Science.gov

Sample records for 17o nmr study

  1. NMR study of a 17O enriched LaMnO3 stoichiometric crystal

    NASA Astrophysics Data System (ADS)

    Pinsard-Gaudart, L.; Trokiner, A.; Verkhovskii, S.; Gerashenko, A.; Dragoe, N.

    2011-12-01

    We present the synthesis and the NMR characterization of a 17O enriched LaMnO 3 crystalline sample. We checked that it is single phase and, more important, stoichiometric in oxygen. Its 17O enrichment estimated by NMR is about 5.5%. These first 17O NMR results obtained at T=415 K in an undoped parent LaMnO 3 manganite demonstrate that the two oxygen sites of the structure probe very different Mn spin correlations in the paramagnetic orbital ordered phase. This work opens the way to study experimentally the interactions responsible for the orbital order.

  2. Dynamic NMR of low-sensitivity fast-relaxing nuclei: (17)O NMR and DFT study of acetoxysilanes.

    PubMed

    Fusaro, Luca; Mameli, Giulia; Mocci, Francesca; Luhmer, Michel; Cerioni, Giovanni

    2012-02-01

    (17)O NMR is not routinely used for structure characterization, and kinetic studies of fluxional organic compounds are seldom undertaken because poor sensitivity and fast quadrupole relaxation are frequently regarded as intractable issues. This work shows how, nowadays, quantitative (17)O dynamic NMR studies on small organic molecules are feasible without enrichment being needed. It reports on acetoxysilanes, a class of fluxional compounds whose structure and dynamics were to be clarified. Natural abundance (17)O NMR spectra were recorded over a wide range of temperatures using standard instrumentation. The analysis relies on simple linewidth measurements and directly provides the activation parameters. The activation enthalpy is found to decrease with increasing number of acetoxy groups bound to silicon. Density functional theory calculations properly predict this trend and show that a single oxygen atom of the acetoxy group is bound to silicon, excluding chelation as binding mode, and that the dynamic process involves the shift of the silicon atom between the two oxygen atoms of the acetoxy group. PMID:22374872

  3. {sup 17}O NMR investigations of oxidative degradation in polymers

    SciTech Connect

    Alam, T.M.; Celina, M.; Assink, R.A.; Gillen, K.T.; Clough, R.L.

    1996-12-31

    We have initiated studies using both solution and solid state magic angle spinning {sup 17}O NMR for a series of oxidatively aged polymers. This short note reports the solution {sup 17}O NMR for oxidatively degraded polypropylene, ethylene-propylene-diene, polyisoprene, and nitrile rubber. Enriched O{sub 2} is used during the accelerated aging. 3 figs, 7 refs.

  4. Solid-State 17O NMR Study of Benzoic Acid Adsorption On Metal Oxide Surfaces

    SciTech Connect

    Hagaman, Edward {Ed} W; Chen, Banghao; Jiao, Jian; Parsons, Williams

    2012-01-01

    Solid-state 17O NMR spectra of 17O-labeled benzoic and anisic acids are reported and benzoic acid is used to probe the surface of metal oxides. Complexes formed when benzoic acid is dry-mixed with mesoporous silica, and nonporous titania and alumina are characterized. Chemical reactions with silica are not observed. The nature of benzoic acid on silica is a function of the water content of the oxide. The acid disperses in the pores of the silica if the silica is in equilibrium with ambient laboratory humidity. The acid displays high mobility as evidenced by a liquid-like, Lorentzian resonance. Excess benzoic acid remains as the crystalline hydrogen-bonded dimer. Benzoic acid reacts with titania and alumina surfaces in equilibrium with laboratory air to form the corresponding titanium and aluminum benzoates. In both materials the oxygen of the 17O-labeled acid is bound to the metal, showing the reaction proceeds by bond formation between oxygen deficient metal sites and the oxygen of the carboxylic acid. 27Al MAS NMR confirms this mechanism for the reaction on alumina. Dry mixing of benzoic acid with alumina rapidly quenches pentacoordinate aluminum sites, excellent evidence that these sites are confined to the surface of the alumina particles.

  5. Joint experimental and computational 17O solid state NMR study of Brownmillerite Ba2In2O5.

    PubMed

    Dervişoğlu, Rıza; Middlemiss, Derek S; Blanc, Frédéric; Holmes, Lesley A; Lee, Yueh-Lin; Morgan, Dane; Grey, Clare P

    2014-02-14

    Structural characterization of Brownmillerite Ba2In2O5 was achieved by an approach combining experimental solid-state NMR spectroscopy, density functional theory (DFT) energetics, and GIPAW NMR calculations. While in the previous study of Ba2In2O5 by Adler et al. (S. B. Adler, J. A. Reimer, J. Baltisberger and U. Werner, J. Am. Chem. Soc., 1994, 116, 675-681), three oxygen resonances were observed in the (17)O NMR spectra and assigned to the three crystallographically unique O sites, the present high resolution (17)O NMR measurements under magic angle spinning (MAS) find only two resonances. The resonances have been assigned using first principles (17)O GIPAW NMR calculations to the combination of the O ions connecting the InO4 tetrahedra and the O ions in equatorial sites in octahedral InO6 coordination, and to the axial O ions linking the four- and six-fold coordinated In(3+) ions. Possible structural disorder was investigated in two ways: firstly, by inclusion of the high-energy structure also previously studied by Mohn et al. (C. E. Mohn, N. L. Allan, C. L. Freeman, P. Ravindran and S. Stølen, J. Solid State Chem., 2005, 178, 346-355), where the structural O vacancies are stacked rather than staggered as in Brownmillerite and, secondly, by exploring structures derived from the ground-state structure but with randomly perturbed atomic positions. There is no noticeable NMR evidence for any substantial occupancy of the high-energy structure at room temperature. PMID:24382459

  6. 17O NMR study of the doped electrons in lightly oxygen-deficient cubic SrMnO3 -x

    NASA Astrophysics Data System (ADS)

    Trokiner, A.; Verkhovskii, S.; Volkova, Z.; Gerashenko, A.; Mikhalev, K.; Germov, A.; Yakubovskii, A.; Korolev, A.; Dabrowski, B.; Tyutyunnik, A.

    2016-05-01

    The spin susceptibility of the localized Mn (t2 g) electrons, χs, and the spatially distributed spin density of the doped electrons were investigated by 17O nuclear magnetic resonance (NMR) in the paramagnetic (PM) and antiferromagnetic (AF) phases of electron-doped SrMnO3 -x ceramics with the cubic structure. Three lightly doped samples (2 x <0.015 ) were studied with TN=220 K-240 K. In the PM state χs increases gradually from TN and reaches a broad maximum above ˜1.5 TN . The gapped behavior of χs indicates a low-dimensional short-range spin order persisting above TN. These short-range one-dimensional correlations are consistent with 17O NMR results obtained at room temperature, which show that Mn magnetic moments are aligned along the edges of the cubic unit cell. Above 350 K all doped electrons are fast-moving eg electrons. They provide the uniform polarization of the localized spins which increases χs and the increasing doping shifts the oxygen-deficient SrMnO3 -x oxide towards a ferromagnetic (FM) metallic state. At lower T the doped electrons are heterogeneously distributed in the oxide: The fraction of the fast-moving electrons diminishes and vanishes below 100 K, while the remaining doped electrons slow down their hopping and each of them creates a FM domain. These FM domains which are detected below 10 K by 55Mn NMR can be considered as small-size magnetic polarons. Their T -activated hopping in the G-type AF lattice was probed by 17O spin-echo experiments. The energy barrier of hopping shows a trend to grow with increasing doping, indicating that the de Gennes metallic ground state cannot be achieved in oxygen-deficient SrMnO3 -x oxides, probably due to detrimental oxygen vacancy defects.

  7. Qualitative study of substituent effects on NMR (15)N and (17)O chemical shifts.

    PubMed

    Contreras, Rubén H; Llorente, Tomás; Pagola, Gabriel I; Bustamante, Manuel G; Pasqualini, Enrique E; Melo, Juan I; Tormena, Cláudio F

    2009-09-10

    A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-beta substituent effects on both (15)N and (17)O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and sigma-hyperconjugative interactions in saturated multicyclic compounds. PMID:19685922

  8. Qualitative Study of Substituent Effects on NMR 15N and 17O Chemical Shifts

    NASA Astrophysics Data System (ADS)

    Contreras, Rubén H.; Llorente, Tomás; Pagola, Gabriel I.; Bustamante, Manuel G.; Pasqualini, Enrique E.; Melo, Juan I.; Tormena, Cláudio F.

    2009-08-01

    A qualitative approach to analyze the electronic origin of substituent effects on the paramagnetic part of chemical shifts is described and applied to few model systems, where its potentiality can be appreciated. The formulation of this approach is based on the following grounds. The influence of different inter- or intramolecular interactions on a second-order property can be qualitatively predicted if it can be known how they affect the main virtual excitations entering into that second-order property. A set of consistent approximations are introduced in order to analyze the behavior of occupied and virtual orbitals that define some experimental trends of magnetic shielding constants. This approach is applied first to study the electronic origin of methyl-β substituent effects on both 15N and 17O chemical shifts, and afterward it is applied to a couple of examples of long-range substituent effects originated in charge transfer interactions such as the conjugative effect in aromatic compounds and σ-hyperconjugative interactions in saturated multicyclic compounds.

  9. ^17O and ^59Co NMR Studies of Strongly Correlated Electrons in NaxCoO2

    NASA Astrophysics Data System (ADS)

    Imai, Takashi

    2006-03-01

    The anomalous electronic properties of triangular-lattice system NaxCoO2 has been attracting strong interest over the last several years since the discovery of superconductivity in hydrated Na1/3CoO2.4/3[H2O]. The electronic phase diagram of these materials is quite rich, as the physical properties depend very strongly on Na concentration. Here we report our ^17O and ^59Co NMR studies of the local electronic properties and low-frequency spin dynamics in these materials for a variety of Na concentrations [1,2]. [1] F.L. Ning, T. Imai, B.W. Statt, and F.C. Chou, PRL 93 (2004) 237201.[2] F.L. Ning and T. Imai, PRL 94 (2005) 227004.

  10. (17)O NMR Investigation of Water Structure and Dynamics.

    PubMed

    Keeler, Eric G; Michaelis, Vladimir K; Griffin, Robert G

    2016-08-18

    The structure and dynamics of the bound water in barium chlorate monohydrate were studied with (17)O nuclear magnetic resonance (NMR) spectroscopy in samples that are stationary and spinning at the magic-angle in magnetic fields ranging from 14.1 to 21.1 T. (17)O NMR parameters of the water were determined, and the effects of torsional oscillations of the water molecule on the (17)O quadrupolar coupling constant (CQ) were delineated with variable temperature MAS NMR. With decreasing temperature and reduction of the librational motion, we observe an increase in the experimentally measured CQ explaining the discrepancy between experiments and predictions from density functional theory. In addition, at low temperatures and in the absence of (1)H decoupling, we observe a well-resolved (1)H-(17)O dipole splitting in the spectra, which provides information on the structure of the H2O molecule. The splitting arises because of the homogeneous nature of the coupling between the two (1)H-(17)O dipoles and the (1)H-(1)H dipole. PMID:27454747

  11. Solid-State 17O NMR of Paramagnetic Coordination Compounds**

    PubMed Central

    Kong, Xianqi; Terskikh, Victor V.; Khade, Rahul L.; Yang, Liu; Rorick, Amber; Zhang, Yong; He, Peng; Huang, Yining; Wu, Gang

    2015-01-01

    We demonstrate that high-quality solid-state 17O (I = 5/2) NMR spectra can be successfully obtained for paramagnetic coordination compounds in which oxygen atoms are directly bonded to the paramagnetic metal centers. For complexes containing V(III) (S = 1), Cu(II) (S = 1/2), and Mn(III) (S = 2) metal centers, the 17O isotropic paramagnetic shifts were found to span a range of more than 10000 ppm. In several cases, high-resolution 17O NMR spectra were recorded under very fast magic-angle spinning (MAS) conditions at 21.1 T. Quantum chemical computations using density functional theory (DFT) qualitatively reproduced the experimental 17O hyperfine shift tensors. PMID:25694203

  12. Joint Experimental and Computational 17O and 1H Solid State NMR Study of Ba2In2O4(OH)2 Structure and Dynamics

    PubMed Central

    2015-01-01

    A structural characterization of the hydrated form of the brownmillerite-type phase Ba2In2O5, Ba2In2O4(OH)2, is reported using experimental multinuclear NMR spectroscopy and density functional theory (DFT) energy and GIPAW NMR calculations. When the oxygen ions from H2O fill the inherent O vacancies of the brownmillerite structure, one of the water protons remains in the same layer (O3) while the second proton is located in the neighboring layer (O2) in sites with partial occupancies, as previously demonstrated by Jayaraman et al. (Solid State Ionics2004, 170, 25−32) using X-ray and neutron studies. Calculations of possible proton arrangements within the partially occupied layer of Ba2In2O4(OH)2 yield a set of low energy structures; GIPAW NMR calculations on these configurations yield 1H and 17O chemical shifts and peak intensity ratios, which are then used to help assign the experimental MAS NMR spectra. Three distinct 1H resonances in a 2:1:1 ratio are obtained experimentally, the most intense resonance being assigned to the proton in the O3 layer. The two weaker signals are due to O2 layer protons, one set hydrogen bonding to the O3 layer and the other hydrogen bonding alternately toward the O3 and O1 layers. 1H magnetization exchange experiments reveal that all three resonances originate from protons in the same crystallographic phase, the protons exchanging with each other above approximately 150 °C. Three distinct types of oxygen atoms are evident from the DFT GIPAW calculations bare oxygens (O), oxygens directly bonded to a proton (H-donor O), and oxygen ions that are hydrogen bonded to a proton (H-acceptor O). The 17O calculated shifts and quadrupolar parameters are used to assign the experimental spectra, the assignments being confirmed by 1H–17O double resonance experiments. PMID:26321789

  13. Simple (17) O NMR method for studying electron self-exchange reaction between UO2 (2+) and U(4+) aqua ions in acidic solution.

    PubMed

    Bányai, István; Farkas, Ildikó; Tóth, Imre

    2016-06-01

    (17) O NMR spectroscopy is proven to be suitable and convenient method for studying the electron exchange by following the decrease of (17) O-enrichment in U(17) OO(2+) ion in the presence of U(4+) ion in aqueous solution. The reactions have been performed at room temperature using I = 5 M ClO4 (-) ionic medium in acidic solutions in order to determine the kinetics of electron exchange between the U(4+) and UO2 (2+) aqua ions. The rate equation is given as R = a[H(+) ](-2)  + R', where R' is an acid independent parallel path. R' depends on the concentration of the uranium species according to the following empirical rate equation: R' = k1 [UO(2 +) ](1/2) [U(4 +) ](1/2)  + k2 [UO(2 +) ](3/2) [U(4 +) ](1/2) . The mechanism of the inverse H(+) concentration-dependent path is interpreted as equilibrium formation of reactive UO2 (+) species from UO2 (2+) and U(4+) aqua ions and its electron exchange with UO2 (2+) . The determined rate constant of this reaction path is in agreement with the rate constant of UO2 (2+) -UO2 (+) , one electron exchange step calculated by Marcus theory, match the range given experimentally of it in an early study. Our value lies in the same order of magnitude as the recently calculated ones by quantum chemical methods. The acid independent part is attributed to the formation of less hydrolyzed U(V) species, i.e. UO(3+) , which loses enrichment mainly by electron exchange with UO2 (2+) ions. One can also conclude that (17) O NMR spectroscopy, or in general NMR spectroscopy with careful kinetic analysis, is a powerful tool for studying isotope exchange reactions without the use of sophisticated separation processes. Copyright © 2015 John Wiley & Sons, Ltd. PMID:25854521

  14. A solid-state 17O NMR, X-ray, and quantum chemical study of N-α-Fmoc-protected amino acids

    NASA Astrophysics Data System (ADS)

    Yamada, Kazuhiko; Hashizume, Daisuke; Shimizu, Tadashi; Ohki, Shinobu; Yokoyama, Shigeyuki

    2008-10-01

    We report the results of a solid-state 17O NMR and X-ray investigation of 17O-enriched N-α-fluoren-9-ylmethoxycarbonyl- L-alanine (Fmoc- L-ALA) and N-α-fluoren-9-ylmethoxycarbonyl- O- t-butyl- L-serine (Fmoc- L-SER). The present X-ray results for Fmoc- L-SER show that the compound crystallized in the monoclinic space group P2 1 with unit-cell dimensions a = 5.843, b = 11.937, c = 15.042 Å, and β = 96.19°. Analysis of 17O magic-angle spinning (MAS) spectra and stationary NMR spectra recorded at multiple magnetic fields of the present Fmoc-protected amino acids yields the magnitudes of hydroxyl and carbonyl 17O electric-field-gradient (EFG) and chemical shielding (CS) tensors with the relative orientations between the two NMR tensors. The 17O quadrupole coupling constants ( CQ) are found to be 7.05-7.60 MHz and 7.90-8.35 MHz, and the spans of the CS tensors are 218-236 ppm and 450-521 ppm, for hydroxyl and carbonyl oxygen atoms, respectively. We also carry out quantum chemical calculations using density functional theory in order to investigate the effects of hydrogen-bond angles on 17O NMR parameters. It is demonstrated that, in addition to the hydrogen bond distances, hydrogen bond angles are an important factor in determining the magnitudes of these tensor components.

  15. Natural abundance 17O, 6Li NMR and molecular modeling studies of the solvation structures of lithium bis(fluorosulfonyl)imide/1,2-dimethoxyethane liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Wan, Chuan; Hu, Mary Y.; Borodin, Oleg; Qian, Jiangfeng; Qin, Zhaohai; Zhang, Ji-Guang; Hu, Jian Zhi

    2016-03-01

    Natural abundance 17O and 6Li NMR experiments, quantum chemistry and molecular dynamics studies were employed to investigate the solvation structures of Li+ at various concentrations of LiFSI in DME electrolytes. It was found that the chemical shifts of both 17O and 6Li changed with the concentration of LiFSI, indicating the changes of solvation structures with concentration. For the quantum chemistry calculations, the coordinated cluster LiFSI(DME)2 forms at first, and its relative ratio increases with increasing LiFSI concentration to 1 M. Then the solvation structure LiFSI(DME) become the dominant component. As a result, the coordination of forming contact ion pairs between Li+ and FSI- ion increases, but the association between Li+ and DME molecule decreases. Furthermore, at LiFSI concentration of 4 M the solvation structures associated with Li+(FSI-)2(DME), Li+2(FSI-)(DME)4 and (LiFSI)2(DME)3 become the dominant components. For the molecular dynamics simulation, with increasing concentration, the association between DME and Li+ decreases, and the coordinated number of FSI- increases, which is in perfect accord with the DFT results.

  16. Ab initio and sup 17 O NMR study of aromatic compounds with dicoordinate oxygen atoms. (1) Methoxy- and (methylenedioxy)benzene derivatives

    SciTech Connect

    Biekofsky, R.R.; Pomilio, A.B.; Contreras, R.H. ); Orendt, A.M.; Facelli, J.C. )

    1990-09-20

    {sup 17}O NMR data at natural abundance in toluene-d{sub 8} at 74{degree}C were obtained for aromatic compounds containing methoxy and methylenedioxy groups as side-chains substituents. {sup 17}O chemical shifts of this series of compounds are significantly influenced by both electronic and steric effects. Ortho electronic and steric substituent chemical shift effects for methoxy and methylenedioxy groups were estimated. Ab initio calculations at the 4-31G level were used to determine geometries of the compounds to gain insight into the structural aspects of these compounds. A correlation between the calculated bond orders, P{sub C{sub Ar}P{minus}O}, and the {sup 17}O chemical shift was found.

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

    PubMed

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

    2016-08-01

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

  18. Solid-state {sup 17}O magic-angle and dynamic-angle spinning NMR study of the SiO{sub 2} polymorph coesite

    SciTech Connect

    Grandinetti, P.J.; Baltisberger, J.H.; Farnan, I.; Stebbins, J.F.; Werner, U.; Pines, A. |

    1995-08-10

    Five distinctly resolved {sup 17}O solid-state NMR resonances in room temperature coesite, an SiO{sub 2} polymorph, have been observed and assigned using dynamic angle spinning (DAS) at 11.7 T along with magic angle spinning (MAS) spectra at 9.4 and 11.7 T. The {sup 17}O quadrupolar parameters for each of the five oxygen environments in coesite are correlated with the Si-O-Si bridging bond angles determined by diffraction experiments. The sign of e{sup 2}-qQ/h along with the orientation of the electric field gradient for oxygen in the Si-O-Si linkage were determined from a Townes-Dailey analysis of the data. 41 refs., 7 figs., 5 tabs.

  19. Spin excitations in the (Sr,Ca)14Cu24O41 family of spin ladders: 63Cu and 17O NMR studies under pressure

    NASA Astrophysics Data System (ADS)

    Piskunov, Y.; Jérome, D.; Auban-Senzier, P.; Wzietek, P.; Yakubovsky, A.

    2004-01-01

    We report the results of a NMR study of hole doped spin ladders belonging to the series Sr14-xCaxCu24O41+δ performed on 63Cu and 17O nuclei. The new results obtained on Ca0 and Ca12 single crystals at ambient pressure and also under 32 kbar confirm the onset of low-lying spin fluctuations modes at zero energy coexisting with spin-gapped excitations when superconductivity can be stabilized under pressure in Ca12. We found that the theoretical two and three magnons mechanisms explain fairly well the spin-lattice relaxation data using the magnitude of the pressure dependent magnon spin gap Δs derived from the Knight shifts data as long as most of the spectral weight for low-frequency spin fluctuations is provided by the magnon dispersion of isolated ladders. The cross over between spin gapped and paramagnetic regimes of decoupled Heisenberg chains can be identified in heavily doped ladders via the temperature dependence of dynamical structure factors at q˜(π,π) and q˜(0,0) wave vectors. The cross over temperature scales under pressure with Δs/2.

  20. Probing oxidative degradation in polymers using {sup 17}O NMR spectroscopy

    SciTech Connect

    Alam, T.M.; Click, C.A.; Assink, R.A.

    1997-09-01

    Understanding the mechanism of oxidative degradation remains an important goal in being able to predict the aging process in polymer materials. Nuclear magnetic resonance (NMR) spectroscopy has previously been utilized to investigate polymer degradation, including both proton ({sup 1}H) and carbon ({sup 13}C) studies. These previous NMR studies, as well as other spectroscopic investigations, are complicated by the almost overwhelming signal arising from the native undegraded polymer. This makes the identification and quantification of degradation species at small concentrations difficult. In this note we discuss recent investigation into the use of oxygen ({sup 17}O) NMR spectroscopy to probe the oxidative degradation process in polymers at a molecular level. Due to the low natural abundance (0.037%) and a nuclear spin of I=5/2 possessing an appreciable quadrupolar moment, the use of {sup 17}O NMR in polymer investigations has been limited. By utilizing synthetically enriched oxygen gas during the accelerated aging process, both the difficulties of low natural abundance and background interference signals are eliminated. For enriched samples {sup 17}O NMR spectra now provide a unique probe since all of the observed NMR resonances are the direct result of oxidative degradation.

  1. Chemometric Analysis of Two Dimensional Decay Data: Application to {sup 17}O NMR Relaxation Matrices

    SciTech Connect

    Alam, M.K.; Alam, T.M.

    1999-03-18

    The use of {sup 17}O NMR spectroscopy as a tool to investigate aging in polymer systems has recently been demonstrated. Because the natural abundance of {sup 17}O is extremely low (0.037%), the use of labeled {sup 17}O{sub 2} during the oxidation of polymers produces {sup 17}O NMR spectra whose signals arise entirely from the degradation species (i.e. signals from the bulk or unaged material are not observed). This selective isotopic labeling eliminates the impact of interference from the unaged material, cause (1) above. As discussed by Alam et al. spectral overlap between different degradation species as well as errors in quantification remains a major difficulty in {sup 17}O NMR spectroscopy. As a demonstration of the DECRA and CTBSA methods, relaxation matrices obtained from {sup 17}O NMR for model alcohol systems are evaluated. The benefits and limitations of these newly developed chemometric techniques are discussed.

  2. Natural abundant (17) O NMR in a 1.5-T Halbach magnet.

    PubMed

    Sørensen, Morten K; Bakharev, Oleg N; Jensen, Ole; Nielsen, Niels Chr

    2016-06-01

    We present mobile, low-field (17) O NMR as a means for monitoring oxygen in liquids. Whereas oxygen is one of the most important elements, oxygen NMR is limited by a poor sensitivity related to low natural abundance and gyro-magnetic ratio of the NMR active (17) O isotope. Here, we demonstrate (17) O NMR detection at a Larmor frequency of 8.74 MHz in a 1.5-T Halbach neodymium magnet with a home-built digital NMR instrument suitable for large-scale production and in-line monitoring applications. The proposed (17) O NMR sensor may be applied for direct, noninvasive measurements of water content in, for example, oil, manure, or food in automated quality or process control. Copyright © 2015 John Wiley & Sons, Ltd. PMID:25641664

  3. {sup 13}C and {sup 17}O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

    SciTech Connect

    Clark, D.L.; Newton, T.W.; Palmer, P.D.; Zwick, B.D.

    1995-01-01

    Valuable structural information, much of it unavailable by other methods, can be obtained about complexes in solution through NMR spectroscopy. From chemical shift and intensity measurements of complexed species, NMR can serve as a species-specific structural probe for molecules in solution and can be used to validate thermodynamic constants used in geochemical modeling. Fourier-transform nuclear magnetic resonance (FT-NMR) spectroscopy has been employed to study the speciation of uranium(VI) ions in aqueous carbonate solutions as a function of pH, ionic strength, carbonate concentration, uranium concentration, and temperature. Carbon-13 and oxygen-17 NMR spectroscopy were used to monitor the fractions, and hence thermodynamic binding constants of two different uranyl species U0{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} and (UO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} in aqueous solution. Synthetic buffer solutions were prepared under the ionic strength conditions used in the NMR studies in order to obtain an accurate measure of the hydrogen ion concentration, and a discussion of pH = {minus}log(a{sub H}{sup +}) versus p[H] = {minus}log[H+] is provided. It is shown that for quantitative studies, the quantity p[H] needs to be used. Fourteen uranium(VI) binding constants recommended by the OECD NEA literature review were corrected to the ionic strengths employed in the NMR study using specific ion interaction theory (SIT), and the predicted species distributions were compared with the actual species observed by multinuclear NMR. Agreement between observed and predicted stability fields is excellent. This establishes the utility of multinuclear NMR as a species-specific tool for the study of the actinide carbonate complexation constants, and serves as a means for validating the recommendations provided by the OECD NEA.

  4. /sup 13/C and /sup 17/O NMR and IR spectroscopic study of a series of carbonyl(4-substituted pyridine)(meso-tetraphenylporphinato)iron(II) complexes. Correlations between NMR chemical shifts and IR stretching frequencies of the carbonyl ligand and Taft parameters of the pyridine substituent

    SciTech Connect

    Box, J.W.; Gray, G.M.

    1987-08-26

    The results of a /sup 13/C and /sup 17/O NMR and IR spectroscopic study of a series of carbonyl(4 substituted pyridine)(meso-tetraphenylporphinato)iron(II) (Fe(TPP)(CO)(py-4-X)) complexes are presented. Good to excellent linear correlations between the /sup 13/ and /sup 17/O NMR chemical shifts and the IR stretching frequencies of the carbonyl ligand are observed as the pyridine substituent is varied. Good to excellent linear correlations are also observed between these NMR chemical shifts and IR stretching frequencies and the NMR chemical shifts and IR stretching force constants for the trans carbonyls of a series of cis-Mo(CO)/sub 4/(py-4-X)/sub 2/ complexes as the pyridine substituent is varied. The relationship between the donor ability of the pyridine ligands and the /sup 13/C and /sup 17/O NMR chemical shifts and the IR stretching frequencies of the carbonyl ligands in the Fe(TPP)(CO)(py-4-X) complexes has been quantitated by fitting the spectroscopic data to the single and the dual Taft substituent parameters of the pyridine substituent. Good to excellent correlations are observed. The upfield shift in the /sup 13/C NMR resonance of the carbonyl ligand as the electron-donor ability of the pyridine increases is unique. This has been rationalized by using the Buchner and Schenk description of metal carbonyl /sup 13/C NMR chemical shifts. 49 references, 3 figures, 6 tables.

  5. Solid-State (17)O NMR of Oxygen-Nitrogen Singly Bonded Compounds: Hydroxylammonium Chloride and Sodium Trioxodinitrate (Angeli's Salt).

    PubMed

    Lu, Jiasheng; Kong, Xianqi; Terskikh, Victor; Wu, Gang

    2015-07-23

    We report a solid-state NMR study of (17)O-labeled hydroxylammonium chloride ([H(17)O-NH3]Cl) and sodium trioxodinitrate monohydrate (Na2[(17)ONNO2]·H2O, Angeli's salt). The common feature in these two compounds is that they both contain oxygen atoms that are singly bonded to nitrogen. For this class of oxygen-containing functional groups, there is very limited solid-state (17)O NMR data in the literature. In this work, we experimentally measured the (17)O chemical shift and quadrupolar coupling tensors. With the aid of plane-wave DFT computation, the (17)O NMR tensor orientations were determined in the molecular frame of reference. We found that the characteristic feature of an O-N single bond is that the (17)O nucleus exhibits a large quadrupolar coupling constant (13-15 MHz) but a rather small chemical shift anisotropy (100-250 ppm), in sharp contrast with the nitroso (O═N) functional group for which both quantities are very large (e.g., 16 MHz and 3000 ppm, respectively). PMID:26107984

  6. Natural abundance 17O DNP two-dimensional and surface-enhanced NMR spectroscopy

    DOE PAGESBeta

    Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek

    2015-06-22

    Due to its extremely low natural abundance and quadrupolar nature, the 17O nuclide is very rarely used for spectroscopic investigation of solids by NMR without isotope enrichment. Additionally, the applicability of dynamic nuclear polarization (DNP), which leads to sensitivity enhancements of 2 orders of magnitude, to 17O is wrought with challenges due to the lack of spin diffusion and low polarization transfer efficiency from 1H. Here, we demonstrate new DNP-based measurements that extend 17O solid-state NMR beyond its current capabilities. The use of the PRESTO technique instead of conventional 1H–17O cross-polarization greatly improves the sensitivity and enables the facile measurementmore » of undistorted line shapes and two-dimensional 1H–17O HETCOR NMR spectra as well as accurate internuclear distance measurements at natural abundance. This was applied for distinguishing hydrogen-bonded and lone 17O sites on the surface of silica gel; the one-dimensional spectrum of which could not be used to extract such detail. As a result, this greatly enhanced sensitivity has enabled, for the first time, the detection of surface hydroxyl sites on mesoporous silica at natural abundance, thereby extending the concept of DNP surface-enhanced NMR spectroscopy to the 17O nuclide.« less

  7. Effect of iron content on the structure and disorder of iron-bearing sodium silicate glasses: A high-resolution 29Si and 17O solid-state NMR study

    NASA Astrophysics Data System (ADS)

    Kim, Hyo-Im; Sur, Jung Chul; Lee, Sung Keun

    2016-01-01

    increase with iron content and that Fe3+ is predominantly a network-former. The 17O NMR spectra suggest a moderate degree of preferential partitioning of iron between NBO and BO clusters. The present results bear strong promise for studying iron-bearing silicate glasses using solid-state NMR techniques, constraining the effect of iron content on the degree of polymerization. The observed changes in atomic structures of iron-bearing sodium silicate glasses will be helpful for unraveling atomic origins of the properties of natural silicate melts.

  8. GC-MS and /sup 17/O NMR tracer studies of Et/sub 3/PO formation from auranofin and H/sub 2//sup 17/O in the presence of bovine serum albumin: an in vitro model for auranofin metabolism

    SciTech Connect

    Isab, A.A.; Shaw, C.F. III; Locke, J.

    1988-09-21

    /sup 17/O NMR spectroscopy and gas chromatographic-mass spectral analysis have been used to monitor the source of oxygen in the triethylphosphine oxide formed by the reaction of the antiarthritic drug auranofin ((2,3,4,6-tetra-O-acetyl-..beta..-D-1-glucopyranosato)(triethylphosphine)gold(I)) and bovine serum albumin (BSA) in the presence of reduced glutathione (GtSH). A procedure to extract Et/sub 3/PO from aqueous solutions and concentrate it for subsequent analyses was developed. When the in vitro reaction is carried out aerobically in /sup 17/O-enriched water, Et/sub 3/P/sup 17/O is generated. The chemical ionization (CH/sub 4/) mass measurement, (m + 1)/z = 135, and the /sup 17/O NMR parameters (delta/sub O/ = 40.6 and /sup 1/J/sub PO/ = 156 /plus minus/ 5 Hz) unambiguously establish its identity. The SH titer of the albumin (mole ratio of protein SH groups to BSA) increases during the reaction, confirming that albumin disulfide bonds are reduced in the reaction. Under aerobic conditions, the enriched Et/sub 3/PO accounts for at least 60% of the Et/sub 3/PO formed. The significance of these results for the in vivo formation of Et/sub 3/PO, an auranofin metabolite, is discussed. 25 references, 2 figures.

  9. Investigation of Oxidative Degradation in Polymers Using (17)O NMR Spectroscopy

    SciTech Connect

    Alam, Todd M.; Celina, Mathew; Assink, Roger A.; Clough, Roger L.; Gillen, Kenneth T.; Wheeler David R.

    1999-07-20

    The thermal oxidation of pentacontane (C{sub 50}H{sub 102}), and of the homopolymer polyisoprene, has been investigated using {sup 17}O NMR spectroscopy. By performing the oxidation using {sup 17}O labeled O{sub 2} gas, it is possible to easily identify degradation products, even at relatively low concentrations. It is demonstrated that details of the degradation mechanism can be obtained from analysis of the {sup 17}O NMR spectra as a function of total oxidation. Pentacontane reveals the widest variety of reaction products, and exhibits changes in the relative product distributions with increasing O{sub 2} consumption. At low levels of oxygen incorporation, peroxides are the major oxidation product, while at later stages of degradation these species are replaced by increasing concentrations of ketones, alcohols, carboxylic acids and esters. Analyzing the product distribution can help in identification of the different free-radical decomposition pathways of hydroperoxides, including recombination, proton abstraction and chain scission, as well as secondary reactions. The {sup 17}O NMR spectra of thermally oxidized polyisoprene reveal fewer degradation functionalities, but exhibit an increased complexity in the type of observed degradation species due to structural features such as unsaturation and methyl branching. Alcohols and ethers formed from hydrogen abstraction and free radical termination.

  10. Identification of different oxygen species in oxide nanostructures with (17)O solid-state NMR spectroscopy.

    PubMed

    Wang, Meng; Wu, Xin-Ping; Zheng, Sujuan; Zhao, Li; Li, Lei; Shen, Li; Gao, Yuxian; Xue, Nianhua; Guo, Xuefeng; Huang, Weixin; Gan, Zhehong; Blanc, Frédéric; Yu, Zhiwu; Ke, Xiaokang; Ding, Weiping; Gong, Xue-Qing; Grey, Clare P; Peng, Luming

    2015-02-01

    Nanostructured oxides find multiple uses in a diverse range of applications including catalysis, energy storage, and environmental management, their higher surface areas, and, in some cases, electronic properties resulting in different physical properties from their bulk counterparts. Developing structure-property relations for these materials requires a determination of surface and subsurface structure. Although microscopy plays a critical role owing to the fact that the volumes sampled by such techniques may not be representative of the whole sample, complementary characterization methods are urgently required. We develop a simple nuclear magnetic resonance (NMR) strategy to detect the first few layers of a nanomaterial, demonstrating the approach with technologically relevant ceria nanoparticles. We show that the (17)O resonances arising from the first to third surface layer oxygen ions, hydroxyl sites, and oxygen species near vacancies can be distinguished from the oxygen ions in the bulk, with higher-frequency (17)O chemical shifts being observed for the lower coordinated surface sites. H2 (17)O can be used to selectively enrich surface sites, allowing only these particular active sites to be monitored in a chemical process. (17)O NMR spectra of thermally treated nanosized ceria clearly show how different oxygen species interconvert at elevated temperature. Density functional theory calculations confirm the assignments and reveal a strong dependence of chemical shift on the nature of the surface. These results open up new strategies for characterizing nanostructured oxides and their applications. PMID:26601133

  11. Site-assignment of 17O-NMR signals in itinerant metamagnetic compound Sr 3Ru 2O 7

    NASA Astrophysics Data System (ADS)

    Kitagawa, Kentaro; Ishida, Kenji; Perry, Robin S.; Maeno, Yoshiteru

    2006-05-01

    We have performed an 17O-NMR measurement in the bilayered perovskite ruthenate Sr 3Ru 2O 7 which shows itinerant metamagnetism at low temperatures. Three oxygen sites are identified in the 17O-NMR spectrum. NMR lines arising from the outer-apical O site are observable in the vicinity of a metamagnetic quantum critical point in spite of strong spin fluctuations. The field dependence of the Knight shift scales with the bulk magnetization.

  12. Predicting (17)O NMR chemical shifts of polyoxometalates using density functional theory.

    PubMed

    Sharma, Rupali; Zhang, Jie; Ohlin, C André

    2016-03-21

    We have investigated the computation of (17)O NMR chemical shifts of a wide range of polyoxometalates using density functional theory. The effects of basis sets and exchange-correlation functionals are explored, and whereas pure DFT functionals generally predict the chemical shifts of terminal oxygen sites quite well, hybrid functionals are required for the prediction of accurate chemical shifts in conjunction with linear regression. By using PBE0/def2-tzvp//PBE0/cc-pvtz(H-Ar), lanl2dz(K-) we have computed the chemical shifts of 37 polyoxometalates, corresponding to 209 (17)O NMR signals. We also show that at this level of theory the protonation-induced pH dependence of the chemical shift of the triprotic hexaniobate Lindqvist anion, [HxNb6O19]((8-x)), can be reproduced, which suggests that hypotheses regarding loci of protonation can be confidently tested. PMID:26925832

  13. New insights into the bonding arrangements of L- and D-glutamates from solid state 17O NMR

    NASA Astrophysics Data System (ADS)

    Lemaitre, V.; Pike, K. J.; Watts, A.; Anupold, T.; Samoson, A.; Smith, M. E.; Dupree, R.

    2003-03-01

    Magic angle spinning (MAS) from L- and D-glutamic acid-HCl at 14.1 T produces highly structured and very similar NMR spectra. Lines from all 4 oxygen sites are readily distinguished and assigned. These 17O NMR spectra are very different from the previously reported 17O spectrum of the D, L-form presumably because that was a racemic crystal. 17O NMR from L-monosodium glutamate-HCl is very different again requiring the application of double angle rotation and 3 quantum MAS NMR to provide resolution of 5 different sites. Hence high resolution 17O solid state NMR techniques offer possible new insight into biochemical bonding processes.

  14. Microsolvation of methylmercury: structures, energies, bonding and NMR constants ((199)Hg, (13)C and (17)O).

    PubMed

    Flórez, Edison; Maldonado, Alejandro F; Aucar, Gustavo A; David, Jorge; Restrepo, Albeiro

    2016-01-21

    Hartree-Fock (HF) and second order perturbation theory (MP2) calculations within the scalar and full relativistic frames were carried out in order to determine the equilibrium geometries and interaction energies between cationic methylmercury (CH3Hg(+)) and up to three water molecules. A total of nine structures were obtained. Bonding properties were analyzed using the Quantum Theory of Atoms In Molecules (QTAIM). The analyses of the topology of electron densities reveal that all structures exhibit a partially covalent HgO interaction between methylmercury and one water molecule. Consideration of additional water molecules suggests that they solvate the (CH3HgOH2)(+) unit. Nuclear magnetic shielding constants σ((199)Hg), σ((13)C) and σ((17)O), as well as indirect spin-spin coupling constants J((199)Hg-(13)C), J((199)Hg-(17)O) and J((13)C-(17)O), were calculated for each one of the geometries. Thermodynamic stability and the values of NMR constants correlate with the ability of the system to directly coordinate oxygen atoms of water molecules to the mercury atom in methylmercury and with the formation of hydrogen bonds among solvating water molecules. Relativistic effects account for 11% on σ((13)C) and 14% on σ((17)O), which is due to the presence of Hg (heavy atom on light atom, HALA effect), while the relativistic effects on σ((199)Hg) are close to 50% (heavy atom on heavy atom itself, HAHA effect). J-coupling constants are highly influenced by relativity when mercury is involved as in J((199)Hg-(13)C) and J((199)Hg-(17)O). On the other hand, our results show that the values of NMR constants for carbon and oxygen, atoms which are connected through mercury (C-HgO), are highly correlated and are greatly influenced by the presence of water molecules. Water molecules introduce additional electronic effects to the relativistic effects due to the mercury atom. PMID:26670708

  15. Identification of different oxygen species in oxide nanostructures with 17O solid-state NMR spectroscopy

    PubMed Central

    Wang, Meng; Wu, Xin-Ping; Zheng, Sujuan; Zhao, Li; Li, Lei; Shen, Li; Gao, Yuxian; Xue, Nianhua; Guo, Xuefeng; Huang, Weixin; Gan, Zhehong; Blanc, Frédéric; Yu, Zhiwu; Ke, Xiaokang; Ding, Weiping; Gong, Xue-Qing; Grey, Clare P.; Peng, Luming

    2015-01-01

    Nanostructured oxides find multiple uses in a diverse range of applications including catalysis, energy storage, and environmental management, their higher surface areas, and, in some cases, electronic properties resulting in different physical properties from their bulk counterparts. Developing structure-property relations for these materials requires a determination of surface and subsurface structure. Although microscopy plays a critical role owing to the fact that the volumes sampled by such techniques may not be representative of the whole sample, complementary characterization methods are urgently required. We develop a simple nuclear magnetic resonance (NMR) strategy to detect the first few layers of a nanomaterial, demonstrating the approach with technologically relevant ceria nanoparticles. We show that the 17O resonances arising from the first to third surface layer oxygen ions, hydroxyl sites, and oxygen species near vacancies can be distinguished from the oxygen ions in the bulk, with higher-frequency 17O chemical shifts being observed for the lower coordinated surface sites. H217O can be used to selectively enrich surface sites, allowing only these particular active sites to be monitored in a chemical process. 17O NMR spectra of thermally treated nanosized ceria clearly show how different oxygen species interconvert at elevated temperature. Density functional theory calculations confirm the assignments and reveal a strong dependence of chemical shift on the nature of the surface. These results open up new strategies for characterizing nanostructured oxides and their applications. PMID:26601133

  16. 17O-NMR Knight shift study of the interplay between superconductivity and pseudogap in (CaxLa1-x)(Ba1.75-xLa0.25+x)Cu3Oy

    NASA Astrophysics Data System (ADS)

    Cvitanić, T.; Pelc, D.; Požek, M.; Amit, E.; Keren, A.

    2014-08-01

    We report systematic 17O-NMR measurements on the high-Tc cuprate (CaxLa1-x)(Ba1.75-xLa0.25+x)Cu3Oy, for four different families (different x). Using Knight shift data, we show that the pseudogap opening temperature T* is much higher than Tc near optimal doping, unlike structurally similar YBCO. In addition, at constant doping the pseudogap temperature does not vary with x, in contrast to Tc. This puts constraints on the nature of the pseudogap and position of the quantum critical point inside the superconducting dome.

  17. Toward Relatively General and Accurate Quantum Chemical Predictions of Solid-State 17O NMR Chemical Shifts in Various Biologically Relevant Oxygen-containing Compounds

    PubMed Central

    Rorick, Amber; Michael, Matthew A.; Yang, Liu; Zhang, Yong

    2015-01-01

    Oxygen is an important element in most biologically significant molecules and experimental solid-state 17O NMR studies have provided numerous useful structural probes to study these systems. However, computational predictions of solid-state 17O NMR chemical shift tensor properties are still challenging in many cases and in particular each of the prior computational work is basically limited to one type of oxygen-containing systems. This work provides the first systematic study of the effects of geometry refinement, method and basis sets for metal and non-metal elements in both geometry optimization and NMR property calculations of some biologically relevant oxygen-containing compounds with a good variety of XO bonding groups, X= H, C, N, P, and metal. The experimental range studied is of 1455 ppm, a major part of the reported 17O NMR chemical shifts in organic and organometallic compounds. A number of computational factors towards relatively general and accurate predictions of 17O NMR chemical shifts were studied to provide helpful and detailed suggestions for future work. For the studied various kinds of oxygen-containing compounds, the best computational approach results in a theory-versus-experiment correlation coefficient R2 of 0.9880 and mean absolute deviation of 13 ppm (1.9% of the experimental range) for isotropic NMR shifts and R2 of 0.9926 for all shift tensor properties. These results shall facilitate future computational studies of 17O NMR chemical shifts in many biologically relevant systems, and the high accuracy may also help refinement and determination of active-site structures of some oxygen-containing substrate bound proteins. PMID:26274812

  18. Probing surface hydrogen bonding and dynamics by natural abundance, multidimensional, 17O DNP-NMR spectroscopy

    DOE PAGESBeta

    Perras, Frederic A.; Chaudhary, Umesh; Slowing, Igor I.; Pruski, Marek

    2016-05-06

    Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR) spectroscopy is increasingly being used as a tool for the atomic-level characterization of surface sites. DNP surface-enhanced SSNMR spectroscopy of materials has, however, been limited to studying relatively receptive nuclei, and the particularly rare 17O nuclide, which is of great interest for materials science, has not been utilized. We demonstrate that advanced 17O SSNMR experiments can be performed on surface species at natural isotopic abundance using DNP. We use 17O DNP surface-enhanced 2D SSNMR to measure 17O{1H} HETCOR spectra as well as dipolar oscillations on a series of thermally treatedmore » mesoporous silica nanoparticle samples having different pore diameters. These experiments allow for a nonintrusive and unambiguous characterization of hydrogen bonding and dynamics at the surface of the material; no other single experiment can give such details about the interactions at the surface. Lastly, our data show that, upon drying, strongly hydrogen-bonded surface silanols, whose motions are greatly restricted by the interaction when compared to lone silanols, are selectively dehydroxylated.« less

  19. Physicochemical characterization of the dimeric lanthanide complexes [en{Ln(DO3A)(H2O)}2] and [pi{Ln(DTTA)(H2O)}2]2-: a variable-temperature 17O NMR study.

    PubMed

    Lee, Tzu-Ming; Cheng, Tsan-Hwang; Ou, Ming-Hung; Chang, C Allen; Liu, Gin-Chung; Wang, Yun-Ming

    2004-03-01

    The Gd(III) complexes of the two dimeric ligands [en(DO3A)2] {N,N'-bis[1,4,7-tris(carboxymethyl)-1,4,7,10-tetraazacyclododecan-10-yl-methylcarbonyl]-N,N'-ethylenediamine} and [pi(DTTA)2]8- [bisdiethylenetriaminepentaacetic acid (trans-1,2-cyclohexanediamine)] were synthesized and characterized. The 17O NMR chemical shift of H2O induced by [en{Dy(DO3A)}2] and [pi{Dy(DTTA)}2]2- at pH 6.80 proved the presence of 2.1 and 2.2 inner-sphere water molecules, respectively. Water proton spin-lattice relaxation rates for [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H2O)}2]2- at 37.0 +/- 0.1 degrees C and 20 MHz are 3.60 +/- 0.05 and 5.25 +/- 0.05 mM(-1) s(-1) per Gd, respectively. The EPR transverse electronic relaxation rate and 17O NMR transverse relaxation time for the exchange lifetime of the coordinated H2O molecule and the 2H NMR longitudinal relaxation rate of the deuterated diamagnetic lanthanum complex for the rotational correlation time were thoroughly investigated, and the results were compared with those reported previously for other lanthanide(III) complexes. The exchange lifetimes for [en{Gd(DO3A)(H2O)}2] (769 +/- 10 ns) and [pi{Gd(DTTA)(H2O)}2]2- (910 +/- 10 ns) are significantly higher than those of [Gd(DOTA)(H2O)]- (243 ns) and [Gd(DTPA)(H2O)]2- (303 ns) complexes. The rotational correlation times for [en{Gd(DO3A)(H2O)}2] (150 +/- 11 ps) and [pi{Gd(DTTA)(H2O)}2]2- (130 +/- 12 ps) are slightly greater than those of [Gd(DOTA)(H2O)]- (77 ps) and [Gd(DTPA)(H2O)]2- (58 ps) complexes. The marked increase in relaxivity (r1) of [en{Gd(DO3A)(H2O)}2] and [pi{Gd(DTTA)(H2O)}2]2- result mainly from their longer rotational correlation time and higher molecular weight. PMID:14971018

  20. Computational 17O-NMR spectroscopy of organic acids and peracids: comparison of solvation models.

    PubMed

    Baggioli, Alberto; Crescenzi, Orlando; Field, Martin J; Castiglione, Franca; Raos, Guido

    2013-01-28

    We examine several computational strategies for the prediction of the (17)O-NMR shielding constants for a selection of organic acids and peracids in aqueous solution. In particular, we consider water (the solvent and reference for the chemical shifts), hydrogen peroxide, acetic acid, lactic acid and peracetic acid. First of all, we demonstrate that the PBE0 density functional in combination with the 6-311+G(d,p) basis set provides an excellent compromise between computational cost and accuracy in the calculation of the shielding constants. Next, we move on to the problem of the solvent representation. Our results confirm the shortcomings of the Polarizable Continuum Model (PCM) in the description of systems susceptible to strong hydrogen bonding interactions, while at the same time they demonstrate its usefulness within a molecular-continuum approach, whereby PCM is applied to describe the solvation of the solute surrounded by some explicit solvent molecules. We examine different models of the solvation shells, sampling their configurations using both energy minimizations of finite clusters and molecular dynamics simulations of bulk systems. Hybrid molecular dynamics simulations, in which the solute is described at the PM6 semiempirical level and the solvent by the TIP3P model, prove to be a promising sampling method for medium-to-large sized systems. The roles of solvent shell size and structure are also briefly discussed. PMID:23223608

  1. Correlations between 29Si, 17O and 1H NMR properties and local structures in silicates: an ab initio calculation

    NASA Astrophysics Data System (ADS)

    Xue, X.; Kanzaki, M.

    In order to gain insight into the correlations between 29Si, 17O and 1H NMR properties (chemical shift and quadrupolar coupling parameters) and local structures in silicates, ab initio self-consistent field Hartree-Fock molecular orbital calculations have been carried out on silicate clusters of various polymerizations and intertetrahedral (Si-O-Si) angles. These include Si(OH)4 monomers (isolated as well as interacting), Si2O(OH)6 dimers (C2 symmetry) with the Si-O-Si angle fixed at 5° intervals from 120° to 180°, Si3O2(OH)8 linear trimers (C2 symmetry) with varying Si-O-Si angles, Si3O3(OH)6 three-membered rings (D3 and C1 symmetries), Si4O4(OH)8 four-membered ring (C4 symmetry) and Si8O12(OH)8 octamer (D4 symmetry). The calculated 29Si, 17O and 1H isotropic chemical shifts (δiSi, δiO and δiH) for these clusters are all close to experimental NMR data for similar local structures in crystalline silicates. The calculated 17O quadrupolar coupling constants (QCC) of the bridging oxygens (Si-O-Si) are also in good agreement with experimental data. The calculated 17O QCC of silanols (Si-O-H) are much larger than those of the bridging oxygens, but unfortunately there are no experimental data for similar groups in well-characterized crystalline phases for comparison. There is a good correlation between δiSi and the mean Si-O-Si angle for both Q1 and Q2, where Qn denotes Si with n other tetrahedral Si next-nearest neighbors. Both the δiO and the 17O electric field gradient asymmetry parameter, η of the bridging oxygens have been found to depend strongly on the O site symmetry, in addition to the Si-O-Si angle. On the other hand, the 17O QCC seems to be influenced little by structural parameters other than the Si-O-Si angle, and is thus expected to be the most reliable 17O NMR parameter that can be used to decipher Si-O-Si angle distribution information. Both the 17O QCC and the 2H QCC of silanols decrease with decreasing length of hydrogen bond to a second O atom

  2. Probing Oxide-Ion Mobility in the Mixed Ionic-Electronic Conductor La2NiO4+δ by Solid-State (17)O MAS NMR Spectroscopy.

    PubMed

    Halat, David M; Dervişoğlu, Rıza; Kim, Gunwoo; Dunstan, Matthew T; Blanc, Frédéric; Middlemiss, Derek S; Grey, Clare P

    2016-09-14

    While solid-state NMR spectroscopic techniques have helped clarify the local structure and dynamics of ionic conductors, similar studies of mixed ionic-electronic conductors (MIECs) have been hampered by the paramagnetic behavior of these systems. Here we report high-resolution (17)O (I = 5/2) solid-state NMR spectra of the mixed-conducting solid oxide fuel cell (SOFC) cathode material La2NiO4+δ, a paramagnetic transition-metal oxide. Three distinct oxygen environments (equatorial, axial, and interstitial) can be assigned on the basis of hyperfine (Fermi contact) shifts and quadrupolar nutation behavior, aided by results from periodic DFT calculations. Distinct structural distortions among the axial sites, arising from the nonstoichiometric incorporation of interstitial oxygen, can be resolved by advanced magic angle turning and phase-adjusted sideband separation (MATPASS) NMR experiments. Finally, variable-temperature spectra reveal the onset of rapid interstitial oxide motion and exchange with axial sites at ∼130 °C, associated with the reported orthorhombic-to-tetragonal phase transition of La2NiO4+δ. From the variable-temperature spectra, we develop a model of oxide-ion dynamics on the spectral time scale that accounts for motional differences of all distinct oxygen sites. Though we treat La2NiO4+δ as a model system for a combined paramagnetic (17)O NMR and DFT methodology, the approach presented herein should prove applicable to MIECs and other functionally important paramagnetic oxides. PMID:27538437

  3. Study of {sup 17}O(p,{alpha}){sup 14}N reaction via the Trojan Horse Method for application to {sup 17}O nucleosynthesis

    SciTech Connect

    Sergi, M. L.; Spitaleri, C.; Pizzone, R. G.; Gulino, M.; Cherubini, S.; Crucilla, V.; La Cognata, M.; Lamia, L.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Tudisco, S.; Tumino, A.; Coc, A.; Hammache, F.; Sereville, N. de; Kiss, G.

    2008-05-21

    Because of the still present uncertainties on its rate, the {sup 17}O(p,{alpha}){sup 14}N is one of the most important reaction to be studied in order to get more information about the fate of {sup 17}O in different astrophysical scenarios. The preliminary study of the three-body reaction {sup 2}H({sup 17}O,{alpha}{sup 14}N)n is presented here as a first stage of the indirect study of this important {sup 17}O(p,{alpha}){sup 14}N reaction through the Trojan Horse Method (THM)

  4. Constraining 17O and 27Al NMR spectra of high-pressure crystals and glasses: New data for jadeite, pyrope, grossular, and mullite

    USGS Publications Warehouse

    Kelsey, K.E.; Stebbins, J.F.; Du, L.-S.; Hankins, B.

    2007-01-01

    The 17O NMR spectra of glasses quenched from melts at high pressure are often difficult to interpret due to overlapping peaks and lack of crystalline model compounds. High-pressure aluminosilicate glasses often contain significant amounts of [5]Al and [6]Al, thus these high-pressure glasses must contain oxygen bonded to high-coordinated aluminum. The 17O NMR parameters for the minerals jadeite, pyrope, grossular, and mullite are presented to assist interpretation of glass spectra and to help test quantum chemical calculations. The 17O NMR parameters for jadeite and grossular support previous peak assignments of oxygen bonded to Si and high-coordinated Al in high-pressure glasses as well as quantum chemical calculations. The oxygen tricluster in mullite is very similar to the previously observed tricluster in grossite (CaAl4 O7) and suspected triclusters in glasses. We also present 27Al NMR spectra for pyrope, grossular, and mullite.

  5. Vortex Lattice Formation in High Magnetic Fields in an Underdoped Single Crystal of Hg1201 from 17O NMR

    NASA Astrophysics Data System (ADS)

    Lee, Jeongseop; Xin, Yizhou; Halperin, W. P.; Reyes, A. P.; Kuhns, P. L.

    The vortex lattice in HgBa2CuO4+δ forms at a vortex melting temperature, Tv, typically ~40K for underdoped crystals with a hole doping ~ 0.11. We present our results from 17O NMR for investigation of the vortex lattice as a function of external magnetic field up to 30 T and temperature as low as 5 K. The vortex contribution to the NMR linewidth can be separated from inhomogeneous broadening by deconvolution of the normal state spectra which was measured separately above, Tv. The vortex melting temperature was measured for two underdoped samples marked by the onset of extra linewidth broadening due to the inhomogeneous magnetic field distribution from the solid vortex lattice consistent with transverse relaxation measurements. We have found evidence for a change in the vortex lattice symmetry as a function of external fields. This work was supported by the DOE BES under Grant No. DE-FG02-05ER46248 and the NHMFL through the NSF and State of Florida.

  6. Experimental Study of 17O(p,{alpha})14N and 17O(p,{gamma})18F for Classical Nova Nucleosynthesis

    SciTech Connect

    Chafa, A.; Ouichaoui, S.; Tatischeff, V.; Coc, A.; Garrido, F.; Kiener, J.; Lefebvre-Schuhl, A.; Thibaud, J.-P.; Aguer, P.; Barhoumi, S.; Hernanz, M.; Jose, J.; Sereville, N. de

    2006-04-26

    We investigated the proton-capture reactions on 17O occurring in classical nova explosions. We observed a previously undiscovered resonance at E{sub R}{sup lab}=194.1{+-}0.6 keV in the 17O(p,{alpha})14N reaction, with a measured resonance strength {omega}{gamma}p{alpha}=1.6{+-}0.2 meV. We studied in the same experiment the 17O(p,{gamma})18F reaction by an activation method and the resonance-strength ratio was found to be {omega}{gamma}p{alpha}/{omega}{gamma}p{gamma}=470{+-}50. The corresponding excitation energy in the 18F compound nucleus was determined to be 5789.8{+-}0.3 keV by {gamma}-ray measurements using the 14N({alpha},{gamma})18F reaction. These new resonance properties have important consequences for 17O nucleosynthesis and {gamma}-ray astronomy of classical novae.

  7. Enrichment of H(2)(17)O from tap water, characterization of the enriched water, and properties of several (17)O-labeled compounds.

    PubMed

    Prasad, Brinda; Lewis, Andrew R; Plettner, Erika

    2011-01-01

    A low-abundance form of water, H(2)(17)O, was enriched from 0.04% to ∼90% by slow evaporation and fractional distillation of tap water. The density and refractive index for H(2)(17)O are reported. Gas chromatography-mass spectrometry (GC-MS) of (16)O- and (17)O-1-hexanols and their trimethyl silyl ethers and of (16)O- and (17)O-hexamethyl disiloxanes was used to determine the percentage of (17)O enrichment in the H(2)(17)O. Furthermore, the chemical shifts of labeled and nonlabeled water dissolved in CDCl(3) differed sufficiently that we could verify the enrichment of H(2)(17)O. (17)O hexanol was synthesized by the reaction of iodohexane with Na(17)OH. (17)O-Labeled trimethylsilanol and (17)O-labeled hexamethyldisiloxane were prepared by the reaction of H(2)(17)O with bis(trimethylsilyl)trifluoroacetamide (BSTFA). To generate standards for (17)O NMR, H(2)(17)O(2), and (17)O camphor were prepared. H(2)(17)O was electrolyzed to form (17)O-labeled hydrogen peroxide which was quantified using two colorimetric assays. (17)O-Labeled camphor was prepared by exchanging the ketone oxygen of camphor using H(2)(17)O. The (17)O-labeled compounds were characterized using (17)O, (1)H, and (13)C NMR and GC-MS. While we were characterizing the labeled camphor, we also detected an unexpected oxygen exchange reaction of primary alcohols, catalyzed by electrophilic ketones such as camphor. The reaction is a displacement of the alcohol OH group by water. This is an example of the usefulness of (17)O NMR in the study of a reaction mechanism that has not been noticed previously. PMID:21128590

  8. Natural abundance 17O nuclear magnetic resonance and computational modeling studies of lithium based liquid electrolytes

    NASA Astrophysics Data System (ADS)

    Deng, Xuchu; Hu, Mary Y.; Wei, Xiaoliang; Wang, Wei; Chen, Zhong; Liu, Jun; Hu, Jian Zhi

    2015-07-01

    Natural abundance 17O NMR measurements were conducted on electrolyte solutions consisting of Li[CF3SO2NSO2CF3] (LiTFSI) dissolved in the solvents of ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and their mixtures at various concentrations. It was observed that 17O chemical shifts of solvent molecules change with the concentration of LiTFSI. The chemical shift displacements of carbonyl oxygen are evidently greater than those of ethereal oxygen, strongly indicating that Li+ ion is coordinated with carbonyl oxygen rather than ethereal oxygen. To understand the detailed molecular interaction, computational modeling of 17O chemical shifts was carried out on proposed solvation structures. By comparing the predicted chemical shifts with the experimental values, it is found that a Li+ ion is coordinated with four double bond oxygen atoms from EC, PC, EMC and TFSI- anion. In the case of excessive amount of solvents of EC, PC and EMC the Li+ coordinated solvent molecules are undergoing quick exchange with bulk solvent molecules, resulting in average 17O chemical shifts. Several kinds of solvation structures are identified, where the proportion of each structure in the liquid electrolytes investigated depends on the concentration of LiTFSI.

  9. Natural Abundance 17O Nuclear Magnetic Resonance and Computational Modeling Studies of Lithium Based Liquid Electrolytes

    SciTech Connect

    Deng, Xuchu; Hu, Mary Y.; Wei, Xiaoliang; Wang, Wei; Chen, Zhong; Liu, Jun; Hu, Jian Z.

    2015-07-01

    Natural abundance 17O NMR measurements were conducted on electrolyte solutions consisting of Li[CF3SO2NSO2CF3] (LiTFSI) dissolved in the solvents of ethylene carbonate (EC), propylene carbonate (PC), ethyl methyl carbonate (EMC), and their mixtures at various concentrations. It was observed that 17O chemical shifts of solvent molecules change with the concentration of LiTFSI. The chemical shift displacements of carbonyl oxygen are evidently greater than those of ethereal oxygen, strongly indicating that Li+ ion is coordinated with carbonyl oxygen rather than ethereal oxygen. To understand the detailed molecular interaction, computational modeling of 17O chemical shifts was carried out on proposed solvation structures. By comparing the predicted chemical shifts with the experimental values, it is found that a Li+ ion is coordinated with four double bond oxygen atoms from EC, PC, EMC and TFSI- anion. In the case of excessive amount of solvents of EC, PC and EMC the Li+ coordinated solvent molecules are undergoing quick exchange with bulk solvent molecules, resulting in average 17O chemical shifts. Several kinds of solvation structures are identified, where the proportion of each structure in the liquid electrolytes investigated depends on the concentration of LiTFSI.

  10. sup 17 O nuclear-magnetic-resonance spectroscopic study of high- T sub c superconductors

    SciTech Connect

    Oldfield, E.; Coretsopoulos, C.; Yang, S.; Reven, L.; Lee, H.C.; Shore, J.; Han, O.H.; Ramli, E. Materials Research Laboratory, University of Illinois at Urbana; Hinks, D.

    1989-10-01

    We have obtained solid-state {sup 17}O NMR spectra of a number of {sup 17}O-enriched oxides and high-temperature oxide superconductors, including Cu{sub 2}{sup I}O, Cu{sup II}O, KCu{sup III}O{sub 2}, Bi{sub 2}O{sub 3}, Tl{sub 2}O{sub 3}, La{sub 1.85}Sr{sub 0.15}CuO{sub 4}, YBa{sub 2}Cu{sub 3}O{sub 7{minus}{ital x}}, Bi{sub 2}Sr{sub 2}CaCu{sub 2}O{sub 8+{ital x}}, Tl{sub 2}Ba{sub 2}CaCu{sub 2}O{sub 8+{ital x}}, and Ba{sub 0.6}K{sub 0.4}BiO{sub 3}. Spectra of all of the simple diamagnetic oxides contain relatively sharp resonances in a diamagnetic'' region of {similar to}{minus}200 to +700 ppm (from H{sub 2}O, International Union of Pure and Applied Chemistry {delta} scale). Cu{sup II}O exhibits a broad resonance centered at {similar to}4500 ppm.

  11. The relationship between environmental abundant electromagnetic fields and packaging shape to their effects on the 17O NMR and Raman spectra of H2O-NaCl

    NASA Astrophysics Data System (ADS)

    Abdelsamie, Maher A. A.; Rahman, Russly B. Abdul; Mustafa, Shuhaimi; Hashim, Dzulkifly

    2015-07-01

    In this study, two identical groups of four containers with different packaging shapes made of polymethyl methacrylate (PMMA) were used to store H2O-NaCl solution for seven days at ambient room temperature (25 °C). Faraday shield was used to shield one group. The surrounding electromagnetic fields were measured during the storage period by using R&S®TS-EMF EMF measurement system. Samples of H2O-NaCl were collected at the end of the storage period and examined by 17Oxygene nuclear magnetic resonance spectroscopy (17O NMR) and Raman spectroscopy. Electromagnetic simulation was used to explore the relationship between the packaging shape of H2O-NaCl containers and the environmentally abundant electromagnetic fields to their effects on the cluster size of water. The study showed variations in the cluster size of water stored inside the two groups of containers. It was observed that the cluster size of water stored in the unshielded containers was lower than that of the shielded containers. The cluster size of water stored in the unshielded pyramidal container was lower than the cluster size of water stored in the unshielded rectangular, square, and cylindrical containers. The EM simulation results showed significant variations in the total specific absorption rate SAR and maximum point SAR values induced in the H2O-NaCl solution in the unshielded container models at 2400 MHz for both vertical and horizontal polarization. It can be concluded that the variations in the values of SAR induced in H2O-NaCl solution are directly related to the variations in the cluster size of the stored water.

  12. Study of the soft dipole modes in 140Ce via inelastic scattering of 17O

    NASA Astrophysics Data System (ADS)

    Krzysiek, M.; Kmiecik, M.; Maj, A.; Bednarczyk, P.; Ciemała, M.; Fornal, B.; Grȩbosz, J.; Mazurek, K.; Mȩczyński, W.; Ziȩbliński, M.; Crespi, F. C. L.; Bracco, A.; Benzoni, G.; Blasi, N.; Boiano, C.; Bottoni, S.; Brambilla, S.; Camera, F.; Giaz, A.; Leoni, S.; Million, B.; Morales, A. I.; Nicolini, R.; Pellegri, L.; Riboldi, S.; Vandone, V.; Wieland, O.; De Angelis, G.; Napoli, D. R.; Valiente-Dobon, J. J.; Bazzacco, D.; Farnea, E.; Gottardo, A.; Lenzi, S.; Lunardi, S.; Mengoni, D.; Michelagnoli, C.; Recchia, F.; Ur, C.; Gadea, A.; Huyuk, T.; Barrientos, D.; Birkenbach, B.; Geibel, K.; Hess, H.; Reiter, P.; Steinbach, T.; Wiens, A.; Bürger, A.; Görgen, A.; Guttormsen, M.; Larsen, A. C.; Siem, S.

    2014-05-01

    The main aim of this study was a deeper understanding of the nuclear structure properties of the soft dipole modes in 140Ce, excited via inelastic scattering of weakly bound 17O projectiles. An important aim was to investigate the ‘splitting’ of the PDR into two parts: a low-energy isoscalar component dominated by neutron-skin oscillations and a higher-energy component lying on the tail of the giant dipole resonance of a rather isovector character. This was already observed for this nucleus, investigated in (α, α‧) and (γ, γ‧) experiments. The experiment was performed at Laboratori Nazionali di Legnaro, Italy. Inelastic scattering of 17O ion beam at 20 MeV A-1 was used to excite the resonance modes in the 140Ce target. Gamma-rays were registered by five triple clusters of AGATA-Demonstrator and nine large volume scintillators (LaBr3). The scattered 17O ions were identified by two ΔE - E Si telescopes of the TRACE array mounted inside the scattering chamber. The telescopes consisted of two segmented Si-pad detectors, each of 60 pixels. Very preliminary data have shown a strong domination of the E1 transitions in the ‘pygmy’ region with a character more similar to the one obtained in alpha scattering experiment.

  13. /sup 17/O NMR spectroscopy of magnetically ordered YBa/sub 2/Cu/sub 3/O/sub 7-//sub x/ microcrystals

    SciTech Connect

    Coretsopoulos, C.; Lee, H.C.; Ramli, E.; Reven, L.; Rauchfuss, T.B.; Oldfield, E.

    1989-01-01

    We have obtained /sup 17/O NMR spectra of powder samples of YBa/sub 2/Cu/sub 3/O/sub 7-//sub x/ and EuBa/sub 2/Cu/sub 3/O/sub 7-//sub x/, as well as magnetically ordered YBa/sub 2/Cu/sub 3/O/sub 7-//sub x/. Two major features are observed in YBa/sub 2/Cu/sub 3/O/sub 7-//sub x/: a sharp resonance at approx. =1800 ppm (from external H/sub 2//sup 17/O, International Union of Pure and Applied Chemistry delta scale) and a broader series of features centered at approx. =400 ppm. The 1800-ppm feature undergoes a diamagnetic shift of approx. =800 ppm on cooling to 77 K, and a similar magnitude shift on Eu substitution, suggesting assignment to the plane oxygens, O(2,3). Measurements on magnetically ordered samples at 8.45 and 11.7 T give the magnitude of the diagonal terms of the electric field gradient tensor, which are 2.3, 3.5, and 5.8 MHz. For the columnar oxygen, O(1), we find e/sup 2/qQ/h = 7.7 MHz, with a chemical shift anisotropy of approx. =660 ppm.

  14. Rate of water exchange between Al(C 2O 4)(H 2O) 4+(aq) complexes and aqueous solutions determined by 17O-NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Phillips, Brian L.; Crawford, Susan Neugebauer; Casey, William H.

    1997-12-01

    Substitution of an oxalate molecule for two inner-coordination-sphere waters of Al(H 2O) 63+(aq) enhances, by a factor of ≈ 10 2, the rate of exchange of water molecules from the innercoordination sphere to the bulk solution. The rate parameters for chemical exchange are: k ex298 = 109 s -1, ΔH ‡ = 68.9 ± 2.4 kJ/mol, and ΔS ‡ = 25.3 ± 6.7 J/mol/K, measured via dynamic 17O-NMR. This reactivity enhancement of coordinated waters by oxalate results from a change in bonding between Al(III) and oxygens throughout the complex upon ligation by oxalate. A similar process has been proposed to explain ligand-enhanced dissolution of oxide minerals (e.g., Stumm, 1991; Casey and Ludwig, 1995; Phillips et al., 1997) where a stable adsorbate increases the flux of metals from a surface. These new rate coefficients for aluminum-oxalate complexes, along with previous work on aluminum-fluoride complexes, show a correlation with the respective equilibrium constants similar to that obtained by Ludwig et al. (1995, 1996).

  15. Resonance Strength Measurement at Astrophysical Energies: The 17O(p,α)14N Reaction Studied via THM

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Rapisarda, G. G.; Mukhamedzhanov, A.; Irgaziev, B.; Tang, X. D.; Wischer, M.; Mrazek, J.; Kroha, V.

    2016-05-01

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on 17O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the 17O(p,α)14N reaction via the Trojan Horse Method by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. The mean value of the strengths obtained in the two measurements was calculated and compared with the direct data available in literature.

  16. Resonance strength measurement at astrophysical energies: The 17O(p,α)14N reaction studied via Trojan Horse Method

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Rapisarda, G. G.; Mukhamedzhanov, A.; Irgaziev, B.; Tang, X. D.; Wiescher, M.; Mrazek, J.; Kroha, V.

    2015-10-01

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on 17O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the 17O(p,α)14N reaction via the THM by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. Two measurements will be described and the experimental THM cross sections will be shown for both experiments.

  17. 224} studied by NMR

    SciTech Connect

    Furukawa, Y; Fang, X; Kögerler, P

    2014-05-14

    7Li nuclear magnetic resonance (NMR) studies have been performed to investigate magnetic properties and spin dynamics of Mn3+ (S = 2) spins in the giant polyoxometalate molecule {Mn40W224}. The 7Li-NMR line width is proportional to the external magnetic field H as expected in a paramagnetic state above 3 K. Below this temperature the line width shows a sudden increase and is almost independent of H, which indicates freezing of the local Mn3+ spins. The temperature dependence of T1 for both 1H and 7Li reveals slow spin dynamics at low temperatures, consistent with spin freezing. The slow spin dynamics is also evidenced by the observation of a peak of 1/T2 around 3 K, where the fluctuation frequency of spins is of the order of ~200 kHz. An explicit form of the temperature dependence of the fluctuation frequency of Mn3+ spins is derived from the nuclear relaxation data.

  18. NMR Studies of Peroxidases.

    NASA Astrophysics Data System (ADS)

    Veitch, Nigel Charles

    Available from UMI in association with The British Library. Requires signed TDF. Peroxidases are a haem-containing group of enzymes with a wide diversity of function within biological systems. While a common characteristic is the ability to catalyse the conversion of hydrogen peroxide to water, it is the accompanying processes of hormone synthesis and degradation which have generated such a high level of interest. However, information at the molecular level is limited to a single well-resolved crystal structure, that of yeast cytochrome c peroxidase. This thesis presents a strategy for the investigation of peroxidase structure and function based on proton nuclear magnetic resonance spectroscopy, a technique which has the ability to address aspects of both protein structure and protein dynamics in solution. The application of one- and two-dimensional NMR techniques has been developed in the context of plant peroxidases, notably the isoenzyme HRP-C derived from the horseradish root. Characterisation of the proton NMR spectra of HRP -C in resting and ligated states provided new information enabling the structure of the binding site for aromatic donor molecules, such as indole-3-propionic, ferulic and benzhydroxamic acids, to be resolved. In order to overcome difficulties encountered with a protein of the complexity of peroxidase, additional information was obtained from chemical shift parameters and the use of peroxidase variants produced by site-directed mutagenesis. A comparative study using NMR spectroscopy was undertaken for wild-type recombinant HRP-C expressed in Escherichia coli, and two protein variants with substitutions made to residues located on the distal side of the haem pocket, Phe41 to Val and Arg38 to Lys. NMR analyses of a plant peroxidase from barley grains and the fungal peroxidase from Coprinus cinereus were also successful using methods conceived with HRP-C. Examination of three specifically constructed recombinant protein variants of C. cinereus

  19. Local moment and inhomogeneous hyperfine interaction in the CuO2 plane of Bi2Sr2CaCu2O8+δ (Bi2212) single crystal by ^17O NMR

    NASA Astrophysics Data System (ADS)

    Chen, Bo; Mukhopadhyay, Sutirtha; Halperin, William

    2007-03-01

    The ^17O NMR spectra of Bi2Sr2CaCu2O8+δ (Bi2212) single crystals were measured in the magnetic field of 8 T from 4 K to 200 K. The linewidth of the oxygen in CuO2 plane, O(1), was found to follow a Curie temperature dependence in the normal state, where the Curie coefficient decreases with the increase of δ oxygen in the crystal. In the superconductive state, it decreases with deceasing temperature, proportional to the decreasing Knight shift. This temperature dependence of the linewidth identifies the existence of local moment and inhomogeneous hyperfine interaction in the CuO2 plane.

  20. Application of the Trojan Horse Method to study neutron induced reactions: the 17O(n, α)14C reaction

    NASA Astrophysics Data System (ADS)

    Gulino, M.; Spitaleri, C.; Tang, X. D.; Guardo, G. L.; Lamia, L.; Cherubini, S.; Bucher, B.; Burjan, V.; Couder, M.; Davies, P.; deBoer, R.; Fang, X.; Goldberg, V. Z.; Hons, Z.; Kroha, V.; Lamm, L.; La Cognata, M.; Li, C.; Ma, C.; Mrazek, J.; Mukhamedzhanov, A. M.; Notani, M.; O'Brien, S.; Pizzone, R. G.; Rapisarda, G. G.; Roberson, D.; Sergi, M. L.; Tan, W.; Thompson, I. J.; Wiescher, M.

    2014-03-01

    The reaction 17O(n, α)14C was studied using virtual neutrons coming from the quasi-free deuteron break-up in the three body reaction 17O+d → α+14C+p. This technique, called virtual neutron method, extends the Trojan Horse method to neutron-induced reactions allowing to study the reaction cross section avoiding the suppression effects coming from the penetrability of the centrifugal barrier. For incident neutron energies from thermal up to a few hundred keV, direct experiments have shown the population of two out of three expected excited states at energies 8213 keV and 8282 keV and the influence of the sub-threshold level at 8038 keV. In the present experiment the 18O excited state at E* = 8.125 MeV, missing in the direct measurement, is observed. The angular distributions of the populated resonances have been measured for the first time. The results unambiguously indicate the ability of the method to overcome the centrifugal barrier suppression effect and to pick out the contribution of the bare nuclear interaction.

  1. Study of the 17O(n,α)14C reaction: Extension of the Trojan Horse Method to neutron induced reactions

    NASA Astrophysics Data System (ADS)

    Guardo, G. L.; Lamia, L.; Spitaleri, C.; Gulino, M.; Tang, X. D.; Bucher, B.; Burjan, V.; Cherubini, S.; Couder, M.; Davies, P.; deBoer*, R.; Fang, X.; Goldberg, V. Z.; Hons, Z.; Kroha, V.; Lamm, L.; La Cognata, M.; Li, C.; Ma, C.; Mrazek, J.; Mukhamedzhanov, A. M.; Notani, M.; OBrien, S.; Pizzone, R. G.; Rapisarda, G. G.; Roberson, D.; Sergi, M. L.; Tan, W.; Thompson, I. J.; Wiescher, M.

