaxation measurements. These results emphasize the importance of hydrogen bonds and local steric interactions in restricting conformational fluctuations, and the absence of such interactions in allowing conformational adaptation to substrate binding.

  8. An XPS investigation of the interaction of CH 4, C 2H 2, C 2H 4 and C 2H 6 with a barium surface

    NASA Astrophysics Data System (ADS)

    Verhoeven, J. A. Th.; Van Doveren, H.

    1982-12-01

    The generation and pumping of hydrocarbon gases by a barium getter layer in electronic vacuum devices has been investigated by characterizing a barium film in an ultra high vacuum equipment by means of XPS before, during and after exposures to respectively CH 4, C 2H 2, C 2H 4 and C 2H 6. The reaction conditions (temperatures and pretreatment of the surface, background pressure and exposure doses) closely resemble those in electronic vacuum devices. The probability that a barium layer will react with CH 4 and C 2H 6 was below the detection limit. C 2H 2 and C 2H 4 give rise to the formation of barium carbide compounds and with a high reaction probability. In addition, the interaction with C 2H 2 reveals the formation of carbon-containing surface complexes. Investigations by means of XPS on the C Is spectral features show the presence of at least two groups of carbon-containing surface complexes, which behave differently in response to moderate heating and to an exposure to water vapour. In cases where oxygen is present at the surface, oxygen-containing (hydro) carbon adsorbates are present too. XPS observations of the behaviour of these surface complexes show similarities with reaction steps in the mechanisms proposed for the hydrogenation of CO in the Fischer-Tropsch synthesis of hydrocarbons. Low-pressure hydrogenation of these adsorbates containing hydrocarbons and oxygen can led to the formation of hydrocarbon gases in electronic vacuum devices.

  9. Probing porous media with gas diffusion NMR.

    PubMed

    Mair, R W; Wong, G P; Hoffmann, D; Hurlimann, M D; Patz, S; Schwartz, L M; Walsworth, R L

    1999-10-18

    We show that gas diffusion nuclear magnetic resonance (GD-NMR) provides a powerful technique for probing the structure of porous media. In random packs of glass beads, using both laser-polarized and thermally polarized xenon gas, we find that GD-NMR can accurately measure the pore space surface-area-to-volume ratio, S/V rho, and the tortuosity, alpha (the latter quantity being directly related to the system's transport properties). We also show that GD-NMR provides a good measure of the tortuosity of sandstone and complex carbonate rocks. PMID:11543587

  10. Probing porous media with gas diffusion NMR

    NASA Technical Reports Server (NTRS)

    Mair, R. W.; Wong, G. P.; Hoffmann, D.; Hurlimann, M. D.; Patz, S.; Schwartz, L. M.; Walsworth, R. L.

    1999-01-01

    We show that gas diffusion nuclear magnetic resonance (GD-NMR) provides a powerful technique for probing the structure of porous media. In random packs of glass beads, using both laser-polarized and thermally polarized xenon gas, we find that GD-NMR can accurately measure the pore space surface-area-to-volume ratio, S/V rho, and the tortuosity, alpha (the latter quantity being directly related to the system's transport properties). We also show that GD-NMR provides a good measure of the tortuosity of sandstone and complex carbonate rocks.

  11. NMR and MRI apparatus and method

    DOEpatents

    Clarke, John; Kelso, Nathan; Lee, SeungKyun; Moessle, Michael; Myers, Whittier; McDermott, Robert; ten Haken, Bernard; Pines, Alexander; Trabesinger, Andreas

    2007-03-06

    Nuclear magnetic resonance (NMR) signals are detected in microtesla fields. Prepolarization in millitesla fields is followed by detection with an untuned dc superconducting quantum interference device (SQUID) magnetometer. Because the sensitivity of the SQUID is frequency independent, both signal-to-noise ratio (SNR) and spectral resolution are enhanced by detecting the NMR signal in extremely low magnetic fields, where the NMR lines become very narrow even for grossly inhomogeneous measurement fields. Additional signal to noise benefits are obtained by use of a low noise polarization coil, comprising litz wire or superconducting materials. MRI in ultralow magnetic field is based on the NMR at ultralow fields. Gradient magnetic fields are applied, and images are constructed from the detected NMR signals.

  12. Relative high-resolution absorption cross sections of C2H6 at low temperatures

    NASA Astrophysics Data System (ADS)

    Hargreaves, R. J.; Bernath, P. F.; Appadoo, D. R. T.

    2015-09-01

    Synchrotron radiation has been used to record absorption cross sections of ethane, C2H6, in the far-infrared with very high spectral resolution (up to 0.00096 cm-1). C2H6 is present in the atmospheres of the Gas Giant planets and Titan but the vapor pressure at relevant atmospheric temperatures (i.e., between 70 and 200 K) is low. This makes laboratory measurements difficult. We demonstrate the effectiveness of a unique "enclosive flow" cold cell, located at the Australian Synchrotron, that enables high-resolution absorption cross sections of gaseous C2H6 to be recorded at 90 K.

  13. Determination of the delta(2H/1H)of Water: RSIL Lab Code 1574

    USGS Publications Warehouse

    Revesz, Kinga; Coplen, Tyler B.

    2008-01-01

    Reston Stable Isotope Laboratory (RSIL) lab code 1574 describes a method used to determine the relative hydrogen isotope-ratio delta(2H,1H), abbreviated hereafter as d2H of water. The d2H measurement of water also is a component of the National Water Quality Laboratory (NWQL) schedules 1142 and 1172. The water is collected unfiltered in a 60-mL glass bottle and capped with a Polyseal cap. In the laboratory, the water sample is equilibrated with gaseous hydrogen using a platinum catalyst (Horita, 1988; Horita and others, 1989; Coplen and others, 1991). The reaction for the exchange of one hydrogen atom is shown in equation 1.

  14. Determination of de novo synthesized amino acids in cellular proteins revisited by 13C NMR spectroscopy.

    PubMed

    Flögel, U; Willker, W; Leibfritz, D

    1997-04-01

    13C nuclear magnetic resonance spectroscopy was used to determine the absolute amounts to de novo synthesized amino acids in both the perchloric acid extracts and the hydrolyzed protein fractions of F98 glioma cells incubated for 2 h with 5 mmol/l [U-13C]glucose. 13C NMR spectra of the hydrolyzed protein fraction revealed a marked incorporation of 13C-labelled alanine, aspartate and glutamate into the proteins of F98 cells within the incubation period. Additionally, small amounts of 13C-labelled glycine, proline and serine could unambiguously be identified in the protein fraction. Astonishingly, approximately equal amounts of 13C-labelled glutamate and aspartate were incorporated into the cellular proteins, although the cytosolic steady-state concentration of aspartate was below 13C NMR detectability. Hypertonic stress decreased the incorporation of 13C-labelled amino acids into the total protein, albeit their cytosolic concentrations were increased, which reflects an inhibition of protein synthesis under these conditions. On the other hand, hypotonic stress increased the amount of 13C-labelled proline incorporated into the cellular proteins even though the cytosolic concentration of 13C-labelled proline was largely decreased. Apparently, hypoosmotic conditions stimulate the synthesis of proteins or peptides with a high proline content. The results show that already after 2 h of incubation with [U-13C]glucose there is a pronounced flux of 13C label into the cellular proteins, which is usually disregarded if cytosolic fluids are examined only. This means that calculations of metabolic fluxes based on 13C NMR spectroscopic data obtained from perchloric acid extracts of cells or tissues and also from in vivo measurements consider only the labelled 'NMR visible' cytosolic metabolites, which may have to be corrected for fast label flowing off into other compartments.

  15. NMR studies of multiphase flows II

    SciTech Connect

    Altobelli, S.A.; Caprihan, A.; Fukushima, E.

    1995-12-31

    NMR techniques for measurements of spatial distribution of material phase, velocity and velocity fluctuation are being developed and refined. Versions of these techniques which provide time average liquid fraction and fluid phase velocity have been applied to several concentrated suspension systems which will not be discussed extensively here. Technical developments required to further extend the use of NMR to the multi-phase flow arena and to provide measurements of previously unobtainable parameters are the focus of this report.

  16. Site-resolved multiple-quantum filtered correlations and distance measurements by magic-angle spinning NMR: Theory and applications to spins with weak to vanishing quadrupolar couplings.

    PubMed

    Eliav, U; Haimovich, A; Goldbourt, A

    2016-01-14

    We discuss and analyze four magic-angle spinning solid-state NMR methods that can be used to measure internuclear distances and to obtain correlation spectra between a spin I = 1/2 and a half-integer spin S > 1/2 having a small quadrupolar coupling constant. Three of the methods are based on the heteronuclear multiple-quantum and single-quantum correlation experiments, that is, high rank tensors that involve the half spin and the quadrupolar spin are generated. Here, both zero and single-quantum coherence of the half spins are allowed and various coherence orders of the quadrupolar spin are generated, and filtered, via active recoupling of the dipolar interaction. As a result of generating coherence orders larger than one, the spectral resolution for the quadrupolar nucleus increases linearly with the coherence order. Since the formation of high rank tensors is independent of the existence of a finite quadrupolar interaction, these experiments are also suitable to materials in which there is high symmetry around the quadrupolar spin. A fourth experiment is based on the initial quadrupolar-driven excitation of symmetric high order coherences (up to p = 2S, where S is the spin number) and subsequently generating by the heteronuclear dipolar interaction higher rank (l + 1 or higher) tensors that involve also the half spins. Due to the nature of this technique, it also provides information on the relative orientations of the quadrupolar and dipolar interaction tensors. For the ideal case in which the pulses are sufficiently strong with respect to other interactions, we derive analytical expressions for all experiments as well as for the transferred echo double resonance experiment involving a quadrupolar spin. We show by comparison of the fitting of simulations and the analytical expressions to experimental data that the analytical expressions are sufficiently accurate to provide experimental (7)Li-(13)C distances in a complex of lithium, glycine, and water. Discussion

  17. Relationship between the crystallization rates of amorphous nifedipine, phenobarbital, and flopropione, and their molecular mobility as measured by their enthalpy relaxation and (1)H NMR relaxation times.

    PubMed

    Aso, Y; Yoshioka, S; Kojima, S

    2000-03-01

    Isothermal crystallization of amorphous nifedipine, phenobarbital, and flopropione was studied at temperatures above and below their glass transition temperatures (T(g)). A sharp decrease in the crystallization rate with decreasing temperature was observed for phenobarbital and flopropione, such that no crystallization was observed at temperatures 20-30 degrees C lower than their T(g) within ordinary experimental time periods. In contrast, the crystallization rate of nifedipine decreased moderately with decreasing temperature, and considerable crystallization was observed at 40 degrees C below its T(g) within 4 months. The molecular mobility of these amorphous drugs was assessed by enthalpy relaxation and (1)H-NMR relaxation measurements. The enthalpy relaxation time of nifedipine was smaller than that of phenobarbital or flopropinone at the same T - T(g) values, suggesting higher molecular mobility of nifedipine. The spin-lattice relaxation time in the rotating frame (T(1rho)) decreased markedly at temperature above T(g). The slope of the Arrhenius type plot of the T(1rho) for nifedipine protons changed at about 10 degrees C below the T(g), whereas the slope for phenobarbital protons became discontinuous at about 10 degrees C above the T(g). Even at temperatures below its T(g), the spin-spin relaxation process of nifedipine could be described by the sum of its Gaussian relaxation, which is characteristic of solid protons, and its Lorentzian relaxation, which is characteristic of protons with higher mobility. In contrast, no Lorentzian relaxation was observed for phenobarbital or flopropione at temperatures below their T(g). These results also suggest that nifedipine has higher molecular mobility than phenobarbital and flopropione at temperatures below T(g). The faster crystallization of nifedipine than that of phenobarbital or flopropione observed at temperatures below its T(g) may be partly ascribed to its higher molecular mobility at these temperatures.

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

    PubMed

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

    2016-09-01

    Transverse relaxation rate measurements in magic-angle spinning solid-state nuclear magnetic resonance provide information about molecular motions occurring on nanosecond-to-millisecond (ns-ms) time scales. The measurement of heteronuclear ((13)C, (15)N) relaxation rate constants in the presence of a spin-lock radiofrequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins have been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely, (1) the role of CSA/dipolar cross-correlated relaxation (CCR) and (2) 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 the CCR rate constant depends on ns-ms motions; it can thus provide insight into dynamics. We find that proton spin diffusion attenuates this CCR 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 this article reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation. PMID:27500976

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

    PubMed

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

    2016-09-01

    Transverse relaxation rate measurements in magic-angle spinning solid-state nuclear magnetic resonance provide information about molecular motions occurring on nanosecond-to-millisecond (ns-ms) time scales. The measurement of heteronuclear ((13)C, (15)N) relaxation rate constants in the presence of a spin-lock radiofrequency field (R1ρ relaxation) provides access to such motions, and an increasing number of studies involving R1ρ relaxation in proteins have been reported. However, two factors that influence the observed relaxation rate constants have so far been neglected, namely, (1) the role of CSA/dipolar cross-correlated relaxation (CCR) and (2) 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 the CCR rate constant depends on ns-ms motions; it can thus provide insight into dynamics. We find that proton spin diffusion attenuates this CCR 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 this article reveals factors that have so far been disregarded and which are important for accurate measurements and interpretation.

  20. High resolution deuterium NMR studies of bacterial metabolism

    SciTech Connect

    Aguayo, J.B.; Gamcsik, M.P.; Dick, J.D.

