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Sample records for 2h nmr study

  1. 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.

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

    NASA Astrophysics Data System (ADS)

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

    2012-03-01

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

  3. 2H NMR studies of glycerol dynamics in protein matrices.

    PubMed

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

    2012-03-28

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

  4. A 2H and 14N NMR study of molecular motion in polycrystalline choline salts

    NASA Astrophysics Data System (ADS)

    Pratum, T. K.; Klein, M. P.

    2H and 14N solid-state NMR spectra of polycrystalline choline chloride, bromide, and iodide indicate that 180° cation flipping motion occurs in all three salts. From the temperature dependence of these spectra, the activation energy for this motion is determined to be 5.8 ± I kcal/mol in the iodide salt and 11 ± 1.5 kcal/mol in the chloride salt. In the bromide salt the reorientation rate is too rapid to be determined from the NMR lineshape, but the temperature dependence of the 2H quadrupole coupling parameters is indicative of a second-order phase transition at approximately 273 K. The spectral distortions in the 14N NMR spectra of the chloride and iodide salts are adequately explained using the motional model derived from the 2H NMR results, while the 14N spectra of the bromide salt show no motional effects. The axis of reorientation which is inferred from these data appears to be consistent with that indicated in a previous X-ray crystallographic study.

  5. (2)H NMR study of the water dynamics in hydrated myoglobin.

    PubMed

    Lusceac, S A; Vogel, M

    2010-08-12

    We use 1D and 2D (2)H NMR to study the temperature-dependent mechanism for the rotational motion of myoglobin hydration water. The results show that isotropic and anisotropic water reorientation is observed at high and low temperatures, respectively, with a continuous crossover in the temperature range of 200-230 K. The anisotropic low-temperature motion has a large angular amplitude. It exhibits a broad distribution of geometries and pronounced dynamical heterogeneities, which are long-lived at least at T approximately 176 K. Exploiting the possibility to vary the angular resolution of (2)H NMR experiments, we find that the large solid angle accessible to low-temperature water reorientation is explored via large-angle rather than small-angle elementary steps; i.e., the rotational motion is not diffusive. Quantitative analysis of the NMR data using random-walk simulations implies that the number of sites involved in the observed water reorientation decreases from an infinite number during essentially isotropic motion above 230 K to a few, possibly two, below 165 K. Although the changes in the mechanism for water rotational motion may be accompanied by a mild change in the temperature dependence of the rotational correlation times, the (2)H NMR data provide strong evidence against the existence of a sharp fragile-to-strong transition at about 225 K. The present results are discussed in the context of previous experimental findings for hydrated proteins.

  6. Chain orientation in natural rubber, Part II: 2H-NMR study.

    PubMed

    Rault, J; Marchal, J; Judeinstein, P; Albouy, P A

    2006-11-01

    Stress-induced crystallisation (SIC) and stress-induced melting (SIM) in natural rubbers (NR), unfilled and filled with carbon black (CB) have been studied by (2)H-NMR measurements. Various materials have been swollen with small amount (< 2%) of deuterated alkane chains. The orientation of the amorphous chains, then the local deformation of the amorphous chains during deformation cycles and during stress relaxation, permits to clarify the SIC and SIM processes during hardening and recovery. By mechanical, WAXS and NMR measurements one determines the same critical draw ratio for appearance lambda(A) and disappearance lambda(E) of the crystallites. It is demonstrated that the hysteresis observed by the different techniques (stress sigma, crystallinity chi, NMR splitting Deltanu) are due to the supercooling effect ( lambda(A) > lambda(E), at constant temperature). During hardening at constant strain rate it is found that the local draw ratio remains constant and equal to lambda(A), whereas the crystallinity increases linearly with the macroscopic draw ratio lambda. The hardening sigma approximately (lambda - lambda(A))(2) is then interpreted as a reinforcement effect due to the crystallites, which act as new crosslinks. This confirms the prediction of Flory. In filled rubber the same effects are observed, and the stress amplification factor is determined as a function of the CB content. It is found that the fillers act as nucleation centres for the NR crystallites. The reinforcement of such materials is due principally to this nucleation effect and to the presence of a super network formed by both the NR crystallites and the CB fillers.

  7. Docosahexaenoic Acid Enhances Segregation of Lipids between Raft and Nonraft Domains: 2H-NMR Study

    PubMed Central

    Soni, Smita P.; LoCascio, Daniel S.; Liu, Yidong; Williams, Justin A.; Bittman, Robert; Stillwell, William; Wassall, Stephen R.

    2008-01-01

    Solid-state 2H-NMR of [2H31]-N-palmitoylsphingomyelin ([2H31]16:0SM, PSM*), supplemented by differential scanning calorimetry, was used for the first time, to our knowledge, to investigate the molecular organization of the sphingolipid in 1:1:1 mol mixtures with 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine (16:0–18:1PE, POPE) or 1-palmitoyl-2-docosahexaenoyl-sn-glycero-3-phosphoethanolamine (16:0–22:6PE, PDPE) and cholesterol. When compared with 2H-NMR data for analogous mixtures of [2H31]16:0–18:1PE (POPE*) or [2H31]16:0-22:6PE (PDPE*) with egg SM and cholesterol, molecular interactions of oleic acid (OA) versus docosahexaenoic acid (DHA) are distinguished, and details of membrane architecture emerge. SM-rich, characterized by higher-order, and PE-rich, characterized by lower-order, domains <20 nm in size are formed in the absence and presence of cholesterol in both OA- and DHA-containing membranes. Although acyl chain order within both domains increases on the addition of sterol to the two systems, the resultant differential in order between SM- and PE-rich domains is almost a factor of 3 greater with DHA than with OA. Our interpretation is that the aversion that cholesterol has for DHA—but not for OA—excludes the sterol from DHA-containing, PE-rich (nonraft) domains and excludes DHA from SM-rich/cholesterol-rich (raft) domains. We attribute, in part, the diverse health benefits associated with dietary consumption of DHA to an alteration in membrane domains. PMID:18339742

  8. Interactions of saturated diacylglycerols with phosphatidylcholine bilayers: A sup 2 H NMR study

    SciTech Connect

    de Boeck, H.; Zidovetzki, R. )