    2014-05-01

    The experimental study of the 17O(n,α)14C reaction has been performed in the energy range 0-350 keV. This reaction could play an important role in explaining heavy elements (s-process) nucleosynthesis in various astrophysical scenario. To overcome the practical problems arising from the neutrons production, a new application of the Trojan Horse Method has been recently suggested. In more details, the 17O(n,α)14C reaction has been studied using the quasi-free 2H(17O,α14C)1H reaction, induced at an energy of 43.5 MeV. The measurement allows one to investigate the ℓ=3, 75 keV resonance (E*=8.125 MeV, Jπ=5-), absent in the available direct measurements because of centrifugal suppression effects.

  2. Study of the {sup 17}O(n,α){sup 14}C reaction: Extension of the Trojan Horse Method to neutron induced reactions

    SciTech Connect

    Guardo, G. L.; Lamia, L.; Spitaleri, C.; Cherubini, S.; Rapisarda, G. G.; Sergi, M. L.; Gulino, M.; Tang, X. D.; Bucher, B.; Couder, M.; Davies, P.; Boer, R. de; Fang, X.; Lamm, L.; Ma, C.; Notani, M.; OBrien, S.; Roberson, D.; Tan, W.; Wiescher, M.; and others

    2014-05-02

    The experimental study of the {sup 17}O(n,α){sup 14}C reaction has been performed in the energy range 0-350 keV. This reaction could play an important role in explaining heavy elements (s-process) nucleosynthesis in various astrophysical scenario. To overcome the practical problems arising from the neutrons production, a new application of the Trojan Horse Method has been recently suggested. In more details, the {sup 17}O(n,α){sup 14}C reaction has been studied using the quasi-free {sup 2}H({sup 17}O,α{sup 14}C){sup 1}H reaction, induced at an energy of 43.5 MeV. The measurement allows one to investigate the ℓ=3, 75 keV resonance (E*=8.125 MeV, J{sup π}=5{sup −}), absent in the available direct measurements because of centrifugal suppression effects.

  3. Resonance strength measurement at astrophysical energies: The {sup 17}O(p,α){sup 14}N reaction studied via Trojan Horse Method

    SciTech Connect

    Sergi, M. L. La Cognata, M.; Pizzone, R. G.; Spitaleri, C.; Lamia, L.; Rapisarda, G. G.; Mukhamedzhanov, A.; Irgaziev, B.; Tang, X. D.; Wiescher, M.; Mrazek, J.; Kroha, V.

    2015-10-15

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on {sup 17}O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the {sup 17}O(p,α){sup 14}N reaction via the THM by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. Two measurements will be described and the experimental THM cross sections will be shown for both experiments.

  4. Characterization of the Dynamics in the Protonic Conductor CsH2PO4 by 17O Solid-State NMR Spectroscopy and First-Principles Calculations: Correlating Phosphate and Protonic Motion

    PubMed Central

    2015-01-01

    17O NMR spectroscopy combined with first-principles calculations was employed to understand the local structure and dynamics of the phosphate ions and protons in the paraelectric phase of the proton conductor CsH2PO4. For the room-temperature structure, the results confirm that one proton (H1) is localized in an asymmetric H-bond (between O1 donor and O2 acceptor oxygen atoms), whereas the H2 proton undergoes rapid exchange between two sites in a hydrogen bond with a symmetric double potential well at a rate ≥107 Hz. Variable-temperature 17O NMR spectra recorded from 22 to 214 °C were interpreted by considering different models for the rotation of the phosphate anions. At least two distinct rate constants for rotations about four pseudo C3 axes of the phosphate ion were required in order to achieve good agreement with the experimental data. An activation energy of 0.21 ± 0.06 eV was observed for rotation about the P–O1 axis, with a higher activation energy of 0.50 ± 0.07 eV being obtained for rotation about the P–O2, P–O3d, and P–O3a axes, with the superscripts denoting, respectively, dynamic donor and acceptor oxygen atoms of the H-bond. The higher activation energy of the second process is most likely associated with the cost of breaking an O1–H1 bond. The activation energy of this process is slightly lower than that obtained from the 1H exchange process (0.70 ± 0.07 eV) (Kim, G.; Blanc, F.; Hu, Y.-Y.; Grey, C. P. J. Phys. Chem. C2013, 117, 6504−6515) associated with the translational motion of the protons. The relationship between proton jumps and phosphate rotation was analyzed in detail by considering uncorrelated motion, motion of individual PO4 ions and the four connected/H-bonded protons, and concerted motions of adjacent phosphate units, mediated by proton hops. We conclude that, while phosphate rotations aid proton motion, not all phosphate rotations result in proton jumps. PMID:25732257

  5. Protein-Inhibitor Interaction Studies Using NMR

    PubMed Central

    Ishima, Rieko

    2015-01-01

    Solution-state NMR has been widely applied to determine the three-dimensional structure, dynamics, and molecular interactions of proteins. The designs of experiments used in protein NMR differ from those used for small-molecule NMR, primarily because the information available prior to an experiment, such as molecular mass and knowledge of the primary structure, is unique for proteins compared to small molecules. In this review article, protein NMR for structural biology is introduced with comparisons to small-molecule NMR, such as descriptions of labeling strategies and the effects of molecular dynamics on relaxation. Next, applications for protein NMR are reviewed, especially practical aspects for protein-observed ligand-protein interaction studies. Overall, the following topics are described: (1) characteristics of protein NMR, (2) methods to detect protein-ligand interactions by NMR, and (3) practical aspects of carrying out protein-observed inhibitor-protein interaction studies. PMID:26361636

  6. 17O Single Crystal NMR Evidence for a Gapped Spin-liquid Ground State in the S=1/2 Kagome Lattice ZnCu3 (OH)6Cl2

    NASA Astrophysics Data System (ADS)

    Fu, Mingxuan; Imai, Takashi; Han, Tianheng; Lee, Young. S.

    2015-03-01

    The two-dimensional S=1/2 Kagome lattice in Herbersmithite ZnCu3(OH)6Cl2 is the best candidate for experimental realization of a quantum spin liquid ground state known to date. The recent discovery of a continuum of spinon excitations using inelastic neutron scattering has drawn strong attention to its exotic magnetic properties. Understanding the nature of the paramagnetic ground state of ZnCu3(OH)6Cl2 , however, remains a challenge, due to excess magnetic Cu defects occupying the interlayer Zn sites. We conducted single crystal NMR measurements of the 17 O Knight shift, and succeeded in measuring the intrinsic spin susceptibility of the Kagome layer down to T ~ 0 . 01 J (J ~ 17 meV) for the first time. We demonstrate that the intrinsic spin susceptibility decays exponentially at low temperatures, revealing the presence of a spin gap Δ ~ 0 . 1 J . Moreover, we show that application of a high magnetic field suppresses the gap. These results provide direct evidence for a gapped spin-liquid ground state realized in ZnCu3(OH)6Cl2.

  7. NMR studies of oriented molecules

    SciTech Connect

    Sinton, S.W.

    1981-11-01

    Deuterium and proton magnetic resonance are used in experiments on a number of compounds which either form liquid crystal mesophases themselves or are dissolved in a liquid crystal solvent. Proton multiple quantum NMR is used to simplify complicated spectra. The theory of nonselective multiple quantum NMR is briefly reviewed. Benzene dissolved in a liquid crystal are used to demonstrate several outcomes of the theory. Experimental studies include proton and deuterium single quantum (..delta..M = +-1) and proton multiple quantum spectra of several molecules which contain the biphenyl moiety. 4-Cyano-4'-n-pentyl-d/sub 11/-biphenyl (5CB-d/sub 11/) is studied as a pure compound in the nematic phase. The obtained chain order parameters and dipolar couplings agree closely with previous results. Models for the effective symmetry of the biphenyl group in 5CB-d/sub 11/ are tested against the experimental spectra. The dihedral angle, defined by the planes containing the rings of the biphenyl group, is found to be 30 +- 2/sup 0/ for 5DB-d/sub 11/. Experiments are also described for 4,4'-d/sub 2/-biphenyl, 4,4' - dibromo-biphenyl, and unsubstituted biphenyl.

  8. Study of the γ decay of high-lying states in 208Pb via inelastic scattering of 17O ions

    NASA Astrophysics Data System (ADS)

    Crespi, F. C. L.; Kmiecik, M.; Bracco, A.; Leoni, S.; Maj, A.; Benzoni, G.; Blasi, N.; Boiano, C.; Bottoni, S.; Brambilla, S.; Camera, F.; Ceruti, S.; Giaz, A.; Million, B.; Morales, A. I.; Nicolini, R.; Pellegri, L.; Riboldi, S.; Vandone, V.; Wieland, O.; Bednarczyk, P.; Ciemala, M.; Grebosz, J.; Krzysiek, M.; Mazurek, K.; Zieblinski, M.; Bazzacco, D.; Bellato, M.; Birkenbach, B.; Bortolato, D.; Calore, E.; De Angelis, G.; Farnea, E.; Gadea, A.; Görgen, A.; Gottardo, A.; Isocrate, R.; Lenzi, S.; Lunardi, S.; Mengoni, D.; Michelagnoli, C.; Molini, P.; Napoli, D. R.; Recchia, F.; Sahin, E.; Siebeck, B.; Siem, S.; Ur, C.; Valiente Dobon, J. J.

    2014-03-01

    A measurement of the high-lying states in 208Pb has been made using 17O beams at 20 MeV/u. The gamma decay following inelastic excitation was measured with the detector system AGATA Demonstrator based on segmented HPGe detectors, coupled to an array of large volume LaBr3:Ce scintillators and to an array of Si detectors. Preliminary results in comparison with (γ,γ') data, for states in the 5-8 MeV energy interval, are presented.

  9. NMR studies of isotopically labeled RNA

    SciTech Connect

    Pardi, A.

    1994-12-01

    In summary, the ability to generate NMR quantities of {sup 15}N and {sup 13}C-labeled RNAs has led to the development of heteronuclear multi-dimensional NMR techniques for simplifying the resonance assignment and structure determination of RNAs. These methods for synthesizing isotopically labeled RNAs are only several years old, and thus there are still relatively few applications of heteronuclear multi-dimensional NMR techniques to RNA. However, given the critical role that RNAs play in cellular function, one can expect to see an increasing number of NMR structural studies of biologically active RNAs.

  10. The thermonuclear reaction rate of 17O(p, γ)18F--a low-energy, high beam current study at LENA

    NASA Astrophysics Data System (ADS)

    Buckner, Matthew; Iliadis, Christian; Kelly, Keegan; Downen, Lori; Champagne, Arthur; Cesaratto, John; Longland, Richard

    2014-03-01

    Classical novae are thought to be the dominant source of 17O in our Galaxy. These energetic events produce 18F that, as it decays to 18O, drives the ejection of nuclear ``ash'' into the interstellar medium. The importance of the non-resonant component of the 17O(p, γ)18F reaction is well established, and numerous studies have been performed to analyze this reaction. However, the temperature regime relevant to explosive hydrogen burning during classical novae corresponds to very low proton bombarding energies. At these low energies, the Coulomb barrier suppresses the reaction yield in the laboratory, and environmental backgrounds dominate the detected signal making it difficult to differentiate the direct capture γ-cascade from background. At the Laboratory for Experimental Nuclear Astrophysics (LENA), our electron cyclotron resonance (ECR) ion source produces intense, low-energy protons (~ 2.0 mA at the target), and these high currents boost the thermonuclear reaction yield. The LENA facility also has a coincidence detector setup that reduces environmental background contributions. Improved 17O(p, γ)18F direct capture reaction rates are currently being determined, and our progress will be reported. The DOE NNSA Stewardship Science Graduate Fellowship under Grant no. DE-FC52-08NA28752.

  11. 17O nuclear quadrupole coupling constants of water bound to a metal ion: A gadolinium(III) case study

    NASA Astrophysics Data System (ADS)

    Yazyev, Oleg V.; Helm, Lothar

    2006-08-01

    Rotational correlation times of metal ion aqua complexes can be determined from O17 NMR relaxation rates if the quadrupole coupling constant of the bound water oxygen-17 nucleus is known. The rotational correlation time is an important parameter for the efficiency of Gd3+ complexes as magnetic resonance imaging contrast agents. Using a combination of density functional theory with classical and Car-Parrinello molecular dynamics simulations we performed a computational study of the O17 quadrupole coupling constants in model aqua ions and the [Gd(DOTA)(H2O)]- complex used in clinical diagnostics. For the inner sphere water molecule in the [Gd(DOTA)(H2O)]- complex the determined quadrupole coupling parameter χ√1+η2/3 of 8.7MHz is very similar to that of the liquid water (9.0MHz ). Very close values were also predicted for the the homoleptic aqua ions of Gd3+ and Ca2+. We conclude that the O17 quadrupole coupling parameters of water molecules coordinated to closed shell and lanthanide metal ions are similar to water molecules in the liquid state.

  12. Triple isotope (δD, δ17O, δ18O) study on precipitation, drip water and speleothem fluid inclusions for a Western Central European cave (NW Switzerland)

    NASA Astrophysics Data System (ADS)

    Affolter, Stéphane; Häuselmann, Anamaria D.; Fleitmann, Dominik; Häuselmann, Philipp; Leuenberger, Markus

    2015-11-01

    Deuterium (δD) and oxygen (δ18O) isotopes are powerful tracers of the hydrological cycle and have been extensively used for paleoclimate reconstructions as they can provide information on past precipitation, temperature and atmospheric circulation. More recently, the use of 17Oexcess derived from precise measurement of δ17O and δ18O gives new and additional insights in tracing the hydrological cycle whereas uncertainties surround this proxy. However, 17Oexcess could provide additional information on the atmospheric conditions at the moisture source as well as about fractionations associated with transport and site processes. In this paper we trace water stable isotopes (δD, δ17O and δ18O) along their path from precipitation to cave drip water and finally to speleothem fluid inclusions for Milandre cave in northwestern Switzerland. A two year-long daily resolved precipitation isotope record close to the cave site is compared to collected cave drip water (3 months average resolution) and fluid inclusions of modern and Holocene stalagmites. Amount weighted mean δD, δ18O and δ17O are -71.0‰, -9.9‰, -5.2‰ for precipitation, -60.3‰, -8.7‰, -4.6‰ for cave drip water and -61.3‰, -8.3‰, -4.7‰ for recent fluid inclusions respectively. Second order parameters have also been derived in precipitation and drip water and present similar values with 18 per meg for 17Oexcess whereas d-excess is 1.5‰ more negative in drip water. Furthermore, the atmospheric signal is shifted towards enriched values in the drip water and fluid inclusions (Δ of ˜ + 10‰ for δD). The isotopic composition of cave drip water exhibits a weak seasonal signal which is shifted by around 8-10 months (groundwater residence time) when compared to the precipitation. Moreover, we carried out the first δ17O measurement in speleothem fluid inclusions, as well as the first comparison of the δ17O behaviour from the meteoric water to the fluid inclusions entrapment in speleothems

  13. A multinuclear solid state NMR spectroscopic study of the structural evolution of disordered calcium silicate sol-gel biomaterials.

    PubMed

    Lin, Zhongjie; Jones, Julian R; Hanna, John V; Smith, Mark E

    2015-01-28

    Disordered sol-gel prepared calcium silicate biomaterials show significant, composition dependent ability to bond with bone. Bone bonding is attributed to rapid hydroxycarbonate apatite (HCA) formation on the glass surface after immersion in body fluid (or implantation). Atomic scale details of the development of the structure of (CaO)x(SiO2)1-x (x = 0.2, 0.3 and 0.5) under heat treatment and subsequent dissolution in simulated body fluid (SBF) are revealed through a multinuclear solid state NMR approach using one-dimensional (17)O, (29)Si, (31)P and (1)H. Central to this study is the combination of conventional static and magic angle spinning (MAS) and two-dimensional (2D) triple quantum (3Q) (17)O NMR experiments that can readily distinguish and quantify the bridging (BOs) and non-bridging (NBOs) oxygens in the silicate network. Although soluble calcium is present in the sol, the (17)O NMR results reveal that the sol-gel produced network structure is initially dominated by BOs after gelation, aging and drying (e.g. at 120 °C), indicating a nanoscale mixture of the calcium salt and a predominantly silicate network. Only once the calcium salt is decomposed at elevated temperatures do the Ca(2+) ions become available to break BO. Apatite forming ability in SBF depends strongly on the surface OH and calcium content. The presence of calcium aids HCA formation via promotion of surface hydration and the ready availability of Ca(2+) ions. (17)O NMR shows the rapid loss of NBOs charge balanced by calcium as it is leached into the SBF. The formation of nanocrystalline, partially ordered HCA can be detected via(31)P NMR. This data indicates the importance of achieving the right balance of BO/NBO for optimal biochemical response and network properties. PMID:25494341

  14. FTS Studies of the 17O Enriched Isotopologues of CO_2 Toward Creating a Complete and Highly Accurate Reference Standard

    NASA Astrophysics Data System (ADS)

    Elliott, Ben; Sung, Keeyoon; Brown, Linda; Miller, Charles

    2014-06-01

    The proliferation and increased abilities of remote sensing missions for the monitoring of planetary atmospheric gas species has spurred the need for complete and accurate spectroscopic reference standards. As a part of our ongoing effort toward creating a global carbon dioxide (CO2) frequency reference standard, we report new FTS measurements of the 17O enriched isotopologues of CO2. The first measurements were taken in the ν3 region (2200 - 2450 cm-1, 65 - 75 THz), have absolute calibration accuracies of 100 kHz (3E-6 cm-1), comparable to the uncertainties for typical sub-millimeter/THz spectroscopy. Such high absolute calibration accuracy has become regular procedure for the cases of linear molecules such as CO2 and CO for FTS measurements at JPL, and enables us to produce measured transition frequencies for entire bands with accuracies that rival those of early heterodyne measurements for individual beat notes. Additionally, by acquiring spectra of multiple carbon dioxide isotopologues simultaneously, we have begun to construct a self-consistent frequency grid based on CO2 that extends from 20 - 200 THz. These new spectroscopic reference standards are a significant step towards minimizing CO2 retrieval errors from remote sensing applications, especially those involving targets with predominantly CO2 atmospheres such as Mars, Venus and candidate terrestrial exoplanets where minor isotopologues will make significant contributions to the radiance signals.

  15. NMR and optical studies of piezoelectric polymers

    SciTech Connect

    Schmidt, V.H.; Tuthill, G.F.

    1993-01-01

    Progress is reported in several areas dealing with piezoelectric (electroactive) polymers (mostly vinylidene fluoride, trifluoroethylene, copolymers, PVF[sub 2]) and liquid crystals. Optical studies, neutron scattering, NMR, thermal, theory and modeling were done.

  16. Tracing Nitrate Deposition Using Δ 17O

    NASA Astrophysics Data System (ADS)

    Michalski, G m; Hernandez, L.; Meixner, T.; Fenn, M.; Thiemens, M.

    2001-12-01

    Assessing the impact of atmospheric deposition of fixed nitrogen on local, regional, and global biogeochemical cycles has received much attention in recent years. Local and regional ecosystems can suffer from eutrophication and shrinking biodiversity from the increased nitrogen flux, in addition to degradation associated with acid rain ( an increasing proportion of which is as HNO3 ). On a global scale, the effect of nitrogen fertilization on CO2 uptake rates is one of the biggest unknowns in global warming research. This renewed interest has led to new attempts to utilize current, and in the development of new, analytical techniques in order to better understand the source, sink and transport mechanisms of atmospheric nitrogen deposition. Its role as the primary sink of the NOx cycle makes atmospheric nitrate (as particulate nitrate or nitric acid ) the primary source of nitrogen deposition. Stable isotopes of nitrogen and oxygen have been used by several researchers to trace atmospheric nitrate through the biogeochemical system. 15N ratios have been problematic due to the lack of large fractionations and an overlap of 15N ratios between sources. Initial studies of 18O ratios showed promise due to the large enrichment (60 ‰ ) in atmospheric nitrate. However, subsequent studies showed an δ 18O spread of 25 - 80 ‰ and have made quantitative analysis of mixing reservoirs difficult. No studies of δ 17O nitrates have been published. For δ 17O, thermodynamic, kinetic, and equilibrium isotope effects dictate that δ 17O = .52 x δ 18O . Certain photochemical processes violate this rule due to quantum effects and are quantified by Δ 17O = δ 17O -.52 x δ 18O which are called mass independent fractionations (MIF). Atmospheric nitrates have now been measured and have been found to have a large MIF; Δ 17O ~ 25 ‰ and a small range +/- 4‰ . The large variations in δ 18O of atmospheric nitrate are due to mass dependent fractions from transport and source ratios

  17. Interfaces in polymer nanocomposites - An NMR study

    NASA Astrophysics Data System (ADS)

    Böhme, Ute; Scheler, Ulrich

    2016-03-01

    Nuclear Magnetic Resonance (NMR) is applied for the investigation of polymer nanocomposites. Solid-state NMR is applied to study the modification steps to compatibilize layered double hydroxides with non-polar polymers. 1H relaxation NMR gives insight on the polymer dynamics over a wide range of correlation times. For the polymer chain dynamics the transverse relaxation time T2 is most suited. In this presentation we report on two applications of T2 measurements under external mechanical stress. In a low-field system relaxation NMR studies are performed in-situ under uniaxial stress. High-temperature experiments in a Couette cell permit the investigation of the polymer dynamics in the melt under shear flow.

  18. Covalency in La2CuO4: A study of 17O hyperfine couplings in the paramagnetic phase

    NASA Astrophysics Data System (ADS)

    Walstedt, R. E.; Cheong, S.-W.

    2001-07-01

    17O nuclear magnetic resonance spectra from single crystals of La2CuO4 are reported for temperatures ranging from 285 to 800 K. Hyperfine tensor data for the planar sites are analyzed using a spin Hamiltonian model that includes spin-orbit coupling effects. The results show a 7.7% hybridization effect of the oxygen 2pσ orbital from a single copper neighbor, in good agreement with recent density-functional (DF) calculations by Hüsser et al. (HSSM). A large, positive isotropic shift component is also reported, presumably originating from the contact interaction with a hybridized 2s orbital component. First-order quadrupolar-splitting data lead to complete characterization of the electric-field gradient (EFG) tensor, which varies only slightly with temperature up to 800 K. EFG tensors for both doped and undoped La2CuO4 are fitted with a two-component model, which incorporates a substantial anisotropy in for the 2pσ wave functions, an effect that originated in the DF calculations of HSSM. This analysis reveals an increased charge density on the planar oxygens for the superconducting phase, in accord with the original Zhang-Rice model. However, the increase is found to correspond to only ~80% of the nominal doped-hole density, corroborating a similar conclusion reached recently by Hammel et al. Regarding the anomalous spin HF interaction reported in a previous paper for the weakly ferromagnetic state, the present results show that its effects extend all the way to and slightly beyond the orthorhombic-tetragonal phase boundary (TO-T~=550 K). Further, the predominant 2s contact HF interaction reported here supports the notion, suggested earlier, that a 2s admixture underlies the anomaly. However, the basic mechanism of the anomaly remains obscure.

  19. Optically detected magnetic resonance studies of photoexcited /sup 17/O-benzophenone. Orbital rotation in the lowest triplet state

    SciTech Connect

    Waeckerle, G.; Baer, M.; Zimmermann, H.; Dinse, K.H.; Yamauchi, S.; Kashmar, R.J.; Pratt, D.W.

    1982-03-01

    The magnetically active isotope of oxygen /sup 17/O has been used to probe the changes in the electron charge and spin density distributions in oxygen valence orbitals which occur when benzophenone is excited to its lowest triplet state. The data obtained include the optically detected magnetic resonance (ODMR) and electron-nuclear double resonance spectra at both zero and high magnetic fields. New methods of analysis of zero-field ODMR spectra, appropriate when the second-order hyperfine splitting exceeds the quadrupole coupling, are described. This analysis yields the principal values of the electron fine-structure (D), oxygen hyperfine (A), and oxygen quadrupole (Q) tensors, and the orientation of their principal axes with respect to the molecular frame. It is found, consistent with expectations for an n..pi..( state, that the direction of the largest component of Q is different from that of the ground state. It is also found, by two independent methods, that the principal transverse axes of A and Q do not conform to the local C/sub 2v/ symmetry axes of the carbonyl group. This result is interpreted to mean that the axis of the n-type oxygen 2p orbital is rotated out of the carbonyl plane, a rotation which appears to be direct consequence of n..pi..(/..pi pi..( configurational mixing. In agreement with this, the principal values of D, A, and Q are different from those expected for a ''pure'' n..pi..( state. Other consequences of n..pi..(/..pi pi..( mixing, not only in benzophenone but also in the lowest triplet states of other aromatic carbonyls, are discussed briefly.

  20. NMR Methods to Study Dynamic Allostery

    PubMed Central

    Grutsch, Sarina; Brüschweiler, Sven; Tollinger, Martin

    2016-01-01

    Nuclear magnetic resonance (NMR) spectroscopy provides a unique toolbox of experimental probes for studying dynamic processes on a wide range of timescales, ranging from picoseconds to milliseconds and beyond. Along with NMR hardware developments, recent methodological advancements have enabled the characterization of allosteric proteins at unprecedented detail, revealing intriguing aspects of allosteric mechanisms and increasing the proportion of the conformational ensemble that can be observed by experiment. Here, we present an overview of NMR spectroscopic methods for characterizing equilibrium fluctuations in free and bound states of allosteric proteins that have been most influential in the field. By combining NMR experimental approaches with molecular simulations, atomistic-level descriptions of the mechanisms by which allosteric phenomena take place are now within reach. PMID:26964042

  1. An NMR study and ab initio molecular orbital calculation of substituted benzofuroxans and the salt of 4,6-dinitrobenzofuroxan

    NASA Astrophysics Data System (ADS)

    Cmoch, P.; Wiench, J. W.; Stefaniak, L.; Webb, G. A.

    1999-09-01

    13C, 15N and 17O NMR data are reported for a series of substituted benzofuroxans in aprotic and acidic solutions and for a potassium salt of a substituted benzofuroxan. Some of the title compounds can exhibit fast furoxan valence equilibrium at room temperature regardless of a solvent used, whereas for the others no evidence of above-mentioned process exists. The NMR parameters most sensitive to salt formation are the chemical shifts of the C7, N1, N3 and all of the oxygen nuclei. Hence these are reported as the most satisfactory chemical shifts to be used in distinguishing between the salt and non-ionic forms of the substituted benzofuroxans studied. Calculated energies at the self-consistent field (SCF) level of theory for both tautomeric forms (N1- and N3-oxide) of some compounds studied are used for predicting the tautomeric equilibrium constants. Absolute 17O shieldings are employed in the reversal of the assignments of 17O NMR signals existing in the literature.

  2. 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.

  3. NMR structural studies on antifreeze proteins.

    PubMed

    Sönnichsen, F D; Davies, P L; Sykes, B D

    1998-01-01

    Antifreeze proteins (AFPs) are a structurally diverse class of proteins that bind to ice and inhibit its growth in a noncolligative manner. This adsorption-inhibition mechanism operating at the ice surface results in a lowering of the (nonequilibrium) freezing point below the melting point. A lowering of approximately 1 degree C, which is sufficient to prevent fish from freezing in ice-laden seawater, requires millimolar AFP levels in the blood. The solubility of AFPs at these millimolar concentrations and the small size of the AFPs (typically 3-15 kDa) make them ideal subjects for NMR analysis. Although fish AFPs are naturally abundant, seasonal expression, restricted access to polar fishes, and difficulties in separating numerous similar isoforms have made protein expression the method of choice for producing AFPs for structural studies. Expression of recombinant AFPs has also facilitated NMR analysis by permitting isotopic labeling with 15N and 13C and has permitted mutations to be made to help with the interpretation of NMR data. NMR analysis has recently solved two AFP structures and provided valuable information about the disposition of ice-binding side chains in a third. The potential exists to solve other AFP structures, including the newly described insect AFPs, and to use solid-state NMR techniques to address fundamental questions about the nature of the interaction between AFPs and ice. PMID:9923697

  4. Structural Studies of Biological Solids Using NMR

    NASA Astrophysics Data System (ADS)

    Ramamoorthy, Ayyalusamy

    2011-03-01

    High-resolution structure and dynamics of biological molecules are important in understanding their function. While studies have been successful in solving the structures of water-soluble biomolecules, it has been proven difficult to determine the structures of membrane proteins and fibril systems. Recent studies have shown that solid-state NMR is a promising technique and could be highly valuable in studying such non-crystalline and non-soluble biosystems. I will present strategies to study the structures of such challenging systems and also about the applications of solid-state NMR to study the modes of membrane-peptide interactions for a better assessment of the prospects of antimicrobial peptides as substitutes to antibiotics in the control of human disease. Our studies on the mechanism of membrane disruption by LL-37 (a human antimicrobial peptide), analogs of the naturally occurring antimicrobial peptide magainin2 extracted from the skin of the African frog Xenopus Laevis, and pardaxin will be presented. Solid-state NMR experiments were used to determine the secondary structure, dynamics and topology of these peptides in lipid bilayers. Similarities and difference in the cell-lysing mechanism, and their dependence on the membrane composition, of these peptides will be discussed. Atomic-level resolution NMR structures of amyloidogenic proteins revealing the misfolding pathway and early intermediates that play key roles in amyloid toxicity will also be presented.

  5. An oxygen-17 dynamic NMR study of the Pr-DOTA complex.

    PubMed

    Fusaro, Luca; Luhmer, Michel

    2014-01-21

    The complex between (17)O-enriched DOTA (tetraazacyclododecanetetraacetic acid) and praseodymium(III) (Pr(3+)) was studied in aqueous solution by variable-temperature (17)O NMR at 14.1 T. pH effects as well as the influence of metal ions free in solution were investigated. At low temperature, the so-called TSAP and SAP conformations give rise to distinct signals for the oxygen atoms coordinated to the metal ion (O2); coalescence occurs between 20 and 30 °C. In contrast, a single signal was detected for the noncoordinated oxygen atoms (O1) in the entire investigated temperature range, i.e. between -3 and 135 °C. At high temperature, the spectra exhibit signal broadening that reveals the interchange of the O1 and O2 oxygen atoms of the carboxylate groups. The linewidths measured for O1 were deconvolved into contributions from quadrupole relaxation and chemical exchange, allowing the corresponding activation barriers to be determined. The present (17)O dynamic NMR study provides the first quantitative experimental data characterizing the interchange of the oxygen atoms in a DOTA chelate of a lanthanide metal ion. The activation entropy of this process is negligible and the activation enthalpy is found to range between 66 and 77 kJ mol(-1), depending on the pH and the presence of free Pr(3+) ions in solution. These data support the results of a previous computational study according to which the exchange mechanism involves the internal rotation of the carboxylate groups. PMID:24158053

  6. An NMR Study of Microvoids in Polymers

    NASA Technical Reports Server (NTRS)

    Toy, James; Mattrix, Larry

    1996-01-01

    An understanding of polymer defect structures, like microvoids in polymeric matrices, is most crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally not be found naturally in polymer or in NMR probe materials. There are two NMR active Xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb and Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe-129-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts in Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of Xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A series of spectra were obtained interspersed with applications of vacuum and heating to drive out the adsorbed Xe and determine the role of Xe-Xe interactions in the observed chemical shift.

  7. NMR techniques in the study of cardiovascular structure and functions

    SciTech Connect

    Osbakken, M.; Haselgrove, J.

    1987-01-01

    The chapter titles of this book are: Introduction to NMR Techniques;Theory of NMR Probe Design;Overview of Magnetic Resonance Imaging to Study the Cardiovascular System;Vascular Anatomy and Physiology Studied with NMR Techniques;Assessment of Myocardial Ischemia and Infarction by Nuclear Magnetic Resonance Imaging;The Use of MRI in Congenital Heart Disease;Cardiomyopathies and Myocarditis Studied with NMR Techniques;Determination of Myocardial Mechanical Function with Magnetic Resonance Imaging Techniques;Determination of Flow Using NMR Techniques;The Use of Contrast Agents in Cardiac MRI;Can Cardiovascular Disease Be Effectively Evaluated with NMR Spectroscopy. NMR Studies of ATP Synthesis Reactions in the Isolated Heart;Studies of Intermediary Metabolism in the Heart by 13C NMR Spectroscopy;23Na and 39K NMR Spectroscopic Studies of the Intact Beating Heart;and Evaluation of Skeletal Muscle Metabolism in Patients with Congestive Heart Failure Using Phosphorus Nuclear Magnetic Resonance.

  8. Solid-state NMR studies of supercapacitors.

    PubMed

    Griffin, John M; Forse, Alexander C; Grey, Clare P

    2016-01-01

    Electrochemical double-layer capacitors, or 'supercapacitors' are attracting increasing attention as high-power energy storage devices for a wide range of technological applications. These devices store charge through electrostatic interactions between liquid electrolyte ions and the surfaces of porous carbon electrodes. However, many aspects of the fundamental mechanism of supercapacitance are still not well understood, and there is a lack of experimental techniques which are capable of studying working devices. Recently, solid-state NMR has emerged as a powerful tool for studying the local environments and behaviour of electrolyte ions in supercapacitor electrodes. In this Trends article, we review these recent developments and applications. We first discuss the basic principles underlying the mechanism of supercapacitance, as well as the key NMR observables that are relevant to the study of supercapacitor electrodes. We then review some practical aspects of the study of working devices using ex situ and in situ methodologies and explain the key advances that these techniques have allowed on the study of supercapacitor charging mechanisms. NMR experiments have revealed that the pores of the carbon electrodes contain a significant number of electrolyte ions in the absence of any charging potential. This has important implications for the molecular mechanisms of supercapacitance, as charge can be stored by different ion adsorption/desorption processes. Crucially, we show how in situ NMR experiments can be used to quantitatively study and characterise the charging mechanism, with the experiments providing the most detailed picture of charge storage to date, offering the opportunity to design enhanced devices. Finally, an outlook for future directions for solid-state NMR in supercapacitor research is offered. PMID:26974032

  9. Two dimensional NMR and NMR relaxation studies of coal structure

    SciTech Connect

    Zilm, K.W.

    1992-05-27

    This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed a delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.

  10. An NMR study of microvoids in polymers

    NASA Technical Reports Server (NTRS)

    Toy, James; Mattix, Larry

    1995-01-01

    An understanding of polymer defect structures, like microvoids in polymeric matrices, is crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally be found naturally in polymer or in NMR probe materials. There are two NMR active xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb the Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe(129)-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts line Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A single Xe-129 line at 83.003498 Mhz (with protons at 300 Mhz) was observed for the gas. With the xenon charged PMR-15 samples, a second broader line is observed 190 ppm downfield from the gas line (also observed). The width of the NMR line from the Xe-129 absorbed in the polymer is at least partially due to the distribution of microvoid sizes. From the chemical shift (relative to the gas line) and the line width, we estimate the average void sizes to be 2.74 +/- 0.20 angstroms. Since Xe-129 has such a large chemical shift range (approximately 5000 ppm), we expect the chemical shift anisotropy to contribute to the

  11. First Principles NMR Study of Fluorapatite under Pressure

    PubMed Central

    Pavan, Barbara; Ceresoli, Davide; Tecklenburg, Mary M. J.; Fornari, Marco

    2012-01-01

    NMR is the technique of election to probe the local properties of materials. Herein we present the results of density functional theory (DFT) ab initio calculations of the NMR parameters for fluorapatite (FAp), a calcium orthophosphate mineral belonging to the apatite family, by using the GIPAW method [Pickard and Mauri, 2001]. Understanding the local effects of pressure on apatites is particularly relevant because of their important role in many solid state and biomedical applications. Apatites are open structures, which can undergo complex anisotropic deformations, and the response of NMR can elucidate the microscopic changes induced by an applied pressure. The computed NMR parameters proved to be in good agreement with the available experimental data. The structural evaluation of the material behavior under hydrostatic pressure (from −5 to +100 kbar) indicated a shrinkage of the diameter of the apatitic channel, and a strong correlation between NMR shielding and pressure, proving the sensitivity of this technique to even small changes in the chemical environment around the nuclei. This theoretical approach allows the exploration of all the different nuclei composing the material, thus providing a very useful guidance in the interpretation of experimental results, particularly valuable for the more challenging nuclei such as 43Ca and 17O. PMID:22770669

  12. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    SciTech Connect

    Bevilaqua, Rochele C. A.; Miranda, Caetano R.; Rigo, Vagner A.; Veríssimo-Alves, Marcos

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca{sup 2+}. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO{sub 3} (101{sup ¯}4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for {sup 43}Ca, {sup 13}C, and {sup 17}O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  13. NMR characterization of hydrocarbon adsorption on calcite surfaces: a first principles study.

    PubMed

    Bevilaqua, Rochele C A; Rigo, Vagner A; Veríssimo-Alves, Marcos; Miranda, Caetano R

    2014-11-28

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca(2+). Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for (43)Ca, (13)C, and (17)O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated. PMID:25429955

  14. NMR characterization of hydrocarbon adsorption on calcite surfaces: A first principles study

    NASA Astrophysics Data System (ADS)

    Bevilaqua, Rochele C. A.; Rigo, Vagner A.; Veríssimo-Alves, Marcos; Miranda, Caetano R.

    2014-11-01

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca2+. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 ( {10bar 14} )). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for 43Ca, 13C, and 17O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated.

  15. Ab initio DFT study of bisphosphonate derivatives as a drug for inhibition of cancer: NMR and NQR parameters.

    PubMed

    Aghabozorg, Hussein; Sohrabi, Beheshteh; Mashkouri, Sara; Aghabozorg, Hamid Reza

    2012-03-01

    DFT computations were carried out to characterize the (17)Oand (2)H electric field gradient, EFG, in various bisphosphonate derivatives. The computations were performed at the B3LYP level with 6-311++G (d,P) standard basis set. Calculated EFG tensors were used to determine the (17)O and (2)H nuclear quadrupole coupling constant, χ and asymmetry parameter, η. For better understanding of the bonding and electronic structure of bisphosphonates, isotropic and anisotropic NMR chemical shieldings were calculated for the (13)C, (17)O and (31)P nuclei using GIAO method for the optimized structure of intermediate bisphosphonates at B3LYP level of theory using 6-311++G (d, p) basis set. The results showed that various substituents have a strong effect on the nuclear quadrupole resonance (NQR) parameters (χ, η) of (17)O in contrast with (2)H NQR parameters. The NMR and NQR parameters were studied in order to find the correlation between electronic structure and the activity of the desired bisphosphonates. In addition, the effect of substitutions on the bisphosphonates polarity was investigated. Molecular polarity was determined via the DFT calculated dipole moment vectors and the results showed that substitution of bromine atom on the ring would increase the activity of bisphosphonates. PMID:21633790

  16. NMR methodologies for studying mitochondrial bioenergetics.

    PubMed

    Alves, Tiago C; Jarak, Ivana; Carvalho, Rui A

    2012-01-01

    Nuclear magnetic resonance (NMR) spectroscopy is a technique with an increasing importance in the study of metabolic diseases. Its initial important role in the determination of chemical structures (1, 2) has been considerably overcome by its potential for the in vivo study of metabolism (3-5). The main characteristic that makes this technique so attractive is its noninvasiveness. Only nuclei capable of transitioning between energy states, in the presence of an intense and constant magnetic field, are studied. This includes abundant nuclei such as proton ((1)H) and phosphorous ((31)P), as well as stable isotopes such as deuterium ((2)H) and carbon 13 ((13)C). This allows a wide range of applications that vary from the determination of water distribution in tissues (as obtained in a magnetic resonance imaging scan) to the calculation of metabolic fluxes under ex vivo and in vivo conditions without the need to use radioactive tracers or tissue biopsies (as in a magnetic resonance spectroscopy (MRS) scan). In this chapter, some technical aspects of the methodology of an NMR/MRS experiment as well as how it can be used to study mitochondrial bioenergetics are overviewed. Advantages and disadvantages of in vivo MRS versus high-resolution NMR using proton high rotation magic angle spinning (HRMAS) of tissue biopsies and tissue extracts are also discussed. PMID:22057574

  17. Spin fluctuations in the exotic metallic state of Sr2RuO4 studied with β -NMR

    NASA Astrophysics Data System (ADS)

    Cortie, D. L.; Buck, T.; Dehn, M. H.; Kiefl, R. F.; Levy, C. D. P.; McFadden, R. M. L.; Morris, G. D.; Pearson, M. R.; Salman, Z.; Maeno, Y.; MacFarlane, W. A.

    2015-06-01

    A β -NMR study was performed on a Sr2RuO4 crystal in the metallic state using a beam of spin-polarized +8Li implanted at a mean depth of 90 nm. The +8Li spin-lattice relaxation rate is strongly influenced by the onset of incommensurate spin fluctuations. The nuclear relaxation rate can be explained using previously published bulk 17O NMR and inelastic neutron spectroscopy measurements of the dynamic magnetic susceptibility to model the hyperfine coupling. A well-resolved quadrupolar-split NMR for +8Li implies a static stopping position in an interstitial site. The +8Li Knight shift is highly sensitive to the anisotropic static susceptibility.

  18. An Experimental Study on What Controls the Ratios of 18O/16O and 17O/16O of O2 During Microbial Respiration

    NASA Astrophysics Data System (ADS)

    Stolper, D. A.; Ward, B. B.; Fischer, W. W.; Bender, M. L.

    2015-12-01

    18O/16O and 17O/16O ratios of atmospheric and dissolved oceanic O2 are key biogeochemical tracers of total photosynthesis and respiration on global to local length scales and glacial/interglacial time scales (Luz et al., 1999). Critical to the use of these ratios as biogeochemical tracers is knowledge of how they are affected by production, consumption, and transport of O2. We present new measurements of O2 respiration by E. coli and N. oceanus, an ammonia oxidizing bacterium, to test three assumptions of isotopically enabled models of the O2 cycle: (i) laboratory-measured respiratory 18O/16O isotope effects (18α) of microorganisms are constant under all experimental and natural conditions (e.g., temperature and growth rate); (ii) the respiratory 'mass law' relationship between 18O/16O and 17O/16O [17α = (18α)β] is universal; and (iii) 18α and β for aerobic ammonia and organic carbon oxidation are identical. For E. coli, we find that both 18α and β are variable. From 37°C to 15°C, 18α varies linearly with temperature from 17 to 14‰, and β varies linearly from 0.513 to 0.508. 18α and β do not appear to vary with growth rate (as tested using different carbon sources). Both 18α and β are lower than previous observations for bacteria: 18α = 17-20‰ (Kiddon et al., 1993) and β = 0.515 (Luz and Barkan, 2005). We were able to simulate the observed temperature dependence of 18α and β using a model of respiration with two isotopically discriminating steps: O2 binding to cytochrome bo oxidase (the respiratory enzyme) and reduction of O2 to H2O. Finally, initial results on N. oceanus suggest it has similar values for 18α and β as previously studied aerobic bacteria that consume organic carbon, providing the first support for assumption (iii). Based on these results, isotopically constrained biogeochemical models of O2 cycling may need to consider a temperature dependence for 18α and β for microbial respiration. For example, these results may

  19. NMR Studies of the original magnetic properties of the cuprates: influence of impurities and defects.

    NASA Astrophysics Data System (ADS)

    Alloul, Henri

    1998-03-01

    The cuprates display original magnetic properties, both in their insulating and metallic phases. In underdoped metallic systems, a pseudo gap in the density of magnetic q=3D0 excitations is observed from local susceptibility measurements, as well as from specific heat and transport properties. A pseudo spin-gap in the AF excitations at the AF wave vector is detected both by NMR and inelastic neutron scattering. From the NMR measurements it can be concluded that these magnetic anomalies are quite similar in single layer(J. Bobroff, H.. Alloul, P. Mendels, V. Viallet, J. F. Marucco and D. Colson, Phys. Rev. Letters 78, 3757 (1997).), bilayer and trilayer underdoped cuprates. The modifications of magnetic properties induced by substitutions or defects in the planes, which do not modify appreciably the charge transfer have been studied. The spatial dependence of the spin susceptibility \\chi ' (r) of the pure material can be directly probed through the study of the modifications of the NMR spectra of various nuclei (^89Y, ^17O, ^63Cu) induced by such localised magnetic impurities. Large qualitative differences between the underdoped and slightly overdoped YBCO are evidenced from ^17O NMR line broadening in Ni substituted YBCO. This allows us to propose a quite powerful method for studying the q and T dependence of the static magnetic susceptibility (J. Bobroff et al, Phys. Rev. Letters 78, 3757 (1997).). The impurity magnetic state also directly reflects the occurence of electronic correlations in the metallic state. The case of Zn will be examined in some detail. ^89Y NMR has revealed that the substitution of this 3d^10 non magnetic atom on a Cu site induces a Curie like contribution to the local susceptibility on the near neighbour coppers ( A. V. Mahajan, H. Alloul, G. Collin and J. F. Marucco, Physical Review Letters 72, 3100 (1994).). The effective induced moment decreases with hole doping and becomes rather weak, but is still present for optimal doping

  20. Rhodopsin-lipid interactions studied by NMR.

    PubMed

    Soubias, Olivier; Gawrisch, Klaus

    2013-01-01

    The biophysical properties of the lipid matrix are known to influence function of integral membrane proteins. We report on a sample preparation method for reconstitution of membrane proteins which uses porous anodic aluminum oxide (AAO) filters with 200-nm-wide pores of high density. The substrate permits formation of tubular, single membranes that line the inner surface of pores. One square centimeter of filter with a thickness of 60μm yields on the order of 500cm(2) of solid-supported single bilayer surface, sufficient for NMR studies. The tubular bilayers are free of detergent, fully hydrated, and accessible for ligands from one side of the membrane. The use of AAO filters greatly improves reproducibility of the reconstitution process such that the influence of protein on lipid order parameters can be studied with high resolution. As an example, results for the G protein-coupled receptor of class A, bovine rhodopsin, are shown. By (2)H NMR order parameter measurements, it is detected that rhodopsin insertion elastically deforms membranes near the protein. Furthermore, by (1)H saturation-transfer NMR under conditions of magic angle spinning, we demonstrate detection of preferences in interactions of rhodopsin with particular lipid species. It is assumed that function of integral membrane proteins depends on both protein-induced elastic deformations of the lipid matrix and preferences for interaction of the protein with particular lipid species in the first layer of lipids surrounding the protein. PMID:23374188

  1. Study of Electromagnetic Multipole Transition Half-Lives of One-Hole 15O-15N and One-Particle 17O-17F Mirror Nuclei

    NASA Astrophysics Data System (ADS)

    Pahlavani, Mohammadreza; Firoozi, Behnam

    2013-11-01

    Energy spectrum and wave functions are obtained numerically with a potential consisting of Woods-Saxon, Coulomb, and spin-orbit coupling parts for the nuclei 15O, 15N, 17O, and 17F. The radial parts of the wave functions are used to calculate some matrix elements of electromagnetic transitions. These results are applied to calculate half-lives of low-lying exited states in the one-particle 17O and 17F as well as in the one-hole 15O and 15N isotopes. The calculated half-lives are compared with available experimental and theoretical results based on harmonic oscillator wave functions and Weisskopf units. In comparison with the results calculated from the other methods, our results based on the Woods-Saxon potential indicate a satisfactory agreement with accessible experimental data.

  2. Validation of a Rapid and Sensitive LC-MS/MS Method for Determination of Exemestane and Its Metabolites, 17β-Hydroxyexemestane and 17β-Hydroxyexemestane-17-O-β-D-Glucuronide: Application to Human Pharmacokinetics Study

    PubMed Central

    Wang, Ling-Zhi; Goh, Sok-Hwei; Wong, Andrea Li-Ann; Thuya, Win-Lwin; Lau, Jie-Ying Amelia; Wan, Seow-Ching; Lee, Soo-Chin; Ho, Paul C.; Goh, Boon-Cher

    2015-01-01

    A novel, rapid and sensitive liquid chromatography-tandem mass spectrometric (LC-MS/MS) method was developed and validated for the evaluation of exemestane pharmacokinetics and its metabolites, 17β-dihydroexemestane (active metabolite) and 17β-dihydroexemestane-17-O-β-D-glucuronide (inactive metabolite) in human plasma. Their respective D3 isotopes were used as internal standards. Chromatographic separation of analytes was achieved using Thermo Fisher BDS Hypersil C18 analytic HPLC column (100 × 2.1 mm, 5 μm). The mobile phase was delivered at a rate of 0.5 mL/min by gradient elution with 0.1 % aqueous formic acid and acetonitrile. The column effluents were detected by API 4000 triple quadrupole mass spectrometer using electrospray ionisation (ESI) and monitored by multiple reaction monitoring (MRM) in positive mode. Mass transitions 297 > 121 m/z, 300 > 121 m/z, 299 > 135 m/z, 302 > 135 m/z, 475 > 281 m/z, and 478 > 284 m/z were monitored for exemestane, exemestane-d3, 17β-dihydroexemestane, 17β-dihydroexemestane-d3, 17β-dihydroexemestane-17-O-β-D-glucuronide, and 17β-dihydroexemestane-17-O-β-D-glucuronide-d3 respectively. The assay demonstrated linear ranges of 0.4 – 40.0 ng/mL, for exemestane; and 0.2 – 15.0 ng/mL, for 17β-dihydroexemestane and 17β-dihydroexemestane-17-O-β-D-glucuronide, with coefficient of determination (r2) of > 0.998. The precision (coefficient of variation) were ≤10.7%, 7.7% and 9.5% and the accuracies ranged from 88.8 to 103.1% for exemestane, 98.5 to 106.1% for 17β-dihydroexemestane and 92.0 to 103.2% for 17β-dihydroexemestane-17-O-β-D-glucuronide. The method was successfully applied to a pharmacokinetics/dynamics study in breast cancer patients receiving exemestane 25mg daily orally. For a representative patient, 20.7% of exemestane in plasma was converted into 17β-dihydroexemestane and 29.0% of 17β-dihydroexemestane was inactivated as 17β-dihydroexemestane-17-O-β-D-glucuronide 24 hours after ingestion of

  3. Isotope labeling for NMR studies of macromolecular structure and interactions

    SciTech Connect

    Wright, P.E.

    1994-12-01

    Implementation of biosynthetic methods for uniform or specific isotope labeling of proteins, coupled with the recent development of powerful heteronuclear multidimensional NMR methods, has led to a dramatic increase in the size and complexity of macromolecular systems that are now amenable to NMR structural analysis. In recent years, a new technology has emerged that combines uniform {sup 13}C, {sup 15}N labeling with heteronuclear multidimensional NMR methods to allow NMR structural studies of systems approaching 25 to 30 kDa in molecular weight. In addition, with the introduction of specific {sup 13}C and {sup 15}N labels into ligands, meaningful NMR studies of complexes of even higher molecular weight have become feasible. These advances usher in a new era in which the earlier, rather stringent molecular weight limitations have been greatly surpassed and NMR can begin to address many central biological problems that involve macromolecular structure, dynamics, and interactions.

  4. NMR-Metabolic Methodology in the Study of GM Foods

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The 1H NMR methodology used in the study of genetically modified (GM) foodstuff is discussed. The study of transgenic lettuce (Lactuca sativa cv "Luxor") over-expressing the KNAT1 gene from Arabidopsis is presented as a novel study-case. The 1H NMR metabolic profiling was carried out. Twenty-two wat...

  5. Magic-angle-spinning NMR studies of zeolite SAPO-5

    NASA Astrophysics Data System (ADS)

    Freude, D.; Ernst, H.; Hunger, M.; Pfeifer, H.; Jahn, E.

    1988-01-01

    SAPO-5 was synthesized using triethylamine as template. Magic-angle-spinning (MAS) NMR of 1H, 27Al, 29Si and 31P was used to study the silicon incorporation into the framework and the nature of the Brønsted sites. 1H MAS NMR shows two types of bridging hydroxyl groups. 29Si MAS NMR indicates that silicon substitutes mostly for phosphorus and that there is a small amount of crystalline SiO 2 in the zeolite powder.

  6. Chemical Equilibrium in Supramolecular Systems as Studied by NMR Spectrometry

    ERIC Educational Resources Information Center

    Gonzalez-Gaitano, Gustavo; Tardajos, Gloria

    2004-01-01

    Undergraduate students are required to study the chemical balance in supramolecular assemblies constituting two or more interacting species, by using proton NMR spectrometry. A good knowledge of physical chemistry, fundamentals of chemical balance, and NMR are pre-requisites for conducting this study.

  7. Multichannel study of the {sup 13}C({alpha},n){sup 16}O and {sup 16}O(n,{gamma}){sup 17}O reactions

    SciTech Connect

    Dufour, M.; Descouvemont, P.

    2005-07-01

    The {sup 13}C({alpha},n){sup 16}O reaction is investigated in a microscopic two-cluster model with an effective interaction recently developed for transfer reactions. The wave functions are defined in the generator coordinate method. The basis includes all {sup 13}C+{alpha} and {sup 16}O+n channels with {sup 13}C and {sup 16}O described in the p shell. Particle-hole excitations in the sd shell are also taken into account in order to include the {sup 16}O(3{sup -})+n channel. The {sup 17}O spectroscopy is in good agreement with experiment. In particular, the width of the astrophysically relevant 1/2{sub 2}{sup +} state is well reproduced ({gamma}=121 keV as compared to the experimental value {gamma}=124{+-}12 keV). The calculation of the {sup 13}C({alpha},n){sup 16}O S factor shows the importance of the 3/2{sub 3}{sup +} resonance, and provides S(0.2 MeV)=2.1x10{sup 6} MeV b, slightly lower than the NACRE recommended value (2.5x10{sup 6} MeV b). The same model is applied to the {sup 16}O(n,{gamma}){sup 17}O radiative-capture reaction at thermal and astrophysical energies.

  8. Observation of the Second-Order Quadrupolar Interaction as a Dominating NMR Relaxation Mechanism in Liquids: The Ultraslow Regime of Motion.

    PubMed

    Shen, Jiahui; Terskikh, Victor; Wu, Gang

    2016-09-01

    We report variable-temperature (VT) (17)O NMR spectra of [5-(17)O]-d-glucose in an aqueous solution and in glycerol at 14.1 and 21.1 T. The VT (17)O NMR data cover a wide range of motion for which the molecular rotational correlation time (τc) of glucose changes more than 5 orders of magnitude. The observed line width of the (17)O NMR signal for [5-(17)O]-d-glucose displays a maximum at ω0τc ≈ 1 and a minimum at ω0τc ≈ 150, where ω0 is the angular Larmor frequency of (17)O. Under the ultraslow motion condition (i.e., ω0τc > 150), the line width of the observed (17)O NMR signal increases drastically with τc, suggesting that the second-order quadrupolar interaction becomes the predominant relaxation mechanism. While this relaxation mechanism has long been predicted by theory, the current study reports the first experimental observation of such a phenomenon. The implications of this new relaxation mechanism on the spectral resolution limit in liquid-state NMR spectroscopy for half-integer spins are discussed. PMID:27525537

  9. 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.

  10. NMR Studies of Enzyme Structure and Mechanism

    NASA Astrophysics Data System (ADS)

    Mildvan, Albert

    2006-03-01

    At least three NMR methodologies pioneered by Al Redfield, have greatly benefited enzymology: (1) the suppression of strong water signals without pre-saturation; (2) sequence specific NH/ND exchange; and (3) dynamic studies of mobile loops of proteins. Water suppression has enabled us to identify unusually short, strong H-bonds at the active sites of five enzymes (three isomerases and two esterases), and to measure their lengths from both the chemical shifts and D/H fractionation factors of the deshielded protons involved (J. Mol. Struct. 615, 163 (2002)). Backbone NH exchange studies were used to detect regions of an NTP pyrophosphohydrolase in which NH groups became selectively protected against exchange on Mg(2+) binding, and further protected on product (NMP) binding, thus locating binding sites as well as conformationally linked remote sites (Biochemistry 42, 10140 (2003)). Dynamic studies were used to elucidate the frequency of motion of a flexible loop of GDP-mannose hydrolase (66,000/sec) containing the catalytic base His-124, from exchange broadening of the side chain NH signals of His-124 in the free enzyme. The binding of Mg(2+) and GDP-mannose lock His-124 in position to deprotonate the entering water and complete the reaction.

  11. A multinuclear static NMR study of geopolymerisation

    SciTech Connect

    Favier, Aurélie; Habert, Guillaume; Roussel, Nicolas; D'Espinose de Lacaillerie, Jean-Baptiste

    2015-09-15

    Geopolymers are inorganic binders obtained by alkali activation of aluminosilicates. While the structure of geopolymers is now well understood, the details of the geopolymerisation reaction and their impact on the rheology of the paste remain uncertain. In this work, we follow the elastic properties of a paste made with metakaolin and sodium silicate solution. After the first sharp increase of elastic modulus occurring a few hundred of seconds after mixing and related to the heterogeneous formation of an alumina–silicate gel with a molar ratio Si/Al < 4 located at the grains boundaries, we focus on the progressive increase in elastic modulus on a period of few hours during the setting of the geopolymer. In this study, we combine the study of rheological properties of the paste with {sup 23}Na, {sup 27}Al and {sup 29}Si static NMR measurement in order to better understand the origin of this second increase in elastic modulus. Our results show that, after a few hours, Al and Na evolution in the liquid phase are concomitant. This suggests the precipitation of an aluminosilicate phase where Al is in tetrahedral position and Na compensates the charge. Furthermore, Si speciation confirms this result and allows us to identify the precipitation of a product, which has a chemical composition close to the final composition of geopolymer. This study provides strong evidence for a heterogeneous formation of an aluminosilicate glass directly from the first gel and the silicate solution without the need for a reorganisation of Gel 1 into Gel 2.

  12. Studies of organic paint binders by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Spyros, A.; Anglos, D.

    2006-06-01

    Nuclear magnetic resonance spectroscopy is applied to the study of aged binding media used in paintings, namely linseed oil, egg tempera and an acrylic medium. High resolution 1D and 2D NMR experiments establish the state of hydrolysis and oxidation of the linseed and egg tempera binders after five years of aging, by determining several markers sensitive to the hydrolytic and oxidative processes of the binder lipid fraction. The composition of the acrylic binder co-polymer is determined by 2D NMR spectroscopy, while the identification of a surfactant, poly(ethylene glycol), found in greater amounts in aged acrylic medium, is reported. The non-destructive nature of the proposed analytical NMR methodology, and minimization of the amount of binder material needed through the use of sophisticated cryoprobes and hyphenated LC-NMR techniques, make NMR attractive for the arts analyst, in view of its rapid nature and experimental simplicity.

  13. Understanding the symmetric line shape in the 17O MAS spectra for hexagonal ice

    NASA Astrophysics Data System (ADS)

    Yamada, Kazuhiko; Oki, Shinobu; Deguchi, Kenzo; Shimizu, Tadashi

    2016-06-01

    Solid-state 17O Magic-Angle Spinning (MAS) nuclear magnetic resonance (NMR) spectra of 17O-enriched hexagonal ice, [17O]-Ih, between 173 and 253 K were presented. Marked changes in the line shape were clearly observed, indicating water molecular reorientation in the crystal structure. At 173 K, molecular motions were considered to be frozen and analysis of the 1D MAS spectrum yielded the following parameters: quadrupole coupling constant (CQ) = 6.6 ± 0.2 MHz and asymmetry parameter (ηQ) = 0.95 ± 0.05. At 232 K and above, contrary to the conventional explanation, pseudo-symmetric line shapes appeared in the 17O MAS NMR spectra arising from the contribution of second-order quadrupole interactions. As a chemical exchange model to describe these isotropic 17O MAS NMR spectra, a modified Ratcliffe model, which consider the effects of proton disorder, was proposed, and the resulting theoretical spectra could well reproduce the experimental spectra.

  14. NMR studies of metallic tin confined within porous matrices

    SciTech Connect

    Charnaya, E. V.; Tien, Cheng; Lee, M. K.; Kumzerov, Yu. A.

    2007-04-01

    {sup 119}Sn NMR studies were carried out for metallic tin confined within synthetic opal and porous glass. Tin was embedded into nanoporous matrices in the melted state under pressure. The Knight shift for liquid confined tin was found to decrease with decreasing pore size. Correlations between NMR line shapes, Knight shift, and pore filling were observed. The melting and freezing phase transitions of tin under confinement were studied through temperature dependences of NMR signals upon warming and cooling. Melting of tin within the opal matrix agreed well with the liquid skin model suggested for small isolated particles. The influence of the pore filling on the melting process was shown.

  15. NMR studies of nucleic acid dynamics

    PubMed Central

    Al-Hashimi, Hashim M.

    2014-01-01

    Nucleic acid structures have to satisfy two diametrically opposite requirements; on one hand they have to adopt well-defined 3D structures that can be specifically recognized by proteins; on the other hand, their structures must be sufficiently flexible to undergo very large conformational changes that are required during key biochemical processes, including replication, transcription, and translation. How do nucleic acids introduce flexibility into their 3D structure without losing biological specificity? Here, I describe the development and application of NMR spectroscopic techniques in my laboratory for characterizing the dynamic properties of nucleic acids that tightly integrate a broad set of NMR measurements, including residual dipolar couplings, spin relaxation, and relaxation dispersion with sample engineering and computational approaches. This approach allowed us to obtain fundamental new insights into directional flexibility in nucleic acids that enable their structures to change in a very specific functional manner. PMID:24149218

  16. Some nitrogen-14 NMR studies in solids

    SciTech Connect

    Pratum, T.K.

    1983-11-01

    The first order quadrupolar perturbation of the /sup 14/N NMR spectrum yields information regarding the static and dynamic properties of the surrounding electronic environment. Signal to noise problems caused by long /sup 14/N longitudinal relaxation times (T/sub 1/) and small equilibrium polarizations are reduced by rotating frame cross polarization (CP) experiments between /sup 14/N and /sup 1/H. Using quadrupolar echo and CP techniques, the /sup 14/N quadrupolar coupling constants (e/sup 2/qQ/h) and asymmetry parameters (eta) have been obtained for a variety of tetraalkylammonium compounds by observation of their quadrupolar powder patterns at various temperatures. For choline chloride and iodide the /sup 14/N NMR powder patterns exhibit the effects of anisotropic molecular motion, while choline bromide spectra show no such effects.

  17. NMR studies of nucleic acid dynamics

    NASA Astrophysics Data System (ADS)

    Al-Hashimi, Hashim M.

    2013-12-01

    Nucleic acid structures have to satisfy two diametrically opposite requirements; on one hand they have to adopt well-defined 3D structures that can be specifically recognized by proteins; on the other hand, their structures must be sufficiently flexible to undergo very large conformational changes that are required during key biochemical processes, including replication, transcription, and translation. How do nucleic acids introduce flexibility into their 3D structure without losing biological specificity? Here, I describe the development and application of NMR spectroscopic techniques in my laboratory for characterizing the dynamic properties of nucleic acids that tightly integrate a broad set of NMR measurements, including residual dipolar couplings, spin relaxation, and relaxation dispersion with sample engineering and computational approaches. This approach allowed us to obtain fundamental new insights into directional flexibility in nucleic acids that enable their structures to change in a very specific functional manner.

  18. NMR studies on polyphosphide Ce6Ni6P17

    NASA Astrophysics Data System (ADS)

    Koyama, T.; Yamada, H.; Ueda, K.; Mito, T.; Aoyama, Y.; Nakano, T.; Takeda, N.

    2016-02-01

    We report the result of 31P nuclear magnetic resonance (NMR) studies on Ce6Ni6P17. The observed NMR spectra show a Lorentzian-type and an asymmetric shapes, reflecting the local symmetry around each P site in the cubic unit cell. We have identified the observed NMR lines corresponding to three inequivalent P sites and deduced the temperature dependence of the Knight shift for each site. The Knight shifts increase with decreasing temperature down to 1.5 K, indicating a localized spin system of Ce6Ni6P17. Antiferromagnetic correlation between 4f spins is suggested from the negative sign of the Weiss-temperature.

  19. NMR Studies of Dynamic Biomolecular Conformational Ensembles

    PubMed Central

    Torchia, Dennis A.

    2015-01-01

    Multidimensional heteronuclear NMR approaches can provide nearly complete sequential signal assignments of isotopically enriched biomolecules. The availability of assignments together with measurements of spin relaxation rates, residual spin interactions, J-couplings and chemical shifts provides information at atomic resolution about internal dynamics on timescales ranging from ps to ms, both in solution and in the solid state. However, due to the complexity of biomolecules, it is not possible to extract a unique atomic-resolution description of biomolecular motions even from extensive NMR data when many conformations are sampled on multiple timescales. For this reason, powerful computational approaches are increasingly applied to large NMR data sets to elucidate conformational ensembles sampled by biomolecules. In the past decade, considerable attention has been directed at an important class of biomolecules that function by binding to a wide variety of target molecules. Questions of current interest are: “Does the free biomolecule sample a conformational ensemble that encompasses the conformations found when it binds to various targets; and if so, on what time scale is the ensemble sampled?” This article reviews recent efforts to answer these questions, with a focus on comparing ensembles obtained for the same biomolecules by different investigators. A detailed comparison of results obtained is provided for three biomolecules: ubiquitin, calmodulin and the HIV-1 trans-activation response RNA. PMID:25669739

  20. Study of molecular interactions with 13C DNP-NMR

    NASA Astrophysics Data System (ADS)

    Lerche, Mathilde H.; Meier, Sebastian; Jensen, Pernille R.; Baumann, Herbert; Petersen, Bent O.; Karlsson, Magnus; Duus, Jens Ø.; Ardenkjær-Larsen, Jan H.

    2010-03-01

    NMR spectroscopy is an established, versatile technique for the detection of molecular interactions, even when these interactions are weak. Signal enhancement by several orders of magnitude through dynamic nuclear polarization alleviates several practical limitations of NMR-based interaction studies. This enhanced non-equilibrium polarization contributes sensitivity for the detection of molecular interactions in a single NMR transient. We show that direct 13C NMR ligand binding studies at natural isotopic abundance of 13C gets feasible in this way. Resultant screens are easy to interpret and can be performed at 13C concentrations below μM. In addition to such ligand-detected studies of molecular interaction, ligand binding can be assessed and quantified with enzymatic assays that employ hyperpolarized substrates at varying enzyme inhibitor concentrations. The physical labeling of nuclear spins by hyperpolarization thus provides the opportunity to devise fast novel in vitro experiments with low material requirement and without the need for synthetic modifications of target or ligands.

  1. A 19F NMR Study of Enzyme Activity

    NASA Astrophysics Data System (ADS)

    Peterman, Keith E.; Lentz, Kevin; Duncan, Jeffery

    1998-10-01

    This basic enzyme activity laboratory experiment demonstrates how 19F NMR can be used in biochemical studies and presents the advantages of 19F NMR over 1H NMR for studies of this nature. N-Trifluoroacetylglycine was selected as a commercially available model fluorine-tagged substrate that readily undergoes acylase I-catalyzed hydrolysis to produce trifluoroacetic acid and glycine. Progress of the reaction was monitored by following conversion of the trifluoroacetyl moiety peak of N-trifluoroacetylglycine to trifluoroacetic acid. The extent of hydrolysis was determined by comparing integrated ratios of the two 19F NMR peaks. A plot of percent hydrolysis versus enzyme concentration was used to calculate unit activity of the enzyme. This is a viable laboratory experiment for junior/senior-level courses in instrumental analytical chemistry, biochemistry, molecular biology, or spectroscopy.

  2. Protein folding on the ribosome studied using NMR spectroscopy

    PubMed Central

    Waudby, Christopher A.; Launay, Hélène; Cabrita, Lisa D.; Christodoulou, John

    2013-01-01

    NMR spectroscopy is a powerful tool for the investigation of protein folding and misfolding, providing a characterization of molecular structure, dynamics and exchange processes, across a very wide range of timescales and with near atomic resolution. In recent years NMR methods have also been developed to study protein folding as it might occur within the cell, in a de novo manner, by observing the folding of nascent polypeptides in the process of emerging from the ribosome during synthesis. Despite the 2.3 MDa molecular weight of the bacterial 70S ribosome, many nascent polypeptides, and some ribosomal proteins, have sufficient local flexibility that sharp resonances may be observed in solution-state NMR spectra. In providing information on dynamic regions of the structure, NMR spectroscopy is therefore highly complementary to alternative methods such as X-ray crystallography and cryo-electron microscopy, which have successfully characterized the rigid core of the ribosome particle. However, the low working concentrations and limited sample stability associated with ribosome–nascent chain complexes means that such studies still present significant technical challenges to the NMR spectroscopist. This review will discuss the progress that has been made in this area, surveying all NMR studies that have been published to date, and with a particular focus on strategies for improving experimental sensitivity. PMID:24083462

  3. Theoretical Study of the Electrostatic and Steric Effects on the Spectroscopic Characteristics of the Metal-Ligand Unit of Heme Proteins. 2. C-O Vibrational Frequencies, 17O Isotropic Chemical Shifts, and Nuclear Quadrupole Coupling Constants

    PubMed Central

    Kushkuley, Boris; Stavrov, Solomon S.

    1997-01-01

    The quantum chemical calculations, vibronic theory of activation, and London-Pople approach are used to study the dependence of the C-O vibrational frequency, 17O isotropic chemical shift, and nuclear quadrupole coupling constant on the distortion of the porphyrin ring and geometry of the CO coordination, changes in the iron-carbon and iron-imidazole distances, magnitude of the iron displacement out of the porphyrin plane, and presence of the charged groups in the heme environment. It is shown that only the electrostatic interactions can cause the variation of all these parameters experimentally observed in different heme proteins, and the heme distortions could modulate this variation. The correlations between the theoretically calculated parameters are shown to be close to the experimentally observed ones. The study of the effect of the electric field of the distal histidine shows that the presence of the four C-O vibrational bands in the infrared absorption spectra of the carbon monoxide complexes of different myoglobins and hemoglobins can be caused by the different orientations of the different tautomeric forms of the distal histidine. The dependence of the 17O isotropic chemical shift and nuclear quadrupole coupling constant on pH and the distal histidine substitution can be also explained from the same point of view. PMID:9017215

  4. NMR study of compressed supercritical water

    NASA Astrophysics Data System (ADS)

    Lamb, W. J.; Jonas, J.

    1981-01-01

    The proton spin-lattice relaxation time T1 in water has been measured as a function of pressure in the temperature range 150 to 700°C. This study focuses on the supercritical region (tc=374°C) where the spin-rotation interaction mechanism dominates the observed proton relaxation rate. Since water is an asymmetric top molecule, the analysis of the experimental data involves a number of simplifying assumptions discussed in detail. The experimental finding that in supercritical water the spin-rotation relaxation time T 1SR is a linear function of density ρ, up to relatively high densities (ρ≃ 1.5 ρc) provides rationale for analysis of the NMR experimental data in terms of a model used for dilute gases. The T 1SR data are analyzed on the basis of the assumption that the collision modulated spin-rotation interactions can be described by a single correlation function which is an exponential function of time. Using this procedure, we find that T 1SR/ρ αT-2, i.e.T 1SR/ρ exhibits a stronger temperature dependence than that found (T 1SR/ρ αT-3/2) for many polar and nonpolar gases. The calculated effective cross sections for the transfer of angular momentum σeff which show strong temperature dependence (σeff αT-1.5) are several times larger than the kinetic cross sections. By assuming applicability of expressions derived for isotropic reorientation of spherical-top molecules and using the effective spin-rotation interaction constant as obtained from microwave measurements, we are able to calculate the angular momentum correlation time τJ, over the range of temperatures and densities studied. In the supercritical region τJ⩾τΘ, where τΘ is the reorientational correlation time, and the estimated mean angle of reorientation ΔΘ¯ is in the range 50° to 800°. The T 1SR data are also interpreted in terms of the modified rough hard sphere (RHS) model which for ρ<2ρc takes into account the effect of attractive forces. We find that 1/T 1SR is a linear

  5. The Kinetics of Dissociations of Aluminum - Oxygen Bonds in Aqueous Complexes - An NMR Study

    SciTech Connect

    Dr. William Casey

    2003-09-03

    OAK B262 The Kinetics of Dissociations of Aluminum--Oxygen Bonds in Aqueous Complexes--An NMR Study. In this project we determined rates and mechanisms of Al(III)-O bond rupture at mineral surfaces and in dissolved aluminum complexes. We then compared the experimental results to simulations in an attempt to predict rate coefficients. Most of the low-temperature reactions that are geochemically important involve a bonded atom or molecule that is replaced with another. We probe these reactions at the most fundamental level in order to establish a model to predict rates for the wide range of reactions that cannot be experimentally studied. The chemistry of small aluminum cluster (Figure) provides a window into the hydrolytic processes that control rates of mineral formation and the transformation of adsorbates into extended structures. The molecule shown below as an example exposes several types of oxygens to the bulk solution including seven structurally distinct sets of bridging hydroxyls. This molecule is a rich model for the aqueous interface of aluminum (hydr)oxide minerals, since it approaches colloidal dimensions in size, yet is a dissolved complex with +18 charge. We have conducted both {sup 17}O- {sup 27}Al- and {sup 19}F-NMR experiments to identify the reactive sites and to determine the rates of isotopic exchange between these sites and the bulk solution. The research was enormously successful and led to a series of papers that are being used as touchstones for assessing the accuracy of computer models of bond ruptures in water.

  6. Crystal structure and proton conductivity of BaSn0.6Sc0.4O3–δ: insights from neutron powder diffraction and solid-state NMR spectroscopy† †Electronic supplementary information (ESI) available: Rietveld fit of dry BaSn0.6Sc0.4O3–δ sample (Fig. S1). 119Sn (Fig. S2), 45Sc (Fig. S3–S6) and 17O (Fig. S7) spectra of all materials as a function of Sc doping concentration, 45Sc MQMAS of deuterated BaSn0.9Sc0.1O3–δ (Fig. S4), 45Sc MQMAS of dry and deuterated BaSn0.8Sc0.2O3–δ (Fig. S5), 45Sc MQMAS of dry and deuterated BaSn0.7Sc0.3O3–δ (Fig. S6), 17O MQMAS of 17O enriched BaSn0.8Sc0.2O3–δ and BaSn0.6Sc0.4O3–δ (Fig. S8). See DOI: 10.1039/c5ta09744d Click here for additional data file.

    PubMed Central

    Norberg, Stefan T.; Knee, Christopher S.; Ahmed, Istaq; Hull, Stephen; Buannic, Lucienne; Hung, Ivan; Gan, Zhehong; Blanc, Frédéric; Grey, Clare P.; Eriksson, Sten G.

    2016-01-01

    The solid-state synthesis and structural characterisation of perovskite BaSn1–xScxO3–δ (x = 0.0, 0.1, 0.2, 0.3, 0.4) and its corresponding hydrated ceramics are reported. Powder and neutron X-ray diffractions reveal the presence of cubic perovskites (space group Pm3m) with an increasing cell parameter as a function of scandium concentration along with some indication of phase segregation. 119Sn and 45Sc solid-state NMR spectroscopy data highlight the existence of oxygen vacancies in the dry materials, and their filling upon hydrothermal treatment with D2O. It also indicates that the Sn4+ and Sc3+ local distribution at the B-site of the perovskite is inhomogeneous and suggests that the oxygen vacancies are located in the scandium dopant coordination shell at low concentrations (x ≤ 0.2) and in the tin coordination shell at high concentrations (x ≥ 0.3). 17O NMR spectra on 17O enriched BaSn1–xScxO3–δ materials show the existence of Sn–O–Sn, Sn–O–Sc and Sc–O–Sc bridging oxygen environments. A further room temperature neutron powder diffraction study on deuterated BaSn0.6Sc0.4O3–δ refines the deuteron position at the 24k crystallographic site (x, y, 0) with x = 0.579(3) and y = 0.217(3) which leads to an O–D bond distance of 0.96(1) Å and suggests tilting of the proton towards the next nearest oxygen. Proton conduction was found to dominate in wet argon below 700 °C with total conductivity values in the range 1.8 × 10–4 to 1.1 × 10–3 S cm–1 between 300 and 600 °C. Electron holes govern the conduction process in dry oxidizing conditions, whilst in wet oxygen they compete with protonic defects leading to a wide mixed conduction region in the 200 to 600 °C temperature region, and a suppression of the conductivity at higher temperature. PMID:27358734

  7. 17O excess transfer during the NO2 + O3 → NO3 + O2 reaction

    NASA Astrophysics Data System (ADS)

    Berhanu, Tesfaye Ayalneh; Savarino, Joël; Bhattacharya, S. K.; Vicars, Willliam C.

    2012-01-01

    The ozone molecule possesses a unique and distinctive 17O excess (Δ17O), which can be transferred to some of the atmospheric molecules via oxidation. This isotopic signal can be used to trace oxidation reactions in the atmosphere. However, such an approach depends on a robust and quantitative understanding of the oxygen transfer mechanism, which is currently lacking for the gas-phase NO2 + O3 reaction, an important step in the nocturnal production of atmospheric nitrate. In the present study, the transfer of Δ17O from ozone to nitrate radical (NO3) during the gas-phase NO2 + O3 → NO3 + O2 reaction was investigated in a series of laboratory experiments. The isotopic composition (δ17O, δ18O) of the bulk ozone and the oxygen gas produced in the reaction was determined via isotope ratio mass spectrometry. The Δ17O transfer function for the NO2 + O3 reaction was determined to be: Δ17O(O3*) = (1.23 ± 0.19) × Δ17O(O3)bulk + (9.02 ± 0.99). The intramolecular oxygen isotope distribution of ozone was evaluated and results suggest that the excess enrichment resides predominantly on the terminal oxygen atoms of ozone. The results obtained in this study will be useful in the interpretation of high Δ17O values measured for atmospheric nitrate, thus leading to a better understanding of the natural cycling of atmospheric reactive nitrogen.