    1988-12-25

    High resolution deuterium NMR spectra were obtained from suspensions of five bacterial strains: Escherichia coli, Clostridium perfringens, Klebsiella pneumoniae, Proteus mirabilis, and Staphylococcus aureus. Deuterium-labeled D-glucose at C-1, C-2, and C-6 was used to monitor dynamically anaerobic metabolism. The flux of glucose through the various bacterial metabolic pathways could be determined by following the disappearance of glucose and the appearance of the major end products in the 2H NMR spectrum. The presence of both labeled and unlabeled metabolites could be detected using 1H NMR spectroscopy since the proton resonances in the labeled species are shifted upfield due to an isotopic chemical shift effect. The 1H-1H scalar coupling observed in both the 2H and 1H NMR spectra was used to assign definitively the resonances of labeled species. An increase in the intensity of natural abundance deuterium signal of water can be used to monitor pathways in which a deuteron is lost from the labeled metabolite. The steps in which label loss can occur are outlined, and the influence these processes have on the ability of 2H NMR spectroscopy to monitor metabolism are assessed.

  1. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

    2004-07-20

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfones and [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure: ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing methyl aryl sulfones and methyl aryl sulfoxides.

  2. Ligand-induced substrate steering and reshaping of [Ag2(H)](+) scaffold for selective CO2 extrusion from formic acid.

    PubMed

    Zavras, Athanasios; Khairallah, George N; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A J

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)](+) by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)](+) and [Ph3PAg2(H)](+) react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)](+) is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)(+) scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)](+) and H2. Decarboxylation of [dppmAg2(O2CH)](+) via CID regenerates [dppmAg2(H)](+). These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  3. Ligand-induced substrate steering and reshaping of [Ag2(H)]+ scaffold for selective CO2 extrusion from formic acid

    PubMed Central

    Zavras, Athanasios; Khairallah, George N.; Krstić, Marjan; Girod, Marion; Daly, Steven; Antoine, Rodolphe; Maitre, Philippe; Mulder, Roger J.; Alexander, Stefanie-Ann; Bonačić-Koutecký, Vlasta; Dugourd, Philippe; O'Hair, Richard A. J.

    2016-01-01

    Metalloenzymes preorganize the reaction environment to steer substrate(s) along the required reaction coordinate. Here, we show that phosphine ligands selectively facilitate protonation of binuclear silver hydride cations, [LAg2(H)]+ by optimizing the geometry of the active site. This is a key step in the selective, catalysed extrusion of carbon dioxide from formic acid, HO2CH, with important applications (for example, hydrogen storage). Gas-phase ion-molecule reactions, collision-induced dissociation (CID), infrared and ultraviolet action spectroscopy and computational chemistry link structure to reactivity and mechanism. [Ag2(H)]+ and [Ph3PAg2(H)]+ react with formic acid yielding Lewis adducts, while [(Ph3P)2Ag2(H)]+ is unreactive. Using bis(diphenylphosphino)methane (dppm) reshapes the geometry of the binuclear Ag2(H)+ scaffold, triggering reactivity towards formic acid, to produce [dppmAg2(O2CH)]+ and H2. Decarboxylation of [dppmAg2(O2CH)]+ via CID regenerates [dppmAg2(H)]+. These gas-phase insights inspired variable temperature NMR studies that show CO2 and H2 production at 70 °C from solutions containing dppm, AgBF4, NaO2CH and HO2CH. PMID:27265868

  4. Osmium(IV) complexes with 1H- and 2H-indazoles: tautomer identity versus spectroscopic properties and antiproliferative activity.

    PubMed

    Büchel, Gabriel E; Stepanenko, Iryna N; Hejl, Michaela; Jakupec, Michael A; Keppler, Bernhard K; Heffeter, Petra; Berger, Walter; Arion, Vladimir B

    2012-08-01

    A one-pot synthesis of osmium(IV) complexes with two different tautomers of indazole, 1H-indazole and 2H-indazole, namely (H(2)ind)[Os(IV)Cl(5)(2H-ind)] (1) and (H(2)ind)[Os(IV)Cl(5)(1H-ind)] (2) is reported. Both compounds have been comprehensively characterized by NMR spectroscopy, ESI (electrospray ionization) mass spectrometry, electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry and tested for antiproliferative activity in vitro in three human cancer cell lines, CH1 (ovarian carcinoma), A549 (non-small cell lung cancer) and SW480 (colon carcinoma), as well as in vivo in a Hep3B SCID mouse xeno-transplantation model. 2H-Indazole tautomer stabilization in 1 has been confirmed by X-ray diffraction.

  5. Osmium(IV) complexes with 1H- and 2H-indazoles: Tautomer identity versus spectroscopic properties and antiproliferative activity

    PubMed Central

    Büchel, Gabriel E.; Stepanenko, Iryna N.; Hejl, Michaela; Jakupec, Michael A.; Keppler, Bernhard K.; Heffeter, Petra; Berger, Walter; Arion, Vladimir B.

    2012-01-01

    A one-pot synthesis of osmium(IV) complexes with two different tautomers of indazole, 1H-indazole and 2H-indazole, namely (H2ind)[OsIVCl5(2H-ind)] (1) and (H2ind)[OsIVCl5(1H-ind)] (2) is reported. Both compounds have been comprehensively characterized by NMR spectroscopy, ESI (electrospray ionization) mass spectrometry, electronic absorption spectroscopy, IR spectroscopy, cyclic voltammetry and tested for antiproliferative activity in vitro in three human cancer cell lines, CH1 (ovarian carcinoma), A549 (non-small cell lung cancer) and SW480 (colon carcinoma), as well as in vivo in a Hep3B SCID mouse xeno-transplantation model. 2H-Indazole tautomer stabilization in 1 has been confirmed by X-ray diffraction. PMID:22687494

  6. Model dependence of the {sup 2}H electric dipole moment

    SciTech Connect

    Afnan, I. R.; Gibson, B. F.

    2010-12-15

    Background: Direct measurement of the electric dipole moment (EDM) of the neutron is in the future; measurement of a nuclear EDM may well come first. The deuteron is one nucleus for which exact model calculations are feasible. Purpose: We explore the model dependence of deuteron EDM calculations. Methods: Using a separable potential formulation of the Hamiltonian, we examine the sensitivity of the deuteron EDM to variation in the nucleon-nucleon interaction. We write the EDM as the sum of two terms, the first depending on the target wave function with plane-wave intermediate states, and the second depending on intermediate multiple scattering in the {sup 3}P{sub 1} channel, the latter being sensitive to the off-shell behavior of the {sup 3}P{sub 1} amplitude. Results: We compare the full calculation with the plane-wave approximation result, examine the tensor force contribution to the model results, and explore the effect of short-range repulsion found in realistic, contemporary potential models of the deuteron. Conclusions: Because one-pion exchange dominates the EDM calculation, separable potential model calculations will provide an adequate description of the {sup 2}H EDM until such time as a measurement better than 10% is obtained.

  7. Lectures on pulsed NMR

    SciTech Connect

    Pines, A.

    1986-09-01

    These lectures discuss some recent developments in pulsed NMR, emphasizing fundamental principles with selected illustrative applications. Major topics covered include multiple-quantum spectroscopy, spin decoupling, the interaction of spins with a quantized field, adiabatic rapid passage, spin temperature and statistics of cross-polarization, coherent averaging, and zero field NMR. 55 figs.

  8. Lectures on pulsed NMR

    SciTech Connect

    Pines, A.

    1988-08-01

    These lectures discuss some recent developments in pulsed NMR, emphasizing fundamental principles with selected illustrative applications. Major topics covered include multiple-quantum spectroscopy, spin decoupling, the interaction of spins with a quantized field, adiabatic rapid passage, spin temperature and statistics of cross-polarization, coherent averaging, and zero field NMR. 32 refs., 56 figs.

  9. NMR studies of metalloproteins.

    PubMed

    Li, Hongyan; Sun, Hongzhe

    2012-01-01

    Metalloproteins represent a large share of the proteomes, with the intrinsic metal ions providing catalytic, regulatory, and structural roles critical to protein functions. Structural characterization of metalloproteins and identification of metal coordination features including numbers and types of ligands and metal-ligand geometry, and mapping the structural and dynamic changes upon metal binding are significant for understanding biological functions of metalloproteins. NMR spectroscopy has long been used as an invaluable tool for structure and dynamic studies of macromolecules. Here we focus on the application of NMR spectroscopy in characterization of metalloproteins, including structural studies and identification of metal coordination spheres by hetero-/homo-nuclear metal NMR spectroscopy. Paramagnetic NMR as well as (13)C directly detected protonless NMR spectroscopy will also be addressed for application to paramagnetic metalloproteins. Moreover, these techniques offer great potential for studies of other non-metal binding macromolecules.

  10. SQUID detected NMR and MRI at ultralow fields

    SciTech Connect

    Clarke, John; McDermott, Robert; Pines, Alexander; Trabesinger, Andreas Heinz

    2006-10-03

    Nuclear magnetic resonance (NMR) signals are detected in microtesla fields. Prepolarization in millitesla fields is followed by detection with an untuned dc superconducting quantum interference device (SQUID) magnetometer. Because the sensitivity of the SQUID is frequency independent, both signal-to-noise ratio (SNR) and spectral resolution are enhanced by detecting the NMR signal in extremely low magnetic fields, where the NMR lines become very narrow even for grossly inhomogeneous measurement fields. MRI in ultralow magnetic field is based on the NMR at ultralow fields. Gradient magnetic fields are applied, and images are constructed from the detected NMR signals.

  11. Squid detected NMR and MRI at ultralow fields

    DOEpatents

    Clarke, John; McDermott, Robert; Pines, Alexander; Trabesinger, Andreas Heinz

    2006-05-30

    Nuclear magnetic resonance (NMR) signals are detected in microtesla fields. Prepolarization in millitesla fields is followed by detection with an untuned dc superconducting quantum interference device (SQUID) magnetometer. Because the sensitivity of the SQUID is frequency independent, both signal-to-noise ratio (SNR) and spectral resolution are enhanced by detecting the NMR signal in extremely low magnetic fields, where the NMR lines become very narrow even for grossly inhomogeneous measurement fields. MRI in ultralow magnetic field is based on the NMR at ultralow fields. Gradient magnetic fields are applied, and images are constructed from the detected NMR signals.

  12. Squid detected NMR and MRI at ultralow fields

    DOEpatents

    Clarke, John; McDermott, Robert; Pines, Alexander; Trabesinger, Andreas Heinz

    2007-05-15

    Nuclear magnetic resonance (NMR) signals are detected in microtesla fields. Prepolarization in millitesla fields is followed by detection with an untuned dc superconducting quantum interference device (SQUID) magnetometer. Because the sensitivity of the SQUID is frequency independent, both signal-to-noise ratio (SNR) and spectral resolution are enhanced by detecting the NMR signal in extremely low magnetic fields, where the NMR lines become very narrow even for grossly inhomogeneous measurement fields. MRI in ultralow magnetic field is based on the NMR at ultralow fields. Gradient magnetic fields are applied, and images are constructed from the detected NMR signals.

  13. Squid detected NMR and MRI at ultralow fields

    SciTech Connect

    Clarke, John; Pines, Alexander; McDermott, Robert F.; Trabesinger, Andreas H.

    2008-12-16

    Nuclear magnetic resonance (NMR) signals are detected in microtesla fields. Prepolarization in millitesla fields is followed by detection with an untuned dc superconducting quantum interference device (SQUID) magnetometer. Because the sensitivity of the SQUID is frequency independent, both signal-to-noise ratio (SNR) and spectral resolution are enhanced by detecting the NMR signal in extremely low magnetic fields, where the NMR lines become very narrow even for grossly inhomogeneous measurement fields. MRI in ultralow magnetic field is based on the NMR at ultralow fields. Gradient magnetic fields are applied, and images are constructed from the detected NMR signals.

  14. Photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 in the VUV region

    NASA Technical Reports Server (NTRS)

    Xia, T. J.; Chien, T. S.; Wu, C. Y. Robert; Judge, D. L.

    1991-01-01

    Using synchrotron radiation as a continuum light source, the photoabsorption and photoionization cross sections of NH3, PH3, H2S, C2H2, and C2H4 have been measured from their respective ionization thresholds to 1060 A. The vibrational constants associated with the nu(2) totally symmetric, out-of-plane bending vibration of the ground electronic state of PH3(+) have been obtained. The cross sections and quantum yields for producing neutral products through photoexcitation of these molecules in the given spectral regions have also been determined. In the present work, autoionization processes were found to be less important than dissociation and predissociation processes in NH3, PH3, and C2H4. Several experimental techniques have been employed in order to examine the various possible systematic errors critically.

  15. Epitaxial growth and electronic structure of oxyhydride SrVO2H thin films

    NASA Astrophysics Data System (ADS)

    Katayama, Tsukasa; Chikamatsu, Akira; Yamada, Keisuke; Shigematsu, Kei; Onozuka, Tomoya; Minohara, Makoto; Kumigashira, Hiroshi; Ikenaga, Eiji; Hasegawa, Tetsuya

    2016-08-01

    Oxyhydride SrVO2H epitaxial thin films were fabricated on SrTiO3 substrates via topotactic hydridation of oxide SrVO3 films using CaH2. Structural and composition analyses suggested that the SrVO2H film possessed one-dimensionally ordered V-H--V bonds along the out-of-plane direction. The synthesis temperature could be lowered by reducing the film thickness, and the SrVO2H film was reversible to SrVO3 by oxidation through annealing in air. Photoemission and X-ray absorption spectroscopy measurements revealed the V3+ valence state in the SrVO2H film, indicating that the hydrogen existed as hydride. Furthermore, the electronic density of states was highly suppressed at the Fermi energy, consistent with the prediction that tetragonal distortion induces metal to insulation transition.