    1992-01-21

    The interactions of a series of saturated diacylglycerols (DAGs) with fatty acid side chain lengths of 6-14 carbons with multilamellar phospholipid bilayers consisting either of dipalmitoylphosphatidylcholine (DPPC) or of a mixture of DPPC and bovine liver phosphatidylcholine (BL-PC) extracts were studied by {sup 2}H NMR spectrometry. The authors found that the perturbation induced by the DAGs into the bilayer structure strongly depends on the length of the DAG fatty acid side chain. Shorter chain 1,2-sn-dihexanoylglycerol and, to a larger degree, 1,2-sn-dioctanoylglycerol (diC{sub 8}) induce transverse perturbation of the bilayer structure: the order parameters of the phospholipid side chains are increased by the intercalating DAG molecules in the region adjacent to the phospholipid headgroups and decreased toward the terminal methyls, corresponding to the bilayer interior. Each of the DAGs studied induces a decrease in the area per phospholipid molecule, and a corresponding increase in the lateral surface pressure of the bilayers. Since numerous biochemical studies consistently report that diC{sub 8} is the most effective of saturated DAGs in activating protein kinase C, they may conclude that the activation of this enzyme is associated with a transverse perturbation of the lipid bilayer structure and a decreased ordering in the interior of the bilayer membrane, and is less affected by the lateral phase separation of the lipids into regions of different fluidities, as induced by the longer chain DAGs.

  9. Lightweight hydrogen-storage material Mg(0.65)Sc(0.35)D2 studied with 2H and 2H-{45Sc} MAS NMR exchange spectroscopy.

    PubMed

    Srinivasan, S; Magusin, P C M M

    2011-01-01

    Using double-quantum (2)H MAS NMR with (45)Sc recoupling and Bloch-Siegert compensated (2)H-{(45)Sc} TRAPDOR we have identified the overlapping NMR signals of deuterium with and without scandium neighbors in Mg(0.65)Sc(0.35)D(2), a candidate lightweight material for hydrogen storage. At room temperature we also observe a third type of mobile deuterium. Deuterium mobility among the three NMR-distinct sites has been investigated by means of one-and two-dimensional exchange spectroscopy (Exsy). Complete deuterium exchange within 0.1s is observed, which indicates that the three NMR-distinct sites are close together in the crystal lattice. The weak temperature- and MAS-rate dependences observed in Exsy are indicative for a combination of chemical exchange and spin diffusion. Copyright © 2011 Elsevier Inc. All rights reserved.

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

    SciTech Connect

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

    1987-04-01

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

  11. Flexibility of Ras Lipid Modifications Studied by 2H Solid-State NMR and Molecular Dynamics Simulations

    PubMed Central

    Vogel, Alexander; Tan, Kui-Thong; Waldmann, Herbert; Feller, Scott E.; Brown, Michael F.; Huster, Daniel

    2007-01-01

    Human posttranslationally modified N-ras oncogenes are known to be implicated in numerous human cancers. Here, we applied a combination of experimental and computational techniques to determine structural and dynamical details of the lipid chain modifications of an N-ras heptapeptide in 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) membranes. Experimentally, 2H NMR spectroscopy was used to study oriented membranes that incorporated ras heptapeptides with two covalently attached perdeuterated hexadecyl chains. Atomistic molecular dynamics simulations of the same system were carried out over 100 ns including 60 DMPC and 4 ras molecules. Several structural and dynamical experimental parameters could be directly compared to the simulation. Experimental and simulated 2H NMR order parameters for the methylene groups of the ras lipid chains exhibited a systematic difference attributable to the absence of collective motions in the simulation and to geometrical effects. In contrast, experimental 2H NMR spin-lattice relaxation rates for Zeeman order were well reproduced in the simulation. The lack of slower collective motions in the simulation did not appreciably influence the relaxation rates at a Larmor frequency of 115.1 MHz. The experimental angular dependence of the 2H NMR relaxation rates with respect to the external magnetic field was also relatively well simulated. These relaxation rates showed a weak angular dependence, suggesting that the lipid modifications of ras are very flexible and highly mobile in agreement with the low order parameters. To quantify these results, the angular dependence of the 2H relaxation rates was calculated by an analytical model considering both molecular and collective motions. Peptide dynamics in the membrane could be modeled by an anisotropic diffusion tensor with principal values of D‖ = 2.1 × 109 s−1 and D⊥ = 4.5 × 105 s−1. A viscoelastic fitting parameter describing the membrane elasticity, viscosity, and temperature

  12. 1H and 2H NMR studies of water in work-free wheat flour doughs.

    PubMed

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

    1991-01-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    SciTech Connect

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

    1987-11-03

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

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

    NASA Astrophysics Data System (ADS)

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

    2017-04-01

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

  16. sup 31 P and sup 2 H NMR studies of structure and motion in bilayers of phosphatidylcholine and phosphatidylethanolamine

    SciTech Connect

    Ghosh, R. )

    1988-10-04

    The structural and motional properties of mixed bilayers of phosphatidylcholine (PC) and phosphatidylethanolamine (PE) have been examined by using wide-line {sup 31}P, {sup 14}N, and {sup 2H} NMR. {sup 2}H and {sup 14}N NMR data showed that in mixed bilayers containing both PC and PE the conformations of the head-group moieties are essentially identical with those observed for bilayers containing a single phospholipid species. Equimolar amounts of cholesterol induce also only a small change in head-group conformation. For all phospholipid mixtures studied, the {sup 31}P T{sub 1} relaxation was homogeneous over the whole powder spectrum and could be fitted to a single-exponential decay. The {sup 31}P vs temperature profiles were analyzed by a simple correlation model. The presence of equimolar amounts of PE containing either the same (POPE) or a different (Escherichia coli PE) fatty acid composition had essentially no effect on the rate of rotational diffusion of the phosphate groups, with the correlation time being found to be 0.68 ns at 20{degree}C. The presence of equimolar amounts of cholesterol decreased the correlation time to 0.65 ns, and also the activation energy was reduced to 22.6 kJ mol{sup {minus}1}. The authors interpret the decrease in activation energy as being due to the spacing effect of cholesterol which reduces the H-bonding interactions between head-groups, allowing them to rotate more freely. For all cases examined, the rotational diffusion of the phosphate moieties was slower than that observed for the rigid glycerol backbone of the molecule, the latter probably corresponding to overall phospholipid rotation.