  8. NMR and protein folding: equilibrium and stopped-flow studies.

    PubMed Central

    Frieden, C.; Hoeltzli, S. D.; Ropson, I. J.

    1993-01-01

    NMR studies are now unraveling the structure of intermediates of protein folding using hydrogen-deuterium exchange methodologies. These studies provide information about the time dependence of formation of secondary structure. They require the ability to assign specific resonances in the NMR spectra to specific amide protons of a protein followed by experiments involving competition between folding and exchange reactions. Another approach is to use 19F-substituted amino acids to follow changes in side-chain environment upon folding. Current techniques of molecular biology allow assignments of 19F resonances to specific amino acids by site-directed mutagenesis. It is possible to follow changes and to analyze results from 19F spectra in real time using a stopped-flow device incorporated into the NMR spectrometer. PMID:8298453

  9. Some specific features of the NMR study of fluid flows

    NASA Astrophysics Data System (ADS)

    Davydov, V. V.

    2016-07-01

    Some specific features of studying fluid flows with a NMR spectrometer are considered. The consideration of these features in the NMR spectrometer design makes it possible to determine the relative concentrations of paramagnetic ions and measure the longitudinal and transverse relaxation times ( T 1 and T 2, respectively) in fluid flows with an error no larger than 0.5%. This approach allows one to completely avoid errors in determining the state of a fluid from measured relaxation constants T 1 and T 2, which is especially urgent when working with medical suspensions and biological solutions. The results of an experimental study of fluid flows are presented.

  10. NMR study of the potential composition of Titan's lakes

    NASA Astrophysics Data System (ADS)

    He, Chao; Smith, Mark A.

    2015-05-01

    A large number of hydrocarbon lakes have been discovered in Titan's surface. However, the chemical composition and physical properties of these lakes are not fully understood. We investigate the potential composition of Titan's lakes by NMR. Based upon NMR data, the 1H and 13C NMR spectra of the hydrocarbons in Titan's lakes are simulated on a 1 T spectrometer [being developed at the NASA Jet Propulsion Laboratory (JPL) for future in situ characterization of Titan's lakes]. The study indicates that the dominant composition (all components>1% of the lake composition by mole fraction) in Titan's lakes can be determined and the major soluble organics quantitatively identified from either quantitative 1H or 13C spectra on a 1 T NMR spectrometer. The proton T1 relaxation times are determined for a number of candidate organics in hydrocarbon solution, a necessary determinant for quantitative NMR. The gas solubility of these organics is also investigated to understand the equilibrium of composition between Titan's lakes and atmosphere and the precipitation rates of the molecules at Titan's ground level. Our results are significant for the ongoing discussion regarding the development of in situ, low bias analysis methods and instruments for Titan missions and other outer planet exploration.

  11. Experimental determination of the {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates

    SciTech Connect

    Chafa, A.; Ouichaoui, S.; Tatischeff, V.; Coc, A.; Garrido, F.; Kiener, J.; Lefebvre-Schuhl, A.; Thibaud, J.-P.; Aguer, P.; Barhoumi, S.; Hernanz, M.; Jose, J.; Sereville, N. de

    2007-03-15

    The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reactions are of major importance to hydrogen-burning nucleosynthesis in a number of different stellar sites. In particular, {sup 17}O and {sup 18}F nucleosynthesis in classical novae is strongly dependent on the thermonuclear rates of these two reactions. The previously estimated rate for {sup 17}O(p,{alpha}){sup 14}N carries very large uncertainties in the temperature range of classical novae (T=0.01-0.4 GK), whereas a recent measurement has reduced the uncertainty of the {sup 17}O(p,{gamma}){sup 18}F rate. We report on the observation of a previously undiscovered resonance at E{sub c.m.}=183.3 keV in the {sup 17}O(p,{alpha}){sup 14}N reaction, with a measured resonance strength {omega}{gamma}{sub p{alpha}}=(1.6{+-}0.2)x10{sup -3} eV. We studied in the same experiment the {sup 17}O(p,{gamma}){sup 18}F reaction by an activation method, and the resonance strength was found to amount to {omega}{gamma}{sub p{gamma}}=(2.2{+-}0.4)x10{sup -6} eV. The excitation energy of the corresponding level in {sup 18}F was determined to be 5789.8{+-}0.3 keV in a Doppler shift attenuation method measurement, which yielded a value of {tau}<2.6 fs for the level lifetime. The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates were calculated using the measured resonance properties and reconsidering some previous analyses of the contributions of other levels or processes. The {sup 17}O(p,{alpha}){sup 14}N rate is now well established below T=1.5 GK, with uncertainties reduced by orders of magnitude in the temperature range T=0.1-0.4 GK. The uncertainty in the {sup 17}O(p,{gamma}){sup 18}F rate is somewhat larger because of remaining obscurities in the knowledge of the direct capture process. These new resonance properties have important consequences for {sup 17}O nucleosynthesis and {gamma}-ray emission of classical novae.

  12. NMR study in sodium-hydrogen-C{sub 60} superconductor

    SciTech Connect

    Ogata, H.; Miyajima, S.; Imaeda, K.; Inokuchi, H.

    1998-12-31

    {sup 23}Na and {sup 1}H NMR studies have been carried out for a Na{sub x}H{sub y}C{sub 60} superconductor. The peak position of the {sup 23}Na NMR spectrum exhibits discontinuous upfield shift of 30 ppm at about 250 K, indicates a first order phase transition. From the line shape of the {sup 23}Na spectrum obtained at 7 K, the quadrupole coupling constant tensor is evaluated to be {vert_bar}e{sup 2}Qq/h{vert_bar} = 3.7 MHz with the asymmetry parameter {eta} = 0.95. The {sup 1}H NMR spectrum suggests an anionic hydrogen state with weakly delocalized nature.

  13. Continental scale variation in 17O-excess of meteoric waters in the United States

    NASA Astrophysics Data System (ADS)

    Li, Shuning; Levin, Naomi E.; Chesson, Lesley A.

    2015-09-01

    High-precision triple oxygen isotope analysis of waters is an emerging tool in hydrological and paleoclimate research. The existing research on 17O-excess in waters includes surveys of meteoric waters and region-specific studies of high-latitude snow and tropical storms. However, a better understanding of the variation in 17O-excess of waters across large geographic regions is needed to expand the utility of triple oxygen isotope measurements. Here we present 17O-excess data from tap waters across the continental U.S., which we used as a proxy for precipitation. The 17O-excess values of tap waters ranged from -6 to +43 per meg and averaged 17 ± 11 per meg which is lower than the average 17O-excess reported for global meteoric waters, but overlaps with reported 17O-excess values of rainfall from the tropics. We observed relatively high 17O-excess values (>25 per meg) of tap waters in the northwestern U.S. and some of the lowest 17O-excess values (<5 per meg) in the states bordering the Gulf of Mexico. The latitudinal variation of 17O-excess among tap waters likely reflects the different controls on 17O-excess in precipitation. For example, re-evaporation of precipitation and convective processes influence the isotopic composition of tap waters from the southern portions of the U.S., resulting in relatively low 17O-excess values. In contrast, these effects are reduced in tap waters from the northern portions of the U.S. where snow and cold-season rainfall are primarily responsible for the majority of annual precipitation. Exceptions to the latitudinal trend are prevalent in the central portions of the U.S., where mixing and convection are likely responsible for 17O-excess values that are lower than would be expected at their latitudes. The results of this study provide both a first look at the variation of 17O-excess in meteoric waters on a continental scale and a predictive map for 17O-excess of meteoric waters in the U.S.

  14. MAS PFG NMR Studies of Mixtures in Porous Materials

    NASA Astrophysics Data System (ADS)

    Gratz, Marcel; Hertel, Stefan; Wehring, Markus; Schlayer, Stefan; Stallmach, Frank; Galvosas, Petrik

    2011-03-01

    Pulsed field gradient (PFG) and magic angle spinning (MAS) NMR techniques have been successfully combined for the study of mixture diffusion in porous materials. Using a modular setup of commercially available components, gradient pulses of up to ±2.6 T/m can be applied coinciding with fast sample rotation at the magic angle. Methods for the proper alignment of all components are presented along with protocols for MAS PFG NMR experiments. Finally, first diffusion measurements of n-hexane and benzene being adsorbed together in the metal-organic framework MOF-5 are presented.

  15. Novel Dodecaarylporphyrins: Synthesis and Variable Temperature NMR Studies

    SciTech Connect

    Cancilla, Mark; Lebrilla, Carlito; Ma, Jian-Guo; Medforth, Craig J.; Muzzi, Cinzia M.; Shelnutt, John A.; Smith, Kevin M.; Voss, Lisa

    1999-05-05

    An investigation of the synthesis of novel dodecaarylporphyrins using the Suzuki coupling reaction of arylboronic acids with octabromotetraarylporphyrins is reported. Studies of the dynamic properties of these new porphyrins using variable temperature (VT) 1H NMR spectroscopy and molecular mechanics provide interesting insights into their dynamic properties, including the first determination of {beta} aryl rotation in a porphyrin system.

  16. NMR studies of structure and dynamics in fruit cuticle polyesters.

    PubMed

    Stark, R E; Yan, B; Ray, A K; Chen, Z; Fang, X; Garbow, J R

    2000-05-01

    Cutin and suberin are support polymers involved in waterproofing the leaves and fruits of higher plants, regulating the flow of nutrients among various plant organs, and minimizing the deleterious impact of microbial pathogens. Despite the complexity and intractable nature of these plant biopolyesters, their molecular structure and development are amenable to study by suitable solid-state and solution-state NMR techniques. Interactions of tomato cutin with water were examined by solid-state 2H and 13C NMR, showing that water films enhance rapid segmental motions of the acyl chains and are associated with a fivefold increase in surface elasticity upon cutin hydration. The suberization of wounded potato tissues was studied by solid-state 13C NMR, revealing the likely phenylpropanoid structures that permit dense cross-linking of the suberin structure and their proximity to the cell-wall polysaccharides. Finally, two new approaches were developed to elucidate the molecular structures of these biopolymers: partial depolymerization followed by spectroscopic analysis of the soluble oligomers; and swelling of the intact materials followed by magic-angle spinning (MAS) NMR analysis. PMID:10811427

  17. Study of correlations in molecular motion by multiple quantum NMR

    SciTech Connect

    Tang, J.H.

    1981-11-01

    Nuclear magnetic resonance is a very useful tool for characterizing molecular configurations through the measurement of transition frequencies and dipolar couplings. The measurement of spectral lineshapes, spin-lattice relaxation times, and transverse relaxation times also provide us with valuable information about correlations in molecular motion. The new technique of multiple quantum nuclear magnetic resonance has numerous advantages over the conventional single quantum NMR techniques in obtaining information about static and dynamic interactions of coupled spin systems. In the first two chapters, the theoretical background of spin Hamiltonians and the density matrix formalism of multiple quantum NMR is discussed. The creation and detection of multiple quantum coherence by multiple pulse sequence are discussed. Prototype multiple quantum spectra of oriented benzene are presented. Redfield relaxation theory and the application of multiple quantum NMR to the study of correlations in fluctuations are presented. A specific example of an oriented methyl group relaxed by paramagnetic impurities is studied in detail. The study of possible correlated motion between two coupled methyl groups by multiple quantum NMR is presented. For a six spin system it is shown that the four-quantum spectrum is sensitive to two-body correlations, and serves a ready test of correlated motion. The study of the spin-lattice dynamics of orienting or tunneling methyl groups (CH/sub 3/ and CD/sub 3/) at low temperatures is presented. The anisotropic spin-lattice relaxation of deuterated hexamethylbenzene, caused by the sixfold reorientation of the molecules, is investigated, and the NMR spectrometers and other experimental details are discussed.

  18. Solution oxygen-17 NMR application for observing a peroxidized cysteine residue in oxidized human SOD1

    NASA Astrophysics Data System (ADS)

    Fujiwara, Noriko; Yoshihara, Daisaku; Sakiyama, Haruhiko; Eguchi, Hironobu; Suzuki, Keiichiro

    2016-12-01

    NMR active nuclei, 1H, 13C and 15N, are usually used for determination of protein structure. However, solution 17O-NMR application to proteins is extremely limited although oxygen is an essential element in biomolecules. Proteins are oxidized through cysteine residues by two types of oxidation. One is reversible oxidation such as disulphide bonding (Cys-S-S-Cys) and the other is irreversible oxidation to cysteine sulfinic acid (Cys-SO 2H) and cysteine sulfonic acid (Cys-SO 3H). Copper,Zinc-superoxide dismutase (SOD1) is a key enzyme in the protection of cells from the superoxide anion radical. The SH group at Cys 111 residue in human SOD1 is selectively oxidized to -SO 2H and -SO 3H with atmospheric oxygen, and this oxidized human SOD1 is also suggested to play an important role in the pathophysiology of various neurodegenerative diseases, probably mainly via protein aggregation. Therefore, information on the structural and the dynamics of the oxidized cysteine residue would be crucial for the understanding of protein aggregation mechanism. Although the -SO 3H group on proteins cannot be directly detected by conventional NMR techniques, we successfully performed the site-specific 17O-labeling of Cys 111 in SOD1 using ^{17}it {O}2 gas and the 17O-NMR analysis for the first time. We observed clear 17O signal derived from a protein molecule and show that 17O-NMR is a sensitive probe for studying the structure and dynamics of the 17O-labeled protein molecule. This novel and unique strategy can have great impact on many research fields in biology and chemistry.

  19. Hydrogen Burning of {sup 17}O in Classical Novae

    SciTech Connect

    Chafa, A.; Ouichaoui, S.; Tatischeff, V.; Coc, A.; Garrido, F.; Kiener, J.; Lefebvre-Schuhl, A.; Thibaud, J.-P.; Aguer, P.; Barhoumi, S.; Hernanz, M.; Jose, J.; Sereville, N. de

    2005-07-15

    We report on the observation of a previously unknown resonance at E{sub R}{sup lab}=194.1{+-}0.6 keV in the {sup 17}O(p,{alpha}){sup 14}N reaction, with a measured resonance strength {omega}{gamma}{sub p{alpha}}=1.6{+-}0.2 meV. We studied in the same experiment the {sup 17}O(p,{gamma}){sup 18}F reaction by an activation method and the resonance-strength ratio was found to be {omega}{gamma}{sub p{alpha}}/{omega}{gamma}{sub p{gamma}}=470{+-}50. The corresponding excitation energy in the {sup 18}F compound nucleus was determined to be 5789.8{+-}0.3 keV by {gamma}-ray measurements using the {sup 14}N({alpha},{gamma}){sup 18}F reaction. These new resonance properties have important consequences for {sup 17}O nucleosynthesis and {gamma}-ray astronomy of classical novae.

  20. NMR studies of bond arrangements in alkali phosphate glasses

    SciTech Connect

    Alam, T.M.; Brow, R.K.

    1998-01-01

    Solid-state magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy has become a powerful tool for the investigation of local structure and medium range order in glasses. Previous {sup 31}P MAS NMR studies have detailed the local structure for a series of phosphate glasses. Phosphate tetrahedra within the glass network are commonly described using the Q{sup n} notation, where n = 0, 1, 2, 3 and represents the number of bridging oxygens attached to the phosphate. Using {sup 31}P MAS NMR different phosphate environments are readily identified and quantified. In this paper, the authors present a brief description of recent one dimensional (1D) {sup 6}Li, {sup 7}Li and {sup 31}P MAS experiments along with two-dimensional (2D) {sup 31}P exchange NMR experiments for a series of lithium ultraphosphate glasses. From the 2D exchange experiments the connectivities between different Q{sup n} phosphate tetrahedra were directly measured, while the 1D experiments provided a measure of the P-O-P bond angle distribution and lithium coordination number as a function of Li{sub 2}O concentration.

  1. Time-resolved NMR studies of RNA folding.

    PubMed

    Fürtig, Boris; Buck, Janina; Manoharan, Vijayalaxmi; Bermel, Wolfgang; Jäschke, Andres; Wenter, Philipp; Pitsch, Stefan; Schwalbe, Harald

    The application of real-time NMR experiments to the study of RNA folding, as reviewed in this article, is relatively new. For many RNA folding events, current investigations suggest that the time scales are in the second to minute regime. In addition, the initial investigations suggest that different folding rates are observed for one structural transition may be due to the hierarchical folding units of RNA. Many of the experiments developed in the field of NMR of protein folding cannot directly be transferred to RNA: hydrogen exchange experiments outside the spectrometer cannot be applied since the intrinsic exchange rates are too fast in RNA, relaxation dispersion experiments on the other require faster structural transitions than those observed in RNA. On the other hand, information derived from time-resolved NMR experiments, namely the acquisition of native chemical shifts, can be readily interpreted in light of formation of a single long-range hydrogen bonding interaction. Together with mutational data that can readily be obtained for RNA and new ligation technologies that enhance site resolution even further, time-resolved NMR may become a powerful tool to decipher RNA folding. Such understanding will be of importance to understand the functions of coding and non-coding RNAs in cells. PMID:17595685

  2. An NMR Study of Enzyme Activity.

    ERIC Educational Resources Information Center

    Peterman, Keith E.; And Others

    1989-01-01

    A laboratory experiment designed as a model for studying enzyme activity with a basic spectrometer is presented. Included are background information, experimental procedures, and a discussion of probable results. Stressed is the value of the use of Nuclear Magnetic Resonance in biochemistry. (CW)

  3. Proton NMR studies of functionalized nanoparticles in aqueous environments

    NASA Astrophysics Data System (ADS)

    Tataurova, Yulia Nikolaevna

    Nanoscience is an emerging field that can provide potential routes towards addressing critical issues such as clean and sustainable energy, environmental remediation and human health. Specifically, porous nanomaterials, such as zeolites and mesoporous silica, are found in a wide range of applications including catalysis, drug delivery, imaging, environmental protection, and sensing. The characterization of the physical and chemical properties of nanocrystalline materials is essential to the realization of these innovative applications. The great advantage of porous nanocrystals is their increased external surface area that can control their biological, chemical and catalytic activities. Specific functional groups synthesized on the surface of nanoparticles are able to absorb heavy metals from the solution or target disease cells, such as cancer cells. In these studies, three main issues related to functionalized nanomaterials will be addressed through the application of nuclear magnetic resonance (NMR) techniques including: 1) surface composition and structure of functionalized nanocrystalline particles; 2) chemical properties of the guest molecules on the surface of nanomaterials, and 3) adsorption and reactivity of surface bound functional groups. Nuclear magnetic resonance (NMR) is one of the major spectroscopic techniques available for the characterization of molecular structure and conformational dynamics with atomic level detail. This thesis deals with the application of 1H solution state NMR to porous nanomaterial in an aqueous environment. Understanding the aqueous phase behavior of functionalized nanomaterials is a key factor in the design and development of safe nanomaterials because their interactions with living systems are always mediated through the aqueous phase. This is often due to a lack of fundamental knowledge in interfacial chemical and physical phenomena that occur on the surface of nanoparticles. The use of solution NMR spectroscopy results

  4. NMR studies and applications of perfluorocarbon gases

    NASA Astrophysics Data System (ADS)

    Chang, Yulin

    Hyperpolarized 3He has been very successful in magnetic resonance imaging (MRI) of the lungs. It provides ways to study the physiological properties of the lungs and lung function. However, the high costs of the polarizing apparatus and the complicated polarizing procedure are preventing this technique from being clinically used routinely. Recent developments have shown that several fluorinated gases have the potential to replace 3He in some of its applications. This thesis presents some preliminary results of human excised lung imaging using C2F6 and C3F8. These two fluorinated gases were able to yield images with good signal-to-noise ratio and reasonable resolutions in a 1.5 T magnet. Using diffusion MRI of these two gases can distinguish emphysematous lungs from healthy ones. An important application of these gases would be to determine local lung surface-to-volume (S/V) ratio in vivo, which requires the unrestricted (free) diffusivity in each pixel to be known. We present data in this thesis which allow free diffusivities to be calculated from the relaxation time T1. Samples of pure C 2F6 and C3F8 at different pressures and in mixtures with oxygen at different concentrations were made. Measurements were done at two different magnetic fields and temperature was regulated to study the temperature dependence over a small range. These two gases were also used in studies of carbon-block filters, where the strong adsorption of the gases to the high surface-area carbon is beneficial. A brief review of our work on mouse lung imaging using hyperpolarized 3He is presented in Appendix A; Appendix B is a study of the longitudinal spin magnetization in the presence of a strong magnetic field gradient; the construction of the pulsed field gradient waveform measurement coils and some experimental results using these coils are contained in Appendix C.

  5. High-Temperature NMR Studies of Quasicrystals and Polymers

    NASA Astrophysics Data System (ADS)

    Hill, Edward Arthur

    1995-01-01

    Icosahedral alloys such as rm Al _{65}Cu_{20}Ru_ {15}, Al_{62.5}Cu_ {24.5}Fe_{13}, and rm Al_{70}Pd_{20}Re _{10} have motivated a great deal of experimental and theoretical effort to understand fundamental issues such as the electronic structure, "lattice" dynamics, and thermodynamic stability of quasicrystalline materials. It has been shown here that Nuclear Magnetic Resonance (NMR) is a useful tool for exploring many of the essential properties of quasicrystal alloys and the so-called approximant phase alloys. Specifically, the ^{27 }Al Knight shift has been used here to study the electronic density of states in these alloys up to temperatures of 1200 K. Furthermore, ^{27}Al nuclear spin-lattice and spin-spin relaxation measurements across a wide temperature range have been used to show that the dynamic processes found in quasicrystals are quite different from those found in some crystalline alloys of similar compositions. In addition, two-dimensional exchange experiments have been employed to study the dynamics of these materials. Finally, the semiconducting alloy rm Al_2Ru has also been studied by the techniques mentioned above. It has also been demonstrated here that high temperature NMR techniques are useful in the study of organic polymers. These experiments focus on determining the timescales and other aspects of molecular motion for several specific samples. ^2H NMR measurements, including the ^2H two-dimensional exchange technique, on the high temperature polymer polybenzamidazole (PBI) are described here. ^2H NMR results for high melting temperature copolyester liquid crystals of the PCnNBB family will also be discussed. An assessment of the high temperature motion in these samples is relevant to an understanding of the physical properties that influence their high temperature applications and high temperature processing.

  6. ADVANCED SOLIDS NMR STUDIES OF COAL STRUCTURE AND CHEMISTRY

    SciTech Connect

    1997-03-01

    This report covers the progress made on the title project for the project period. The study of coal chemical structure is a vital component of research efforts to develop better chemical utilization of coals, and for furthering our basic understanding of coal geochemistry. In this grant we are addressing several structural questions pertaining to coals with advances in state of the art solids NMR methods. Our goals are twofold. First, we are interested in developing new methods that will enable us to measure important structural parameters in whole coals not directly accessible by other techniques. In parallel with these efforts we will apply these NMR methods in a study of the chemical differences between gas-sourcing and oil-sourcing coals. The NMR methods work will specifically focus on determination of the number and types of methylene groups, determination of the number and types of methane groups, identification of carbons adjacent to nitrogen and sites with exchangeable protons, and methods to more finely characterize the distribution of hydrogen in coals. The motivation for investigating these specific structural features of coals arises from their relevance to the chemical reactivity of coals, and their suitability for possible correlations with the oil sourcing potential of some types of coals. The coals to be studied and contrasted include oil-prone coals from Australia and Indonesia, those comprising the Argonne Premium Coal Sample bank, and other relevant samples. In this report period we have focused our work on 1 segment of the program. Our last report outlined progress in using our NMR editing methods with higher field operation where higher magic angle spinning rates are required. Significant difficulties were identified, and these have been the main subject of study during the most recent granting period.

  7. Theoretical and experimental study of 15N NMR protonation shifts.

    PubMed

    Semenov, Valentin A; Samultsev, Dmitry O; Krivdin, Leonid B

    2015-06-01

    A combined theoretical and experimental study revealed that the nature of the upfield (shielding) protonation effect in 15N NMR originates in the change of the contribution of the sp(2)-hybridized nitrogen lone pair on protonation resulting in a marked shielding of nitrogen of about 100 ppm. On the contrary, for amine-type nitrogen, protonation of the nitrogen lone pair results in the deshielding protonation effect of about 25 ppm, so that the total deshielding protonation effect of about 10 ppm is due to the interplay of the contributions of adjacent natural bond orbitals. A versatile computational scheme for the calculation of 15N NMR chemical shifts of protonated nitrogen species and their neutral precursors is proposed at the density functional theory level taking into account solvent effects within the supermolecule solvation model. PMID:25891386

  8. 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.

  9. Double rotation NMR studies of zeolites and aluminophosphate molecular sieves

    SciTech Connect

    Jelinek, R. |

    1993-07-01

    Goal is to study the organization and structures of guest atoms and molecules and their reactions on internal surfaces within pores of zeolites and aluminophosphate molecular sieves. {sup 27}Al and {sup 23}Na double rotation NMR (DOR) is used since it removes the anisotropic broadening in NMR spectra of quadrupolar nuclei, thus increasing resolution. This work concentrates on probing aluminum framework atoms in aluminophosphate molecular sieves and sodium extra framework cations in porous aluminosilicates. In aluminophosphates, ordering and electronic environments of the framework {sup 27}Al nuclei are modified upon adsorption of water molecules within the channels; a relation is sought between the sieve channel topology and the organization of adsorbed water, as well as the interaction between the Al nuclei and the water molecules. Extra framework Na{sup +} cations are directly involved in adsorption processes and reactions in zeolite cavities.

  10. 7Li NMR study of normal human erythrocytes

    NASA Astrophysics Data System (ADS)

    Pettegrew, J. W.; Post, J. F. M.; Panchalingam, K.; Withers, G.; Woessner, D. E.

    The biological action of lithium is of great interest because of the therapeutic efficacy of the cation in manic-depressive illness. To investigate possible molecular interactions of lithium, 7Li NMR studies were conducted on normal human erythrocytes which had been incubated with lithium chloride. The uptake of lithium ions was followed by 7Li NMR, using a dysprosium, tripolyphosphate shift reagent. Lithium uptake followed single-exponential kinetics with a time constant of 14.7 h. The intracellular lithium relaxation times were T 1 ⋍ 5 s and T 2 ⋍ 0.15 s, which implies a lengthening of the lithium correlation time. It was found that lithium does not interact significantly with hemoglobin, the erythrocyte membrane, or artificial phospholipid membranes. Based on measurements of lithium T1 and T2 in concentrated agar gels, the large difference between T1 and T2 for intracellular lithium ions may be due to diffusion of the hydrated lithium ion through heterogeneous electrostatic field gradients created by the erythrocyte membrane-associated cytoskeletal network. Lithium binding to the membrane-associated cytoskeleton, however, cannot be ruled out. Because of the large differences between T1 and T2 of intracellular lithium ions, 1Li NMR may be a sensitive and promising noninvasive method to probe the intracellular environment.

  11. A 13C-NMR study of azacryptand complexes.

    PubMed

    Wild, Aljoscha A C; Fennell, Kevin; Morgan, Grace G; Hewage, Chandralal M; Malthouse, J Paul G

    2014-09-28

    An azacryptand has been solubilised in aqueous media containing 50% (v/v) dimethyl sulphoxide. (13)C-NMR has been used to determine how the azacryptand is affected by zinc binding at pH 10. Using (13)C-NMR and (13)C-enriched bicarbonate we have been able to observe the formation of 4 different carbamate derivatives of the azacryptand at pH 10. The azacryptand was shown to solubilise zinc or cadmium at alkaline pHs. Two moles of zinc are bound per mole of azacryptand and this complex binds 1 mole of carbonate. By replacing the zinc with cadmium-113 we have shown that the (13)C-NMR signal of the (13)C-enriched carbon of the bound carbonate is split into two triplets at 2.2 °C. This shows that two cadmium complexes are formed and in each of these complexes the carbonate group is bound by two magnetically equivalent metal ions. It also demonstrates that these cadmium complexes are not in fast exchange. From temperature studies we show that in the zinc complexes both complexes are in fast exchange with each other but are in slow exchange with free bicarbonate. HOESY is used to determine the position of the carbonate carbon in the complex. The solution and crystal structures of the zinc-carbonate-azacryptand complexes are compared. PMID:25091182

  12. NMR study of new ruthenates with high magnetic ordering

    NASA Astrophysics Data System (ADS)

    Paulose, P. L.; Chakrabarty, Tanmoy

    The Ru based compounds, Ca3LiRuO6 and Ca3NaRuO6 show unusually high magnetic ordering temperature. Extended super exchange model is invoked to explain the magnetic behavior in the isostructural compound Ca3LiOsO6. We have carried out NMR investigation on these two Ru-based compounds. Ca3LiRuO6 is a weak ferromagnet with a magnetic ordering temperature (TC) of 115 K which is explored by the temperature dependence of 7Li NMR line shift, line-width and spin-lattice relaxation rate (1/T1) . Above TC, a broad maximum is observed in the evolution of line-width of the spectra. We speculate that this feature might be attributed to some low-dimensional magnetic behavior. Contrastingly, Ca3NaRuO6 with similar structure and local geometry of the Ru5+ ions is a conventional antiferromagnet with a transition temperature of 90 K. The temperature dependence of 23Na NMR line shift and 1/T1 is studied across magnetic transition in Ca3NaRuO6. The temperature variation of line-width is found to be different compared to Ca3LiRuO6. In both these systems, 1/T1 decreases significantly below ordering temperature, characteristic of many antiferromagnetic systems.

  13. 17O(p,α)14N reaction measurement at astrophysical energies

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; Pizzone, R. G.; Burjan, S. V.; Cherubini, S.; Coc, A.; Gulino, M.; Hammache, F.; Hons, Z.; Irgaziev, B.; Kiss, G. G.; Kroha, V.; La Cognata, M.; Lamia, L.; Mukhamedzhanov, A.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; de Séréville, N.; Somorjai, E.; Tumino, A.

    2014-05-01

    The 17O(p,α)14N reaction is of paramount importance for the nucleosynthesis in a number of stellar sites, including red giants (RG), asymptotic giant branch (AGB) stars, massive stars and classical novae. We report on the indirect study of the 17O(p,α)14N reaction via the Trojan Horse Method by applying the approach recently developed for extracting the resonance strength of narrow resonance in the ultra-low energy region.

  14. MRI and unilateral NMR study of reindeer skin tanning processes.

    PubMed

    Zhu, Lizheng; Del Federico, Eleonora; Ilott, Andrew J; Klokkernes, Torunn; Kehlet, Cindie; Jerschow, Alexej

    2015-04-01

    The study of arctic or subarctic indigenous skin clothing material, known for its design and ability to keep the body warm, provides information about the tanning materials and techniques. The study also provides clues about the culture that created it, since tanning processes are often specific to certain indigenous groups. Untreated skin samples and samples treated with willow (Salix sp) bark extract and cod liver oil are compared in this study using both MRI and unilateral NMR techniques. The two types of samples show different proton spatial distributions and different relaxation times, which may also provide information about the tanning technique and aging behavior. PMID:25719858

  15. NMR Studies of Biodegradation Reactions in Porous Media

    NASA Astrophysics Data System (ADS)

    Mitreiter, I.; Oswald, S. E.; Stallmach, F.

    2007-12-01

    Subsurface contamination caused by organic compounds is a widespread environmental problem. Biodegradation is the main process to reduce the mass of organic contaminants in soils and groundwater. Often the biodegradation is limited by the supply of electron acceptors at the location of the contaminants, and mixing and diffusion are therefore coupled to the degradation process. Nuclear magnetic resonance (NMR) allows non- invasive and non-destructive insight into diffusion processes and effects of microbial biomass on the pore scale, where the mixing and degradation processes actually are taking place. Studying key processes non-invasively with high temporal resolution will contribute to a better understanding of the effective biodegradation rates of organic contaminants in saturated porous systems. The application of 1H NMR relaxometry and PFG NMR diffusometry provide the possibilities to study diffusive transport at the mixing zones in porous media, where contaminants and electron acceptors show strong concentration gradients due to degradation reactions. Nuclear spin relaxation times of water reflect its interaction with the porous media as well as the biomass. To localize microbial biomass the mobility of the water molecules (relaxation times) can be classified corresponding to bound water in the biomass and bulk water. Oxygen is the most important electron acceptor that stimulate the activity and growth of aerobic microbes, and iron(III) a major one for anaerobes. In our work we applied low field (0.2 T) and high field (3 T) NMR measurements to analyze the diffusion in water and biomass and to monitor the concentration changes of electron acceptors. The experimental setup consists of small columns containing saturated porous media applying inversion recovery (IR) and pulsed field gradient (PFG) sequences. We show that both, oxygen as well as iron(III) affect the relaxation times by their paramagnetic properties, and can be determined by NMR relaxometry in

  16. NMR spectroscopic study of organic phosphate esters coprecipitated with calcite

    NASA Astrophysics Data System (ADS)

    Phillips, Brian L.; Zhang, Zelong; Kubista, Laura; Frisia, Silvia; Borsato, Andrea

    2016-06-01

    Organic phosphorus incorporated in calcite during laboratory precipitation experiments and in natural cave deposits was investigated by solid-state NMR spectroscopy. For calcite precipitated in the presence of organic phosphoesters of varying size and functionality, solid-state 31P{1H} CP/MAS NMR shows that the phosphoesters were incorporated intact into the solid. Systematic changes in the 31P NMR chemical shift of the phosphate group were observed between the solid phosphoester and that incorporated in the solid precipitate, yielding 31P NMR chemical shifts of the coprecipitates in the range of +1.8 to -2.2 ppm. These chemical shifts are distinct from that of similarly prepared calcite coprecipitated with inorganic phosphate, 3.5 ppm. Only minor changes were noted in the phosphoester 31P chemical shift anisotropy (CSA) which suggests no significant change in the local structure of the phosphate group, which is dominated by C-O-P bonding. Close spatial proximity of the organic phosphate group to calcite structural components was revealed by 31P/13C rotational echo double resonance (REDOR) experiments for coprecipitates prepared with 13C-labeled carbonate. All coprecipitates showed significant 31P dephasing effects upon 13C-irradiation, signaling atomic-scale proximity to carbonate carbon. The dephasing rate for smaller organophosphate molecules is similar to that observed for inorganic phosphate, whereas much slower dephasing was observed for larger molecules having long and/or bulky side-chains. This result suggests that small organic molecules can be tightly enclosed within the calcite structure, whereas significant structural disruption required to accommodate the larger organic molecules leads to longer phosphate-carbonate distances. Comparison of 31P NMR spectroscopic data from the synthetic coprecipitates with those from calcite moonmilk speleothems indicates that phosphorus occurs mainly as inorganic orthophosphate in the natural deposits, although small

  17. NMR Studies of 3He Films on Boron Nitride

    NASA Astrophysics Data System (ADS)

    Tang, Y.; Sullivan, N. S.

    2014-12-01

    We report the results of NMR studies of the dynamics of 3He adsorbed on hexagonal boron nitride. These studies can identify the phase transitions of the 2D films as a function of temperature. A thermally activated temperature dependence is observed for 2.6 < T < 8 K compared to a linear temperature dependence for 0.7 < T < 2.6 K. This linear dependence is consistent with that expected for thermal diffusion in a fluid for coverages of 0.4 - 0.6 of a monolayer.

  18. {sup 17}O({alpha},{gamma}){sup 21}Ne and {sup 17}O({alpha},n){sup 20}Ne for the weak s process

    SciTech Connect

    Best, A.; Goerres, J.; Beard, M.; Couder, M.; Boer, R. de; Falahat, S.; Gueray, R. T.; Kontos, A.; Kratz, K.-L.; LeBlanc, P. J.; Li, Q.; O'Brien, S.; Oezkan, N.; Pignatari, M.; Sonnabend, K.; Talwar, R.; Tan, W.; Uberseder, E.; Wiescher, M.

    2012-11-20

    The ratio of the reaction rates of the competing channels {sup 17}O({alpha}{gamma}){sup 21}Ne and {sup 17}O({alpha},n){sup 20}Ne determines the efficiency of {sup 16}O as a neutron poison in the s process in low metallicity rotating stars. It has a large impact on the element production, either producing elements to the mass range of A=90 in case of a significant poisoning effect or extending the mass range up to the region of A=150 if the {gamma} channel is of negligible strength. We present an improved study of the reaction {sup 17}O({alpha},n){sup 20}Ne, including an independent measurement of the {sup 17}O({alpha},n{sub 1}){sup 20}Ne channel. A simultaneous R-Matrix fit to both the n{sub 0} and the n{sub 1} channels has been performed. New reaction rates, including recent data on the {sup 17}O({alpha},{gamma}){sup 21}Ne reaction, have been calculated and used as input for stellar network calculations and their impact on the s process in rotating massive stars is discussed.

  19. Dynamic 1H NMR Studies of Schiff Base Derivatives

    NASA Astrophysics Data System (ADS)

    Köylü, M. Z.; Ekinci, A.; Böyükata, M.; Temel, H.

    2016-01-01

    The spin-lattice relaxation time T 1 and the spin-spin relaxation time T 2 of two Schiff base derivatives, N,N'-ethylenebis(salicylidene)-1,2-diaminoethane (H2L1) and N,N'-ethylenebis (salicylidene)-1,3-diaminopropane (H2L2), in DMSO-d6 solvent were studied as a function of temperature in the range of 20-50°C using a Bruker Avance 400.132 MHz 1H NMR spectrometer. Based on the activation energy ( E a) and correlation time (τc), we believe that the Schiff base derivatives perform a molecular tumbling motion.

  20. ADVANCED SOLIDS NMR STUDIES OF COAL STRUCTURE AND CHEMISTRY

    SciTech Connect

    1997-09-01

    This report covers the progress made on the title project for the project period. The study of coal chemical structure is a vital component of research efforts to develop better chemical utilization of coals, and for furthering our basic understanding of coal geochemistry. In this grant we are addressing several structural questions pertaining to coals with advances in state of the art solids NMR methods. The main activity during this granting period was a completion of a detailed comparative analysis of the suite of spectral editing techniques developed in our laboratory for this purpose. The appended report is a manuscript being submitted to the Journal of Magnetic Resonance on this subject.

  1. Application of NMR techniques for studying coking of FCC catalysts

    SciTech Connect

    Bonardet, J.J.; Barrage, M.C.; Fraissard, J.

    1995-12-31

    NMR occupies an important place in the study of the deactivation of zeolites by coking. Indeed, association of the resonances of several nuclei has shown that it is possible to investigate: the nature of the, carbonaceous; deposits; under certain conditions, the coke content; the mode of zeolite deactivation; the exact location of the internal coke and the evolution of its distribution with the coke content, the presence of carbonaceous; residues at the crystallite surface; the effect of zeolite structure and the nature of the reactant on coking and regeneration. It also reveals the role of extra framework aluminium species and that of certain lattice Al atoms in the coking process.

  2. ADVANCED SOLIDS NMR STUDIES OF COAL STRUCTURE AND CHEMISTRY

    SciTech Connect

    1998-03-01

    This report covers the progress made on the title project for the project period. The study of coal chemical structure is a vital component of research efforts to develop better chemical utilization of coals, and for furthering our basic understanding of coal geochemistry. In this grant we are addressing several structural questions pertaining to coals with advances in state of the art solids NMR methods. The main activity during this granting period was a detailed comparative analysis of the suite of spectral editing results obtained on the Argonne coals. We have extended our fitting procedure to include carbons of all types in the analysis.

  3. Synthesis and carbon-13 NMR studies of liquid crystals

    NASA Astrophysics Data System (ADS)

    Sun, Hong

    2000-08-01

    The orientation of different segments of 4'-cyanophenyl 4-heptylbenzoate (7CPB) has been investigated using 13C NMR. The method of proton encoded local field (PELF) spectroscopy was used in combination with off-magic-angle spinning (OMAS) of the sample. High-resolution 2D spectra were obtained and the order parameters were calculated from the spectra. Linear relationships between the obtained order parameters and anisotropic chemical shifts determined by 1D 13C NMR were established and semi-empirical parameters were obtained. A 1:2 mixture of 7CPB and its chain-perfluorinated analog (7PFCPB) shows interesting phase behavior with changing of temperature. The mixture was studied by the use of 13C NMR and polarizing optical microscopy. The order parameters of 7CPB in the smectic A phase of the mixture were calculated using the semi-empirical parameters obtained by the 2D NMR method. Eight series of liquid crystals containing an electron- donating group at one end of a conjugated system and an electron-withdrawing group at the other end have been synthesized. The electron-donating group is 4- n-alkylpiperazinyl group, the electron- withdrawing group is nitro group and the conjugated system is diphenyldiazene with zero, one or two substituents on the phenyl rings. The substituents are -F, -Cl, and -CH3. Two series of compounds with cyano group as electron-withdrawing group were also synthesized. Most of the compounds synthesized are nematogenic and exhibit rather broad liquid crystalline ranges. The effects of the lateral substituents on the optical absorption and phase transition temperatures are correlated with their nature and position of substitution. Birefringence, dielectric anisotropy, elastic constant ratio and rise time of the liquid crystals were carried out using 10 wt% LC mixtures in E7. It has been found that lateral substituents have subtle effects on the properties. The presence of lateral substituents depresses melting points and clearing points of the

  4. NMR studies of p7 protein from hepatitis C virus.

    PubMed

    Cook, Gabriel A; Opella, Stanley J

    2010-06-01

    The p7 protein of hepatitis C virus (HCV) plays an important role in the viral lifecycle. Like other members of the viroporin family of small membrane proteins, the amino acid sequence of p7 is largely conserved over the entire range of genotypes, and it forms ion channels that can be blocked by a number of established channel-blocking compounds. Its characteristics as a membrane protein make it difficult to study by most structural techniques, since it requires the presence of lipids to fold and function properly. Purified p7 can be incorporated into phospholipid bilayers and micelles. Initial solid-state nuclear magnetic resonance (NMR) studies of p7 in 14-O-PC/6-O-PC bicelles indicate that the protein contains helical segments that are tilted approximately 10 degrees and 25 degrees relative to the bilayer normal. A truncated construct corresponding to the second transmembrane domain of p7 is shown to have properties similar to those of the full-length protein, and was used to determine that the helix segment tilted at 10 degrees is in the C-terminal portion of the protein. The addition of the channel blocker amantadine to the full-length protein resulted in selective chemical shift changes, demonstrating that NMR has a potential role in the development of drugs targeted to p7. PMID:19727701

  5. sup 31 Phosphorus NMR studies of renal membrane phospholipids

    SciTech Connect

    Boylan, J.G.

    1988-01-01

    A research program was undertaken in order to study the effects of toxin-induced acute renal failure and streptozotozin-induced diabetes mellitus on the organization and motion of phospholipids in kidney membranes. The method of study included {sup 31}P NMR and computer simulated lineshape analyses and apparent lipid diffusion rate measurements. These were performed with selected tissue samples and disease models, and the results were compared with those of healthy renal tissues in order to identify changes associated with the diseased state. A new selective-excitation NMR pulse sequence was developed in which a portion of the lipid molecules were excited with a series of short equally-spaced RF pulses. As the position of the molecules changed on the membrane by lateral diffusion, the shape of the hole was seen to change. Experimental spectra were compared with calculated lineshapes in order to obtain estimates of useful molecular parameters including relation times and lateral lipid diffusion rates. The lineshape calculations were based on a solution to the Bloch equations for complex magnetization components with exchange terms added for diffusion.

  6. On the Δ17O budget of atmospheric O2

    NASA Astrophysics Data System (ADS)

    Young, Edward D.; Yeung, Laurence Y.; Kohl, Issaku E.

    2014-06-01

    We modeled the Δ17O of atmospheric O2 using 27 ordinary differential equations comprising a box model composed of the stratosphere, troposphere, geosphere, hydrosphere and biosphere. Results show that 57% of the deficit in 17O in O2 relative to a reference water fractionation line is the result of kinetic isotope fractionation attending the Dole effect, 33% balances the positive Δ17O of O(1D) in the stratosphere, and 10% is from evapotranspiration. The predicted Δ‧17O O2 relative to waters is -0.410‰ as measured at the δ18O of air. The value for Δ‧17O O2 varies at fixed δ18O with the concentration of atmospheric CO2, gross primary production, and net primary production as well as with reaction rates in the stratosphere. Our model prediction is consistent with our measurements of the oxygen isotopic composition of air O2 compared with rocks if rocks define a fractionation line with an intercept in δ‧17O = 103ln(δ17O/103 + 1) vs. δ‧18O = 103ln(δ18O/103 + 1) space less than SMOW but more positive than some recent measurements imply. The predicted Δ17O is less negative than that obtained from recent measurements of O2 directly against SMOW. Underestimation of Δ‧17O O2 can only be ameliorated if the integrated (bulk) Δ‧17O for stratospheric CO2 is significantly greater than measurements currently allow. Our results underscore the need for high-precision comparisons of the 17O/16O and 18O/16O ratios of atmospheric O2, VSMOW, and rocks.

  7. NMR studies of DOXP reductoisomerase and its inhibitor complex.

    PubMed

    Englert, Nadine E; Richter, Christian; Wiesner, Jochen; Hintz, Martin; Jomaa, Hassan; Schwalbe, Harald

    2011-02-11

    1-Deoxy-D-xylulose 5-phosphate (DOXP) reductoisomerase (EC1.1.1.267) catalyses the second step of the 2-C-methyl-D-erythritol 4-phosphate (MEP) pathway of isoprenoid biosynthesis. The enzyme is used by most bacteria, apicomplexan parasites and the plastids of plants, but not by humans, and therefore represents an attractive target for antibacterial, antiparasitic and herbicidal compounds. Fosmidomycin, an inhibitor of DXR, has been found to be active against bacterial infections and malaria in early clinical studies. Here, we report sample optimisation, partial backbone assignment and secondary-structure prediction of E. coli DXR by heteronuclear NMR analysis for further NMR-aided drug discovery. Perdeuterated (15)N,(13)C-labelled samples were prepared under oxygen exclusion in the presence of Mg(2+), NADPH and the inhibitor FR-900098, a close derivative of fosmidomycin. (1)H and (15)N backbone assignment was achieved for 44 % of the primary structure, and (13)C backbone assignment was achieved for 50 % of the primary structure. Comparison with previously solved crystal structures revealed that the assigned fragments were located mainly in helical regions on the solvent-exposed surface of the enzyme. Torsion angle likelihood obtained from shift and sequence similarity (TALOS) was used for secondary structure prediction, resulting in agreement with eight available crystal structures; deviations could be observed for the catalytic loop region. PMID:21290548

  8. Frozen State and Spin Liquid Physics in Na4 Ir3 O8 : An NMR Study

    NASA Astrophysics Data System (ADS)

    Shockley, A. C.; Bert, F.; Orain, J.-C.; Okamoto, Y.; Mendels, P.

    2015-07-01

    Na4Ir3 O8 is a unique case of a hyperkagome 3D corner sharing triangular lattice that can be decorated with quantum spins. It has spurred a lot of theoretical interest as a spin liquid candidate. We present a comprehensive set of NMR data taken on both the 23Na and 17O sites. We show that disordered magnetic freezing of all Ir sites sets in below Tf˜7 K , well below J =300 K , with a drastic slowing down of fluctuations to a static state revealed by our T1 measurements. Above typically 2 Tf, physical properties are relevant to the spin liquid state induced by this exotic geometry. While the shift data show that the susceptibility levels off below 80 K, 1 /T1 has little variation from 300 K to 2 Tf. We discuss the implication of our results in the context of published experimental and theoretical work.

  9. Dynamic Nuclear Polarization of 17O: Direct Polarization

    PubMed Central

    Michaelis, Vladimir K.; Corzilius, Björn; Smith, Albert A.; Griffin, Robert G.

    2014-01-01

    Dynamic nuclear polarization of 17O was studied using four different polarizing agents – the biradical TOTAPOL, and the monoradicals trityl and SA-BDPA, as well as a mixture of the latter two. Field profiles, DNP mechanisms and enhancements were measured to better understand and optimize directly polarizing this low-gamma quadrupolar nucleus using both mono- and bi-radical polarizing agents. Enhancements were recorded < 88 K and were > 100 using the trityl (OX063) radical and < 10 with the other polarizing agents. The > 10,000 fold savings in acquisition time enabled a series of biologically relevant small molecules to be studied with small sample sizes and the measurement of various quadrupolar parameters. The results are discussed with comparison to room temperature studies and GIPAW quantum chemical calculations. These experimental results illustrate the strength of high field DNP and the importance of radical selection for studying low-gamma nuclei. PMID:24195759

  10. NMR Studies on the Aqueous Phase Photochemical Degradation of TNT

    SciTech Connect

    Thorn, Kevin A.; Cox, Larry G.

    2008-04-06

    Aqueous phase photochemical degradation of 2,4,6-trinitrotoluene (TNT) is an important pathway in several environments, including washout lagoon soils, impact craters from partially detonated munitions that fill with rain or groundwater, and shallow marine environments containing unexploded munitions that have corroded. Knowledge of the degradation products is necessary for compliance issues on military firing ranges and formerly used defense sites. Previous laboratory studies have indicated that UV irradiation of aqueous TNT solutions results in a multicomponent product mixture, including polymerization compounds, that has been only partially resolved by mass spectrometric analyses. This study illustrates how a combination of solid and liquid state 1H, 13C, and 15N NMR spectroscopy, including two dimensional analyses, provides complementary information on the total product mixture from aqueous photolysis of TNT, and the effect of reaction conditions. Among the degradation products detected were amine, amide, azoxy, azo, and carboxylic acid compounds.

  11. NMR relaxation studies in doped poly-3-methylthiophene

    NASA Astrophysics Data System (ADS)

    Singh, K. Jugeshwar; Clark, W. G.; Gaidos, G.; Reyes, A. P.; Kuhns, P.; Thompson, J. D.; Menon, R.; Ramesh, K. P.

    2015-05-01

    NMR relaxation rates (1 /T1 ), magnetic susceptibility, and electrical conductivity studies in doped poly-3-methylthiophene are reported in this paper. The magnetic susceptibility data show the contributions from both Pauli and Curie spins, with the size of the Pauli term depending strongly on the doping level. Proton and fluorine NMR relaxation rates have been studied as a function of temperature (3-300 K) and field (for protons at 0.9, 9.0, 16.4, and 23.4 T, and for fluorine at 9.0 T). The temperature dependence of T1 is classified into three regimes: (a) For T <(g μBB /2 kB ) , the relaxation mechanism follows a modified Korringa relation due to electron-electron interactions and disorder. 1H - T1 is due to the electron-nuclear dipolar interaction in addition to the contact term. (b) For the intermediate temperature range (g μBB /2 kB ) study. Fluorine relaxation data have been analyzed and attributed to the P F6 reorientation. The cross relaxation among the 1H and 19F nuclei has been observed in the entire temperature range suggesting the role of magnetic dipolar interaction modulated by the reorientation of the symmetric molecular subgroups. The data analysis shows that the enhancement in the Korringa ratio is greater in a less conducting sample. Intra- and interchain hopping of charge carriers is found to be a dominant relaxation mechanism at low temperature. Frequency dependence of T1-1 on temperature shows that at low temperature [T <(g μBB /2 kB ) ] the system shows three dimensions and changes to quasi one dimension at

  12. NMR studies of two spliced leader RNAs using isotope labeling

    SciTech Connect

    Lapham, J.; Crothers, D.M.

    1994-12-01

    Spliced leader RNAs are a class of RNA molecules (<200 nts) involved in the trans splicing of messenger RNA found in trypanosomes, nematodes, and other lower eukaryotes. The spliced leader RNA from the trypanosome Leptomonas Collosoma exists in two alternate structural forms with similar thermal stabilities. The 54 nucleotides on the 5{prime} end of the SL molecule is structurally independent from the 3{prime} half of the RNA, and displays the two structural forms. Furthermore, the favored of the two structures was shown to contain anomalous nuclease sensitivity and thermal stability features, which suggests that there may be tertiary interactions between the splice site and other nucleotides in the 5{prime} end. Multidimensional NMR studies are underway to elucidate the structural elements present in the SL RNAs that give rise to their physical properties. Two spliced leader sequences have been studied. The first, the 54 nucleotides on the 5{prime} end of the L. Collosoma sequence, was selected because of earlier studies in our laboratory. The second sequence is the 5{prime} end of the trypanosome Crithidia Fasciculata, which was chosen because of its greater sequence homology to other SL sequences. Given the complexity of the NMR spectra for RNA molecules of this size, we have incorporated {sup 15}N/{sup 13}C-labeled nucleotides into the RNA. One of the techniques we have developed to simplify the spectra of these RNA molecules is isotope labeling of specific regions of the RNA. This has been especially helpful in assigning the secondary structure of molecules that may be able to adopt multiple conformations. Using this technique one can examine a part of the molecule without spectral interference from the unlabeled portion. We hope this approach will promote an avenue for studying the structure of larger RNAs in their native surroundings.

  13. The 17O(p,α)14N reaction measurement via the Trojan horse method and its application to 17O nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; Pizzone, R. G.; Burjan, S. V.; Cherubini, S.; Coc, A.; Gulino, M.; Hammache, F.; Hons, Z.; Irgaziev, B.; Kiss, G. G.; Kroha, V.; La Cognata, M.; Lamia, L.; Mukhamedzhanov, A.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; de Séréville, N.; Somorjai, E.; Tumino, A.

    2014-05-01

    The role of oxygen in astrophysics is related to different problems as novae nucleosynthesis and gamma-ray astronomy. In particular, owing to the still present uncertainties on its rate, the 17O(p,α)14N is one of the most important reaction to be studied in order to get more information about the fate of oxygen in different astrophysical scenarios.

  14. Oxygen isotope dynamics of atmospheric nitrate over the Antarctic plateau: First combined measurements of ozone and nitrate 17O-excess (Δ17O)

    NASA Astrophysics Data System (ADS)

    Vicars, William; Savarino, Joël; Erbland, Joseph; Preunkert, Susanne; Jourdain, Bruno; Frey, Markus; Gil, Jaime; Legrand, Michel

    2013-04-01

    Variations in the isotopic composition of atmospheric nitrate (NO3-) provide novel indicators for important processes in boundary layer chemistry, often acting as source markers for reactive nitrogen (NOx = NO + NO2) and providing both qualitative and quantitative constraints on the pathways that determine its fate. Stable isotope ratios of nitrate (δ15N, δ17O, δ18O) offer direct insight into the nature and magnitude of the fluxes associated with different processes, thus providing unique information regarding phenomena that are often difficult to quantify from concentration measurements alone. The unique and distinctive 17O-excess (Δ17O = δ17O - 0.52 × δ18O ) of ozone (O3), which is transferred to NOx via oxidation reactions in the atmosphere, has been found to be a particularly useful isotopic fingerprint in studies of NOx transformations. Constraining the propagation of 17O-excess within the NOx cycle is critical in polar areas where there exists the possibility of extending atmospheric interpretations to the glacial/interglacial time scale using deep ice core records of nitrate. Here we present measurements of the comprehensive isotopic composition of atmospheric nitrate collected at Dome C, Antarctica during December 2011 to January 2012. Sampling was conducted within the framework of the OPALE (Oxidant Production over Antarctic Land and its Export) project, thus providing an opportunity to combine our isotopic observations with a wealth of meteorological and chemical data, including in-situ concentration measurements of the gas-phase precursors involved in nitrate production (NOx, O3, OH, HO2, etc.). Furthermore, nitrate isotope analysis has been combined in this study for the first time with parallel observations of the transferrable Δ17O of surface ozone, which was measured concurrently at Dome C using our recently developed analytical approach. This unique dataset has allowed for a direct comparison of observed Δ17O(NO3-) values to those that are

  15. Infrared spectroscopy of 17O- and 18O-enriched carbon dioxide: Line positions and intensities in the 4681-5337 cm-1 region

    NASA Astrophysics Data System (ADS)

    Borkov, Yu. G.; Jacquemart, D.; Lyulin, O. M.; Tashkun, S. A.; Perevalov, V. I.

    2015-07-01

    The line positions and intensities of carbon dioxide isotopologues have been retrieved in the 4681-5337 cm-1 spectral range from Fourier transform spectra of carbon dioxide recorded in LADIR (Paris, France) with the Bruker IFS 125-HR [Jacquemart D, et al., J Quant Spectrosc Radiat Transf 2012;113:961-975]. In total 6386 line positions and intensities of 89 bands of 12 isotopologues 16O12C16O, 16O13C16O, 16O12C18O, 16O12C17O, 16O13C18O, 16O13C17O, 18O12C18O, 17O12C18O, 17O12C17O, 18O13C18O, 17O13C18O, and 17O13C17O have been retrieved. 23 bands were newly assigned. All studied bands belong to the ΔP=7 series of transitions, where P = 2V1 +V2 + 3V3 is the polyad number (Vi are vibrational quantum numbers). The accuracy of the line position measurement is about 0.3×10-3 cm-1 for the unblended and not very weak lines. The accuracy of the line intensities varies from 4% to 15% depending on the isotopologue, on the intensity of the line and on the extent of the line overlapping. The observed intensities were used to fit the effective dipole moment parameters for the ΔP=7 series of transitions in 16O12C18O, 16O12C17O, 12C17O2, 17O12C18O, 16O13C17O, 13C17O2 and 17O13C18O isotopologues of carbon dioxide.

  16. Simulating the budget and distribution of Δ17O in CO2 with a global atmosphere-biosphere model

    NASA Astrophysics Data System (ADS)

    Peters, Wouter; Schneider, Linda; Hofmann, Magdalena E. G.; van der Velde, Ivar; Röckmann, Thomas

    2015-04-01

    The isotope ratios of 16O, 17O and 18O in CO2 are referred to as the triple-oxygen isotope composition of CO2, and have long held promise to better understand terrestrial carbon cycling. However, measurement precision as well as an incomplete understanding of fractionation during equilibrium exchange and diffusion of CO2 have been a challenge, especially for the estimation of gross primary production (GPP) and respiration from measured δ17O and δ18O isotope ratios in CO2. The excess-17O in CO2 (Δ17O), defined as the deviation of the δ17O and δ18O ratios from an expected mass-dependent fractionation line, is in principle easier to interpret as many processes that simultaneously affect δ17O and δ18O are not reflected in Δ17O. Two global box model simulations suggest that atmospheric Δ17O is therefore mostly determined by transport of relatively δ17O enriched CO2 from the stratosphere, and its equilibration in leaf-water back to an excess of close to zero, following diffusion as part of photosynthetic CO2 uptake by vegetation. This makes Δ17O an interesting tracer for photosynthesis at the global scale, and the first decadal time series have recently been published that indeed suggest strong GPP-driven variations in atmospheric Δ17O. In this study, we expand the modeling of Δ17O beyond the current two global box model results published by explicitly simulating the global atmospheric Δ17O distribution over a five year period. We specifically are interested whether regional gradients in Δ17O in areas with large GPP such as Amazonia leave an imprint on Δ17O that can be measured with the rapidly improving measurement precision (10-40 permeg currently). Therefore, we used the SIBCASA biosphere model at 1x1 degrees globally to simulate hourly fluxes of Δ17O into and out of C3 and C4 vegetation as well as soils. These fluxes were then fed into the TM5 atmospheric transport model at 6x4 degrees horizontal resolution to simulate the hourly spatial gradients in

  17. Overcoming the Solubility Limit with Solubility-Enhancement Tags: Successful Applications in Biomolecular NMR Studies

    PubMed Central

    Zhou, Pei; Wagner, Gerhard

    2010-01-01

    Although the rapid progress of NMR technology has significantly expanded the range of NMR-trackable systems, preparation of NMR-suitable samples that are highly soluble and stable remains a bottleneck for studies of many biological systems. The application of solubility-enhancement tags (SETs) has been highly effective in overcoming solubility and sample stability issues and has enabled structural studies of important biological systems previously deemed unapproachable by solution NMR techniques. In this review, we provide a brief survey of the development and successful applications of the SET strategy in biomolecular NMR. We also comment on the criteria for choosing optimal SETs, such as for differently charged target proteins, and recent new developments on NMR-invisible SETs. PMID:19731047

  18. Survey of {sup 17}O excited states selectively populated by five-particle transfer reactions

    SciTech Connect

    Crisp, A. M.; Roeder, B. T.; Momotyuk, O. A.; Kemper, K. W.; Weintraub, W.; Wiedeking, M.; Keeley, N.

    2008-04-15

    The highly selective reactions {sup 12}C({sup 7}Li,d){sup 17}O and {sup 12}C({sup 6}Li,p){sup 17}O have been used to populate high-lying excited states in {sup 17}O up to 16 MeV in excitation. Several of the states are newly observed, and the existence of others in a previous study of {sup 12}C({sup 6}Li,p){sup 17}O is confirmed. The observed spectra show a clear gap of about 3 MeV, indicating an energy gap between 3p-2h and 5p-4h states in {sup 17}O. Differential cross section angular distributions have been extracted from the data for both reactions and they have been compared with finite-range DWBA calculations by assuming a ''{sup 5}He'' cluster transfer. Possible spins and parities are reported for states at 11.82 MeV (7/2{sup +}), 12.00 MeV (9/2{sup +}),12.22 MeV (7/2{sup -}), and 12.42 MeV (9/2{sup +})

  19. Measurments and Modeling of Δ 17O Vatiations in Atmospheric Nitrate

    NASA Astrophysics Data System (ADS)

    Michalski, G. M.; Thiemens, M. H.

    2002-12-01

    , the ability to more accurately quantify nitrate deposition, and its insensitivity to post deposition fractionations (chemical, physical, biological) make Δ 17O measurements superior to current δ 18O methods for deposition studies.

  20. Solid-State NMR Studies of Amyloid Fibril Structure

    NASA Astrophysics Data System (ADS)

    Tycko, Robert

    2011-05-01

    Current interest in amyloid fibrils stems from their involvement in neurodegenerative and other diseases and from their role as an alternative structural state for many peptides and proteins. Solid-state nuclear magnetic resonance (NMR) methods have the unique capability of providing detailed structural constraints for amyloid fibrils, sufficient for the development of full molecular models. In this article, recent progress in the application of solid-state NMR to fibrils associated with Alzheimer's disease, prion fibrils, and related systems is reviewed, along with relevant developments in solid-state NMR techniques and technology.

  1. Solid State NMR Studies of Amyloid Fibril Structure

    PubMed Central

    Tycko, Robert

    2011-01-01

    Current interest in amyloid fibrils stems from their involvement in neurodegenerative and other diseases and from their role as an alternative structural state for many peptides and proteins. Solid state NMR methods have the unique capability of providing detailed structural constraints for amyloid fibrils, sufficient for the development of full molecular models. In this article, recent progress in the application of solid state NMR to fibrils associated with Alzheimer’s disease, prion fibrils, and related systems is reviewed, along with relevant developments in solid state NMR techniques and technology. PMID:21219138

  2. Cation-π versus anion-π interactions: A theoretical NMR study

    NASA Astrophysics Data System (ADS)

    Ebrahimi, Ali; Khorassani, Mostafa Habibi; Masoodi, Hamid Reza

    2011-03-01

    The influences of cation-π and anion-π interactions on NMR data have been investigated in complexes of cations and anions with 1,3,5-trifluorobenzene (TFB). Cation-π interaction increases 1JC-F, 1JC-H and the chemical shifts of hydrogen and fluorine while it decreases 1JC-C. The changes are in reverse direction in the presence of anion-π interaction. The role of geometry and electronic effects on the NMR data was considered. The distance dependence of NMR parameters has been studied in these complexes. The NMR data have been investigated in isoelectronic complexes.

  3. NMR study of some coumarins and furocoumarins methylated

    NASA Astrophysics Data System (ADS)

    Miranda, R.; Santana, L.; Uriarte, E.; Zagotto, G.

    1994-01-01

    The 1H and 13C NMR spectra of various methylcoumarins and methylfurocoumarins are reported. All signals were assigned and the influence on chemical shifts of methylation at various positions was determined.

  4. Improvement of the high-accuracy 17O(p ,α )14N reaction-rate measurement via the Trojan Horse method for application to 17O nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Rapisarda, G. G.; Tang, X. D.; Bucher, B.; Couder, M.; Davies, P.; deBoer, R.; Fang, X.; Lamm, L.; Ma, C.; Notani, M.; O'Brien, S.; Roberson, D.; Tan, W.; Wiescher, M.; Irgaziev, B.; Mukhamedzhanov, A.; Mrazek, J.; Kroha, V.

    2015-06-01

    The 17O(p ,α )14N and 17O(p ,γ )18F reactions are of paramount importance for the nucleosynthesis in a number of stellar sites, including red giants (RGs), asymptotic giant branch (AGB) stars, massive stars, and classical novae. In particular, they govern the destruction of 17O and the formation of the short-lived radioisotope 18F, which is of special interest for γ -ray astronomy. At temperatures typical of the above-mentioned astrophysical scenario, T =0.01 -0.1 GK for RG, AGB, and massive stars and T =0.1 -0.4 GK for a classical nova explosion, the 17O(p ,α )14N reaction cross section is dominated by two resonances: one at about ERc m=65 keV above the 18F proton threshold energy, corresponding to the EX=5.673 MeV level in 18F, and another one at ERc m=183 keV (EX=5.786 MeV). We report on the indirect study of the 17O(p ,α )14N reaction via the Trojan Horse method by applying the approach recently developed for extracting the strength of narrow resonance at ultralow energies. The mean value of the strengths obtained in the two measurements was calculated and compared with the direct data available in literature. This value was used as input parameter for reaction-rate determination and its comparison with the result of the direct measurement is also discussed in the light of the electron screening effect.

  5. Estimation of the regional cerebral metabolic rate of oxygen consumption with proton detected 17O MRI during precision 17O2 inhalation in swine

    PubMed Central

    Mellon, Eric A.; Beesam, R. Shashank; Baumgardner, James E.; Borthakur, Arijitt; Witschey, Walter R.; Reddy, Ravinder

    2009-01-01

    Despite the importance of metabolic disturbances in many diseases, there are currently no clinically used methods for the detection of oxidative metabolism in vivo. To address this deficiency, 17O MRI techniques are scaled from small animals to swine as a large animal model of human inhalation and circulation. The hemispheric cerebral metabolic rate of oxygen consumption (CMRO2) is estimated in swine by detection of metabolically produced H217O by rapid T1ρ-weighted proton magnetic resonance imaging on a 1.5 Tesla clinical scanner. The 17O is delivered as oxygen gas by a custom, minimal-loss, precision-delivery breathing circuit and converted to H217O by oxidative metabolism. A model for gas arterial input is presented for the deeply breathing large animal. The arterial input function for recirculation of metabolic water is measured by arterial blood sampling and high field 17O spectroscopy. It is found that minimal metabolic water “wash-in” occurs before 60 seconds. A high temporal resolution pulse sequence is employed to measure CMRO2 during those 60 seconds after delivery begins. Only about one tidal volume of 17O enriched oxygen gas is used per measurement. Proton measurements of signal change due to metabolically produced water are correlated with 17O in vivo spectroscopy. Using these techniques, the hemispheric CMRO2 in swine is estimated to be 1.23 ± 0.26 μmol/g/min, consistent with existing literature values. All of the technology used to perform these CMRO2 estimates can easily be adapted to clinical MR scanners, and it is hoped that this work will lead to future studies of human disease. PMID:19428508

  6. NMR Relaxation and Diffusion Study of Ultrasound Recycling of Polyurethanes

    NASA Astrophysics Data System (ADS)

    von Meerwall, E.; Ghose, S.; Isayev, A. I.

    2004-04-01

    We have examined the effect of intense ultrasound on unfilled polyurethane foam and rubber using proton NMR transverse relaxation and pulsed-gradient diffusion studies, sol extraction, GPC characterization, and glass transition measurements. Results correlate well with ultrasound amplitude. The proton T2 relaxation at 70.5 deg. C exhibits three discrete components, due to heavily entangled sol and crosslinked network; unentangled polymeric sol plus dangling network chain ends; and oligomer remnants. Devulcanizing produces heavy sol, increases segmental mobility of all species, and generates more dangling chain ends. In foams, but not in rubber, additional light sol is generated at the expense of network. All mobilities are significantly lower than in the other rubbers we have studied, an effect unrelated to the glass transition, nearly constant at -60 deg. C. Diffusion measurements, possible only in foams, show a bimodal spectrum whose fast component slows markedly with ultrasound amplitude, attesting to the production of fragments heavier than the original oligomers, as confirmed by GPC analysis. This work is the first to study ultrasound devulcanization in industrial rubbery foams.

  7. Explosive hydrogen burning of 17O in classical novae.

    PubMed

    Fox, C; Iliadis, C; Champagne, A E; Coc, A; José, J; Longland, R; Newton, J; Pollanen, J; Runkle, R

    2004-08-20

    We report on the observation of a new resonance at E(lab)(R)=190 keV in the 17O(p,gamma)18F reaction. The measured resonance strength amounts to omegagamma(pgamma)=(1.2+/-0.2)x10(-6) eV. With this new value, the uncertainties in the 17O(p,gamma)18F and 17O(p,alpha)14N thermonuclear reaction rates are reduced by orders of magnitude at nova temperatures. Our significantly improved reaction rates have major implications for the galactic synthesis of 17O, the stellar production of the radioisotope 18F, and the predicted oxygen isotopic ratios in nova ejecta. PMID:15447168

  8. Diffusion NMR methods applied to xenon gas for materials study.

    PubMed

    Mair, R W; Rosen, M S; Wang, R; Cory, D G; Walsworth, R L

    2002-12-01

    We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. PMID:12807139

  9. Diffusion NMR methods applied to xenon gas for materials study

    NASA Technical Reports Server (NTRS)

    Mair, R. W.; Rosen, M. S.; Wang, R.; Cory, D. G.; Walsworth, R. L.

    2002-01-01

    We report initial NMR studies of (i) xenon gas diffusion in model heterogeneous porous media and (ii) continuous flow laser-polarized xenon gas. Both areas utilize the pulsed gradient spin-echo (PGSE) techniques in the gas phase, with the aim of obtaining more sophisticated information than just translational self-diffusion coefficients--a brief overview of this area is provided in the Introduction. The heterogeneous or multiple-length scale model porous media consisted of random packs of mixed glass beads of two different sizes. We focus on observing the approach of the time-dependent gas diffusion coefficient, D(t) (an indicator of mean squared displacement), to the long-time asymptote, with the aim of understanding the long-length scale structural information that may be derived from a heterogeneous porous system. We find that D(t) of imbibed xenon gas at short diffusion times is similar for the mixed bead pack and a pack of the smaller sized beads alone, hence reflecting the pore surface area to volume ratio of the smaller bead sample. The approach of D(t) to the long-time limit follows that of a pack of the larger sized beads alone, although the limiting D(t) for the mixed bead pack is lower, reflecting the lower porosity of the sample compared to that of a pack of mono-sized glass beads. The Pade approximation is used to interpolate D(t) data between the short- and long-time limits. Initial studies of continuous flow laser-polarized xenon gas demonstrate velocity-sensitive imaging of much higher flows than can generally be obtained with liquids (20-200 mm s-1). Gas velocity imaging is, however, found to be limited to a resolution of about 1 mm s-1 owing to the high diffusivity of gases compared with liquids. We also present the first gas-phase NMR scattering, or diffusive-diffraction, data, namely flow-enhanced structural features in the echo attenuation data from laser-polarized xenon flowing through a 2 mm glass bead pack. c2002 John Wiley & Sons, Ltd.

  10. 1H NMR metabolomics study of age profiling in children

    PubMed Central

    Gu, Haiwei; Pan, Zhengzheng; Xi, Bowei; Hainline, Bryan E.; Shanaiah, Narasimhamurthy; Asiago, Vincent; Nagana Gowda, G. A.; Raftery, Daniel

    2014-01-01

    Metabolic profiling of urine provides a fingerprint of personalized endogenous metabolite markers that correlate to a number of factors such as gender, disease, diet, toxicity, medication, and age. It is important to study these factors individually, if possible to unravel their unique contributions. In this study, age-related metabolic changes in children of age 12 years and below were analyzed by 1H NMR spectroscopy of urine. The effect of age on the urinary metabolite profile was observed as a distinct age-dependent clustering even from the unsupervised principal component analysis. Further analysis, using partial least squares with orthogonal signal correction regression with respect to age, resulted in the identification of an age-related metabolic profile. Metabolites that correlated with age included creatinine, creatine, glycine, betaine/TMAO, citrate, succinate, and acetone. Although creatinine increased with age, all the other metabolites decreased. These results may be potentially useful in assessing the biological age (as opposed to chronological) of young humans as well as in providing a deeper understanding of the confounding factors in the application of metabolomics. PMID:19441074

  11. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, N.

    1996-10-17

    Various hydrogenation reactions on transition metals are important commercially whereas certain hydrogenolysis reactions are useful from fundamental point of view. Understanding the hydrogen mobility and kinetics of adsorption-desorption of hydrogen is important in understanding the mechanisms of such reactions involving hydrogen. The kinetics of hydrogen chemisorption was studied by means of selective excitation NMR on silica supported Pt, Rh and Pt-Rh catalysts. The activation energy of hydrogen desorption was found to be lower on silica supported Pt catalysts as compared to Rh and Pt-Rh catalysts. It was found that the rates of hydrogen adsorption and desorption on Pt-Rh catalyst were similar to those on Rh catalyst and much higher as compared to Pt catalyst. The Ru-Ag bimetallic system is much simpler to study than the Pt-Rh system and serves as a model system to characterize more complicated systems such as the K/Ru system. Ag was found to decrease the amounts of adsorbed hydrogen and the hydrogen-to-ruthenium stoichiometry. Ag reduced the populations of states with low and intermediate binding energies of hydrogen on silica supported Ru catalyst. The rates of hydrogen adsorption and desorption were also lower on silica supported Ru-Ag catalyst as compared to Ru catalyst. This report contains introductory information, the literature review, general conclusions, and four appendices. An additional four chapters and one appendix have been processed separately for inclusion on the data base.

  12. NMR Study of Strontium Binding by a Micaceous Mineral

    SciTech Connect

    Bowers, Geoffrey M.; Ravella, Ramesh; Komarneni, S.; Mueller, Karl T.

    2006-04-13

    The nature of strontium binding by soil minerals directly affects the transport and sequestration/remediation of radioactive strontium species released from leaking high-level nuclear waste storage tanks. However, the molecular-level structure of strontium binding sites has seldom been explored in phyllosilicate minerals by direct spectroscopic means and is not well-understood. In this work, we use solid-state NMR to analyze strontium directly and indirectly in a fully strontium-exchanged synthetic mica of nominal composition Na4Mg6Al4Si4O20F4. Thermogravimetric analysis, X-ray diffraction analysis, and NMR evidence supports that heat treatment at 500 °C for 4 h fully dehydrates the mica, creating a hydrogen-free interlayer. Analysis of the strontium NMR spectrum of the heat-treated mica shows a single strontium environment with a quadrupolar coupling constant of 9.02 MHz and a quadrupolar asymmetry parameter of 1.0. These quadrupolar parameters are consistent with a highly distorted and asymmetric coordination environment that would be produced by strontium cations without water in the coordination sphere bound deep within the ditrigonal holes. Evidence for at least one additional strontium environment, where proton-strontium couplings may occur, was found via a 1H-87Sr transfer of populations by double resonance NMR experiment. We conclude that the strontium cations in the proton-free interlayer are observable by 87Sr NMR and bound through electrostatic interactions as nine coordinate inner-sphere complexes sitting in the ditrigonal holes. Partially hydrated strontium cations invisible to direct 87Sr NMR are also present and located on the external mica surfaces, which are known to hydrate upon exposure to atmospheric moisture. These results demonstrate that modern pulsed NMR techniques and high fields can be used effectively to provide structural details of strontium binding by phyllosilicate minerals.