  16. Infrared and Ultraviolet Spectra of Diborane(6): B2H6 and B2D6.

    PubMed

    Peng, Yu-Chain; Chou, Sheng-Lung; Lo, Jen-Iu; Lin, Meng-Yeh; Lu, Hsiao-Chi; Cheng, Bing-Ming; Ogilvie, J F

    2016-07-21

    We recorded absorption spectra of diborane(6), B2H6 and B2D6, dispersed in solid neon near 4 K in both mid-infrared and ultraviolet regions. For gaseous B2H6 from 105 to 300 nm, we report quantitative absolute cross sections; for solid B2H6 and for B2H6 dispersed in solid neon, we measured ultraviolet absorbance with relative intensities over a wide range. To assign the mid-infrared spectra to specific isotopic variants, we applied the abundance of (11)B and (10)B in natural proportions; we undertook quantum-chemical calculations of wavenumbers associated with anharmonic vibrational modes and the intensities of the harmonic vibrational modes. To aid an interpretation of the ultraviolet spectra, we calculated the energies of electronically excited singlet and triplet states and oscillator strengths for electronic transitions from the electronic ground state. PMID:27351464

  17. Single crystal to single crystal topochemical photoreactions: measuring the degree of disorder in the [2+2] photodimerization of trans-cinnamic acid using single-crystal 13C NMR spectroscopy.

    PubMed

    Nieuwendaal, Ryan C; Mattler, Sarah J; Bertmer, Marko; Hayes, Sophia E

    2011-05-19

    A single crystal of α-trans-cinnamic acid was synthesized with a (13)C-label at the β-carbon position and photoreacted to yield the [2+2] cycloaddition product, α-truxillic acid. (13)C{(1)H} cross-polarization (CP) single-crystal NMR experiments were performed on the unreacted and sequentially photoreacted samples for different goniometer orientations, and the spectra were simulated using the SIMMOL and SIMPSON software packages. Atomic coordinates from single-crystal X-ray diffraction data were used as inputs in the simulations, which allowed the chemical shift tensor to be precisely measured and related to the unit cell (or molecular) reference frame of cinnamic acid. The line widths of the (13)C resonances observed at different goniometer rotations were utilized to estimate the orientational dispersion of the cinnamic acid species, which ultimately provides a measure of disorder in the single crystal. The photoreacted sample, a solid solution of cinnamic and truxillic acids, maintained its single-crystal nature, even up to 44% conversion to truxillic acid, keeping its P2(1)/n symmetry. Upon photoirradiation, however, a slight loss of order was observed in the cinnamic acid species as evidenced by an increase in the (13)C NMR line widths, demonstrating that NMR can be used to monitor subtle orientational imperfections in single crystal to single crystal photoreactions.

  18. Nuclear magnetic resonance study of the ferroelastic phase transition of order-disorder type in [N(C2H5)4]2CdCl4

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran; Kim, Min Soo; Lim, Kye-Young

    2016-08-01

    This study uses nuclear magnetic resonance (NMR) techniques to examine the detailed changes in [N(C2H5)4]2CdCl4 around its phase transition at the temperature TC = 284 K. The chemical shifts and spin-lattice relaxation times in the rotating frame (T1ρ) were determined from 1H magic angle spinning (MAS) NMR and 13C cross-polarization (CP)/MAS NMR spectra. The two sets of inequivalent 1H and 13C nuclei in CH3 and CH2 were distinguished. A ferroelastic phase transition was observed at TC, without structural symmetry change. The phase transition is mainly attributed to the orientational ordering of the [N(C2H5)4]+ cations, and the spectral splitting at low temperature is associated with different ferroelastic domains.

  19. Preferred conformation and dynamics of the glycerol backbone in phospholipids. An NMR and X-ray single-crystal analysis

    SciTech Connect

    Hauser, H.; Pascher, I.; Sundell, S. )

    1988-12-27

    The conformation of the glycerol group of a number of diacyl and monoacyl (lyso) phospholipids differing in the chemical nature of the head group was studied by {sup 1}H high-resolution NMR and X-ray crystallography. The NMR measurements were carried out with solutions or micellar dispersions of the lipids in deuteriated organic solvents or {sup 2}H{sub 2}O. Both solutions, in which the lipid is present as monomers, and lipid micelles give rise to good high-resolution NMR spectra exhibiting spin coupling hyperfine interactions. From {sup 1}H spin coupling it is concluded that there are two stable conformations about the glycerol C(2)-C(3) bond of phospholipids. By comparison of NMR and single-crystal X-ray data it is obvious that both conformations are minimum free energy conformations. Rotamer A is the conformation prevailing in phospholipid single-crystal structures. The conformation of rotamer B is also found in phospholipid single-crystal structures though to a lesser extent. NMR measurements indicate that in liquid crystals the diacylglycerol part of phospholipids fluctuates between the two stable staggered conformations of rotamers A and B. The transition between rotamers A and B is fast on the NMR time scale and must be accompanied by appropriate changes in the torsion angles {beta}{sub 1} to {beta}{sub 4} and {gamma}{sub 1} to {gamma}{sub 4} of the two fatty acyl chains. It is clear from the data presented that the parallel alignment of the hydrocarbon chains or chain stacking in phospholipid aggregates such as bilayers or micelles is the fundamental principle governing the conformation of the C(2)-C(3) glycerol bond.

  20. NMR methods in combinatorial chemistry.

    PubMed

    Shapiro, M J; Wareing, J R

    1998-06-01

    The use of NMR spectroscopy in combinatorial chemistry has provided a versatile tool for monitoring combinatorial chemistry reactions and for assessing ligand-receptor interactions. The application of magic angle spinning NMR is widespread and has allowed structure determination to be performed on compounds attached to solid supports. A variety of two-dimensional NMR techniques have been applied to enhance the usability of the magic angle spinning NMR data. New developments for solution NMR analysis include high performance liquid chromatography, NMR, mass spectroscopy and flow NMR. NMR based methods currently being investigated may prove valuable as compound screening tools.

  1. DFT 2H quadrupolar coupling constants of ruthenium complexes: a good probe of the coordination of hydrides in conjuction with experiments.

    PubMed

    del Rosal, Iker; Gutmann, Torsten; Maron, Laurent; Jolibois, Franck; Chaudret, Bruno; Walaszek, Bernadeta; Limbach, Hans-Heinrich; Poteau, Romuald; Buntkowsky, Gerd

    2009-07-21

    Transition metal (TM) hydrides are of great interest in chemistry because of their reactivity and their potential as catalysts for hydrogenation reactions. 2H solid-state NMR can be used in order to get information about the local environment of hydrogen atoms, and more particularly the coordination mode of hydrides in such complexes. In this work we will show that it is possible to establish at the level of density functional theory (DFT) a viable methodological strategy that allows the determination of 2H NMR parameters, namely the quadrupolar coupling constant (C(Q)) respectively the quadrupolar splitting (deltanuQ) and the asymmetry parameter (etaQ). The reliability of the method (B3PW91-DFT) and basis set effects have been first evaluated for simple organic compounds (benzene and fluorene). A good correlation between experimental and theoretical values is systematically obtained if the large basis set cc-pVTZ is used for the computations. 2H NMR properties of five mononuclear ruthenium complexes (namely Cp*RuD3(PPh3), Tp*RuD(THT)2, Tp*RuD(D2)(THT) and Tp*RuD(D2)2 and RuD2(D2)2(PCy3)2) which exhibit different ligands and hydrides involved in different coordination modes (terminal-H or eta2-H2), have been calculated and compared to previous experimental data. The results obtained are in excellent agreement with experiments. Although 2H NMR spectra are not always easy to analyze, assistance by quantum chemistry calculations allows unambiguous assignment of the signals of such spectra. As far as experiments can be achieved at very low temperatures in order to avoid dynamic effects, this hybrid theoretical/experimental tool may give useful insights in the context of the characterization of ruthenium surfaces or nanoparticles with solid-state NMR. PMID:19842483

  2. NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

    PubMed

    Schreckenbach, Georg

    2002-12-16

    In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

  3. On the sensitivity of running-fluid NMR magnetometers

    NASA Astrophysics Data System (ADS)

    Davydov, V. V.; Dudkin, V. I.; Petrov, A. A.; Myazin, N. S.

    2016-07-01

    A new procedure for determining the sensitivity of running-fluid NMR magnetometers is considered. The procedure is based on mathematical processing of experimental data that are related to measuring the gradient of a nutation-line slope at the point at which an inverted NMR signal crosses zero. The procedure allows one to determine the sensitivity of running-fluid NMR magnetometers for resonance frequencies of magnetic-field measurements within a range of 0.5 Hz to 840 MHz.

  4. MICROWAVE SPECTRA AND GEOMETRIES OF C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}

    NASA Astrophysics Data System (ADS)

    Stephens, Susanna L.; Tew, David Peter; Walker, Nick; Legon, Anthony

    2015-06-01

    A chirped-pulse Fourier transform microwave spectrometer has been used to measure the microwave spectra of both C2H_{2\\cdots AgI} and C2H_{4\\cdots AgI}. These complexes are generated via laser ablation at 532 nm of a silver surface in the presence of CF3I and either C2H_{2} or C2H_{4} and argon and are stabilized by a supersonic expansion. Rotational (A0, B0, C0) and centrifugal distortion constants (ΔJ and ΔJK) of each molecule have been determined as well the nuclear electric quadrupole coupling constants the iodine atom (χaa(I) and χbb-χcc(I)). The spectrum of each molecule is consistent with a C2v structure in which the metal atom interacts with the π-orbital of the ethene or ethyne molecule. Isotopic substitutions of atoms within the C2H_{2} or C2H_{4} subunits are in progress and in conjunction with high level ab initio calculations will allow for accurate determination of the geometry of each molecule. These to complexes are put in the context of the recently studied H2S\\cdots AgI, OC\\cdotsAgI, H3N\\cdots AgI and (CH3)_{3N\\cdots AgI}. S.Z. Riaz, S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, Chem. Phys. Let., 531, 1-12 (2012) S.L. Stephens, W. Mizukami, D.P. Tew, N.R. Walker, A.C. Legon, J. Chem. Phys., 136(6), 064306 (2012) D.M. Bittner, D.P. Zaleski, S.L. Stephens, N.R. Walker, A.C. Legon, Study in progress.

  5. REASSESSMENT OF THE DISSOCIATIVE RECOMBINATION OF N{sub 2}H{sup +} AT CRYRING

    SciTech Connect

    Vigren, E.; Zhaunerchyk, V.; Hamberg, M.; Af Ugglas, M.; Larsson, M.; Thomas, R. D.; Geppert, W. D.; Kaminska, M.; Semaniak, J.

    2012-09-20

    The dissociative recombination (DR) of N{sub 2}H{sup +} has been reinvestigated at the heavy ion storage ring CRYRING at the Manne Siegbahn Laboratory in Stockholm, Sweden. Thermal rate coefficients for electron temperatures between 10 and 1000 K have been deduced. We show that electron recombination is expected to play an approximately equally important role as CO in the removal of N{sub 2}H{sup +} in dark interstellar clouds. We note that a deeper knowledge on the influence of the ions' rotational temperature in the DR of N{sub 2}H{sup +} would be helpful to set further constraints on the relative importance of the different destruction mechanisms for N{sub 2}H{sup +} in these environments. The branching fractions in the DR of N{sub 2}H{sup +} have been reinvestigated at {approx}0 eV relative kinetic energy, showing a strong dominance of the N{sub 2} + H production channel (93{sup +4}{sub -2}%) with the rest leading to NH + N. These results are in good agreement with flowing afterglow experiments and in disagreement with an earlier measurement at CRYRING.

  6. Low-temperature rate coefficients for the reaction of ethynyl radical (C2H) with benzene.

    PubMed

    Goulay, Fabien; Leone, Stephen R

    2006-02-01

    The reaction of the C2H radical with benzene is studied at low temperature using a pulsed Laval nozzle apparatus. The C2H radical is prepared by 193-nm photolysis of acetylene, and the C2H concentration is monitored using CH(A2Delta) chemiluminescence from the C2H + O2 reaction. Measurements at very low photolysis energy are performed using CF3C2H as the C2H precursor to study the influence of benzene photodissociation on the rate coefficient. Rate coefficients are obtained over a temperature range between 105 and 298 K. The average rate coefficient is found to be five times greater than the estimated value presently used in the photochemical modeling of Titan's atmosphere. The reaction exhibits a slight negative temperature dependence which can be fitted to the expression k(cm3 molecule(-1) s(-1)) = 3.28(+/-1.0) x 10(-10) (T/298)(-0.18(+/-0.18)). The results show that this reaction has no barrier and may play an important role in the formation of large molecules and aerosols at low temperature. Our results are consistent with the formation of a short lifetime intermediate that decomposes to give the final products.

  7. REDOR NMR for Drug Discovery

    PubMed Central

    Cegelski, Lynette

    2014-01-01

    Rotational-Echo DOuble-Resonance (REDOR) NMR is a powerful and versatile solid-state NMR measurement that has been recruited to elucidate drug modes of action and to drive the design of new therapeutics. REDOR has been implemented to examine composition, structure, and dynamics in diverse macromolecular and whole-cell systems, including taxol-bound microtubules, enzyme-cofactor-inhibitor ternary complexes, and antibiotic-whole-cell complexes. The REDOR approach involves the integrated design of specific isotopic labeling strategies and the selection of appropriate REDOR experiments. By way of example, this digest illustrates the versatility of the REDOR approach, with an emphasis on the practical considerations of experimental design and data interpretation. PMID:24035486

  8. Nuclear magnetic resonance apparatus having semitoroidal rf coil for use in topical NMR and NMR imaging

    DOEpatents

    Fukushima, Eiichi; Roeder, Stephen B. W.; Assink, Roger A.; Gibson, Atholl A. V.

    1986-01-01

    An improved nuclear magnetic resonance (NMR) apparatus for use in topical magnetic resonance (TMR) spectroscopy and other remote sensing NMR applications includes a semitoroidal radio-frequency (rf) coil. The semitoroidal rf coil produces an effective alternating magnetic field at a distance from the poles of the coil, so as to enable NMR measurements to be taken from selected regions inside an object, particularly including human and other living subjects. The semitoroidal rf coil is relatively insensitive to magnetic interference from metallic objects located behind the coil, thereby rendering the coil particularly suited for use in both conventional and superconducting NMR magnets. The semitoroidal NMR coil can be constructed so that it emits little or no excess rf electric field associated with the rf magnetic field, thus avoiding adverse effects due to dielectric heating of the sample or to any other interaction of the electric field with the sample.