  17. Use of rotary echoes in 2H magic-angle spinning NMR for the quantitative study of molecular dynamics

    NASA Astrophysics Data System (ADS)

    Hogg, Naomi H. M.; Boulton, Paul J. T.; Zorin, Vadim E.; Harris, Robin K.; Hodgkinson, Paul

    2009-06-01

    The interaction of sample spinning and chemical dynamics is analysed in the context of 2H magic-angle spinning NMR. We develop previous analyses and show that a metric based on the intensity of rotational echoes allows kinetic information to be derived without the need for full modelling of the NMR response. This approach is illustrated on the conformational exchange of 1,4-dioxane included in the channel solvate hydrate formed with finasteride. An activation barrier in excellent agreement with previous experimental and theoretical estimates is obtained, without the need for modelling which would be very challenging due to the anisotropic tumbling of the solvent molecules.

  18. Reorientational dynamics and solid-phase transformation of ammonium dicyanamide into dicyandiamide: a (2)H solid-state NMR study.

    PubMed

    Lotsch, Bettina V; Schnick, Wolfgang; Naumann, Ernst; Senker, Jürgen

    2007-10-11

    The reorientational dynamics of ammonium dicyanamide ND4[N(C[triple bond]N)2] and the kinetics as well as the mechanism of the solid-state isomerization reaction from ammonium dicyanamide into dicyandiamide (N[triple bond]C-N==C(NH2)2) was studied by means of 2H and 14N solid-state NMR spectroscopy in a temperature range between 38 and 390 K. Whereas in previous investigations the mechanism of the solid-state transformation was investigated by means of vibrational and magic angle spinning solid-state NMR spectroscopy as well as neutron diffraction, we here present a comprehensive 2H study of the ammonium ion dynamics prior to and during the course of the reaction, thereby highlighting possible cross correlations between dynamics and reactivity involving the ammonium ion. The ND4+ group was found to undergo thermally activated random jumps in a tetrahedral potential, which is increasingly distorted with increasing temperature, giving rise to an asymmetrically compressed or elongated tetrahedron with deviations from the tetrahedral angle of up to 6 degrees . The correlation time follows an Arrhenius law with an activation energy of Ea = 25.8(2) kJ mol(-1) and an attempt frequency of tau0(-1) = 440(80) THz. The spin-lattice relaxation times were fitted according to a simple Bloembergen-Purcell-Pound type model with a T1 minimum of 4 ms at 230 K. Temperature-dependent librational amplitudes were extracted by line-shape simulations between 38 and 390 K and contrasted with those obtained by neutron diffraction, their values ranging between 5 and 28 degrees . The onset and progress of the solid-phase transformation were followed in situ at temperatures above 372 K and could be classified as a strongly temperature-dependent, heterogeneous two-step reaction proceeding with rapid evolution of ammonia and comparatively slow subsequent reintegration into the solid. On the microscopic level, this correlates with a rapid proton transfer -- possibly triggered by a coupling

  19. Order and dynamics in mixtures of membrane glucolipids from Acholeplasma laidlawii studied by sup 2 H NMR

    SciTech Connect

    Eriksson, P.O.; Rilfors, L.; Lundberg, A.; Lindblom, G.; Wieslander, A. )

    1991-05-21

    The two dominant glucolipids in Acholeplasma laidlawii, viz., 1,2-diacyl-3-O-({alpha}-D-glucopyranosyl)-sn-glycerol (MGlcDG) and 1,2-diacyl-3-O-({alpha}-D-glucopyranosyl-(1{yields}2)-O-{alpha}-D-glucopyranosyl)-sn-glycerol (DGlcDG), have markedly different phase behavior. MGlcDG has an ability to form nonlamellar phases, whereas DGlcDG only forms lamellar phases. For maintenance of a stable lipid bilayer, the polar headgroup composition in A. laidlawii is metabolically regulated in vivo, in response to changes in the growth conditions. To investigate the mechanism behind the lipid regulation the authors have here studied bilayers of mixtures of unsaturated MGlcDG and DGlcDG, containing a small fraction of biosynthetically incorporated per-deuterated palmitic acid, with {sup 2}H NMR. The order-parameter profile of the acyl chains and an apparent transverse spin relaxation rate (R{sub 2}) were determined from dePaked quadrupole-echo spectra. The variation of order with lipid composition is rationalized from simple packing constraints. The relaxation data indicate the presence of slow reorientational motions, such as collective bilayer fluctuations and/or lipid lateral diffusion over a curved bilayer surface. The variation of acyl-chain order and bilayer curvature and/or fluctuations with sample composition are discussed in relation to the tendency of MGlcDG to form nonlamellar phases in vitro and in relation to the lipid regulation in vivo.

  20. Effects of various types of molecular dynamics on 1D and 2D (2)H NMR studied by random walk simulations

    PubMed

    Vogel; Rossler

    2000-11-01

    By carrying out random walk simulations we systematically study the effects of various types of complex molecular dynamics on (2)H NMR experiments in solids. More precisely, we calculate one-dimensional (1D) (2)H NMR spectra and the results of two dimensional (2D) (2)H NMR experiments in time domain, taking into account isotropic as well as highly restricted motions which involve rotational jumps about different finite angles. Although the dynamical models are chosen to mimic the primary and secondary relaxation in supercooled liquids and glasses, we do not intend to describe experimental results quantitatively but rather to show general effects appearing for complex reorientations. We carefully investigate whether 2D (2)H NMR in time domain, which was originally designed to measure correlation times of ultraslow motions (tau >/= 1 ms), can be used to obtain shorter tau, too. It is demonstrated that an extension of the time window to tau >/= 10 &mgr;s is possible when dealing with exponential relaxation, but that it will fail if there is a distribution of correlation times G(lgtau). Vice versa, we show that 1D (2)H NMR spectra, usually recorded to look at dynamics with tau in the microsecond regime, are also applicable for studying ultraslow motions provided that the loss of correlation is achieved step by step. Therefore, it is useful to carry out 1D and 2D NMR experiments simultaneously in order to reveal the mechanism of complex molecular motions. In addition, we demonstrate that highly restricted dynamics can be clearly observed in 1D spectra and in 2D NMR in time domain if long solid-echo delays and large evolution times are applied, respectively. Finally, unexpected observations are described which appear in the latter experiment when considering very broad distributions G(lgtau). Because of these effects, time scale and geometry of a considered motion cannot be extracted from a straightforward analysis of experimental results. Copyright 2000 Academic Press.