  13. Comprehensive multiphase NMR: a promising technology to study plants in their native state.

    PubMed

    Wheeler, Heather L; Soong, Ronald; Courtier-Murias, Denis; Botana, Adolfo; Fortier-Mcgill, Blythe; Maas, Werner E; Fey, Michael; Hutchins, Howard; Krishnamurthy, Sridevi; Kumar, Rajeev; Monette, Martine; Stronks, Henry J; Campbell, Malcolm M; Simpson, Andre

    2015-09-01

    Nuclear magnetic resonance (NMR) spectroscopy is arguably one the most powerful tools to study the interactions and molecular structure within plants. Traditionally, however, NMR has developed as two separate fields, one dealing with liquids and the other dealing with solids. Plants in their native state contain components that are soluble, swollen, and true solids. Here, a new form of NMR spectroscopy, developed in 2012, termed comprehensive multiphase (CMP)-NMR is applied for plant analysis. The technology composes all aspects of solution, gel, and solid-state NMR into a single NMR probe such that all components in all phases in native unaltered samples can be studied and differentiated in situ. The technology is evaluated using wild-type Arabidopsis thaliana and the cellulose-deficient mutant ectopic lignification1 (eli1) as examples. Using CMP-NMR to study intact samples eliminated the bias introduced by extraction methods and enabled the acquisition of a more complete structural and metabolic profile; thus, CMP-NMR revealed molecular differences between wild type (WT) and eli1 that could be overlooked by conventional methods. Methanol, fatty acids and/or lipids, glutamine, phenylalanine, starch, and nucleic acids were more abundant in eli1 than in WT. Pentaglycine was present in A. thaliana seedlings and more abundant in eli1 than in WT. PMID:25855560

  14. Solid-state NMR study of fluorinated steroids.

    PubMed

    Yang, Kai-Jay; Lin, Su-Ching; Huang, Shing-Jong; Ching, Wei-Min; Hung, Chen-Hsiung; Tzou, Der-Lii M

    2014-02-01

    Solid-state {(1)H}(13)C cross-polarization/magic angle spinning (CP/MAS) NMR spectroscopy was performed to analyze two fluorinated steroids, i.e., betamethasone (BMS) and fludrocortisone acetate (FCA), that have fluorine attached to C9, as well as two non-fluorinated analogs, i.e., prednisolone (PRD) and hydrocortisone 21-acetate (HCA). The (13)C signals of BMS revealed multiplet patterns with splittings of 16-215Hz, indicating multiple ring conformations, whereas the (13)C signals of FCA, HCA, and PRD exhibited only singlet patterns, implying a unique conformation. In addition, BMS and FCA exhibited substantial deviation (>3.5ppm) in approximately half of the (13)C signals and significant deviation (>45ppm) in the (13)C9 signal compared to PRD and HCA, respectively. In this study, we demonstrate that fluorinated steroids, such as BMS and FCA, have steroidal ring conformation(s) that are distinct from non-fluorinated analogs, such as PRD and HCA. PMID:24316163

  15. NMR relaxation studies of the interaction of thiocyanate with lactoperoxidase.

    PubMed

    Crull, G B; Goff, H M

    1993-05-15

    The interaction of lactoperoxidase, LPO, with its substrate, thiocyanate, SCN-, has been investigated by 13C and 15N NMR relaxation measurements. When 0.1 M SCN-, enriched with either 13C or 15N, was titrated with native ferric lactoperoxidase a large change in the spin-lattice relaxation time of the respective nucleus was observed. In the presence of saturating amounts of CN-, a high affinity ligand for the heme iron, a similar but much smaller change in the relaxation time for SCN- was found. Studies of the rate of carbon relaxation as a function of temperature have shown that thiocyanate is in fast exchange between a site on the enzyme and bulk solution. When LPO in either the absence or presence of CN- was titrated with SCN- a linear increase in the relaxation time was observed. Dissociation constants (Kd values) have been determined from a least-squares analysis of these data. Apparent distances between the heme iron of lactoperoxidase and either the carbon or nitrogen atoms of bound thiocyanate ion have been determined through application of the Solomon-Bloembergen equation. These distances demonstrate that the observed association does not involve iron-thiocyanate coordination, suggesting the possibility of an anion binding site. PMID:8501464

  16. An NMR structural study of nickel-substituted rubredoxin.

    PubMed

    Goodfellow, Brian J; Duarte, Iven C N; Macedo, Anjos L; Volkman, Brian F; Nunes, Sofia G; Moura, I; Markley, John L; Moura, José J G

    2010-03-01

    The Ni(II) and Zn(II) derivatives of Desulfovibrio vulgaris rubredoxin (DvRd) have been studied by NMR spectroscopy to probe the structure at the metal centre. The beta CH(2) proton pairs from the cysteines that bind the Ni(II) atom have been identified using 1D nuclear Overhauser enhancement (NOE) difference spectra and sequence specifically assigned via NOE correlations to neighbouring protons and by comparison with the published X-ray crystal structure of a Ni(II) derivative of Clostridium pasteurianum rubredoxin. The solution structures of DvRd(Zn) and DvRd(Ni) have been determined and the paramagnetic form refined using pseudocontact shifts. The determination of the magnetic susceptibility anisotropy tensor allowed the contact and pseudocontact contributions to the observed chemical shifts to be obtained. Analysis of the pseudocontact and contact chemical shifts of the cysteine H beta protons and backbone protons close to the metal centre allowed conclusions to be drawn as to the geometry and hydrogen-bonding pattern at the metal binding site. The importance of NH-S hydrogen bonds at the metal centre for the delocalization of electron spin density is confirmed for rubredoxins and can be extrapolated to metal centres in Cu proteins: amicyanin, plastocyanin, stellacyanin, azurin and pseudoazurin. PMID:19997764

  17. A computational NMR study on zigzag aluminum nitride nanotubes

    NASA Astrophysics Data System (ADS)

    Bodaghi, Ali; Mirzaei, Mahmoud; Seif, Ahmad; Giahi, Masoud

    2008-12-01

    A computational nuclear magnetic resonance (NMR) study is performed to investigate the electronic structure properties of the single-walled zigzag aluminum nitride nanotubes (AlNNTs). The chemical-shielding (CS) tensors are calculated at the sites of Al-27 and N-15 nuclei in three structural forms of AlNNT including H-saturated, Al-terminated, and N-terminated ones. The structural forms are firstly optimized and then the calculated CS tensors in the optimized structures are converted to chemical-shielding isotropic (CSI) and chemical-shielding anisotropic (CSA) parameters. The calculated parameters reveal that various Al-27 and N-15 nuclei are divided into some layers with equivalent electrostatic properties; furthermore, Al and N can act as Lewis base and acid, respectively. In the Al-terminated and N-terminated forms of AlNNT, in which one mouth of the nanotube is terminated by aluminum and nitrogen nuclei, respectively, just the CS tensors of the nearest nuclei to the mouth of the nanotube are significantly changed due to removal of saturating hydrogen atoms. Density functional theory (DFT) calculations are performed using GAUSSIAN 98 package of program.

  18. A Deuterium NMR Study of Bent-Core Liquid Crystals

    NASA Astrophysics Data System (ADS)

    Dingemans, Theo J.; Madsen, Louis A.; Samulski, Edward T.

    2002-10-01

    We have synthesized two deuterated boomerang-shaped liquid crystals based on 2,5-bis(4-hydroxyphenyl)-1,3,4-oxadiazole (ODBP). Deuterium was introduced in the rigid 2,5-diphenyl-1,3,4-oxadiazole core and in the aromatic ring of the terminal 4-dodecyloxyphenyl moiety using standard acid catalyzed deuterium exchange conditions. Both compounds, (4,4'(1,3,4-oxadiazole-2,5-diyl-d4) di-4-dodecyloxybenzoate: ODBP-d4-Ph-O-C12) and (4,4'(1,3,4-oxadiazole-2,5-diyl) di-4-dodecyloxy-benzoate-d4; ODBP-Ph-d4-O-C12) were investigated by nuclear magnetic resonance, optical microscopy and differential scanning calorimetry. The optical textures and thermal behavior of both compounds were found to be identical to the non-deuterated analog 4,4(1,3,4-oxadiazole-2,5-diyl) di-4-dodecyloxybenzoate (ODBP-Ph-O-C12) which we reported earlier. These compounds exhibit behavior indicative of a biaxial nematic liquid crystal phase, which we hope to confirm using deuterium NMR spectroscopy in the next phase of this study.

  19. Diamond deposition and defect chemistry studied via solid state NMR

    NASA Astrophysics Data System (ADS)

    Gleason, Karen K.

    1994-06-01

    Diamond defects were quantified by nuclear magnetic resonance (NMR). While maintaining the macroscopic integrity of the films, concentrations between 0.001 and 1.0 at.% H were measured, among the lowest ever reported by solid-state 1H NMR. These concentrations were correlated to infrared absorption in the 8 to 10 micron region and to thermal conductivity. Despite the low concentrations, Multiple Quantum NMR reveals a high degree of hydrogen clustering consistent with grain boundary passivation. Most hydrogen is rigidly held, but some, probably in -OCH3 and -NCH3 defects, undergoes rotation at room temperature. Similar results were obtained for hot-filament, microwave-plasma and DC arc-jet films, suggesting a common surface chemistry, but no hydrogen was detected in an as-deposited combustion film. 13C NMR provided the first quantitative determination of non-diamond bonded carbon defects, providing a benchmark for Raman spectroscopy, the primary characterization method for diamond. Selective 13C labeling demonstrated heterogeneous reactions involving carbon occur at the hot-filament. With high-speed magic-angle-spinning 19F NMR, CFx (x=1-3) functionalities were resolved on the surface of plasma-treated diamond powder. Understanding these defects impacts the understanding of film growth mechanisms and structure-property relationships for CVD diamond.

  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. Chromatographic NMR in NMR solvents

    NASA Astrophysics Data System (ADS)

    Carrara, Caroline; Viel, Stéphane; Delaurent, Corinne; Ziarelli, Fabio; Excoffier, Grégory; Caldarelli, Stefano

    2008-10-01

    Recently, it was demonstrated that pseudo-chromatographic NMR experiments could be performed using typical chromatographic solids and solvents. This first setup yielded improved separation of the spectral components of the NMR spectra of mixtures using PFG self-diffusion measurements. The method (dubbed Chromatographic NMR) was successively shown to possess, in favorable cases, superior resolving power on non-functionalized silica, compared to its LC counterpart. To further investigate the applicability of the method, we studied here the feasibility of Chromatographic NMR in common deuterated solvents. Two examples are provided, using deuterated chloroform and water, for homologous compounds soluble in these solvents, namely aromatic molecules and alcohols, respectively.

  2. Solid state NMR studies of gels derived from low molecular mass gelators.

    PubMed

    Nonappa; Kolehmainen, E

    2016-07-13

    Since its invention more than six decades ago, nuclear magnetic resonance (NMR) spectroscopy has evolved as an inevitable part of chemical as well as structural analysis of small molecules, polymers, biomaterials and hybrid materials. In the solution state, due to the increased viscosity of complex viscoelastic fluids such as gels, liquid crystals and other soft materials, the rate of molecular tumbling is reduced, which in turn affects the chemical shift anisotropy, dipolar and quadrupolar interactions. As a consequence the solution state NMR spectra show broad lines, and therefore, extracting detailed structural information is a challenging task. In this context, solid state (SS) NMR has the ability to distinguish between a minute amount of polymorphic forms, conformational changes, and the number of non-equivalent molecules in an asymmetric unit of a crystal lattice, and to provide both qualitative as well as quantitative analytical data with a short-range order. Therefore, SS NMR has continued to evolve as an indispensable tool for structural analysis and gave birth to a new field called NMR crystallography. Solid state cross polarization (CP) and high resolution (HR) magic angle spinning (MAS) NMR spectroscopy has been used to study weak interactions in polymer gels. However, the application of SS NMR spectroscopy to study gels derived from low molecular weight gelators has been limited until recently. In this review, we will focus on the importance of solid state NMR spectroscopy in understanding and elucidating the structure of supramolecular gels derived from low molecular weight gelators with selected examples. PMID:27374054

  3. Deuterium NMR Studies of the Structure and Dynamics of Gramicidin.

    NASA Astrophysics Data System (ADS)

    Hing, Andrew William

    1990-01-01

    The structure and dynamics of the membrane peptide gramicidin are investigated by deuterium NMR. A specific structural and dynamical question about the peptide backbone of gramicidin is investigated by deuterating the alpha carbon of the third alanine residue. Deuterium NMR experiments performed on this analog in oriented lipid bilayers indicate that the c_alpha- ^2H bond makes an angle relative to the helical axis that is in agreement with the bond angle predicted by the beta^{6.3} helical model. A second structural and dynamical question about the peptide backbone of gramicidin is investigated by deuterating the formyl group of two different analogs. Deuterium NMR experiments performed on these analogs show that the spectra of the two analogs are very similar. However, the analog possessing D-leucine as the second residue also appears to exist in a second, minor conformation which does not seem to exist for the analog possessing glycine as the second residue.

  4. Study of the New Pulse NMR System for the Jefferson Lab Helium-3 Polarized Target

    NASA Astrophysics Data System (ADS)

    Newton, Joseph

    2013-10-01

    At Jefferson Lab, a polarized Helium-3 target is used to study the neutron. The Helium-3 target is undergoing an upgrade to improve its polarization. Measuring it involved a new technique known as pulse Nuclear Magnetic Resonance (NMR). The focus of this project was to find noise in the Pulse NMR signal and to compute the calibration constant to make the polarization easier to deduce. Pulse NMR calibration tests were performed by doing AFP NMR measurements followed by Pulse NMR measurements while varying certain conditions. These included the convection heater, the operation of the oven, and the operation of the laser. Data analysis was done by fitting the pulse NMR signal from the oscilloscope and utilizing the Fourier Transform. Noise was analyzed in the fitting and the Fourier Transform. The calibration constants were affected by the convection heater. The values deviated between the pumping and target chambers of the cell when there was no convection but the values were closer when convection was induced. As far as the noise, it was found to be significant. These results will enable the calculation of the polarization with pulse NMR. In addition, the signal analysis provided insight into the influence of background noise on the pulse NMR measurement. This research was done though the SULI program of the Department of Energy.

  5. NMR studies of the conformation and motion of tetrahydrofuran in graphite intercalation compounds

    SciTech Connect

    Caplan, D. F.

    1991-11-01

    The behavior of tetrahydrofuran (THF) molecules intercalated in graphite layers in compounds Cs(THF){sub 1.3}C{sub 24} and K(THF){sub 2.5}C{sub 24} was studied by proton NMR. The graphite layers in these compounds impose a uniform ordering on the THF molecules, giving rise to sharp NMR spectra. Experimental and simulated proton NMR spectra were used to investigate geometry, orientation and conformation of intercalated THF, and to determine whether pseudorotation, a large amplitude low-frequency vibration observed in gaseous THF, can also occur in the constrained environment provided by the graphite intercalation compounds. Deuterium and multiple quantum proton NMR spectra were also simulated in order to determine if these techniques could further refine the proton NMR results.

  6. Corrections for 17O interference, effects on Δ47 determination

    NASA Astrophysics Data System (ADS)

    Olack, G.; He, B.; Colman, A. S.

    2013-12-01

    The measurements of 13C on CO2 samples are routinely corrected for 17O contribution to the m/z 45 signal (Craig, 1957; Santrock, et al., 1985). The 17O abundance affects the Δ47 calculation, and the amount of 17O present is routinely determined using the relationship between 18O and 17O presented in IAEA TECDOC 825 (Dennis, et al., 2011; Huntington, et al., 2009; Gonfiantini, et al., 1995). In 2010, the IAEA released new recommendations for 17O determinations to be used for 13C corrections (Brand, et al., 2010). We compare the effect of using different ways to determine 17O interference, as well as using the currently accepted N(13C)/N(12C) value for VPDB (Brand, et al., 2010), on heated gas lines, model data, and on CO2 gases made to have similar δ47 and Δ47, but with highly contrasting δ18O and δ13C values. The 2010 IAEA recommendations give a better fit for heated gas data than the TECDOC 825 recommendations. Comparing differences in the data points relative to their respective fitted lines, we see differences on the order of 5 to 10 ppm in Δ47. That corresponds to a systematic error of 2 °C in the temperature estimate (room temperature range), and one that varies with δ13C and δ18O, but not necessarily with δ47. The preliminary work on equilibrated CO2 gases having similar δ47, but very different δ13C and δ18O, showed large (ca. 70 ppm) differences in Δ47 when using the (standard) TECDOC 825 recommendations. The Δ47 values were much closer when the 2010 IUPAC recommendations were used. This also serves as a test of the updated factors for 17O determination, as well as the overall robustness of the Δ47 measurement.

  7. NMR studies of osmoregulation in methanogenic archaebacteria. [NMR (nuclear magnetic resonance)

    SciTech Connect

    Robertson, D.E.

    1991-01-01

    Methanogens are strict anaerobic archaebacteria whose metabolism centers around the reduction of CO[sub 2] to CH[sub 4]. Their environments are often extreme (high temperatures, high salt, few nutrients, etc.) and they may have evolved unique ways to handle these stresses. It is proposed that methanogenic archaebacteria respond to osmotic stress by accumulating a series of organic solutes. In two strains of marine methanogens, Methanogenium cariaci and Methanococcus thermolithotrophicus, four key organic solutes are observed: L-[alpha]-glutamate, [beta]-glutamate, N[sup e]-acetyl-[beta]-lysine, and glycine betaine. The first three of these are synthesized de novo; glycine betaine is transported into the Mg. cariaci cells from the medium. In the absence of betaine, Mg. cariaci synthesizes N[sup e]-acetyl-[beta]-lysine as the dominant osmolyte. Mc. thermolithotrophicus also synthesizes N[sup e]-acetyl-[beta]-lysine but only at salt concentrations greater than 1 M. In Mc. thermolithotrophicus intracellular potassium ion concentrations, determined by [sup 39]K NMR spectroscopy, are balanced by the total concentration of anionic amino acid species, [alpha]-glutamate and [beta]-glutamate. Turnover of the organic solutes has been monitored using [sup 13]C-pulse/[sup 12]C-chase, and [sup 15]N-pulse/[sup 14]N-chase experiments. The [beta]-amino acids exhibit slower turnover rates compared to L-[alpha]-glutamate or aspartate, consistent with their role as compatible solutes. Biosynthetic information for the [beta]-amino acids was provided by [sup 13]C-label incorporation and steady state labeling experiments. [beta]-glutamate shows a lag in [sup 13]C uptake from [sup 13]CO[sub 2], indicative of its biosynthesis from a precursor not in equilibrium with the soluble L-[alpha]-glutamate pool, probably a macromolecule. A novel biosynthetic pathway is proposed for N[sup e]-acetyl-[beta]-lysine from the diaminopimelate pathway.

  8. Hydrogen Adsorption in Carbon-Based Materials Studied by NMR

    NASA Astrophysics Data System (ADS)

    Wu, Yue; Kleinhammes, Alfred; Anderson, Robert; Mao, Shenghua

    2007-03-01

    Hydrogen adsorption in carbon-based materials such as boron-doped graphite and boron-doped single-walled carbon nanotubes (SWNTs) were investigated by nuclear magnetic resonance (NMR). ^1H NMR is shown to be a sensitive and quantitative probe for detecting adsorbed gas molecules such as H2, methane, and ethane. NMR measurements were carried out in-situ under given H2 pressure up to a pressure of over 100 atm. From such ^1H NMR measurement, the amount of adsorbed H2 molecules was determined versus pressure. This gives an alternative method for measuring the adsorption isotherms where the H2 signature is identified based on spin properties rather than weight or volume as in gravimetric and volumetric measurements. The measurement shows that boron doping has a favorable effect on increasing the adsorption enthalpy of H2 in carbon-based systems. This work was done in collaboration with NREL and Department of Chemistry, University of Pennsylvania, within the DOE Center of Excellence on Carbon-based Hydrogen Storage Materials and is supported by DOE.

  9. NMR Studies of the Li-Mg-N-H Phases.

    NASA Astrophysics Data System (ADS)

    Bowman, Robert; Reiter, J. W.; Kulleck, J. G.; Hwang, S.-J.; Luo, Weifang

    2007-03-01

    Solid state NMR including magic-angle-spinning (MAS) and cross-polarization (CP) MAS experiments have been used to characterize various amide and imide phases containing Li and/or Mg. MAS-NMR spectra for the ^1H, ^6Li, ^7Li, and ^15N nuclei have been obtained to improve understanding on formation, processing, and degradation behavior. Only limited information could be obtained from the proton and ^7Li MAS-NMR spectra to due large dipolar interactions and small chemical shifts. However, more success was obtained from the ^6Li and ^15N nuclei although their very long spin-lattice relaxation times did impact signal acquisition times. For example, three distinct ^6Li peaks were resolved from LiNH2 phases that were clearly separated from the LiH secondary phase in these samples. While the ^15N spectra for LiNH2 phase in isotopically enriched samples exhibited only a single peak at least three distinct ^15N peaks were observed from the similarly enriched Mg amide samples. These differences will be related to crystal structures. The NMR spectra also revealed very little motion in these hydrides upon to nearly 500 K.

  10. NMR Studies of Biomass and its Reaction Products

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biomass refers to biological material derived from living or recently living organisms, such as wood, agricultural products and wastes, and alcohol fuels. An increasingly popular R&D approach is to convert biomass into industrial polymers or chemicals. NMR is an excellent technique for the character...

  11. NMR and NQR study of the thermodynamically stable quasicrystals

    SciTech Connect

    Shastri, A.

    1995-02-10

    {sup 27}Al and {sup 61,65}Cu NMR measurements are reported for powder samples of stable AlCuFe and AlCuRu icosahedral quasicrystals and their crystalline approximants, and for a AlPdMn single grain quasicrystal. Furthermore, {sup 27}Al NQR spectra at 4.2 K have been observed in the AlCuFe and AlCuRu samples. From the quadrupole perturbed NMR spectra at different magnetic fields, and from the zero field NQR spectra, a wide distribution of local electric field gradient (EFG) tensor components and principal axis system orientations was found at the Al site. A model EFG calculation based on a 1/1 AlCuFe approximant was successful in explaining the observed NQR spectra. It is concluded that the average local gradient is largely determined by the p-electron wave function at the Al site, while the width of the distribution is due to the lattice contribution to the EFG. Comparison of {sup 63}Cu NMR with {sup 27}Al NMR shows that the EFG distribution at the two sites is similar, but that the electronic contribution to the EFG is considerably smaller at the Cu site, in agreement with a more s-type wave function of the conduction electrons.

  12. Selectively Labeling the Heterologous Protein in Escherichia coli for NMR Studies: A Strategy to Speed Up NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Almeida, F. C. L.; Amorim, G. C.; Moreau, V. H.; Sousa, V. O.; Creazola, A. T.; Américo, T. A.; Pais, A. P. N.; Leite, A.; Netto, L. E. S.; Giordano, R. J.; Valente, A. P.

    2001-01-01

    Nuclear magnetic resonance is an important tool for high-resolution structural studies of proteins. It demands high protein concentration and high purity; however, the expression of proteins at high levels often leads to protein aggregation and the protein purification step can correspond to a high percentage of the overall time in the structural determination process. In the present article we show that the step of sample optimization can be simplified by selective labeling the heterologous protein expressed in Escherichia coli by the use of rifampicin. Yeast thioredoxin and a coix transcription factor Opaque 2 leucine zipper (LZ) were used to show the effectiveness of the protocol. The 1H/15N heteronuclear correlation two-dimensional NMR spectrum (HMQC) of the selective 15N-labeled thioredoxin without any purification is remarkably similar to the spectrum of the purified protein. The method has high yields and a good 1H/15N HMQC spectrum can be obtained with 50 ml of M9 growth medium. Opaque 2 LZ, a difficult protein due to the lower expression level and high hydrophobicity, was also probed. The 15N-edited spectrum of Opaque 2 LZ showed only the resonances of the protein of heterologous expression (Opaque 2 LZ) while the 1H spectrum shows several other resonances from other proteins of the cell lysate. The demand for a fast methodology for structural determination is increasing with the advent of genome/proteome projects. Selective labeling the heterologous protein can speed up NMR structural studies as well as NMR-based drug screening. This methodology is especially effective for difficult proteins such as hydrophobic transcription factors, membrane proteins, and others.

  13. High pressure NMR study of a small protein, gurmarin.

    PubMed

    Inoue, K; Yamada, H; Imoto, T; Akasaka, K

    1998-11-01

    The effect of pressure on the structure of gurmarin, a globular, 35-residue protein from Gymnema sylvestre, was studied in aqueous environment (95% 1H2O/5% 2H2O, pH 2.0) with an on-line variable pressure NMR system operating at 750 MHz. Two-dimensional TOCSY and NOESY spectra were measured as functions of pressure between 1 and 2000 bar at 40 degrees C. Practically all the proton signals of gurmarin underwent some shifts with pressure, showing that the entire protein structure responds to, and is altered by, pressure. Most amide protons showed different degrees of low field shifts with pressure, namely 0-0.2 ppm with an average of 0.051 ppm at 2000 bar, showing that they are involved in hydrogen bonding and that these hydrogen bonds are shortened by pressure by different degrees. The tendency was also confirmed that the chemical shifts of the amide protons exposed to the solvent (water) are more sensitive to pressure than those internally hydrogen bonded with carbonyls. The pressure-induced shifts of the H alpha signals of the residues in the beta-sheet showed a negative correlation with the 'folding' shifts (difference between the shift at 1 bar and that of a random coil), suggesting that the main-chain torsion angles of the beta-sheet are slightly altered by pressure. Significant pressure-induced shifts were also observed for the side-chain protons (but no larger than 10% of the 'folding' shifts), demonstrating that the tertiary structure of gurmarin is also affected by pressure. Finally, the linearity of the pressure-induced shifts suggest that the compressibility of gurmarin is invariant in the pressure range between 1 and 2000 bar. PMID:9862129

  14. Measurements and Modeling of (16)O(12)C(17)O Spectroscopic Parameters at 2µm

    NASA Astrophysics Data System (ADS)

    Jacquemart, D.; Sung, K.; Brown, L. R.; Coleman, M.; Mantz, A. W.; Smith, M. A. H.

    2014-06-01

    In the present study, line-intensity measurements for 16O12C17O were performed using a high-resolution Fourier transform spectrometer (Bruker IFS-125HR) together with a Herriott cell allowing a 20.956 m absorption path. For this, a 17O-enriched CO2 gas sample mixture was used. The 16O12C17O isotopologue abundance in the sample was determined to be 0.3991 by mass spectrometry. Since a collisional narrowing effect has been observed, the Rautian profile was systematically used instead of the Voigt profile. Finally, around 1000 transitions were studied between 4604 and 5126 cm-1 involving 15 bands of the 16O12C17O isotopologue. For each of the 15 bands, transition dipole moments and Herman-Wallis factors were derived, which also enabled a global comparison with theoretical calculations and predictions achieved for carbon dioxide. For the measured and calculated line positions, the accuracy is between 0.1 - 1×10-3 cm-1. For line intensities, depending on the intensity of the band, accuracies are between 2 - 3 % for 5 cold bands and 2 hot bands and between 6 - 30 % for 8 weaker hot bands. Results from this work are compared to previous works and to HITRAN 2012. Complete line lists were generated to support atmospheric remote sensing for the Earth (e.g. GOSAT, OCO-2 ...), Mars and Venus.

  15. NMR spectroscopy in studies of light-induced structural changes in mammalian rhodopsin: applicability of solution (19)F NMR.

    PubMed

    Klein-Seetharaman, J; Getmanova, E V; Loewen, M C; Reeves, P J; Khorana, H G

    1999-11-23

    We report high resolution solution (19)F NMR spectra of fluorine-labeled rhodopsin mutants in detergent micelles. Single cysteine substitution mutants in the cytoplasmic face of rhodopsin were labeled by attachment of the trifluoroethylthio (TET), CF(3)-CH(2)-S, group through a disulfide linkage. TET-labeled cysteine mutants at amino acid positions 67, 140, 245, 248, 311, and 316 in rhodopsin were thus prepared. Purified mutant rhodopsins (6-10 mg), in dodecylmaltoside, were analyzed at 20 degrees C by solution (19)F NMR spectroscopy. The spectra recorded in the dark showed the following chemical shifts relative to trifluoroacetate: Cys-67, 9.8 ppm; Cys-140, 10.6 ppm; Cys-245, 9.9 ppm; Cys-248, 9.5 ppm; Cys-311, 9.9 ppm; and Cys-316, 10.0 ppm. Thus, all mutants showed chemical shifts downfield that of free TET (6.5 ppm). On illumination to form metarhodopsin II, upfield changes in chemical shift were observed for (19)F labels at positions 67 (-0.2 ppm) and 140 (-0.4 ppm) and downfield changes for positions 248 (+0.1 ppm) and 316 (+0.1 ppm) whereas little or no change was observed at positions 311 and 245. On decay of metarhodopsin II, the chemical shifts reverted largely to those originally observed in the dark. The results demonstrate the applicability of solution (19)F NMR spectroscopy to studies of the tertiary structures in the cytoplasmic face of intact rhodopsin in the dark and on light activation. PMID:10570143

  16. NMR and optical studies of piezoelectric polymers. Annual progress report, April 1, 1990--September 30, 1992

    SciTech Connect

    Schmidt, V.H.; Tuthill, G.F.

    1993-04-01

    Progress is reported in several areas dealing with piezoelectric (electroactive) polymers (mostly vinylidene fluoride, trifluoroethylene, copolymers, PVF{sub 2}) and liquid crystals. Optical studies, neutron scattering, NMR, thermal, theory and modeling were done.

  17. The application of NMR imaging to the studies of enhanced oil recovery in China.

    PubMed

    Weimin, W; Dongjiang, L; Wei, L

    1996-01-01

    The advantages of the application of NMR imaging to the studies of enhanced oil recovery methods that include polymer slug flooding, combination slug flooding, and thermal soaking are described. PMID:8970120

  18. Solid-state NMR studies of theophylline co-crystals with dicarboxylic acids.

    PubMed

    Pindelska, Edyta; Sokal, Agnieszka; Szeleszczuk, Lukasz; Pisklak, Dariusz Maciej; Kolodziejski, Waclaw

    2014-11-01

    In this work, three polycrystalline materials containing co-crystals of theophylline with malonic, maleic, and glutaric acids were studied using (13)C, (15)N and (1)H solid-state NMR and FT-IR spectroscopy. The NMR assignments were supported by gauge including projector augmented waves (GIPAW) calculations of chemical shielding, performed using X-ray determined geometry. The experimental (13)C cross polarization/magic angle spinning (CP/MAS) NMR results and the calculated isotropic chemical shifts were in excellent agreement. A rapid and convenient method for theophylline co-crystals crystal structure analysis has been proposed for co-crystals, which are potentially new APIs. PMID:25194346

  19. 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.

  20. Studies of 27Al NMR in EuAl4

    NASA Astrophysics Data System (ADS)

    Niki, H.; Nakamura, S.; Higa, N.; Kuroshima, H.; Toji, T.; Yogi, M.; Nakamura, A.; Hedo, M.; Nakama, T.; Ōnuki, Y.; Harima, H.

    2015-03-01

    EuAl4 orders antiferromagnetically at TN ≈ 16 K with an effective magnetic moment of 8.02 μB. In the paramagnetic phase, the magnetic susceptibility of EuAl4 follows the Curie-Weiss law with a positive Curie-Weiss temperature θP = +14 K. The antiferromagnetic state is changed into the field induced ferromagnetic state at a critical field Hc of approximately 2 T. In order to microscopically investigate the magnetic and electronic properties in EuAl4, the NMR measurements of EuAl4 have been carried out at temperatures between 2 and 300 K, applying an external magnetic field of approximately 6.5 T. The 27Al NMR spectra corresponding to Al(I) and Al(II) sites are obtained. From the 27Al NMR spectra, the isotropic part Kiso and anisotropic part Kaniso of Knight shift, and nuclear quadrupole frequncy νQ are obtained. The Kiso and Kaniso shift to negative side with decreasing temperature due to the RKKY interaction. These temperature dependences follow the Curie-Weiss law with θP = +14 K, which is consistent with that of the magnetic susceptibility. From the K - χ plot, the values of the hyperfine fields Hhf_iso and Hhf_aniso are -3.231 and -0.162 kOe/μB for Al(I) site, and -1.823 and -0.264 kOe/μB for Al(II) site, respectively. The values of νQ of 27Al nucleus for Al(I) and Al(II) sites are approximately 0.865 and 0.409 MHz, respectively. The nuclear relaxation time T1 of 27Al NMR for both sites is almost constant in the paramagnetic phase, while the value of 1/T1 is abruptly decreased in the ordered ferromagnetic state.

  1. NMR studies of selective population inversion and spin clustering

    SciTech Connect

    Baum, J.S.

    1986-02-01

    This work describes the development and application of selective excitation techniques in Nuclear Magnetic Resonance. Composite pulses and multiple-quantum methods are used to accomplish various goals, such as broadband and narrowband excitation in liquids, and collective excitation of groups of spins in solids. These methods are applied to a variety of problems, including non-invasive spatial localization, spin cluster size characterization in disordered solids and solid state NMR imaging.

  2. Studies of electrolyte penetration in carbon anodes by NMR techniques.

    SciTech Connect

    Sandi, G.

    1998-12-09

    A toroid cavity nuclear magnetic resonance (NMR) detector capable of recording radial concentration profiles, diffusion constants, and displacements of charge carriers was employed to investigate the lithium ion distribution in an electrochemical cell containing a carbonaceous material synthesized from pyrene and pillared clays as inorganic templates. A carbon rod was used in a control experiment to assign the Li{sup +} spectrum and to calibrate the one dimensional radial images.

  3. Automated sample preparation station for studying self-diffusion in porous solids with NMR spectroscopy

    SciTech Connect

    Hedin, Niklas; DeMartin, Gregory J.; Reyes, Sebastian C.

    2006-03-15

    In studies of gas diffusion in porous solids with nuclear magnetic resonance (NMR) spectroscopy the sample preparation procedure becomes very important. An apparatus is presented here that pretreats the sample ex situ and accurately sets the desired pressure and temperature within the NMR tube prior to its introduction in the spectrometer. The gas manifold that supplies the NMR tube is also connected to a microbalance containing another portion of the same sample, which is kept at the same temperature as the sample in the NMR tube. This arrangement permits the simultaneous measurement of the adsorption loading on the sample, which is required for the interpretation of the NMR diffusion experiments. Furthermore, to ensure a good seal of the NMR tube, a hybrid valve design composed of titanium, a Teflon registered seat, and Kalrez registered O-rings is utilized. A computer controlled algorithm ensures the accuracy and reproducibility of all the procedures, enabling the NMR diffusion experiments to be performed at well controlled conditions of pressure, temperature, and amount of gas adsorbed on the porous sample.

  4. NMR studies of molecules in liquid crystals and graphite

    SciTech Connect

    Rosen, M.E.

    1992-06-01

    NMR experiments to measure proton dipole couplings were performed on a series of n-alkanes (n-hexane through n-decane) dissolved in nematic liquid crystals. Computer modeling of the experimental NMR-spectra was done using several different models for intermolecular interactions in these systems. The model of Photinos et al. was found to be best in describing the intermolecular interactions in these systems and can provide a statistical picture of the conformation and orientation of the alkane molecules in their partially-oriented environment. Order parameters and conformational distributions for the alkanes can be calculated from the modeling. The alkanes are found to have conformational distributions very much like those found in liquid alkanes. Proton NMR spectra of tetrahydrofuran (THF) intercalated in two graphite intercalation compounds were also measured. Computer simulations of these spectra provide a picture of THF in the constrained environment between the graphene layers where the THF is oriented at a particular angle, can translate and rotate freely, but does not appear to pseudorotate.

  5. Solid State NMR Studies of the Aluminum Hydride Phases

    NASA Technical Reports Server (NTRS)

    Hwang, Son-Jong; Bowman, R. C., Jr.; Graetz, Jason; Reilly, J. J.

    2006-01-01

    Several solid state NMR techniques including magic-angle-spinning (MAS) and multiple-quantum (MQ) MAS experiments have been used to characterize various AlH3 samples. MAS-NMR spectra for the 1H and 27Al nuclei have been obtained on a variety of AlH3 samples that include the (beta)- and (gamma)- phases as well as the most stable (alpha)-phase. While the dominant components in these NMR spectra correspond to the aluminum hydride phases, other species were found that include Al metal, molecular hydrogen (H2), as well as peaks that can be assigned to Al-O species in different configurations. The occurrence and concentration of these extraneous components are dependent upon the initial AlH3 phase composition and preparation procedures. Both the (beta)-AlH3 and (gamma)-AlH3 phases were found to generate substantial amounts of Al metal when the materials were stored at room temperature while the (alpha)-phase materials do not exhibit these changes.

  6. NMR study of ferroelastic phase transition of tetramethylammonium tetrabromocobaltate

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran; Kim, Sun Ha

    2016-09-01

    Static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) experiments were carried out on 1H, 13C, and 14N nuclei in order to understand the structural changes of the N(CH3)4 groups in [N(CH3)4]2CoBr4 near the ferroelastic phase transition temperature TC. The two chemically inequivalent N(CH3)4 groups were distinguished using 13C cross-polarization/(CP)MAS and 14N static NMR. The changes in chemical shifts, line intensities, and the spin-lattice relaxation time near TC can be correlated with the changing structural geometry, which underlies the phase transition. The 14N NMR spectra indicated a crystal symmetry change at TC, which is related to the ferroelastic domain with different orientations of the N(CH3)4 groups. The ferroelastic domain walls were confirmed by optical polarizing microscopy, and the wall orientations were described by the Sapriel theory. The transition to the ferroelastic phase was found to be related to the orientational ordering of the N(CH3)4 groups.

  7. (15)N NMR studies of a nitrile-modified nucleoside.

    PubMed

    Gillies, Anne T; Gai, Xin Sonia; Buckwalter, Beth L; Fenlon, Edward E; Brewer, Scott H

    2010-12-30

    Nitrile-modified molecules have proven to be excellent probes of local environments in biomolecules via both vibrational and fluorescence spectroscopy. The utility of the nitrile group as a spectroscopic probe has been expanded here to (15)N NMR spectroscopy by selective (15)N incorporation. The (15)N NMR chemical shift (δ((15)N)) of the (15)N-labeled 5-cyano-2'-deoxyuridine (C(15)NdU, 1a) was found to change from 153.47 to 143.80 ppm in going from THF-d(8) to D(2)O. A 0.81 ppm downfield shift was measured upon formation of a hydrogen-bond-mediated heterodimer between 2,6-diheptanamidopyridine and a silyl ether analogue of 1a in chloroform, and the small intrinsic temperature dependence of δ((15)N) of C(15)NdU was measured as a 0.38 ppm downfield shift from 298 to 338 K. The experiments were complemented with density functional theory calculations exploring the effect of solvation on the (15)N NMR chemical shift. PMID:21126044

  8. Perspectives of solution NMR spectroscopy for structural and functional studies of integral membrane proteins

    NASA Astrophysics Data System (ADS)

    Reckel, Sina; Hiller, Sebastian

    2013-04-01

    This article discusses future perspectives of solution NMR spectroscopy to study structures and functions of integral membrane proteins at atomic resolution, based on a review of recent progress in this area. Several selected examples of structure determinations, as well as functional studies of integral membrane proteins are highlighted. We expect NMR spectroscopy to make future key scientific contributions to understanding membrane protein function, in particular for large membrane protein systems with known three-dimensional structure. Such situations can benefit from the fact that functional NMR studies have substantially less limitations by molecular size than a full de novo structure determination. Therefore, the general potential for NMR spectroscopy to solve biologic key questions associated with integral membrane proteins is very promising.

  9. Solution- and solid-state NMR studies of GPCRs and their ligands.

    PubMed

    Tapaneeyakorn, Satita; Goddard, Alan D; Oates, Joanne; Willis, Christine L; Watts, Anthony

    2011-06-01

    G protein-coupled receptors (GPCRs) represent one of the major targets of new drugs on the market given their roles as key membrane receptors in many cellular signalling pathways. Structure-based drug design has potential to be the most reliable method for novel drug discovery. Unfortunately, GPCR-ligand crystallisation for X-ray diffraction studies is very difficult to achieve. However, solution- and solid-state NMR approaches have been developed and have provided new insights, particularly focussing on the study of protein-ligand interactions which are vital for drug discovery. This review provides an introduction for new investigators of GPCRs/ligand interactions using NMR spectroscopy. The guidelines for choosing a system for efficient isotope labelling of GPCRs and their ligands for NMR studies will be presented, along with an overview of the different sample environments suitable for generation of high resolution structural information from NMR spectra. PMID:20951674

  10. Backbone dynamics of barstar: a (15)N NMR relaxation study.

    PubMed

    Sahu, S C; Bhuyan, A K; Majumdar, A; Udgaonkar, J B

    2000-12-01

    Backbone dynamics of uniformly (15)N-labeled barstar have been studied at 32 degrees C, pH 6.7, by using (15)N relaxation data obtained from proton-detected 2D (1)H-(15)N NMR spectroscopy. (15)N spin-lattice relaxation rate constants (R(1)), spin-spin relaxation rate constants (R(2)), and steady-state heteronuclear (1)H-(15)N NOEs have been determined for 69 of the 86 (excluding two prolines and the N-terminal residue) backbone amide (15)N at a magnetic field strength of 14.1 Tesla. The primary relaxation data have been analyzed by using the model-free formalism of molecular dynamics, using both isotropic and axially symmetric diffusion of the molecule, to determine the overall rotational correlation time (tau(m)), the generalized order parameter (S(2)), the effective correlation time for internal motions (tau(e)), and NH exchange broadening contributions (R(ex)) for each residue. As per the axially symmetric diffusion, the ratio of diffusion rates about the unique and perpendicular axes (D( parallel)/D( perpendicular)) is 0.82 +/- 0.03. The two results have only marginal differences. The relaxation data have also been used to map reduced spectral densities for the NH vectors of these residues at three frequencies: 0, omega(H), and omega(N), where omega(H),(N) are proton and nitrogen Larmor frequencies. The value of tau(m) obtained from model-free analysis of the relaxation data is 5.2 ns. The reduced spectral density analysis, however, yields a value of 5.7 ns. The tau(m) determined here is different from that calculated previously from time-resolved fluorescence data (4.1 ns). The order parameter ranges from 0.68 to 0.98, with an average value of 0.85 +/- 0.02. A comparison of the order parameters with the X-ray B-factors for the backbone nitrogens of wild-type barstar does not show any considerable correlation. Model-free analysis of the relaxation data for seven residues required the inclusion of an exchange broadening term, the magnitude of which ranges from 2

  11. Using dual-bacterial denitrification to improve δ15N determinations of nitrates containing mass-independent 17O

    USGS Publications Warehouse

    Coplen, T.B.; Böhlke, J.K.; Casciotti, K.L.

    2004-01-01

    The bacterial denitrification method for isotopic analysis of nitrate using N2O generated from Pseudomonas aureofaciens may overestimate ??15N values by as much as 1-2??? for samples containing atmospheric nitrate because of mass-independent 17O variations in such samples. By analyzing such samples for ??15N and ??18O using the denitrifier Pseudomonas chlororaphis, one obtains nearly correct ??15N values because oxygen in N 2O generated by P. chlororaphis is primarily derived from H 2O. The difference between the apparent ??15N value determined with P. aureofaciens and that determined with P. chlororaphis, assuming mass-dependent oxygen isotopic fractionation, reflects the amount of mass-independent 17O in a nitrate sample. By interspersing nitrate isotopic reference materials having substantially different ?? 18O values with samples, one can normalize oxygen isotope ratios and determine the fractions of oxygen in N2O derived from the nitrate and from water with each denitrifier. This information can be used to improve ??15N values of nitrates having excess 17O. The same analyses also yield estimates of the magnitude of 17O excess in the nitrate (expressed as ??17O) that may be useful in some environmental studies. The 1-?? uncertainties of ??15N, ??18O and ??17O measurements are ??0.2, ??0.3 and ??5???, respectively. Copyright ?? 2004 John Wiley & Sons, Ltd.

  12. 119 Sn NMR studies on the heavy fermion compound CeSn3

    NASA Astrophysics Data System (ADS)

    Crocker, John; Kim, Andrew; Klavins, Peter; Curro, Nicholas

    2015-03-01

    CeSn3 does not exhibit long-range order at low temperatures, thus it provides an interesting baseline for NMR studies of the Knight shift. We report the synthesis and characterization of single crystals of CeSn3, as well as 119Sn nuclear magnetic resonance (NMR) measurements from 4.5K to room temperature. Our data reveal a broad peak in the knight shift (K) at Tmax ~ 135K, and a knight shift anomaly at T* ~ 85K.

  13. Multiple-quantum NMR studies of spin clusters in liquid crystals and zeolites

    SciTech Connect

    Pearson, J. . Dept. of Chemistry Lawrence Berkeley Lab., CA )

    1991-07-01

    This work will describe the use of MQ NMR to study spin clusters in anisotropic materials. A technique known as multiple-quantum spin counting was used to determine average spin cluster sizes liquid crystalline materials and in faujacitic zeolites containing aromatic hydrocarbons. The first half of the thesis will describe MQ NMR and the MQ spin counting technique, and the second half of the thesis will describe the actual experiments and their results.

  14. Lemna minor L. as a model organism for ecotoxicological studies performing 1H NMR fingerprinting.

    PubMed

    Aliferis, Konstantinos A; Materzok, Sylwia; Paziotou, Georgia N; Chrysayi-Tokousbalides, Maria

    2009-08-01

    A validated method applying (1)H NMR fingerprinting for the study of metabolic changes caused in Lemna minor L. by various phytotoxic substances is presented. (1)H NMR spectra of crude extracts from untreated and treated colonies with the herbicides glyphosate, mesotrione, norflurazon, paraquat and the phytotoxin pyrenophorol were subjected to multivariate analyses for detecting differences between groups of treatments. Partial least squares-discriminant analysis (PLS-DA) and hierarchical cluster analysis (HCA) were carried out in order to discriminate and classify treatments according to the observed changes in the metabolome of the plant. Although the compounds at the concentrations used did not cause macroscopically observable symptoms of phytotoxicity, characteristic metabolic changes were detectable by analyzing (1)H NMR spectra. Analyses results revealed that metabonomics applying (1)H NMR fingerprinting is a potential method for the investigation of toxicological effects of xenobiotics on L. minor, and possibly on other duckweed species, helping in the understanding of such interactions. PMID:19443011

  15. NMR Studies of Spin Decoherence in Phosphorus-doped Silicon

    NASA Astrophysics Data System (ADS)

    Li, D.; Dementyev, A. E.; Liu, M.; Barrett, S. E.

    2002-03-01

    Understanding nuclear spin dynamics in Si:P is an important step(B.E. Kane, quant-ph/0003031.) towards the realization of semiconductor spin-based qubits(B.E. Kane, Nature 393, 133 (1998).). We present measurements of NMR spectra and relaxation times for both ^29Si and ^31P, in fields up to 15.3 Tesla. Our progress towards Optically Pumped Nuclear Magnetic Resonance(A.E. Dementyev, P.Khandelwal, N.N. Kuzma, S.E. Barrett, L.N. Pfeiffer, K.W.West, Solid State Commun. 119, 217 (2001).) (OPNMR) of Si:P will be described.

  16. /sup 31/P NMR saturation-transfer and /sup 13/C NMR kinetic studies of glycolytic regulation during anaerobic and aerobic glycolysis

    SciTech Connect

    Campbell-Burk, S.L.; den Hollander, J.A.; Alger, J.R.; Shulman, R.G.

    1987-11-17

    /sup 31/P NMR saturation-transfer techniques have been employed in glucose-gown derepressed yeast to determine unidirectional fluxes in the upper part of the Embden-Meyerhof-Parnas pathway. The experiments were performed during anaerobic and aerobic glycolysis by saturating the ATP/sub ..gamma../ resonances and monitoring changes in the phosphomonoester signals from glucose 6-phosphate and fructose 1,6-bisphosphate. These experiments were supplemented with /sup 13/C NMR measurements of glucose utilization rates and /sup 13/C NMR label distribution studies. Combined with data obtained previously from radioisotope measurement, these /sup 31/P and /sup 13/C NMR kinetic studies allowed estimation of the net glycolytic flow in addition to relative flows through phosphofructokinase (PFK) and Fru-1,6-P/sub 2/ase during anaerobic and aerobic glycolysis. The /sup 31/P NMR saturation-transfer results are consistent with previous results obtained from measurements of metabolite levels, radioisotope data, and /sup 13/C NMR studies, providing additional support for in vivo measurement of the flows during glycolysis.

  17. Theoretical and experimental NMR studies on muscimol from fly agaric mushroom (Amanita muscaria)

    NASA Astrophysics Data System (ADS)

    Kupka, Teobald; Wieczorek, Piotr P.

    2016-01-01

    In this article we report results of combined theoretical and experimental NMR studies on muscimol, the bioactive alkaloid from fly agaric mushroom (Amanita muscaria). The assignment of 1H and 13C NMR spectra of muscimol in DMSO-d6 was supported by additional two-dimensional heteronuclear correlated spectra (2D NMR) and gauge independent atomic orbital (GIAO) NMR calculations using density functional theory (DFT). The effect of solvent in theoretical calculations was included via polarized continuum model (PCM) and the hybrid three-parameter B3LYP density functional in combination with 6-311++G(3df,2pd) basis set enabled calculation of reliable structures of non-ionized (neutral) molecule and its NH and zwitterionic forms in the gas phase, chloroform, DMSO and water. GIAO NMR calculations, using equilibrium and rovibrationally averaged geometry, at B3LYP/6-31G* and B3LYP/aug-cc-pVTZ-J levels of theory provided muscimol nuclear magnetic shieldings. The theoretical proton and carbon chemical shifts were critically compared with experimental NMR spectra measured in DMSO. Our results provide useful information on its structure in solution. We believe that such data could improve the understanding of basic features of muscimol at atomistic level and provide another tool in studies related to GABA analogs.

  18. Theoretical and experimental NMR studies on muscimol from fly agaric mushroom (Amanita muscaria).

    PubMed

    Kupka, Teobald; Wieczorek, Piotr P

    2016-01-15

    In this article we report results of combined theoretical and experimental NMR studies on muscimol, the bioactive alkaloid from fly agaric mushroom (Amanita muscaria). The assignment of (1)H and (13)C NMR spectra of muscimol in DMSO-d6 was supported by additional two-dimensional heteronuclear correlated spectra (2D NMR) and gauge independent atomic orbital (GIAO) NMR calculations using density functional theory (DFT). The effect of solvent in theoretical calculations was included via polarized continuum model (PCM) and the hybrid three-parameter B3LYP density functional in combination with 6-311++G(3df,2pd) basis set enabled calculation of reliable structures of non-ionized (neutral) molecule and its NH and zwitterionic forms in the gas phase, chloroform, DMSO and water. GIAO NMR calculations, using equilibrium and rovibrationally averaged geometry, at B3LYP/6-31G* and B3LYP/aug-cc-pVTZ-J levels of theory provided muscimol nuclear magnetic shieldings. The theoretical proton and carbon chemical shifts were critically compared with experimental NMR spectra measured in DMSO. Our results provide useful information on its structure in solution. We believe that such data could improve the understanding of basic features of muscimol at atomistic level and provide another tool in studies related to GABA analogs. PMID:26312739

  19. Role of NMR in diagnosis and evaluation of stroke: 303 studies of 152 patients

    SciTech Connect

    Nicholson, R.L.; Kertesz, A.; Black, S.; Carr, T.; McFadden, L.; Cooper, P.E.; Stewart, S.

    1985-05-01

    Nuclear Magnetic Resonance (NMR) proton imaging of 158 patients with clinical stroke was done over 18 months (0.15T Technicare resistive prototype imager). Spin echo (TR250-2150, TE30-240 m sec.) and inversion spin echo (TR1600, TI450, TE30 m sec.) sequences were used. Early sensitivity of NMR was superior to CT and 24 and 48 hours but not at 48-72 hours from clinical onset. Cerebral hemorrhage was studied by NMR in 18 patients (7 within 72 hours); all could be diagnosed as hemorrhage within 72 hours though findings were more subtle than CT. NMR findings became striking by 5 days and persisted longer than CT on late follow-up. Increased NMR signal on spin echo imaging in acute stroke correlated with tissue oedema and necrosis on pathologic study, while high signal in sub-acute stroke corresponded to gliosis, microcystic change, and macrophage infiltration. Zones of altered TI-weighted signal are presently under comparison by digitizer to pathologic zones in a patient with cerebral hemorrhage. NMR convincingly demonstrates superior early sensitivity in diagnoses of stroke but uncertainty remains concerning reliable detection of early hemorrhage.

  20. An NMR Study of Biomimetic Fluorapatite - Gelatine Mesocrystals

    NASA Astrophysics Data System (ADS)

    Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

    2015-10-01

    The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43- groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals.

  1. An NMR Study of Biomimetic Fluorapatite – Gelatine Mesocrystals

    PubMed Central

    Vyalikh, Anastasia; Simon, Paul; Rosseeva, Elena; Buder, Jana; Scheler, Ulrich; Kniep, Rüdiger

    2015-01-01

    The mesocrystal system fluoroapatite—gelatine grown by double-diffusion is characterized by hierarchical composite structure on a mesoscale. In the present work we apply solid state NMR to characterize its structure on the molecular level and provide a link between the structural organisation on the mesoscale and atomistic computer simulations. Thus, we find that the individual nanocrystals are composed of crystalline fluorapatite domains covered by a thin boundary apatite-like layer. The latter is in contact with an amorphous layer, which fills the interparticle space. The amorphous layer is comprised of the organic matrix impregnated by isolated phosphate groups, Ca3F motifs and water molecules. Our NMR data provide clear evidence for the existence of precursor complexes in the gelatine phase, which were not involved in the formation of apatite crystals, proving hence theoretical predictions on the structural pre-treatment of gelatine by ion impregnation. The interfacial interactions, which may be described as the glue holding the composite materials together, comprise hydrogen bond interactions with the apatite PO43− groups. The reported results are in a good agreement with molecular dynamics simulations, which address the mechanisms of a growth control by collagen fibers, and with experimental observations of an amorphous cover layer in biominerals. PMID:26515127

  2. NMR study of cluster-assembled nanophase copper

    SciTech Connect

    Suits, B.H.; Meng, M. . Dept. of Physics); Siegel, R.W.; Liao, Y.X. )

    1992-12-01

    [sup 63]Cu and [sup 65]Cu NMR spectra from cluster-assembled nanophase copper with an average grain size between 5 and 10mn show a broadened peak, at the normal Knight-shifted frequency for copper meta which arises from only the central 1/2 to -1/2 transition. A very broad background is observed on either side of that peak. Some samples exhibit a second broad peak at a position normally associated with non-metallic copper. Pulsed NMR measurements of the central peak show that virtually all the copper signals are significantly broadened and have a spin-spin relaxation time longer than larger grained copper samples. Line shape measurements, using spin echoes, as a function of delay between rf excitation and measurement show there are a number of copper sites with longer relaxation times which have a significantly larger broadening. Those sites are tentatively identified as being at or near a grain boundary or free surface. A small orientation effect is observed indicating an anisotropy within the samples. An isochronal anneal of one sample showed significant, but not complete, line narrowing after an anneal at 450C consistent with other nanophase metals which show grain growth above 40--50% of the melting temperature.

  3. NMR study of cluster-assembled nanophase copper

    SciTech Connect

    Suits, B.H.; Meng, M.; Siegel, R.W.; Liao, Y.X.

    1992-12-01

    {sup 63}Cu and {sup 65}Cu NMR spectra from cluster-assembled nanophase copper with an average grain size between 5 and 10mn show a broadened peak, at the normal Knight-shifted frequency for copper meta which arises from only the central 1/2 to -1/2 transition. A very broad background is observed on either side of that peak. Some samples exhibit a second broad peak at a position normally associated with non-metallic copper. Pulsed NMR measurements of the central peak show that virtually all the copper signals are significantly broadened and have a spin-spin relaxation time longer than larger grained copper samples. Line shape measurements, using spin echoes, as a function of delay between rf excitation and measurement show there are a number of copper sites with longer relaxation times which have a significantly larger broadening. Those sites are tentatively identified as being at or near a grain boundary or free surface. A small orientation effect is observed indicating an anisotropy within the samples. An isochronal anneal of one sample showed significant, but not complete, line narrowing after an anneal at 450C consistent with other nanophase metals which show grain growth above 40--50% of the melting temperature.

  4. Quantitative constraints on the 17O-excess (Δ17O) signature of surface ozone: Ambient measurements from 50°N to 50°S using the nitrite-coated filter technique

    NASA Astrophysics Data System (ADS)

    Vicars, William C.; Savarino, Joël

    2014-06-01

    The unique and distinctive 17O-excess (Δ17O) of ozone (O3) provides a conservative tracer for oxidative processes in both modern and paleo-atmospheres and has acted as the primary driver of theoretical and experimental research into non-mass-dependent fractionation (NMDF) for over three decades. However, due to the inherent complexity of extracting O3 from ambient air, the existing observational dataset for tropospheric O3 isotopic composition remains quite small. Recent analytical developments have provided a robust and reliable means for determining Δ17O(O3)trans., the transferrable Δ17O signature of ozone in the troposphere (Vicars et al., 2012). We have employed this new methodology in a systematic investigation of the spatial and seasonal features of Δ17O(O3)trans. in two separate field campaigns: a weekly sampling effort at our laboratory in Grenoble, France (45°N) throughout 2012 (n = 47) and a four-week campaign onboard the Research Vessel (R/V) Polarstern along a latitudinal transect from 50°S to 50°N in the Atlantic Ocean (n = 30). The bulk 17O-excess of ozone, denoted Δ17O(O3)bulk, exhibited mean (±1σ) values of 26.2 ± 1.3‰ (Δ17O(O3)trans. = 39.3 ± 2.0‰) and 25.9 ± 1.1‰ (Δ17O(O3)trans. = 38.8 ± 1.6‰) for the Grenoble and R/V Polarstern collections, respectively. This range of values is in excellent quantitative agreement with the two previous studies of ozone triple-isotope composition, which have yielded mean (±1σ) Δ17O(O3)bulk values of 25.4 ± 9.0‰ (n = 89). However, the magnitude of variability detected in the present study is much smaller than that formerly reported. In fact, the standard deviation of Δ17O(O3)bulk in each new dataset is lower than the uncertainty previously estimated for the filter technique (±1.7‰), indicating a low level of natural spatial and temporal variation in the 17O-excess of surface ozone. For instance, no clear temporal pattern in Δ17O(O3) is evident in the annual record from Grenoble

  5. Studies of Lung Micromechanics via Hyperpolarized Helium-3 Diffusion NMR

    NASA Astrophysics Data System (ADS)

    Hajari, Adam James

    While high quality MR Images of lungs are difficult to obtain with conventional proton MRI due to the organ's low tissue density, the advent of techniques in noble gas polarization have enabled MR investigations of the lung's more abundant air space rather than its tissue. In addition to high-resolution images of lung ventilation, lung morphometry via gas diffusion NMR provides information about the size and shape of the microscopic airways that account for over 95% of the lung's airspace. Consequently, gas diffusion NMR provides an important new tool for investigating changes in lung microstructure during macroscopic changes in lung volume. Despite decades of research into the mechanisms of lung inflation and deflation, there is little consensus about whether macroscopic changes in lung volume occur due to changes in the size and/or shape of alveoli and alveolar ducts or by alveolar recruitment and derecruitment. In this dissertation lung morphometry is performed via 3He diffusion MRI in order to measure the average alveolar depth and alveolar duct radius at multiple levels of both inspiration and expiration in in vivo human subjects and in explanted human and canine lungs. Average alveolar volume, surface area, and the total number of alveoli at each lung volume are calculated from the 3He morphometric parameters. The results suggest that human lungs inflate/deflate primarily by recruitment/derecruitment of alveoli, and that individual alveolar ducts in both human and canine lungs increase in volume non-isotropically by accordion-like extension. The results further suggest that this change in alveolar duct volume is the primary mechanism of lung volume change in canine lungs but is secondary to alveolar recruitment/derecruitment in humans.

  6. Practice and applications of 17-O-excess measurements of water using novel laser spectroscopy

    NASA Astrophysics Data System (ADS)

    Dennis, K. J.; Steig, E. J.; Vasileios, G.; Schauer, A. J.; Schoenemann, S. W.; Hoffnagle, J.

    2014-12-01

    17O-excess, defined as the deviation from the Global Meteoric Water Line (GMWL) in a plot of ln(δ18O+1) vs. ln(δ17O+1), is an evolving tool for understanding the modern water cycle and reconstructing past climate regimes. Because of competing effects between equilibrium and kinetic fractionation small variations in 17O-excess can be used, for example, to (i) infer changes in temperature and sea ice across glacial-interglacial cycles in Antarctica (Schoenemann et al., 2014), (ii) study the role of rain re-evaporation during convective events thereby improving the incorporation of isotopes into GCMs (Landais et al., 2010), and (iii) assess the role of stratospheric water vapor intrusions at high altitudes or in polar regions (Winkler et al., 2013). In natural waters, variability in 17O-excess is very small (on the order of tens of per meg, where 1 per meg is 0.001‰). Until recently, only measurements made via Isotope Ratio Mass Spectrometry (IRMS) could achieve the required precision, following time-consuming front-end chemistry that converted H2O into O2 for analysis of m/z+ 32, 33 and 34. Recent improvements in laser-based spectroscopy, e.g., Cavity Ring-Down Spectroscopy (CRDS), are enabling quicker and easier measurement of 17O-excess in water (Steig et al., 2013; 2014). The Picarro L2140-i is certified with a precision of ≤ 0.015‰; however implementation of best practices can result in an achievable precision of ≤ 0.008‰, thereby demonstrating comparable performance to IRMS. We will review our recommendations for achieving high-precision measurements of 17O-excess on the Picarro L2140-i, including how to calibrate the system, the frequency of standards analysis, the number of replicate injections and vials required, and approaches to dealing with sample-to-sample memory. We will also compare the external accuracy achieved by three distinct Picarro L2140-i analyzers for multiple waters with distinct isotopic composition.

  7. The NMR study of biologically active metallated alkanol ammoinium ionic liquids

    NASA Astrophysics Data System (ADS)

    Ushakov, I. A.; Voronov, V. K.; Adamovich, S. N.; Mirskov, R. G.; Mirskova, A. N.

    2016-01-01

    The 1H, 13C, 15N, and 111Cd NMR spectra of a series of metallated alkanol ammonium ionic liquids (MAIL) series [n N(CH2CH2OH;)3M]+ · mX-, where M = Cd, Mg, Zn, Fe, Rh; X = Cl, OOCCH3, obtained in a wide range of temperatures of the studied samples, have been analyzed. It is found that, under biomimetic conditions (H2O, 25 °C), the compounds studied exist as mono- bi- and the tricyclic structures, which are in equilibrium. Shift of the equilibrium depends upon nature of a metal and effects all the parameters of the NMR spectra. Peculiarities of ligand exchange, typical for the studied compounds, have been studied in a wide range of temperatures. It is found that the NMR data can be used to control structure of the compounds formed in the course of synthesis.

  8. NMR studies in chemistry. I. Organometallic tin and geramanium compounds. II. The sorbitol pathway in intact lenses

    SciTech Connect

    Williams, W.F.

    1985-01-01

    Nuclear magnetic resonance spectroscopy has been utilized in the study of two very different chemical problems. The bonding and structure of various cyclopropyl derivatives of tin and germanium has been investigated by means of Sn-119, Ge-73, C-13, and H-1 NMR spectroscopy. Intact rabbit lenses have also been studied using NMR spectroscopy with regard to diabetic cataract formation. C-13 and P-31 NMR spectroscopies have been utilized in the study of the sorbitol pathway and aldose reductase inhibition.

  9. NMR study of the reversible trapping of SF6 by cucurbit[6]uril in aqueous solution.

    PubMed

    Fusaro, Luca; Locci, Emanuela; Lai, Adolfo; Luhmer, Michel

    2008-11-27

    The complexation of sulfur hexafluoride (SF(6)), a highly potent greenhouse gas, by cucurbit[6]uril (CB) was studied at various temperatures in Na(2)SO(4) aqueous solutions by (19)F and (1)H NMR. CB shows a remarkable affinity for SF(6), suggesting that it is a suitable molecular container for the design of materials tailored for SF(6) trapping. At 298 K, the equilibrium constant characterizing the inclusion of SF(6) by CB is 3.1 x 10(4) M(-1) and the residence time of SF(6) within the CB cavity is estimated to be of the order of a few seconds. The enthalpic and entropic contributions to the free energy of encapsulation were determined and are discussed. This work also reports on the interest of SF(6) in the framework of the spin-spy methodology. The advantages and drawbacks of solution-state (19)F NMR of SF(6) with respect to (129)Xe NMR are discussed. SF(6) comes forward as a versatile and informative spin-spy molecule for probing systems in solution because its detection limit by (19)F NMR reaches the micromolar range with standard equipment and because quantitative integral measurements, relaxation time measurements, and demanding experiments, such as translational diffusion coefficient measurements, are easily carried out in addition to chemical shift measurements. Solution-state (19)F NMR of SF(6) emerges as a promising alternative to (129)Xe NMR for probing cavities and for other applications relying on the encapsulation of an NMR active gaseous probe. PMID:18956898

  10. A Solid-State NMR Study of Selenium Substitution into Nanocrystalline Hydroxyapatite

    PubMed Central

    Kolmas, Joanna; Kuras, Marzena; Oledzka, Ewa; Sobczak, Marcin

    2015-01-01

    The substitution of selenium oxyanions in the hydroxyapatite structure was examined using multinuclear solid-state resonance spectroscopy (ssNMR). The study was supported by powder X-ray diffractometry (PXRD) and wavelength dispersion X-ray fluorescence (WD-XRF). Samples of pure hydroxyapatite (HA300) and selenate (HA300-1.2SeO4) or selenite (HA300-1.2SeO3) substituted hydroxyapatites were synthesized using the standard wet method and heated at 300 °C to remove loosely bonded water. PXRD data showed that all samples are single-phase, nanocrystalline hydroxyapatite. The incorporation of selenite and selenate ions affected the lattice constants. In selenium-containing samples the concentration of Se was very similar and amounted to 9.55% and 9.64%, for HA300-1.2SeO4 and HA300-1.2SeO3, respectively. PXRD and ssNMR data showed that the selenite doping significantly decreases the crystallite size and crystallinity degree. 31P and 1H NMR experiments demonstrated the developed surface hydrated layer in all samples, especially in HA300-1.2SeO3. 1H NMR studies showed the dehydroxylation of HA during the selenium oxyanions substitution and the existence of hydrogen bonding in structural hydroxyl group channels. 1H→77Se cross polarization NMR experiments indicated that selenites and selenates are located in the crystal lattice and on the crystal surface. PMID:25997001

  11. (13)C-(1)H NMR relaxation and fluorescence anisotropy decay study of tyrosine dynamics in motilin.

    PubMed Central

    Damberg, Peter; Jarvet, Jüri; Allard, Peter; Mets, Ulo; Rigler, Rudolf; Gräslund, Astrid

    2002-01-01

    Tyrosine ring dynamics of the gastrointestinal hormone motilin was studied using two independent physical methods: fluorescence polarization anisotropy decay and NMR relaxation. Motilin, a 22-residue peptide, was selectively (13)C labeled in the ring epsilon-carbons of the single tyrosine residue. To eliminate effects of differences in peptide concentration, the same motilin sample was used in both experiments. NMR relaxation rates of the tyrosine ring C(epsilon)-H(epsilon) vectors, measured at four magnetic field strengths (9.4, 11.7, 14.1, and 18.8 Tesla) were used to map the spectral density function. When the data were analyzed using dynamic models with the same number of components, the dynamic parameters from NMR and fluorescence are in excellent agreement. However, the estimated rotational correlation times depend on the choice of dynamic model. The correlation times estimated from the two-component model-free approach and the three-component models were significantly different (1.7 ns and 2.2 ns, respectively). Various earlier studies of protein dynamics by NMR and fluorescence were compared. The rotational correlation times estimated by NMR for samples with high protein concentration were on average 18% longer for folded monomeric proteins than the corresponding times estimated by fluorescence polarization anisotropy decay, after correction for differences in viscosity due to temperature and D(2)O/H(2)O ratio. PMID:12414713

  12. Investigation of different apple cultivars by high resolution magic angle spinning NMR. A feasibility study.

    PubMed

    Vermathen, Martina; Marzorati, Mattia; Baumgartner, Daniel; Good, Claudia; Vermathen, Peter

    2011-12-28

    (1)H HR-MAS NMR spectroscopy was applied to apple tissue samples deriving from 3 different cultivars. The NMR data were statistically evaluated by analysis of variance (ANOVA), principal component analysis (PCA), and partial least-squares-discriminant analysis (PLS-DA). The intra-apple variability of the compounds was found to be significantly lower than the inter-apple variability within one cultivar. A clear separation of the three different apple cultivars could be obtained by multivariate analysis. Direct comparison of the NMR spectra obtained from apple tissue (with HR-MAS) and juice (with liquid-state HR NMR) showed distinct differences in some metabolites, which are probably due to changes induced by juice preparation. This preliminary study demonstrates the feasibility of (1)H HR-MAS NMR in combination with multivariate analysis as a tool for future chemometric studies applied to intact fruit tissues, e.g. for investigating compositional changes due to physiological disorders, specific growth or storage conditions. PMID:22084979

  13. NMR relaxometry study of plaster mortar with polymer additives

    SciTech Connect

    Jumate, E.; Manea, D.; Moldovan, D.; Fechete, R.

    2013-11-13

    The cement mixed with water forms a plastic paste or slurry which stiffness in time and finally hardens into a resistant stone. The addition of sand aggregates, polymers (Walocel) and/or calcium carbonate will modify dramatically the final mortar mechanic and thermal properties. The hydration processes can be observed using the 1D NMR measurements of transverse T{sub 2} relaxation times distributions analysed by a Laplace inversion algorithm. These distributions were obtained for mortar pasta measured at 2 hours after preparation then at 3, 7 and 28 days after preparation. Multiple components are identified in the T{sub 2} distributions. These can be associated with the proton bounded chemical or physical to the mortar minerals characterized by a short T{sub 2} relaxation time and to water protons in pores with three different pore sizes as observed from SEM images. The evaporation process is faster in the first hours after preparation, while the mortar hydration (bonding of water molecules to mortar minerals) can be still observed after days or months from preparation. Finally, the mechanic resistance was correlated with the transverse T{sub 2} relaxation rates corresponding to the bound water.

  14. Investigations of the structure and "interfacial" surface chemistry of Bioglass (RTM) materials by solid-state multinuclear NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Sarkar, Gautam

    Bioactive materials such as BioglassRTM 45S5 (45% SiO 2, 24.5% CaO, 24.5% Na2O, and 6% P2O5 by weight) are sodium-phosphosilicate glasses containing independent three-dimensional silicate and phosphate networks and Na+ and Ca2+ ions as modifying cations. Due to their bioactivity, these materials are currently used as implants and for other surgical and clinical applications. The bioactivity of BioglassesRTM is due to their unique capability to form chemical bonds to tissues through an octacalciumphosphate (OCP)- and/or hydroxyapatite-like (HA) "interfacial" matrix. The formation of OCP and/or HA is preceded by the formation of a silica-rich surface layer and the subsequent growth of an amorphous calcium phosphate (a-CP) layer. Structural characterization of a series of commercial and synthesized Bioglass materials 45S5 52S, 55S, 60S, and synthesized 17O-labelled "Bioglass materials 45S, 52S, 55S and 60S" have been obtained using solid-state single-pulse magic-angle spinning (SP/MAS) 17O, 23Na, 29Si and 31P NMR. The 17O NMR isotropic chemical shifts and estimates of the quadrupole coupling constants (Cq) [at fixed asymmetry parameter ( hQ ) values of zero] have been obtained from solid-state spin-echo 17O SP/MAS NMR spectra of 17O-labelled "Bioglasses". The simulation results of these spectra reveal the presence of both bridging-oxygens (BO, i.e. ≡ Si-17OSi ≡ ) and non-bridging oxygens (NBO, i.e. ≡ Si-17O-Na+/Ca2+ ) in the silicate networks in these materials. 17O NMR spectra of these Bioglass materials do not show any direct evidence for the presence of BO and NBO atoms in the phosphate units; however, they are expected to be present in small amounts. In vitro reactions of BioglassRTM 45S5, 60S and 77S powders have been used to study the "interfacial" surface chemistry of these materials in simulated body-fluid (SBF, Kyoto or K9 solution) and/or 17O-enriched tris-buffer solution. 29Si and 31P SP/MAS NMR have been used to identify and quantify the extent of

  15. Expression and Purification of Src-family Kinases for Solution NMR Studies

    PubMed Central

    Piserchio, Andrea; Cowburn, David; Ghose, Ranajeet

    2012-01-01

    Summary NMR analyses of the structure, dynamics and interactions of the Src family kinases (SFKs) have been hindered by the limited ability to obtain sufficient amounts of properly folded, soluble protein from bacterial expression systems, to allow these studies to be performed in an economically viable manner. In this chapter we detail our attempts to overcome these difficulties using the catalytic domain (SrcCD) of c-Src, the prototypical SFK, as an illustrative example. We describe in detail two general methods to express and purify SrcCD from E. coli expression systems in both fully active wild-type and kinase-deficient mutant forms, allowing the efficient and cost-effective labeling by NMR-active isotopes for solution NMR studies. PMID:22167671

  16. NQR-NMR studies of higher alcohol synthesis Cu-Co catalysts

    SciTech Connect

    Not Available

    1991-12-17

    Our previous studies (1,2) on the zerofield NMR spectra of Cu/Co catalysts revealed that the method of preparation sensitively influences the magnetic character of the Catalyst. Catalytic studies of the earlier investigators also (3) show similar influence on the product selectivity and indicate reproducible performance is critically dependent on the control and rigor of the preparation technique. To compliment the NMR results, we have made a thorough investigation of the Hysteresis character of the Cu/Co catalysts with the metal ratio varying from 0.2 to 4.0.

  17. Dynamic NMR study of dinitrophenyl derivatives of seven-membered cyclic ketals of pyridoxine.

    PubMed

    Rakhmatullin, Ilfat Z; Galiullina, Leisan F; Garipov, Marsel' R; Strel'nik, Alexey D; Shtyrlin, Yurii G; Klochkov, Vladimir V

    2015-10-01

    Two pyridoxine derivatives containing a dinitrophenyl moiety were investigated by (1)H NMR spectroscopy. Conformational dynamics in solution were studied for each compound using dynamic NMR experiments. It was shown that both compounds studied are involved into two conformational exchange processes. The first process is a transformation of the seven-membered cycle conformation between the enantiomeric P-twist and M-twist forms, and the second is a rotation of the dinitrophenyl fragment of the molecules around the C-O bond. Energy barriers of both conformational transitions were determined. PMID:26194937

  18. Seasonal variations in 35S and Δ17O of sulfate aerosols on the Antarctic plateau

    NASA Astrophysics Data System (ADS)

    Hill-Falkenthal, Jason; Priyadarshi, Antra; Savarino, Joel; Thiemens, Mark

    2013-08-01

    The first reported seasonal Δ17O anomaly in sulfate aerosols and measurements of radioactive 35SO42- activities collected from Dome C, Antarctica, are reported. Δ17O values exhibit minima during summer (as low as 0.91‰) when tropospheric oxidation patterns are dominated by OH/H2O2 mechanisms. Significant enrichment during autumn and spring is observed (up to 2.40‰) as ozone oxidation increases in the troposphere relative to summer and both stratospheric sources and long-range transport become more significant to the total sulfate budget. An unexpected decrease in Δ17O is seen as winter progresses. This decline is concluded to potentially arise due to a reduction in vertical mixing in the troposphere or linked to variations in the long-range transport of sulfur species to Antarctica. 35SO42- activities exhibit maxima during summer (up to 1219 atoms 35S/m3) that correlate with the peak in stratospheric flux and minima during winter (as low as 146 atoms 35S/m3) when the lack of solar radiation substantially reduces photochemical activity. It is shown that 35S offers the potential to be used as an additional tracer to study stratospheric and tropospheric interactions and is used to estimate stratospheric input of sulfur (combination of SO2 and SO42-). Stratospheric sulfur input produces maxima during summer/autumn with an upper limit of 5.5 ng/m3 and minima during winter/spring with an upper limit of 1.1 ng/m3. From these results, it is concluded that the variation in Δ17O is more reliant upon shifts in tropospheric oxidation mechanisms and long-range transport than on changes in the stratospheric flux.

  19. Molecular dynamics in paramagnetic materials as studied by magic-angle spinning 2H NMR spectra.

    PubMed

    Mizuno, Motohiro; Suzuki, You; Endo, Kazunaka; Murakami, Miwa; Tansho, Masataka; Shimizu, Tadashi

    2007-12-20

    A magic-angle spinning (MAS) 2H NMR experiment was applied to study the molecular motion in paramagnetic compounds. The temperature dependences of 2H MAS NMR spectra were measured for paramagnetic [M(H2O)6][SiF6] (M=Ni2+, Mn2+, Co2+) and diamagnetic [Zn(H2O)6][SiF6]. The paramagnetic compounds exhibited an asymmetric line shape in 2H MAS NMR spectra because of the electron-nuclear dipolar coupling. The drastic changes in the shape of spinning sideband patterns and in the line width of spinning sidebands due to the 180 degrees flip of water molecules and the reorientation of [M(H2O)6]2+ about its C3 axis were observed. In the paramagnetic compounds, paramagnetic spin-spin relaxation and anisotropic g-factor result in additional linebroadening of each of the spinning sidebands. The spectral simulation of MAS 2H NMR, including the effects of paramagnetic shift and anisotropic spin-spin relaxation due to electron-nuclear dipolar coupling and anisotropic g-factor, was performed for several molecular motions. Information about molecular motions in the dynamic range of 10(2) s(-1)NMR spectra when these paramagnetic effects are taken into account. PMID:18027914

  20. NMR-BASED METABOLOMIC STUDIES OF ENDOCRINE DISRUPTION IN SMALL FISH MODELS

    EPA Science Inventory

    Metabolomics is now being widely used to obtain complementary information to genomic and proteomic studies. Among the various approaches used in metabolomics, NMR spectroscopy is particularly powerful, in part because it is relatively non-selective, and is amenable to the study o...

  1. Studies of 27Al NMR in SrAl4

    NASA Astrophysics Data System (ADS)

    Niki, Haruo; Higa, Nonoka; Kuroshima, Hiroko; Toji, Tatsuki; Morishima, Mach; Minei, Motofumi; Yogi, Mamoru; Nakamura, Ai; Hedo, Masato; Nakama, Takao; Ōnuki, Yoshichika; Harima, Hisatomo

    A charge density wave (CDW) transition at TCDW = 243 K and a structural phase (SP) transition at approximately 100 K occur in SrAl4 with the BaAl4-type body center tetragonal structure, which is the divalent and non-4f electron reference compound of EuAl4. To understand the behaviors of the CDW and SP transitions, the 27Al NMR measurements using a single crystal and a powder sample of SrAl4 have been carried out. The line width below TCDW is modulated by an electrical quadruple interaction between 27Al nucleus and CDW charge modulation. The incommensurate CDW state below TCDW changes into a different structure below TSP. The temperature dependences of Knight shifts of 27Al(I) and 27Al(II) show the different behaviors. The temperature variation of 27Al(I) Knight shift shows anomalies at the CDW and SP transition temperatures, revealing the shift to negative side below TCDW, which is attributable to the core polarization of the d-electrons. However, 27Al(II) Knight shift keeps almost constant except for the small shift due to the SP transition. The 1/T1T of 27Al(I) indicates the obvious changes due to the CDW and SP transitions, while that of 27Al(II) takes a constant value. The density of state at the Fermi level at Al(I) site below 60 K would be about 0.9 times less than that above TCDW.