  9. Reactions of ethynyl radicals - Rate constants with CH4, C2H6, and C2D6

    NASA Technical Reports Server (NTRS)

    Laufer, A. H.

    1981-01-01

    An experiment to measure ethynyl radical reactivity with other simple molecules is described. Flash photolysis of CF3C2H, a C2H precursor, was kinetically and spectroscopically analyzed for C2H reactions with CH4, C2H6, and C2D6 and rate constants for the abstraction reaction at room temperature were determined. The experimental apparatus is described, and the acetylene feedstock purification procedures are outlined. Rate constants are provided, and additional examination of the effects of added helium showed no alterations over the pressure range 20-700 torr.

  10. Temperature and pressure dependent rate coefficients for the reaction of C2H4 + HO2 on the C2H4O2H potential energy surface.

    PubMed

    Guo, JunJiang; Xu, JiaQi; Li, ZeRong; Tan, NingXin; Li, XiangYuan

    2015-04-01

    The potential energy surface (PES) for reaction C2H4 + HO2 was examined by using the quantum chemical methods. All rates were determined computationally using the CBS-QB3 composite method combined with conventional transition state theory(TST), variational transition-state theory (VTST) and Rice-Ramsberger-Kassel-Marcus/master-equation (RRKM/ME) theory. The geometries optimization and the vibrational frequency analysis of reactants, transition states, and products were performed at the B3LYP/CBSB7 level. The composite CBS-QB3 method was applied for energy calculations. The major product channel of reaction C2H4 + HO2 is the formation C2H4O2H via an OH(···)π complex with 3.7 kcal/mol binding energy which exhibits negative-temperature dependence. We further investigated the reactions related to this complex, which were ignored in previous studies. Thermochemical properties of the species involved in the reactions were determined using the CBS-QB3 method, and enthalpies of formation of species were compared with literature values. The calculated rate constants are in good agreement with those available from literature and given in modified Arrhenius equation form, which are serviceable in combustion modeling of hydrocarbons. Finally, in order to illustrate the effect for low-temperature ignition of our new rate constants, we have implemented them into the existing mechanisms, which can predict ethylene ignition in a shock tube with better performance.

  11. Temperature and pressure dependent rate coefficients for the reaction of C2H4 + HO2 on the C2H4O2H potential energy surface.

    PubMed

    Guo, JunJiang; Xu, JiaQi; Li, ZeRong; Tan, NingXin; Li, XiangYuan

    2015-04-01

    The potential energy surface (PES) for reaction C2H4 + HO2 was examined by using the quantum chemical methods. All rates were determined computationally using the CBS-QB3 composite method combined with conventional transition state theory(TST), variational transition-state theory (VTST) and Rice-Ramsberger-Kassel-Marcus/master-equation (RRKM/ME) theory. The geometries optimization and the vibrational frequency analysis of reactants, transition states, and products were performed at the B3LYP/CBSB7 level. The composite CBS-QB3 method was applied for energy calculations. The major product channel of reaction C2H4 + HO2 is the formation C2H4O2H via an OH(···)π complex with 3.7 kcal/mol binding energy which exhibits negative-temperature dependence. We further investigated the reactions related to this complex, which were ignored in previous studies. Thermochemical properties of the species involved in the reactions were determined using the CBS-QB3 method, and enthalpies of formation of species were compared with literature values. The calculated rate constants are in good agreement with those available from literature and given in modified Arrhenius equation form, which are serviceable in combustion modeling of hydrocarbons. Finally, in order to illustrate the effect for low-temperature ignition of our new rate constants, we have implemented them into the existing mechanisms, which can predict ethylene ignition in a shock tube with better performance. PMID:25774424

  12. Terahertz Spectroscopy of the Bending Vibrations of Acetylene 12C2H2

    NASA Astrophysics Data System (ADS)

    Yu, Shanshan; Drouin, Brian J.; Pearson, John C.

    2009-11-01

    Twenty P-branch transitions of 12C2H2 have been measured in the 0.8-1.6 THz region of its bending vibrational difference band. The accuracy of these measurements is estimated to be 100 kHz. The 12C2H2 molecules were generated under room temperature by passing 150 mTorr H2O vapor through calcium carbide (CaC2) powder. The observed transitions were modeled together with prior far-infrared data involving the bending levels with ∑\

  13. Pure shift NMR.

    PubMed

    Zangger, Klaus

    2015-04-01

    Although scalar-coupling provides important structural information, the resulting signal splittings significantly reduce the resolution of NMR spectra. Limited resolution is a particular problem in proton NMR experiments, resulting in part from the limited proton chemical shift range (∼10 ppm) but even more from the splittings due to scalar coupling to nearby protons. "Pure shift" NMR spectroscopy (also known as broadband homonuclear decoupling) has been developed for disentangling overlapped proton NMR spectra. The resulting spectra are considerably simplified as they consist of single lines, reminiscent of proton-decoupled C-13 spectra at natural abundance, with no multiplet structure. The different approaches to obtaining pure shift spectra are reviewed here and several applications presented. Pure shift spectra are especially useful for highly overlapped proton spectra, as found for example in reaction mixtures, natural products and biomacromolecules.

  14. NMR studies of structure and dynamics of liquid molecules confined in extended nanospaces.

    PubMed

    Tsukahara, Takehiko; Mizutani, Wataru; Mawatari, Kazuma; Kitamori, Takehiko

    2009-08-01

    We fabricated an NMR cell equipped with 10-100 nm scale spaces on a glass substrate (called extended nanospaces), and investigated molecular structure and dynamics of water confined in the extended nanospaces by (1)H NMR chemical shift (delta(H)) and (1)H and (2)H NMR spin-lattice relaxation rate ((1)H- and (2)H-1/T(1)), (1)H NMR spin-spin relaxation rate ((1)H-1/T(2)), and (1)H NMR rotating-frame spin-lattice relaxation rate ((1)H-1/T(1rho)) measurements of H(2)O and (2)H(2)O. The delta(H) and (1)H- and (2)H-1/T(1) results showed that size-confinement produces slower translational motions and higher proton mobility of water, but does not affect the hydrogen-bonding structure and rotational motions. Such unique phenomena appeared in the space size of 40 to 800 nm. However, the (1)H-1/T(1) value at 40 nm was still different from that in 4 nm porous nanomaterial, because translational and rotational motions were inhibited for H(2)O molecules in the nanomaterial. By examining temperature- and deuterium-dependence of the (1)H-1/T(1) values, the molecular translational motions of the confined water were found to be controlled by protonic diffusion invoking a proton hopping pathway between adjacent water rather than hydrodynamic translational diffusion. Furthermore, we clarified that proton exchange between adjacent water molecules in extended nanospaces could be enhanced by the chemical exchange of protons between water and SiOH groups on glass surfaces, ( identical with SiO(-)...H(+)...H(2)O) + H(2)O --> triple bond SiO(-) + (H(3)O(+) + H(2)O) --> triple bond SiO(-) + (H(2)O + H(3)O(+)), based on (1)H-1/T(2) measurements. An enhancement of proton exchange rate of water due to the reduction of space sizes was verified from the results of (1)H-1/T(1rho) values, and the rate of water in the 100 nm sized spaces is larger by a factor of more than ten from that of bulk water. Such size-confinement effects were distinctly observed for hydrogen-bond solvents with strong proton

  15. Saturn's latitudinal C 2H 2 and C 2H 6 abundance profiles from Cassini/CIRS and ground-based observations

    NASA Astrophysics Data System (ADS)

    Hesman, Brigette E.; Jennings, Donald E.; Sada, Pedro V.; Bjoraker, Gordon L.; Achterberg, Richard K.; Simon-Miller, Amy A.; Anderson, Carrie M.; Boyle, Robert J.; Nixon, Conor A.; Fletcher, Leigh N.; McCabe, George H.

    2009-07-01

    Hydrocarbons in the upper atmosphere of Saturn are known, from Voyager, ground-based, and early Cassini results, to vary in emission intensity with latitude. Of particular interest is the marked increase in hydrocarbon line intensity near the south pole during southern summer, as the increased line intensity cannot be simply explained by the increased temperatures observed in that region since the variations between C2H2 and C2H6 emission in the south pole region are different. In order to measure the latitudinal variations of hydrocarbons in Saturn's southern hemisphere we have used 3 cm-1 resolution Cassini CIRS data from 2006 and combined this with measurements from the ground in October 2006 at NASA's IRTF using Celeste, an infrared high-resolution cryogenic grating spectrometer. These two data sets have been used to infer the molecular abundances of C2H2 and C2H6 across the southern hemisphere in the 1-10 mbar altitude region. We find that the latitudinal acetylene profile follows the yearly average mean daily insolation except at the southern pole where it peaks in abundance. Near the equator (5° S) the C2H2 abundance at the 1.2 mbar level is (1.6 ± 0.19) ×10-7 and it decreases by a factor of 2.7 from the equator toward the pole. However, at the pole (∼87° S) the C2H2 abundance jumps to (1.8 ± 0.3) ×10-7, approximately the equatorial value. The C2H6 abundance near the equator at the 2 mbar level is (0.7 ± 0.1) ×10-5 and stays approximately constant until mid-latitudes where it increases gradually toward the pole, attaining a value of (1.4 ± 0.4) ×10-5 there. The increase in ethane toward the pole with the corresponding decrease in acetylene is consistent with southern hemisphere meridional winds [Greathouse, T.K., Lacy, J.H., Bézard, B., Moses, J.I., Griffith, C.A., Richter, M.J., 2005. Icarus 177, 18-31]. The localized increase in acetylene at the pole provides evidence that there is dynamical transport of hydrocarbons from the equator to the

  16. Preparation of hydrogen from water by reduction with lithium aluminium hydride for the analysis of delta(2)H by isotope ratio mass spectrometry.

    PubMed

    Ward, S; Scantlebury, M; Król, E; Thomson, P J; Sparling, C; Speakman, J R

    2000-01-01

    An off-line technique is described for the preparation of H(2) from water prior to analysis of delta(2)H by dual-inlet isotope ratio mass spectrometry. H(2) is produced from sample water by reaction with LiAlH(4). This provides a rapid and inexpensive method for the analysis of delta(2)H in small (10 microL) samples of water. Precision was +/- 4.2 to 8.0 (1sigma(n), n = 8) delta(2)H(VSMOW) for samples between 428 and 1500 delta(2)H(VSMOW), +/- 14.5 delta(2)H(VSMOW) for water enriched to 3750 delta(2)H(VSMOW) and +/- 26.0 delta(2)H(VSMOW) for water enriched to 6100 delta(2)H(VSMOW). Accuracy was +/- 1.1 to 4.2 delta(2)H(VSMOW) for water standards from natural abundance to 1000 delta(2)H(VSMOW) (the highest enrichment at which water of accepted delta(2)H is currently available). This method for delta(2)H determination is most appropriate for use with small (<50 microL) samples of high delta(2)H enrichment such as those produced from doubly labelled water studies of small animals. The levels of measurement precision of delta(2)H would contribute 2.6-3.8% to the precision error in estimates of small animal energy expenditure made using the doubly labelled water technique when duplicate analyses are performed. PMID:10717654

  17. Rotational Doppler Effect and Barnett Field in Spinning NMR

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

    We report the observation of the rotational Doppler effect using nuclear magnetic resonance (NMR). We have developed a coil-spinning technique that enables measurements by rotating a detector and fixing a sample. We found that the rotational Doppler effect gives rise to NMR frequency shifts equal to the rotation frequency. We formulate the rotational Doppler effect and the Barnett field using a vector model for the nuclear magnetic moment. This formulation reveals that, with just the sample rotating, both effects cancel each other, thereby explaining the absence of an NMR frequency shift in conventional sample-spinning NMR measurements.

  18. The source of NMR-detected motional anisotropy of water in blood vessel walls.

    PubMed Central

    Sharf, Y; Knubovets, T; Dayan, D; Hirshberg, A; Akselrod, S; Navon, G

    1997-01-01

    2H Double quantum-filtered (DQF) NMR spectroscopy of deuterated water is sensitive to the presence of order in biological systems. This is because the only nuclei that are detected are those with residual quadrupolar interactions due to their anisotropic motion. In the present study, samples of aorta, coronary and carotid arteries, and vena cava were studied in parallel by 2H DQF NMR and by light microscopy. The average quadrupolar splitting, calculated from the NMR data, varies considerably among the different blood vessels, with high reproducibility for each type of vessel. Polarization microscopy examinations using collagen-specific staining with picrosirius red, have shown a variety of color profiles for the different blood vessels. These reflect different physical modes of aggregation (packing and thickness) of collagen fibers. A correlation was found between the NMR parameters and the color profiles of the picrosirius red-stained sections. Treating the blood vessels with 90% formic acid resulted in the elimination of the 2H DQF NMR signal. Histological analysis demonstrated a complete degradation of collagen and muscle, whereas the elastin filaments were preserved. Evidence is given that the 2H DQF NMR signal is dominated by the contribution of water molecules interacting with the collagen fibers. Images FIGURE 3 PMID:9284287

  19. Solid-state NMR studies of the dynamics and structure of mouse keratin intermediate filaments

    SciTech Connect

    Mack, J.W.; Torchia, D.A.; Steinert, P.M.