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

    SciTech Connect

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

    1991-05-02

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

  2. 2H and 27Al solid-state NMR study of the local environments in Al-doped 2-line ferrihydrite, goethite, and lepidocrocite

    DOE PAGES

    Kim, Jongsik; Ilott, Andrew J.; Middlemiss, Derek S.; ...

    2015-05-13

    Although substitution of aluminum into iron oxides and oxyhydroxides has been extensively studied, it is difficult to obtain accurate incorporation levels. Assessing the distribution of dopants within these materials has proven especially challenging because bulk analytical techniques cannot typically determine whether dopants are substituted directly into the bulk iron oxide or oxyhydroxide phase or if they form separate, minor phase impurities. These differences have important implications for the chemistry of these iron-containing materials, which are ubiquitous in the environment. In this work, 27Al and 2H NMR experiments are performed on series of Al-substituted goethite, lepidocrocite, and 2-line ferrihydrite in ordermore » to develop an NMR method to track Al substitution. The extent of Al substitution into the structural frameworks of each compound is quantified by comparing quantitative 27Al MAS NMR results with those from elemental analysis. Magnetic measurements are performed for the goethite series to compare with NMR measurements. Static 27Al spin–echo mapping experiments are used to probe the local environments around the Al substituents, providing clear evidence that they are incorporated into the bulk iron phases. As a result, predictions of the 2H and 27Al NMR hyperfine contact shifts in Al-doped goethite and lepidocrocite, obtained from a combined first-principles and empirical magnetic scaling approach, give further insight into the distribution of the dopants within these phases.« less

  3. Vanishing amplitude of backbone dynamics causes a true protein dynamical transition: 2H NMR studies on perdeuterated C-phycocyanin.

    PubMed

    Kämpf, Kerstin; Kremmling, Beke; Vogel, Michael

    2014-03-01

    Using a combination of H2 nuclear magnetic resonance (NMR) methods, we study internal rotational dynamics of the perdeuterated protein C-phycocyanin (CPC) in dry and hydrated states over broad temperature and dynamic ranges with high angular resolution. Separating H2 NMR signals from methyl deuterons, we show that basically all backbone deuterons exhibit highly restricted motion occurring on time scales faster than microseconds. The amplitude of this motion increases when a hydration shell exists, while it decreases upon cooling and vanishes near 175 K. We conclude that the vanishing of the highly restricted motion marks a dynamical transition, which is independent of the time window and of a fundamental importance. This conclusion is supported by results from experimental and computational studies of the proteins myoglobin and elastin. In particular, we argue based on findings in molecular dynamics simulations that the behavior of the highly restricted motion of proteins at the dynamical transition resembles that of a characteristic secondary relaxation of liquids at the glass transition, namely the nearly constant loss. Furthermore, H2 NMR studies on perdeuterated CPC reveal that, in addition to highly restricted motion, small fractions of backbone segments exhibit weakly restricted dynamics when temperature and hydration are sufficiently high.

  4. Phase transition behavior of hydrogen bonded liquid crystal (6BA)2-(BPy) x as studied by 2H NMR

    NASA Astrophysics Data System (ADS)

    Mizuno, M.; Tabota, K.; Oigawa, T.; Miyatou, T.; Kumagai, Y.; Ohashi, R.; Ida, T.

    2016-12-01

    The thermal properties and the orientational order of hydrogen-bonded liquid crystals (6BA)2-(BPy)0.4 and (6BA)2-(BPy)0.3 (6BA: 4- n-hexylbenzoicacid, BPy: 4,4'-bipyridine) were investigated by DSC and 2H NMR. On cooling, isotropic liquid - liquid crystal phase transition temperatures were T C= 409 and 405 K for (6BA)2-(BPy)0.4 and (6BA)2-(BPy)0.3, respectively. Thermal anomalies in the liquid crystal phase were observed at T LC1= 402 and T LC2= 375 K for (6BA)2-(BPy)0.4 and at T LC1= 398 and T LC2= 375 K for (6BA)2-(BPy)0.3. For (6BA)2-(BPy)0.4, only the smectic component was created above T LC1. In addition, the nematic component was created below T LC1. The nematic component gradually changed to the smectic component with decreasing temperature and only the smectic component was observed below T LC2. For (6BA)2-(BPy)0.3, only the nematic component was created above T LC2. The phase transition from the nematic phase to the smectic phase took place at around T LC2.

  5. Phase Transitions, Hydrogen Bond and Crystal Dynamics of p-Methylbenzyl Alcohol as Studied by Single Crystal X-ray Diffraction and 2H NMR

    NASA Astrophysics Data System (ADS)

    Hashimoto, Masao; Harada, Michiko; Mizunoa, Motohiro; Hamada, Masanori; Ida, Tomonori; Suhara, Masahiko

    2002-07-01

    The title compound (pMBA) was found to undergo a first-order phase transition at 211 K (Tc1). Another transition with subtle enthalpy change appeared at 172 K (Tc2). Crystal structure determinations at various temperatures revealed that the transition at Tc1 was accompanied by remarkable changes in the molecular conformations around the CH2-C and O-CH2 bonds and a reversal of the direction of the O-H O hydrogen bond. Experiments of 2H NMR were carried out on pMBA-d where the hydroxyl hydrogen of pMBA was selectively deuterated. Analyses of the 2H NMR spectra and the temperature dependence of T1 of the 2H NMR indicated occurrence of jumping motions of 2H between asymmetric potential wells at temperatures lower than Tc1

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

    NASA Astrophysics Data System (ADS)

    Shaghaghi, Mehran; Thewalt, Jenifer; Zuckermann, Martin

    2012-10-01

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

  7. 2H and 13C NMR studies on the temperature-dependent water and protein dynamics in hydrated elastin, myoglobin and collagen.