  2. NMR Relaxation in Systems with Magnetic Nanoparticles: A Temperature Study

    PubMed Central

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

    2013-01-01

    Purpose To measure and model NMR relaxation enhancement due to the presence of Gd substituted Zn-Mn ferrite magnetic nanoparticles at different temperatures. Materials and Methods Relaxation rates were measured at 1.5 T using FSE sequences in samples of agarose gel doped with uncoated and polyethylene glycol (PEG) coated Mn0.5Zn0.5Gd0.02Fe1.98O4 nanoparticles over the temperature range 8 to 58°C. Physical characterization of the magnetic nanoparticles synthesized using chemical co-precipitation included scanning (SEM) and transmission (TEM) electron microscopy, inductively coupled plasma (ICP), dynamic light scattering (DLS), and magnetometry. Results Relaxivity (in s−1 mM−1 Fe) for the uncoated and coated particles, respectively, increased as follows: from 2.5 to 3.2 and 0.4 to 0.7 for T1, while for T2 it increased from 162.3 to 253.7 and 59.7 to 82.2 over the temperature range 8 to 58°C. T2 data was fitted to the echo limited motional regime using one fitting parameter that reflects the degree of agglomeration of particles into a cluster. This parameter was found to increase linearly with temperature and was larger for the PEG coated particles than the uncoated ones. Conclusion The increase of 1/T2 with temperature is modeled successfully using echo limited motional regime where both diffusion of the protons and nanoparticle cluster size increase with temperature. Both transverse and longitudinal relaxation efficiencies are reduced by PEG coating at all temperatures. If prediction of relaxation rates under different particle concentrations and operating temperatures is possible then the use of MNP in temperature monitoring and hyperthermia applications may be achieved. PMID:23720101

  3. High resolution 1H solid state NMR studies of polyethyleneterephthalate

    NASA Astrophysics Data System (ADS)

    Cheung, T. T. P.; Gerstein, B. C.; Ryan, L. M.; Taylor, R. E.; Dybowski, D. R.

    1980-12-01

    Molecular motions and spatial properties of the solid polymer polyethyleneterephthalate have been investigated using high resolution 1H solid state NMR techniques. The longitudinal spin relaxation time T1ρ of protons (1H) in the rotating frame was measured for a spin locking field ranging from 5 to 20 G. The decay of the 1H magnetization indicated the existence of two distinct T1ρ's and their field dependence shows that they are associated with two mobile phases of the polymer. The 1H magnetization also relaxes under the dipolar narrowed Carr-Purcell (DNCP) multipulse sequence with two dintinct T1y relaxation times. The ratios T1y's and T1ρ's deviate significantly from the expected theoretical values. The combined experiment with magic angle spinning and the DNCP sequence followed by homonuclear dipolar decoupling reveals the individual T1y relaxation of the resolved methylene and aromatic protons. These two species of protons were found to relax with the same T1y's, thus implying that spin diffusion must have taken place under the homonuclear dipolar decoupling multipulse. The qualitative description of spin diffusion under homonuclear decoupling is given. The combined experiment with spin locking and the DNCP sequence yields the correspondence between the two T1ρ's and the two T1y's. The long T1ρ corresponds to the short T1y whereas the short T1ρ corresponds to the long T1y. Communication between the two spatial phases via spin diffusion was also observed in this experiment by monitoring the recovery of the 1H magnitization associated with the short T1ρ after it has been eliminated during the spin locking. The total 1H magnetization is allowed to equilibrate in the laboratory frame for a variable time much shorter than T1 after the spin locking field has been turned off. The spatial relationship between the two phases is discussed.

  4. Deuterium and lithium-6 MAS NMR studies of manganese oxide electrode materials

    NASA Astrophysics Data System (ADS)

    Paik, Younkee

    Electrolytic manganese dioxide (EMD) is used world wide as the cathode materials in both lithium and alkaline primary (non-rechargeable) batteries. We have developed deuterium and lithium MAS NMR techniques to study EMD and related manganese oxides and hydroxides, where diffraction techniques are of limited value due to a highly defective nature of the structures. Deuterons in EMD, manganite, groutite, and deuterium-intercalated pyrolusite and ramsdellite were detected by NMR, for the first time, and their locations and motions in the structures were analyzed by applying variable temperature NMR techniques. Discharge mechanisms of EMD in alkaline (aqueous) electrolytes were studied, in conjunction with step potential electrochemical spectroscopic (SPECS) method, and five distinctive discharge processes were proposed. EMD is usually heat-treated at about 300--400°C to remove water to be used in lithium batteries. Details of the effects of heat-treatment, such as structural and compositional changes as a function of heat-treatment temperature, were studied by a combination of MAS NMR, XRD, and thermogravimetric analysis. Lithium local environments in heat-treated EMD (HEMD) that were discharged in lithium cells, were described in terms of related environments found in model compounds pyrolusite and ramsdellite where specific Li + sites were detected by MAS NMR and the hyperfine shift scale method of Grey et al. Acid-leaching of Li2MnO3 represents an approach for synthesizing new or modified manganese oxide electrode materials for lithium rechargeable batteries. Progressive removal of lithium from specific crystallographic sites, followed by a gradual change of the crystal structure, was monitored by a combination of NMR and XRD techniques.

  5. Genetic analysis of 16 NMR-lipoprotein fractions in humans, the GOLDN study.

    PubMed

    Kraja, Aldi T; Borecki, Ingrid B; Tsai, Michael Y; Ordovas, Jose M; Hopkins, Paul N; Lai, Chao-Qiang; Frazier-Wood, Alexis C; Straka, Robert J; Hixson, James E; Province, Michael A; Arnett, Donna K

    2013-02-01

    Sixteen nuclear magnetic resonance (NMR) spectroscopy lipoprotein measurements of more than 1,000 subjects of GOLDN study, at fasting and at 3.5 and 6 h after a postprandial fat (PPL) challenge at visits 2 and 4, before and after a 3 weeks Fenofibrate (FF) treatment, were included in 6 time-independent multivariate factor analyses. Their top 1,541 unique SNPs were assessed for association with GOLDN NMR-particles and classical lipids. Several SNPs with -log₁₀ p > 7.3 and MAF ≥ 0.10, mostly intergenic associated with NMR-single traits near genes FAM84B (8q24.21), CRIPT (2p21), ACOXL (2q13), BCL2L11 (2q13), PCDH10 (4q28.3), NXPH1 (7p22), and SLC24A4 (14q32.12) in association with NMR-LDLs; HOMER1 (5q14.2), KIT (4q11-q12), VSNL1 (2p24.3), QPRT (16p11.2), SYNPR (3p14.2), NXPH1 (7p22), NELL1 (11p15.1), and RUNX3 (1p36) with NMR-HDLs; and DOK5-CBLN4-MC3R (20q13), NELL1 (11p15.1), STXBP6 (14q12), APOB (2p24-p23), GPR133 (12q24.33), FAM84B (8q24.21) and NR5A2 (1q32.1) in association with NMR-VLDLs particles. NMR single traits associations produced 75 % of 114 significant candidates, 7 % belonged to classical lipids and 18 % overlapped, and 16 % matched for time of discovery between NMR- and classical traits. Five proxy genes, (ACOXL, FAM84B, NXPH1, STK40 and VAPA) showed pleiotropic effects. While tagged for significant associations in our study and with some extra evidence from the literature, candidates as CBNL4, FAM84B, NXPH1, SLC24A4 remain unclear for their functional relation to lipid metabolism. Although GOLDN study is one of the largest in studying PPL and FF treatment effects, the relatively small samples (over 700-1,000 subjects) in association tests appeals for a replication of such a study. Thus, further investigation is needed. PMID:23192668

  6. Chiral Recognition Studies of α-(Nonafluoro-tert-butoxy)carboxylic Acids by NMR Spectroscopy.

    PubMed

    Nemes, Anikó; Csóka, Tamás; Béni, Szabolcs; Farkas, Viktor; Rábai, József; Szabó, Dénes

    2015-06-19

    Three chiral α-(nonafluoro-tert-butoxy)carboxylic acids (R)-1, (RS)-2, (R)-3 were synthesized to examine their application as chiral solvating agents with amines. As a model compound, first (S)- and/or (RS)-α-phenylethylamine was used, and their diastereomeric salts were investigated by (1)H and (19)F NMR and ECD spectroscopy. The NMR spectroscopic studies were carried out at room temperature using the slightly polar CDCl3 and apolar C6D6 as solvents in 5 mM and 54 mM concentrations. The difference of the chemical shifts (Δδ) in the diastereomeric complexes is comparable with other, well-known chiral derivatizing and solvating agents (e.g., Mosher's acid, Pirkle's alcohol). Diastereomeric salts of racemic acids (RS)-1 and (RS)-2 with biologically active amines (1R,2S)-ephedrine and (S)-dapoxetine were also investigated by (19)F NMR spectroscopy. PMID:26024423

  7. Prediction of (19)F NMR Chemical Shifts in Labeled Proteins: Computational Protocol and Case Study.

    PubMed

    Isley, William C; Urick, Andrew K; Pomerantz, William C K; Cramer, Christopher J

    2016-07-01

    The structural analysis of ligand complexation in biomolecular systems is important in the design of new medicinal therapeutic agents; however, monitoring subtle structural changes in a protein's microenvironment is a challenging and complex problem. In this regard, the use of protein-based (19)F NMR for screening low-molecular-weight molecules (i.e., fragments) can be an especially powerful tool to aid in drug design. Resonance assignment of the protein's (19)F NMR spectrum is necessary for structural analysis. Here, a quantum chemical method has been developed as an initial approach to facilitate the assignment of a fluorinated protein's (19)F NMR spectrum. The epigenetic "reader" domain of protein Brd4 was taken as a case study to assess the strengths and limitations of the method. The overall modeling protocol predicts chemical shifts for residues in rigid proteins with good accuracy; proper accounting for explicit solvation of fluorinated residues by water is critical. PMID:27218275

  8. NMR and Infrared Study of Thermal Oxidation of cis-1, 4-Polybutadiene

    NASA Technical Reports Server (NTRS)

    Gemmer, Robert V.; Golub, Morton A.

    1978-01-01

    A study of the microstructural changes occuring in CB during thermal, uncatalyzed oxidation was carried out. Although the oxidation of CB is accompanied by extensive crosslinking with attendant insolubilization, it was found possible to follow the oxidation of solid CB directly with C-13 NMR spectroscopy. The predominant products appearing in the C-13 NMR spectra of oxidized CB are epoxides. The presence of lesser amounts of alcohols, peroxides, and carbonyl structures was adduced from complementary infrared and NMR spectra of soluble extracts obtained from the oxidized, crosslinked CB. This distribution of functional groups contrasts with that previously reported for the autooxidation of 1,4-polyisoprene. The difference was rationalized in terms of the relative stabilities of intermediate radical species involved in the autoxidation of CB and 1,4-polyisoprene.

  9. NMR Study on Type-I Copper-doped Germanium Clathrate

    NASA Astrophysics Data System (ADS)

    Gou, Weiping; Li, Yang; Ross, Joseph H.

    2002-10-01

    NMR Study on Type-I Copper-doped Germanium Clathrate Weiping Gou, Yang Li and Joseph H. Ross, Jr. Department of Physics, Texas A University, College Station, TX 77843-4242 Germanium clathrates are new materials containing a network of nanometer-size cages, in which a wide variety of electronic and magnetic behavior is observed. We have prepared a single-phase clathrate of the composition Ba8Ge44Cu2, Ba8Ge42Cu4 and Ba8Ge40Cu6. From 63Cu nuclear magnetic resonance (NMR) we have identified two distinct sites, and we associate these sites with random occupancy of 6c sites on the Ge network, giving different local environments for Cu atoms. We identify a large paramagnetic Knight shift for these NMR lines, and a measure of the spin-lattice relaxation time (T1) shows that the Korringa ratio is obeyed. We will discuss the current understanding of this behavior.

  10. Multinuclear solid film state NMR studies of metal oxide catalysts and minerals

    SciTech Connect

    Maxwell, R.S.; Stec, D.F.; Ellis, P.D.

    1996-10-01

    Several of our investigations of heterogeneous process by novel NMR experiments and analyses are reviewed and the utility and limitations of NMR spectroscopy for these areas discussed. Out studies have included the following: dynamics and arrangements of proton-containing adsorbates, primarily Bronsted acid sites and water, on the surface of zirconia and alumina catalysts; hydrogen dynamics and coordinates in synthetic aluminum oxyhydroxides; phase separation and crystallinity of synthetic minerals. In combination with the complementary results obtained in our laboratory via infrared spectroscopy, thermal analysis (primarily TGA and DSC), and catalytic activity measurements, these NMR data provide unique and valuable information on atomic and molecular dynamics, identities, and structures without requiring pristine, single crystal specimens.

  11. Multivalent ligand mimetics of LecA from P. aeruginosa: synthesis and NMR studies.

    PubMed

    Bini, Davide; Marchetti, Roberta; Russo, Laura; Molinaro, Antonio; Silipo, Alba; Cipolla, Laura

    2016-06-24

    Molecular recognition of glycans plays an important role in glycomic and glycobiology studies. For example, pathogens have a number of different types of lectin for targeting host sugars. In bacteria, lectins exist sometimes as domains of bacterial toxins and exploit adhesion to glycoconjugates as a means of entering host cells. Herein, we describe the synthesis of three glycodendrons with the aim to dissect the fine structural details involved in the multivalent carbohydrate-protein interactions. LecA, from the pathogen Pseudomonas aeruginosa, has been used to characterize galactose dendrons interaction using one of the most widespread NMR technique for the elucidation of receptor-ligand binding in solution, the saturation transfer difference (STD) NMR. Furthermore, the effective hydrodynamic radius of each dendrimer recognized by LecA was estimated from the diffusion coefficients determined by pulsed-field-gradient stimulated echo (PFG-STE) NMR experiments. PMID:27185108

  12. TC and H NMR studies of PQQ and selected derivatives. [Pyrroloquinoline quinone

    SciTech Connect

    Houck, D.R.; Unkefer, C.J.

    1988-01-01

    The ortho-quinone structure of pyrroloquinoline quinone (PQQ) is famous for its reactivity with nucleophilic species of carbon, nitrogen, and oxygen(Duine et. al. 1987). In fact, the crystal structure of PQQ was solved in the form of the C-5 acetone adduct(Salisbury et. al 1979). The propensity of the ortho-quinone to accept nucleophiles is the chemical basis of the function of PQQ at enzyme active sites. The present study focuses on the NMR of PQQ and various derivatives formed with oxygen and nitrogen nucleophiles. Our goals are to assign the H, TC, and VN NMR spectra and to rigorously confirm the structures of the adducts. Once the NMR data of the relevant adducts are well defined, we will use TC and VN labeled substrates to probe the active sites of PQQ containing enzymes. 7 refs., 2 figs., 1 tab.

  13. Carbon-13 NMR spectroscopy study of L-zeolite- and silica-supported platinum catalysts

    SciTech Connect

    Sharma, S.B.; Laska, T.E.; Balaraman, P.; Root, T.W.; Dumesic, J.A.

    1994-12-01

    NMR studies of CO adsorbed on small Pt particles show evidence of changes in the metallic nature of these particles with size. Large particles on silica or the exterior of zeolite crystallites have conduction-band electrons that cause a Knight shift for adsorbed CO. Small particles in zeolite cavities are diamagnetic clusters, and yield spectra for linear and bridging carbonyls similar to those of transition-metal cluster compounds. {sup 13}C NMR of CO offers a simple probe of metal dispersion and particle size for these Pt catalysts and other noble metal systems. 29 refs., 7 figs., 2 tabs.

  14. Simple cylindrical magic-angle spinner for NMR studies in electromagnets

    NASA Astrophysics Data System (ADS)

    Mai, Michael T.; Ribeiro, Anthony; Jardetzky, Oleg

    A novel cylindrical magic-angle spinner for use in electromagnet systems is described. It features radial and thrust air bearings and easily constructed rotors of relatively large sample volume (˜0.7 cm 3) assembled into a removable spinner/coil Teflon housing. The design allows stable spinning speeds in the range 0.3 to 2.4 kHz with excellent rotor-to-rotor magic-angle resettabilities. High resolution, solid-state NMR studies are illustrated with 13C NMR spectra for crystalline adamantane and a macromolecule, lysozyme.

  15. Vibrational, XRD and (13)C NMR studies of DL-phenylglycinium methanesulfonate crystal.

    PubMed

    Wołoszyn, Łukasz; Ilczyszyn, Marek; Ilczyszyn, Maria M; Haupa, Karolina

    2016-11-01

    A new crystal formed by DL-phenylglycine and methanesulfonic acid (PGLYMS) was obtained and studied by X-ray diffraction, IR and Raman spectroscopy, solid state NMR and DSC methods. Additionally, theoretical computations for the phenylglycine cation were carried out (DFT/B3LYP/aug-cc-pVDZ). Our results show that PGLYMS does not exhibit any phase transitions and crystallizes in the P21/c space group of monoclinic system (Z=4). Detailed analysis of its structure and its IR, Raman and NMR spectra is presented. PMID:27289350

  16. Protein functional dynamics in multiple timescales as studied by NMR spectroscopy.

    PubMed

    Ortega, Gabriel; Pons, Miquel; Millet, Oscar

    2013-01-01

    Protein functional dynamics are defined as the atomic thermal fluctuations or the segmental motions that are essential for the function of the biomolecule. NMR is a very versatile technique that allows obtaining quantitative information from these processes at atomic resolution. This review is focused on the use of 15N spin relaxation methods to study functional dynamics although the connections with other NMR methods and biophysical techniques will be briefly mentioned. In the first part of the chapter, methodological aspects will be considered, while a set of selected cases will be described in more detail in the second part. PMID:23954103

  17. Progress of a 140 GHz gyro-amplifier for DNP NMR Studies

    NASA Astrophysics Data System (ADS)

    Soane, Alexander; Nanni, Emilio; Shapiro, Michael; Temkin, Richard

    2012-10-01

    We report on the experimental progress of a 140 GHz pulsed gyro-amplifier being developed at MIT for enhanced Dynamic Nuclear Polarization for NMR (DNP-NMR). A confocal geometry configuration is being studied as an approach to an overmoded interaction waveguide. The system has achieved 20 dB of gain and 150 watts of peak power over a 2 μs pulse. Additionally, computational work has been performed that investigates the effect of the cylindrically-asymmetric confocal geometry on predicted gain. The computational results show that while linear gain is equivalent to that of a circular interaction waveguide, saturated gain is lower by as much as 50%.

  18. Solid-state NMR studies of biomineralization peptides and proteins.

    PubMed

    Roehrich, Adrienne; Drobny, Gary

    2013-09-17

    unanswered. This is largely due to a lack of methods capable of providing high-resolution structural information for proteins adsorbed to material surfaces under physiologically relevant conditions. In this Account, we highlight recent work that is providing insight into the structure and crystal recognition mechanisms of a salivary protein model system, as well as the structure and interactions of a peptide that catalyzes the formation of biosilica composites. To develop a better understanding of the structure and interactions of proteins in biomaterials, we have used solid-state NMR techniques to determine the molecular structure and dynamics of proteins and peptides adsorbed onto inorganic crystal surfaces and embedded within biomineral composites. This work adds to the understanding of the structure and crystal recognition mechanisms of an acidic human salivary phosphoprotein, statherin. PMID:23932180

  19. Ab Initio Molecular Dynamics Simulations and GIPAW NMR Calculations of a Lithium Borate Glass Melt.

    PubMed

    Ohkubo, Takahiro; Tsuchida, Eiji; Takahashi, Takafumi; Iwadate, Yasuhiko

    2016-04-14

    The atomic structure of a molten 0.3Li2O-0.7B2O3 glass at 1250 K was investigated using ab initio molecular dynamics (AIMD) simulations. The gauge including projector augmented wave (GIPAW) method was then employed for computing the chemical shift and quadrupolar coupling constant of (11)B, (17)O, and (7)Li from 764 AIMD derived structures. The chemical shift and quadrupolar coupling constant distributions were directly estimated from the dynamical structure of the molten glass. (11)B NMR parameters of well-known structural units such as the three-coordinated ring, nonring, and four-coordinated tetrahedron were found to be in good agreement with the experimental results. In this study, more detailed classification of B units was presented based on the number of O species bonded to the B atoms. This highlights the limitations of (11)B NMR sensitivity for resolving (11)B local environment using the experimentally obtained spectra only. The (17)O NMR parameter distributions can theoretically resolve the bridging and nonbridging O atoms with different structural units such as nonring, single boroxol ring, and double boroxol ring. Slight but clear differences in the number of bridging O atoms surrounding Li that have not been reported experimentally were observed in the theoretically obtained (7)Li NMR parameters. PMID:27010637

  20. Water speciation in sodium silicate glasses (quenched melts): A comprehensive NMR study

    NASA Astrophysics Data System (ADS)

    Xue, X.; Kanzaki, M.; Eguchi, J.

    2012-12-01

    Dissolution mechanism of water is an important factor governing how the dissolved water affects the physical and thermodynamic properties of silicate melts and glasses. Our previous studies have demonstrated that 1H MAS NMR in combination with 29Si-1H and 27Al-1H double-resonance NMR experiments is an effective approach for unambiguously differentiating and quantifying different water species in quenched silicate melts (glasses). Several contrasting dissolution mechanisms have been revealed depending on the melt composition: for relatively polymerized melts, the formation of SiOH/AlOH species (plus molecular H2O) and depolymerization of the network structure dominate; whereas for depolymerized Ca-Mg silicate melts, free OH (e.g. MgOH) become increasingly important (cf. [1]). The proportion of free OH species has been shown to decrease with both increasing melt polymerization (silica content) and decreasing field strength of the network modifying cations (from Mg to Ca). Our previous 1H and 29Si MAS NMR results for hydrous Na silicate glasses of limited compositions (Na2Si4O9 and Na2Si2O5) were consistent with negligible free OH (NaOH) species and depolymerizing effect of water dissolution [2]. On the other hand, there were also other studies that proposed the presence of significant NaOH species in hydrous glasses near the Na2Si2O5 composition. The purpose of this study is apply the approach of combined 1H MAS NMR and double-resonance (29Si-1H and 23Na-1H) NMR to gain unambiguous evidence for the OH speciation in Na silicate glasses (melts) as a function of composition. Hydrous Na silicate glasses containing mostly ≤ 1 wt% H2O for a range of Na/Si ratios from 0.33 to 1.33 have been synthesized by rapidly quenching melts either at 0.2 GPa using an internally heated gas pressure vessel or at 1 GPa using a piston cylinder high-pressure apparatus. NMR spectra have been acquired using a 9.4 T Varian Unity-Inova spectrometer. The 29Si and 1H chemical shifts are

  1. Genetic analysis of 16 NMR-lipoprotein fractions in humans, the GOLDN study

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Sixteen nuclear magnetic resonance (NMR) spectroscopy lipoprotein measurements of more than 1,000 subjects of GOLDN study, at fasting and at 3.5 and 6 h after a postprandial fat (PPL) challenge at visits 2 and 4, before and after a 3 weeks Fenofibrate (FF) treatment, were included in 6 time-independ...

  2. Solid-state NMR and ESR studies of activated carbons produced from pecan shells

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Activated carbon from pecan shells has shown promise as an adsorbent in water treatment and sugar refining. However, the chemistry of the material is complex and not fully understood. We report here the application of solid state NMR and ESR to study the chemical structure, mobility, and pore volu...

  3. Ultra-high field NMR studies of antibody binding and site-specific phosphorylation of {alpha}-synuclein

    SciTech Connect

    Sasakawa, Hiroaki |; Sakata, Eri; Yamaguchi, Yoshiki; Masuda, Masami |; Mori, Tetsuya; Kurimoto, Eiji; Iguchi, Takeshi; Hisanaga, Shin-ichi; Iwatsubo, Takeshi; Hasegawa, Masato; Kato, Koichi |

    2007-11-23

    Although biological importance of intrinsically disordered proteins is becoming recognized, NMR analyses of this class of proteins remain as tasks with more challenge because of poor chemical shift dispersion. It is expected that ultra-high field NMR spectroscopy offers improved resolution to cope with this difficulty. Here, we report an ultra-high field NMR study of {alpha}-synuclein, an intrinsically disordered protein identified as the major component of the Lewy bodies. Based on NMR spectral data collected at a 920 MHz proton frequency, we performed epitope mapping of an anti-{alpha}-synuclein monoclonal antibody, and furthermore, characterized conformational effects of phosphorylation at Ser129 of {alpha}-synuclein.

  4. Tracing Atmospheric Sulfate Through a Subalpine Ecosystem Using 17O and 35S, Loch Vale Watershed, Colorado

    NASA Astrophysics Data System (ADS)

    Kester, C. L.; Johnson, C. A.; Mast, M. A.; Michel, R. L.

    2002-12-01

    Over the past several decades, sulfur cycles have been examined in numerous watersheds worldwide to assess the impacts of changes in sulfuric acid deposition rates. A thorough understanding of sulfur behavior in these systems requires that the sulfate influxes from bedrock weathering and from atmospheric deposition be known, and that the extent of sulfur uptake by biomass be determined. Following the discovery of excess 17O in atmospheric sulfate (Lee et al, 2001, GRL 28:1783), we used 17O to help constrain sulfur dynamics and fluxes in alpine/subalpine watersheds in the Rocky Mountains of Colorado (Johnson et al, 2001, GRL 28:4483). Building on this work, and on our previous studies employing cosmogenic 35S (t1/2=87 d, Michel et al, 2000, WRR 36:27), we report a combined 17O-35S study of sulfate in an undisturbed subalpine watershed, Loch Vale, Colorado. In this study, both isotopes were measured in sulfate from a suite of stream and spring waters collected in 1999, and in sulfate from the 1999 snowpack. The snowpack sulfate represents the dominant fraction of annual atmospheric deposition to the watershed. Individual sampling sites show linear correlations between excess 17O and 35S, suggesting that there are two dominant sources of surface water sulfate. The data arrays extend neither toward the measured compositions of snowpack sulfate (Δ17O=1.3‰ , 35S=53 mBq/mg sulfate at Julian day 90), nor toward the compositions characteristic of sulfate from bedrock weathering (Δ17O =0, 35S=0). Thus, the mixing components are themselves composites of different sulfate types. One component appears to be sulfate from bedrock weathering plus atmospheric sulfate with watershed residence times great enough for its 35S to have decayed to below detection (> approx 1 yr). The second mixing component is atmospheric sulfate, a portion of which was subject to redox cycling in soil organic matter - thereby erasing the excess 17O fingerprint - on timescales short enough that 35S is

  5. NMR studies of fructose-1,6-bisphosphate aldolase from E. coli

    SciTech Connect

    Szwergold, B.S.

    1986-01-01

    Previous NMR studies of intact E. coli showed that during steady state anaerobic catabolism of glucose the main glycolytic intermediate detectable in these cells is fructose-1,6-bisphosphate (FBP), levels of which remain constant while the levels of glucose, lactate and succinate vary considerably. Upon feeding these cells glucose labeled with /sup 13/C at the C1 or C6 position, the level of scrambling of label between the C1 and C6 positions of FBP was low suggesting that the FBP-aldolase reaction is far from equilibrium. In order to account for these observations, a study was undertaken on FBP-aldolase from this organism. This enzyme is a dimeric Zn/sup + +/ metalloenzyme with a M/sub r/ of 80,000. It was purified in gram quantities from an overproducer strain and was characterized by standard biochemical techniques prior to the NMR studies. /sup 13/C NMR experiments were conducted using (2-/sup 13/C)dihydroxyacetone phosphate (DHAP) and (2,5-/sup 13/C)fructose-1,6-biphosphate (FBP). Since these substrates can exist in solution in a number of interconvertible forms, the initial experiments determined the relative amounts of these forms and the rates of their interconversion. Subsequently, NMR experiments with the purified enzyme were conducted. Based upon these results, the author concludes that in E. coli the FBP-alkolase reaction appears to be the rate limiting step of anaerobic glycolysis.

  6. Report on neptunium speciation by NMR and optical spectroscopies

    SciTech Connect

    Tait, C.D.; Palmer, P.D.; Ekberg, S.A.; Clark, D.L.

    1995-11-01

    Hydrolysis and carbonate complexation reactions were examined for NpO{sub 2}{sup 2+} and NpO{sub 2}{sup +} ions by a variety of techniques including potentiometric titration, UV-Vis-NIR and NMR spectroscopy. The equilibrium constant for the reaction 3NpO{sub 2}(CO{sub 3}){sub 3}{sup 4{minus}} + 3H{sup +} {rightleftharpoons} (NpO{sub 2}){sub 3}(CO{sub 3}){sub 6}{sup 6{minus}} + 3HCO{sub 3}{sup {minus}} was determined to be logK = 19.7 ({plus_minus} 0.8) (I = 2.5 m). {sup 17}O NMR spectroscopy of NpO{sub 2}{sup n+} ions (n = 1,2) reveals a readily observable {sup 17}O resonance for n = 2, but not for n = 1. The first hydrolysis constant for NpO{sub 2}{sup +} was studied as a function of temperature, and the functional form for the temperature-dependent equilibrium constant for the reaction written as NpO{sub 2}{sup +} + H{sub 2}O {rightleftharpoons} NpO{sub 2}OH + H{sup +} was found to be logK = 2.28 {minus} 3780/T, where T is in {degree}K. Finally, the temperature dependence of neptunium(V) carbonate complexation constants was studied. For the first carbonate complexation constant, the appropriate functional form was found to be log{beta}{sub 01} = 1.47 + 786/T.

  7. Development of an in Situ NMR Photoreactor To Study Environmental Photochemistry.

    PubMed

    Bliumkin, Liora; Dutta Majumdar, Rudraksha; Soong, Ronald; Adamo, Antonio; Abbatt, Jonathan P D; Zhao, Ran; Reiner, Eric; Simpson, André J

    2016-06-01

    Photochemistry is a key environmental process directly linked to the fate, source, and toxicity of pollutants in the environment. This study explores two approaches for integrating light sources with nuclear magnetic resonance (NMR) spectroscopy: sample irradiation using a "sunlight simulator" outside the magnet versus direct irradiation of the sample inside the magnet. To assess their applicability, the in situ NMR photoreactors were applied to a series of environmental systems: an atmospheric pollutant (p-nitrophenol), crude oil extracts, and groundwater. The study successfully illustrates that environmentally relevant aqueous photochemical processes can be monitored in situ and in real time using NMR spectroscopy. A range of intermediates and degradation products were identified and matched to the literature. Preliminary measurements of half-lives were also obtained from kinetic curves. The sunlight simulator was shown to be the most suitable model to explore environmental photolytic processes in situ. Other light sources with more intense UV output hold potential for evaluating UV as a remediation alternative in areas such as wastewater treatment plants or oil spills. Finally, the ability to analyze the photolytic fate of trace chemicals at natural abundance in groundwater, using a cryogenic probe, demonstrates the viability of NMR spectroscopy as a powerful and complementary technique for environmental applications in general. PMID:27172272

  8. Tracing the Atmospheric Source of Desert Nitrates Using Δ 17O

    NASA Astrophysics Data System (ADS)

    Michalski, G. M.; Holve, M.; Feldmeier, J.; Bao, H.; Reheis, M.; Bockheim, J. G.; Thiemens, M. H.

    2001-05-01

    Mineral, caliche, and soil nitrates are found throughout the worlds deserts, including the cold dry Wright Valley of Antarctica, the Atacama desert in Chile and the Mojave desert in the southwest United States. Several authors have suggested biologic sources of these nitrates while others have postulated atmospheric deposition. A recent study utilizing 18O indicated that 30%, and perhaps 100%, of nitrates found in the Atacama and Mojave were of atmospheric origin [1]. A more quantitative assessment of the source strength of atmospheric nitrates was impossible because of the high variability of δ 18 18O of atmospheric nitrates and uncertainties in conditions of biologic production. Mass independently fractionated (MIF) processes are defined and quantified by the equation Δ 17O = δ 17O - .52x δ 18O. MIF processes are associated with the photochemistry of trace gases in the atmosphere and have been found in O3, N2O, CO, and sulfate aerosols . A large MIF (Δ 17O ~ 28 ‰ ) in nitrate aerosols collected in polluted regions was recently reported [2]. Here we extend measurements of MIF in nitrate to the dry deposition of nitrate in less polluted areas (Mojave desert). In addition we trace the MIF signal as it accumulates in the regolith as nitrate salts and minerals and is mixed with biologically produced nitrate (nitrification). Also examined were the isotopic composition of soil nitrates from Antarctic dry valleys. Dust samples were collected as part of the NADP program and soils were collected throughout the Mojave and Death Valley regions of California. Isotope analysis was done in addition to soluble ion content (Cl, NO3, SO4). Dust samples collected by dry deposition samplers showed a large MIF > 20‰ approaching values measured in urban nitrate aerosol. Soils collected throughout the region showed large variations in Δ 17O from ~ 0 to 18 ‰ . The low Δ 17O values are nitrates dominated by biologic nitrification and higher values are nitrates derived by

  9. Arterial metabolism as studied in vitro by NMR: preliminary results in normotensive and hypertensive aortas.

    PubMed

    Carlier, P G; Grandjean, J; Michel, P; D'Orio, V; Rorive, G L

    1985-12-01

    Arterial tissue has been analysed by 31P-, 13C-, 23Na- and 1H-NMR spectroscopy. Rabbit thoracic aortas were mounted on a system with perfusate circulation and studied in basal conditions. Phosphorus spectra remained stable for hours and showed low levels of phosphocreatine (PCr) compared to skeletal, cardiac or even to nonvascular smooth muscle. Significant levels of sugar-phosphates (SP), phosphodiesters (PDE) were detected, as well as occasionnally a peak in the diphosphodiester region. Experiments with phosphate-free perfusate demonstrated a very low level of intracellular inorganic phosphate. As expected from previous data, free ADP levels in tonic arterial tissue were found much higher than in any other muscle. Addition of norepinephrine into the perfusate induced transient decrease in ATP and PCr levels, associated with an increased production of phosphorylated intermediates. At the early stage of renovascular hypertension, aortic energetic pattern was characterized by an increased ADP/ATP ratio. Natural abundant 13C spectra were recorded from dog aortic fragments and showed mainly resonances attributed to fatty components. After addition of a shift-reagent, dysprosium tripolyphosphate, 23Na-NMR allowed separation of intra- and extracellular Na of perfused rabbits aortas. Proton NMR of lyophilized aortic fragments revealed several peaks originating from biologically relevant molecules, lactate, creatine, taurine... These preliminary data demonstrate the feasability of multinuclear NMR spectroscopy of vascular tissue and are suggestive of the potential of the method when it will be combined with monitoring of functional parameters. PMID:2424380

  10. {sup 1}H NMR spectroscopic studies establish that heparanase is a retaining glycosidase

    SciTech Connect

    Wilson, Jennifer C.; Laloo, Andrew Elohim; Singh, Sanjesh; Ferro, Vito

    2014-01-03

    Highlights: •{sup 1}H and {sup 13}C NMR chemical shifts of fondaparinux were fully assigned by 1D and 2D NMR techniques. •Hydrolysis of fondaparinux by heparanase was monitored by {sup 1}H NMR spectroscopy. •Heparanase is established to be a retaining glycosidase. -- Abstract: Heparanase is an endo-β-glucuronidase that cleaves heparan sulfate side chains of proteoglycans in basement membranes and the extracellular matrix (ECM). Heparanase is implicated in several diverse pathological processes associated with ECM degradation such as metastasis, inflammation and angiogenesis and is thus an important target for anti-cancer and anti-inflammatory drug discovery. Heparanase has been classed as belonging to the clan A glycoside hydrolase family 79 based on sequence analysis, secondary structure predictions and mutagenic analysis, and thus it has been inferred that it is a retaining glycosidase. However, there has been no direct experimental evidence to support this conclusion. Herein we describe {sup 1}H NMR spectroscopic studies of the hydrolysis of the pentasaccharide substrate fondaparinux by heparanase, and provide conclusive evidence that heparanase hydrolyses its substrate with retention of configuration and is thus established as a retaining glycosidase. Knowledge of the mechanism of hydrolysis may have implications for future design of inhibitors for this important drug target.

  11. Comparative study of inversion methods of three-dimensional NMR and sensitivity to fluids

    NASA Astrophysics Data System (ADS)

    Tan, Maojin; Wang, Peng; Mao, Keyu

    2014-04-01

    Three-dimensional nuclear magnetic resonance (3D NMR) logging can simultaneously measure transverse relaxation time (T2), longitudinal relaxation time (T1), and diffusion coefficient (D). These parameters can be used to distinguish fluids in the porous reservoirs. For 3D NMR logging, the relaxation mechanism and mathematical model, Fredholm equation, are introduced, and the inversion methods including Singular Value Decomposition (SVD), Butler-Reeds-Dawson (BRD), and Global Inversion (GI) methods are studied in detail, respectively. During one simulation test, multi-echo CPMG sequence activation is designed firstly, echo trains of the ideal fluid models are synthesized, then an inversion algorithm is carried on these synthetic echo trains, and finally T2-T1-D map is built. Futhermore, SVD, BRD, and GI methods are respectively applied into a same fluid model, and the computing speed and inversion accuracy are compared and analyzed. When the optimal inversion method and matrix dimention are applied, the inversion results are in good aggreement with the supposed fluid model, which indicates that the inversion method of 3D NMR is applieable for fluid typing of oil and gas reservoirs. Additionally, the forward modeling and inversion tests are made in oil-water and gas-water models, respectively, the sensitivity to the fluids in different magnetic field gradients is also examined in detail. The effect of magnetic gradient on fluid typing in 3D NMR logging is stuied and the optimal manetic gradient is choosen.

  12. High field and 2D-nmr studies with the aporphine alkaloid glaucine.

    PubMed

    Kerr, K M; Kook, A M; Davis, P J

    1986-01-01

    The aporphine alkaloid glaucine (1) was examined by comparison of the high field (600 MHz) 1H-nmr spectra of 1 vs. racemic 6a,7,7-trideutereoglaucine (4,5), by computer-simulated 1H-nmr spectra at 600 MHz, by using decoupled proton spectra, and two-dimensional COSY and HETCOR experiments with 1 at 500 and 360 MHz, respectively, and using high field (90 MHZ) 13C-nmr of S-(+)-glaucine (1). Emphasis was placed on the resolution of the chemical shifts and coupling constants for the H-4 alpha, H-4 beta, H-5 alpha, H-5 beta, H-6 alpha, H-7 alpha, and H-7 beta alicyclic protons of the molecule, which were previously unassigned. The complete assignment of the alicyclic protons of 1 by 1H-nmr was required for the structural elucidation of deuterated analogs of glaucine, which will be used in microbial transformation studies to determine the stereochemical course of aporphine dehydrogenation by the fungi Fusarium solani (ATCC 12823) and Aspergillus flavipes (ATCC 1030). PMID:3783155

  13. Layered structure of room-temperature ionic liquids in microemulsions by multinuclear NMR spectroscopic studies.

    PubMed

    Falcone, R Dario; Baruah, Bharat; Gaidamauskas, Ernestas; Rithner, Christopher D; Correa, N Mariano; Silber, Juana J; Crans, Debbie C; Levinger, Nancy E

    2011-06-01

    Microemulsions form in mixtures of polar, nonpolar, and amphiphilic molecules. Typical microemulsions employ water as the polar phase. However, microemulsions can form with a polar phase other than water, which hold promise to diversify the range of properties, and hence utility, of microemulsions. Here microemulsions formed by using a room-temperature ionic liquid (RTIL) as the polar phase were created and characterized by using multinuclear NMR spectroscopy. (1)H, (11)B, and (19)F NMR spectroscopy was applied to explore differences between microemulsions formed by using 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim][BF(4)]) as the polar phase with a cationic surfactant, benzylhexadecyldimethylammonium chloride (BHDC), and a nonionic surfactant, Triton X-100 (TX-100). NMR spectroscopy showed distinct differences in the behavior of the RTIL as the charge of the surfactant head group varies in the different microemulsion environments. Minor changes in the chemical shifts were observed for [bmim](+) and [BF(4)](-) in the presence of TX-100 suggesting that the surfactant and the ionic liquid are separated in the microemulsion. The large changes in spectroscopic parameters observed are consistent with microstructure formation with layering of [bmim](+) and [BF(4)](-) and migration of Cl(-) within the BHDC microemulsions. Comparisons with NMR results for related ionic compounds in organic and aqueous environments as well as literature studies assisted the development of a simple organizational model for these microstructures. PMID:21547960

  14. Ammonia fixation by humic substances: A nitrogen-15 and carbon-13 NMR study

    USGS Publications Warehouse

    Thorn, K.A.; Mikita, M.A.

    1992-01-01

    The process of ammonia fixation has been studied in three well characterized and structurally diverse fulvic and humic acid samples. The Suwannee River fulvic acid, and the IHSS peat and leonardite humic acids, were reacted with 15N-labelled ammonium hydroxide, and analyzed by liquid phase 15N NMR spectrometry. Elemental analyses and liquid phase 13C NMR spectra also were recorded on the samples before and after reaction with ammonium hydroxide. The largest increase in percent nitrogen occurred with the Suwannee River fulvic acid, which had a nitrogen content of 0.88% before fixation and 3.17% after fixation. The 15N NMR spectra revealed that ammonia reacted similarly with all three samples, indicating that the functional groups which react with ammonia exist in structural configurations common to all three samples. The majority of nitrogcn incorporated into the samples appears to be in the form of indole and pyrrole nitrogen, followed by pyridine, pyrazine, amide and aminohydroquinone nitrogen. Chemical changes in the individual samples upon fixation could not be discerned from the 13C NMR spectra.

  15. Li NMR study of heavy-fermion LiV2O4 containing magnetic defects

    SciTech Connect

    Zong, X.; Das, S.; Borsa, F.; Vannette, M.; Prozorov, R.; Schmalian, J.; Johnston, D.

    2008-04-21

    We present a systematic study of the variations of the {sup 7}Li NMR properties versus magnetic defect concentration up to 0.83 mol% within the spinel structure of polycrystalline powder samples and a collection of small single crystals of LiV2O4 in the temperature range from 0.5 to 4.2 K. We also report static magnetization measurements and ac magnetic susceptibility measurements at 14 MHz on the samples at low temperatures. Both the NMR spectrum and nuclear spin-lattice relaxation rate are inhomogeneous in the presence of the magnetic defects. The NMR data for the powders are well explained by assuming that (i) there is a random distribution of magnetic point defects, (ii) the same heavy Fermi liquid is present in the samples containing the magnetic defects as in magnetically pure LiV2O4, and (iii) the influences of the magnetic defects and of the Fermi liquid on the magnetization and NMR properties are separable. In the single crystals, somewhat different behaviors are observed. Remarkably, the magnetic defects in the powder samples show evidence of spin freezing below T {approx} 1.0 K, whereas in the single crystals with similar magnetic defect concentration no spin freezing was found down to 0.5 K. Thus different types of magnetic defects and/or interactions between them appear to arise in the powders versus the crystals, possibly due to the substantially different synthesis conditions of the powders and crystals.

  16. 75 As and 59Co NMR studies of SrCo2As2

    NASA Astrophysics Data System (ADS)

    Furukawa, Yuji; Ogloblichev, Vasily; Pandey, Abhisek; Johnston, David C.

    2015-03-01

    After the discovery of unconventional superconductivity in Fe pnictides with the ThCr2Si2-type structure, much attention has been paid to the related materials AM2As2(A = Ca, Sr, and Ba, and M = Co, Ni, Mn, and Cu). We have been studying the electronic and magnetic properties of these related materials systematically. Among them, metallic SrCo2As2 is an interesting system because inelastic neutron scattering measurements indicate strong stripe-type antiferromagnetic correlations, similar to the Fe pnictide superconductors. In order to investigate the magnetic and electronic properties of SrCo2As2 from a microscopic point of view, we carried out 59Co and 75As NMR in the temperature range T = 1.3 - 300 K. In this talk, based on 59Co NMR data including 75As NMR results published previously, we discuss the characteristic magnetic fluctuations in the system and compare them with those measured from NMR data for another cobalt arsenide BaCo2As2. Supported by USDOE under Contract No. DE-AC02-07CH11358.

  17. Two dimensional NMR and NMR relaxation studies of coal structure. Progress report, January 1, 1992--March 31, 1992

    SciTech Connect

    Zilm, K.W.

    1992-07-01

    This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed at delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.

  18. Two dimensional NMR and NMR relaxation studies of coal structure. Progress report, October 1, 1993--December 31, 1993

    SciTech Connect

    Zilm, K.W.

    1993-12-31

    Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed at delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.

  19. Two dimensional NMR and NMR relaxation studies of coal structure. Progress report, September 13, 1991--December 31, 1991

    SciTech Connect

    Zilm, K.W.

    1992-05-27

    This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed a delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.

  20. Two dimensional NMR and NMR relaxation studies of coal structure. Progress report, October 1, 1992--December 31, 1992

    SciTech Connect

    Zilm, K.W.

    1992-12-31

    This report covers the progress made on the title project for the project period. Four major areas of inquiry are being pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups that determine the reactivity of coals. Special attention is being paid to methods that are compatible with the very high magic angle sample spinning rates needed for operation at the high magnetic field strengths available today. Polarization inversion methods utilizing the difference in heat capacities of small groups of spins are particularly promising. Methods combining proton-proton spin diffusion with {sup 13}C CPMAS readout are being developed to determine the connectivity of functional groups in coals in a high sensitivity relay type of experiment. Additional work is aimed at delineating the role of methyl group rotation in the proton NMR relaxation behavior of coals.

  1. Properties of small molecular drug loading and diffusion in a fluorinated PEG hydrogel studied by H molecular diffusion NMR and F spin diffusion NMR.

    PubMed

    Mathias, Errol V; Aponte, Julia; Kornfield, Julia A; Ba, Yong

    2010-12-01

    R(f)-PEG (fluoroalkyl double-ended poly(ethylene glycol)) hydrogel is potentially useful as a drug delivery depot due to its advanced properties of sol-gel two-phase coexistence and low surface erosion. In this study, (1)H molecular diffusion nuclear magnetic resonance (NMR) and (19)F spin diffusion NMR were used to probe the drug loading and diffusion properties of the R(f)-PEG hydrogel for small anticancer drugs, 5-fluorouracil (FU) and its hydrophobic analog, 1,3-dimethyl-5-fluorouracil (DMFU). It was found that FU has a larger apparent diffusion coefficient than that of DMFU, and the diffusion of the latter was more hindered. The result of (19)F spin diffusion NMR for the corresponding freeze-dried samples indicates that a larger portion of DMFU resided in the R(f) core/IPDU intermediate-layer region (where IPDU refers to isophorone diurethane, as a linker to interconnect the R(f) group and the PEG chain) than that of FU while the opposite is true in the PEG-water phase. To understand the experimental data, a diffusion model was proposed to include: (1) hindered diffusion of the drug molecules in the R(f) core/IPDU-intermediate-layer region; (2) relatively free diffusion of the drug molecules in the PEG-water phase (or region); and (3) diffusive exchange of the probe molecules between the above two regions. This study also shows that molecular diffusion NMR combined with spin diffusion NMR is useful in studying the drug loading and diffusion properties in hydrogels for the purpose of drug delivery applications. PMID:21170115

  2. Solid state NMR study of SEI formation in lithium ion batteries

    NASA Astrophysics Data System (ADS)

    Zhao, Dachun

    Recently, rechargeable lithium ion batteries, which offer high energy density and long cycle life, are in great demand as power sources for our mobile electronic society. The formation of a solid electrolyte interphase (SEI) on the surface of electrodes in lithium ion batteries plays an essential role in their performance. This thesis presents solid state NMR and MAS NMR results on the SEI, which contribute to our understanding of SEI formation on both cathodes and anodes. This thesis is organized as following: Chapter 1 surveys the history of batteries and the challenges to further development of the lithium ion battery. Fundamental aspects and SEI formation mechanisms are also included in Chapter l. Chapter 2 deals with the principles and experimental techniques of solid state NMR. Chapter 3 presents studies of SEI formation on anode and cathode in lithium ion batteries using electrochemical impedance spectroscopy (EIS) and NMR. The results provide EIS and NMR evidence that cells containing electrolytes with high EC content display less irreversible capacity after high temperature storage. The irreversible capacity is attributed to SEI growth on electrode surfaces. NMR results on cathodes, on the other hand, imply that the presence of Ni in the cathode may reduce cell performance due to the oxidation of Ni 3+ to Ni4+. Our simulations show that a lower EC/DMC ratio is associated with a smaller SEI intensity for the cathode and higher intensity for the anode. Chapter 4 discusses the effect of temperature on SEI formation on anodes and cathodes. NMR measurements show that MCMB graphite based anodes exhibit high stability no chemical shift is evident over a wide temperature range. On cathodes, however, NMR does reveal changes in SEI intensity as a function of temperature. These changes are believed to be the result of decomposition of the SEI. Evidently, then, changes in the performance of the cell as a factor of temperature are, at least in part, due to changes in

  3. NMR study of the magnetization of superfluid helium-3-boron and NMR of superfluid helium-3 in aerogel

    NASA Astrophysics Data System (ADS)

    Haard, Thomas Michael

    Pulsed NMR measurements of superfluid 3He confined in 98.2% porosity silica aerogel are reported. The aerogel suppressed the superfluid transition temperature TC and the order parameter magnitude from their bulk values in qualitative agreement with impurity scattering models. Magnetization measurements showed that the superfluid is an equal spin pairing state (ESP). The superfluid exhibited positive NMR frequency shifts with similar temperature dependence to those of the bulk A-phase, only smaller. TC was independent of the magnetic field for H < 1.8 kOe to within the experimental error. At 2.18 kOe an increased suppression of TC and the order parameter was observed. Two layers of solid 3He were adsorbed to the aerogel strands. When these were replaced with solid 4He a non-ESP superfluid state was observed. An experimental cell for measuring the heat capacity of 3He in aerogel was designed and fabricated. It was tested without aerogel by measuring the heat capacity of liquid 3He over a range of temperatures from 1 to 25 mK and at pressures of 7.0, 14.0, and 28.0 bar. The measurements in both the normal and superfluid phases were consistent with the data of Greywall. The discrepancy between static and dynamic measurements of the magnetization of superfluid 3He-B was characterized over a region of the phase diagram by comparison of nuclear magnetic resonance (NMR) data and recent SQUID data from other researchers. At the B- to A-phase transition, TAB, the discrepancy was absent at low pressure, but increased to 20% at 26.6 bar and 1.2 kOe. The NMR data were consistent with the weak-coupling-plus (wcp) theory at TAB for most pressures and fields. The Ginzburg-Landau strong-coupling parameter gz/( gz)wcp was determined from NMR results to equal 1.00 +/- 0.03 for all pressures. Combinations of the Ginzburg-Landau beta-parameters are reported that are consistent with this observation.

  4. Diethylstilbestrol can effectively accelerate estradiol-17-O-glucuronidation, while potently inhibiting estradiol-3-O-glucuronidation

    SciTech Connect

    Zhu, Liangliang; Xiao, Ling; Xia, Yangliu; Zhou, Kun; Wang, Huili; Huang, Minyi; Ge, Guangbo; Wu, Yan; Wu, Ganlin; Yang, Ling

    2015-03-01

    This in vitro study investigates the effects of diethylstilbestrol (DES), a widely used toxic synthetic estrogen, on estradiol-3- and 17-O- (E2-3/17-O) glucuronidation, via culturing human liver microsomes (HLMs) or recombinant UDP-glucuronosyltransferases (UGTs) with DES and E2. DES can potently inhibit E2-3-O-glucuronidation in HLM, a probe reaction for UGT1A1. Kinetic assays indicate that the inhibition follows a competitive inhibition mechanism, with the Ki value of 2.1 ± 0.3 μM, which is less than the possible in vivo level. In contrast to the inhibition on E2-3-O-glucuronidation, the acceleration is observed on E2-17-O-glucuronidation in HLM, in which cholestatic E2-17-O-glucuronide is generated. In the presence of DES (0–6.25 μM), K{sub m} values for E2-17-O-glucuronidation are located in the range of 7.2–7.4 μM, while V{sub max} values range from 0.38 to 1.54 nmol/min/mg. The mechanism behind the activation in HLM is further demonstrated by the fact that DES can efficiently elevate the activity of UGT1A4 in catalyzing E2-17-O-glucuronidation. The presence of DES (2 μM) can elevate V{sub max} from 0.016 to 0.81 nmol/min/mg, while lifting K{sub m} in a much lesser extent from 4.4 to 11 μM. Activation of E2-17-O-glucuronidation is well described by a two binding site model, with K{sub A}, α, and β values of 0.077 ± 0.18 μM, 3.3 ± 1.1 and 104 ± 56, respectively. However, diverse effects of DES towards E2-3/17-O-glucuronidation are not observed in liver microsomes from several common experimental animals. In summary, this study issues new potential toxic mechanisms for DES: potently inhibiting the activity of UGT1A1 and powerfully accelerating the formation of cholestatic E2-17-O-glucuronide by UGT1A4. - Highlights: • E2-3-O-glucuronidation in HLM is inhibited when co-incubated with DES. • E2-17-O-glucuronidation in HLM is stimulated when co-incubated with DES. • Acceleration of E2-17-O-glucuronidationin in HLM by DES is via activating the

  5. Reaction of vanadate with aquatic humic substances: An ESR and {sup 51}V NMR study

    SciTech Connect

    Lu, Xi.; Johnson, W.D.; Hook, J.

    1998-08-01

    Electron spin resonance (ESR) spectroscopy and {sup 51}V nuclear magnetic resonance (NMR) spectroscopy have been used to study the interaction of vanadate with aqueous solutions of humic substances (HS) at different pH values and at different concentrations. Under acidic pH conditions, ESR spectra show that humic substances reduce vanadium(V) to vanadium(IV) without further reduction to vanadium(III). The reduced vanadium(IV) ion is bound to oxygen donor atoms, probably at carboxylic acid sites in the humic substances. {sup 51}V NMR spectra show that the VO{sub 2}{sup +} cation is immediately reduced and that the decavanadate cation decomposes to the VO{sub 2}{sup +} cation prior to reduction. The overall rate of reduction depends on both concentration and pH. There is no reduction above pH 6, which suggests that the standard reduction potential of humic substances is about +0.65 V. Near pH 7, vanadate is stabilized by binding to humic substances. As the concentration of humic substances increases, the total vanadium NMR signal intensity decreases. This is due to the quadrupolar nature of the {sup 51}V nucleus that, when bound to humic substances, is invisible in NMR measurements. Quantitative models applied to intensity changes show that the vanadate monomer forms HS0V(V) complexes. The formation equilibrium constant is estimated to be 108 M{sup {minus}1}. At pH above 9, NMR signals appear at {minus}623.6 and at {minus}763.2 ppm when humic substances are added to vanadate solution. The intensities of the signals increase with increasing pH and with increasing concentration of humic substances. These signals appear to be associated with peroxyvanadate anions, which are not bound to humic substances.

  6. DFT study of zigzag (n, 0) single-walled carbon nanotubes: (13)C NMR chemical shifts.

    PubMed

    Kupka, Teobald; Stachów, Michal; Stobiński, Leszek; Kaminský, Jakub

    2016-06-01

    (13)C NMR chemical shifts of selected finite-size models of pristine zigzag single walled carbon nanotubes (SWCNTs) with a diameter of ∼0.4-0.8nm and length up to 2.2nm were studied theoretically. Results for finite SWCNTs models containing 1, 4 and 10 adjacent bamboo-type units were compared with data obtained for infinite tubes in order to estimate the reliability of small finite models in predicting magnetic properties of real-size nanotubes and to assess their tube-length dependence. SWCNTs were fully optimized using unrestricted density functional theory (DFT-UB3LYP/6-31G*). Cyclacenes, as the shortest models of open-ended zigzag SWCNTs, with systematically varying diameter were calculated as well. GIAO NMR calculations on the SWCNT and cyclacene models were performed using the BHandH density functional combined with relatively small STO-3Gmag basis set, developed by Leszczyński and coworkers for accurate description of magnetic properties. Regular changes of carbon (13)C chemical shifts along the tube axis of real size (6, 0) and (9, 0) zigzag carbon nanotubes were shown. The (13)C NMR shifts according to increasing diameter calculated for zigzag (n, 0, n=5-10) cyclacenes followed the trends observed for zigzag (n, 0) SWCNTs. The results for 4-units long SWCNTs match reasonably well with the data obtained for infinite zigzag (n, 0) SWCNTs, especially to those with bigger diameter (n=8-15). The presence of rim hydrogens obviously affects theoretical (13)C chemical shieldings and shifts in cyclacenes and thus cyclacenes can provide only approximate estimation of (13)C NMR parameters of real-size SWCNTs. The NMR properties predicted for the longest 10-units long models of SWCNTs reliably correspond to results obtained for infinite nanotubes. They were thus able to accurately predict also recently reported experimental chemical shift of chiral (6, 5) SWCNT. PMID:27155813

  7. Calcium binding of transglutaminases: a 43Ca NMR study combined with surface polarity analysis.

    PubMed

    Ambrus, A; Bányai, I; Weiss, M S; Hilgenfeld, R; Keresztessy, Z; Muszbek, L; Fésüs, L

    2001-08-01

    Transglutaminases (TGases) form cross-links between glutamine and lysine side-chains of polypeptides in a Ca2+-dependent reaction. The structural basis of the Ca2+-effect is poorly defined. 43Ca NMR, surface polarity analysis combined with multiple sequence alignment and the construction of a new homology model of human tissue transglutaminase (tTGase) were used to obtain structural information about Ca2+ binding properties of factor XIII-A2, tTGase and TGase 3 (each of human origin). 43Ca NMR provided higher average dissociation constants titrating on a wide Ca2+-concentration scale than previous studies with equilibrium dialysis performed in shorter ranges. These results suggest the existence of low affinity Ca2+ binding sites on both FXIII-A and tTGase in addition to high affinity ones in accordance with our surface polarity analysis identifying high numbers of negatively charged clusters. Upon increasing the salt concentration or activating with thrombin, FXIII-A2 partially lost its original Ca2+ affinity; the NMR data suggested different mechanisms for the two activation processes. The NMR provided structural evidence of GTP-induced conformational changes on the tTGase molecule diminishing all of its Ca2+ binding sites. NMR data on the Ca2+ binding properties of the TGase 3 are presented here; it binds Ca2+ the most tightly, which is weakened after its proteolytic activation. The investigated TGases seem to have very symmetric Ca2+ binding sites and no EF-hand motifs. PMID:11565852

  8. Oxygen-17 and copper-63 NMR study of spindynamics in low- dimensional spin 1/2 antiferromagnets

    NASA Astrophysics Data System (ADS)

    Thurber, Kent Robert

    63Cu and 17O nuclear magnetic resonance (NMR) and nuclear quadrupole resonance (NQR) experiments are reported on copper-oxide compounds related to high temperature superconductors that are nearly ideal realizations of spin 1/2 Heisenberg antiferromagnets with different geometries of the magnetic interactions: 1 dimensional spin chains, 2 dimensional planes, two coupled chains (two-leg ladder), and three coupled chains (three-leg ladder). Comparison of the spin-lattice relaxation rate, 1/T1, for 63Cu and 17O reveals the wave-vector, q, dependence of low-energy magnetic fluctuations, and 1/T2 G the Gaussian spin-spin relaxation rate provides information about the electron spin correlation length, ξ. In the 1d material, Sr 2CuO3, 171/T1(q = 0) ~ aT + bT2 over the whole temperature range 10 to 700 K. Frequency dependence measurements show that diffusive contributions dominate T1(q ~ 0) for the double chain 1d material, SrCuO2. For the undoped 2d copper oxide material, Sr2CuO2Cl2, we demonstrate that 17O 1/T1 measures the spin wave damping in the undoped antiferromagnet for short wavelengths. We find that the spin wave damping is small, clarifying one of the unique properties of these 2d copper-oxide antiferromagnetic materials: there is a wide temperature range where short range spin excitations exist with long lifetimes, without long range 3-dimensional order. The two-leg ladder materials, SrCu2O3 and A 14Cu24O41 (A = La,Sr,Ca), have a large energy gap for spin excitations. There is a crossover in magnetic fluctuations from temperatures below the spin gap to above the spin gap. For the doped two-leg ladders, the effective doping of the ladders changes with temperature, and this temperature is correlated to the magnetic spin gap energy. The three-leg ladder material, Sr2Cu3O5, demonstrates a crossover in the temperature dependence of the spin correlation length, ξ. At high temperatures, we find the ξ ~ 1/T behavior characteristic of a 1d structure (isolated three

  9. Methyl-specific isotopic labeling: a molecular tool box for solution NMR studies of large proteins.

    PubMed

    Kerfah, Rime; Plevin, Michael J; Sounier, Remy; Gans, Pierre; Boisbouvier, Jerome

    2015-06-01

    Nuclear magnetic resonance (NMR) spectroscopy is a uniquely powerful tool for studying the structure, dynamics and interactions of biomolecules at atomic resolution. In the past 15 years, the development of new isotopic labeling strategies has opened the possibility of exploiting NMR spectroscopy in the study of supra-molecular complexes with molecular weights of up to 1MDa. At the core of these isotopic labeling developments is the specific introduction of [(1)H,(13)C]-labeled methyl probes into perdeuterated proteins. Here, we describe the evolution of these approaches and discuss their impact on structural and biological studies. The relevant protocols are succinctly reviewed for single and combinatorial isotopic-labeling of methyl-containing residues, and examples of applications on challenging biological systems, including high molecular weight and membrane proteins, are presented. PMID:25881211

  10. STRAFI-NMR studies of water transport in soil.

    PubMed

    Preston, A R; Bird, N R; Kinchesh, P; Randall, E W; Whalley, W R

    2001-01-01

    1-D STRAFI (STRAy FIeld) imaging is used to study water distribution in a sandy loam. The matric potential of the soil can be varied during acquisition of 1-D profiles. Results at a range of potentials are presented showing both the equilibrium distribution and the evolution of the profile following an abrupt change in matric potential. The air breakthrough point and variations in draining behaviour due to differences in soil compaction are identified. PMID:11445357

  11. NMR studies of methane and hydrogen in microporous materials

    NASA Astrophysics Data System (ADS)

    Ji, Yu; Hamida, J. A.; Tang, Yibing; Sullivan, N. S.

    2016-02-01

    We review the results of nuclear magnetic resonance studies of the molecular dynamics of the quantum gases HD and CH4 adsorbed in the cages of microporous structures. Measurements of the variation of the nuclear spin-lattice and nuclear spin-spin relaxation times with temperature provide detailed information about the translational and rotational dynamics of the adsorbed molecules over a wide temperature range.

  12. Preparation of Protein Samples for NMR Structure, Function, and Small Molecule Screening Studies

    PubMed Central

    Acton, Thomas B.; Xiao, Rong; Anderson, Stephen; Aramini, James; Buchwald, William A.; Ciccosanti, Colleen; Conover, Ken; Everett, John; Hamilton, Keith; Huang, Yuanpeng Janet; Janjua, Haleema; Kornhaber, Gregory; Lau, Jessica; Lee, Dong Yup; Liu, Gaohua; Maglaqui, Melissa; Ma, Lichung; Mao, Lei; Patel, Dayaban; Rossi, Paolo; Sahdev, Seema; Shastry, Ritu; Swapna, G.V.T.; Tang, Yeufeng; Tong, Saichiu; Wang, Dongyan; Wang, Huang; Zhao, Li; Montelione, Gaetano T.

    2014-01-01

    In this chapter, we concentrate on the production of high quality protein samples for NMR studies. In particular, we provide an in-depth description of recent advances in the production of NMR samples and their synergistic use with recent advancements in NMR hardware. We describe the protein production platform of the Northeast Structural Genomics Consortium, and outline our high-throughput strategies for producing high quality protein samples for nuclear magnetic resonance (NMR) studies. Our strategy is based on the cloning, expression and purification of 6X-His-tagged proteins using T7-based Escherichia coli systems and isotope enrichment in minimal media. We describe 96-well ligation-independent cloning and analytical expression systems, parallel preparative scale fermentation, and high-throughput purification protocols. The 6X-His affinity tag allows for a similar two-step purification procedure implemented in a parallel high-throughput fashion that routinely results in purity levels sufficient for NMR studies (> 97% homogeneity). Using this platform, the protein open reading frames of over 17,500 different targeted proteins (or domains) have been cloned as over 28,000 constructs. Nearly 5,000 of these proteins have been purified to homogeneity in tens of milligram quantities (see Summary Statistics, http://nesg.org/statistics.html), resulting in more than 950 new protein structures, including more than 400 NMR structures, deposited in the Protein Data Bank. The Northeast Structural Genomics Consortium pipeline has been effective in producing protein samples of both prokaryotic and eukaryotic origin. Although this paper describes our entire pipeline for producing isotope-enriched protein samples, it focuses on the major updates introduced during the last 5 years (Phase 2 of the National Institute of General Medical Sciences Protein Structure Initiative). Our advanced automated and/or parallel cloning, expression, purification, and biophysical screening

  13. THM determination of the 65 keV resonance strength intervening in the 17O ( p ,α)14N reaction rate

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; Burjan, S. V.; Cherubini, S.; Coc, A.; Gulino, M.; Hammache, F.; Hons, Z.; Irgaziev, B.; Kiss, G. G.; Kroha, V.; La Cognata, M.; Lamia, L.; Mukhamedzhanov, A.; Pizzone, R. G.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; de Séréville, N.; Somorjai, E.; Tumino, A.

    2015-02-01

    The 17O ( p ,α)14N reaction is of paramount importance for the nucleosynthesis in a number of stellar sites, including red giants (RG), asymptotic giant branch (AGB) stars, massive stars and classical novae. We report on the indirect study of the 17O ( p ,α)14N reaction via the Trojan Horse Method by applying the approach recently developed for extracting the resonance strength of the narrow resonance at Ec.m.R = 65 keV (EX =5.673 MeV). The strength of the 65 keV resonance in the 17O ( p ,α)14N reaction, measured by means of the THM, has been used to renormalize the corresponding resonance strength in the 17O + p radiative capture channel.

  14. THM determination of the 65 keV resonance strength intervening in the {sup 17}O(p,α){sup 14}N reaction rate

    SciTech Connect

    Sergi, M. L.; La Cognata, M.; Pizzone, R. G.; Spitaleri, C.; Cherubini, S.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Burjan, S. V.; Hons, Z.; Kroha, V.; Coc, A.; Hammache, F.; Irgaziev, B.; Kiss, G. G.; Somorjai, E.; Lamia, L.; Mukhamedzhanov, A.; and others

    2015-02-24

    The {sup 17}O(p,α){sup 14}N reaction is of paramount importance for the nucleosynthesis in a number of stellar sites, including red giants (RG), asymptotic giant branch (AGB) stars, massive stars and classical novae. We report on the indirect study of the {sup 17}O(p,α){sup 14}N reaction via the Trojan Horse Method by applying the approach recently developed for extracting the resonance strength of the narrow resonance at E{sub c.m.}{sup R} = 65 keV (E{sub X} =5.673 MeV). The strength of the 65 keV resonance in the {sup 17}O(p,α){sup 14}N reaction, measured by means of the THM, has been used to renormalize the corresponding resonance strength in the {sup 17}O+p radiative capture channel.

  15. Investigation of Synthetic Mg(1.3)V(1.7)O4 Spinel with MgO Inclusions: Case Study of a Spinel with an Apparently occupied Interstitial Site

    NASA Technical Reports Server (NTRS)

    Uchida, Hinako; Righter, Kevin; Lavina, Barbara; Nowell, Matthew M.; Wright, Stuart I.; Downs, Robert T.; Yang, Hexiong

    2007-01-01

    A magnesium vanadate spinel crystal, ideally MgV2O4, synthesized at 1 bar, 1200 C and equilibrated under FMQ + 1.3 log f(sub o2) condition, was investigated using single-crystal X-ray diffraction, electron microprobe, and electron backscatter (EBSD). The initial X-ray structure refinements gave tetrahedral and octahedral site occupancies, along with the presence of 0.053 apfu Mg at an interstitial octahedral site . Back-scattered electron (BSE) images and electron microprobe analyses revealed the existence of an Mg-rich phase in the spinel matrix, which was too small (less than or equal to 3microns) for an accurate chemical determination. The EBSD analysis combined with X-ray energy dispersive spectroscop[y (XEDS) suggested that the Mg-rich inclusions are periclase oriented coherently with the spinel matrix. The final structure refinements were optimized by subtracting the X-ray intensity contributions (approx. 9%) of periclase reflections, which eliminated the interstitial Mg. This study provides insight into possible origins of refined interstitial cations reported in the the literature for spinel, and points to the difficulty of using only X-ray diffraction data to distinguish a spinel with interstitial cations from one with coherently oriented MgO inclusions.

  16. Preliminary 1H NMR study on archaeological waterlogged wood.

    PubMed

    Maccotta, Antonella; Fantazzini, Paola; Garavaglia, Carla; Donato, Ines D; Perzia, Patrizia; Brai, Maria; Morreale, Filippa

    2005-01-01

    Magnetic Resonance Relaxation (MRR) and Magnetic Resonance Imaging (MRI) are powerful tools to obtain detailed information on the pore space structure that one is unlikely to obtain in other ways. These techniques are particularly suitable for Cultural Heritage materials, because they use water 1H nuclei as a probe. Interaction with water is one of the main causes of deterioration of materials. Porous structure in wood, for example, favours the penetration of water, which can carry polluting substances and promote mould growth. A particular case is waterlogged wood from underwater discoveries and moist sites; in fact, these finds are very fragile because of chemical, physical and biological decay from the long contact with the water. When wood artefacts are brought to the surface and directly dried in air, there is the collapse of the cellular structures, and wood loses its original form and dimensions and cannot be used for study and museum exhibits. In this work we have undertaken the study of some wood finds coming from Ercolano's harbour by MRR and MRI under different conditions, and we have obtained a characterization of pore space in wood and images of the spatial distribution of the confined water in the wood. PMID:16485652

  17. NMR studies of Phase Transitions in Alkali Metal Films on Glass Substrates

    NASA Astrophysics Data System (ADS)

    Ishikawa, K.; Patton, B.; Jau, Y.-Y.; Happer, W.

    2006-05-01

    We report NMR spectra of thin ^87Rb films on glass in an investigation of the ``curing'' process which is commonly observed in alkali cells. The cells were cycled in temperature over a range of 5 C to 170 C and the rubidium solid-liquid phase transition was studied. The spectra of these two phases are resolvable at 9.4 T because of their different Knight shifts. Hysteresis in the observed phases confirmed reports of a curing phenomenon, and after time a supercooled liquid Rb peak could be detected at temperatures far below the predicted freezing point of 39 C. Moreover, a third NMR peak was observed at temperatures below the melting point whose frequency varied with temperature and spanned the solid and liquid frequency ranges. To our knowledge, this is the first study to characterize this additional resonance. We have also performed analogous measurements on ^133Cs films.

  18. Proton NMR study of the state of water in fibrin gels, plasma, and blood clots

    SciTech Connect

    Blinc, A.; Lahajnar, G.; Blinc, R.; Zidansek, A.; Sepe, A. )

    1990-04-01

    A proton NMR relaxation and pulsed field gradient self-diffusion study of water in fibrin gels, plasma, and blood clots has been performed with special emphasis on the effect of the sol-gel and shrinkage transitions. Deuteron NMR in fibrin gels was also studied to supplement the proton data. It is shown that a measurement of the water proton or deuteron T1/T2 ratio allows for a determination of the bound water fraction in all these systems. The change in the T1/T2 ratio at the shrinkage transition further allows for a determination of the surface fractal dimension of the gel if the change in the volume of the gel is known. The self-diffusion coefficient of water in these systems, which determines the transport properties of the gel, is found to be proportional to the free water fraction in both the nonshrunken and shrunken state.

  19. Structural studies of pravastatin and simvastatin and their complexes with SDS micelles by NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Rakhmatullin, I. Z.; Galiullina, L. F.; Klochkova, E. A.; Latfullin, I. A.; Aganov, A. V.; Klochkov, V. V.

    2016-02-01

    Conformational features of pravastatin and simvastatin molecules in solution and in their complexes with sodium dodecyl sulfate micelles (SDS) were studied by 2D NOESY NMR spectroscopy. On the basis of the nuclear magnetic resonance experiments it was established that pravastatin and simvastatin can form molecular complex with SDS micelles which were considered as the model of cell membrane. In addition, interatomic distances for studied compounds were calculated based on 2D NOESY NMR experiments. It was shown that pravastatin interacts only with a surface of model membrane. However, in contrast to pravastatin, simvastatin penetrates into the inner part of SDS micelles. Observed distinctions in the mechanisms of interaction of pravastatin and simvastatin with models of cell membranes could explain the differences in their pharmacological properties.

  20. Gel synthesis of magnesium silicates: A 29Si magic angle spinning NMR study

    NASA Astrophysics Data System (ADS)

    Hartman, J. Stephen; Millard, Roberta L.

    1990-01-01

    The formation of the magnesium silicate minerals forsterite, enstatite, and roedderite by heating of amorphous “protosilicate” gels precipitated from aqueous solution has been studied by 29Si MAS nmr. Gentle drying of the hydrogels at 110° C gives materials with broad nmr signals that do not differ appreciably with preparation conditions, but the minerals formed by heating at 750° C or higher are greatly dependent on the precipitation and washing conditions of the original gel. The rare mineral roedderite, best known from studies of unequilibrated enstatite chondrite meteorites, becomes a major species along with forsterite when the hydrogels are washed with sodium hydroxide solution before drying and heating to 750° C.

  1. Protein-Carbohydrate Interactions Studied by NMR: From Molecular Recognition to Drug Design

    PubMed Central

    Fernández-Alonso, María del Carmen; Díaz, Dolores; Berbis, Manuel Álvaro; Marcelo, Filipa; Cañada, Javier; Jiménez-Barbero, Jesús

    2012-01-01

    Diseases that result from infection are, in general, a consequence of specific interactions between a pathogenic organism and the cells. The study of host-pathogen interactions has provided insights for the design of drugs with therapeutic properties. One area that has proved to be promising for such studies is the constituted by carbohydrates which participate in biological processes of paramount importance. On the one hand, carbohydrates have shown to be information carriers with similar, if not higher, importance than traditionally considered carriers as amino acids and nucleic acids. On the other hand, the knowledge on molecular recognition of sugars by lectins and other carbohydrate-binding proteins has been employed for the development of new biomedical strategies. Biophysical techniques such as X-Ray crystallography and NMR spectroscopy lead currently the investigation on this field. In this review, a description of traditional and novel NMR methodologies employed in the study of sugar-protein interactions is briefly presented in combination with a palette of NMR-based studies related to biologically and/or pharmaceutically relevant applications. PMID:23305367

  2. Nmr/on Studies of Iron, Iron-Cobalt and Iron-Germanium

    NASA Astrophysics Data System (ADS)

    Sabbas, Albert Mark

    The techniques of ultra low temperature nuclear orientation, and NMR on oriented nuclei (NMR/ON) were applied to polycrystalline and single crystal ferromagnetic materials, doped with traces of radioactive nuclei, for the study of the hyperfine interactions. The samples were cooled to 0.012K by a ('3)He/('4)He dilution refrigerator. Moderate external fields were used to magnetically saturate the ferromagnetic samples. The resulting large unidirectional hyperfine fields, in conjunction with the ultra low temperatures, then orient the nuclei. The anisotropy of the emitted nuclear radiations from the oriented ensemble of nuclei is a function of the spin and magnetic moment of the source nuclei, the hyperfine field and the lattice temperature. Two methods were used to obtain information concerning the hyperfine interactions. (A) The anisotropy of radiation emitted by the oriented source nuclei was measured as a function of the lattice temperature. (B) The nuclear hyperfine splittings were measured using the NMR/ON method. In NMR/ON the nuclear magnetic resonance is detected as a change in the anisotropy of the radiation emitted by the oriented nuclei. On resonance the rf photons absorbed by the oriented nuclei change the degree of orientation and, consequently, change the anisotropy of the emitted radiation. The measurements carried out include the following: (1) The effects of rf power, bandwidth and frequency modulation on the NMR/ON signal was investigated for ('60)Co Fe. (2) The resonance frequency for ('60)Co Fe was measured as a function of applied field and the Knight shift and the hyperfine field in zero applied field were deduced. (3) The hyperfine fields for ('60)Co, ('56)Co, and ('58)Co in permendur (an alloy consisting of 49% Co, 49% Fe, 2% V) were measured and the hyperfine anomalies were determined. (4) A comprehensive study of the spin-lattice relaxation of ('60)Co Fe as a function of lattice temperature and applied field was carried out using NMR/ON. (5

  3. INSTRUMENTS AND METHODS OF INVESTIGATION: NMR potentials for studying physical processes in fossil coals

    NASA Astrophysics Data System (ADS)

    Alekseev, Anatolii D.; Ul'yanova, Ekaterina V.; Vasilenko, Tat'yana A.