    1988-07-26

    The molecular dynamics and structural organization of mouse epidermal keratin intermediate filaments (IF) have been studied via solid-state nuclear magnetic resonance (NMR) experiments performed on IF labeled both in vivo and in vitro with isotopically enriched amino acids. As a probe of the organization of the peripheral glycine-rich end domains of the IF, carbon-13 NMR experiments have been performed on subfilamentous forms (prekeratin) and on IF reassembled in vitro that had been labeled with either (1-/sup 13/C)glycine or (2-/sup 13/C)glycine, as more than 90% of the glycines of the keratins are located in the end domains. Measurements of carbon relaxation times, nuclear Overhauser enhancements, and signal intensities show that the motions of the peptide backbone in the end domains are effectively isotropic. These results indicate that the end domains of IF are remarkably flexible and have little or no structural order. To probe the structural organization of the coiled-coil rod domains of the IF, separate samples of native keratin IF, raised in primary tissue culture, were labeled with L-(1-/sup 13/C)leucine, L-(/sup 2/H/sub 10/)leucine, or L-(2,3,3-/sup 2/H/sub 3/)leucine, as greater than 90% of the leucyl residues of the keratin IF types studied are located in the coiled coils which form the central core of IF. Deuterium NMR experiments performed on IF labeled with deuteriated leucines indeed reveal a marked degree of peptide backbone rigidity within the coiled coils, confirming the initial conclusions of the carbon-13 data. These data, demonstrating relative peptide backbone rigidity yet side-chain flexibility, are interpreted to mean that the coiled coils of these keratin IF are not tightly packed together but rather form a somewhat looser structure which permits a significant degree of side-chain mobility.

  20. sup 2 H Nuclear magnetic resonance of the gramicidin A backbone in a phospholipid bilayer

    SciTech Connect

    Prosser, R.S.; Davis, J.H. ); Dahlquist, F.W.; Lindorfer, M.A. )

    1991-05-14

    Solid-state {sup 2}H NMR spectroscopy has been employed to study the channel conformation of gramicidin A (GA) in unoriented 1,2-dimyristoyl-sn-glycerol-3-phosphocholine (DMPC) multilayers. Quadrupolar echo spectra were obtained at 44{degree}C and 53{degree}C, from gramicidin A labels in which the proton attached to the {alpha} carbon of residue 3,4,5,10,12, or 14 was replaced with deuterium. Because of the nearly axially symmetric electric field gradient tensor, the quadrupolar splittings obtained from an unoriented multilamellar dispersion of DMPC and singly labeled GA directly yield unambiguous orientational constraints on the C-{sup 2}H bonds. The authors conclude that the helix sense of the channel conformation of GA is right-handed. Assuming that the dominant motions are fast axial diffusion of the gramicidin molecule and reorientation of the diffusion axis with respect to the local bilayer normal, then the theoretical splittings may all be scaled down by a constant motional narrowing factor.

  1. Affordable uniform isotope labeling with (2)H, (13)C and (15)N in insect cells.

    PubMed

    Sitarska, Agnieszka; Skora, Lukasz; Klopp, Julia; Roest, Susan; Fernández, César; Shrestha, Binesh; Gossert, Alvar D

    2015-06-01

    For a wide range of proteins of high interest, the major obstacle for NMR studies is the lack of an affordable eukaryotic expression system for isotope labeling. Here, a simple and affordable protocol is presented to produce uniform labeled proteins in the most prevalent eukaryotic expression system for structural biology, namely Spodoptera frugiperda insect cells. Incorporation levels of 80% can be achieved for (15)N and (13)C with yields comparable to expression in full media. For (2)H,(15)N and (2)H,(13)C,(15)N labeling, incorporation is only slightly lower with 75 and 73%, respectively, and yields are typically twofold reduced. The media were optimized for isotope incorporation, reproducibility, simplicity and cost. High isotope incorporation levels for all labeling patterns are achieved by using labeled algal amino acid extracts and exploiting well-known biochemical pathways. The final formulation consists of just five commercially available components, at costs 12-fold lower than labeling media from vendors. The approach was applied to several cytosolic and secreted target proteins. PMID:25929326

  2. New determination of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reaction rates at astrophysical energies

    SciTech Connect

    Tumino, A.; Spartà, R.; Spitaleri, C.; Pizzone, R. G.; La Cognata, M.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Mukhamedzhanov, A. M.; Typel, S.; Tognelli, E.; Degl'Innocenti, S.; Prada Moroni, P. G.; Burjan, V.; Kroha, V.; Hons, Z.; Mrazek, J.; Piskor, S.; Lamia, L.

    2014-04-20

    The cross sections of the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions have been measured via the Trojan Horse method applied to the quasi-free {sup 2}H({sup 3}He,p {sup 3}H){sup 1}H and {sup 2}H({sup 3}He,n {sup 3}He){sup 1}H processes at 18 MeV off the proton in {sup 3}He. For the first time, the bare nucleus S(E) factors have been determined from 1.5 MeV, across the relevant region for standard Big Bang nucleosynthesis, down to the thermal energies of deuterium burning in the pre-main-sequence (PMS) phase of stellar evolution, as well as of future fusion reactors. Both the energy dependence and the absolute value of the S(E) factors deviate by more than 15% from the available direct data and existing fitting curves, with substantial variations in the electron screening by more than 50%. As a consequence, the reaction rates for astrophysics experience relevant changes, with a maximum increase of up to 20% at the temperatures of the PMS phase. From a recent primordial abundance sensitivity study, it turns out that the {sup 2}H(d,n){sup 3}He reaction is quite influential on {sup 7}Li, and the present change in the reaction rate leads to a decrease in its abundance by up to 10%. The present reaction rates have also been included in an updated version of the FRANEC evolutionary code to analyze their influence on the central deuterium abundance in PMS stars with different masses. The largest variation of about 10%-15% pertains to young stars (≤1 Myr) with masses ≥1 M {sub ☉}.

  3. Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Romani, P. N.; Abbas, M.; LeClair, A.; Strobel, D.

    2004-01-01

    Hydrocarbons such as acetylene (C2H2) and ethane (C2H6) are important tracers in Jupiter's atmosphere, constraining our models of the chemical and dynamical processes. However, our knowledge of the vertical and meridional variations of their abundances has remained sparse. During the flyby of the Cassini spacecraft in December 2000, the Composite Infrared Spectrometer (CIRS) instrument was used to map the spatial variation of emissions from 10-1400 cm(sup -1) (1000-7 microns). In this paper we analyze a zonally-averaged set of CIRS spectra taken at the highest (0.5 cm(sup -1)) resolution, to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 band of CH4, and in the troposphere at 150-400 mbar, via the H2 absorption at 600-800 cm(sup -1). Simultaneously, we retrieve the abundances of C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIRS resolution, introducing a non-uniqueness into the retrievals, such that vertical gradient and column abundance cannot both be found without additional constraints. Assuming profile gradients from photochemical calculations, we show that the column abundance of C2H2 decreases sharply towards the poles by a factor approximately 4, while C2H6 is unchanged in the north and increasing in the south, by a factor approximately 1.8. An explanation for the meridional trends is proposed in terms of a combination of photochemistry and dynamics. Poleward, the decreasing UV flux is predicted to decrease the abundances of C2H2 and C2H6 by factors 2.7 and 3.5 respectively at a latitude 70 deg. However, the lifetime of C2H6 in the stratosphere (5 x 10(exp 9)) is much longer than the dynamical timescale for meridional motions inferred from SL-9 debris (5 x 10(exp 8 s)), and therefore the constant or rising abundance towards high latitudes likely indicates that meridional mixing dominates over photochemical effects. For C2H2, the opposite

  4. Measurement of boundaries between two-phase and three-phase regions in emulsified systems by titration calorimetry. 3: C{sub 6}H{sub 13}(OC{sub 2}H{sub 4}){sub 2}OH/n-tetradecane/water

    SciTech Connect

    Smith, D.H. |; Covatch, G.L.

    1995-04-01

    Isoperibolic titration calorimetry has been used to determine tietriangles (i.e., compositions or conjugate top, middle, and bottom phases) of the system C{sub 6}H{sub 13}(OC{sub 2}H{sub 4}){sub 2}OH/n-tetradecane/water at seven temperatures from 15 through 45 C. The concentration of each component in each phase was approximately a linear function of temperature over this temperature range. The density of C{sub 6}H{sub 13}(OC{sub 2}H{sub 4}){sub 2}OH from 24 to 50 C also is reported.

  5. NMR imaging microscopy

    SciTech Connect

    Not Available

    1986-10-01

    In the past several years, proton nuclear magnetic resonance (NMR) imaging has become an established technique in diagnostic medicine and biomedical research. Although much of the work in this field has been directed toward development of whole-body imagers, James Aguayo, Stephen Blackband, and Joseph Schoeninger of the Johns Hopkins University School of Medicine working with Markus Hintermann and Mark Mattingly of Bruker Medical Instruments, recently developed a small-bore NMR microscope with sufficient resolution to image a single African clawed toad cell (Nature 1986, 322, 190-91). This improved resolution should lead to increased use of NMR imaging for chemical, as well as biological or physiological, applications. The future of NMR microscopy, like that of many other newly emerging techniques, is ripe with possibilities. Because of its high cost, however, it is likely to remain primarily a research tool for some time. ''It's like having a camera,'' says Smith. ''You've got a way to look at things at very fine levels, and people are going to find lots of uses for it. But it is a very expensive technique - it costs $100,000 to add imaging capability once you have a high-resolution NMR, which itself is at least a $300,000 instrument. If it can answer even a few questions that can't be answered any other way, though, it may be well worth the cost.''

  6. Fluorescence from photoexcitation of C2H5OH by vacuum ultraviolet radiation

    NASA Technical Reports Server (NTRS)

    Han, J. C.; Suto, Masako; Lee, L. C.

    1989-01-01

    The photoabsorption and fluorescence cross sections of C2H5OH have been measured in the 46-200 nm region. Fluorescence is dispersed to identify the emission systems, which are mainly OH(A-X), CH(A,B-X), and the H Balmer series. The photodissociation processes that produce the observed emissions are discussed.

  7. NMR Stark Spectroscopy: New Methods to Calibrate NMR Sensitivity to Electric Fields

    NASA Astrophysics Data System (ADS)

    Tarasek, Matthew R.

    The influence of electrostatics on NMR parameters is well accepted. Thus, NMR is a promising route to probe electrical features within molecules and materials. However, applications of NMR Stark effects (E-field induced changes in spin energy levels) have been elusive. I have developed new approaches to resolve NMR Stark effects from an applied E field. This calibrates nuclear probes whose spectral response might later be used to evaluate internal E fields that are critical to function, such as those due to local charge distributions or sample structure. I will present two novel experimental approaches for direct calibration of NMR quadrupolar Stark effects (QSEs). In the first, steady-state (few-second) excitation by an E field at twice the NMR frequency (2ω 0) is used to saturate spin magnetization. The extent of saturation vs. E-field amplitude calibrates the QSE response rate, while measurements vs sample orientation determine tensorial character. The second method instead synchronizes short (few µs) pulses of the 2ω0 E field with a multiple-pulse NMR sequence. This, “POWER” (Perturbations Observed With Enhanced Resolution) approach enables more accurate measure of small QSEs (i.e. few Hz spectral changes). A 2nd key advantage is the ability to define tensorial response without reorienting the sample, but instead varying the phase of the 2ω0 field. I will describe these experiments and my home-built NMR “Stark probe”, employed on a conventional wide-bore solid-state NMR system. Results with GaAs demonstrate each method, while extensions to a wider array of molecular and material systems may now be possible using these methods.

  8. High-resolution absorption cross sections of C2H6 at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Hargreaves, Robert J.; Buzan, Eric; Dulick, Michael; Bernath, Peter F.

    2015-11-01

    Infrared absorption cross sections near 3.3 μm have been obtained for ethane, C2H6. These were acquired at elevated temperatures (up to 773 K) using a Fourier transform infrared spectrometer and tube furnace with a resolution of 0.005 cm-1. The integrated absorption was calibrated using composite infrared spectra taken from the Pacific Northwest National Laboratory (PNNL). These new measurements are the first high-resolution infrared C2H6 cross sections at elevated temperatures.

  9. Imidacloprid inhibits IgE-mediated RBL-2H3 cell degranulation and passive cutaneous anaphylaxis

    PubMed Central

    Shi, Linbo; Zou, Li; Gao, Jinyan; Xu, Huaing; Shi, Xiaoyun

    2016-01-01

    Background Imidacloprid has been commonly used as a pesticide for crop protection and acts as nicotinic acetylcholine receptor agonists. Little information about the relationship between imidacloprid and allergy is available. Objective This study aims to examine the effects of imidacoprid on IgE-mediated mast cell activation. Methods The rat basophilic leukemia cell line RBL-2H3 (RBL-2H3 cells) were treated with 10-3 – 10-12 mol/L imidacloprid, followed by measuring the mediator production, influx of Ca2+ in IgE-activated RBL-2H3 cells, and the possible effects of imidacoprid on anti-dinitrophenyl IgE-induced passive cutaneous anaphylaxis (PCA). Results It was shown that imidacoprid suppressed the production of histamine, β-hexosaminidase, leukotriene C4, interleukin-6, tumor necrosis factor-α, and Ca2+ mobilization in IgE-activated RBL-2H3 cells and decreased vascular extravasation in IgE-induced PCA. Conclusion It is the first time to show that imidacloprid suppressed the activation of RBL-2H3 cells. PMID:27803884

  10. Detection of C2H4 Neptune from ISO/PHT-S Observations

    NASA Technical Reports Server (NTRS)

    Schulz, B.; Encrenaz, Th.; Bezard, B.; Romani, P. N.; Lellouch, E.; Atreya, S. K.

    1999-01-01

    The 6-12 micrometer spectrum of Neptune has been recorded with the PHT-S instrument of the Infrared Space Observatory (ISO) at a resolution of 0.095 micrometer. In addition to the emissions of CH4, CH3D and C2H6 previously identified, the spectrum shows the first firm identification of ethylene C2H4. The inferred column density above the 0.2-mbar level is in the range (1.1 - 3) x 10(exp 14) molecules/cm. To produce this low amount, previous photochemical models invoked rapid mixing between the source and sink regions of C2H4. We show that this requirement can be relaxed if recent laboratory measurements of CH4 photolysis branching ratios at Lyman alpha are used.

  11. NMR Investigation of the Quasi-Brine Layer in Ice/Brine Mixtures

    SciTech Connect

    Cho, Herman M.; Shepson, Paul B.; Barrie, Leonard A.; Cowin, James P.; Zaveri, Rahul A.