    PubMed

    Lusceac, Sorin A; Vogel, Michael R; Herbers, Claudia R

    2010-01-01

    (2)H NMR spin-lattice relaxation and line-shape analyses are performed to study the temperature-dependent dynamics of water in the hydration shells of myoglobin, elastin, and collagen. The results show that the dynamical behaviors of the hydration waters are similar for these proteins when using comparable hydration levels of h=0.25-0.43. Since water dynamics is characterized by strongly nonexponential correlation functions, we use a Cole-Cole spectral density for spin-lattice relaxation analysis, leading to correlation times, which are in nice agreement with results for the main dielectric relaxation process observed for various proteins in the literature. The temperature dependence can roughly be described by an Arrhenius law, with the possibility of a weak crossover in the vicinity of 220 K. Near ambient temperatures, the results substantially depend on the exact shape of the spectral density so that deviations from an Arrhenius behavior cannot be excluded in the high-temperature regime. However, for the studied proteins, the data give no evidence for the existence of a sharp fragile-to-strong transition reported for lysozyme at about 220 K. Line-shape analysis reveals that the mechanism for the rotational motion of hydration waters changes in the vicinity of 220 K. For myoglobin, we observe an isotropic motion at high temperatures and an anisotropic large-amplitude motion at low temperatures. Both mechanisms coexist in the vicinity of 220 K. (13)C CP MAS spectra show that hydration results in enhanced elastin dynamics at ambient temperatures, where the enhancement varies among different amino acids. Upon cooling, the enhanced mobility decreases. Comparison of (2)H and (13)C NMR data reveals that the observed protein dynamics is slower than the water dynamics.

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

    PubMed

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

    1998-07-13

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

  9. 2H NMR study of dynamics of benzene-d6 interacting with humic and fulvic acids.

    PubMed

    Eastman, Margaret A; Brothers, Lucinda A; Nanny, Mark A

    2011-05-05

    Samples of three humic acids and one fulvic acid with 1% loading of benzene-d(6) in sealed glass tubes have been studied with solid-state deuterium quadrupole-echo nuclear magnetic resonance spectroscopy. Calculated spectra combining three motional models, two isotropic models and a third more restricted small-angle wobble (SAW) motional model, are fit to the experimental spectra. One isotropic motion (ISO(v)) is assigned to vaporous benzene-d(6) due to the small line width, short T(1), and the loss of this component by about -25 °C when the temperature is lowered. The remaining two motional components, ISO(s) and SAW, are sorbed by the humic or fulvic acid. Benzene-d(6) slowly interacts with the humic substances, progressively filling SAW sites as ISO(s) motion diminishes. Both the sorption and increase in percentage of SAW motion are for the most part complete within 200 days but continue to a lesser extent over a period of a few years. For the SAW motion there are at least two and most likely a series of T(1) values, indicating more than one adsorption environment. Enthalpies of sorption, obtained from application of the van't Hoff equation to the percentages of the different motional models derived from a series of variable temperature spectra, are comparable in magnitude to the enthalpy of vaporization of benzene. In Leonardite humic acid, ΔH and ΔS for the ISO(s) to SAW transition change from positive to negative values with age, implying a transition in the driving force from an entropic effect associated with expansion and deformation in the molecular structure of the humic substance to accommodate benzene-d(6) to an enthalpic effect of strong benzene-d(6)-humic substance interactions. In contrast, at advanced ages, Suwannee River humic and fulvic acids have small positive or near zero ΔH and positive ΔS for the ISO(s) to SAW transition.

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

    PubMed Central

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

    1995-01-01

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

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

    PubMed

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

    1995-11-01

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

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

    SciTech Connect

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

    1987-12-15

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

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

    PubMed

    Thomas, Freddy; Jamin, Eric

    2009-09-01

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

  14. Molecular dynamics of poly(L-lactide) biopolymer studied by wide-line solid-state 1H and 2H NMR spectroscopy.

    PubMed

    Nozirov, Farhod; Nazirov, Alovidin; Jurga, Stefan; Fu, Riqiang

    2006-06-01

    The molecular dynamics of poly(L-lactide) (PLLA) biopolymer was characterized through analyses of 1H and 2H NMR line-shapes and spin-lattice relaxation times at different temperatures. At low temperatures (e.g. 90 K), the methyl group rotation is dominant leading to a significant reduction in the proton second moment. Fast methyl group reorientation occurs at ca. 130 K. In additional to the fast methyl group rotation, hydroxyl groups start to reorient as the temperature increases further, eventually leading to the breakdown of the segments of the biopolymer chains above its glass transition temperature Tg of 323 K. The analyses of the 2H NMR line-shapes indicate that both the methyl and hydroxyl reorientations can be described by the so-called cone model, in which the former has three equilibrium positions with theta(C-D) = 70.5 degrees and phi = 120 degrees while the latter one exhibits two equilibrium positions with theta(O-D) = 78 degrees and phi = 180 degrees .

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

  16. Ionic motion and Disordered Structure in the Rotator Phase of Butylammonium Chloride Studied by Temperature Dependences of 35Cl and 2H NMR

    NASA Astrophysics Data System (ADS)

    Hattori, Mineyuki; Onoda, Yoshito; Erata, Tomoki; Smith, M. E.; Hattori, Masakazu; Ohki, Hiroshi; Ikeda, Ryuichi

    1994-02-01

    Temperature dependences of 35Cl and 2H quadrupole coupling constants and 35Cl NMR spin-lat­tice relaxation times in polycrystalline samples were measured in the rotator phase of the butylammonium chlorides C4H9NH3C1 and C4H9ND3C1, obtainable above the phase transition temperature of 241 K. A rapid decrease o f the quadrupole coupling constants of both nuclei upon heating is attributed to increasing dynamic disorder formed around the polar head. The presence of self-diffussion of Cl- ions was revealed from the spin-spin relaxation time and resonance line-width in single crystals, and confirmed by measuring the dc electrical conductivity.