    2005-11-01

    High-resolution, pulsed, and wide-line NMR studies of fossil coals are reviewed. Coal substance conversion due to outbursts is discussed. Results on water and methane interactions with coal substance, which provide insight into the dynamic characteristics of boundary water, the location of methane in coal structure, and water and methane's hazard implications for coal beds (gas- or geodynamic phenomena) are presented; these are shown to have potential for predicting and preventing life threatening situations.

  4. Relationships between solid dispersion preparation process, particle size and drug release--an NMR and NMR microimaging study.

    PubMed

    Dahlberg, Carina; Millqvist-Fureby, Anna; Schuleit, Michael; Furó, István

    2010-10-01

    Solid dispersion tablets prepared by either spray drying or rotoevaporation and exhibiting different grain and pore sizes were investigated under the process of hydration-swelling-gelation. (2)H and (1)H NMR microimaging experiments were used to selectively follow water penetration and polymer mobilization kinetics, respectively, while the drug release kinetics was followed by (1)H NMR spectroscopy. The obtained data, in combination with morphological information by scanning electron microscopy (SEM), reveal a complex process that ultimately leads to release of the drug into the aqueous phase. We find that the rate of water ingress has no direct influence on release kinetics, which also renders air in the tablets a secondary factor. On the other hand, drug release is directly correlated with the polymer mobilization kinetics. Water diffusion into the originally dry polymer grains determines the rate of grain swelling and the hydration within the grains varies strongly with grain size. We propose that this sets the stage for creating homogeneous gels for small grain sizes and heterogeneous gels for large grain sizes. Fast diffusion through water-rich sections of the inhomogeneous gels that exhibit a large mesh size is the factor which yields a faster drug release from tablets prepared by rotoevaporation. PMID:20561585

  5. Structural studies of proteins by paramagnetic solid-state NMR spectroscopy

    PubMed Central

    Jaroniec, Christopher P.

    2015-01-01

    Paramagnetism-based nuclear pseudocontact shifts and spin relaxation enhancements contain a wealth of information in solid-state NMR spectra about electron-nucleus distances on the ~20 Å length scale, far beyond that normally probed through measurements of nuclear dipolar couplings. Such data are especially vital in the context of structural studies of proteins and other biological molecules that suffer from a sparse number of experimentally-accessible atomic distances constraining their three-dimensional fold or intermolecular interactions. This perspective provides a brief overview of the recent developments and applications of paramagnetic magic-angle spinning NMR to biological systems, with primary focus on the investigations of metalloproteins and natively diamagnetic proteins modified with covalent paramagnetic tags. PMID:25797004

  6. Solution structure of sialyl Lewis X mimics studied by two-dimensional NMR

    NASA Astrophysics Data System (ADS)

    Demura, Makoto; Noda, Masatoshi; Kajimoto, Tetsuya; Uchiyama, Taketo; Umemoto, Kimiko; Wong, Chi-Huey; Asakura, Tetsuo

    2002-01-01

    A structure of the peptidic mimic of sialyl Lewis X (Sle X) (α- N-acetyl-neuraminyl-(2,3)-β- D-galactopyranosyl-(1,4)-[α- L-fucopyranosyl-(1,3)-β- D- N-acetyl-glucosamine]) in an aqueous solution was studied using two-dimensional 1H NMR spectroscopy. Complete assignments of 1H NMR chemical shift of the SLe X mimic have been performed. The presence of three conformers of the SLe X mimic in a solution was proposed by using distance geometry calculation based on NOE constraints, which were obtained from NOESY experiments. In addition, intermolecular interaction between the mimic and the crystal structure of E-selectin was refined using molecular dynamics. This suggested the conformational rearrangement of the functional groups of the conformers to the active sites of E-selectin. The relationship between the binding activities toward E-selectin and the three-dimensional structures of other mimics was also discussed.

  7. NMR study of the ternary carbides M2 AlC (M=Ti,V,Cr)

    NASA Astrophysics Data System (ADS)

    Lue, C. S.; Lin, J. Y.; Xie, B. X.

    2006-01-01

    We have performed a systematic study of the layered ternary carbides Ti2AlC , V2AlC , and Cr2AlC using Al27 NMR spectroscopy. The quadrupole splittings, Knight shifts, as well as spin-lattice relaxation times on each material have been identified. The sign of the isotropic Knight shift varies from positive for Ti2AlC and V2AlC to negative for Cr2AlC , attributed to the enhancement of hybridization with increasing valence electron count in the transition metal. Universally long relaxation times are found for these alloys. Results provide a measure of Al-s Fermi-level density of states Ns(EF) for Ti2AlC and V2AlC . In addition, the evidence that Ns(EF) correlates with the transition metal d -electron count has been explored in the present NMR investigation.

  8. Decomposition of adsorbed VX on activated carbons studied by {sup 31}P MAS NMR

    SciTech Connect

    Ishay Columbus; Daniel Waysbort; Liora Shmueli; Ido Nir; Doron Kaplan

    2006-06-15

    The fate of the persistent OP nerve agent O-ethyl S-(2-(diisopropylamino)ethyl) methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. Four types of activated carbon were used, including coal-based BPL. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) ((DES){sub 2}). Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed. 17 refs., 6 figs., 3 tabs.

  9. Structural studies of proteins by paramagnetic solid-state NMR spectroscopy.

    PubMed

    Jaroniec, Christopher P

    2015-04-01

    Paramagnetism-based nuclear pseudocontact shifts and spin relaxation enhancements contain a wealth of information in solid-state NMR spectra about electron-nucleus distances on the ∼20 Å length scale, far beyond that normally probed through measurements of nuclear dipolar couplings. Such data are especially vital in the context of structural studies of proteins and other biological molecules that suffer from a sparse number of experimentally-accessible atomic distances constraining their three-dimensional fold or intermolecular interactions. This perspective provides a brief overview of the recent developments and applications of paramagnetic magic-angle spinning NMR to biological systems, with primary focus on the investigations of metalloproteins and natively diamagnetic proteins modified with covalent paramagnetic tags. PMID:25797004

  10. Decomposition of adsorbed VX on activated carbons studied by 31P MAS NMR.

    PubMed

    Columbus, Ishay; Waysbort, Daniel; Shmueli, Liora; Nir, Ido; Kaplan, Doron

    2006-06-15

    The fate of the persistent OP nerve agent O-ethyl S-[2-(diisopropylamino)ethyl] methylphosphonothioate (VX) on granular activated carbons that are used for gas filtration was studied by means of 31P magic angle spinning (MAS) NMR spectroscopy. VX as vapor or liquid was adsorbed on carbon granules, and MAS NMR spectra were recorded periodically. The results show that at least 90% of the adsorbed VX decomposes within 20 days or less to the nontoxic ethyl methylphosphonic acid (EMPA) and bis(S-2-diisopropylaminoethane) {(DES)2}. Decomposition occurred irrespective of the phase from which VX was loaded, the presence of metal impregnation on the carbon surface, and the water content of the carbon. Theoretical and practical aspects of the degradation are discussed. PMID:16830567

  11. Structural studies of proteins by paramagnetic solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Jaroniec, Christopher P.

    2015-04-01

    Paramagnetism-based nuclear pseudocontact shifts and spin relaxation enhancements contain a wealth of information in solid-state NMR spectra about electron-nucleus distances on the ∼20 Å length scale, far beyond that normally probed through measurements of nuclear dipolar couplings. Such data are especially vital in the context of structural studies of proteins and other biological molecules that suffer from a sparse number of experimentally-accessible atomic distances constraining their three-dimensional fold or intermolecular interactions. This perspective provides a brief overview of the recent developments and applications of paramagnetic magic-angle spinning NMR to biological systems, with primary focus on the investigations of metalloproteins and natively diamagnetic proteins modified with covalent paramagnetic tags.

  12. Chiral Magnetism in an Itinerant Helical Magnet, MnSi - An Extended 29Si NMR Study

    NASA Astrophysics Data System (ADS)

    Yasuoka, Hiroshi; Motoya, Kiyoichiro; Majumder, Mayukh; Witt, Sebastian; Krellner, Cornelius; Baenitz, Michael

    2016-07-01

    The microscopic magnetism in the helical, conical and ferromagnetically polarized phases in an itinerant helical magnet, MnSi, has been studied by an extended 29Si NMR at zero field and under external magnetic fields. The temperature dependence of the staggered moment, MQ(T), determined by the 29Si NMR frequency, ν(T), and the nuclear relaxation rate, 1/T1(T), at zero field is in general accord with the SCR theory for weak itinerant ferromagnetic metals and its extension to helical magnets. The external field dependence of resonance frequency, ν(H), follows a vector sum of the contributions from the atomic hyperfine and macroscopic fields with a field induced moment characteristic to itinerant magnets. A discontinuous jump of the resonance frequency at the critical field, Hc, between the conical and the polarized phases has also been found, which suggests a first order like change of the electronic states at Hc.

  13. Solid state 13C NMR characterisation study on fourth generation Ziegler-Natta catalysts.

    PubMed

    Heikkinen, Harri; Liitiä, Tiina; Virkkunen, Ville; Leinonen, Timo; Helaja, Tuulamari; Denifl, Peter

    2012-01-01

    In this study, solid state (13)C NMR spectroscopy was utilised to characterize and identify the metal-ester coordination in active fourth generation (phthalate) Ziegler-Natta catalysts. It is known that different donors affect the active species in ZN catalysts. However, there is still limited data available of detailed molecular information how the donors and the active species are interplaying. One of the main goals of this work was to get better insight into the interactions of donor and active species. Based on the anisotropy tensor values (δ(11), δ(22), δ(33)) from low magic-angle spinning (MAS) (13)C NMR spectra in combination with chemical shift anisotropy (CSA) calculations (δ(aniso) and η), both the coordinative metal (Mg/Ti) and the symmetry of this interaction between metal and the internal donor in the active catalyst (MgCl(2)/TiCl(4)/electron donor) system could be identified. PMID:22425229

  14. 1H-NMR study of the three low temperature phases of DPPC-water systems.

    PubMed

    Trahms, L; Klabe, W D; Boroske, E

    1983-06-01

    The three phases of dipalmitoylphosphatidylcholine-water dispersions, occurring below the main transition are studied by a moment analysis of 1H-nuclear magnetic resonance (NMR) spectra. The subtransition, recently detected by Chen, S. C., J. M. Sturtevant, and B. J. Gaffney, 1980, Pro. Natl. Acad. Sci. USA, 77:5060-5063, is characterized by a sharp drop in the second moment at 12 degrees C as a result of increasing the temperature. Interesting features of this phase transition are a hysteresis of 11 K and extremely slow kinetics. It is interpreted as the onset of a flip-flop of the hydrocarbon chains about their long axis. At the pretransition, this type of motion is assumed to change into a fast rotation. The proposed models for the three phases are confirmed by computer calculations of theoretical values for the second and fourth moments of the corresponding NMR signals. PMID:6688190

  15. A comprehensive NMR structural study of Titan aerosol analogs: Implications for Titan's atmospheric chemistry

    NASA Astrophysics Data System (ADS)

    He, Chao; Smith, Mark A.

    2014-11-01

    Titan has a thick atmosphere composed primarily of nitrogen and methane. Complex organic chemistry induced by solar ultraviolet radiation and energetic particles, takes place in Titan's upper atmosphere, producing an optically thick reddish brown carbon based haze encircling this moon. The chemistry in Titan's atmosphere and its resulting chemical structures are still not fully understood in spite of a great many efforts being made. In our previous work, we have investigated the structure of the 13C and 15N labeled, simulated Titan haze aerosols (tholin) by NMR and identified several dominant small molecules in the tholin. Here we report our expanded structural investigation of the bulk of the tholin by more comprehensive NMR study. The NMR results show that the tholin materials are dominated by heavily nitrogenated compounds, in which the macromolecular structures are highly branched polymeric or oligomeric compounds terminated in methyl, amine, and nitrile groups. The structural characteristic suggest that the tholin materials are formed via different copolymerization or incorporation mechanisms of small precursors, such as HCN, CH2dbnd NH, NH3 and C2H2. This study helps to understand the formation process of nitrogenated organic aerosols in Titan's atmosphere and their prebiotic implications.

  16. Simulation of the diurnal variations of the isotope anomaly (?17O) of reactive trace gases (NOx, HOx) and implications for the ?17O of nitrate.

    NASA Astrophysics Data System (ADS)

    Morin, Samuel; Sander, Rolf; Savarino, Joël.

    2010-05-01

    The isotope anomaly of secondary atmospheric species such as nitrate (NO3-) has potential to provide useful constrains on their formation pathways. Indeed, the ?17O of their precursors (NOx, HOx etc.) differs and depends on their interactions with ozone, which is the main source of non-zero ?17O in the atmosphere. Interpreting variations of ?17O in nitrate requires an in-depth understanding of the ?17O of its precursors taking into account non-linear chemical regimes operating under various environmental settings. In addition, the role of isotope exchange reactions must be carefully accounted for. To investigate the relevance of various assessments of the isotopic signature of nitrate production pathways that have recently been proposed in the literature, an atmospheric chemistry box model (MECCA, Sander et al., 2005, ACP)) was used to explicitly compute the diurnal variations of the isotope anomaly of NOx, HOx under several conditions prevailing in the marine boundary layer. ?17O was propagated from ozone to other species (NO, NO2, OH, HO2, RO2, NO3, N2O5, HONO, HNO3, HNO4, H2O2) according to the classical mass-balance equation applied at each time step of the model (30 seconds typically). The model confirms that diurnal variations in ?17O of NOx are well predicted by the photochemical steady-state relationship introduced by Michalski et al. (2003, GRL) during the day, but that at night a different approach must be employed (e.g. « fossilization » of the ?17O of NOx as soon as the photochemical lifetime of NOx drops below ca. 5 minutes). The model also allows to evaluate the impact on ?17O of NOx and nitrate of the frequently made simplifying assumption that ?17O(HOx)=0 permil, with and without mass-independent fractionation during the H+O2-HO2 reaction. Recommendations for the modeling of ?17O of nitrate will be given, based on the extensive model work carried out. In addition, the link between diurnal variations of the ?17O of nitrate precursors and seasonal

  17. Elastic scattering of 17O+208Pb at energies near the Coulomb barrier

    NASA Astrophysics Data System (ADS)

    Torresi, D.; Strano, E.; Mazzocco, M.; Boiano, A.; Boiano, C.; Di Meo, P.; La Commara, M.; Manea, C.; Nicoletto, M.; Grebosz, J.; Guglielmetti, A.; Molini, P.; Parascandolo, C.; Pierroutsakou, D.; Signorini, C.; Soramel, F.; Toniolo, N.; Filipescu, D.; Gheorghe, A.; Glodariu, T.; Jeong, S.; Kim, Y. H.; Lay, J. A.; Miyatake, H.; Pakou, A.; Sgouros, O.; Soukeras, V.; Stroe, L.; Vitturi, A.; Watanabe, Y.; Zerva, K.

    2016-05-01

    Within the frame of the commissioning of a new experimental apparatus EXPADES we undertook the measurement of the elastic scattering angular distribution for the system 17O+208Pb at energy around the Coulomb barrier. The reaction dynamics induced by loosely bound Radioactive Ion Beams is currently being extensively studied [4]. In particular the study of the elastic scattering process allows to obtain direct information on the total reaction cross section of the exotic nuclei. In order to understand the effect of the low binding energy on the reaction mechanism it is important to compare radioactive weakly bound nuclei with stable strongly-bound nuclei. In this framework the study of the 17O+208Pb elastic scattering can be considered to be complementary to a previous measurement of the total reaction cross section for the system 17F+208Pb at energies of 86, 90.4 MeV [5, 6]. The data will be compared with those obtained for the neighboring systems 16,18O+208Pb and others available in literature.

  18. Tracing atmospheric nitrate deposition in a complex semiarid ecosystem using delta17O.

    PubMed

    Michalski, Greg; Meixner, Thomas; Fenn, Mark; Hernandez, Larry; Sirulnik, Abby; Allen, Edith; Thiemens, Mark

    2004-04-01

    The isotopic composition of nitrate collected from aerosols, fog, and precipitation was measured and found to have a large 17O anomaly with delta17O values ranging from 20 percent per thousand to 30% percent per thousand (delta17O = delta17O - 0.52(delta18O)). This 17O anomaly was used to trace atmospheric deposition of nitrate to a semiarid ecosystem in southern California. We demonstrate that the delta17O signal is a conserved tracer of atmospheric nitrate deposition and is a more robust indicator of N deposition relative to standard delta18O techniques. The data indicate that a substantial portion of nitrate found in the local soil, stream, and groundwater is of atmospheric origin and does not undergo biologic processing before being exported from the system. PMID:15112822

  19. Benchmark fragment-based (1)H, (13)C, (15)N and (17)O chemical shift predictions in molecular crystals.

    PubMed

    Hartman, Joshua D; Kudla, Ryan A; Day, Graeme M; Mueller, Leonard J; Beran, Gregory J O

    2016-08-21

    The performance of fragment-based ab initio(1)H, (13)C, (15)N and (17)O chemical shift predictions is assessed against experimental NMR chemical shift data in four benchmark sets of molecular crystals. Employing a variety of commonly used density functionals (PBE0, B3LYP, TPSSh, OPBE, PBE, TPSS), we explore the relative performance of cluster, two-body fragment, and combined cluster/fragment models. The hybrid density functionals (PBE0, B3LYP and TPSSh) generally out-perform their generalized gradient approximation (GGA)-based counterparts. (1)H, (13)C, (15)N, and (17)O isotropic chemical shifts can be predicted with root-mean-square errors of 0.3, 1.5, 4.2, and 9.8 ppm, respectively, using a computationally inexpensive electrostatically embedded two-body PBE0 fragment model. Oxygen chemical shieldings prove particularly sensitive to local many-body effects, and using a combined cluster/fragment model instead of the simple two-body fragment model decreases the root-mean-square errors to 7.6 ppm. These fragment-based model errors compare favorably with GIPAW PBE ones of 0.4, 2.2, 5.4, and 7.2 ppm for the same (1)H, (13)C, (15)N, and (17)O test sets. Using these benchmark calculations, a set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided and their robustness assessed using statistical cross-validation. We demonstrate the utility of these approaches and the reported scaling parameters on applications to 9-tert-butyl anthracene, several histidine co-crystals, benzoic acid and the C-nitrosoarene SnCl2(CH3)2(NODMA)2. PMID:27431490

  20. Investigation of the Herzberg (C1Σ+→A1Π) band system in 12C17O

    NASA Astrophysics Data System (ADS)

    Hakalla, Rafał

    2015-10-01

    The C→A (0,1), (0,2) and (0,3) rovibronic bands of the less-abundant 12C17O isotopologue are studied in high resolution using a high-accuracy dispersive optical spectroscopy in the region of 22,800-26,100 cm-1. Calibration with respect to simultaneously recorded thorium atomic lines, obtained from several overlapped orders of the spectrum in the visible range, as well as a stainless steel hollow-cathode molecular lamp with two anodes, yields an absolute accuracy of wavenumbers measurements of about 0.0025 cm-1 for the CO spectra. All 261 spectra lines of the Herzberg band system in 12C17O, up to Jmax=34, were precisely measured and rotationally analyzed. As a result, the merged rotational constants and rotational equilibrium constants for the C1Σ+ Rydberg state, as well as the band origins, the isotope shifts, the RKR turning points, Franck-Condon factors, relative intensities, and r-centroids of the C→A system in the 12C17O isotopologue were obtained. An experimental RKR potential energy curve and vibrational levels of the C1Σ+ state in 12C17O together with highly excited k3Π, c3Π, E1Π, B1Σ+ and D‧1Σ+ states lying in the region between the first dissociation limit and the ionization potential of CO were plotted. A detailed investigation of possible perturbations that should occur in the C1Σ+(υ=0) Rydberg state of less-abundant 12C17O isotopologue in the close vicinity of the k3Π(υ=1, 2) and c3Π(υ=0) states in the region 92,000 cm-1 was performed. In the A1Π, υ=3 state of 12C17O, extensive, multi-state rotational perturbations were found and analyzed. Also, a global isotopic analysis of the C1Σ+ Rydberg state was carried out in the 12C16O, 12C17O, 13C16O, 12C18O, 13C17O, and 13C18O as well as in 14C16O and 14C18O isotopologues. This analysis enabled us to determine, amongst others, the vibrational equilibrium constants in 12C17O for the C1Σ+ state, to improve these constants in the 12C16O, 13C16O, 12C18O, 13C17O, and 13C18O isotopologues and

  1. Moving NMR

    NASA Astrophysics Data System (ADS)

    Blümich, Bernhard; Casanova, Federico; Danieli, Ernesto; Gong, Qingxia; Greferath, Marcus; Haber, Agnes; Kolz, Jürgen; Perlo, Juan

    2008-12-01

    Initiated by the use of NMR for well logging, portable NMR instruments are being developed for a variety of novel applications in materials testing and process analysis and control. Open sensors enable non-destructive testing of large objects, and small, cup-size magnets become available for high throughput analysis by NMR relaxation and spectroscopy. Some recent developments of mobile NMR are reviewed which delineate the direction into which portable NMR is moving.

  2. Synthesis, spectroscopic (UV-vis and GIAO NMR), crystallographic and theoretical studies of triazine heterocyclic derivatives

    NASA Astrophysics Data System (ADS)

    Khan, Salman A.; Obaid, Abdullah Y.; Al-Harbi, Laila M.; Arshad, Muhammad Nadeem; Şahin, Onur; Ersanlı, Cem Cüneyt; Abdel-Rehman, R. M.; Asiri, Abdullah M.; Hursthouse, Michael B.

    2015-09-01

    This work presents the synthesis and characterization of triazine heterocyclic derivatives. The spectroscopic properties like nuclear magnetic resonance [NMR, (1H and 13C)] were recorded in CDCl3 solution and Ultraviolet-Visible (UV-vis) absorption spectrums of compounds, 5,6-diphenyl-[1,2,4]triazin-3-ylamine (1), (5,6-diphenyl-[1,2,4]triazin-3-yl)-hydrazine (2) and 5,6-diphenyl-4H-[1,2,4] triazine-3-thione (3), were recorded in the range of 200-800 nm, using chloroform as base solvent. Molecular geometry of compounds with triazine heterocyclic derivative in the ground state have been calculated using the density functional theory (DFT) with 6-31G(d,p) basis set and compared with the X-ray experimental data. The calculated results show that the optimized geometry can well reproduce the crystal structures. Total static dipole moment (μ), the average linear polarizability (α) and the first hyperpolarizability (β) values of the investigated molecules have been computed using the same methods. The energetic behavior of compounds in solvent media has been examined using B3LYP method with the 6-31G(d,p) basis set by applying the polarizable continuum model (PCM). The total energy of compounds decreases with increasing polarity of the solvent. Frontier molecular orbitals and the molecular electrostatic potential (MEP), 1H NMR, and 13C NMR of three triazine derivatives were investigated using theoretical calculations. The linear polarizabilities and first hyperpolarizabilities of the studied molecules indicate that the compounds 1-3 can be used as a good nonlinear optical material (NLO). Isotropic chemical shifts were calculated using the gauge-invariant atomic orbital (GIAO) method. Comparison of the NMR chemical shifts, absorption wavelengths with the experimental values revealed that DFT and time dependent-density functional theory (TD-DFT) method produce generally closer to good results.

  3. Tetrahedral site ordering in synthetic gallium albite: A 29Si MAS NMR study

    NASA Astrophysics Data System (ADS)

    Sherriff, Barbara L.; Fleet, Michael E.; Burns, Peter C.

    1991-09-01

    The ordering of Si in the tetrahedral sites of gallium albite (NaGaSi 3O 8) has been studied by MAS NMR and Rietveld structure refinement of X-ray powder diffraction data. Low structural state (ordered) material was annealed at about 800°C under a load pressure of 1 kbar, and by Rietveld refinement has tetrahedral-site occupancies for Si of T1O = 0.24(3), T1m = 0.89(2), T2O = 0.98(2), and T2m = 0.89(2), respectively. Corresponding Si occupancies for high structural state (disordered) material are 0.71(2), 0.78(1), 0.76(2), and 0.74(2), respectively. The 29Si MAS NMR spectra of low gallium albite is equivalent to the three-peak spectrum of natural (Amelia) albite, with resonances at -89.6, -96.4, and -104.2 ppm but with relative peak areas of 0.79:1.0:0.77. The tetrahedral-site occupancies derived from the MAS NMR spectrum are in good agreement with those obtained by Rietveld refinement and, in particular, indicate that the -96.4 ppm peak must correspond to Si in T2O. This is the first independent assignment of the 29Si peak at -96 ppm in the spectrum of ordered albite to the T2O site. A peak at -96 ppm is also resolved in the spectrum of high gallium albite. The systematic differences in peak position between the 29Si MAS NMR spectra of low gallium albite and those of Amelia albite cannot be explained simply by the direct replacement of Al by Ga, without a change in angle at the bridging oxygen atoms.

  4. Structure and motion of phospholipids in human plasma lipoproteins. A sup 31 P NMR study

    SciTech Connect

    Fenske, D.B.; Chana, R.S.; Parmar, Y.I.; Treleaven, W.D.; Cushley, R.J. )

    1990-04-24

    The structure and motion of phospholipids in human plasma lipoproteins have been studied by using {sup 31}P NMR. Lateral diffusion coefficients, D{sub T}, obtained from the viscosity dependence of the {sup 31}P NMR line widths, were obtained for very low density lipoprotein (VLDL), low-density lipoprotein (LDL), high-density lipoproteins (HDL{sub 2}, HDL{sub 3}), and egg PC/TO microemulsions at 25{degree}C, for VLDL at 40{degree}C, and for LDL at 45{degree}C. In order to prove the orientation and/or order of the phospholipid head-group, estimates of the residual chemical shift anistropy, {Delta}{sigma}, have been obtained for all the lipoproteins and the microemulsions from the viscosity and field dependence for the {sup 31}P NMR line widths. These results suggest differences in the orientation and/or ordering of the head-group in the HDLs. The dynamic behavior of the phosphate moiety in LDL and HDL{sub 3} has been obtained from the temperature dependence of the {sup 31}P spin-lattice relaxation rates. Values of the correlation time for phosphate group reorientation and the activation energy for the motion are nearly identical in LDL and HDL{sub 3} and are similar to values obtained for phospholipid bilayers. This argues against long-lived protein-lipid interactions being the source of either the slow diffusion in LDL or the altered head-group orientation in the HDLs.

  5. Novel electrolytes for use in new and improved batteries: An NMR study

    NASA Astrophysics Data System (ADS)

    Berman, Marc B.

    This thesis focuses on the use of nuclear magnetic resonance (NMR) spectroscopy in order to study materials for use as electrolytes in batteries. The details of four projects are described in this thesis as well as a brief theoretical background of NMR. Structural and dynamics properties were determined using several NMR techniques such as static, MAS, PFG diffusion, and relaxation to understand microscopic and macroscopic properties of the materials described within. Nuclei investigate were 1H, 2H, 7Li, 13C, 19F, 23Na, and 27Al. The first project focuses on an exciting new material to be used as a solid electrolyte membrane. T. The second project focuses on the dynamics of ionic liquid-solvent mixtures and their comparison to molecular dynamics computer simulations. The third project involves a solvent-free film containing NaTFSI salt mixed in to PEO for use in sodium-ion batteries. This final project focuses on a composite electrolyte consisting of a ceramic and solid: LiI:PEO:LiAlO2.

  6. Rotational diffusion of colloid spheres in concentrated suspensions studied by deuteron NMR

    NASA Astrophysics Data System (ADS)

    Kanetakis, J.; Töautlle, A.; Sillescu, H.

    1997-03-01

    We present a study of the application of deuteron-nuclear magnetic resonance spectroscopy (NMR) to the investigation of the rotational diffusion of spherical colloidal particles. We performed NMR pulse experiments on colloidal suspensions of polystyrene latex spheres in water-glycerol mixtures in a wide range of particle volume fractions φ from the dilute suspension up to φ=0.504. We have analyzed the stimulated echo NMR signal in the time domain. The full shape of the orientational correlation function deviates from an exponential behavior in the whole φ range examined. We evaluate the rotational diffusion coefficient and calculate its φ dependence up to the φ2 term in view of the theory proposed recently [V. Degiorgio, R. Piazza, and R. B. Jones, Phys. Rev. E 52, 2707 (1995)], which considers the effect of two- and three-body hydrodynamic interactions upon particle reorientation. We find considerable slowing down of sphere reorientation for φ>=0.2. The agreement between experimental results and theoretical considerations is satisfactory.

  7. A 140 GHz pulsed EPR/212 MHz NMR spectrometer for DNP studies

    NASA Astrophysics Data System (ADS)

    Smith, Albert A.; Corzilius, Björn; Bryant, Jeffrey A.; DeRocher, Ronald; Woskov, Paul P.; Temkin, Richard J.; Griffin, Robert G.

    2012-10-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz (1H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE011 resonator acts as both an NMR coil and microwave resonator, and a double balanced (1H, 13C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S = 1/2 electron spins, 100 kHz on 1H, and 50 kHz on 13C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (⩾3 T).

  8. [sup 31]P NMR study of immobilized artificial membrane surfaces. Structure and dynamics of immobilized phospholipids

    SciTech Connect

    Qiu, X.; Pidgeon, C. )

    1993-11-25

    Chromatography surfaces were prepared by immobilizing a single-chain ether phospholipid at approximately a monolayer density on silica particles. The chromatography particles are denoted as [sup ether]IAM.PC[sup C10/C3], and they are stable to all solvents. The structure and dynamics of the interphase created by immobilizing phospholipids on silica particles were studied by [sup 31]P NMR methods. [sup ether]IAM.PC[sup C10/C3] spontaneously wets when suspended in both aqueous and organic solvents, and [sup 31]P NMR spectra were obtained in water, methanol, chloroform, acetonitrile, and acetone. [sup 31]P NMR spectra were subjected to line-shape analysis. From line-shape analysis, the correlation times for rapid internal motion ([tau]-PLL) and wobbling ([tau]-PRP) of the phospholipid headgroup were calculated for each solvent. Immobilized phospholipid headgroups comprising the IAM interfacial region undergo rapid reorientation similar to the case of the phospholipids forming liposome membranes with [tau]-PLL approximately 1 ns. Phospholipids in liposome membranes exhibit slower wobbling motion ([tau]-PRP approximately 1 ms) in the plane of the membrane. However, the immobilized phospholipids on [sup ether]IAM.PC[sup C10/C3] surfaces wobble with correlation times [tau]-PRP that depend on the solvent bathing the [sup ether]IAM.PC[sup C10/C3] surface. 41 refs., 9 figs., 2 tabs.

  9. (13)C NMR Studies, Molecular Order, and Mesophase Properties of Thiophene Mesogens.

    PubMed

    Veeraprakash, B; Lobo, Nitin P; Narasimhaswamy, T

    2015-12-01

    Three-ring mesogens with a core comprising thiophene linked to one phenyl ring directly and to the other via flexible ester are synthesized with terminal alkoxy chains to probe the mesophase properties and find the molecular order. The phenyl thiophene link in the core offers a comparison of the mesophase features with the molecular shape of the mesogen. The synthesized mesogens display enantiotropic polymesomorphism and accordingly nematic, smectic A, smectic C and smectic B mesophases are perceived depending upon the terminal chain length. For some of the homologues, monotropic higher order smectic phases such as smectic F and crystal E are also witnessed. The existence of polymesomorphism are originally observed by HOPM and DSC and further confirmed by powder X-ray diffraction studies. For the C8 homologue, high resolution solid state (13)C NMR spectroscopy is employed to find the molecular structure in the liquid crystalline phase and using the 2D SLF technique, the (13)C-(1)H dipolar couplings are extracted to calculate the order parameter. By comparing the ratio of local order of thiophene as well as phenyl rings, we establish the bent-core shape of the mesogen. Importantly, for assigning the carbon chemical shifts of the core unit of aligned C8 mesogen, the (13)C NMR measured in mesophase of the synthetic intermediate is employed. Thus, the proposed approach addresses the key step in the spectral assignment of target mesogens with the use of (13)C NMR data of mesomorphic intermediate. PMID:26551439

  10. Intrinsic Proton NMR Studies of Mg(OH)2 and Ca(OH)2

    NASA Astrophysics Data System (ADS)

    Itoh, Yutaka; Isobe, Masahiko

    2016-09-01

    We studied the short proton free induction decay signals and the broad 1H NMR spectra of Mg(OH)2 and Ca(OH)2 powders at 77-355 K and 42 MHz using pulsed NMR techniques. Using a Gaussian-type back extrapolation procedure for the obscured data of the proton free induction decay signals, we obtained more precise values of the second moments of the Fourier-transformed broad NMR spectra than those in a previous report [Y. Itoh and M. Isobe, J. Phys. Soc. Jpn. 84, 113601 (2015)] and compared with the theoretical second moments. The decrease in the second moment could not account for the large decrease in the magnitude of the intrinsic proton spin-lattice relaxation rate 1/T1 from Mg(OH)2 to Ca(OH)2. The analysis of 1/T1 ∝ exp(-Eg/kBT) with Eg ˜ 0.01 eV points to a local hopping mechanism, and that of 1/T1 ∝ Tn with n ˜ 0.5 points to an anharmonic rattling mechanism.

  11. Molecular ordering of mixed surfactants in mesoporous silicas: A solid-state NMR study

    SciTech Connect

    Kobayashi, Takeshi; Mao, Kanmi; Wang, Shy-Guey; Lin, Victor S.-Y.; Pruski, Marek

    2011-02-17

    The use of mixed surfactants in the synthesis of mesoporous silica nanoparticles (MSNs) is of importance in the context of adjusting pore structures, sizes and morphologies. In the present study, the arrangement of molecules in micelles produced from a mixture of two surfactants, cetyltrimethylammonium bromide (CTAB) and cetylpyridinium bromide (CPB) was detailed by solid-state NMR spectroscopy. Proximities of methyl protons in the trimethylammonium headgroup of CTAB and protons in the pyridinium headgroup of CPB were observed under fast magic angle spinning (MAS) by {sup 1}H-{sup 1}H double quantum (DQ) MAS NMR and NOESY. This result suggested that CTAB and CPB co-exist in the pores without forming significant monocomponent domain structures. {sup 1}H-{sup 29}Si heteronuclear correlation (HETCOR) NMR showed that protons in the headgroups of CTAB are in closer proximity to the silica surface than those in the CPB headgroups. The structural information obtained in this investigation leads to better understanding of the mechanisms of self-assembly and their role in determining the structure and morphology of mesoporous materials.

  12. A 140 GHz Pulsed EPR/212 MHz NMR Spectrometer for DNP Studies

    PubMed Central

    Smith, Albert A.; Corzilius, Björn; Bryant, Jeffrey A.; DeRocher, Ronald; Woskov, Paul P.; Temkin, Richard J.; Griffin, Robert G.

    2012-01-01

    We described a versatile spectrometer designed for the study of dynamic nuclear polarization (DNP) at low temperatures and high fields. The instrument functions both as an NMR spectrometer operating at 212 MHz (1H frequency) with DNP capabilities, and as a pulsed-EPR operating at 140 GHz. A coiled TE011 resonator acts as both an NMR coil and microwave resonator, and a double balanced (1H, 13C) radio frequency circuit greatly stabilizes the NMR performance. A new 140 GHz microwave bridge has also been developed, which utilizes a four-phase network and ELDOR channel at 8.75 GHz, that is then multiplied and mixed to obtain 140 GHz microwave pulses with an output power of 120 mW. Nutation frequencies obtained are as follows: 6 MHz on S = ½ electron spins, 100 kHz on 1H, and 50 kHz on 13C. We demonstrate basic EPR, ELDOR, ENDOR, and DNP experiments here. Our solid effect DNP results demonstrate an enhancement of 144 and sensitivity gain of 310 using OX063 trityl at 80 K and an enhancement of 157 and maximum sensitivity gain of 234 using Gd-DOTA at 20 K, which is significantly better performance than previously reported at high fields (>3 T). PMID:22975246

  13. Studying metal ion binding properties of a three-way junction RNA by heteronuclear NMR.

    PubMed

    Bartova, Simona; Pechlaner, Maria; Donghi, Daniela; Sigel, Roland K O

    2016-06-01

    Self-splicing group II introns are highly structured RNA molecules, containing a characteristic secondary and catalytically active tertiary structure, which is formed only in the presence of Mg(II). Mg(II) initiates the first folding step governed by the κζ element within domain 1 (D1κζ). We recently solved the NMR structure of D1κζ derived from the mitochondrial group II intron ribozyme Sc.ai5γ and demonstrated that Mg(II) is essential for its stabilization. Here, we performed a detailed multinuclear NMR study of metal ion interactions with D1κζ, using Cd(II) and cobalt(III)hexammine to probe inner- and outer-sphere coordination of Mg(II) and thus to better characterize its binding sites. Accordingly, we mapped (1)H, (15)N, (13)C, and (31)P spectral changes upon addition of different amounts of the metal ions. Our NMR data reveal a Cd(II)-assisted macrochelate formation at the 5'-end triphosphate, a preferential Cd(II) binding to guanines in a helical context, an electrostatic interaction in the ζ tetraloop receptor and various metal ion interactions in the GAAA tetraloop and κ element. These results together with our recently published data on Mg(II) interaction provide a much better understanding of Mg(II) binding to D1κζ, and reveal how intricate and complex metal ion interactions can be. PMID:26880094

  14. Topotecan dynamics, tautomerism and reactivity--1H/13C NMR and ESI MS study.

    PubMed

    Hyz, Karolina; Kawecki, Robert; Bednarek, Elzbieta; Bocian, Wojciech; Sitkowski, Jerzy; Kozerski, Lech

    2010-08-01

    Topotecan (TPT) is in clinical use as an antitumor agent, hycamtin. Because of this, it requires both biologically and chemically useful information to be available. TPT acts by binding to the covalent complex formed by nicked DNA and topoisomerase I. This has a poisonous effect since inserted into the single-strand nick and TPT inhibits its religation. We used NMR to trace TPT dynamics, tautomerism and solvolysis products in various solvents and conditions. Chemical stability was assessed in methanol and DMSO as compared to water, and the regioselectivity of the N- and O-methylation was studied using various alkylating agents. The reaction products of quaternization of the nitrogen atom and methylation of the oxygen atom were characterized by means of ESI MS, (1)H/(13)C-HMBC and -HSQCAD NMR. We have focused on the NMR characterization of TPT with an anticipation that its aggregation, tumbling properties and the intramolecular dipolar interactions will be a common feature for other compounds described in this article. These features can also be useful in tracing the interactions of this class of topoisomerase I (TopoI) poisons with DNA. Moreover, the results explained shed light on the recently disclosed problem of lack of stability of TPT in the heart tissue homogenate samples using the analytical assays developed for this class of compounds carried out in the presence of methanol. PMID:20623719

  15. Measurement of δ18O, δ17O, and 17O-excess in water by off-axis integrated cavity output spectroscopy and isotope ratio mass spectrometry.

    PubMed

    Berman, Elena S F; Levin, Naomi E; Landais, Amaelle; Li, Shuning; Owano, Thomas

    2013-11-01

    Stable isotopes of water have long been used to improve understanding of the hydrological cycle, catchment hydrology, and polar climate. Recently, there has been increasing interest in measurement and use of the less-abundant (17)O isotope in addition to (2)H and (18)O. Off-axis integrated cavity output spectroscopy (OA-ICOS) is demonstrated for accurate and precise measurements δ(18)O, δ(17)O, and (17)O-excess in liquid water. OA-ICOS involves no sample conversion and has a small footprint, allowing measurements to be made by researchers collecting the samples. Repeated (514) high-throughput measurements of the international isotopic reference water standard Greenland Ice Sheet Precipitation (GISP) demonstrate the precision and accuracy of OA-ICOS: δ(18)OVSMOW-SLAP = -24.74 ± 0.07‰ (1σ) and δ(17)OVSMOW-SLAP = -13.12 ± 0.05‰ (1σ). For comparison, the International Atomic Energy Agency (IAEA) value for δ(18)OVSMOW-SLAP is -24.76 ± 0.09‰ (1σ) and an average of previously reported values for δ(17)OVSMOW-SLAP is -13.12 ± 0.06‰ (1σ). Multiple (26) high-precision measurements of GISP provide a (17)O-excessVSMOW-SLAP of 23 ± 10 per meg (1σ); an average of previously reported values for (17)O-excessVSMOW-SLAP is 22 ± 11 per meg (1σ). For all these OA-ICOS measurements, precision can be further enhanced by additional averaging. OA-ICOS measurements were compared with two independent isotope ratio mass spectrometry (IRMS) laboratories and shown to have comparable accuracy and precision as the current fluorination-IRMS techniques in δ(18)O, δ(17)O, and (17)O-excess. The ability to measure accurately δ(18)O, δ(17)O, and (17)O-excess in liquid water inexpensively and without sample conversion is expected to increase vastly the application of δ(17)O and (17)O-excess measurements for scientific understanding of the water cycle, atmospheric convection, and climate modeling among others. PMID:24032448

  16. Curie-type paramagnetic NMR relaxation in the aqueous solution of Ni(II).

    PubMed

    Mareš, Jiří; Hanni, Matti; Lantto, Perttu; Lounila, Juhani; Vaara, Juha

    2014-04-21

    Ni(2+)(aq) has been used for many decades as a model system for paramagnetic nuclear magnetic resonance (pNMR) relaxation studies. More recently, its magnetic properties and also nuclear magnetic relaxation rates have been studied computationally. We have calculated electron paramagnetic resonance and NMR parameters using quantum-mechanical (QM) computation of molecular dynamics snapshots, obtained using a polarizable empirical force field. Statistical averages of hyperfine coupling, g- and zero-field splitting tensors, as well as the pNMR shielding terms, are compared to the available experimental and computational data. In accordance with our previous work, the isotropic hyperfine coupling as well as nuclear shielding values agree well with experimental measurements for the (17)O nuclei of water molecules in the first solvation shell of the nickel ion, whereas larger deviations are found for (1)H centers. We report, for the first time, the Curie-type contribution to the pNMR relaxation rate using QM calculations together with Redfield relaxation theory. The Curie relaxation mechanism is analogous to chemical shift anisotropy relaxation, well-known in diamagnetic NMR. Due to the predominance of other types of paramagnetic relaxation mechanisms for this system, it is possible to extract the Curie term only computationally. The Curie mechanism alone would result in around 16 and 20 s(-1) of relaxation rates (R1 and R2 respectively) for the (1)H nuclei of water molecules bonded to the Ni(2+) center, in a magnetic field of 11.7 T. The corresponding (17)O relaxation rates are around 33 and 38 s(-1). We also report the Curie contribution to the relaxation rate for molecules beyond the first solvation shell in a 1 M solution of Ni(2+) in water. PMID:24595457

  17. Applications of carbon-13 and sodium-23 NMR in the study of plants, animal, and human cells

    SciTech Connect

    Sillerud, L.O.; Heyser, J.W.; Han, C.H.; Bitensky, M.W.

    1984-01-01

    Carbon-13 and sodium-23 NMR have been applied to the study of a variety of plant, animal and human cell types. Sodium NMR, in combination with dysprosium shift reagents, has been used to monitor sodium transport kinetics in salt-adapted, and non-adapted cells of P. milliaceum and whole D. spicata plants. The sodium content of human erythrocytes and leukemic macrophages was measured. Carbon-13 NMR was used to determine the structure and metabolism of rat epididymal fat pad adipocytes in real time. Insulin and isoproterenol-stimulated triacylglycerol turnover could be monitored in fat cell suspensions. (1-/sup 13/C) glucose was used as a substrate to demonstrate futile metabolic cycling from glucose to glycerol during lypolysis. Cell wall polysaccharide synthesis was followed in suspensions of P. milliaceum cells using (1-/sup 13/C) glucose as a precursor. These results illustrate the wide range of living systems which are amenable to study with NMR. 14 refs., 21 figs.

  18. {sup 7}Li NMR study of poly(p-phenylene) electrochemically doped with lithium

    SciTech Connect

    Shteinberg, V.G.; Shumm, B.A.; Zueva, A.F.

    1994-09-01

    Lithium ions in electrochemically doped poly(p-phenylene) (PPP) were studied by {sup 7}Li NMR. Two types of lithium cations exhibiting different mobility are found to exist. The fraction of more mobile cations increases with temperature but does not exceed 0.5. In the PPP{sup -}-Li{sup +} system, ion mobility is considerably lower than that found in the previously studied PPP{sup +}-AsF{sub 6}{sup -} (BF{sub 4}{sup -}) system, and up to 400 K no chemical reactions of polymer destruction occur.

  19. Can we determine what controls the spatio-temporal distribution of d-excess and 17O-excess in precipitation using the LMDZ general circulation model?

    NASA Astrophysics Data System (ADS)

    Risi, C.; Landais, A.; Winkler, R.; Vimeux, F.

    2013-09-01

    Combined measurements of the H218O and HDO isotopic ratios in precipitation, leading to second-order parameter D-excess, have provided additional constraints on past climates compared to the H218O isotopic ratio alone. More recently, measurements of H217O have led to another second-order parameter: 17O-excess. Recent studies suggest that 17O-excess in polar ice may provide information on evaporative conditions at the moisture source. However, the processes controlling the spatio-temporal distribution of 17O-excess are still far from being fully understood. We use the isotopic general circulation model (GCM) LMDZ to better understand what controls d-excess and 17O-excess in precipitation at present-day (PD) and during the last glacial maximum (LGM). The simulation of D-excess and 17O-excess is evaluated against measurements in meteoric water, water vapor and polar ice cores. A set of sensitivity tests and diagnostics are used to quantify the relative effects of evaporative conditions (sea surface temperature and relative humidity), Rayleigh distillation, mixing between vapors from different origins, precipitation re-evaporation and supersaturation during condensation at low temperature. In LMDZ, simulations suggest that in the tropics convective processes and rain re-evaporation are important controls on precipitation D-excess and 17O-excess. In higher latitudes, the effect of distillation, mixing between vapors from different origins and supersaturation are the most important controls. For example, the lower d-excess and 17O-excess at LGM simulated at LGM are mainly due to the supersaturation effect. The effect of supersaturation is however very sensitive to a parameter whose tuning would require more measurements and laboratory experiments. Evaporative conditions had previously been suggested to be key controlling factors of d-excess and 17O-excess, but LMDZ underestimates their role. More generally, some shortcomings in the simulation of 17O-excess by LMDZ

  20. NMR STUDIES OF LIQUID CRYSTALS AND MOLECULES DISSOLVED IN LIQUID CRYSTAL SOLVENTS

    SciTech Connect

    Drobny, G.P.

    1982-11-01

    This thesis describes several studies in which nuclear magnetic resonance (nmr) spectroscopy has been used to probe the structure, orientation and dynamics of liquid crystal mesogens and molecules dissolved in liquid crystalline phases. In addition, a modern high field nmr spectrometer is described which has been used to perform such nmr studies. Chapter 1 introduces the quantum mechanical formalisms used throughout this thesis and briefly reviews the fundamentals of nuclear spin physics and pulsed nmr spectroscopy. First the density operator is described and a specific form for the canonical ensemble is derived. Then Clebsch-Gordon coefficients, Wigner rotation matrices, and irreducible tensor operators are reviewed. An expression for the equilibrium (Curie) magnetization is obtained and the linear response of a spin system to a strong pulsed r.f. irradiation is described. Finally, the spin interaction Hamiltonians relevant to this work are reviewed together with their truncated forms. Chapter 2 is a deuterium magnetic resonance study of two 'nom' liquid crystals which possess several low temperature mesomorphic phases. Specifically, deuterium quadrupolar echo spectroscopy is used to determine the orientation of the liquid crystal molecules in smectic phases, the changes in molecular orientation and motion that occur at smectic-smectic phase transitions, and the order of the phase transitions. For both compounds, the phase sequence is determined to be isotropic, nematic, smectic A, smectic C, smectic B{sub A}, smectic B{sub C}, and crystalline. The structure of the smectic A phase is found to be consistent with the well-known model of a two dimensional liquid in which molecules are rapidly rotating about their long axes and oriented at right angles to the plane of the layers. Molecules in the smectic C phase are found to have their long axes tilted with respect to the layer normal, and the tilt angle is temperature dependent, increasing from zero at the smectic A

  1. Mixed Aggregates of the Dilithiated Koga Tetraamine: NMR Spectroscopic and Computational Studies.

    PubMed

    Ma, Yun; Mack, Kyle A; Liang, Jun; Keresztes, Ivan; Collum, David B; Zakarian, Armen

    2016-08-16

    A combination of (1) H, (6) Li, (13) C, and (15) N NMR spectroscopies and density functional theory computations explores the formation of mixed aggregates by a dilithium salt of a C2 -symmetric chiral tetraamine (Koga's base). Lithium halides, acetylides, alkoxides, and monoalkylamides form isostructural trilithiated mixed aggregates with few exceptions. (6) Li-(13) C and (6) Li-(15) N couplings reveal heretofore undetected transannular contacts (laddering) with lithium acetylides and lithium monoalkylamides. Marked temperature-dependent (15) N chemical shifts seem to be associated with this laddering. Computational studies shed light on the general structures of the aggregates, their penchant for laddering, and the stereochemical consequences of aggregation. PMID:27435147

  2. Solid state NMR study of dietary fiber powders from aronia, bilberry, black currant and apple.

    PubMed

    Wawer, I; Wolniak, M; Paradowska, K

    2006-09-01

    13C CPMAS NMR spectra of dietary fiber powders from aronia (chokeberry), bilberry, black currant and apple were recorded. The spectra are complex owing to superposition of resonances from different polysaccharides and polyphenolic compounds. Standard, dipolar dephased and the TH(1rho) partially relaxed spectra enabled the identification of several constituents: microcrystalline cellulose, pectins, lignins, cutin-like polymers and condensed tannins. The fiber powders obtained from berries contain significant amounts of anthocyanins, as indicated by their dark violet color, but not verified by chemical shifts. The anthocyanin-rich extract from aronia berries and its major components, cyanidin-3-O-galactoside and (-)epicatechin were also studied. PMID:16750905

  3. 1H-NMR study of the spin dynamics of fine superparamagnetic nanoparticles

    SciTech Connect

    Bordonali, L.; Furukawa, Y.; Kraken, M.; Litterst, F.J.; Sangregorio, C.; Casula, M.F.; Lascialfari, A.

    2012-05-25

    We report a broadband 1H-NMR study of the temperature spin dynamics of nearly monodisperse dextran-coated γ-Fe2O3 magnetic nanoparticles. We observed a maximum in T1−1(T) that decreases in amplitude and shifts toward higher temperatures with increasing field. We suggest that this is related to the progressive superparamagnetic spin blocking of the ferrite core. The data can be explained by assuming a single electronic spin-spin correlation time and introducing a field-dependent distribution of anisotropy energy barriers.

  4. Xenon-129 NMR study of the microporous structure of clays and pillared clays

    SciTech Connect

    Tsiao, C.; Carrado, K.A.

    1990-01-01

    {sup 129}Xe NMR studies have been carried out using xenon gas adsorbed in clays and pillared clays. Data from the measurements provide information on the pore structure of clays before and after pillaring. The results indicate that the effective pore diameter of montmorillonite increases, for example, from 5.4 {Angstrom} to 8.0 {Angstrom} after pillaring cheto-montmorillonite with aluminum polyoxohydroxy Keggin cations. The data are consistent with X-ray powder diffraction results, which show a corresponding increase in the interlamellar gallery height from 5.6 {Angstrom} to 8.4 {Angstrom}.

  5. In vivo NMR study of yeast fermentative metabolism in the presence of ferric irons.

    PubMed

    Ricci, Maso; Martini, Silvia; Bonechi, Claudia; Braconi, Daniela; Santucci, Annalisa; Rossi, Claudio

    2011-03-01

    Mathematical modelling analysis of experimental data, obtained with in vivo NMR spectroscopy and 13C-labelled substrates, allowed us to describe how the fermentative metabolism in Saccharomyces cerevisiae, taken as eukaryotic cell model, is influenced by stress factors. Experiments on cellular cultures subject to increasing concentrations of ferric ions were conducted in order to study the effect of oxidative stress on the dynamics of the fermentative process. The developed mathematical model was able to simulate the cellular activity, the metabolic yield and the main metabolic fluxes occurring during fermentation and to describe how these are modulated by the presence of ferric ions. PMID:21451251

  6. Synthesis of a new quaternary phosphonium salt: NMR study of the conformational structure and dynamics.

    PubMed

    Aganova, Oksana V; Galiullina, Leysan F; Aganov, Albert V; Shtyrlin, Nikita V; Pugachev, Mikhail V; Strel'nik, Alexey D; Koshkin, Sergey A; Shtyrlin, Yurii G; Klochkov, Vladimir V

    2016-04-01

    A novel phosphonium salt based on pyridoxine was synthesized. Conformational analysis of the compound in solution was performed using dynamic NMR experiments and calculations. The obtained results revealed some differences in the conformational transitions and the energy parameters of the conformational exchange of the studied compound in comparison to previously reported data for other phosphorus-containing pyridoxine derivatives. It was shown that increasing the substituent at the C-11 carbon leads to greater differences in the populations of stable states and the corresponding equilibrium energies. Copyright © 2015 John Wiley & Sons, Ltd. PMID:26661926

  7. Low-lying 1- and 2+ states in 124Sn via inelastic scattering of 17O

    NASA Astrophysics Data System (ADS)

    Pellegri, L.; Bracco, A.; Crespi, F. C. L.

    2016-05-01

    The γ decay of low-lying 1-and 2+ states up to the neutron separation energy in 124Sn populate by the inelastic scattering of 17O was measured. The Angular distributions were measured both for the γ rays and the scattered 17O ions. The results are presented.

  8. UV-visible and (1)H-(15)N NMR spectroscopic studies of colorimetric thiosemicarbazide anion sensors.

    PubMed

    Farrugia, Kristina N; Makuc, Damjan; Podborska, Agnieszka; Szaciłowski, Konrad; Plavec, Janez; Magri, David C

    2015-02-14

    Four model thiosemicarbazide anion chemosensors containing three N-H bonds, substituted with phenyl and/or 4-nitrophenyl units, were synthesised and studied for their anion binding abilities with hydroxide, fluoride, acetate, dihydrogen phosphate and chloride. The anion binding properties were studied in DMSO and 9 : 1 DMSO-H2O by UV-visible absorption and (1)H/(13)C/(15)N NMR spectroscopic techniques and corroborated with DFT studies. Significant changes were observed in the UV-visible absorption spectra with all anions, except for chloride, accompanied by dramatic colour changes visible to the naked eye. These changes were determined to be due to the deprotonation of the central N-H proton and not due to hydrogen bonding based on (1)H/(15)N NMR titration studies with acetate in DMSO-d6-0.5% water. Direct evidence for deprotonation was confirmed by the disappearance of the central thiourea proton and the formation of acetic acid. DFT and charge distribution calculations suggest that for all four compounds the central N-H proton is the most acidic. Hence, the anion chemosensors operate by a deprotonation mechanism of the central N-H proton rather than by hydrogen bonding as is often reported. PMID:25451865

  9. Solid-state NMR studies of proteins immobilized on inorganic surfaces

    SciTech Connect

    Shaw, Wendy J.

    2015-09-01

    Solid state NMR is the primary tool for studying the quantitative, site-specific structure, orientation, and dynamics of biomineralization proteins under biologically relevant conditions. Two calcium phosphate proteins, statherin and leucine rich amelogenin protein (LRAP), have been studied in depth and have different features, challenging our ability to extract design principles. More recent studies of the significantly larger full-length amelogenin represent a challenging but necessary step to ultimately investigate the full diversity of biomineralization proteins. Interactions of amino acids and silaffin peptide with silica are also being studied, along with qualitative studies of proteins interacting with calcium carbonate. Dipolar recoupling techniques have formed the core of the quantitative studies, yet, the need for isolated spin pairs makes this approach costly and time intensive. The use of multi-dimensional techniques is advancing, methodology which, despite its challenges with these difficult-to-study proteins, will continue to drive future advancements in this area..

  10. Solid-state NMR studies of proteins immobilized on inorganic surfaces

    DOE PAGESBeta

    Shaw, Wendy J.

    2014-10-29

    Solid state NMR is the primary tool for studying the quantitative, site-specific structure, orientation, and dynamics of biomineralization proteins under biologically relevant conditions. Two calcium phosphate proteins, statherin and leucine rich amelogenin protein (LRAP), have been studied in depth and have different features, challenging our ability to extract design principles. More recent studies of the significantly larger full-length amelogenin represent a challenging but necessary step to ultimately investigate the full diversity of biomineralization proteins. Interactions of amino acids and silaffin peptide with silica are also being studied, along with qualitative studies of proteins interacting with calcium carbonate. Dipolar recoupling techniquesmore » have formed the core of the quantitative studies, yet, the need for isolated spin pairs makes this approach costly and time intensive. The use of multi-dimensional techniques is advancing, methodology which, despite its challenges with these difficult-to-study proteins, will continue to drive future advancements in this area.« less

  11. Solid-state NMR studies of proteins immobilized on inorganic surfaces

    SciTech Connect

    Shaw, Wendy J.

    2014-10-29

    Solid state NMR is the primary tool for studying the quantitative, site-specific structure, orientation, and dynamics of biomineralization proteins under biologically relevant conditions. Two calcium phosphate proteins, statherin and leucine rich amelogenin protein (LRAP), have been studied in depth and have different features, challenging our ability to extract design principles. More recent studies of the significantly larger full-length amelogenin represent a challenging but necessary step to ultimately investigate the full diversity of biomineralization proteins. Interactions of amino acids and silaffin peptide with silica are also being studied, along with qualitative studies of proteins interacting with calcium carbonate. Dipolar recoupling techniques have formed the core of the quantitative studies, yet, the need for isolated spin pairs makes this approach costly and time intensive. The use of multi-dimensional techniques is advancing, methodology which, despite its challenges with these difficult-to-study proteins, will continue to drive future advancements in this area.

  12. Combined NMR and PDF studies of positive electrode materials for rechargeable lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Breger, Julien

    Layered lithium nickel manganese oxides are promising, inexpensive and nontoxic alternative positive electrodes materials to the commercial LiCoO 2 electrode used in Li-ion batteries. Among these materials, Li(NiMn) 0.5O2 is particularly attractive due to its high theoretical capacity (280 mAh/g). The motivation for the research presented here was to understand the detailed long-range and short-range structure of these materials, particularly Li(NiMn)0.5O2, both as-synthesised and upon cycling. It is indeed important to know what the cation environments are, especially for the Li ions, since they strongly affect the electrochemical performance. The local environments and short-range ordering of Li(NiMn)0.5O 2, a potential Li-ion battery positive electrode material, were investigated by using a combination of X-ray and neutron diffraction and isotopic substitution (NDIS) techniques, 6Li Magic Angle Spinning (MAS) NMR spectroscopy and, for the first time, X-ray and neutron Pair Distribution Function (PDF) analysis, associated with Reverse Monte Carlo (RMC) calculations. Two Li(NiMn) 0.5O2 samples were studied in detail: one obtained from regular solid-state synthesis (SS), and another one obtained from ion-exchange routes (IE). 6Li MAS NMR experiments showed less Li/Ni site exchange (between the Li and the Ni/Mn layers) for the IE compound than for the SS compound, explaining its improved Li diffusivity and rate capability. For the SS compound, the Ni/Ni and Mn/Mn repulsion seen by PDF/RMC and the Li/Mn proximity seen by NMR were consistent with an ordering scheme intermediate between the ideal structures proposed so far (the "honey-comb" and "flower" structures). Ordering of Ni and Mn atoms in the transition metal layers was also detected in IE-Li(NiMn)0.5O2: Ni atoms tend to be surrounded by more Mn atoms in the first coordination shell, while the second coordination shell shows that zigzag ordering scheme is preferred over the chain. Ex-situ neutron diffraction

  13. Ab initio and DFT study of 31P-NMR chemical shifts of sphingomyelin and dihydrosphingomyelin lipid molecule

    NASA Astrophysics Data System (ADS)

    Sugimori, K.; Kawabe, H.; Nagao, H.; Nishikawa, K.

    One of the phospholipids, sphingomyelin (SM, N-acyl-sphingosine-1-phosphorylcholine) is the most abundant component of mammalian membranes in brain, nervous tissues, and human ocular lens. It plays an important role for apoptosis, aging, and signal transduction. Recently, Yappert and coworkers have shown that human lens sphingomyelin and its hydrogenated derivative, dihydrosphingomyelin (DHSM) are interacted with Ca2+ ions to develop human cataracts. Previously, we have investigated conformational differences between an isolated SM/DHSM molecule and Ca2+-coordinated form by using density functional theory (DFT) for geometry optimization and normal mode analysis. As a result, one of stable conformers of SMs has a hydrogen bonding between hydroxyl group and phosphate group, whereas another conformer has a hydrogen bonding between hydroxyl and phosphate amide group. In this study, 31P-Nuclear Magnetic Resonance (NMR) shielding constants of the obtained conformers are investigated by using ab initio and DFT with NMR-gauge invariant atomic orbitals (NMR-GIAO) calculations. The experimental 31P-NMR chemical shifts of SMs and DHSMs have significant small value around 0.1 ppm. We consider the relative conformational changes between SMs and DHSMs affect the slight deviations of 31P-NMR chemical shifts, and discuss intramolecular hydrogen bondings and the solvent effect in relation to NMR experimental reference.

  14. 1H NMR study of proton dynamics in the inorganic solid acid Rb3 H( SO4 )2

    NASA Astrophysics Data System (ADS)

    Suzuki, Koh-Ichi; Hayashi, Shigenobu

    2006-01-01

    Proton dynamics in Rb3H(SO4)2 has been studied by means of H1 NMR. The H1 magic-angle-spinning (MAS) NMR spectra were traced at room temperature (RT) at Larmor frequency of 400.13MHz . H1 static NMR spectra were measured at frequencies of 200.13MHz and 400.13MHz in the ranges of 165-513 and 300-513K , respectively. H1 spin-lattice relaxation times, T1 , were measured at 200.13 and 19.65MHz in the ranges of 260-513 and 260-470K , respectively. The H1 MAS NMR spectrum at 294K has an isotropic chemical shift of 16.3ppm from tetramethylsilane, demonstrating very strong hydrogen bonds. In RT phase, a wobbling motion of the O-H axis in one direction at the fast motional limit takes place above 400K , being supported by the H1 static NMR spectral line shapes and by the H1 T1 values. In the high temperature (HT) phase, the sharp H1 static NMR spectra indicate translational proton diffusion. From the analysis of H1 T1 , protons diffuse with the inverse of the frequency factor (τ0) of 9.5×10-13s and the activation energy (Ea) of 25kJmol-1 . These parameters can well explain the macroscopic electric conductivity in HT phase.

  15. Interaction of melittin with mixed phospholipid membranes composed of dimyristoylphosphatidylcholine and dimyristoylphosphatidylserine studied by deuterium NMR

    SciTech Connect

    Dempsey, C.; Bitbol, M.; Watts, A. )

    1989-08-08

    The interaction of bee venom melittin with mixed phospholipid bilayers composed of dimyristoylphosphatidylcholine deuterated in the {alpha}- and {beta}-methylenes of the choline head group (DMPC-d{sub 4}) and dimyristoylphosphatidylserine deuterated in the {alpha}-methylene and {beta}-CH positions of the serine head group (DMPS-d{sub 3}) was studied in ternary mixtures by using deuterium NMR spectroscopy. The changes in the deuterium quadrupole splittings of the head-group deuteriomethylenes of DMPC-d{sub 4} induced by DMPS in binary mixtures were systematically reversed by increasing concentrations of melittin, so that at a melittin concentration of 4 mol % relative to total lipid the deuterium NMR spectrum from DMPC-d{sub 4} in the ternary mixture was similar to the spectrum from pure DMPC-d{sub 4} bilayers. The absence of deuterium NMR signals arising from melittin-bound DMPS in ternary mixtures containing DMPS-d{sub 3} indicates that the reversal by melittin of the effects of DMPS on the quadrupole splittings of DMPC-d{sub 4} results from the response of the choline head group to the net surface charge rather than from phase separation of melittin-DMPS complexes. The similarity in the effects of the two cationic but otherwise dissimilar peptides indicates that the DMPS head group responds to the surface charge resulting from the presence in the bilayer of charged amphiphiles, in a manner analogous to the response of the choline head group of phosphatidylcholine to the bilayer surface charge. The presence of DMPS greatly stabilized DMPC bilayers with respect to melittin-induced micellization, indicating that the latter effect of melittin may not be important for the hemolytic activity of the peptide.

  16. Structural studies of bacterial transcriptional regulatory proteins by multidimensional heteronuclear NMR

    SciTech Connect

    Volkman, B.F.

    1995-02-01

    Nuclear magnetic resonance spectroscopy was used to elucidate detailed structural information for peptide and protein molecules. A small peptide was designed and synthesized, and its three-dimensional structure was calculated using distance information derived from two-dimensional NMR measurements. The peptide was used to induce antibodies in mice, and the cross-reactivity of the antibodies with a related protein was analyzed with enzyme-linked immunosorbent assays. Two proteins which are involved in regulation of transcription in bacteria were also studied. The ferric uptake regulation (Fur) protein is a metal-dependent repressor which controls iron uptake in bacteria. Two- and three-dimensional NMR techniques, coupled with uniform and selective isotope labeling allowed the nearly complete assignment of the resonances of the metal-binding domain of the Fur protein. NTRC is a transcriptional enhancer binding protein whose N-terminal domain is a {open_quote}receiver domain{close_quote} in the family of {open_quote}two-component{close_quote} regulatory systems. Phosphorylation of the N-terminal domain of NTRC activates the initiation of transcription of aeries encoding proteins involved in nitrogen regulation. Three- and four-dimensional NMR spectroscopy methods have been used to complete the resonance assignments and determine the solution structure of the N-terminal receiver domain of the NTRC protein. Comparison of the solution structure of the NTRC receiver domain with the crystal structures of the homologous protein CheY reveals a very similar fold, with the only significant difference being the position of helix 4 relative to the rest of the protein. The determination of the structure of the NTRC receiver domain is the first step toward understanding a mechanism of signal transduction which is common to many bacterial regulatory systems.

  17. Membrane topology of a 14-mer model amphipathic peptide: a solid-state NMR spectroscopy study.

    PubMed

    Ouellet, Marise; Doucet, Jean-Daniel; Voyer, Normand; Auger, Michèle

    2007-06-01

    We have investigated the interaction between a synthetic amphipathic 14-mer peptide and model membranes by solid-state NMR. The 14-mer peptide is composed of leucines and phenylalanines modified by the addition of crown ethers and forms a helical amphipathic structure in solution and bound to lipid membranes. To shed light on its membrane topology, 31P, 2H, 15N solid-state NMR experiments have been performed on the 14-mer peptide in interaction with mechanically oriented bilayers of dilauroylphosphatidylcholine (DLPC), dimyristoylphosphatidylcholine (DMPC), and dipalmitoylphosphatidylcholine (DPPC). The 31P, 2H, and 15N NMR results indicate that the 14-mer peptide remains at the surface of the DLPC, DMPC, and DPPC bilayers stacked between glass plates and perturbs the lipid orientation relative to the magnetic field direction. Its membrane topology is similar in DLPC and DMPC bilayers, whereas the peptide seems to be more deeply inserted in DPPC bilayers, as revealed by the greater orientational and motional disorder of the DPPC lipid headgroup and acyl chains. 15N{31P} rotational echo double resonance experiments have also been used to measure the intermolecular dipole-dipole interaction between the 14-mer peptide and the phospholipid headgroup of DMPC multilamellar vesicles, and the results indicate that the 14-mer peptide is in contact with the polar region of the DMPC lipids. On the basis of these studies, the mechanism of membrane perturbation of the 14-mer peptide is associated to the induction of a positive curvature strain induced by the peptide lying on the bilayer surface and seems to be independent of the bilayer hydrophobic thickness. PMID:17487978

  18. Solid state NMR and LVSEM studies on the hardening of latex modified tile mortar systems

    SciTech Connect

    Rottstegge, J.; Arnold, M.; Herschke, L.; Glasser, G.; Wilhelm, M.; Spiess, H.W. . E-mail: spiess@mpip-mainz.mpg.de; Hergeth, W.D.

    2005-12-15

    Construction mortars contain a broad variety of both inorganic and organic additives beside the cement powder. Here we present a study of tile mortar systems based on portland cement, quartz, methyl cellulose and different latex additives. As known, the methyl cellulose stabilizes the freshly prepared cement paste, the latex additive enhances final hydrophobicity, flexibility and adhesion. Measurements were performed by solid state nuclear magnetic resonance (NMR) and low voltage scanning electron microscopy (LVSEM) to probe the influence of the latex additives on the hydration, hardening and the final tile mortar properties. While solid state NMR enables monitoring of the bulk composition, scanning electron microscopy affords visualization of particles and textures with respect to their shape and the distribution of the different phases. Within the alkaline cement paste, the poly(vinyl acetate) (VAc)-based latex dispersions stabilized by poly(vinyl alcohol) (PVA) were found to be relatively stable against hydrolysis. The influence of the combined organic additives methyl cellulose, poly(vinyl alcohol) and latexes stabilized by poly(vinyl alcohol) on the final silicate structure of the cement hydration products is small. But even small amounts of additives result in an increased ratio of ettringite to monosulfate within the final hydrated tile mortar as monitored by {sup 27}Al NMR. The latex was found to be adsorbed to the inorganic surfaces, acting as glue to the inorganic components. For similar latex water interfaces built up by poly(vinyl alcohol), a variation in the latex polymer composition results in modified organic textures. In addition to the networks of the inorganic cement and of the latex, there is a weak network build up by thin polymer fibers, most probably originating from poly(vinyl alcohol). Besides the weak network, polymer fibers form well-ordered textures covering inorganic crystals such as portlandite.

  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. PMID:23604391

  20. On the acidity of saponite materials: a combined HRTEM, FTIR, and solid-state NMR study.

    PubMed

    Bisio, C; Gatti, G; Boccaleri, E; Marchese, L; Bertinetti, L; Coluccia, S

    2008-03-18

    Acid clays were prepared by exchanging a synthetic saponite in HCl solutions of different concentration (0.01 and 1M, respectively). A combined experimental approach (XRD, HRTEM, N2 physisorption, solid-state MAS NMR, and TGA) was used to investigate on the structural, morphological, and textural features of the samples treated under mild and strong acid conditions. FTIR spectroscopy of adsorbed probe molecules with different basicity (e.g., CO and NH3) was used to monitor the surface acid properties and acid site distribution. XRD and SS-MAS NMR indicated that the activation under mild acid conditions does not alter the clay structure, while a deep modification of the saponite framework occurred after ion exchange in 1 M HCl solution. The presence of porous amorphous silica phase after treatment under strong acid conditions was confirmed by TEM inspection augmented by SS-MAS NMR and FTIR spectroscopy. N2 and Ar physisorption measurements suggested that cavitation phenomena occurred in saponite structure. N2 physisorption confirmed that the porosity and surface area of the samples are strongly modified upon strong acid treatment. FTIR spectroscopy of adsorbed NH3 pointed out that the H-exchange in mild conditions increased the number of surface Brønsted acid sites. Conversely, these sites are significantly depleted after treatment under strong acid conditions. The use of CO as a FTIR probe molecule, which is applied for the first time to study synthetic acid clays, allowed to monitor distribution and strength of Brønsted acid sites, whose acidity is similar to that of strong acid zeolites. The Al-OH sites with medium acidity are also found in acid-activated saponites. The distribution of strong and medium acid sites is strictly dependent on the acid conditions adopted. PMID:18251562

  1. Optimizing nanodiscs and bicelles for solution NMR studies of two β-barrel membrane proteins

    PubMed Central

    Kucharska, Iga; Edrington, Thomas C.; Liang, Binyong

    2015-01-01

    Solution NMR spectroscopy has become a robust method to determine structures and explore the dynamics of integral membrane proteins. The vast majority of previous studies on membrane proteins by solution NMR have been conducted in lipid micelles. Contrary to the lipids that form a lipid bilayer in biological membranes, micellar lipids typically contain only a single hydrocarbon chain or two chains that are too short to form a bilayer. Therefore, there is a need to explore alternative more bilayer-like media to mimic the natural environment of membrane proteins. Lipid bicelles and lipid nanodiscs have emerged as two alternative membrane mimetics that are compatible with solution NMR spectroscopy. Here, we have conducted a comprehensive comparison of the physical and spectroscopic behavior of two outer membrane proteins from Pseudomonas aeruginosa, OprG and OprH, in lipid micelles, bicelles, and nanodiscs of five different sizes. Bicelles stabilized with a fraction of negatively charged lipids yielded spectra of almost comparable quality as in the best micellar solutions and the secondary structures were found to be almost indistinguishable in the two environments. Of the five nanodiscs tested, nanodiscs assembled from MSP1D1ΔH5 performed the best with both proteins in terms of sample stability and spectral resolution. Even in these optimal nanodiscs some broad signals from the membrane embedded barrel were severely overlapped with sharp signals from the flexible loops making their assignments difficult. A mutant OprH that had two of the flexible loops truncated yielded very promising spectra for further structural and dynamical analysis in MSP1D1ΔH5 nanodiscs. PMID:25869397

  2. Proton NMR spectral study of UV treated live Escherichia coli Bacteria

    NASA Astrophysics Data System (ADS)

    Sorokopud, Michael

    The lethal effects of ultraviolet radiation on microorganisms have been known and utilized for many years. In sufficiently high photon fluences, light and in particular, UV light, is an effective and subtle means of killing or at least immobilizing most, if not all cells and micro-organisms. Because of their small size, light can penetrate the enclosing protective walls and enter the inner volumes where it can break organic bonds in components that are vital to cell function. Despite the fact that a very low dose of UV light (1-9 mJ/cm2) has been shown to inactivate many micro-organisms, there remains a dearth of biological information about light induced effects in molecules and their interactions within living microbial systems. The use of 1H NMR as a spectroscopic tool was chosen to undertake an examination of the possible effects resulting from exposing E. coli to lethal fluencies of UV radiation. Once sample preparation, treatment, and NMR mounting methods were optimized, the high sensitivity and high resolution capabilities of the method produced reproducible results for a series of experiments. These results reveal significant changes in the ratio of the 1H NMR spectra of the treated to untreated E.coli samples when the treated sample was exposed to a lethal fluence of 275nm light. Photons at the 275nm wavelength, used in this study, have enough energy to break all of the principle bonds in an organic molecule. The difference spectrum between treated to untreated samples appears to be fitted well using specific component spectra from these groups of compounds. Increases in NMR peak amplitudes are observed and appear to be correlated with the spectral locations of several amino acids, membrane components and several sugars/saccharides. Increases in peak intensities of 4-8% were observed in the 0.8-1.1 ppm chemical shift region, characteristic of lipid and amino acid groups. A 3.5-4% increase was observed in the 2 ppm and 3.4-4 ppm region characteristic of

  3. Molecular docking and NMR binding studies to identify novel inhibitors of human phosphomevalonate kinase

    SciTech Connect

    Boonsri, Pornthip; Neumann, Terrence S.; Olson, Andrew L.; Cai, Sheng; Herdendorf, Timothy J.; Miziorko, Henry M.; Hannongbua, Supa; Sem, Daniel S.

    2013-01-04

    Highlights: Black-Right-Pointing-Pointer Natural and synthetic inhibitors of human phosphomevalonate kinase identified. Black-Right-Pointing-Pointer Virtual screening yielded a hit rate of 15%, with inhibitor K{sub d}'s of 10-60 {mu}M. Black-Right-Pointing-Pointer NMR studies indicate significant protein conformational changes upon binding. -- Abstract: Phosphomevalonate kinase (PMK) phosphorylates mevalonate-5-phosphate (M5P) in the mevalonate pathway, which is the sole source of isoprenoids and steroids in humans. We have identified new PMK inhibitors with virtual screening, using autodock. Promising hits were verified and their affinity measured using NMR-based {sup 1}H-{sup 15}N heteronuclear single quantum coherence (HSQC) chemical shift perturbation and fluorescence titrations. Chemical shift changes were monitored, plotted, and fitted to obtain dissociation constants (K{sub d}). Tight binding compounds with K{sub d}'s ranging from 6-60 {mu}M were identified. These compounds tended to have significant polarity and negative charge, similar to the natural substrates (M5P and ATP). HSQC cross peak changes suggest that binding induces a global conformational change, such as domain closure. Compounds identified in this study serve as chemical genetic probes of human PMK, to explore pharmacology of the mevalonate pathway, as well as starting points for further drug development.

  4. Conformations of banana-shaped molecules studied by 2H NMR spectroscopy in liquid crystalline solvents.

    PubMed

    Calucci, Lucia; Forte, Claudia; Csorba, Katalin Fodor; Mennucci, Benedetta; Pizzanelli, Silvia

    2007-01-11

    ClPbis11BB and Pbis11BB, two banana-shaped mesogens differing by a chlorine substituent on the central phenyl ring, show a nematic and a B2 phase, respectively. To obtain information on the structural features responsible for their different mesomorphic behavior, a study of the preferred conformations of these mesogens has been performed by NMR spectroscopy in two nematic media (Phase IV and ZLI1167), which should mimic the environment of the molecules in their own mesophases, avoiding problems of sample alignment by a magnetic field. To this aim, 2H NMR experiments have been performed on selectively deuterated isotopomers of ClPbis11BB and Pbis11BB and of two parent molecules, ClPbisB and PbisB, assumed as models in previous theoretical and experimental conformational studies. We found that only a limited number of conformations is compatible with experimental data, often very different from those inferred from theoretical calculations in vacuo, indicating a strong influence of the liquid crystalline environment on molecular conformation. No significant differences between chlorinated and non-chlorinated molecules were found, this suggesting that chlorine does not change the molecular conformational equilibrium, as previously proposed. PMID:17201428

  5. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    DOE PAGESBeta

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulkmore » IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.« less

  6. Ionic Liquid–Solute Interactions Studied by 2D NOE NMR Spectroscopy

    SciTech Connect

    Khatun, Sufia; Castner, Edward W.