    2002-10-31

    We report the study of a liquid-like phase that is found in dilute NaCl aqueous solutions frozen at temperatures below the liquid-to-solid phase transition temperatures of H2O and NaCl-2H2O. The fractions of water and NaCl in this sub-eutectic quasi-liquid phase were measured by NMR spectroscopy, and the experimental results compared to predictions derived from an equilibrium thermodynamic analysis. A numerical model derived from the NaCl water phase diagram and freezing point depression curve was found to provide a quantitative description of the quasi-liquid fraction for data measured above the eutectic temperature. The relevance and application of these findings to the study of chemistry in polar regions are discussed.

  12. Structure and reactivity of lithium amides. /sup 6/Li, /sup 13/C, and /sup 15/N NMR spectroscopic studies and colligative measurements of lithium diphenylamide and lithium diphenylamide-lithium bromide complex solvated by tetrahydrofuran

    SciTech Connect

    DePue, J.S.; Collum, D.B.

    1988-08-03

    /sup 6/Li, /sup 13/C, and /sup 15/N NMR spectroscopic studies of lithium diphenylamide in THF/hydrocarbon solutions (THF = tetrahydrofuran) detected two different species. /sup 6/Li and /sup 15/N NMR spectroscopic studies of (/sup 6/Li, /sup 15/N)lithium diphenylamide showed the species observed at low THF concentrations to be a cyclic oligomer. Structural analogies provided strong support for a dimer while colligative measurements at 0/degrees/C indicated the dimer to be di- or trisolvated. On the basis of the observed mass action effects, the species appearing at intermediate THF concentrations is assigned as a contact or solvent-separated ion-paired monomer. Lithium diphenylamide forms a 1:1 adduct with lithium bromide at low THF concentrations. A combination of /sup 6/Li-/sup 15/N double labeling studies and colligative measurements supports a trisolvated cyclic mixed dimer structure. Although detailed spectroscopic studies at elevated THF concentrations were precluded by high fluctionality, the similarity of the /sup 13/C chemical shifts of lithium diphenylamide in the presence and absence of lithium bromide provide indirect evidence that the mixed dimer undergoes a THF concentration dependent dissociation to the monomeric amide and free lithium bromide. 24 references, 9 figures, 2 tables.

  13. Direct Comparison of (19)F qNMR and (1)H qNMR by Characterizing Atorvastatin Calcium Content.

    PubMed

    Liu, Yang; Liu, Zhaoxia; Yang, Huaxin; He, Lan

    2016-01-01

    Quantitative nuclear magnetic resonance (qNMR) is a powerful tool in measuring drug content because of its high speed, sensitivity, and precision. Most of the reports were based on proton qNMR ((1)H qNMR) and only a few fluorine qNMR ((19)F qNMR) were reported. No research has been conducted to directly compare the advantage and disadvantage between these two methods. In the present study, both (19)F and (1)H qNMR were performed to characterize the content of atorvastatin calcium with the same internal standard. Linearity, precision, and results from two methods were compared. Results showed that (19)F qNMR has similar precision and sensitivity to (1)H qNMR. Both methods generate similar results compared to mass balance method. Major advantage from (19)F qNMR is that the analyte signal is with less or no interference from impurities. (19)F qNMR is an excellent approach to quantify fluorine-containing analytes. PMID:27688925

  14. Direct Comparison of 19F qNMR and 1H qNMR by Characterizing Atorvastatin Calcium Content

    PubMed Central

    Liu, Yang; Liu, Zhaoxia; Yang, Huaxin

    2016-01-01

    Quantitative nuclear magnetic resonance (qNMR) is a powerful tool in measuring drug content because of its high speed, sensitivity, and precision. Most of the reports were based on proton qNMR (1H qNMR) and only a few fluorine qNMR (19F qNMR) were reported. No research has been conducted to directly compare the advantage and disadvantage between these two methods. In the present study, both 19F and 1H qNMR were performed to characterize the content of atorvastatin calcium with the same internal standard. Linearity, precision, and results from two methods were compared. Results showed that 19F qNMR has similar precision and sensitivity to 1H qNMR. Both methods generate similar results compared to mass balance method. Major advantage from 19F qNMR is that the analyte signal is with less or no interference from impurities. 19F qNMR is an excellent approach to quantify fluorine-containing analytes. PMID:27688925

  15. Direct Comparison of 19F qNMR and 1H qNMR by Characterizing Atorvastatin Calcium Content

    PubMed Central

    Liu, Yang; Liu, Zhaoxia; Yang, Huaxin

    2016-01-01

    Quantitative nuclear magnetic resonance (qNMR) is a powerful tool in measuring drug content because of its high speed, sensitivity, and precision. Most of the reports were based on proton qNMR (1H qNMR) and only a few fluorine qNMR (19F qNMR) were reported. No research has been conducted to directly compare the advantage and disadvantage between these two methods. In the present study, both 19F and 1H qNMR were performed to characterize the content of atorvastatin calcium with the same internal standard. Linearity, precision, and results from two methods were compared. Results showed that 19F qNMR has similar precision and sensitivity to 1H qNMR. Both methods generate similar results compared to mass balance method. Major advantage from 19F qNMR is that the analyte signal is with less or no interference from impurities. 19F qNMR is an excellent approach to quantify fluorine-containing analytes.

  16. Resolution and measurement of heteronuclear dipolar couplings of a noncrystalline protein immobilized in a biological supramolecular assembly by proton-detected MAS solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Park, Sang Ho; Yang, Chen; Opella, Stanley J.; Mueller, Leonard J.

    2013-12-01

    Two-dimensional 15N chemical shift/1H chemical shift and three-dimensional 1H-15N dipolar coupling/15N chemical shift/1H chemical shift MAS solid-state NMR correlation spectra of the filamentous bacteriophage Pf1 major coat protein show single-site resolution in noncrystalline, intact-phage preparations. The high sensitivity and resolution result from 1H detection at 600 MHz under 50 kHz magic angle spinning using ∼0.5 mg of perdeuterated and uniformly 15N-labeled protein in which the exchangeable amide sites are partially or completely back-exchanged (reprotonated). Notably, the heteronuclear 1H-15N dipolar coupling frequency dimension is shown to select among 15N resonances, which will be useful in structural studies of larger proteins where the resonances exhibit a high degree of overlap in multidimensional chemical shift correlation spectra.

  17. Combined NMR-observation of cold denaturation in supercooled water and heat denaturation enables accurate measurement of deltaC(p) of protein unfolding.

    PubMed

    Szyperski, Thomas; Mills, Jeffrey L; Perl, Dieter; Balbach, Jochen

    2006-04-01

    Cold and heat denaturation of the double mutant Arg 3-->Glu/Leu 66-->Glu of cold shock protein Csp of Bacillus caldolyticus was monitored using 1D (1)H NMR spectroscopy in the temperature range from -12 degrees C in supercooled water up to +70 degrees C. The fraction of unfolded protein, f (u), was determined as a function of the temperature. The data characterizing the unfolding transitions could be consistently interpreted in the framework of two-state models: cold and heat denaturation temperatures were determined to be -11 degrees C and 39 degrees C, respectively. A joint fit to both cold and heat transition data enabled the accurate spectroscopic determination of the heat capacity difference between native and denatured state, DeltaC(p) of unfolding. The approach described in this letter, or a variant thereof, is generally applicable and promises to be of value for routine studies of protein folding.

  18. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids. PMID:26203019

  19. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  20. Selective excitation enables assignment of proton resonances and {sup 1}H-{sup 1}H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of {sup 1}H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as {sup 13}C or {sup 15}N. In this method, after the initial preparation of proton magnetization and cross-polarization to {sup 13}C nuclei, transverse magnetization of desired {sup 13}C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific {sup 13}C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of {sup 1}H-{sup 1}H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  1. Selective excitation enables assignment of proton resonances and 1H-1H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-01

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of 1H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as 13C or 15N. In this method, after the initial preparation of proton magnetization and cross-polarization to 13C nuclei, transverse magnetization of desired 13C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific 13C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of 1H-1H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  2. The Rate Constant for the Reaction H + C2H5 at T = 295 - 150K

    NASA Technical Reports Server (NTRS)

    Pimentel, Andre S.; Payne, Walter A.; Nesbitt, Fred L.; Cody, Regina J.; Stief, Louis J.

    2004-01-01

    The reaction between the hydrogen atom and the ethyl (C2H3) radical is predicted by photochemical modeling to be the most important loss process for C2H5 radicals in the atmospheres of Jupiter and Saturn. This reaction is also one of the major sources for the methyl radicals in these atmospheres. These two simplest hydrocarbon radicals are the initial species for the synthesis of larger hydrocarbons. Previous measurements of the rate constant for the H + C2H5 reaction varied by a factor of five at room temperature, and some studies showed a dependence upon temperature while others showed no such dependence. In addition, the previous studies were at higher temperatures and generally higher pressures than that needed for use in planetary atmospheric models. The rate constant for the reaction H + C2H5 has been measured directly at T = 150, 202 and 295 K and at P = 1.0 Torr He for all temperatures and additionally at P = 0.5 and 2.0 Torr He at T = 202 K. The measurements were performed in a discharge - fast flow system. The decay of the C2H5 radical in the presence of excess hydrogen was monitored by low-energy electron impact mass spectrometry under pseudo-first order conditions. H atoms and C2H5 radicals were generated rapidly and simultaneously by the reaction of fluorine atoms with H2 and C2H6, respectively. The total rate constant was found to be temperature and pressure independent. The measured total rate constant at each temperature are: k(sub 1)(295K) = (1.02+/-0.24)x10(exp -10), k(sub 1)(202K) = (1.02+/-0.22)x10(exp -10) and k(sub 1)(150K) = (0.93+/-0.21)x10(exp -10), all in units of cu cm/molecule/s. The total rate constant derived from all the combined measurements is k(sub 1) = (l.03+/-0.17)x10(exp -10) cu cm/molecule/s. At room temperature our results are about a factor of two higher than the recommended rate constant and a factor of three lower than the most recently published study.

  3. Meridional Variations of C2H2 and C2H6 in Jupiter's Atmosphere from Cassini CIRS Infrared Spectra

    NASA Technical Reports Server (NTRS)

    Nixon, C. A.; Achterberg, R. K.; Conrath, B. J.; Irwin, P. G. J.; Fouchet, T.; Parrish, P. D.; Abbas, M.; LeClaire, A.; Romani, P. N.; Simon-Miller, A. A.

    2004-01-01

    The abundances of hydrocarbons such as acetylene (C2H2) and ethane (C2H6) in Jupiter's atmosphere are important physical quantities, constraining our models of the chemical and dynamical processes. However, our knowledge of these quantities and their vertical and latitudinal variations has remained sparse. The flyby of the Cassini spacecraft with Jupiter at the end of 2000 provided an excellent opportunity to observe the infrared spectrum with the Composite Infrared Spectrometer (CIRS) instrument, mapping the spatial variation of emissions from 10-1400 cm-1. CIRS spectra taken at the highest resolution (0.5 cm-1) in early December 2000 have been analysed to infer atmospheric temperatures in the stratosphere at 0.5-20 mbar via the v4 of CH4, and in the troposphere at 100-400 mbar, via the hydrogen collision-induced continuum absorption at 600-800 cm. Simultaneously, we have searched for meridional abundance variations in C2H2 and C2H6 via the v5 and vg bands respectively. Tropospheric absorption and stratospheric emission are highly anti-correlated at the CIM resolution, introducing a non-uniqueness into the retrievals, which means that vertical gradient and column abundance cannot be simultaneously found without additional constraints. If we assume the profile shapes from photochemical model calculations, we show that the column abundance of C2H2 must decrease sharply towards the poles, while C2H6 is constant or slightly increasing. The relevance of these results to current photochemical and dynamical knowledge of Jupiter's atmosphere is discussed.

  4. Evaluation of an electrochemical N2/H2 gas separator

    NASA Technical Reports Server (NTRS)

    Marshall, R. D.; Wynveen, R. A.; Carlson, J. N.

    1973-01-01

    A program was successfully completed to evaluate an electrochemical nitrogen/hydrogen (N2/H2) separator for use in a spacecraft nitrogen (N2) generator. Based on the technical data obtained a N2/H2 separator subsystem consisting of an organic polymer gas permeator first stage and an electrochemical second and third stage was estimated to have the lowest total spared equivalent weight, 257 kg (566 lb), for a 15 lb/day N2 generation rate. A pre-design analysis of the electrochemical N2/H2 separator revealed that its use as a first stage resulted in too high a power requirement to be competitive with the organic polymer membrane and the palladium-silver membrane separation methods. As a result, program emphasis was placed on evaluating the electrochemical. A parametric test program characterized cell performance and established second- and third-stage electrochemical N2/H2 separator operating conditions. A design verification test was completed on the second and third stages. The second stage was then successfully endurance tested for 200 hours.

  5. HYDROGEN AND DEUTERIUM NMR OF SOLIDS BY MAGIC ANGLE SPINNING

    SciTech Connect

    Eckman, R.R.

    1982-10-01

    motion. In the general case of large H{sub D}, isotropic spectra were obtained by dilution of {sup 1}H with {sup 2}H combined with magic angle rotation. The resolution obtained represents the practical limit for proton NMR of solids. Theoretical and technical aspects are described in the text with comments on the application of the principles to other nuclei of interest.