  17. Deuterium dynamics in the icosahedral and amorphous phases of the Ti40Zr40Ni20 hydrogen-absorbing alloy studied by 2H NMR

    NASA Astrophysics Data System (ADS)

    Gradišek, A.; Kocjan, A.; McGuiness, P. J.; Apih, T.; Kim, Hae Jin; Dolinšek, J.

    2008-11-01

    The Ti40Zr40Ni20 hydrogen-absorbing alloy was prepared in the icosahedral and amorphous phases by controlling the rotation speed of the melt-spinning method of sample preparation, and the deuterium dynamics was investigated by 2H NMR dynamic lineshape and spin-lattice relaxation. The results were analysed by the lineshape and relaxation models that assume deuterium thermally activated hopping within a manifold of different chemical environments. The observed 8% larger activation energy for the deuterium hopping over the interstitial sites and the 10% larger static spectrum width of the amorphous phase, as compared to the icosahedral phase, can be accounted for by the larger deuterium content of the investigated amorphous sample. From the deuterium dynamics point of view, the icosahedral phase is not special with respect to the amorphous modification of the same material.

  18. A study of dipolar interactions and dynamic processes of water molecules in tendon by 1H and 2H homonuclear and heteronuclear multiple-quantum-filtered NMR spectroscopy.

    PubMed

    Eliav, U; Navon, G

    1999-04-01

    The effect of proton exchange on the measurement of 1H-1H, 1H-2H, and 2H-2H residual dipolar interactions in water molecules in bovine Achilles tendons was investigated using double-quantum-filtered (DQF) NMR and new pulse sequences based on heteronuclear and homonuclear multiple-quantum filtering (MQF). Derivation of theoretical expressions for these techniques allowed evaluation of the 1H-1H and 1H-2H residual dipolar interactions and the proton exchange rate at a temperature of 24 degrees C and above, where no dipolar splitting is evident. The values obtained for these parameters at 24 degrees C were 300 and 50 Hz and 3000 s-1, respectively. The results for the residual dipolar interactions were verified by repeating the above measurements at a temperature of 1.5 degrees C, where the spectra of the H2O molecules were well resolved, so that the 1H-1H dipolar interaction could be determined directly from the observed splitting. Analysis of the MQF experiments at 1.5 degrees C, where the proton exchange was in the intermediate regime for the 1H-2H dipolar interaction, confirmed the result obtained at 24 degrees C for this interaction. A strong dependence of the intensities of the MQF signals on the proton exchange rate, in the intermediate and the fast exchange regimes, was observed and theoretically interpreted. This leads to the conclusion that the MQF techniques are mostly useful for tissues where the residual dipolar interaction is not significantly smaller than the proton exchange rate. Dependence of the relaxation times and signal intensities of the MQF experiments on the orientation of the tendon with respect to the magnetic field was observed and analyzed. One of the results of the theoretical analysis is that, in the fast exchange regime, the signal decay rates in the MQF experiments as well as in the spin echo or CPMG pulse sequences (T2) depend on the orientation as the square of the second-rank Legendre polynomial.

  19. Study of the ferroelastic phase transition in the tetraethylammonium compound [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}ZnBr{sub 4} by magic-angle spinning and static NMR

    SciTech Connect

    Lim, Ae Ran E-mail: arlim@jj.ac.kr

    2016-03-15

    The ferroelastic phase transition of tetraethylammonium compound [N(C{sub 2}H{sub 5}){sub 4}]{sub 2}ZnBr{sub 4} at the phase transition temperature (T{sub C}) = 283 K was characterized by magic-angle spinning (MAS) and static nuclear magnetic resonance (NMR), and confirmed by optical polarizing spectroscopy. The structural geometry near T{sub C} was studied in terms of the chemical shifts and the spin-lattice relaxation times T{sub 1ρ} in the rotating frame for {sup 1}H MAS NMR and {sup 13}C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups were distinguishable in the {sup 13}C NMR spectrum, and the T{sub 1ρ} results indicate that they undergo tumbling motion above T{sub C} in a coupled manner. From the {sup 14}N NMR results, the two nitrogen nuclei in the N(C{sub 2}H{sub 5}){sub 4}{sup +} ions were distinguishable above T{sub C}, and the splitting in the spectra below T{sub C} was related to the ferroelastic domains with different orientations.

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

    PubMed Central

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

    2006-01-01

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

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

    PubMed

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

    2016-09-15

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

  2. 2H-DNP-enhanced 2H–13C solid-state NMR correlation spectroscopy

    PubMed Central

    Maly, Thorsten; Andreas, Loren B.; Smith, Albert A.

    2015-01-01

    Perdeuteration of biological macromolecules for magic angle spinning solid-state NMR spectroscopy can yield high-resolution 2H–13C correlation spectra and the method is therefore of great interest for the structural biology community. Here we demonstrate that the combination of sample deuteration and dynamic nuclear polarization yields resolved 2H–13C correlation spectra with a signal enhancement of ε ≥ 700 compared to a spectrum recorded with microwaves off and otherwise identical conditions. To our knowledge, this is the first time that 2H-DNP has been employed to enhance MAS-NMR spectra of a biologically relevant system. The DNP process is studied using several polarizing agents and the technique is applied to obtain 2H–13C correlation spectra of U-[2H, 13C] proline. PMID:20458422

  3. Sensitivity of 2H NMR spectroscopy to motional models: Proteins and highly viscous liquids as examples

    NASA Astrophysics Data System (ADS)

    Kruk, D.; Mielczarek, A.; Korpala, A.; Kozlowski, A.; Earle, K. A.; Moscicki, J.