    2014-11-26

    Intermolecular interactions between a Ru²⁺(bpy)₃ solute and the anions and cations of four different ionic liquids (ILs) are investigated by 2D NMR nuclear Overhauser effect (NOE) techniques, including {¹H-¹⁹F} HOESY and {¹H-¹H} ROESY. Four ILs are studied, each having the same bis(trifluoromethylsulfonyl)amide anion in common. Two of the ILs have aliphatic 1-alkyl-1-methylpyrrolidinium cations, while the other two ILs have aromatic 1-alkyl-3-methylimidazolium cations. ILs with both shorter (butyl) and longer (octyl or decyl) cationic alkyl substituents are studied. NOE NMR results suggest that the local environment of IL anions and cations near the Ru²⁺(bpy)₃ solute is rather different from the bulk IL structure. The solute-anion and solute-cation interactions are significantly different both for ILs with short vs long alkyl tails and for ILs with aliphatic vs aromatic cation polar head groups. In particular, the solute-anion interactions are observed to be about 3 times stronger for the cations with shorter alkyl tails relative to the ILs with longer alkyl tails. The Ru²⁺(bpy)₃ solute interacts with both the polar head and the nonpolar tail groups of the 1- butyl-1-methylpyrrolidinium cation but only with the nonpolar tail groups of the 1-decyl-1-methylpyrrolidinium cation.

  7. A strategy for co-translational folding studies of ribosome-bound nascent chain complexes using NMR spectroscopy.

    PubMed

    Cassaignau, Anaïs M E; Launay, Hélène M M; Karyadi, Maria-Evangelia; Wang, Xiaolin; Waudby, Christopher A; Deckert, Annika; Robertson, Amy L; Christodoulou, John; Cabrita, Lisa D

    2016-08-01

    During biosynthesis on the ribosome, an elongating nascent polypeptide chain can begin to fold, in a process that is central to all living systems. Detailed structural studies of co-translational protein folding are now beginning to emerge; such studies were previously limited, at least in part, by the inherently dynamic nature of emerging nascent chains, which precluded most structural techniques. NMR spectroscopy is able to provide atomic-resolution information for ribosome-nascent chain complexes (RNCs), but it requires large quantities (≥10 mg) of homogeneous, isotopically labeled RNCs. Further challenges include limited sample working concentration and stability of the RNC sample (which contribute to weak NMR signals) and resonance broadening caused by attachment to the large (2.4-MDa) ribosomal complex. Here, we present a strategy to generate isotopically labeled RNCs in Escherichia coli that are suitable for NMR studies. Uniform translational arrest of the nascent chains is achieved using a stalling motif, and isotopically labeled RNCs are produced at high yield using high-cell-density E. coli growth conditions. Homogeneous RNCs are isolated by combining metal affinity chromatography (to isolate ribosome-bound species) with sucrose density centrifugation (to recover intact 70S monosomes). Sensitivity-optimized NMR spectroscopy is then applied to the RNCs, combined with a suite of parallel NMR and biochemical analyses to cross-validate their integrity, including RNC-optimized NMR diffusion measurements to report on ribosome attachment in situ. Comparative NMR studies of RNCs with the analogous isolated proteins permit a high-resolution description of the structure and dynamics of a nascent chain during its progressive biosynthesis on the ribosome. PMID:27466710

  8. Continuous-flow IRMS technique for determination of Δ17O in (stratospheric) CO2 using complete oxygen isotope exchange with cerium oxide

    NASA Astrophysics Data System (ADS)

    Mrozek, D. J.; Roeckmann, T.

    2012-12-01

    Isotope studies of carbon dioxide (CO2) play an important role in understanding of the global carbon cycle. Stratospheric CO2 is known to undergo an isotopic exchange reaction with ozone (Yung et all 1991). Therefore, stratosphere CO2 shows a mass independent fractionation (MIF) which is a deviation in the 17O content from a purely mass-dependent pattern (MDF): for MDF processes δ17O = 0.52 δ18O, for MIF phenomena Δ17O = δ17O - 0.52 δ18O ≠ 0. The detailled mechanism that controls the 17O anomalies in stratospheric CO2 is not fully understood. Interest in this field has caused innovations in analytical techniques based on Isotope Ratio Mass Spectrometry (IRMS). Our approach was to design an analytical system that allows analysis of δ17O on nanomolar quantities of CO2 suitable for measuring oxygen isotope anomalies in stratospheric air samples. Based on complete oxygen isotope exchange with CeO2 at 650°C (Assonov et al. 2001) we have established an online measurement system for δ17O in CO2. Due to isotopic equilibration with CeO2 the CO2 samples loose their mass independent fractionation information and from the difference between the exchanged and non-exchanged sample Δ17O in the original CO2 can be calculated. The technique is fast and efficient due to its fully automation. A single measurement takes 15 minutes and 2 ml of air (plus flushing of the lines). Analytical precision can be improved by performing multiple measurements on one sample, and the analytical precision for a package of ten measurements is 0.7 ‰ for Δ17O. The new technique is a valuable tool to study the isotopic exchange mechanism between O3 and CO2 in the stratosphere. As a first application, we have determined the isotopic composition of stratospheric CO2 on air samples obtained during the EU project RECONCILE in the Arctic winter/spring season with the high-altitude aircraft Geophysica.

  9. Online, high precision analytical method for determination of Δ17O in stratospheric CO2 with the use of CeO2 isotopic exchange

    NASA Astrophysics Data System (ADS)

    Mrozek, D.; Röckmann, T.

    2012-04-01

    Isotope studies of carbon dioxide (CO2) play an important role in understanding of the global carbon cycle. In the atmosphere CO2 is an important greenhouse gas. Stratospheric CO2 is known to undergo an isotopic exchange reaction with ozone (Yang et all 1991). Therefore, stratosphere CO2 shows a mass independent fractionation (MIF) which is a deviation in the 17O content from a purely mass-dependent pattern (MDF): for MDF phenomena Δ17O = δ17O - 0.52 δ18O=0, for MIF phenomena Δ17O ≠ 0. The detail mechanism that controls the 17O anomalies in stratospheric CO2 is not fully understood. Interest in this field has caused innovations in analytical techniques based on Isotope Rato Mass Spectrometry (IRMS). Our approach was to design an analytical system that allows analysis of 17O on nanomolar quantities of CO2 suitable for measuring oxygen isotope anomalies in the stratospheric air samples. The standard continuous flow-IRMS techniques permit measuring small quantities of CO2 but it is impossible to measure the 17O isotope at mass 45 due to the interference from the much more abundant 13C. Therefore, CO2 has to be either converted to O2 or the oxygen it contains must be exchanged with oxygen of known isotopic composition. Based on complete oxygen isotope exchange with CeO2 at 650°C (Assonov et al. 2001) we have established an online measurement system for δ17O in CO2. The system allows analysis of 17O on nanomolar quantities of CO2 with a good reproducibility of 0.08‰ for δ45CO2. The new technique is a valuable tool to study isotopic exchange mechanism between O3 and CO2 in the stratosphere. We have determined the isotopic composition of stratospheric CO2 on air samples obtained during the EU project RECONCILE in the Arctic winter/spring season with the high-altitude aircraft Geophysica.

  10. Low temperature FTIR, Raman, NMR spectroscopic and theoretical study of hydroxyethylammonium picrate

    NASA Astrophysics Data System (ADS)

    Sudharsana, N.; Sharma, A.; Kuş, N.; Fausto, R.; Luísa Ramos, M.; Krishnakumar, V.; Pal, R.; Guru Row, T. N.; Nagalakshmi, R.

    2016-01-01

    A combined experimental (infrared, Raman and NMR) and theoretical quantum chemical study is performed on the charge-transfer complex hydroxyethylammonium picrate (HEAP). The infrared (IR) spectra for HEAP were recorded at various temperatures, ranging from 16 K to 299 K, and the Raman spectrum was recorded at room temperature. A comparison of the experimental IR and Raman spectra with the corresponding calculated spectra was done, in order to facilitate interpretation of the experimental data. Formation of the HEAP complex is evidenced by the presence of the most prominent characteristic bands of the constituting groups of the charge-transfer complex [e.g., NH3+, CO- and NO2]. Vibrational spectroscopic analysis, together with natural bond orbital (NBO) and theoretical charge density analysis in the crystalline phase, was used to shed light on relevant structural details of HEAP resulting from deprotonation of picric acid followed by formation of a hydrogen bond of the N-H⋯OC type between the hydroxyethylammonium cation and the picrate. 13C and 1H NMR spectroscopic analysis are also presented for the DMSO-d6 solution of the compound revealing that in that medium the HEAP crystal dissolves forming the free picrate and hydroxyethylammonium ions. Finally, the electron excitation analysis of HEAP was performed in an attempt to determine the nature of the most important excited states responsible for the NLO properties exhibited by the compound.

  11. The Physical Properties of Sphingomyelin/Cholesterol Membranes: a Deuterium NMR Study

    NASA Astrophysics Data System (ADS)

    Keyvanloo, Amirmohamad; Shaghaghi, Mehran; Zuckermann, Martin; Thewalt, Jenifer

    2009-05-01

    We have used ^2H NMR to study the effect of cholesterol on N-palmitoyl(D31)-D-erythro-sphingosylphosphorylcholine (PSM) membranes. NMR spectra were taken as a function of temperature and cholesterol concentration. The constructed phase diagram exhibits both solid-ordered (so) + liquid-ordered (lo) and liquid-disordered (ld) + lo phase coexistence regions with a clear three-phase line at 37^oC. The ld + lo region was characterized by examining the cholesterol dependence of the width of resolved peaks in the depaked spectra, as well as the average spectral width (M1), at a given temperature. The so + lo region was defined using spectral subtraction. Analogous experiments were done using 1-palmitoyl,2-palmitoyl(D31)-sn-glycero-3-phosphocholine (DPPC)/cholesterol membranes in order to carefully compare the data obtained using palmitoyl chains which have similar ``kinked'' conformations. The three-phase line in sn-2 perdeuterated DPPC/cholesterol is at 39^oC. The PSM/cholesterol membrane is significantly more ordered than the DPPC/cholesterol membrane in the liquid crystalline phase. This should be compared to the difference between the cholesterol-free membranes at, where the average order of PSM is more than that of DPPC.

  12. NMR study of the tetrameric KcsA potassium channel in detergent micelles

    PubMed Central

    Chill, Jordan H.; Louis, John M.; Miller, Christopher; Bax, Ad

    2006-01-01

    Nuclear magnetic resonance (NMR) studies of large membrane-associated proteins are limited by the difficulties in preparation of stable protein–detergent mixed micelles and by line broadening, which is typical of these macroassemblies. We have used the 68-kDa homotetrameric KcsA, a thermostable N-terminal deletion mutant of a bacterial potassium channel from Streptomyces lividans, as a model system for applying NMR methods to membrane proteins. Optimization of measurement conditions enabled us to perform the backbone assignment of KcsA in SDS micelles and establish its secondary structure, which was found to closely agree with the KcsA crystal structure. The C-terminal cytoplasmic domain, absent in the original structure, contains a 14-residue helix that could participate in tetramerization by forming an intersubunit four-helix bundle. A quantitative estimate of cross- relaxation between detergent and KcsA backbone amide protons, together with relaxation and light scattering data, suggests SDS–KcsA mixed micelles form an oblate spheroid with ~180 SDS molecules per channel. K+ ions bind to the micelle-solubilized channel with a KD of 3 ± 0.5 mM, resulting in chemical shift changes in the selectivity filter. Related pH-induced changes in chemical shift along the “outer” transmembrane helix and the cytoplasmic membrane interface hint at a possible structural explanation for the observed pH-gating of the potassium channel. PMID:16522799

  13. Probing NMR parameters, structure and dynamics of 5-nitroimidazole derivatives. Density functional study of prototypical radiosensitizers.

    PubMed

    Ramalho, Teodorico C; Bühl, Michael

    2005-02-01

    The 15N chemical shifts of metronidazole (1), secnidazole (2), nimorazole (3) and tinidazole (4), radiosensitizers based on the 5-nitroimidazole motif, are reported. A detailed computational study of 1 is presented, calling special attention to the performance of various theoretical methods in reproducing the 13C and 15N data observed in solution. The most sophisticated approach involves density functional-based Car-Parrinello molecular dynamics simulations (CPMD) of 1 in aqueous solution (BP86 level) and averaging chemical shifts over snapshots from the trajectory. In the NMR calculations for these snapshots (performed at the B3LYP level), a small number of discrete water molecules are retained, and the remaining bulk solution effects are included via a polarizable continuum model (PCM). A similarly good accord with experiment is obtained from much less involved, static geometry optimization and NMR computation of pristine 1 employing a PCM approach. Solvent effects on delta(15N), which are of the order of up to 20 ppm, are not due to changes in geometric parameters upon solvation, but arise from the direct response of the electronic wavefunction to the presence of the solvent, which can be represented by discrete molecules and/or the dielectric bulk. PMID:15558660

  14. 1H Nuclear Magnetic Resonance (NMR) Metabolomic Study of Chronic Organophosphate Exposure in Rats

    PubMed Central

    Alam, Todd M.; Neerathilingam, Muniasamy; Alam, M. Kathleen; Volk, David E.; Ansari, G. A. Shakeel; Sarkar, Swapna; Luxon, Bruce A.

    2012-01-01

    1H NMR spectroscopy and chemometric analysis were used to characterize rat urine obtained after chronic exposure to either tributyl phosphate (TBP) or triphenyl phosphate (TPP). In this study, the daily dose exposure was 1.5 mg/kg body weight for TBP, or 2.0 mg/kg body weight for TPP, administered over a 15-week period. Orthogonal signal correction (OSC) -filtered partial least square discriminant analysis (OSC-PLSDA) was used to predict and classify exposure to these organophosphates. During the development of the model, the classification error was evaluated as a function of the number of latent variables. NMR spectral regions and corresponding metabolites important for determination of exposure type were identified using variable importance in projection (VIP) coefficients obtained from the OSC-PLSDA analysis. As expected, the model for classification of chronic (1.5–2.0 mg/kg body weight daily) TBP or TPP exposure was not as strong as the previously reported model developed for identifying acute (15–20 mg/kg body weight) exposure. The set of majorly impacted metabolites identified for chronic TBP or TPP exposure was slightly different than those metabolites previously identified for acute exposure. These metabolites were then mapped to different metabolite pathways and ranked, allowing the metabolic response to chronic organophosphate exposure to be addressed. PMID:24957643

  15. Morphological characterization of DMPC/CHAPSO bicellar mixtures: a combined SANS and NMR study.

    PubMed

    Li, Ming; Morales, Hannah H; Katsaras, John; Kučerka, Norbert; Yang, Yongkun; Macdonald, Peter M; Nieh, Mu-Ping

    2013-12-23

    Spontaneously forming structures of a system composed of dimyristoyl phosphatidylcholine (DMPC) and 3-[(3-cholamidopropyl)dimethylammonio]-2-hydroxy-1-propanesulfonate (CHAPSO) were studied by small-angle neutron scattering (SANS), (31)P NMR, and stimulated echo (STE) pulsed field gradient (PFG) (1)H NMR diffusion measurements. Charged lipid dimyristoyl phosphatidylglycerol (DMPG) was used to induce different surface charge densities. The structures adopted were investigated as a function of temperature and lipid concentration for samples with a constant molar ratio of long-chain to short-chain lipids (= 3). In the absence of DMPG, zwitterionic bicellar mixtures exhibited a phase transition from discoidal bicelles, or ribbons, to multilamellar vesicles either upon dilution or with increased temperature. CHAPSO-containing mixtures showed a higher thermal stability in morphology than DHPC-containing mixtures at the corresponding lipid concentrations. In the presence of DMPG, discoidal bicelles (or ribbons) were also found at low temperature and lower lipid concentration mixtures. At high temperature, perforated lamellae were observed in high-concentration mixtures (≥7.5 wt %) whereas uniform unilamellar vesicles and bicelles formed in low-concentration mixtures (≤2.5 wt %), respectively, when the mixtures were moderately and highly charged. From the results, spontaneous structural diagrams of the zwitterionic and charged systems were constructed. PMID:24059815

  16. Sequences of 12 monoclonal anti-dinitrophenyl spin-label antibodies for NMR studies

    SciTech Connect

    Leahy, D.J.; Rule, G.S.; Whittaker, M.M.; McConnell, H.M. )

    1988-06-01

    Eleven monoclonal antibodies specific for a spin-labeled dinitrophenyl hapten (DNP-SL) have been produces for use in NMR studies. They have been named AN01 and ANO3-AN12. The stability constants for the association of these antibodies with DNP-SL and related haptens were measured by fluorescence quenching. cDNA clones coding for the heavy and light chains of each antibody and of an additional anti-DNP-SL monoclonal antibody, ANO2, have been isolated. The nucleic acid sequence of the 5{prime} end of each clone has been determined, and the amino acid sequence of the variable regions of each antibody has been deduced from the cDNA sequence. The sequences are relatively heterogeneous, but both the heavy and the light chains of ANO1 and ANO3 are derived from the same variable-region gene families as those of the ANO2 antibody. ANO7 has a heavy chain that is related to that of ANO2, and ANO9 has a related light chain. ANO5 and ANO6 are unrelated to ANO2 but share virtually identical heavy and light chains. Preliminary NMR difference spectra comparing related antibodies show that sequence-specific assignment of resonances is possible. Such spectra also provide a measure of structural relatedness.

  17. The dynamic complex of cytochrome c6 and cytochrome f studied with paramagnetic NMR spectroscopy.

    PubMed

    Díaz-Moreno, Irene; Hulsker, Rinske; Skubak, Pavol; Foerster, Johannes M; Cavazzini, Davide; Finiguerra, Michelina G; Díaz-Quintana, Antonio; Moreno-Beltrán, Blas; Rossi, Gian-Luigi; Ullmann, G Matthias; Pannu, Navraj S; De la Rosa, Miguel A; Ubbink, Marcellus

    2014-08-01

    The rapid transfer of electrons in the photosynthetic redox chain is achieved by the formation of short-lived complexes of cytochrome b6f with the electron transfer proteins plastocyanin and cytochrome c6. A balance must exist between fast intermolecular electron transfer and rapid dissociation, which requires the formation of a complex that has limited specificity. The interaction of the soluble fragment of cytochrome f and cytochrome c6 from the cyanobacterium Nostoc sp. PCC 7119 was studied using NMR spectroscopy and X-ray diffraction. The crystal structures of wild type, M58H and M58C cytochrome c6 were determined. The M58C variant is an excellent low potential mimic of the wild type protein and was used in chemical shift perturbation and paramagnetic relaxation NMR experiments to characterize the complex with cytochrome f. The interaction is highly dynamic and can be described as a pure encounter complex, with no dominant stereospecific complex. Ensemble docking calculations and Monte-Carlo simulations suggest a model in which charge-charge interactions pre-orient cytochrome c6 with its haem edge toward cytochrome f to form an ensemble of orientations with extensive contacts between the hydrophobic patches on both cytochromes, bringing the two haem groups sufficiently close to allow for rapid electron transfer. This model of complex formation allows for a gradual increase and decrease of the hydrophobic interactions during association and dissociation, thus avoiding a high transition state barrier that would slow down the dissociation process. PMID:24685428

  18. Hydrogen Bonds in Crystalline Imidazoles Studied by 15N NMR and ab initio MO Calculations

    NASA Astrophysics Data System (ADS)

    Ueda, Takahiro; Nagatomo, Shigenori; Masui, Hirotsugu; Nakamura, Nobuo; Hayashi, Shigenobu

    1999-07-01

    Intermolecular hydrogen bonds of the type N-H...N in crystals of imidazole and its 4-substituted and 4,5-disubstituted derivatives were studied by 15N CP/MAS NMR and an ab initio molecular orbital (MO) calculation. In the 15N CP/MAS NMR spectrum of each of the imidazole derivatives, two peaks due to the two different functional groups, >NH and =N-, were observed. The value of the 15N isotropic chemical shift for each nitrogen atom depends on both the length of the intermolecular hydrogen bond and the kind of the substituent or substituents. It was found that the difference between the experimen-tal chemical shifts of >NH and =N-varies predominantly with the hydrogen bond length but does not show any systematic dependence on the kind of substituent. The ab initio MO calculations suggest that the hydrogen bond formation influences the 15N isotropic chemical shift predominantly, and that the difference between the 15N isotropic chemical shift of >NH and =N-varies linearly with the hydrogen bond length.

  19. Helical stacking in DNA three-way junctions containing two unpaired pyrimidines: proton NMR studies.

    PubMed Central

    Leontis, N B; Hills, M T; Piotto, M; Ouporov, I V; Malhotra, A; Gorenstein, D G

    1995-01-01

    The proton NMR spectra of DNA three-way junction complexes (TWJ) having unpaired pyrimidines, 5'-TT- and 5'-TC- on one strand at the junction site were assigned from 2D NOESY spectra acquired in H2O and D2O solvents and homonuclear 3D NOESY-TOCSY and 3D NOESY-NOESY in D2O solvent. TWJ are the simplest branched structures found in biologically active nucleic acids. Unpaired nucleotides are common features of such structures and have been shown to stabilize junction formation. The NMR data confirm that the component oligonucleotides assemble to form conformationally homogeneous TWJ complexes having three double-helical, B-form arms. Two of the helical arms stack upon each other. The unpaired pyrimidine bases lie in the minor groove of one of the helices and are partly exposed to solvent. The coaxial stacking arrangement deduced is different from that determined by Rosen and Patel (Rosen, M.A., and D.J. Patel. 1993. Biochemistry. 32:6576-6587) for a DNA three-way junction having two unpaired cytosines, but identical to that suggested by Welch et al. (Welch, J. B., D. R. Duckett, D. M. J. Lilley. 1993. Nucleic Acids Res. 21:4548-4555) on the basis of gel electrophoretic studies of DNA three-way junctions containing unpaired adenosines and thymidines. Images FIGURE 2 FIGURE 4 FIGURE 5 FIGURE 6 FIGURE 7 PMID:7711249

  20. Theoretical study of NMR, infrared and Raman spectra on triple-decker phthalocyanines

    NASA Astrophysics Data System (ADS)

    Suzuki, Atsushi; Oku, Takeo

    2016-02-01

    Electronic structures and magnetic properties of multi-decker phthalocyanines were studied by theoretical calculation. Electronic structures, excited processes at multi-states, isotropic chemical shifts of 13C, 14N and 1H-nuclear magnetic resonance (NMR), principle V-tensor in electronic field gradient (EFG) tensor and asymmetry parameters (η), vibration mode in infrared (IR) and Raman spectra of triple-decker phthalocyanines were calculated by density functional theory (DFT) and time-dependent DFT using B3LYP as basis function. Electron density distribution was delocalized on the phthalocyanine rings with electron static potential. Considerable separation of chemical shifts in 13C, 14N and 1H-NMR was originated from nuclear spin interaction between nitrogen and carbon atoms, nuclear quadrupole interaction based on EFG and η of central metal under crystal field. Calculated optical absorption at multi-excited process was derived from overlapping π-orbital on the phthalocyanine rings. The vibration modes in IR and Raman spectra were based on in-plane deformation and stretching vibrations of metal-ligand coordination bond on the deformed structure.

  1. Cannibalism Affects Core Metabolic Processes in Helicoverpa armigera Larvae-A 2D NMR Metabolomics Study.

    PubMed

    Vergara, Fredd; Shino, Amiu; Kikuchi, Jun

    2016-01-01

    Cannibalism is known in many insect species, yet its impact on insect metabolism has not been investigated in detail. This study assessed the effects of cannibalism on the metabolism of fourth-instar larvae of the non-predatory insect Helicoverpa armigera (Lepidotera: Noctuidea). Two groups of larvae were analyzed: one group fed with fourth-instar larvae of H. armigera (cannibal), the other group fed with an artificial plant diet. Water-soluble small organic compounds present in the larvae were analyzed using two-dimensional nuclear magnetic resonance (NMR) and principal component analysis (PCA). Cannibalism negatively affected larval growth. PCA of NMR spectra showed that the metabolic profiles of cannibal and herbivore larvae were statistically different with monomeric sugars, fatty acid- and amino acid-related metabolites as the most variable compounds. Quantitation of ¹H-(13)C HSQC (Heteronuclear Single Quantum Coherence) signals revealed that the concentrations of glucose, glucono-1,5-lactone, glycerol phosphate, glutamine, glycine, leucine, isoleucine, lysine, ornithine, proline, threonine and valine were higher in the herbivore larvae. PMID:27598144

  2. Structural analysis of molybdo-zinc-phosphate glasses: Neutron scattering, FTIR, Raman scattering, MAS NMR studies

    NASA Astrophysics Data System (ADS)

    Renuka, C.; Shinde, A. B.; Krishna, P. S. R.; Reddy, C. Narayana

    2016-08-01

    Vitreous samples were prepared in the xMoO3-17ZnO-(83-x) NaPO3 with 35 ≥ x ≥ 55 glass forming system by energy efficient microwave heating method. Structural evolution of the vitreous network was monitored as a function of composition by differential scanning calorimetry (DSC), Fourier transform infrared spectroscopy (FTIR), Raman scattering, Magic Angle Spin Nuclear magnetic resonance (MAS NMR) and Neutron scattering. Addition of MoO3 to the ZnO-NaPO3 glass leads to a pronounced increase in glass transition temperature (Tg) suggesting a significant increase in network connectivity and strength. In order to analyze FTIR and Raman scattering, a simple structural model is presented to rationalize the experimental observations. A number of structural units are formed due to network modification, and the resulting glass may be characterized by a network polyhedral with different numbers of unshared corners. 31P MAS NMR confirms a clear distinction between structural species having 3, 2, 1, 0 bridging oxygens (BOs). Further, Neutron scattering studies were used to probe the structure of these glasses. The result suggests that all the investigated glasses have structures based on chains of four coordinated phosphate and six coordinated molybdate units, besides, two different lengths of P-O bonds in tetrahedral phosphate units that are assigned to bonds of the P-atom with terminal and bridging oxygen atoms.

  3. NMR Studies of Cu/zeolite SCR Catalysts Hydrothermally Aged with Urea

    SciTech Connect

    Cheng, Yisun; Hoard, John; Lambert, Christine; Kwak, Ja Hun; Peden, Charles HF

    2008-06-26

    The effects of hydrothermal aging of Cu/zeolite urea-SCR catalysts on their reactivity and material properties was assessed by performance tests and multiple characterization techniques that included 27Al NMR and XRD. Three aging protocols were used that consisted of varying temperature during hydrothermal aging with or without exposure to aqueous urea solution. Differences in behavior were even found for samples hydrothermally aged immediately following exposure to the urea solution or if the sample was dried overnight before hydrothermal aging. The combination of urea and high temperature exposure increased the deactivation of Cu/zeolite SCR catalysts beyond that observed by hydrothermal aging alone, with an immediate high temperature exposure following wetting of the catalyst core with aqueous urea causing the most significant deterioration in performance. The impact of urea on SCR catalyst durability was also found to increase with the aging temperature. NMR analysis suggested that aging with urea resulted in relatively more dealumination of the zeolite for the SCR catalysts in this study.

  4. Chiral recognition of imperanene enantiomers by various cyclodextrins: a capillary electrophoresis and NMR spectroscopy study.

    PubMed

    Sohajda, Tamás; Szakács, Zoltán; Szente, Lajos; Noszál, Béla; Béni, Szabolcs

    2012-05-01

    The enantiomers of imperanene, a novel polyphenolic compound of Imperata cylindrica (L.), were separated via cyclodextrin-modified capillary electrophoresis. The anionic form of the analyte at pH 9.0 was subject to complexation and enantioseparation CE studies with neutral and charged cyclodextrins. As chiral selectors 27 CDs were applied differing in cavity size, sidechain, degree of substitution (DS) and charge. Three hydroxypropylated and three sulfoalkylated CD preparations provided enantioseparation and the migration order was successfully interpreted in each case in terms of complex mobilities and stability constants. The best enantioresolution (R(S)  = 1.26) was achieved using sulfobutyl-ether-γ-CD (DS ∼4), but it could be enhanced by extensive investigations on dual selector systems. After optimization (CD concentrations and pH) R(S)  = 4.47 was achieved using a 12.5 mM sulfobutyl-ether-γ-CD and 10 mM 6-monodeoxy-6-mono-(3-hydroxy)-propylamino-β-cyclodextrin dual system. The average stoichiometry of the complex was determined with Job's method using NMR-titration and resulted in a 1:1 complex for both (2-hydroxy)propyl-β- and sulfobutyl-ether-γ-CD. Further NMR experiments suggest that the coniferyl moiety of imperanene is involved in the host-guest interaction. PMID:22648815

  5. Low Temperature 1H MAS NMR Spectroscopy Studies of Proton Motion in Zeolite

    SciTech Connect

    Huo, H.; Peng, L; Grey, C

    2009-01-01

    Low temperature {sup 1}H MAS NMR spectroscopy is used to study protonic motion in zeolite HZSM-5 in both samples that have been dried using procedures that are standard in the literature and samples that have been more carefully dehydrated. A significant enhancement of proton mobility is seen for the ''standard'' dehydrated HZSM-5 sample in comparison to that seen for the much drier sample. This is ascribed to a vehicle-hopping mechanism involving the residual water that is present in these zeolites. A gradual change of the framework structure is observed on cooling to approximately 213 K, as monitored via the change in {sup 1}H chemical shift values of the Broensted acid resonances and by X-ray diffraction. A more sudden change in structure is seen by differential scanning calorimetry and NMR at approximately 220?230 K, which is associated with changes in both the mobility and the modes of binding of the residual water to the Broensted acid sites and the zeolite framework.

  6. Relaxation NMR as a tool to study the dispersion and formulation behavior of nanostructured carbon materials.

    PubMed

    Fairhurst, David; Cosgrove, Terence; Prescott, Stuart W

    2016-06-01

    Solvent relaxation NMR has been used to estimate the surface areas and wettability of various types of nanostructured carbon materials in a range of solvents including water, ethanol, and tetrahydrofuran. We illustrate the application of the technique through several short case studies using samples including nanocarbon blacks, graphene oxide, nanographites, and porous graphenes. The technique is shown to give a good measure of surface area, correlating well with conventional surface area estimates obtained by nitrogen adsorption, transmission electron microscopy, or light scattering for the non-porous samples. NMR relaxation has advantages in terms of speed of analysis and being able to use concentrated, wet, and opaque samples. For samples that are porous, two distinct surface areas can be estimated assuming the two environments ('inner' and 'outer') have the same surface chemistry, and that there is a slow exchange of solvent molecules between them. Furthermore, we show that differences in wettability and dispersability between samples dispersed in water, ethanol, and cyclopentanone can be observed, along with changes to the surface chemistry of the interface. Copyright © 2015 John Wiley & Sons, Ltd. PMID:25989999

  7. Lithium-7 NMR studies of Li(1-x)CoO2 battery cathodes

    NASA Astrophysics Data System (ADS)

    Ouyang, B.; Cao, X.; Lin, H. W.; Slane, S.; Kostov, S.

    1995-05-01

    Lithium-deficient cathode materials Li(1-x)CoO2, where x = 0.1, 0.4 and 0.6 were prepared electrochemically from the stoichiometric parent compound (x = 0.0). The materials were observed to be air-stable, and x-ray diffraction characterization yielded good agreement with the in situ studies of Dahn and co-workers, regarding changes in lattice parameters. In addition to both static and magic angle spinning (MAS) Li-7 NMR, measurements, the samples were investigated by EPR and cobalt K-edge NEXAFS. The removal of Li is accompanied by compensating electrons from the Co d-orbitals, as evidenced by both shifts in the NEXAFS peak and the observation of EPR signals due to spins localized on the Co ions. These spins, in turn, result in dramatic 7Li chemical shifts (89 ppm for x = 0.6) and line broadening. Whereas MAS analysis of Li(0.9)CoO2 indicates two magnetically inequivalent Li sites, the spectra become too broad to resolve different sites for higher values of x. Finally NMR linewidth and spin- lattice relaxation measurements as a function of temperature suggest a modest increase in Li(+) ion mobility for Li-deficient samples as compared to the parent compound.

  8. Density functional theoretical and NMR study of Hammett bases in acidic zeolites

    SciTech Connect

    Nicholas, J.B.; Haw, J.F.; Beck, L.W.; Krawietz, T.R.; Ferguson, D.B.

    1995-12-13

    We demonstrate here that theoretical calculations using density functional theory (DFT) accurately model proton transfer reactions between Bronsted sites in zeolites (the archetypal solid acids) and Hammett bases. The validity of the theoretical results is verified by NMR measurements of key nuclei of the same Hammett bases in zeolites HZSM-5 (MFI) and HY (FAU), the first such experiments. The accuracy of the predictions of the DFT calculations for the HZSM-5 zeolite model suggests that they may be extended to other zeolite cluster models, including those which have not yet been realized experimentally and hence are not available for NMR study. We optimized the adsorbate zeolite complexes with this angle constrained to larger values; to our surprise, the SVWN/DNP calculations resulted in the proton being transferred from p-fluoronitrobenzene back to the zeolite, even if the Si-O-Al angle was held fixed at 180{degree}. Further tests at higher levels of theory are in progress. This investigation used a choice of indicators that necessarily resulted in wide limits on zeolite acid strength, but the theoretical and experimental methodologies have been established. 21 refs., 3 figs.

  9. Two-dimensional /sup 1/H NMR studies on cyclophilin, a cytosolic cyclosporin A binding protein

    SciTech Connect

    Dalgarno, D.C.; Harding, M.W.; Lazarides, A.; Handschumacher, R.E.; Armitage, I.M.

    1986-05-01

    Cyclophilin (CyP) is a specific cytosolic cyclosporin A (CsA) binding protein (163 residues) that has been implicated in the pharmacological action of this potent immunosuppressant. One and two-dimensional /sup 1/H NMR methods are being employed to elucidate the solution structural properties of CyP particularly as they relate to the binding site of CsA. The focal point for these studies is the single Trp (residue number120) in CyP which, in the 1:1 CyP:CsA complex (K/sub d/approx.2 x 10/sup -7/M), shows a 2 fold enhancement in its intrinsic fluorescence. Using 2D /sup 1/H NMR methods, a low resolution structure has been derived for a very hydrophobic domain containing the Trp residue using interresidue n.O.e. data between assigned spin systems and a distance geometry algorithm. The structure of this hydrophobic domain will be discussed in relation to the predicted ..cap alpha../..beta.. secondary structure of this protein and comparisons made between its structure in the drug free and complexed form of the protein.

  10. Improving NMR Protein Structure Quality by Rosetta Refinement: A Molecular Replacement Study

    PubMed Central

    Ramelot, Theresa A.; Raman, Srivatsan; Kuzin, Alexandre P.; Xiao, Rong; Ma, Li-Chung; Acton, Thomas B.; Hunt, John F.; Montelione, Gaetano T.; Baker, David; Kennedy, Michael A.

    2010-01-01

    The structure of human protein HSPC034 has been determined by both solution NMR spectroscopy and X-ray crystallography. Refinement of the NMR structure ensemble, using a Rosetta protocol in the absence of NMR restraints, resulted in significant improvements not only in structure quality, but also in molecular replacement (MR) performance with the raw X-ray diffraction data using MOLREP and Phaser. This method has recently been shown to be generally applicable with improved MR performance demonstrated for eight NMR structures refined using Rosetta.1 Additionally, NMR structures of HSPC034 calculated by standard methods that include NMR restraints, have improvements in the RMSD to the crystal structure and MR performance in the order DYANA, CYANA, XPLOR-NIH, and CNS with explicit water refinement (CNSw). Further Rosetta refinement of the CNSw structures, perhaps due to more thorough conformational sampling and/or a superior force field, was capable of finding alternative low energy protein conformations that were equally consistent with the NMR data according to the RPF scores. Upon further examination, the additional MR-performance shortfall for NMR refined structures as compared to the X-ray structure MR performance were attributed, in part, to crystal-packing effects, real structural differences, and inferior hydrogen bonding in the NMR structures. A good correlation between a decrease in the number of buried unsatisfied hydrogen-bond donors and improved MR performance demonstrates the importance of hydrogen-bond terms in the force field for improving NMR structures. The superior hydrogen-bond network in Rosetta-refined structures, demonstrates that correct identification of hydrogen bonds should be a critical goal of NMR structure refinement. Inclusion of non-bivalent hydrogen bonds identified from Rosetta structures as additional restraints in the structure calculation results in NMR structures with improved MR performance PMID:18816799

  11. Isolation and 2D NMR Studies of Alkaloids from Comptonella sessilifoliola1.

    PubMed

    Pusset, J; Lopez, J L; Pais, M; Neirabeyeh, M A; Veillon, J M

    1991-04-01

    Six known furanoquinoline alkaloids have been isolated from the wood and trunk bark of COMPTONELLA SESSILIFOLIOLA (Guillaumin) Hartley (Rutaceae). 2D NMR experiments gave the assignment of all the signals for both (1)H- and (13)C-NMR spectra. Pteleine and kokusaginine were used as models. The two-dimensional carbon-proton correlation experiments, performed for the first time on furanoquinoline alkaloids, led us to correct (13)C-NMR assignments previously described in the literature. PMID:17226139

  12. Slow-MAS NMR: A New Technology for In Vivo Metabolomic Studies

    SciTech Connect

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

    2005-08-01

    Improvements in the ability to obtain detailed in vivo metabolic information have been identified as key elements of better understanding the efficacy and toxicity of new therapies. A new NMR technology called LOCMAT is discussed that yields substantially increased spectral resolution of spatially localized in vivo 1H NMR metabolite spectra, as illustrated by measurements in the liver and heart of a live mouse. Thus, LOCMAT promises to significantly enhance the utility of NMR spectroscopy for biomedical research.

  13. Sepsis does not alter red blood cell glucose metabolism or Na+ concentration: A 2H-, 23Na-NMR study

    SciTech Connect

    Hotchkiss, R.S.; Song, S.K.; Ling, C.S.; Ackerman, J.J.; Karl, I.E. )

    1990-01-01

    The effects of sepsis on intracellular Na+ concentration ((Na+)i) and glucose metabolism were examined in rat red blood cells (RBCs) by using 23Na- and 2H-nuclear magnetic resonance (NMR) spectroscopy. Sepsis was induced in 15 halothane-anesthetized female Sprague-Dawley rats by using the cecal ligation and perforation technique; 14 control rats underwent cecal manipulation without ligation. The animals were fasted for 36 h, but allowed free access to water. At 36 h postsurgery, RBCs were examined by 23Na-NMR by using dysprosium tripolyphosphate as a chemical shift reagent. Human RBCs from 17 critically ill nonseptic patients and from 7 patients who were diagnosed as septic were also examined for (Na+)i. Five rat RBC specimens had (Na+)i determined by both 23Na-NMR and inductively coupled plasma-atomic emission spectroscopy (ICP-AES). For glucose metabolism studies, RBCs from septic and control rats were suspended in modified Krebs-Henseleit buffer containing (6,6-2H2)glucose and examined by 2H-NMR. No significant differences in (Na+)i or glucose utilization were found in RBCs from control or septic rats. There were no differences in (Na+)i in the two groups of patients. The (Na+)i determined by NMR spectroscopy agreed closely with measurements using ICP-AES and establish that 100% of the (Na+)i of the RBC is visible by NMR. Glucose measurements determined by 2H-NMR correlated closely (correlation coefficient = 0.93) with enzymatic analysis. These studies showed no evidence that sepsis disturbed RBC membrane function or metabolism.

  14. Solid-state NMR/NQR and first-principles study of two niobium halide cluster compounds.

    PubMed

    Perić, Berislav; Gautier, Régis; Pickard, Chris J; Bosiočić, Marko; Grbić, Mihael S; Požek, Miroslav

    2014-01-01

    Two hexanuclear niobium halide cluster compounds with a [Nb6X12](2+) (X=Cl, Br) diamagnetic cluster core, have been studied by a combination of experimental solid-state NMR/NQR techniques and PAW/GIPAW calculations. For niobium sites the NMR parameters were determined by using variable Bo field static broadband NMR measurements and additional NQR measurements. It was found that they possess large positive chemical shifts, contrary to majority of niobium compounds studied so far by solid-state NMR, but in accordance with chemical shifts of (95)Mo nuclei in structurally related compounds containing [Mo6Br8](4+) cluster cores. Experimentally determined δiso((93)Nb) values are in the range from 2,400 to 3,000 ppm. A detailed analysis of geometrical relations between computed electric field gradient (EFG) and chemical shift (CS) tensors with respect to structural features of cluster units was carried out. These tensors on niobium sites are almost axially symmetric with parallel orientation of the largest EFG and the smallest CS principal axes (Vzz and δ33) coinciding with the molecular four-fold axis of the [Nb6X12](2+) unit. Bridging halogen sites are characterized by large asymmetry of EFG and CS tensors, the largest EFG principal axis (Vzz) is perpendicular to the X-Nb bonds, while intermediate EFG principal axis (Vyy) and the largest CS principal axis (δ11) are oriented in the radial direction with respect to the center of the cluster unit. For more symmetrical bromide compound the PAW predictions for EFG parameters are in better correspondence with the NMR/NQR measurements than in the less symmetrical chlorine compound. Theoretically predicted NMR parameters of bridging halogen sites were checked by (79/81)Br NQR and (35)Cl solid-state NMR measurements. PMID:24581866

  15. Solid state NMR method development and studies of biological and biomimetic nanocomposites

    SciTech Connect

    Hu, Yanyan

    2011-02-07

    This thesis describes application and development of advanced solid-state nuclear magnetic resonance techniques for complex materials, in particular organic-inorganic nanocomposites and thermoelectric tellurides. The apatite-collagen interface, essential for understanding the biomineralization process in bone and engineering the interface for controlled bio-mimetic synthesis and optimized mechanical properties, is buried within the nanocomposite of bone. We used multinuclear solid-state NMR to study the composition and structure of the interface. Citrate has been identified as the main organic molecule strongly bound to the apatite surface with a density of 1/(2 nm){sup 2}, covering 1/6 of the total surface area in bovine bone. Citrate provides more carboxylate groups, one of the key functional groups found to affect apatite nucleation and growth, than all the non-collagenous proteins all together in bone; thus we propose that citrate stabilizes apatite crystals at a very small thickness of {approx}3 nm (4 unit cells) to increase bone fracture tolerance. The hypothesis has been confirmed in vitro by adding citrate in the bio-mimetic synthesis of polymerhydroxyapatite nanocomposites. The results have shown that the size of hydroxyapatite nanocrystals decreases as increasing citrate concentration. With citrate concentrations comparable to that in body fluids, similar-sized nanocrystals as in bone have been produced. Besides the dimensions of the apatite crystals, the composition of bone also affects its biofunctional and macroscopic mechanical properties; therefore, our team also extended its effort to enhance the inorganic portion in our bio-mimetic synthesis from originally 15 wt% to current 50 wt% compared to 65 wt% in bovine bone, by using Lysine-Leucine hydroxyapatite nucleating diblock co-polypeptide, which forms a gel at very low concentration. In this thesis, various advanced solid state NMR techniques have been employed to characterize nanocomposites

  16. Water Exchange on [Ln(DO3A)(H2O)2] and [Ln(DTTA-Me)(H2O)2](-) Studied by Variable Temperature, Pressure, and Magnetic Field NMR.

    PubMed

    Karimi, Shima; Helm, Lothar

    2016-05-01

    Water exchange kinetics of [Ln(L)(H2O)2](x) complexes (Ln = Pr, Nd, Dy, Tm, and Yb; L = DO3A and DTTA-Me) were studied by (17)O NMR spectroscopy as a function of temperature, pressure, and frequency and by (1)H nuclear magnetic relaxation dispersion. Water exchange rate constants of both complexes show a maximum at dysprosium. Water exchange on negatively charged complexes of the acyclic DTTA-Me ligand is much faster than on the neutral complexes of the macrocyclic DO3A. Small activation volumes |ΔV(⧧)| < 1 cm(3) mol(-1) measured for water exchange on [Ln(DO3A)(H2O)2] indicate an interchange type of mechanism (I) for the lanthanide complexes studied. In the case of [Ln(DTTA-Me)(H2O)2](-), a change in mechanism is detected from a dissociative mechanism (D, ΔV(⧧) = 7 cm(3) mol(-1)) for complexes with larger ions (Pr to Gd) to an interchange mechanism (Id, I; ΔV(⧧) = +1.8 and +0.4 cm(3) mol(-1)) for complexes with smaller ions (Dy and Tm). PMID:27082861

  17. Spatial (data and model) and temporal variability of 17O-excess in East Antarctica

    NASA Astrophysics Data System (ADS)

    Winkler, Renato; Landais, Amaelle; Umuera, Ryu; Xiao, Cunde; Hoffmann, Georg; Jouzel, Jean; Kelley, Maxwell; Fukui, Kotaro

    2010-05-01

    For many decades stable water isotopes (δD and δ18O) are used as tracers in earth's hydrological cycle in order to get information about climatic parameters such as temperature and precipitation. In particular, δD and δ18O in ice cores permit to reconstruct the polar temperature of the past. Improvements of the analytical devices made it possible to measure also the δ17O of water with high precision. The combination of δ18O and δ17O leads to the definition of the so called 17O-excess (ln(δ17O/1000 +1)-0.528ln(δ18O/1000+1)) by analogy with the d-excess (δD -8δ18O). It has been suggested that 17O-excess in the ice cores is a more direct indicator of relative humidity of the source region than d-excess and that the combination of the two parameters is essential to reconstruct the past climatic conditions in the evaporative regions. Here we show new results for the spatial and temporal distribution of 17O-excess in East Antarctica. We especially explore the isotopic composition of the surface snow in remote regions of East Antarctica characterized by very low δ18O (between -60 and -55 permil). Then, we present the record of 17O-excess over the last deglaciation (26 to 8 kyrs BP) in the EPICA Dome C ice core. Interestingly, this 17O-excess record shows a more stable behavior than the one at Vostok. Finally, we compare our results with the spatial variability of 17O-excess in precipitation obtained by the old version of the GISS GCM model.

  18. δ17O and Δ47—The Heavens can Wait.

    NASA Astrophysics Data System (ADS)

    Olack, G.; Colman, A. S.

    2015-12-01

    Most terrestrial systems fall on or close to the Global Meteoric Water Line, GMWL, for 17O and 18O isotopes. Luz and Barken (2010) recently discussed variations from the GMWL, and typically the differences were in the 50 per meg, or 0.05‰, 17O excess. Landais et al. also looked at water from a Vostok ice core, covering the past 150,000 years, and see differences from GMWL on the order of 45 per meg 17O excess. Carbonate samples are analyze for their 13C and 18O to help understand paleo-climate, water sources, and by looking at clumped isotopes, Δ47, the excess of 13C-18O bonds measured by mass spectroscopy on m/z 47. Those samples will also carry thru the 17O-excess in their waters of formation. We modeled the effect of 17O excess on Δ47 and basically there is little effect in the 50 per meg 17O excess range. We also looked at what would happen with 18O spiked samples, presuming the spike does not add 17O. In that case, a 100 ‰ shift in 18O would give rise to -49‰ 17O excess anomaly. That shows a significant effect, a 1.8 ‰ shift in Δ47 and even a 3.5 ‰ shift in the δ13C reading. So spiked samples are not good candidates for clumped isotope analysis, terrestrial samples probably will not have enough of a 17O excess to affect Δ47 measurements, and extra-terrestrial samples will have to be checked.

  19. The 17O Excess of Stratospheric Nitrous Oxide in Mid-latitude Air

    NASA Astrophysics Data System (ADS)

    Ridley, A.; Kaiser, J.; Laube, J. C.

    2015-12-01

    Tropospheric nitrous oxide (N2O) has a 17O excess of (0.9±0.1) ‰ relative to Vienna Standard Mean Ocean Water (VSMOW). The origin of this 17O excess is under debate: tropospheric and stratospheric in-situ sources as well as isotope fractionation and isotope exchange during biological N2O production are all considered to make a contribution, as might the stratospheric photolysis sink. To constrain the relative contributions of the different processes and to improve our understanding of the underlying atmospheric chemical and microbial processes, more measurements are required. We have measured the 17O excess of stratospheric samples from mid-latitudes, from altitudes between 8 and 26 km. N2O was extracted cryogenically, separated from CO2 and CHF3 by a PoraPlotQ pre-column and then thermally decomposed in a gold furnace at 900 ºC. The precision for the 17O excess of a single 5 nmol N2O aliquot was ±0.3 ‰. This dataset significantly enhances the limited range of oxygen triple isotope measurements in mostly lower stratospheric samples reported by Cliff et al. (1999). The average 17O excess of the stratospheric samples analysed was (-0.19 ±0.46) ‰ relative to tropospheric N2O. Since the 17O excess of the first measurements of stratospheric air is not significantly different to that in tropospheric air, this data suggests that the 17O excess is not of stratospheric origin. This confirms the idea that the origin of the 17O excess is not due to either stratospheric photolysis or reaction with electronically excited oxygen atoms. It suggests that the origin of the 17O excess may therefore be related to tropospheric in situ sources, e.g. NH2+NO2 as proposed by Röckmann et al., 2001, or to microbial nitrogen conversion reactions as suggested by Kaiser and Röckmann, 2005.

  20. Use of /sup 1/H NMR to study molecular motion in cellulose, pectin, and bean cell walls

    SciTech Connect

    Taylor, I.E.P.; Tepfer, M.; Callaghan, P.T.; MacKay, A.L.; Bloom, M.

    1983-01-01

    Growing plant cells are enclosed in a framework, the cell wall, whose rigidity must be overcome for cell enlargement to occur. It has been shown that one of the primary modes of action of plant growth substances is to induce cell wall loosening. The mechansim of cell wall loosening is very poorly understood and may involve large-scale changes in the molecular mobility of the cell wall polysaccharides. Proton magnetic resonance (/sup 1/H NMR) was used to study molecular motion in bean stem cell walls as well as in cellulose, sodium pectate solutions, and calcium pectate gels. All samples were prepared in K/sub 2/O to minimize the contribution of water to the observed signals. The different NMR properties that have been measured are sensitive to molecular motions over a wide range of frequencies (10 kHz-90 MHz). For each sample, a free induction decay was obtained and the second moment as well as spin-lattice (longitudinal), spin-spin (transverse), and dipolar relaxations were measured. As expected, the different samples studied had strikingly different NMR properties. These results have been extended to look for pH-sensitive changes in the NMR properties of calcium pectate gels and bean cell walls, since both show marked pH-sensitive changes in their rheological behavior. Pulsed field gradient NMR studies of very mobile components of polysaccharide systems are discussed.

  1. Optimization and stabilization of Rho small GTPase proteins for solution NMR studies: The case of Rnd1.

    PubMed

    Cao, Shufen; Buck, Matthias

    2011-11-01

    Rho GTPases of the Ras superfamily have important roles in regulating the organization of the actin filament system, morphogenesis and migration of cells. Structural details for these proteins are still emerging, and information on their dynamics in solution is much needed to understand the mechanisms underlying their signaling functions. This report reviews conditions for solution NMR studies of Rho GTPases and describes our optimization and stabilization of Rnd1 for such experiments. Rnd1 belongs to the Rnd protein subfamily branch of Rho small GTPases and functions in neurite outgrowth, dendrite development and in axon guidance. However, as we report here, solution NMR studies of this protein are challenging. Multiple methods have been employed to enhance the stability of Rnd1, including by cleavage of an N-terminal His expression tag and by addition of non-hydrolysable GMPPNP (β: γ-imidoguanosine 5'-triphosphate) nucleotide. Further stabilization of Rnd1 against aggregation was achieved through a structure informed point mutation while maintaining its conformation and binding affinity for a partner protein. The NMR spectrum of the optimized protein reveals significant improvement in NMR signal dispersion and intensity. This work paves the way for structural and protein-protein/protein-ligand interaction studies of Rnd1 by solution NMR and also provides a guide for optimization and stabilization of other Rho GTPases. PMID:22545226

  2. Constraining Oxygen-17 NMR Spectra of High Pressure Crystals and Glasses: New Data for Jadeite, Pyrope, Grossular, and Mullite

    NASA Astrophysics Data System (ADS)

    Kelsey, K. E.; Stebbins, J. F.; Du, L.; Hankins, B.

    2005-12-01

    17O NMR is a direct way of analyzing the immediate environment around oxygen atoms and can provide information on cation ordering, mixing, and network connectivity in glasses and disordered crystals. Due to overlapping peaks and lack of data on crystalline model compounds, 17O NMR spectra of high pressure glasses have been difficult to interpret. Additionally, data on crystalline model compounds are needed to test the validity of quantum chemical calculations. In this study, 17O NMR spectra were collected for crystalline jadeite, pyrope, grossular, and mullite in order to determine the parameters for oxygen bonded to [6]Al in a variety of environments. Jadeite contains three oxygen sites: oxygen bonded to [4]Si, Na, and two [6]Al atoms (O1), oxygen bonded to [4]Si, Na, and [6]Al atoms (O2), and oxygen bonded to two [4]Si and two Na atoms (O3). The NMR parameters for O1 are CQ = 3.3 MHz, δ = 64 ppm, and ν = 0.9; for O2 are CQ = 4.1 MHz, δ = 59 ppm, and ν = 0.15; and for O3 are CQ = 5.0 MHz, δ = 60 ppm, and ν = 0.15. The parameters for O2 are similar to interpretations of recent data for this kind of site in high pressure sodium aluminosilicate glasses (δ = 59 ppm) and to quantum chemical calculations (Lee et al., 2004, J. Phys. Chem., 108, 5897). Pyrope and grossular each contain one oxygen site, oxygen bonded to [4]Si, [6]Al, and two M2+ cations. The 17O NMR parameters for pyrope are CQ = 3.4 MHz, δ = 84 ppm, and ν = 0.3 and for grossular are CQ = 4.1 MHz, δ = 102 ppm, and ν = 0.4. In grossular, the NMR peak for oxygens bonded to [4]Si, Ca, and high coordinated Al seems to fall between those for "normal" bridging and non bridging oxygens, as reported for high pressure CAS glasses by Allwardt et al. (2005). These data will also be useful to help understand Ca-Mg ordering in the pyrope-grossular solid solutions. Mullite contains four oxygen environments: oxygen bonded to three tetrahedral Al or Si (Oc*), oxygen bonded to two tetrahedral Al or Si (Oc), and

  3. Multitude of 2+ discrete states in 124Sn observed via the (17O 17O'γ) reaction: Evidence for pygmy quadrupole states

    NASA Astrophysics Data System (ADS)

    Pellegri, L.; Bracco, A.; Tsoneva, N.; Avigo, R.; Benzoni, G.; Blasi, N.; Bottoni, S.; Camera, F.; Ceruti, S.; Crespi, F. C. L.; Giaz, A.; Leoni, S.; Lenske, H.; Million, B.; Morales, A. I.; Nicolini, R.; Wieland, O.; Bazzacco, D.; Bednarczyk, P.; Birkenbach, B.; Ciemała, M.; de Angelis, G.; Farnea, E.; Gadea, A.; Görgen, A.; Gottardo, A.; Grebosz, J.; Isocrate, R.; Kmiecik, M.; Krzysiek, M.; Lunardi, S.; Maj, A.; Mazurek, K.; Mengoni, D.; Michelagnoli, C.; Napoli, D. R.; Recchia, F.; Siebeck, B.; Siem, S.; Ur, C.; Valiente-Dobón, J. J.

    2015-07-01

    A multitude of discrete 2+ states in 124Sn with energy up to 5 MeV were populated and identified with the (17O, 17O'γ) reaction at 340 MeV. Cross sections were compared with distorted wave Born approximation predictions and in general a good agreement was found. The measured energy and intensity distributions of the 2+ states are very similar to the predictions based on self-consistent density functional theory and extended QRPA approach accounting for multiphonon degrees of freedom. This provides evidence of the excitation of the pygmy quadrupole resonance in skin nuclei.

  4. Phase Diagram for 3He Films on Boron Nitride: NMR Studies

    NASA Astrophysics Data System (ADS)

    Tang, Yibing; Sullivan, Neil

    2014-03-01

    Recent studies of the thermodynamic properties of 3He films on graphite have revealed the existence of a previously undetected self-bound liquid phase at low density coverages. We report the results of NMR relaxation time studies for 3He adsorbed on hexagonal boron nitride designed to explore the dynamics of the adsorbed 3He atoms in order to identify the phase boundaries as a function of temperature. A steep thermally activated temperature dependence is observed at high temperatures (T > 2 . 6) K, followed by a linear dependence for 0 . 77 < T < 2 . 6 K. The linear dependence is consistent with that expected for thermal diffusion in the self-bound liquid state. The research was supported in part by a grant from the National Science Foundation, DMR-1303599.

  5. Dynamic NMR studies of restricted arene rotation in the chromiu tricarbonyl thiophene and selenophene complexes

    SciTech Connect

    Sanger, M.J.

    1994-05-27

    This thesis contains the results of organometallic studies of thiophene and selenophene coordination in transition metal complexes. Chromium tricarbonyl complexes of thiophene, selenophene, and their alkyl-substituted derivatives were prepared and variable-temperature {sup 13}C NMR spectra of these complexes were recorded in dimethyl ether. Bandshape analyses of these spectra yielded activation parameters for restricted rotation of the thiophene and selenophene ligands in these complexes. Extended Hueckel molecular orbital calculations (EHMO) of the free thiophene and selenophene ligands and selected chromium tricarbonyl thiophene complexes were performed to better explain the activation barriers of these complexes. The structure of Cr(CO){sub 3}({eta}{sup 5}-2,5-dimethylthiophene) was established by a single crystal X-ray diffraction study.

  6. Carbon-13 NMR studies of salt shock-induced carbohydrate turnover in the marine cyanobacterium Agmenellum quadruplicatum

    NASA Technical Reports Server (NTRS)

    Tel-Or, E.; Spath, S.; Packer, L.; Mehlhorn, R. J.

    1986-01-01

    Carbon turnover in response to abrupt changes in salinity, including the mobilization of glycogen for use in osmoregulation was studied with pulse-chase strategies utilizing nuclear magnetic resonance (NMR)-silent and NMR-detectable 12C and 13C isotopes, respectively. Growth of Agmenellum quadruplicatum in 30%-enriched 13C bicarbonate provided sufficient NMR-detectability of intracellular organic osmoregulants for these studies. A comparison of NMR spectra of intact cells and their ethanol extracts showed that the intact cell data were suitable for quantitative work, and, when combined with ESR measurements of cell volumes, yielded intracellular glucosylglycerol concentrations without disrupting the cells. NMR pulse-chase experiments were used to show that 13C-enriched glycogen, which had previously been accumulated by the cells under nitrogen-limited growth at low salinities, could be utilized for the synthesis of glucosylglycerol when the cells were abruptly transferred to hypersaline media, but only in the light. It was also shown that the accumulation of glucosylglycerol in the light occurred on a time scale similar to that of cell doubling. Depletion of glucosylglycerol when cells abruptly transferred to lower salinities appeared to be rapid--the intracellular pool of this osmoregulant was decreased 2-fold within 2 hours of hypotonic shock.

  7. Conformational solution studies of neuropeptide gamma using CD and NMR spectroscopy.

    PubMed

    Rodziewicz-Motowidło, Sylwia; Brzozowskl, Krzysztof; Legowska, Anna; Liwo, Adam; Silbering, Jerzy; Smoluch, Marek; Rolka, Krzysztof

    2002-05-01

    Neuropeptide gamma is one of the largest members of the tachykinin family of peptides, exhibiting strong agonistic activity towards the NK-2 tachykinin receptor. This peptide was synthesized by the solid-phase method using the Fmoc chemistry. Circular-dichroism spectroscopy (CD) investigations of this peptide were performed in phosphate buffer, in the presence of sodium dodecylsulphate (SDS) micelles and trifluoroethanol (TFE) solutions and in DMSO-d6 using the 2D NMR technique in conjunction with two different theoretical approaches. The first assumes multiconformational equilibrium of the peptide studied characterized by the values of statistical weights of low-energy conformations. These calculations were performed using three different force fields ECEPP/3, AMBER4.1 and CHARMM (implemented in the X-PLOR program). The second method incorporates interproton distance and dihedral angle constraints into the starting conformation using the Simulated Annealing algorithm (X-PLOR program). The CD experiments revealed that although the peptide studied is flexible in polar solvents, a tendency to adopt a helical structure was observed in the hydrophobic environment. The NMR data (NOE effects) indicate a helical or reverse structure in the Ile7-His12 fragment of the peptide studied in DMSO-d6 solution. The results obtained cannot be interpreted in terms of a single conformation. Most of the conformations obtained with the ECEPP/3 force field possess a high content of a helical structure. None of the conformers, obtained with the AMBER4.1 and CHARMM force fields, can be considered as the dominant one. In all conformations several beta-turns were detected and in some cases gamma-turns were also found. But in fact, it is rather difficult to select the position of the secondary element(s) present in the structure of NPgamma in solution. All conformers calculated with the X-PLOR program (with using NMR derived distance and torsion angle constraints) are stabilized by several

  8. Dynamic and organizational studies by SH NMR of polyisoprenols (PIs) in model membranes

    SciTech Connect

    Troy, F.A.; Knudsen, M.J.

    1987-05-01

    The objective of the authors studies seeks to understand the molecular details of how undecaprenol (C55) and dolichol (C95) function as chemical carriers of glycosyl residues in the membrane-directed synthesis of glycoconjugates. SH NMR studies provide information on the organization and dynamics of PIs in model membranes. Incorporation of polar or omega-terminus SH-labeled PIs into multilamellar membranes of phosphatidylcholine (PC) give rise to SH-NMR spectra interpretable in terms of quadrupole splittings ( vq), a measure of the degree of orderness of the SH-labeled site, and spin lattice relaxation times (T1's), revealing rates of motion. The authors results show: 1) vq of the PIs increased with increase concentration of label and with lowering of temperature; 2) little difference in T1 or vq values between tail-group or headgroup SH-labeled geraniol (C10), farnesol (C15) or solanesol (C45) was observed; and 3) T1 measurements revealed correlation times close to the fatty acyl CH3 termini in PC. These data indicate that both ends of the esterified PI molecules see similar environments in the bilayer (BL) interior, and suggest that the esterified PIs studied here do not adopt a conventional head-group-at-interface orientation of lipids within the BL. These data support the authors earlier conclusions based on spin label EPR studies. Headgroup labeled dolichol (C95-CD2-OH) and dolichol phosphate (C94-CD2-O-PO3H2) have been synthesized. Surprisingly, no anisotropic quadrupole splitting in PC vesicles were observed. This may indicate an unusual conformation of the long poly-cis prenyl chains.

  9. Effect of solvent on proton location and dynamic behavior in short intramolecular hydrogen bonds studied by molecular dynamics simulations and NMR experiments

    NASA Astrophysics Data System (ADS)

    Mori, Yukie; Masuda, Yuichi

    2015-09-01

    Hydrogen phthalate anion has a short strong O-H-O hydrogen bond (H-bond). According to previous experimental studies, the H-bond is asymmetric and two tautomers are interconverted in aqueous solutions. In the present study, the effects of polar solvents on the H-bond in a zwitterionic hydrogen phthalate derivative 1 were investigated by quantum mechanics/molecular mechanics molecular dynamics (MD) simulations. The analyses of the trajectories for the methanol solution showed that the H-bonding proton tends to be located closer to the carboxylate group that forms fewer intermolecular H-bonds, than to the other carboxylate group and that the intramolecular proton transfer in 1 is triggered by the breakage and/or formation of an intermolecular H-bond. The enol form of dibenzoylmethane (2) also has a short H-bond, and the OH bond is reported to be rather long (>1.1 Å) in the crystal. In the present study, the effects of the solvent on the H-bond in 2 were investigated by molecular orbital (MO) calculations, MD simulations and nuclear magnetic resonance (NMR) spectroscopy. Density functional theory (DFT) calculations for 2 in vacuum indicated that the barrier height for the intramolecular proton transfer is almost the same as the zero-point energy of the vibrational ground state, resulting in broad distribution of the proton density along the H-bond, owing to the nuclear quantum effect. The OH distances were determined in CCl4, acetonitrile, and dimethylsulfoxide solutions from the magnetic dipolar interactions between the 17O and 1H nuclei monitoring the nuclear magnetic relaxation times of 1H. The experimental results indicated that the H-bond geometry of 2 is influenced by the interactions with dimethylsulfoxide, suggesting the formation of a bifurcated H-bond, which was supported by the DFT calculations. The MD simulations for the methanol solution of 2 showed that the asymmetry of the OH distance is correlated with the asymmetry in the electrostatic field of the

  10. The NMR and X-ray study of L-arginine derived Schiff bases and its cadmium complexes

    NASA Astrophysics Data System (ADS)

    Kołodziej, B.; Grech, E.; Schilf, W.; Kamieński, B.; Pazio, A.; Woźniak, K.

    2014-04-01

    The structure study of five Schiff bases derived from L-arginine (L-Arg) and 2-hydroxy carbonyl compounds were performed in both solution and solid state using NMR and X-ray methods. Both analytical methods applied to the solid state sample of two Schiff bases showed a significant difference in molecular structures of unsubstituted and 7-CH3 substituted compounds. This effect was explained as a steric interaction of methyl group. Additionally the structure of two Cd2+ complexes with some Schiff bases were determined by NMR methods in DMSO solution and in the solid state. On the base of heteronuclear NMR measurement (13C, 15N and 113Cd) it was possible to define the complexation site on nitrogen atom. The large set of spectral parameters: chemical shifts, homo- and heteronuclear coupling constants, were used in structure study.

  11. Solid state NMR and pair distribution function studies of silicon electrodes for lithium-ion batteries

    NASA Astrophysics Data System (ADS)

    Key, Baris

    The universally used negative electrode material in a LIB is carbon, because of its moderate capacity (372 mAhg-1 for graphite), cyclability and high rate capability. However, new, low cost, safe electrode materials with higher capacities are still urgently required for both portable and transportation applications. Silicon anodes are particularly attractive alternatives to carbon with extremely high gravimetric energy densities (3572 mAhg-1). Compared to graphite, silicon has a massive volumetric capacity of 8322 mAhcm-3 (calculated based on the original volume of silicon) which is approximately ten times that graphite. At room temperature, upon electrochemical lithiation, silicon undergoes a crystalline to amorphous phase transition forming a lithiated amorphous silicide phase. Unfortunately, due to the amorphous nature of the lithiated silicides, it is not possible to monitor all the structural changes that occur during lithium insertion/removal with conventional methods such as diffraction. The short range order of the amorphous materials remains unknown, preventing attempts to optimize performance based on electrochemical-structure correlations. In this work, a combination of local structure probes, ex-situ 7Li nuclear magnetic resonance (NMR) studies and pair distribution function (PDF) analysis of X-ray data was applied to investigate the changes in short range order that occur during the initial charge and discharge cycles. The distinct electrochemical profiles observed subsequent to the 1 st discharge have been shown to be associated with the formation of distinct amorphous lithiated silicide structures. A (de)lithiation model consisting of four different mechanisms, each being valid for regions of the charge or discharge process is proposed to explain the hysteresis and the steps in the electrochemical profile observed during lithiation and delithiation of Si. A spontaneous reaction of the fully lithiated lithium silicide with the electrolyte is directly

  12. Theoretical and Numerical Studies of Dynamics in Nucleic Acids based on Experimental NMR Data

    NASA Astrophysics Data System (ADS)

    Emani, Prashant S.

    The collection of work presented in this thesis is directed towards building an understanding of the dynamics of nucleic acid molecules and their components using data obtained from solid state and solution NMR experiments. The focus of these studies is to develop analytical and numerical methods of elucidating motional trajectories of residues in example molecules, by simulating the impact of specific choices of models on NMR observables. Specifically, the target molecules studied were the unbound HIV-1 TAR RNA, a 29 nucleotide RNA segment, and the unbound dodecamer HhaI methyltransferase-recognition DNA. The data available for various residues in these systems include solid state line shapes, longitudinal (T1Z) and quadrupolar (T1Q) relaxation times, as well as solution longitudinal (T1) and rotating frame (T1rho) relaxation times and Nuclear Overhauser Effects (NOEs). The four projects discussed in this thesis form a cohesive whole, with each succeeding method either building upon previous work or adding a new means of analysis: firstly, a slow exchange theory is presented where discrete-jump motional models derived using solid state NMR data can be tested against solution relaxation times, by the inclusion of both overall molecular tumbling and exchange between conformers occurring at a time scale much slower than the tumbling time scale. The time scale separation allows for a particularly simple weighted summation over the spectral density contributions from the various conformers. The second project, discussed subsequently, removes this assumption of time scale separation, and allows for any rate of exchange between conformers. Both simulation protocols use the TAR RNA molecule as the test system. Parallel work on the HhaI-recognition DNA builds a framework for testing a discrete-jump trajectory constructed using pre-existing rotamers of the molecule against solid state relaxation times. This visualization of the dynamics of a residue is then carried over to

  13. Accessible NMR Experiments Studying the Hydrodynamics of [subscript 15]N-Enriched Ubiquitin at Low Fields

    ERIC Educational Resources Information Center

    Thompson, Laura E.; Rovnyak, David

    2007-01-01

    We have recently developed and implemented two experiments in biomolecular NMR for an undergraduate-level biophysical chemistry laboratory with commercially available [subscript 15]N-enriched human ubiquitin. These experiments take advantage of [subscript 15]N direct detection of the NMR signal. The first experiment develops skills in acquiring…

  14. Accessible NMR Experiments Studying the Hydrodynamics of [superscript 15]N-Enriched Ubiquitin at Low Fields

    ERIC Educational Resources Information Center

    Thompson, Laura E.; Rovnyak, David

    2007-01-01

    We have recently developed and implemented two experiments in biomolecular NMR for an undergraduate-level biophysical chemistry laboratory with commercially available [superscript 15]N-enriched human ubiquitin. These experiments take advantage of [superscript 15]N direct detection of the NMR signal. The first experiment develops skills in…

  15. 1H NMR studies distinguish the water soluble metabolomic profiles of untransformed and RAS-transformed cells

    PubMed Central

    Marks, Vered; Munoz, Anisleidys; Rai, Priyamvada

    2016-01-01

    Metabolomic profiling is an increasingly important method for identifying potential biomarkers in cancer cells with a view towards improved diagnosis and treatment. Nuclear magnetic resonance (NMR) provides a potentially noninvasive means to accurately characterize differences in the metabolomic profiles of cells. In this work, we use 1H NMR to measure the metabolomic profiles of water soluble metabolites extracted from isogenic control and oncogenic HRAS-, KRAS-, and NRAS-transduced BEAS2B lung epithelial cells to determine the robustness of NMR metabolomic profiling in detecting differences between the transformed cells and their untransformed counterparts as well as differences among the RAS-transformed cells. Unique metabolomic signatures between control and RAS-transformed cell lines as well as among the three RAS isoform-transformed lines were found by applying principal component analysis to the NMR data. This study provides a proof of principle demonstration that NMR-based metabolomic profiling can robustly distinguish untransformed and RAS-transformed cells as well as cells transformed with different RAS oncogenic isoforms. Thus, our data may potentially provide new diagnostic signatures for RAS-transformed cells. PMID:27330862

  16. NMR studies on interaction of lauryl maltoside with cytochrome c oxidase: a model for surfactant interaction with the membrane protein.

    PubMed

    Chattopadhyay, Krishnananda; Das, Tapan Kanti; Majumdar, Ananya; Mazumdar, Shyamalava

    2002-07-25

    Interaction of lauryl maltoside (LM) surfactant with bovine heart cytochrome c oxidase (CcO) has been studied by NMR techniques. Detailed 2-D (1)H and (13)C NMR techniques were used to assign the NMR signals of the surfactant nuclei. Paramagnetic dipolar shift of the surfactant (13)C NMR signals were used to identify the atoms close to the enzyme. The diamagnetic carbon monoxide complex of CcO did not cause any shift in the surfactant NMR spectra suggesting that the paramagnetic centres of the native CcO cause the shifts by dipolar interactions. The results showed that the polar head groups of the surfactant comprised of two maltoside rings are more affected, while the hydrophobic tail groups did not show any significant change on binding of the surfactant to the enzyme. This indicated that surfactant head groups possibly bind to the enzyme surface and the hydrophobic tail of the surfactant forms micelles and remains away from the enzyme. Based on the results, we propose that the membrane bound enzyme is possibly stabilised in aqueous solution by association with the micelles of the neutral surfactant so that the polar heads of the micelles bind to the polar surface of the enzyme. These micelles might form a 'belt like' structure around the enzyme helping it to remain monodispersed in the active form. PMID:12121768

  17. An NMR study of pyridine associated with DMPC liposomes and magnetically ordered DMPC-surfactant mixed micelles.

    PubMed Central

    Henderson, J M; Iannucci, R M; Petersheim, M

    1994-01-01

    With molecular dynamics simulations of phospholipid membranes becoming a reality, there is a growing need for experiments that provide the molecular details necessary to test these computational results. Pyridine is used here to explore the interaction of planar aromatic groups with the water-lipid interface of membranes. It is shown by magic angle spinning 13C nuclear magnetic resonance (NMR) to bind between the glycerol and choline groups of dimyristoylphosphatidylcholine (DMPC) liposomes. The axial pattern for the 31P NMR spectrum of DMPC liposomes is preserved even with more than half of the interfacial sites occupied, indicating that pyridine does not disrupt the lamellar phase of this lipid. 2H NMR experiments of liposomes in deuterium oxide demonstrate that pyridine might promote greater penetration of water into restricted regions in the interface. Magnetically oriented DMPC/surfactant micelles were investigated as a means for improving resolution and sensitivity in NMR studies of species bound to bilayers. The quadrupolar splittings in the 2H NMR spectra of d5-pyridine in DMPC liposomes and magnetically oriented DMPC/Trixon X-100 micelles indicate a common bound state for the two bilayer systems. The well resolved quadrupolar splittings of d5-pyridine in oriented micelles were used to establish the tilt of the pyridine ring relative to the bilayer plane. PMID:7918992

  18. Conformations and Conformational Processes of Hexahydrobenzazocines by NMR and DFT Studies.

    PubMed

    Musielak, Bogdan; Holak, Tad A; Rys, Barbara

    2015-09-18

    Conformational processes that occur in hexahydrobenzazocines have been studied with the (1)H and (13)C dynamic nuclear magnetic resonance (DNMR) spectroscopy. The coalescence effects are assigned to two different conformational processes: the ring-inversion of the ground-state conformations and the interconversion between two different conformers. The barriers for these processes are in the range of 42-52 and 42-43 kJ mol(-1), respectively. Molecular modeling on the density functional theory (DFT) level and the gauge invariant atomic orbitals (GIAO)-DFT calculations of isotropic shieldings and coupling constants for the set of low-energy conformations were compared with the experimental NMR data. The ground-state of all compounds in solution is the boat-chair (BC) conformation. The BC form adopts two different conformations because the nitrogen atom can be in the boat or chair parts of the BC structure. These two conformers are engaged in the interconversion process. PMID:26317238

  19. ^13C Solid NMR Study of Devulcanization and Revulcanization of SBR Ne

    NASA Astrophysics Data System (ADS)

    Massey, J.; Levin, V.; Isayev, A.; von Meerwall, E.

    1996-03-01

    As part of a larger effort in support of recycling of rubber-based composites, we have used ^13C CP-MAS NMR spectroscopy and relaxation to study molecular and segmental mobilities in styrene-butadiene random copolymers before and after sulfur crosslinking, after subsequent devulcanization using a thermal ultrasound technique, and following revulcanization. Tracking the cis-trans ratio indicates that overall network crosslink density increases during each of these steps, including devulcanization, which produces mesoscale network aggregates and substantial amounts of sol. This observation is confirmed by the transverse (T_2) relaxation times, which show that molecular/segmental mobilities monotonically decrease in the same sequence. Analysis of these effects requires the invocation of alterations in sulfur crosslinking, i.e. density, distribution, and functionality, including extensive cyclization. Measurements of the glass transition temperatures in melt, network, sol , and revulcanizate are in accord with this picture.

  20. Isotope-edited proton NMR study on the structure of a pepsin/inhibitor complex

    SciTech Connect

    Fesik, S.W.; Luly, J.R.; Erickson, J.W.; Abad-Zapatero, C.

    1988-11-01

    A general approach is illustrated for providing detailed structural information on large enzyme/inhibitor complexes using NMR spectroscopy. The method involves the use of isotopically labeled ligands to simplify two-dimensional NOE spectra of large molecular complexes by isotope-editing techniques. With this approach, the backbone and side-chain conformations (at the P/sub 2/ and P/sub 3/ sites) of a tightly bound inhibitor of porcine pepsin have bene determined. In addition, structural information on the active site of pepsin has been obtained. Due to the sequence homology between porcine pepsin and human renin, this structural information may prove useful for modeling renin/inhibitor complexes with the ultimate goal of designing more effective renin inhibitors. Moreover, this general approach can be applied to study other biological systems of interest such as other enzyme/inhibitor complexes, ligands bound to soluble receptors, and enzyme/substrate interactions.