  6. First-principles characterization of potassium intercalation in the hexagonal 2H-MoS2

    SciTech Connect

    Andersen, Amity; Kathmann, Shawn M.; Lilga, Michael A.; Albrecht, Karl O.; Hallen, Richard T.; Mei, Donghai

    2012-01-12

    Periodic density functional theory calculations were performed to study the structural and electronic properties of potassium intercalated into hexagonal MoS{sub 2} (2H-MoS{sub 2}). Metallic potassium (K) atoms are incrementally loaded in the hexagonal sites of the interstitial spaces between MoS2 sheets of the 2H-MoS{sub 2} bulk structure generating 2H-KxMoS2 (0.125 {<=} x {<=} 1.0) structures. To accommodate the potassium atoms, the interstitial spacing c parameter in the 2H-MoS{sub 2} bulk expands from 12.816 {angstrom} in 2H-MoS{sub 2} to 16.086 {angstrom} in 2H-K{sub 0.125}MoS{sub 2}. The second lowest potassium loading concentration (K{sub 0.25}MoS{sub 2}) results in the largest interstitial spacing expansion (to c = 16.726 {angstrom}). Our calculations show that there is a small gradual contraction of the interstitial spacing as the potassium loading increases with c = 14.839 {angstrom} for KMoS{sub 2}. This interstitial contraction is correlated with an in-plane expansion of the MoS{sub 2} sheets, which is in good agreement with experimental X-ray diffraction (XRD) measurements. The electronic analysis shows that potassium readily donates its 4s electron to the conduction band of the 2H-K{sub x}MoS{sub 2}, and is largely ionic in character. As a result of the electron donation, the 2H-K{sub x}MoS{sub 2} system changes from a semiconductor to a more metallic system with increasing potassium intercalation. For loadings 0.25 {<=} x {<=} 0.625, triangular Mo-Mo-Mo moieties are prominent and tend to form rhombitrihexagonal motifs. Intercalation of H{sub 2}O molecules that solvate the K atoms is likely to occur in catalytic conditions. The inclusion of two H{sub 2}O molecules per K atom in the K{sub 0.25}MoS{sub 2} structure shows good agreement with XRD measurements.

  7. Synthesis and antifungal activity of 2H-1,4-benzoxazin-3(4H)-one derivatives.

    PubMed

    Śmist, Małgorzata; Kwiecień, Halina; Krawczyk, Maria

    2016-01-01

    A series of 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l) was easily synthesized by two-step process involving O-alkylation of 2-nitrophenols with methyl 2-bromoalkanoates and next "green" catalytic reductive cyclization of the obtained 2-nitro ester intermediates (3a-l). Further, 6,7-dibromo (5a-c) and N-acetyl (6) derivatives were prepared by bromination and acetylation of unsubstituted 2-alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-c). The novel compounds (3a-l, 4d-l, 5a-c and 6) were fully characterized by spectroscopic methods (MS, (1)H and (13)C NMR). 2-Alkyl-2H-1,4-benzoxazin-3(4H)-ones (4a-l, 5a-c and 6) were screened for antifungal activity. Preliminary assays were performed using two methods: in vitro against seven phytopathogenic fungi-Botrytis cinerea, Phythophtora cactorum, Rhizoctonia solani, Phoma betae, Fusarium culmorum, Fusarium oxysporum and Alternaria alternata-and in vivo against barley powdery mildew Blumeria graminis. The tested compounds displayed moderate to good antifungal activity at high concentration (200 mg L(-1)). The most potent compounds were 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a), 2-ethyl-7-fluoro-2H-1,4-benzoxazin-3(4H)-one (4g) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6), which completely inhibited the mycelial growth of seven agricultural fungi at the concentration of 200 mg L(-1) in the in vitro tests. Moreover, 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) and 4-acetyl-2-ethyl-2H-1,4-benzoxazin-3(4H)-one (6) were also screened for antifungal activity at concentrations of 100 mg L(-1) and 20 mg L(-1). In the concentration of 100 mg L(-1), the N-acetyl derivative (6) completely inhibited the growth of three strains of fungi (F. culmorum, P. cactorum and R. solani), while 2-ethyl-2H-1,4-benzoxazin-3(4H)-one (4a) completely inhibited only R. solani strain. At the concentration of 20 mg L(-1), compound 6 showed good activity only against P. cactorum strain (72%). PMID:26963527

  8. Modern NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Jelinski, Lynn W.

    1984-01-01

    Discusses direct chemical information that can be obtained from modern nuclear magnetic resonance (NMR) methods, concentrating on the types of problems that can be solved. Shows how selected methods provide information about polymers, bipolymers, biochemistry, small organic molecules, inorganic compounds, and compounds oriented in a magnetic…

  9. Molecular hydrogen complexes of the transition metals. 2. Evidence for a new complex, Mo(CO) (dppe)/sub 2/(H/sub 2/), and for solution equilibrium between dihydrogen and dihydride forms, M-eta/sup 2/-H/sub 2/ in equilibrium H-M-H, in W(CO)/sub 3/(PR/sub 3/)/sub 2/(H/sub 2/)

    SciTech Connect

    Kubas, G.J.; Ryan, R.R.; Wrobleski, D.A.

    1986-03-19

    Coordination of molecular hydrogen to transition metals is now firmly established, initially in the stable, structurally characterized complexes M(CO)/sub 3/(PR/sub 3/)/sub 2/(eta/sup 2/-H/sub 2/) (M = Mo, W; R = Cy, i-Pr), then in low-temperature stable Cr(CO)/sub 5/(H/sub 2/), and recently in IrH(H/sub 2/)(PPh/sub 3/)/sub 2/(C/sub 13/H/sub 8/N))SbF/sub 6/, (IrH/sub 2/(H/sub 2/)/sub 2/L/sub 2/)/sup +/, and (FeH(H/sub 2/)(dppe)/sub 2/)BF/sub 4/. In order to better define the steric and electronic requirements for H/sub 2/ to bind in molecular fashion rather than being cleaved to hydride ligands, reported here is new stable H/sub 2/ complex, Mo(CO)(dppe)/sub 2/(H/sub 2/) (dppe = diphenylphosphinoethane). Also, NMR evidence is presented for a dynamic equilibrium between the H/sub 2/ complex W(CO)/sub 3/(P-i-Pr/sub 3/)/sub 2/(eta/sup 2/-H/sub 2/), and an apparent dihydride complex, WH/sub 2/(CO)/sub 3/)P-i-Pr/sub 3/)/sub 2/, derived by oxidative addition of the H/sub 2/ ligand. 16 references, 2 figures.

  10. Probe for high resolution NMR with sample reorientation

    DOEpatents

    Pines, A.; Samoson, A.

    1990-02-06

    An improved NMR probe and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise orientationally disordered samples. The apparatus mechanically varies the orientation of the sample such that the time average of two or more sets of spherical harmonic functions are zero. 8 figs.

  11. Probe for high resolution NMR with sample reorientation

    DOEpatents

    Pines, Alexander; Samoson, Ago

    1990-01-01

    An improved NMR probe and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise orientationally disordered samples. The apparatus mechanically varies the orientation of the sample such that the time average of two or more sets of spherical harmonic functions are zero.

  12. Characterization of active phosphorus surface sites at synthetic carbonate-free fluorapatite using single-pulse 1H, 31P, and 31P CP MAS NMR.

    PubMed

    Jarlbring, Mathias; Sandström, Dan E; Antzutkin, Oleg N; Forsling, Willis

    2006-05-01

    The chemically active phosphorus surface sites defined as PO(x), PO(x)H, and PO(x)H2, where x = 1, 2, or 3, and the bulk phosphorus groups of PO4(3-) at synthetic carbonate-free fluorapatite (Ca5(PO4)3F) have been studied by means of single-pulse 1H,31P, and 31P CP MAS NMR. The changes in composition and relative amounts of each surface species are evaluated as a function of pH. By combining spectra from single-pulse 1H and 31P MAS NMR and data from 31P CP MAS NMR experiments at varying contact times in the range 0.2-3.0 ms, it has been possible to distinguish between resonance lines in the NMR spectra originating from active surface sites and bulk phosphorus groups and also to assign the peaks in the NMR spectra to the specific phosphorus species. In the 31P CP MAS NMR experiments, the spinning frequency was set to 4.2 kHz; in the single-pulse 1H MAS NMR experiments, the spinning frequency was 10 kHz. The 31P CP MAS NMR spectrum of fluorapatite at pH 5.9 showed one dominating resonance line at 2.9 ppm assigned to originate from PO4(3-) groups and two weaker shoulder peaks at 5.4 and 0.8 ppm which were assigned to the unprotonated PO(x) (PO, PO2-, and PO3(2-)) and protonated PO(x)H (PO2H and PO3H-) surface sites. At pH 12.7, the intensity of the peak representing unprotonated PO(x) surface sites has increased 1.7% relative to the bulk peak, while the intensity of the peaks of the protonated species PO(x)H have decreased 1.4% relative to the bulk peak. At pH 3.5, a resonance peak at -4.5 ppm has appeared in the 31P CP MAS NMR spectrum assigned to the surface species PO(x)H2 (PO3H2). The results from the 1H MAS and 31P CP MAS NMR measurements indicated that H+, OH-, and physisorbed H2O at the surface were released during the drying process at 200 degrees C.

  13. An improved technique for the 2H/1H analysis of urines from diabetic volunteers

    USGS Publications Warehouse

    Coplen, T.B.; Harper, I.T.

    1994-01-01

    The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, ~ 1-2???, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.The H2-H2O ambient-temperature equilibration technique for the determination of 2H/1H ratios in urinary waters from diabetic subjects provides improved accuracy over the conventional Zn reduction technique. The standard deviation, approximately 1-2%, is at least a factor of three better than that of the Zn reduction technique on urinary waters from diabetic volunteers. Experiments with pure water and solutions containing glucose, urea and albumen indicate that there is no measurable bias in the hydrogen equilibration technique.

  14. Interconversion of FeC{sub 2}H{sub 3}{sup +} and HFeC{sub 2}H{sub 2}{sup +}: An FTICR and density functional study

    SciTech Connect

    Chen, H.; Jacobson, D.B.; Freiser, B.S.

    1999-12-20

    The geometries and energetics of four FeC{sub 2}H{sub 3}{sup +} isomers have been studied by a hybrid of density functional theory (DFT) and the Hartree-Fock approach (BECKE3LYP). The bond dissociation energy D{degree}(FeH{sup +}-C{sub 2}H{sub 2}) for the quintet ground state is predicted to be 32.9 kcal/mol, which compares well with the experimentally measured D{degree}(Fe{sup +}-C{sub 2}H{sub 2}) value of 32 kcal/mol. The [Fe, C{sub 2}, H{sub 3}]{sup +} system is also studied experimentally by using Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). In situ synthesis of FeC{sub 2}H{sub 3}{sup +} is achieved by a complex, multistep procedure involving ion/molecule reactions in conjunction with CID and SORI-CID techniques. Kinetics for H/D exchange reactions between FeH{sup +}/FeD{sup +} and C{sub 2}D{sub 4}/C{sub 2}H{sub 4} are also measured and provide complementary information to Schwarz's studies of the [Fe, C{sub 2}, H{sub 5}]{sup +} system.

  15. Picoliter H-1 NMR Spectroscopy

    SciTech Connect

    Minard, Kevin R. ); Wind, Robert A. )

    2002-02-01

    A RF probe that fits inside the bore of a small gradient coil package is described for routine 1H-NMR microscopy measurements on small samples. The probe operates at 500 MHz and houses a 267-um-diameter solenoid transceiver. When used in three dimensional chemical shift imaging (3D-CSI) experiments, the measured signal-to-noise ratio (SNR) is shown to be within 20-30 percent of theoretical limits formulated by only considering the solenoid's resistive losses. This is illustrated using a 100-um-diameter globule of triacylglycerols ({approx}900mM) that may be an oocyte precursor in young Xenopus Laevis frogs, and water sample containing choline at a concentration often found in live cells ({approx}33mM). In chemical shift images generated using a few thousand scans, the choline methyl line is found to have an acceptable SNR in resolved from just 5 picoliters in the Xenopus globule. It is concluded that the probe's sensitivity is sufficient for performing 1H-NMR on picoliter-scale volumes in biological cells and tissues.

  16. Probing anisotropic interaction potentials of unsaturated hydrocarbons with He*(2 3S) metastable atom: Attractive-site preference of σ-direction in C2H2 and π-direction in C2H4

    NASA Astrophysics Data System (ADS)

    Horio, Takuya; Hatamoto, Takuro; Maeda, Satoshi; Kishimoto, Naoki; Ohno, Koichi

    2006-03-01

    State-resolved collision energy dependence of Penning ionization cross sections of acetylene (C2H2) and ethylene (C2H4) with He*(2S3) metastable atoms was observed in a wide collision energy range from 20to350meV. A recently developed discharge nozzle source with a liquid N2 circulator was employed for the measurements in the low-energy range from 20to80meV. Based on classical trajectory calculations for the energy dependence of the partial ionization cross sections, anisotropic potential energy surfaces for the present systems were obtained by optimizing ab initio model potentials for the chemically related systems Li +C2H2 and C2H4. In the case of C2H2, the global minimum was found to be located around the H atom along the molecular axis with a well depth of 48meV (ca. 1.1kcal/mol). On the other hand, a dominant attractive well with a depth of 62meV (ca. 1.4kcal/mol) was found in the πCC electron region of C2H4. These findings were discussed in connection with orbital interactions between molecular orbitals of the target molecules and atomic orbitals of the metastable atom. It is concluded that σ-type unoccupied molecular orbitals of C2H2 and a πCC-type highest occupied molecular orbital of C2H4 play a significant role for the attractive-site preference of σ direction in C2H2 and π direction in C2H4, respectively.

  17. The infrared spectra of C2H4(+) and C2H3 trapped in solid neon.

    PubMed

    Jacox, Marilyn E; Thompson, Warren E

    2011-02-14

    When a mixture of ethylene in a large excess of neon is codeposited at 4.3 K with a beam of neon atoms that have been excited in a microwave discharge, two groups of product absorptions appear in the infrared spectrum of the deposit. Similar studies using C(2)H(4)-1-(13)C and C(2)D(4) aid in product identification. The first group of absorptions arises from a cation product which possesses two identical carbon atoms, giving the first infrared identification of two fundamentals of C(2)H(4)(+) and three of C(2)D(4)(+), as well as a tentative identification of ν(9) of C(2)H(4)(+). The positions of these absorptions are consistent with the results of density functional calculations and of earlier photoelectron studies. All of the members of the second group of product absorptions possess two inequivalent carbon atoms. They are assigned to the vinyl radical, C(2)H(3), and to C(2)D(3), in agreement with other recent infrared assignments for those species.