    2012-06-01

    In order to study to what extent mechanisms of molecular motion can be unambiguously revealed by 2H NMR spectroscopy, 2H spectra for proteins (chicken villin protein headpiece HP36, selectively methyl-deuterated at leucine-69, Cδ D3) and binary systems of high viscosity (benzene-d6 in tricresyl phosphate) have been carefully analyzed as illustrative examples (the spectra are taken from the literature). In the first case, a model of restricted diffusion mediated by jumps between rotameric orientations has been tested against jump- and free diffusion models which describe rotational motion combined with jump dynamics. It has been found that the set of 2H spectra of methyl-deuterated at leucine-69 chicken villin protein headpiece HP36 can be consistently explained by different motional models as well as by a Gaussian distribution of correlation times assuming isotropic rotation (simple Brownian diffusion model). The last finding shows that when the possible distribution of correlation times is not very broad one might not be able to distinguish between heterogeneous and homogenous (but more complex) dynamics by analyzing 2H lineshapes. For benzene-d6 in tricresyl phosphate, the dynamics is heterogeneous and it has been demonstrated that a Gaussian distribution of correlation times reproduces well the experimental lineshapes, while for a Cole-Davidson distribution the agreement is somewhat worse. For inquires into the sensitivity of quadrupolar NMR spectral analysis (by "quadrupolar NMR spectroscopy we understand NMR spectroscopy of nuclei possessing quadrupole moment), the recently presented theoretical approach [Kruk et al., J. Chem. Phys. 135, 224511 (2011)], 10.1063/1.3664783 has been used as it allows simulating quadrupolar spectra for arbitrary motional conditions by employing the stochastic Liouville equation.

  4. Quantifying unfrozen water in frozen soil by high-field 2H NMR.

    PubMed

    Sparrman, Tobias; Oquist, Mats; Klemedtsson, Leif; Schleucher, Jürgen; Nilsson, Mats

    2004-10-15

    To understand wintertime controls of biogeochemical processes in high latitude soils it is essential to distinguish between direct temperature effects and the effects of changes in water availability mediated by freezing. Efforts to separate these controls are hampered by a lack of adequate methods to determine the proportion of unfrozen water. In this study we present a high-field 2H2O NMR method for quantifying unfrozen water content in frozen soil. The experimental material consisted of the humic layer of a boreal spruce forest soil mixed with varying proportions of quartz sand and humidified with deuterium-enriched water. The relative standard deviation of unfrozen water content (measured as NMR signal integral) was less than 2% for repeated measurements on a given sample and 3.5% among all samples, based on a total of 16 measurements. As compared to 1H NMR, this 2H NMR method was found to be superior for several reasons: it is less sensitive to field inhomogeneity and paramagnetic impurities, it gives a bigger line shape difference between the ice and liquid signal, it shows a sharper response to water fusion, and it excludes the possibility of hydrogen in the organic material interfering with the measurement.

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

    PubMed

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

    2014-01-01

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

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

    SciTech Connect

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

    1990-05-01

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

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

    PubMed

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

    2011-06-09

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

  8. Retinal Conformation and Dynamics in Activation of Rhodopsin Illuminated by Solid-state 2H NMR Spectroscopy†

    PubMed Central

    Brown, Michael F.; Martínez-Mayorga, Karina; Nakanishi, Koji; Salgado, Gilmar F. J.; Struts, Andrey V.

    2010-01-01

    Solid-state NMR spectroscopy gives a powerful avenue for investigating G protein-coupled receptors and other integral membrane proteins in a native-like environment. This article reviews the use of solid-state 2H NMR to study the retinal cofactor of rhodopsin in the dark state as well as the meta I and meta II photointermediates. Site-specific 2H NMR labels have been introduced into three regions (methyl groups) of retinal that are crucially important for the photochemical function of rhodopsin. Despite its phenomenal stability 2H NMR spectroscopy indicates retinal undergoes rapid fluctuations within the protein binding cavity. The spectral lineshapes reveal the methyl groups spin rapidly about their three-fold (C3) axes with an order parameter for the off-axial motion of SC3 ≈ 0.9. For the dark state, the 2H NMR structure of 11-cis-retinal manifests torsional twisting of both the polyene chain and the β-ionone ring due to steric interactions of the ligand and the protein. Retinal is accommodated within the rhodopsin binding pocket with a negative pretwist about the C11=C12 double bond. Conformational distortion explains its rapid photochemistry and reveals the trajectory of the 11-cis to trans isomerization. In addition, 2H NMR has been applied to study the retinylidene dynamics in the dark and light-activated states. Upon isomerization there are drastic changes in the mobility of all three methyl groups. The relaxation data support an activation mechanism whereby the β-ionone ring of retinal stays in nearly the same environment, without a large displacement of the ligand. Interactions of the β-ionone ring and the retinylidene Schiff base with the protein transmit the force of the retinal isomerization. Solid-state 2H NMR thus provides information about the flow of energy that triggers changes in hydrogen-bonding networks and helix movements in the activation mechanism of the photoreceptor. PMID:19267870

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

    PubMed

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

    2015-12-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-12-01

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

  11. Critical behavior of KDCO3 from 2H and 39K single crystal NMR.

    PubMed

    Odin, Christophe

    2008-01-01

    Potassium hydrogenocarbonate KDCO3 presents an order/disorder phase transition at Tc approximately 353 K. The critical behavior of this phase transition was studied by single crystal 2H and 39K NMR. The evolution of the order parameter as a function of temperature is quantified, and the critical exponent was determined, indicating a transition close to a tricritical point. The 2H Zeeman relaxation rate is strongly increased near the transition temperature. By calculating the noncritical contribution to the Zeeman relaxation rate, we show that the observed relaxation rate clearly presents a pseudo-divergent behavior near Tc, with a logarithmic singularity. The nature of the phase transition is discussed in the light of these results. Copyright (c) 2007 John Wiley & Sons, Ltd.

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

    PubMed

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

    2007-10-17

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

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

    SciTech Connect

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

    1982-06-01

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

  14. Kinetic isotope effects and tunneling in cyclic double and triple proton transfer between acetic acid and methanol in tetrahydrofuran studied by dynamic /sup 1/H and /sup 2/H NMR spectroscopy

    SciTech Connect

    Gerritzen, D.; Limbach, H.H.