  1. SLOW-MAS NMR METHODS TO STUDY METABOLIC PROCESSES IN VIVO AND IN VITRO

    SciTech Connect

    Wind, Robert A.; Bertram, Hanne Christine; Hu, Jian Zhi

    2005-09-25

    In vitro and in vivo 1H NMR spectroscopy is widely used to measure metabolic profiles in cells, tissues, animals, and humans and to use them, e.g., for diagnosis and therapy response evaluations. However, the spectra often suffer from poor resolution due to variations in the isotropic bulk magnetic susceptibility present in biological objects, resulting in a broadening of the NMR lines. In principle this broadening can be averaged to zero by the technique of magic angle spinning (MAS), where the sample is rotated about an axis making an angle of 54o44’ relative to the external magnetic field. However, a problem is that in a standard MAS experiment spinning speeds of a kHz or more are required in order to avoid the occurrence of spinning sidebands (SSBs) in the spectra, which renders analysis of the spectra difficult again. At these spinning speeds the large centrifugal forces cause severe structural damage in larger biological objects, so that this method cannot be used to study metabolic processes in intact samples. In solid state NMR several methods have been developed where slow MAS is combined with special radio frequency pulse sequences to eliminate spinning side bands or separate them from the isotropic spectrum so that a SSB-free high-resolution isotropic spectrum is obtained. It has been shown recently that two methods, phase-adjusted spinning sidebands (PASS) and phase-corrected magic angle turning (PHORMAT), can successfully be modified for applications in biological materials (1, 2). With PASS MAS speeds as low as 40 Hz can be employed, allowing non or minimally invasive in vitro studies of excised tissues and organs. This method was used, amongst other things, to study post mortem changes in the proton metabolite spectra in excised rabbit muscle tissue (3). With PHORMAT the NMR sensitivity is reduced and longer measuring times are required, but with this methodology the MAS speed can be reduced to ~1 Hz. This makes PHORMAT amenable for in vivo

  2. Aluminum(III) speciation with acetate and oxalate. A potentiometric and sup 27 Al NMR study

    SciTech Connect

    Thomas, F.; Rouiller, J.; Genevrier, F.; Boudot, D. ); Masion, A.; Bottero, J.Y. )

    1991-09-01

    Aluminum (III) hydrolysis and precipitation in the presence of acetic acid and oxalic acid have been studied by combining potentiometric titration and liquid-state {sup 27}Al NMR. The main aluminum species have thus been identified and quantified: unreacted hydrolyzed, complexed monomers, and the Al{sub 13} tridecamer. A solid species appeared when precipitation occurred and was quantified by difference with the other species. The quantitative evolution of these species was followed for pH values up to 5. Acetate forms weak complexes with aluminum. The precipitated phase was hypothesized to be aggregated Al{sub 13}. Oxalate forms strong multiligand complexes to form Al{sub 13} requires higher hydroxyl content. High oxalate contents (L/M > 1) inhibit tridecamer formation and precipitation occurs only at high pH values. With oxalate the precipitated phase seems to be devoid of Al{sub 13} and of a more condensed nature than it is with acetate.

  3. In vitro proton NMR study of collagen in human aortic wall.

    PubMed

    Vinée, P; Meurer, B; Constantinesco, A; Kohlberger, B; Hauenstein, K H; Laubenberger, J

    1993-03-01

    The authors relate the findings in the 1H solid state line shape (at 60 MHz) of human aortic walls (n = 12) in native state and after histologically controlled selective lysis of collagen and elastin. An analysis of the line shape shows a composite free induction decay (FID) consisting of a low amplitude (3-7%) fast decaying component (T2 approximately 20 microseconds) and a slow decaying one (T2 > 1 ms). The fast component is identified as the protons of the collagen macromolecules. The second moment computed from the experimental fast component of the FID is in agreement with published studies examining the motional characteristics of collagen by multinuclear NMR employing spin labeling. A theoretical second moment is computed for the collagen macromolecular backbone from the atomic positions in the superhelix. Comparison with the observed experimental values allows determination of the step angle (29 degrees) of the fast rotational motion of the collagen strands along their long axis. PMID:8383787

  4. 1H NMR Cryoporometry Study of the Melting Behavior of Water in White Cement

    NASA Astrophysics Data System (ADS)

    Boguszyńska, Joanna; Tritt-Goc, Jadwiga

    2004-09-01

    The pore size of white cement samples is studied by the melting behaviour of water confined in it, using 1H NMR cryopormetry. The influence of the preparing method and antifreeze admixture on the pore size and distribution in cement samples is investigated at 283 K. The addition of an antifreeze admixture [containing 1% Sika Rapid 2 by weight of the dry cement] influences the porosity. In wet prepared samples we observed a significant increase in the quantity of mesopores between 0.8 and 5 nm and a smaller increase of mesopores between 5 and 10 nm, when compared to cement without admixture. The compressive strength is related to the porosity of the cement. Therefore the cement with Sika Rapid 2, wet prepared at 278 K shows a higher strength than all other measured samples.

  5. NMR analyses of the cold cataract. III. /sup 13/C acrylamide studies

    SciTech Connect

    Lerman, S.; Megaw, J.M.; Moran, M.N.

    1985-10-01

    /sup 13/C-enriched acrylamide was employed to further delineate the action of this compound in preventing the cold cataract phenomenon when it is incorporated (in vitro) into young human and rabbit lenses. The extent of acrylamide incorporation, in the dark and with concurrent UV exposure, was monitored by /sup 13/C NMR spectroscopy. These studies provide further evidence that UV exposure causes permanent acrylamide photobinding within the lens. In such lenses, the gamma crystallin fraction of the soluble lens proteins is affected to the greatest extent. It appears to become aggregated and/or combined with the alpha and beta fractions resulting in an apparent loss of most of the gamma monomers. There is also an age-related effect with respect to the amount of acrylamide that can be incorporated into the lens. The decrease in acrylamide incorporation with age directly parallels the age-related decline in gamma crystallin levels.

  6. The polymorphic phases of the hexaalkanoyloxytriphenylene liquid crystals, as studied by deuterium NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Goldfarb, D.; Lifshitz, E.; Zimmermann, H.; Luz, Z.

    1985-06-01

    Deuterium NMR spectra are reported for several specifically deuterated hexaalkanoyloxytriphenylenes in their corresponding liquid crystalline phases. The higher homologs of this series are polymorphic and exhibit a variety of discotic mesophases, including both biaxial (D0 and D1) and uniaxial (D2) columnar phases. The ordering characteristics of these phases are studied using the quadrupolar splittings of the aromatic and aliphatic deuterons. The results show that during the transition from the biaxial D1 to the axial D2 phase the major susceptibility tensor switch orientation, apparently due to strong tilting of the molecules with respect to the columnar axis in the biaxial phase. Characteristic features which appear in the spectra of these phases are interpreted in terms of intercolumnar jumps of mesogen molecules.

  7. Comparative NMR study of copper-based intermetallics with ZrCuSiAs-type structure

    NASA Astrophysics Data System (ADS)

    Lue, C. S.; ChangJen, W. J.; Su, T. H.

    2010-07-01

    The electronic characteristics of ZrCuGe2, ZrCuSi2, and HfCuSi2 are systematically investigated using C63u NMR spectroscopy. The quadrupole splittings, Knight shifts, and spin-lattice relaxation times on each individual compound have been identified. We found that the observed electric field gradient is consistent with the covalent bonding nature within the Cu atomic layers. The Knight shifts together with relaxation rates provide a measure of Cu d partial Fermi-level density of states, Nd(EF). Universally small Nd(EF) was found in all studied materials, suggests that the Cu d states are well below the Fermi energy and therefore the characteristic electronic structure near EF is primarily of sp type. We further pointed out that the low Nd(EF) value is an important factor for the lack of superconductivity in these Cu-based intermetallics within the ZrCuSiAs-type structure.

  8. 1H NMR study of the complexation of aromatic drugs with dimethylxanthine derivatives

    NASA Astrophysics Data System (ADS)

    Hernandez Santiago, A. A.; Gonzalez Flores, M.; Rosas Castilla, S. A.; Cervantes Tavera, A. M.; Gutierrez Perez, R.; Khomich, V. V.; Ovchinnikov, D. V.; Parkes, H. G.; Evstigneev, M. P.

    2012-02-01

    With an aim of searching efficient interceptors of aromatic drugs, the self- and hetero-association of dimethylxanthine derivatives with different structures, selected according to Strategy 1 (variation of the position of methyl groups) and Strategy 2 (variation of the length of sbnd (CH2)nsbnd COOH group), with aromatic drug molecules: Ethidium Bromide, Proflavine and Daunomycin, were studied using 1H NMR spectroscopy. It was found that the association proceeds in a form of stacking-type complexation and its energetics is relatively independent on the structure of the dimethylxanthines. However, on average, the dimethylxanthines possess higher hetero-association constant and, hence, higher interceptor ability as compared to the trimethylxanthine, Caffeine, used during the past two decades as a typical interceptor molecule.

  9. NMR and X-ray studies of isomeric 22,23-dihydroxy stigmastanes

    NASA Astrophysics Data System (ADS)

    Khripach, Vladimir A.; Zhabinskii, Vladimir N.; Ivanova, Galina V.; Fando, Galina P.; Tsavlovskii, Dmitrii V.; Khripach, Natalya B.; Lyakhov, Alexander S.; Misharin, Alexander Yu.

    2010-06-01

    A comparative conformational study of steroidal side chain of (22 R,23 R)- and (22 S,23 S)-dihydroxy stigmastane derivatives was performed using single crystal X-ray diffraction and NMR spectroscopy. The preferred conformation in solution was shown to be close to that in the crystal. (22 R,23 R)-Isomers typical for natural plant steroid hormones brassinosteroids adopt a conformation in which both hydroxyl groups are pointed toward unhindered α-side of the steroidal plane and can thus participate in biochemical processes. Unnatural (22 S,23 S)-counterparts exhibit a conformation with the two hydroxyl groups oriented in the opposite direction and sterically hindered by 21-methyl group and terminal side chain fragment.

  10. Porous Structure of Pharmaceutical Tablets Studied Using PGSTE-NMR Technique

    NASA Astrophysics Data System (ADS)

    Porion, Patrice; Tchoreloff, Pierre; Busignies, Virginie; Leclerc, Bernard; Evesque, Pierre

    2009-06-01

    The compaction of pharmaceutical tablets at high pressure (250 MPa) is a complex process that depends on the nature of the chemical compound. The purpose of this work is to characterize the porous structure of tablets obtained by uniaxial compaction, the most used process in pharmaceutical technology. First, three pharmaceutical excipients (microcrystalline cellulose, lactose and anhydrous calcium phosphate) were compacted and their compressibility properties determined. Secondly, the study of the self-diffusion process of a molecular fluid inside the pore space was performed by using pulsed-gradient stimulated-echo (PGSTE) NMR method, for tablets compacted under various pressure, in the directions perpendicular and parallel to the compaction axis. The results are used to determine the tortuosity factor and the anisotropy of the porous space of such compacted materials.

  11. NMR studies of a new family of DNA binding proteins: the THAP proteins.

    PubMed

    Gervais, Virginie; Campagne, Sébastien; Durand, Jade; Muller, Isabelle; Milon, Alain

    2013-05-01

    The THAP (THanatos-Associated Protein) domain is an evolutionary conserved C2CH zinc-coordinating domain shared with a large family of cellular factors (THAP proteins). Many members of the THAP family act as transcription factors that control cell proliferation, cell cycle progression, angiogenesis, apoptosis and epigenetic gene silencing. They recognize specific DNA sequences in the promoters of target genes and subsequently recruit effector proteins. Recent structural and functional studies have allowed getting better insight into the nuclear and cellular functions of some THAP members and the molecular mechanisms by which they recognize DNA. The present article reviews recent advances in the knowledge of the THAP domains structures and their interaction with DNA, with a particular focus on NMR. It provides the solution structure of the THAP domain of THAP11, a recently characterized human THAP protein with important functions in transcription and cell growth in colon cancer. PMID:23306615

  12. Structural studies of homoisoflavonoids: NMR spectroscopy, X-ray diffraction, and theoretical calculations

    NASA Astrophysics Data System (ADS)

    Sievänen, Elina; Toušek, Jaromír; Lunerová, Kamila; Marek, Jaromír; Jankovská, Dagmar; Dvorská, Margita; Marek, Radek

    2010-08-01

    In this article we present a detailed structural investigation for five homoisoflavonoids, molecules important from the pharmacological point of view. For studying the electron distribution as well as its influence on the physicochemical properties, NMR spectroscopy, X-ray diffraction, and theoretical calculations have been used. Nuclear magnetic shieldings obtained by using DFT calculations for optimized molecular geometries are correlated with the experimentally determined chemical shifts. The theoretical data are well in agreement with the experimental values. The single crystal X-ray structures of homoisoflavonoid derivatives 1, 3, and 4 have been solved. The molecular geometries and crystal packing determined by X-ray diffraction are used for characterizing the intermolecular interactions. Electron distribution is crucial for the stability of radicals and hence the antioxidant efficiency of flavonoid structures. The hydrogen bonding governs the formation of complexes of homoisoflavonoids with biological targets.

  13. A Kinetic Study of DDGS Hemicellulose Acid Hydrolysis and NMR Characterization of DDGS Hydrolysate.

    PubMed

    Chen, Hanchi; Liu, Shijie

    2015-09-01

    Liquid hot water (LHW) extraction was used as a pretreatment method to separate the hemicellulose fraction from dried distiller's grain with solubles (DDGS) into liquid phase. Acid hydrolysis using 3.264 % w/w sulfuric acid at 130 °C was performed to convert polysaccharides in LHW extract to monosaccharides. The structure characterization of DDGS in anomeric carbon region based on proton NMR and heteronuclear single quantum coherence (HSQC) during acid hydrolysis was studied in this work. It reveals that the sugar units in DDGS hemicelluloses are constructed with (1-4)-β-D-xylopyranose and α-L-arabinofuranosyl residues. A kinetic model is included to explain the changing concentration of monomer, oligomer, and sugar units. The model was further tested based on the changing concentration of five carbon sugar units during hydrolysis. PMID:26198022

  14. Solid-state NMR study of intercalated species in poly(epsilon-caprolactone)/clay nanocomposites.

    PubMed

    Hrobarikova, J; Robert, J-L; Calberg, C; Jérôme, R; Grandjean, J

    2004-10-26

    The structure and dynamics of surfactant and polymer chains in intercalated poly(epsilon-caprolactone)/clay nanocomposites are characterized by (31)P magic-angle spinning (MAS) and (13)C cross-polarization MAS NMR techniques. To obtain hybrid materials with the low polymer content required for this study, in situ intercalative polymerization was performed by adapting a published procedure. After nanocomposite formation, the chain motion of the surfactant is enhanced in the saponite-based materials but reduced in the Laponite ones. Compared to the starting clay, the trans conformer population of the surfactant hydrocarbon chain in the nanocomposite decreases for the saponite systems. Mobility of the polymer chain is higher in the nanocomposites than in the bulk phase. The charge of the modified saponite does not significantly influence chain mobility in the nanocomposites. PMID:15491221

  15. Spectroscopic (FT-IR, FT-Raman and NMR) and computational studies on 3-methoxyaniline

    NASA Astrophysics Data System (ADS)

    Sivaranjini, T.; Periandy, S.; Govindarajan, M.; Karabacak, M.; Asiri, A. M.

    2014-01-01

    In this work, the molecular structure, vibrational, UV and NMR spectra of 3-methoxyaniline (abbreviated as 3MOA, C7H9NO) were studied. The FT-IR and FT-Raman spectra were recorded. The ground-state molecular geometry and vibrational frequencies were calculated by using the Hartree-Fock (HF) and density functional theory (DFT)/B3LYP methods and 6-311++G(d, p) as a basis set. The fundamental vibrations were assigned on the basis of the total energy distribution (TED) of the vibrational modes, calculated with scaled quantum mechanics (SQM) method and PQS program. Comparison of the observed fundamental vibrational frequencies of 3MOA with calculated results by HF and DFT methods indicates that B3LYP is superior to HF method for molecular vibrational problems. The difference between the observed and scaled wavenumber values is very small. The theoretically predicted FT-IR and FT-Raman spectra of the title molecule have been constructed. A study on the Mulliken atomic charges, the electronic properties were performed by time-dependent DFT (TD-DFT) approach, Frontier molecular orbitals (FMO), molecular electrostatic potential (MEP) and thermodynamic properties were performed and compared with methoxybenzene and aniline. The electric dipole moment (μ) and the first hyperpolarizability (β) values of the investigated molecule were computed using ab initio quantum mechanical calculations. The calculated results also show that the 3MOA molecule might have microscopic nonlinear optical (NLO) behavior with non-zero values. The 13C nuclear magnetic resonance (NMR) chemical shifts of the molecule were calculated by the gauge independent atomic orbital (GIAO) method and compared with experimental results.

  16. Calcination products of gibbsite studied by X-ray diffraction, XPS and solid-state NMR

    SciTech Connect

    Malki, A.; Mekhalif, Z.; Detriche, S.; Fonder, G.; Boumaza, A.; Djelloul, A.

    2014-07-01

    The changes caused by heat treatment of gibbsite powder at 300–1473 K were studied using the X-ray diffraction (XRD), X-ray photoemission (XPS) spectra and {sup 27}Al magic angle spinning nuclear magnetic resonance spectroscopy ({sup 27}Al MAS NMR). XRD analysis indicates that the transformation sequence involves the formation of κ-Al{sub 2}O{sub 3} as an intermediate phase between χ- and α-Al{sub 2}O{sub 3}. The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. XPS analysis indicates that the ratio of aluminium atoms to oxygen atoms in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3} increases, whereas the expected ratio is observed in α-Al{sub 2}O{sub 3}. The percentage of AlO{sub 4} units in the transition aluminas follows the same behaviour as the ratio of Al/O. - Graphical abstract: The percentage of AlO{sub 4} units in transition aluminas follows the same behaviour as the ratio of Al/O. - Highlights: • Calcination products of gibbsite studied by XRD, XPS and solid-state NMR. • The crystallite size of χ-Al{sub 2}O{sub 3} is as small as 10 nm. • The Al/O atomic ratio determined by XPS is larger than 2/3 in χ-Al{sub 2}O{sub 3} and κ-Al{sub 2}O{sub 3}. • The percentage of AlO{sub 4} in the aluminas follows the same behaviour as the Al/O atomic ratio.

  17. An NMR relaxometry and gravimetric study of gelatin-free aqueous polyacrylamide dosimeters

    NASA Astrophysics Data System (ADS)

    Babic, Steven; Schreiner, L. John

    2006-09-01

    In conformal radiation therapy, a high dose of radiation is given to a target volume to increase the probability of cure, and care is taken to minimize the dose to surrounding healthy tissue. The techniques used to achieve this are very complicated and the precise verification of the resulting three-dimensional (3D) dose distribution is required. Polyacrylamide gelatin (PAG) dosimeters with magnetic resonance imaging and optical computed tomography scanning provide the required 3D dosimetry with high spatial resolution. Many basic studies have characterized these chemical dosimeters that polymerize under irradiation. However, the investigation of the fundamental properties of the radiation-induced polymerization in PAG dosimeters is complicated by the presence of the background gelatin matrix. In this work, a gelatin-free model system for the study of the basic radiation-induced polymerization in PAG dosimeters has been developed. Experiments were performed on gelatin-free dosimeters, named aqueous polyacrylamide (APA) dosimeters, containing equal amounts of acrylamide and N,N'-methylene-bisacrylamide. The APA dosimeters were prepared with four different total monomer concentrations (2, 4, 6 and 8% by weight). Nuclear magnetic resonance (NMR) spin-spin and spin-lattice proton relaxation measurements at 20 MHz, and gravimetric analyses performed on all four dosimeters, show a continuous degree of polymerization over the dose range of 0-25 Gy. The developed NMR model explains the relationship observed between the relaxation data and the amount of crosslinked polymer formed at each dose. This model can be extended with gelatin relaxation data to provide a fundamental understanding of radiation-induced polymerization in the conventional PAG dosimeters.

  18. Measurement of the cross section for the reaction 20Ne( n,α)17O in the neutron-energy between 4 and 7 MeV

    NASA Astrophysics Data System (ADS)

    Khryachkov, V. A.; Bondarenko, I. P.; Kuzminov, B. D.; Semenova, N. N.; Sergachev, A. I.

    2012-04-01

    The cross section for the reaction 20Ne( n, α)17O was measured in the neutron-energy range 4-7 MeV. An ionization chamber equipped with a Frisch grid combined with a pulse-shape digitizer was used as a detector. Gaseous neon that served as a target on which the reaction being studied proceeded was added to the gas filling the ionization chamber. The partial cross sections for the α 0, α 1, α 2, and α 3 channels of the reaction 20Ne( n, α)17O were obtained for the first time.

  19. On the macromolecular cellulosic network of paper: changes induced by acid hydrolysis studied by NMR diffusometry and relaxometry.

    PubMed

    Conti, Allegra; Poggi, Giovanna; Baglioni, Piero; De Luca, Francesco

    2014-05-14

    The cellulosic network of artificially acidified paper has been studied by 2D NMR relaxometry, NMR diffusometry and NMR diffusion-diffraction. Results show that the acidifying treatment enlarges the macropore structure of paper increasing the pore connectivity and modifying the exchange between water populations localized in amorphous cellulose. Acidification damage suggests that simple breaking of the amorphous portion of fibrils occurs. Nevertheless, under a specific acidifying condition, a rearrangement in the cellulose network seems to take place, with a reduction of the average macropore size and a loss of pore connectivity. The identification of water populations by 2D relaxation maps allows for monitoring the changes in cellulose water mobility due to the depolymerization process. In general the relaxation and self-diffusion results confirm that water mobility increases with acidification. PMID:24663146

  20. Solid-state NMR studies of proteins immobilized on inorganic surfaces

    PubMed Central

    Shaw, Wendy J.

    2015-01-01

    Solid state NMR is the primary tool for studying the quantitative, site-specific structure, orientation, and dynamics of biomineralization proteins under biologically relevant conditions. Two calcium phosphate proteins, statherin (43 amino acids) and leucine rich amelogenin protein (LRAP; 59 amino acids), have been studied in depth and have different dynamic properties and 2D- and 3D-structural features. These differences make it difficult to extract design principles used in nature for building materials with properties such as high strength, unusual morphologies, or uncommon phases. Consequently, design principles needed for developing synthetic materials controlled by proteins are not clear. Many biomineralization proteins are much larger than statherin and LRAP, necessitating the study of larger biomineralization proteins. More recent studies of the significantly larger full-length amelogenin (180 residues) represent a significant step forward to ultimately investigate the full diversity of biomineralization proteins. Interactions of amino acids, a silaffin derived peptide, and the model LK peptide with silica are also being studied, along with qualitative studies of the organic matrices interacting with calcium carbonate. Dipolar recoupling techniques have formed the core of the quantitative studies, yet the need for isolated spin pairs makes this approach costly and time intensive. The use of multidimensional techniques to study biomineralization proteins is becoming more common, methodology which, despite its challenges with these difficult-to-study proteins, will continue to drive future advancements in this area. PMID:25466354

  1. UV-vis, IR and 1H NMR spectroscopic studies and characterization of ionic-pair crystal violet-oxytetracycline

    NASA Astrophysics Data System (ADS)

    Orellana, Sandra; Soto, César; Toral, M. Inés

    2010-01-01

    The present study shows the formation and characterization of the ionic-pair between the antibiotic oxytetracycline and the dye crystal violet in ammonia solution pH 9.0 ± 0.2 extracted into chloroform. The characterization was demonstrated using UV-vis spectrophotometry, 1H NMR, measurement of relaxation times T1 and IR spectroscopy, using a comparison between the signals of individual pure compounds with the signals with the mixture CV-OTC in different alkaline media. The formation of ionic-pair was also corroborated by new signals and chemical shifts. (2D) NMR spectroscopy experiments show that the interaction is electrostatic.

  2. Dicobalt-μ-oxo polyoxometalate compound, [(α(2)-P2W17O61Co)2O](14-): a potent species for water oxidation, C-H bond activation, and oxygen transfer.

    PubMed

    Barats-Damatov, Delina; Shimon, Linda J W; Weiner, Lev; Schreiber, Roy E; Jiménez-Lozano, Pablo; Poblet, Josep M; de Graaf, Coen; Neumann, Ronny

    2014-02-01

    High-valent oxo compounds of transition metals are often implicated as active species in oxygenation of hydrocarbons through carbon-hydrogen bond activation or oxygen transfer and also in water oxidation. Recently, several examples of cobalt-catalyzed water oxidation have been reported, and cobalt(IV) species have been suggested as active intermediates. A reactive species, formally a dicobalt(IV)-μ-oxo polyoxometalate compound [(α2-P2W17O61Co)2O](14-), [(POMCo)2O], has now been isolated and characterized by the oxidation of a monomeric [α2-P2W17O61Co(II)(H2O)](8-), [POMCo(II)H2O], with ozone in water. The crystal structure shows a nearly linear Co-O-Co moiety with a Co-O bond length of ∼1.77 Å. In aqueous solution [(POMCo)2O] was identified by (31)P NMR, Raman, and UV-vis spectroscopy. Reactivity studies showed that [(POMCo)2O]2O] is an active compound for the oxidation of H2O to O2, direct oxygen transfer to water-soluble sulfoxides and phosphines, indirect epoxidation of alkenes via a Mn porphyrin, and the selective oxidation of alcohols by carbon-hydrogen bond activation. The latter appears to occur via a hydrogen atom transfer mechanism. Density functional and CASSCF calculations strongly indicate that the electronic structure of [(POMCo)2O]2O] is best defined as a compound having two cobalt(III) atoms with two oxidized oxygen atoms. PMID:24437566

  3. Studies of Secondary Melanoma on C57BL/6J Mouse Liver Using 1H NMR Metabolomics

    SciTech Connect

    Feng, Ju; Isern, Nancy G.; Burton, Sarah D.; Hu, Jian Z.

    2013-10-31

    NMR metabolomics, consisting of solid state high resolution (hr) magic angle spinning (MAS) 1H NMR (1H hr-MAS), liquid state high resolution 1H-NMR, and principal components analysis (PCA) has been used to study secondary metastatic B16-F10 melanoma in C57BL/6J mouse liver . The melanoma group can be differentiated from its control group by PCA analysis of the absolute concentrations or by the absolute peak intensities of metabolites from either 1H hr-MAS NMR data on intact liver tissues or liquid state 1H-NMR spectra on liver tissue extracts. In particular, we found that the absolute concentrations of alanine, glutamate, creatine, creatinine, fumarate and cholesterol are elevated in the melanoma group as compared to controls, while the absolute concentrations of succinate, glycine, glucose, and the family of linear lipids including long chain fatty acids, total choline and acylglycerol are decreased. The ratio of glycerophosphocholine to phosphocholine is increased by about 1.5 fold in the melanoma group, while the absolute concentration of total choline is actually lower in melanoma mice. These results suggest the following picture in secondary melanoma metastasis: Linear lipid levels are decreased by beta oxidation in the melanoma group, which contributes to an increase in the synthesis of cholesterol, and also provides an energy source input for TCA cycle. These findings suggest a link between lipid oxidation, the TCA cycle and the hypoxia-inducible factors (HIF) signal pathway in tumor metastases. Thus this study indicates that the metabolic profile derived from NMR analysis can provide a valuable bio-signature of malignancy and cell hypoxia in metastatic melanoma.

  4. Feasibility studies. The use of NMR spectrometry as a possible substitute of or complement to several analytical tests in pharmacopoeia monographs.

    PubMed

    McEwen, I; Arvidsson, T

    2012-04-01

    NMR spectrometry has many analytical applications; for instance, the identification of known substances; the structure elucidation of unknown ones; the quantification of APIs, impurities, solvent and water; kinetic studies, stereochemistry determinations, and the analyses of complex mixtures as in metabonomics. NMR spectrometry has the potential to substitute or complement existing analyses that are performed on APIs. In this work, 4 different NMR analyses were done on 2 APIs: fluvastatin sodium and benzalkonium chloride with good results. PMID:23327894

  5. Architecture of the hepatitis C virus E1 glycoprotein transmembrane domain studied by NMR.

    PubMed

    Zazrin, Hadas; Shaked, Hadassa; Chill, Jordan H

    2014-03-01

    Oligomerization of hepatitis C viral envelope proteins E1 and E2 is essential to virus fusion and assembly. Although interactions within the transmembrane (TM) domains of these glycoproteins have proven contributions to the E1/E2 heterodimerization process and consequent infectivity, there is little structural information on this entry mechanism. Here, as a first step towards our long-term goal of understanding the interaction between E1 and E2 TM-domains, we have expressed, purified and characterized E1-TM using structural biomolecular NMR methods. An MBP-fusion expression system yielded sufficient quantities of pure E1-TM, which was solubilized in two membrane-mimicking environments, SDS- and LPPG-micelles, affording samples amenable to NMR studies. Triple resonance assignment experiments and relaxation measurements provided information on the secondary structure and global fold of E1-TM in these environments. In SDS micelles E1-TM adopts a helical conformation, with helical stretches at residues 354-363 and 371-379 separated by a more flexible segment of residues 364-370. In LPPG micelles a helical conformation was observed for residues 354-377 with greater flexibility in the 366-367 dyad, suggesting LPPG provides a more native environment for the peptide. Replacement of key positively charged residue K370 with an alanine did not affect the secondary structure of E1-TM but did change the relative positioning within the micelle of the two helices. These results lay the foundation for structure determination of E1-TM and a molecular understanding of how E1-TM flexibility enhances its interaction with E2-TM during heterodimerization and membrane fusion. PMID:24192053

  6. 15N NMR study of nitrate ion structure and dynamics in hydrotalcite-like compounds

    USGS Publications Warehouse

    Hou, X.; James, Kirkpatrick R.; Yu, P.; Moore, D.; Kim, Y.

    2000-01-01

    We report here the first nuclear magnetic resonance (NMR) spectroscopic study of the dynamical and structural behavior of nitrate on the surface and in the interlayer of hydrotalcite-like compounds (15NO3--HT). Spectroscopically resolvable surface-absorbed and interlayer NO3- have dramatically different dynamical characteristics. The interlayer nitrate shows a well defined, temperature independent uniaxial chemical shift anisotropy (CS A) powder pattern. It is rigidly held or perhaps undergoes rotation about its threefold axis at all temperatures between -100 ??C and +80 ??C and relative humidities (R.H.) from 0 to 100% at room temperature. For surface nitrate, however, the dynamical behavior depends substantially on temperature and relative humidity. Analysis of the temperature and R.H. dependences of the peak width yields reorieritational frequencies which increase from essentially 0 at -100 ??C to 2.6 ?? 105 Hz at 60 ??C and an activation energy of 12.6 kJ/mol. For example, for samples at R.H. = 33%, the surface nitrate is isotropically mobile at frequencies greater than 105 Hz at room temperature, but it becomes rigid or only rotates on its threefold axis at -100 ??C. For dry samples and samples heated at 200 ??C (R.H. near 0%), the surface nitrate is not isotropically averaged at room temperature. In contrast to our previous results for 35Cl--containing hydrotalcite (35Cl--HT), no NMR detectable structural phase transition is observed for 15NO3--HT. The mobility of interlayer nitrate in HT is intermediate between that of carbonate and chloride.

  7. Methyl quantum tunneling and nitrogen-14 NQR NMR studies using a SQUID magnetic resonance spectrometer

    SciTech Connect

    Black, B.E. |

    1993-07-01

    Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) techniques have been very successful in obtaining molecular conformation and dynamics information. Unfortunately, standard NMR and NQR spectrometers are unable to adequately detect resonances below a few megahertz due to the frequency dependent sensitivity of their Faraday coil detectors. For this reason a new spectrometer with a dc SQUID (Superconducting Quantum Interference Device) detector, which has no such frequency dependence, has been developed. Previously, this spectrometer was used to observe {sup 11}B and {sup 27}Al NQR resonances. The scope of this study was increased to include {sup 23}Na, {sup 51}V, and {sup 55}Mn NQR transitions. Also, a technique was presented to observe {sup 14}N NQR resonances through cross relaxation of the nitrogen polarization to adjacent proton spins. When the proton Zeeman splitting matches one nitrogen quadrupoler transition the remaining two {sup 14}N transitions can be detected by sweeping a saturating rf field through resonance. Additionally, simultaneous excitation of two nitrogen resonances provides signal enhancement which helps to connect transitions from the same site. In this way, nitrogen-14 resonances were observed in several amino acids and polypeptides. This spectrometer has also been useful in the direct detection of methyl quantum tunneling splittings at 4.2 K. Tunneling, frequencies of a homologous series of carboxylic acids were measured and for solids with equivalent crystal structures, an exponential correlation between the tunneling frequency and the enthalpy of fusion is observed. This correlation provides information about the contribution of intermolecular interactions to the energy barrier for methyl rotation.

  8. Structural studies of the activation of the two component receiver domain NTRC by multidimensional heteronuclear NMR

    SciTech Connect

    Nohaile, M J

    1996-05-01

    Multidimensional heteronuclear NMR spectroscopy was used to investigate the N-terminal domain of the transcriptional enhancer NTRC (NiTrogen Regulatory protein C). This domain belongs to the family of receiver domains of two-component regulatory systems involved in signal transduction. Phosphorylation of NTRC at D54 leads to an activated form of the molecule which stimulates transcription of genes involved in nitrogen regulation. Three and four dimensional NMR techniques were used to determine an intermediate resolution structure of the unphosphorylated, inactive form of the N-terminal domain of NTRC. The structure is comprised of five {alpha}-helices and a five-stranded {beta}-sheet in a ({beta}/{alpha}){sub 5} topology. Analysis of the backbone dynamics of NTRC indicate that helix 4 and strand 5 are significantly more flexible than the rest of the secondary structure of the protein and that the loops making up the active site are flexible. The short lifetime of phospho-NTRC hampers the study of this form. However, conditions for determining the resonance assignments and, possibly, the three dimensional structure of phosphorylated NTRC have been obtained. Tentative assignments of the phosphorylated form indicate that the majority of the changes that NTRC experiences upon phosphorylation occur in helix 3, strand 4, helix 4, strand 5, and the loop between strand 5 and helix 5 (the 3445 face of NTRC) as well as near the site of phosphorylation. In order to examine a stable, activated form of the protein, constitutively active mutants of NTRC were investigated.

  9. Polarization transfer solid-state NMR for studying surfactant phase behavior.

    PubMed

    Nowacka, Agnieszka; Mohr, Parveen Choudhary; Norrman, Jens; Martin, Rachel W; Topgaard, Daniel

    2010-11-16

    The phase behavior of amphiphiles, e.g., lipids and surfactants, at low water content is of great interest for many technical and pharmaceutical applications. When put in contact with air having a moderate relative humidity, amphiphiles often exhibit coexistence between solid and liquid crystalline phases, making their complete characterization difficult. This study describes a (13)C solid-state NMR technique for the investigation of amphiphile phase behavior in the water-poor regime. While the (13)C chemical shift is an indicator of molecular conformation, the (13)C signal intensities obtained with the CP and INEPT polarization transfer schemes yield information on molecular dynamics. A theoretical analysis incorporating the effect of molecular segment reorientation, with the correlation time τ(c) and order parameter S, shows that INEPT is most efficient for mobile segments with τ(c) < 0.01 μs and S < 0.05, while CP yields maximal signal for rigid segments with τ(c) > 10 μs and/or S > 0.5 under typical solid-state NMR experimental conditions. For liquid crystalline phases, where τ(c) < 0.01 μs and 0 < S < 0.3, the observed CP and INEPT intensities serve as a gauge of S. The combination of information on molecular conformation and dynamics permits facile phase diagram determination for systems with solid crystalline, solid amorphous, anisotropic liquid crystalline, and isotropic liquid (crystalline) phases as demonstrated by experiments on a series of reference systems with known phase structure. Three solid phases (anhydrous crystal, dihydrate, gel), two anisotropic liquid crystalline phases (normal hexagonal, lamellar), and two isotropic liquid crystalline phases (micellar cubic, bicontinuous cubic) are identified in the temperature-composition phase diagram of the cetyltrimethylammonium succinate/water system. Replacing the succinate counterion with DNA prevents the formation of phases other than hexagonal and leads to a general increase of τ(c). PMID

  10. 1D and 2D NMR studies of isobornyl acrylate - Methyl methacrylate copolymers

    NASA Astrophysics Data System (ADS)

    Khandelwal, Deepika; Hooda, Sunita; Brar, A. S.; Shankar, Ravi

    2011-10-01

    Isobornyl acrylate - methyl methacrylate (B/M) copolymers of different compositions were synthesized by atom transfer radical polymerization (ATRP) using methyl-2-bromopropionate as an initiator and PMDETA copper complex as catalyst under nitrogen atmosphere at 70 °C. 1H NMR spectrum was used to determine the compositions of copolymer. The copolymer compositions were then used to determine the reactivity ratios of monomers. Reactivity ratios of co-monomers in B/M copolymer, determined from linear Kelen-Tudos method (KT) and non linear Error-in-Variable Method (EVM), are rB = 0.41 ± 0.11, rM = 1.11 ± 0.33 and rB = 0.52, rM = 1.31 respectively. The complete resonance assignments of 1H and 13C{ 1H} NMR spectra were carried out with the help of Distortion less Enhancement by Polarization Transfer (DEPT), two-dimensional Heteronuclear Single Quantum Coherence (HSQC). 2D HSQC assignments were further confirmed by 2D Total Correlation Spectroscopy (TOCSY). The carbonyl carbon of B and M units and methyl carbon of M unit were assigned up to triad compositional and configurational sequences whereas β-methylene carbons were assigned up to tetrad compositional and configurational sequences. Similarly the methine carbon of B unit was assigned up to pentad level. 1,3 and 1,4 bond order couplings of carbonyl carbon and quaternary carbon resonances with methine, methylene and methyl protons were studied in detail using 2D Hetero Nuclear Multiple Bond Correlation (HMBC) spectra.

  11. Mobile Permanent Magnet NMR Systems for Field Studies on Antarctic Sea Ice

    NASA Astrophysics Data System (ADS)

    Gädke, Achim; Dykstra, Robin

    2011-03-01

    A permanent magnet based Nuclear Magnetic Resonance (NMR) system has been developed to measure various properties of the brine in sea ice. In contrast to systems utilizing the Earth's field in previous expeditions, the comparatively high field of 0.28 T provided by permanent magnets allows for shorter measurement times and advanced NMR protocols. In November 2009 the instrument was deployed to Antarctica to investigate sea ice grown under natural conditions. In this paper the instrument is described, preliminary results are reported and future options for mobile NMR applications in Antarctica discussed.

  12. Perfluoroalkyl Grignard Reagents: NMR Study of 1-Heptafluoropropylmagnesium Chloride in Solution.

    PubMed

    Guang, Jie; Hopson, Russell; Williard, Paul G; Fujiu, Motohiro; Negishi, Kazuyuki; Mikami, Koichi

    2016-07-15

    We report on the generation of a perfluoroalkyl Grignard reagent ((F)RMgX) by exchange reaction between a perfluoroalkyl iodide ((F)R-I) and a Grignard reagent (RMgX). (19)F NMR was applied to monitor the generation of n-C3F7MgCl. Additional NMR techniques, including (19)F COSY, NOESY, and pulsed gradient spin-echo (PGSE) diffusion NMR, were invoked to assign peaks observed in (19)F spectrum. Schlenk equilibrium was observed and was significantly influenced by solvent, diethyl ether, or THF. PMID:27295419

  13. NMR studies of granular media and two-phase flow in porous media

    NASA Astrophysics Data System (ADS)

    Yang, Xiaoyu

    This dissertation describes two experimental studies of a vibrofluidized granular medium and a preliminary study of two-phase fluid flow in a porous medium using Nuclear Magnetic Resonance (NMR). The first study of granular medium is to test a scaling law of the rise in center of mass in a three-dimensional vibrofluidized granular system. Our granular system consisted of mustard seeds vibrated vertically at 40 Hz from 0g to 14g. We used Magnetic Resonance Imaging (MRI) to measure density profile in vibrated direction. We observed that the rise in center of mass scaled as nu 0alpha/Nlbeta with alpha = 1.0 +/- 0.2 and beta = 0.5 +/- 0.1, where nu 0 is the vibration velocity and Nl is the number of layers of grains in the container. A simple theory was proposed to explain the scaling exponents. In the second study we measured both density and velocity information in the same setup of the first study. Pulsed Field Gradient (PFG)-NMR combined with MRI was used to do this measurement. The granular system was fully fluidized at 14.85g 50 Hz with Nl ≤ 4. The velocity distributions at horizontal and vertical direction at different height were measured. The distributions were nearly-Gaussian far from sample bottom and non-Gaussian near sample bottom. Granular temperature profiles were calculated from the velocity distributions. The density and temperature profile were fit to a hydrodynamic theory. The theory agreed with experiments very well. A temperature inversion near top was also observed and explained by additional transport coefficient from granular hydrodynamics. The third study was the preliminary density measurement of invading phase profile in a two-phase flow in porous media. The purpose of this study was to test an invasion percolation with gradient (IPG) theory in two-phase flow of porous media. Two phases are dodecane and water doped with CuSO4. The porous medium was packed glass beads. The front tail width sigma and front width of invading phase were

  14. MRI and PGSE NMR Studies of Long-range, Pore-pore Interaction Effects in Gas Adsorption

    NASA Astrophysics Data System (ADS)

    Hitchcock, Iain; Rigby, Sean; Chudek, John; Holt, Liz; Lowe, John

    2011-03-01

    In this work MRI and PGSE NMR have been used to directly study the advanced condensation effect during water adsorption in a macroscopically heterogeneous sol-gel silica pellet. It has been found that capillary condensation will occur at unexpectedly lower pressures in regions of much larger pores that lie in close proximity to smaller pores.

  15. NMR spectroscopy applied to the Cultural Heritage: a preliminary study on ancient wood characterisation

    NASA Astrophysics Data System (ADS)

    Viel, S.; Capitani, D.; Proietti, N.; Ziarelli, F.; Segre, A. L.

    High and low resolution solid state NMR methods have been applied to characterise a few samples of ancient wood. In an ancient larch wood sample, by applying 1H low resolution NMR methods as a function of the temperature, the average pore size and its distribution have been determined. In addition, high resolution NMR techniques have allowed addressing of the question of the proximity of water pools to cellulose and lignin. In particular, a model can be hypothesized in which water pools are surrounded by thin layers of amorphous cellulose and/or lignin while the crystalline domains of cellulose surround the layers of amorphous cellulose. Preliminary results obtained using a fully non invasive and portable NMR unilateral relaxometer, the Eureka-Mouse10 (EM10), are reported. This instrumentation is shown to be perfectly suitable for characterizing degradation in ancient wood samples.

  16. Structural studies of PCU-hydrazones: NMR spectroscopy, X-ray diffractions, and DFT calculations

    NASA Astrophysics Data System (ADS)

    Veljković, Jelena; Šekutor, Marina; Molčanov, Krešimir; Lo, Rabindranath; Ganguly, Bishwajit; Mlinarić-Majerski, Kata

    2011-06-01

    In this article we present a detailed structural investigation for the configurational isomers of PCU-hydrazones. The structural characterization of these hydrazones was performed using NMR spectroscopy, X-ray diffraction analysis and theoretical calculations. The single crystal X-ray structures of PCU-hydrazones 6B and 6C have been solved and used to conclusively confirm the characterization obtained via NMR spectra of a particular isomer. Nuclear magnetic shielding values calculated for 6A-C using DFT calculations were correlated with the experimentally determined chemical shifts. The computed results were found to be in good agreement with the observed 13C NMR values. The computed NMR results helped to ascertain the isomers of PCU-hydrazones 4A-C.

  17. /sup 29/Si NMR study of the surface of pyrogenic silica modified by methylchlorosilanes

    SciTech Connect

    Brie, V.V.; Gorlov, Yu.I.; Chuiko, A.A.

    1986-11-01

    Cross-polarization /sup 29/Si NMR spectra have been used for aerosil modified by methyl-chlorosilanes to identify surface organosilicon compounds and their reactions during hydrolysis and methanolysis.

  18. NMR Study of Ion Dynamics and Charge Storage in Ionic Liquid Supercapacitors

    PubMed Central

    2015-01-01

    Ionic liquids are emerging as promising new electrolytes for supercapacitors. While their higher operating voltages allow the storage of more energy than organic electrolytes, they cannot currently compete in terms of power performance. More fundamental studies of the mechanism and dynamics of charge storage are required to facilitate the development and application of these materials. Here we demonstrate the application of nuclear magnetic resonance spectroscopy to study the structure and dynamics of ionic liquids confined in porous carbon electrodes. The measurements reveal that ionic liquids spontaneously wet the carbon micropores in the absence of any applied potential and that on application of a potential supercapacitor charging takes place by adsorption of counterions and desorption of co-ions from the pores. We find that adsorption and desorption of anions surprisingly plays a more dominant role than that of the cations. Having elucidated the charging mechanism, we go on to study the factors that affect the rate of ionic diffusion in the carbon micropores in an effort to understand supercapacitor charging dynamics. We show that the line shape of the resonance arising from adsorbed ions is a sensitive probe of their effective diffusion rate, which is found to depend on the ionic liquid studied, as well as the presence of any solvent additives. Taken as whole, our NMR measurements allow us to rationalize the power performances of different electrolytes in supercapacitors. PMID:25973552

  19. NMR study of the conformation of the 2-aminopurine: Cytosine mismatch in DNA

    SciTech Connect

    Fagan, P.A.; Wemmer, D.E.; Goodman, M.F.

    1996-04-02

    DNA polymerase makes errors by misincorporating natural DNA bases and base analogs. Because of the wide variety of possible mismatches and the varying efficiency with which they are repaired, structural studies are necessary to understand in detail how these mispairs differ and can be distinguished from standard Watson-Crick base pairs. 2-Aminopurine (AP) is a highly mutagenic base analog. The objective of this study was to determine the geometry of the AP{center_dot}C mispair in DNA at neutral pH. Although several studies have focused on the AP{center_dot} mispair in DNA, there is not as of yet consensus on its structure. At least four models have been proposed for this mispair. Through the use of NMR spectroscopy with selective {sup 15}N-labeling of exocyclic amino nitrogens on bases of interest, we are able to resolve ambiguities in previous studies. We find here that, in two different DNA sequences, the AP{center_dot}C mispair at neutral and high pH is in a wobble geometry. The structure and stability of this base mispair is dependent upon the local base sequence. 48 refs., 4 figs., 1 tab.

  20. Interactions between Nafion resin and protonated dodecylamine modified montmorillonite: a solid state NMR study.

    PubMed

    Zhang, Limin; Xu, Jun; Hou, Guangjin; Tang, Huiru; Deng, Feng

    2007-07-01

    A series of nanocomposites have been prepared from perfluorosulfonylfluoride copolymer resin (Nafion) and layered montmorillonite (MMT) modified with protonated dodecylamine by conventional sol-gel intercalation. The structure of these nanocomposite materials have been characterized using FT-IR, elemental analysis, XRD and solid state NMR techniques, including 19F magic-angle spinning (MAS) NMR, 19F NMR relaxation time measurements, 29Si MAS, 1H MAS, 1H-13C cross-polarization magic-angle spinning (CPMAS), and 1H-13C heteronuclear correlation (HETCOR) 2D NMR. The results showed that thermal stability of Nafion was improved moderately by the addition of dodecylamine modified MMT without intercalation. FT-IR and 29Si MAS NMR results indicated that dodecylamine modification did not result in obvious changes in the MMT lattice structure. The XRD results showed that the protonated dodecylamine has been embedded and intercalated into the MMT interlayers, whereas Nafion was not. Elemental analysis results also suggested that some dodecylamine was adsorbed on the surface of MMT. 1H-13C HETCOR 2D NMR experiment clearly indicated that strong electrostatic interactions were present between the NH+3 group of dodecylamine and the fluorine-containing groups (CF3, OCF2, and SCF2) of Nafion resin. Such electrostatic interactions are probably the major contributors for the improved thermal stability of the resultant composite materials. PMID:17382953

  1. Structural heterogeneity in microcrystalline ubiquitin studied by solid-state NMR

    PubMed Central

    Fasshuber, Hannes Klaus; Lakomek, Nils-Alexander; Habenstein, Birgit; Loquet, Antoine; Shi, Chaowei; Giller, Karin; Wolff, Sebastian; Becker, Stefan; Lange, Adam

    2015-01-01

    By applying [1-13C]- and [2-13C]-glucose labeling schemes to the folded globular protein ubiquitin, a strong reduction of spectral crowding and increase in resolution in solid-state NMR (ssNMR) spectra could be achieved. This allowed spectral resonance assignment in a straightforward manner and the collection of a wealth of long-range distance information. A high precision solid-state NMR structure of microcrystalline ubiquitin was calculated with a backbone rmsd of 1.57 to the X-ray structure and 1.32 Å to the solution NMR structure. Interestingly, we can resolve structural heterogeneity as the presence of three slightly different conformations. Structural heterogeneity is most significant for the loop region β1-β2 but also for β-strands β1, β2, β3, and β5 as well as for the loop connecting α1 and β3. This structural polymorphism observed in the solid-state NMR spectra coincides with regions that showed dynamics in solution NMR experiments on different timescales. PMID:25644665

  2. Reconstitution of the Cytb5 -CytP450 Complex in Nanodiscs for Structural Studies using NMR Spectroscopy.

    PubMed

    Zhang, Meng; Huang, Rui; Ackermann, Rose; Im, Sang-Choul; Waskell, Lucy; Schwendeman, Anna; Ramamoorthy, Ayyalusamy

    2016-03-24

    Cytochrome P450s (P450s) are a superfamily of enzymes responsible for the catalysis of a wide range of substrates. Dynamic interactions between full-length membrane-bound P450 and its redox partner cytochrome b5 (cytb5 ) have been found to be important for the enzymatic activity of P450. However, the stability of the circa 70 kDa membrane-bound complex in model membranes renders high-resolution structural NMR studies particularly difficult. To overcome these challenges, reconstitution of the P450-cytb5 complex in peptide-based nanodiscs, containing no detergents, has been demonstrated, which are characterized by size exclusion chromatography and NMR spectroscopy. In addition, NMR experiments are used to identify the binding interface of the P450-cytb5 complex in the nanodisc. This is the first successful demonstration of a protein-protein complex in a nanodisc using NMR structural studies and should be useful to obtain valuable structural information on membrane-bound protein complexes. PMID:26924779

  3. Conformational changes of alamethicin induced by solvent and temperature. A 13C-NMR and circular-dichroism study.

    PubMed

    Jung, G; Dubischar, N

    1975-06-01

    13C nuclear magnetic resonance (NMR) and circular dichroism (CD) have been used for studies on the conformation of alamethicin. The 13C NMR spectrum is assigned with the aid of signals of synthetic partial sequences and selective proton decoupling. The solvent and temperature-dependence of the 13C NMR spectra, T1 measurements and the use of lanthanide-shift reagents allow the differentiation between the amino acids belonging to a rigid alpha-helical portion of the alamethicin sequence and those belonging to a more flexible part. The 13C NMR results are in agreement with results obtained from extended solvent and temperature-dependent CD studies which indicate a highly stabilized nonpolar and intrachenar alpha-helical part. The concentration-dependence of the CD spectrum of alamethicin in a nematic phase revealed aggregation phenomena which might simulate those observed in natural and synthetic membranes. After dissolving alamethicin in aqueous alcohol there is a time-dependence of the ellipticity of the Cotton effects showing a sort of memory effect on the mode of dissolution. Four different conformations can be characterized by CD spectra depending on the solvent and concentration. A model illustrating the dynamic conformations and aggregation phenomena within a membrane is proposed. PMID:1175592

  4. Combined (1)H NMR and LSER study for the compound-specific interactions between organic contaminants and organobentonites.

    PubMed

    Ruan, Xiuxiu; Zhu, Lizhong; Chen, Baoliang; Qian, Guangren; Frost, Ray L

    2015-12-15

    The compound-specific mechanisms for the sorption of organic contaminants onto cetyltrimethylammonium-saturated bentonite (i.e., CTMA-Bentonite) in water were evaluated by (1)H NMR study and Linear Solvation Energy Relationship (LSER) approach. In (1)H NMR study, comparing with pure CTMAB, the up-field shifts of hydrogen peaks for CH2N(+) and CH3N(+) of CTMA(+) in CTMAB-aromatics (1-naphtylamine, aniline and phenol) mixtures are much greater than that in CTMAB-aliphatics (cyclohexanone and cyclohexanol) mixtures. Meanwhile, the peak position of hydrogen on amino- and hydroxyl-groups of aromatic compounds also changes greatly. (1)H NMR data demonstrated the strong molecular interaction between the positive ammonium group of CTMA(+) and the delocalized π-systems of aromatic solutes, whereas the interactions of CTMA(+) with aliphatic compounds having electron-donating groups (such as cyclohexanol and cyclohexanone) or aromatic ring substituted by electron-withdrawing groups (i.e., nitrobenzene) or nonpolar aromatic compounds with single phenyl ring (i.e., toluene) are weak. The derived LSER equation was obtained by a multiple regression of the solid-water sorption coefficients (Kd) of 16 probe solutes upon their solvation parameters, and demonstrates aromatics sorption onto CTMA-Bentonite is concurrently governed by the π-/n-electron pair donor-accepter interaction and the cavity/dispersion interaction, while the predominant mechanism for aliphatic compounds is the cavity/dispersion interaction, consisting with the (1)H NMR results. PMID:26319328

  5. Accurate calculation of (31)P NMR chemical shifts in polyoxometalates.

    PubMed

    Pascual-Borràs, Magda; López, Xavier; Poblet, Josep M

    2015-04-14

    We search for the best density functional theory strategy for the determination of (31)P nuclear magnetic resonance (NMR) chemical shifts, δ((31)P), in polyoxometalates. Among the variables governing the quality of the quantum modelling, we tackle herein the influence of the functional and the basis set. The spin-orbit and solvent effects were routinely included. To do so we analysed the family of structures α-[P2W18-xMxO62](n-) with M = Mo(VI), V(V) or Nb(V); [P2W17O62(M'R)](n-) with M' = Sn(IV), Ge(IV) and Ru(II) and [PW12-xMxO40](n-) with M = Pd(IV), Nb(V) and Ti(IV). The main results suggest that, to date, the best procedure for the accurate calculation of δ((31)P) in polyoxometalates is the combination of TZP/PBE//TZ2P/OPBE (for NMR//optimization step). The hybrid functionals (PBE0, B3LYP) tested herein were applied to the NMR step, besides being more CPU-consuming, do not outperform pure GGA functionals. Although previous studies on (183)W NMR suggested that the use of very large basis sets like QZ4P were needed for geometry optimization, the present results indicate that TZ2P suffices if the functional is optimal. Moreover, scaling corrections were applied to the results providing low mean absolute errors below 1 ppm for δ((31)P), which is a step forward in order to confirm or predict chemical shifts in polyoxometalates. Finally, via a simplified molecular model, we establish how the small variations in δ((31)P) arise from energy changes in the occupied and virtual orbitals of the PO4 group. PMID:25738630

  6. Compositional differences among Chinese soy sauce types studied by (13)C NMR spectroscopy coupled with multivariate statistical analysis.

    PubMed

    Kamal, Ghulam Mustafa; Wang, Xiaohua; Bin Yuan; Wang, Jie; Sun, Peng; Zhang, Xu; Liu, Maili

    2016-09-01

    Soy sauce a well known seasoning all over the world, especially in Asia, is available in global market in a wide range of types based on its purpose and the processing methods. Its composition varies with respect to the fermentation processes and addition of additives, preservatives and flavor enhancers. A comprehensive (1)H NMR based study regarding the metabonomic variations of soy sauce to differentiate among different types of soy sauce available on the global market has been limited due to the complexity of the mixture. In present study, (13)C NMR spectroscopy coupled with multivariate statistical data analysis like principle component analysis (PCA), and orthogonal partial least square-discriminant analysis (OPLS-DA) was applied to investigate metabonomic variations among different types of soy sauce, namely super light, super dark, red cooking and mushroom soy sauce. The main additives in soy sauce like glutamate, sucrose and glucose were easily distinguished and quantified using (13)C NMR spectroscopy which were otherwise difficult to be assigned and quantified due to serious signal overlaps in (1)H NMR spectra. The significantly higher concentration of sucrose in dark, red cooking and mushroom flavored soy sauce can directly be linked to the addition of caramel in soy sauce. Similarly, significantly higher level of glutamate in super light as compared to super dark and mushroom flavored soy sauce may come from the addition of monosodium glutamate. The study highlights the potentiality of (13)C NMR based metabonomics coupled with multivariate statistical data analysis in differentiating between the types of soy sauce on the basis of level of additives, raw materials and fermentation procedures. PMID:27343582

  7. /sup 31/P NMR studies of ATP synthesis and hydrolysis kinetics in the intact myocardium

    SciTech Connect

    Kingsley-Hickman, P.B.; Sako, E.Y.; Mohanakrishnan, P.; Robitaille, P.M.L.; From, A.H.L.; Foker, J.E.; Ugurbil, K.

    1987-11-17

    The origin of the nuclear magnetic resonance (NMR)-measurable ATP in equilibrium P/sub i/ exchange and whether it can be used to determine net oxidative ATP synthesis rates in the intact myocardium were examined by detailed measurements of ATP in equilibrium P/sub i/ exchange rates in both directions as a function of the myocardial oxygen consumption rate (MVO/sub 2/) in (1) glucose-perfused, isovolumic rat hearts with normal glycolytic activity and (2) pyruvate-perfused hearts where glycolytic activity was reduced or eliminated either by depletion of their endogenous glycogen or by use of the inhibitor iodoacetate. In glucose-perfused hearts, the P/sub i/ ..-->.. ATP rate measured by the conventional two-site saturation transfer (CST) technique remained constant while MVO2 was increased approximately 2-fold. When the glycolytic activity was reduced, the P/sub i/ ..-->.. ATP rate decreased significantly, demonstrating the existence of a significant glycolytic contribution. The ATP ..-->.. P/sub i/ rates and rate:MVO ratios measured by the multiple-site saturation transfer method at two MVO/sub 2/ levels were equal to the corresponding P/sub i/..-->.. ATP rates and rate:MVO ratios obtained in the absence of a glycolytic contribution. The following conclusions are drawn from these studies: (1) unless the glycolytic contribution to the ATP in equilibrium P/sub i/ exchange is inhibited or is specifically shown not to exist, the myocardial P/sub i/ in equilibrium ATP exchange due to oxidative phosphorylation cannot be studied by NMR; (2) at moderate MVO/sub 2/ levels, the reaction catalyzed by the two glycolytic enzymes glyceraldehyde-3-phosphate dehydrogenase and 3-phosphoglycerate kinase is near equilibrium; (3) the ATP synthesis by the mitochondrial H/sup +/-ATPase occurs unidirectionally (i.e., the reaction is far out of equilibrium); (4) the operative P:O ratio in the intact myocardium under our conditions is significantly less than the canonically accepted value

  8. sup 13 C and sup 31 P NMR studies of myocardial metabolism

    SciTech Connect

    Laughlin, M.R.

    1988-01-01

    The fluxes through two enzyme systems have been measured in perfused or in in vivo heart using NMR: phosphocreatine kinase, and glycogen synthase and phosphorylase. The rates of synthesis and degradation of glycogen were monitored in vivo in fed, fasted, and diabetic rat heart during infusions of {sup 13}C-1-glucose and insulin using proton-decoupled {sup 13}C-NMR at 1.9 and 4.7 tesla. The enzyme activities of glycogen synthase and glycogen phosphorylase were also measured in this tissue which had been freeze clamped at the end of the experiment, for comparison with the synthetic rates. For normal fed, fasted, and diabetic animals, synthesis rates were 0.28, 0.16, and 0.15 {mu}mol/min.gww respectively. Glycogen synthase i activity was 0.23, 0.14, and 0.14 {mu}mol/min.gww in these hearts at the end of the experiment, when measured at appropriate substrate and activator concentrations, and follow activation time courses that are consistent with being the main rate determinant for net synthesis in all cases. Turnover of glycogen was studied by observing the preformed {sup 13}C-1-glycogen signal during infusion of {sup 12}C-glucose and insulin, and was found to be close to zero. Extracted phosphorylase a activity was approximately ten times that of synthase i under these circumstances. In order to fully interpret the turnover studies, glycogenolysis of preformed {sup 13}C-glycogen was observed after a bolus of glucagon. The glycogen had either been synthesized from {sup 13}C-1-glucose for a single hour, or during an hour of {sup 13}C-glucose and a subsequent hour of {sup 12}C-glucose infusion. The author observed that breakdown follows an exponential time course related to the phosphorylase a activation state and that the last synthesized glycogen breaks down at the rate of 2.5 {mu}mol/min.gww, five times faster than that synthesized an hour earlier.

  9. Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy, a new approach to study humic material?

    NASA Astrophysics Data System (ADS)

    Knicker, Heike; Lange, Sascha; van Rossum, Barth; Oschkinat, Hartmut

    2016-04-01

    Compared to solution NMR spectroscopy, solid-state NMR spectra suffer from broad resonance lines and low resolution. This could be overcome by the use of 2-dimenstional solid-state NMR pulse sequences. Until recently, this approach has been unfeasible as a routine tool in soil chemistry, mainly because of the low NMR sensitivity of the respective samples. A possibility to circumvent those sensitivity problems represents high-field Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy (Barnes et al., 2008), allowing considerable signal enhancements (Akbey et al., 2010). This is achieved by a microwave-driven transfer of polarization from a paramagnetic center to nuclear spins. Application of DNP to MAS spectra of biological systems (frozen solutions) showed enhancements of the factor 40 to 50 (Hall et al., 1997). Enhancements of this magnitude, thus may enable the use of at least some of the 2D solid-state NMR techniques that are presently already applied for pure proteins but are difficult to apply to soil peptides in their complex matrix. After adjusting the required acquisition parameters to the system "soil organic matter", lower but still promising enhancement factors were achieved. Additional optimization was performed and allowed the acquisition of 2D 13C and 15N solid-state NMR spectra of humified 13C and 15N enriched plant residues. Within the present contribution, the first solid-state DNP NMR spectra of humic material are presented. Those data demonstrate the great potential of this approach which certainly opens new doors for a better understanding of biochemical processes in soils, sediments and water. Akbey, Ü., Franks, W.T., Linden, A., Lange, S., Griffin, R.G., van Rossum, B.-J., Oschkinat, H., 2010. Dynamic nuclear polarization of deuterated proteins. Angewandte Chemie International Edition 49, 7803-7806. Barnes, A.B., De Paëpe, G., van der Wel, P.C.A., Hu, K.N., Joo, C.G., Bajaj, V.S., Mak-Jurkauskas, M.L., Sirigiri, J.R., Herzfeld, J

  10. Metabolic Characterization of Advanced Liver Fibrosis in HCV Patients as Studied by Serum 1H-NMR Spectroscopy

    PubMed Central

    Embade, Nieves; Mariño, Zoe; Diercks, Tammo; Cano, Ainara; Lens, Sabela; Cabrera, Diana; Navasa, Miquel; Falcón-Pérez, Juan M.; Caballería, Joan; Castro, Azucena; Bosch, Jaume; Mato, José M.; Millet, Oscar

    2016-01-01

    Several etiologies result in chronic liver diseases including chronic hepatitis C virus infection (HCV). Despite its high incidence and the severe economic and medical consequences, liver disease is still commonly overlooked due to the lack of efficient non-invasive diagnostic methods. While several techniques have been tested for the detection of fibrosis, the available biomarkers still present severe limitations that preclude their use in clinical diagnostics. Liver diseases have also been the subject of metabolomic analysis. Here, we demonstrate the suitability of 1H NMR spectroscopy for characterizing the metabolism of liver fibrosis induced by HCV. Serum samples from HCV patients without fibrosis or with liver cirrhosis were analyzed by NMR spectroscopy and the results were submitted to multivariate and univariate statistical analysis. PLS-DA test was able to discriminate between advanced fibrotic and non-fibrotic patients and several metabolites were found to be up or downregulated in patients with cirrhosis. The suitability of the most significantly regulated metabolites was validated by ROC analysis. Our study reveals that choline, acetoacetate and low-density lipoproteins are the most informative biomarkers for predicting cirrhosis in HCV patients. Our results demonstrate that statistical analysis of 1H-NMR spectra is able to distinguish between fibrotic and non-fibrotic patients suffering from HCV, representing a novel diagnostic application for NMR spectroscopy. PMID:27158896

  11. One new and six known triterpene xylosides from Cimicifuga racemosa: FT-IR, Raman and NMR studies and DFT calculations

    NASA Astrophysics Data System (ADS)

    Jamróz, Marta K.; Jamróz, Michał H.; Cz. Dobrowolski, Jan; Gliński, Jan A.; Gleńsk, Michał

    One new and six known triterpene xylosides were isolated from Cimicifuga racemosa (black cohosh, Actaea racemosa). The structure of a new compound, designated as isocimipodocarpaside (1), was established to be (24S)-3β-hydroxy-24,25-oxiirane-16,23-dione-9,10-seco-9,19-cyclolanost-1(10),7(8),9(11)-trien 3-O-β-D-xylopyranoside, by means of 1H and 13C NMR, IR and Raman spectroscopies and Mass Spectrometry. The six known compounds are: 23-epi-26-deoxycimicifugoside (2), 23-epi-26-deoxyactein (3), 25-anhydrocimigenol xyloside (4), 23-O-acetylshengmanol xyloside (5), 25-O-acetylcimigenol xyloside (6) and 3'-O-acetylcimicifugoside H-1 (7). On the basis of NMR data supported by DFT calculations of NMR shielding constants of (2), its structure, previously described as 26-deoxycimicifugoside was corrected and determined as 23-epi-26-deoxycimicifugoside. The 13C CPMAS NMR spectra of the studied compounds (1)-(7) provided data on their solid-state interactions. The IR and Raman spectra in the Cdbnd O, Cdbnd C, and Csbnd H stretching vibration regions clearly discriminate different triterpenes found in C. racemosa.

  12. Application of (1)h NMR profiling to assess seed metabolomic diversity. A case study on a soybean era population.

    PubMed

    Harrigan, George G; Skogerson, Kirsten; MacIsaac, Susan; Bickel, Anna; Perez, Tim; Li, Xin

    2015-05-13

    (1)H NMR spectroscopy offers advantages in metabolite quantitation and platform robustness when applied in food metabolomics studies. This paper provides a (1)H NMR-based assessment of seed metabolomic diversity in conventional and glyphosate-resistant genetically modified (GM) soybean from a genetic lineage representing ∼35 years of breeding and differing yield potential. (1)H NMR profiling of harvested seed allowed quantitation of 27 metabolites, including free amino acids, sugars, and organic acids, as well as choline, O-acetylcholine, dimethylamine, trigonelline, and p-cresol. Data were analyzed by canonical discriminant analysis (CDA) and principal variance component analysis (PVCA). Results demonstrated that (1)H NMR spectroscopy was effective in highlighting variation in metabolite levels in the genetically diverse sample set presented. The results also confirmed that metabolite variability is influenced by selective breeding and environment, but not genetic modification. Therefore, metabolite variability is an integral part of crop improvement that has occurred for decades and is associated with a history of safe use. PMID:25940152

  13. One new and six known triterpene xylosides from Cimicifuga racemosa: FT-IR, Raman and NMR studies and DFT calculations.

    PubMed

    Jamróz, Marta K; Jamróz, Michał H; Cz Dobrowolski, Jan; Gliński, Jan A; Gleńsk, Michał

    2012-07-01

    One new and six known triterpene xylosides were isolated from Cimicifuga racemosa (black cohosh, Actaea racemosa). The structure of a new compound, designated as isocimipodocarpaside (1), was established to be (24S)-3β-hydroxy-24,25-oxiirane-16,23-dione-9,10-seco-9,19-cyclolanost-1(10),7(8),9(11)-trien 3-O-β-d-xylopyranoside, by means of (1)H and (13)C NMR, IR and Raman spectroscopies and Mass Spectrometry. The six known compounds are: 23-epi-26-deoxycimicifugoside (2), 23-epi-26-deoxyactein (3), 25-anhydrocimigenol xyloside (4), 23-O-acetylshengmanol xyloside (5), 25-O-acetylcimigenol xyloside (6) and 3'-O-acetylcimicifugoside H-1 (7). On the basis of NMR data supported by DFT calculations of NMR shielding constants of (2), its structure, previously described as 26-deoxycimicifugoside was corrected and determined as 23-epi-26-deoxycimicifugoside. The (13)C CPMAS NMR spectra of the studied compounds (1)-(7) provided data on their solid-state interactions. The IR and Raman spectra in the CO, CC, and CH stretching vibration regions clearly discriminate different triterpenes found in C. racemosa. PMID:22465763

  14. Transport Properties of Ibuprofen Encapsulated in Cyclodextrin Nanosponge Hydrogels: A Proton HR-MAS NMR Spectroscopy Study.

    PubMed

    Ferro, Monica; Castiglione, Franca; Punta, Carlo; Melone, Lucio; Panzeri, Walter; Rossi, Barbara; Trotta, Francesco; Mele, Andrea

    2016-01-01

    The chemical cross-linking of β-cyclodextrin (β-CD) with ethylenediaminetetraacetic dianhydride (EDTA) led to branched polymers referred to as cyclodextrin nanosponges (CDNSEDTA). Two different preparations are described with 1:4 and 1:8 CD-EDTA molar ratios. The corresponding cross-linked polymers were contacted with 0.27 M aqueous solution of ibuprofen sodium salt (IP) leading to homogeneous, colorless, drug loaded hydrogels. The systems were characterized by high resolution magic angle spinning (HR-MAS) NMR spectroscopy. Pulsed field gradient spin echo (PGSE) NMR spectroscopy was used to determine the mean square displacement (MSD) of IP inside the polymeric gel at different observation times td. The data were further processed in order to study the time dependence of MSD: MSD = f(td). The proposed methodology is useful to characterize the different diffusion regimes that, in principle, the solute may experience inside the hydrogel, namely normal or anomalous diffusion. The full protocols including the polymer preparation and purification, the obtainment of drug-loaded hydrogels, the NMR sample preparation, the measurement of MSD by HR-MAS NMR spectroscopy and the final data processing to achieve the time dependence of MSD are here reported and discussed. The presented experiments represent a paradigmatic case and the data are discussed in terms of innovative approach to the characterization of the transport properties of an encapsulated guest within a polymeric host of potential application for drug delivery. PMID:27585291

  15. High-resolution NMR studies of structure and dynamics of human ERp27 indicate extensive interdomain flexibility

    PubMed Central

    Amin, Nader T.; Wallis, A. Katrine; Wells, Stephen A.; Rowe, Michelle L.; Williamson, Richard A.; Howard, Mark J.; Freedman, Robert B.

    2012-01-01

    ERp27 (endoplasmic reticulum protein 27.7 kDa) is a homologue of PDI (protein disulfide-isomerase) localized to the endoplasmic reticulum. ERp27 is predicted to consist of two thioredoxin-fold domains homologous with the non-catalytic b and b′ domains of PDI. The structure in solution of the N-terminal b-like domain of ERp27 was solved using high-resolution NMR data. The structure confirms that it has the thioredoxin fold and that ERp27 is a member of the PDI family. 15N-NMR relaxation data were obtained and ModelFree analysis highlighted limited exchange contributions and slow internal motions, and indicated that the domain has an average order parameter S2 of 0.79. Comparison of the single-domain structure determined in the present study with the equivalent domain within full-length ERp27, determined independently by X-ray diffraction, indicated very close agreement. The domain interface inferred from NMR data in solution was much more extensive than that observed in the X-ray structure, suggesting that the domains flex independently and that crystallization selects one specific interdomain orientation. This led us to apply a new rapid method to simulate the flexibility of the full-length protein, establishing that the domains show considerable freedom to flex (tilt and twist) about the interdomain linker, consistent with the NMR data. PMID:23234573

  16. 1H NMR studies of aerosol-OT reverse micelles with alkali and magnesium counterions: preparation and analysis of MAOTs.

    PubMed

    Stahla, Michelle L; Baruah, Bharat; James, Dustin M; Johnson, Michael D; Levinger, Nancy E; Crans, Debbie C

    2008-06-17

    Simple procedures and characterization of a series of well-defined precursors are described for preparation of a unique microenvironment in nanoreactors, reverse micelles. The Na(+), K(+), Rb(+), Cs(+), and Mg(2+) surfactants were prepared using liquid-liquid ion exchange using chloride and nitrate salts. The surfactants were characterized using (1)H NMR spectroscopy and a variety of other techniques. (1)H NMR spectroscopy was found to be a sensitive probe for characterization of the size of the nanoreactor as well as its water content. (1)H NMR spectra can be used for detailed characterization of reactions in confined environments when counterion effects are likely to be important. (1)H NMR spectroscopy revealed two separate peaks corresponding to water in Mg(AOT)2 samples; one peak arises from water coordinated to the Mg(2+) ion while the other peak arises from bulk water. The two water signals arise directly from the slow exchange of the water coordinated to Mg(2+) in these microemulsions with water in the water pool, and provide an opportunity to study hydration of Mg(2+). This work thus extends the potential use of MAOT microemulsions for applications such as in green chemistry. PMID:18484757

  17. Study of Low Molecular Weight Impurities in Pluronic Triblock Copolymers using MALDI, Interaction Chromatography, and NMR

    NASA Astrophysics Data System (ADS)

    Helming, Z.; Zagorevski, D.; Ryu, C. Y.

    2014-03-01

    Poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) triblock copolymers are a group of commercial macromolecular amphiphilic surfactants that have been widely studied for their applications in polymer-based nanotechnology and drug-delivery. It has been well-established that the synthesis of commercial Pluronic triblocks results in low molecular weight ``impurities,'' which are generally disregarded in the applications and study of these polymers. These species have been shown to have significant effects on the rheological properties of the material, as well as altering the supramolecular ``micellar'' structures for which the polymers are most often used. We have isolated the impurities from the bulk Pluronic triblock using Interaction Chromatography (IC) techniques, and subjected them to analysis by H1 NMR and MALDI (Matrix-Assisted Laser Desorption Ionization) Mass Spectrometry to identify relative block composition and molecular weight information. We report significant evidence of at least two polymeric components: a low-molecular-weight homopolymer of poly(ethylene oxide) and a ``blocky'' copolymer of both poly(ethylene oxide) and poly(propylene oxide). This has significant implications, not only for the applied usage of Pluronic triblock copolymers, but for the general scientific acceptance of the impurities and their effects on Pluronic micelle and hydrogel formation.

  18. 1H NMR metabolomics study of metastatic melanoma in C57BL/6J mouse spleen

    DOE PAGESBeta

    Wang, Xuan; Hu, Mary Y.; Feng, Ju; Liu, Maili; Hu, Jian Z.

    2014-04-03

    Melanoma is a malignant tumor of melanocytes. Although extensive investigations have been done to study metabolic changes in primary melanoma in vivo and in vitro, little effort has been devoted to metabolic profiling of metastatic tumors in organs other than lymph nodes. In this work, NMR-based metabolomics combined with multivariate data analysis is used to study metastatic B16-F10 melanoma in C57BL/6J mouse spleen. 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 find important metabolites responsible formore » discriminating the control and the melanoma groups. Two different strategies, i.e., spectral binning and spectral deconvolution, are used to reduce the original spectral data before statistical analysis. Spectral deconvolution is found to be superior for identifying a set of discriminatory metabolites between the control and the melanoma groups, especially when the sample size is small. OPLS results show that the melanoma group can be well separated from its control group. It is found that taurine, glutamate, aspartate, O-Phosphoethanolamine, niacinamide ,ATP, lipids and glycerol derivatives are decreased statistically and significantly while alanine, malate, xanthine, histamine, dCTP, GTP, thymidine, 2'-Deoxyguanosine are statistically and significantly elevated. Furthermore, these significantly changed metabolites are associated with multiple biological pathways and may be potential biomarkers for metastatic melanoma in spleen.« less

  19. Probing the surface of a sweet protein: NMR study of MNEI with a paramagnetic probe

    PubMed Central

    Niccolai, Neri; Spadaccini, Roberta; Scarselli, Maria; Bernini, Andrea; Crescenzi, Orlando; Spiga, Ottavia; Ciutti, Arianna; Di Maro, Daniela; Bracci, Luisa; Dalvit, Claudio; Temussi, Piero A.

    2001-01-01

    The design of safe sweeteners is very important for people who are affected by diabetes, hyperlipemia, and caries and other diseases that are linked to the consumption of sugars. Sweet proteins, which are found in several tropical plants, are many times sweeter than sucrose on a molar basis. A good understanding of their structure–function relationship can complement traditional SAR studies on small molecular weight sweeteners and thus help in the design of safe sweeteners. However, there is virtually no sequence homology and very little structural similarity among known sweet proteins. Studies on mutants of monellin, the best characterized of sweet proteins, proved not decisive in the localization of the main interaction points of monellin with its receptor. Accordingly, we resorted to an unbiased approach to restrict the search of likely areas of interaction on the surface of a typical sweet protein. It has been recently shown that an accurate survey of the surface of proteins by appropriate paramagnetic probes may locate interaction points on protein surface. Here we report the survey of the surface of MNEI, a single chain monellin, by means of a paramagnetic probe, and a direct assessment of bound water based on an application of ePHOGSY, an NMR experiment that is ideally suited to detect interactions of small ligands to a protein. Detailed surface mapping reveals the presence, on the surface of MNEI, of interaction points that include residues previously predicted by ELISA tests and by mutagenesis. PMID:11468346

  20. NMR relaxation study of water dynamics in superparamagnetic iron-oxide-loaded vesicles

    NASA Ast