  18. Observations of CH4, C2H6, and C2H2 in the stratosphere of Jupiter.

    PubMed

    Sada, P V; Bjoraker, G L; Jennings, D E; McCabe, G H; Romani, P N

    1998-12-01

    We have performed high-resolution spectral observations at mid-infrared wavelengths of CH4 (8.14 micrometers), C2H6 (12.16 micrometers), and C2H2 (13.45 micrometers) on Jupiter. These emission features probe the stratosphere of the planet and provide information on the carbon-based photochemical processes taking place in that region of the atmosphere. The observations were performed using our cryogenic echelle spectrometer CELESTE, in conjunction with the McMath-Pierce 1.5-m solar telescope between November 1994 and February 1995. We used the methane observations to derive the temperature profile of the jovian atmosphere in the 1-10 mbar region of the stratosphere. This profile was then used in conjunction with height-dependent mixing ratios of each hydrocarbon to determine global abundances for ethane and acetylene. The resulting mixing ratios are 3.9(+1.9)(-1.3) x 10(-6) for C2H6 (5 mbar pressure level), and 2.3 +/- 0.5 x 10(-8) for C2H2 (8 mbar pressure level), where the quoted uncertainties are derived from model variations in the temperature profile which match the methane observation uncertainties. PMID:11878354

  19. Search for the isomers of C2H3NO and C2H3NS in the Interstellar Medium

    NASA Astrophysics Data System (ADS)

    Etim, Emmanuel; Chakrabarti, Sandip Kumar; Das, Ankan; Gorai, Prasanta; Arunan, Elangannan

    2016-07-01

    With about 40% of all the known interstellar and circumstellar molecules having their isomeric analogues as known astromolecules, isomerism remains one of the leading themes in interstellar chemistry. In this regard, the recent detection of methyl isocyanate (with a number of isomeric analogues) in the Sgr B2(N) giant molecular cloud opens a new window for the possible astronomical detection of other C_2H_3NO isomers. The present work looks at the possibility of detecting other isomers of methyl isocyanate by considering different factors such as thermodynamic stability of the different isomers with respect to the Energy, Stability and Abundance (ESA) relationship, effect of interstellar hydrogen bonding with respect to the formation these isomers on the surface of the interstellar dust grains, possible formation routes for these isomers, spectroscopic parameters for potential astromolecules among these isomers, chemical modeling among other studies. The same studies are repeated for the C_2H_3NS isomers which are the isoelectroninc analogues of the C_2H_3NO isomers taking into account the unique chemistry of S and O-containing interstellar molecular species. Among the C_2H_3NS isomers, methyl isothiocyanate remains the most potential candidate for astronomical observation.

  20. Analysis Of 2H-Evaporator Scale Pot Bottom Sample [HTF-13-11-28H

    SciTech Connect

    Oji, L. N.

    2013-07-15

    Savannah River Remediation (SRR) is planning to remove a buildup of sodium aluminosilicate scale from the 2H-evaporator pot by loading and soaking the pot with heated 1.5 M nitric acid solution. Sampling and analysis of the scale material from the 2H evaporator has been performed so that the evaporator can be chemically cleaned beginning July of 2013. Historically, since the operation of the Defense Waste Processing Facility (DWPF), silicon in the DWPF recycle stream combines with aluminum in the typical tank farm supernate to form sodium aluminosilicate scale mineral deposits in the 2H-evaporator pot and gravity drain line. The 2H-evaporator scale samples analyzed by Savannah River National Laboratory (SRNL) came from the bottom cone sections of the 2H-evaporator pot. The sample holder from the 2H-evaporator wall was virtually empty and was not included in the analysis. It is worth noting that after the delivery of these 2H-evaporator scale samples to SRNL for the analyses, the plant customer determined that the 2H evaporator could be operated for additional period prior to requiring cleaning. Therefore, there was no need for expedited sample analysis as was presented in the Technical Task Request. However, a second set of 2H evaporator scale samples were expected in May of 2013, which would need expedited sample analysis. X-ray diffraction analysis (XRD) confirmed the bottom cone section sample from the 2H-evaporator pot consisted of nitrated cancrinite, (a crystalline sodium aluminosilicate solid), clarkeite and uranium oxide. There were also mercury compound XRD peaks which could not be matched and further X-ray fluorescence (XRF) analysis of the sample confirmed the existence of elemental mercury or mercuric oxide. On ''as received'' basis, the scale contained an average of 7.09E+00 wt % total uranium (n = 3; st.dev. = 8.31E-01 wt %) with a U-235 enrichment of 5.80E-01 % (n = 3; st.dev. = 3.96E-02 %). The measured U-238 concentration was 7.05E+00 wt % (n=3, st

  1. {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions at sub-coulomb energies

    SciTech Connect

    Tumino, A.; Spitaleri, C.; Mukhamedzhanov, A. M.; Typel, S.; Sparta, R.; Aliotta, M.; Kroha, V.; Hons, Z.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Mrazek, J.; Pizzone, R. G.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.

    2012-11-20

    The {sup 2}H({sup 3}He,p{sup 3}H){sup 1}H and {sup 2}H({sup 3}He,n{sup 3}He){sup 1}H processes have been measured in quasi free kinematics to investigate for the first time the {sup 2}H(d,p){sup 3}H and {sup 2}H(d,n){sup 3}He reactions by means of the Trojan Horse Method. The {sup 3}He+d experiment was performed at 18 MeV, corresponding the a d-d energy range from 1.5 MeV down to 2 keV. This range overlaps with the relevant region for Standard Big Bang Nucleosynthesis as well as with the thermal energies of future fusion reactors and deuterium burning in the Pre Main Sequence phase of stellar evolution. This is the first pioneering experiment in quasi free regime where the charged spectator is detected. Both the energy dependence and the absolute value of the bare nucleus S(E) factors have been extracted for the first time. They deviate by more than 15% from available direct data with new S(0) values of 57.4{+-}1.8 MeVb for {sup 3}H+p and 60.1{+-}1.9 MeVb for {sup 3}He+n. None of the existing fitting curves is able to provide the correct slope of the new data in the full range, thus calling for a revision of the theoretical description. This has consequences in the calculation of the reaction rates with more than a 25% increase at the temperatures of future fusion reactors.

  2. New Evidences for the observation of the Higgs boson in the Superconductor 2H-NbSe2

    NASA Astrophysics Data System (ADS)

    Measson, Marie-Aude; Clair, Bertrand; Gallais, Yann; Cazayous, Maximilien; Rodière, Pierre; Cario, Laurent; Sacuto, Alain; Squap Team; Systèmes À Fortes Corrélations Électroniques Collaboration; Imn Collaboration

    2013-03-01

    We provide here new evidences for the observation of the amplitude mode of the superconducting order parameter, the so-called Higgs Boson, in 2H-NbSe2. We report quantitatively comparative electronic Raman measurements on the dichalcogenides 2H-NbSe2, whose superconductivity (SC) coexists with a charge density wave order (CDW), and 2H-NbS2, which exhibits only the SC. A SC pair breaking peak develops below Tc in 2H-NbS2 whose intensity is much smaller than the peak associated with the SC in 2H-NbSe2. Thus, the peak observed in 2H-NbSe2 below Tc certainly doesn't get its intensity only from the superconducting condensate. Moreover, we measure precisely a spectral weight transfer from the amplitude mode of the CDW to the SC peak in 2H-NbSe2, versus decreasing temperature. The total spectral weight for both peaks is constant within +/- 3 % . This result is consistent with the theory of the observation of a Higgs mode thanks to its coupling with an amplitudon developed by Littlewood and Varma. This result complements what was firstly observed by Sooryakumar et Klein under magnetic field.

  3. NMR studies of cation transport across membranes

    SciTech Connect

    Shochet, N.R.

    1985-01-01

    /sup 23/Na NMR Studies of cation transport across membranes were conducted both on model and biological membranes. Two ionophores, the carrier monensin and the channel-former gramicidin, were chosen to induce cation transport in large unilamellar phosphatidylcholine vesicles. The distinction between the NMR signals arising from the two sides of the membrane was achieved by the addition of an anionic paramagnetic shift reagent to the outer solution. The kinetics of the cation transport across the membrane was observed simultaneously monitoring the changes in the /sup 23/Na NMR signals of both compartments. Two mathematical models were developed for the estimation of the transport parameters of the monensin- and gramicidin-induced cation transport. The models were able to fit the experimental data very well. A new method for the estimation of the volume trapped inside the vesicles was developed. The method uses the relative areas of the intra- and extravesicular NMR signals arising from a suspension of vesicles bathed in the same medium they contain, as a measure for the relative volumes of these compartments. Sodium transport across biological membranes was studied by /sup 23/ NMR, using suspensions of cultured nerve cells. The sodium influx through voltage-gated channels was studied using the channel modifier batrachotoxin in combination with scorpion toxin.

  4. NMR methodologies in the analysis of blueberries.

    PubMed

    Capitani, Donatella; Sobolev, Anatoly P; Delfini, Maurizio; Vista, Silvia; Antiochia, Riccarda; Proietti, Noemi; Bubici, Salvatore; Ferrante, Gianni; Carradori, Simone; De Salvador, Flavio Roberto; Mannina, Luisa

    2014-06-01

    An NMR analytical protocol based on complementary high and low field measurements is proposed for blueberry characterization. Untargeted NMR metabolite profiling of blueberries aqueous and organic extracts as well as targeted NMR analysis focused on anthocyanins and other phenols are reported. Bligh-Dyer and microwave-assisted extractions were carried out and compared showing a better recovery of lipidic fraction in the case of microwave procedure. Water-soluble metabolites belonging to different classes such as sugars, amino acids, organic acids, and phenolic compounds, as well as metabolites soluble in organic solvent such as triglycerides, sterols, and fatty acids, were identified. Five anthocyanins (malvidin-3-glucoside, malvidin-3-galactoside, delphinidin-3-glucoside, delphinidin-3-galactoside, and petunidin-3-glucoside) and 3-O-α-l-rhamnopyranosyl quercetin were identified in solid phase extract. The water status of fresh and withered blueberries was monitored by portable NMR and fast-field cycling NMR. (1) H depth profiles, T2 transverse relaxation times and dispersion profiles were found to be sensitive to the withering.

  5. High-resolution NMR of hydrogen in organic solids by DNP enhanced natural abundance deuterium spectroscopy.

    PubMed

    Rossini, Aaron J; Schlagnitweit, Judith; Lesage, Anne; Emsley, Lyndon

    2015-10-01

    We demonstrate that high field (9.4 T) dynamic nuclear polarization (DNP) at cryogenic (∼100 K) sample temperatures enables the rapid acquisition of natural abundance (1)H-(2)H cross-polarization magic angle spinning (CPMAS) solid-state NMR spectra of organic solids. Spectra were obtained by impregnating substrates with a solution of the stable DNP polarizing agent TEKPol in tetrachloroethane. Tetrachloroethane is a non-solvent for the solids, and the unmodified substrates are then polarized through spin diffusion. High quality natural abundance (2)H CPMAS spectra of histidine hydrochloride monohydrate, glycylglycine and theophylline were acquired in less than 2h, providing direct access to hydrogen chemical shifts and quadrupolar couplings. The spectral resolution of the (2)H solid-state NMR spectra is comparable to that of (1)H spectra obtained with state of the art homonuclear decoupling techniques.

  6. High-resolution NMR of hydrogen in organic solids by DNP enhanced natural abundance deuterium spectroscopy

    NASA Astrophysics Data System (ADS)

    Rossini, Aaron J.; Schlagnitweit, Judith; Lesage, Anne; Emsley, Lyndon

    2015-10-01

    We demonstrate that high field (9.4 T) dynamic nuclear polarization (DNP) at cryogenic (∼100 K) sample temperatures enables the rapid acquisition of natural abundance 1H-2H cross-polarization magic angle spinning (CPMAS) solid-state NMR spectra of organic solids. Spectra were obtained by impregnating substrates with a solution of the stable DNP polarizing agent TEKPol in tetrachloroethane. Tetrachloroethane is a non-solvent for the solids, and the unmodified substrates are then polarized through spin diffusion. High quality natural abundance 2H CPMAS spectra of histidine hydrochloride monohydrate, glycylglycine and theophylline were acquired in less than 2 h, providing direct access to hydrogen chemical shifts and quadrupolar couplings. The spectral resolution of the 2H solid-state NMR spectra is comparable to that of 1H spectra obtained with state of the art homonuclear decoupling techniques.

  7. NMR in a Diamond Anvil Pressure Cell

    NASA Astrophysics Data System (ADS)

    Lawson, Matthew; Dioguardi, Adam; Weir, Samuel; Bush, Blaine; Dunuwille, Mihindra; Deemyad, Shanti; Curro, Nichlas

    We present recent advances in the use of diamond anvil pressure cells in nuclear magnetic resonance measurements. This technique allows access to new regions of the phase diagrams of iron pnictide and heavy fermion materials, and promises to allow NMR experiments under pressures not previously accessible.

  8. NMR phase noise in bitter magnets.

    PubMed

    Sigmund, E E; Calder, E S; Thomas, G W; Mitrović, V F; Bachman, H N; Halperin, W P; Kuhns, P L; Reyes, A P

    2001-02-01

    We have studied the temporal instability of a high field resistive Bitter magnet through nuclear magnetic resonance (NMR). This instability leads to transverse spin decoherence in repeated and accumulated NMR experiments as is normally performed during signal averaging. We demonstrate this effect via Hahn echo and Carr--Purcell--Meiboom--Gill (CPMG) transverse relaxation experiments in a 23-T resistive magnet. Quantitative analysis was found to be consistent with separate measurements of the magnetic field frequency fluctuation spectrum, as well as with independent NMR experiments performed in a magnetic field with a controlled instability. Finally, the CPMG sequence with short pulse delays is shown to be successful in recovering the intrinsic spin--spin relaxation even in the presence of magnetic field temporal instability.