    1984-02-22

    Previous studies of proton exchange and hydrogen bonding between acetic acid (A) and methanol (B) in tetrahydrofuran-d/sub 8/ have been extended to the study of the primary kinetic H/D isotope effects of the exchange. For this purpose a new combination of dynamic /sup 1/H and /sup 2/H NMR spectroscopy has been used to perform an ''NMR proton inventory''. The following rate law was obtained at deuterium fractions D=0 and D=1 of the exchangeable protonic sites: NU=k/sup LL/ C/sub A/C/sub B/+k/sub LLL/C/sub A//sup 2/C/sub B/ (L=H,D). This was attributed to a superposition of cyclic double and triple proton exchange involving one and two molecules of acetic acid and one molecule of methanol. Additional experiments were carried out at intermediate deuterium fractions. Thus, the kinetic HH/HD/DD and HHH/HHD/DDD isotope effects of the exchange as a function of the temperature was measured successfully. This has been achieved for the first time for well-defined intermolecular multiple-proton-transfer reactions. The possibility of determining the number of protons transferred in a chemical reaction by performing an NMR proton inventory is discussed. The rule of the geometric mean (RGM) is fulfilled for the kinetic isotope effects of the LLL process, which are almost independent of temperature within the margin of error. By contrast, the RGM is not fullfilled for the LL process, and the kinetic isotope effects depend strongly on the temperature. The energies of activation and frequency factors fit Bell's criteria of tunneling. The kinetic results are in good agreement with predictions of transition-state theory but can be explained by an intermolecular tunneling model. The results are proof that acetic acid and methanol form cyclic hydrogen-bonded 1:1 and 2:1 complexes which have very low concentration in tetrahydrofuran.

  15. 2Q NMR of 2H2O ordering at solid interfaces

    NASA Astrophysics Data System (ADS)

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

    2014-06-01

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

  16. The mitochondrial precursor protein apocytochrome c strongly influences the order of the headgroup and acyl chains of phosphatidylserine dispersions. A sup 2 H and sup 31 P NMR study

    SciTech Connect

    Jordi, W.; de Kroon, A.I.P.M.; Killian, A.; de Kruijff, B. )

    1990-03-06

    Deuterium and phosphorus nuclear magnetic resonance techniques were used to study the interaction of the mitochondrial precursor protein apocytochrome c with headgroup-deuterated (dioleoylphosphatidyl-L-(2-{sup 2}H{sub 1})serine) and acyl chain deuterated (1,2-(11,11-{sup 2}H{sub 2})dioleoylphosphatidylserine) dispersions. Binding of the protein to dioleoylphosphatidylserine liposomes results in phosphorus nuclear magnetic resonance spectra typical of phospholipids undergoing fast axial rotation in extended liquid-crystalline bilayers with a reduced residual chemical shift anisotropy and an increased line width. {sup 2}H NMR spectra on headgroup-deuterated dioleoylphosphatidylserine dispersions showed a decrease in quadrupolar splitting and a broadening of the signal on interaction with apocytochrome c. Addition of increasing amounts of apocytochrome c to the acyl chain deuterated dioleoylphosphatidylserine dispersions results in the gradual appearance of a second component in the spectra with a 44% reduced quadrupolar splitting. Such large reduction of the quadrupolar splitting has never been observed for any protein studied yet. The induction of a new spectral component with a well-defined reduced quadrupolar splitting seems to be confined to the N-terminus since addition of a small hydrophilic amino-terminal peptide (residues 1-38) also induces a second component with a strongly reduced quadrupolar splitting. A chemically synthesized peptide corresponding to amino acid residues 2-17 of the presequence of the mitochondrial protein cytochrome oxidase subunit IV also has a large perturbing effect on the order of the acyl chains, indicating that the observed effects may be a property shared by many mitochondrial precursor proteins. Implications of these data for the import of apocytochrome c into mitochondria will be discussed.

  17. Molecular Motions in Halogen-Bridged One-Dimensional Pt Complexes, [PtII(en)2][PtIVX2(en)2](ClO4)4 (X = Cl, Br) Studied by 2H and 1H NMR

    NASA Astrophysics Data System (ADS)

    Kimura, Noriyoshi; Hachisuka, Toru; Nakano, Yukitaka; Ikeda, Ryuichi

    2002-07-01

    2H and 1H NMR measurements were performed on crystalline [Pt(en)2][PtX2(en)2](ClO4)4 (X = Cl, Br), where the protonated and partially deuterated ethylenediamines (en's), NH2(CH2)2NH2, NH2(CD2)2NH2 and ND2(CH2)2ND2 were used as ligands. Measurements of 2H and 1H NMR spin-lattice relaxation times showed the presence of motions of en chelate rings at the temperatures near the phase transitions, whereas broad 2H NMR spectra and the reported X-ray diffraction data showed no marked motions. These results were consistently explained by introducing the en puckering motion between highly asymmetric potential wells with an energy difference of 10 - 13 kJ mol-1. This difference was shown to be much larger than 2 - 5 kJ mol-1, reported for the iodo-complex, [Pt(en)2][PtI2(en)2](ClO4)4

  18. 13C-NMR studies of the paramagnetic and charge-ordered states of the organic superconductor β''-(BEDT-TTF)3Cl2·2H2O under pressure

    NASA Astrophysics Data System (ADS)

    Nagata, Sanato; Ogura, Takashi; Kawamoto, Atsushi; Taniguchi, Hiromi

    2011-07-01

    β''-(BEDT-TTF)3Cl2·2H2O [BEDT-TTF: b̲is-(e̲thylened̲it̲hio)t̲etrat̲hiaf̲ulvalene] is superconductive under pressures, whereas the salt exhibits metal-insulator (MI) transition under ambient pressure. The insulator phase in the salt was examined using the charge density wave (CDW) phase that was obtained from band calculation. The charge-ordered (CO) state was recently proposed as the insulator phase of the salt, and the mechanism of superconductivity intermediated by charge fluctuation was suggested. We accessed 13C-NMR on β''-(BEDT-TTF)3Cl2·2H2O at ambient pressure and under pressure up to 1.6 GPa. At ambient pressure, the NMR spectrum changed at approximately 100 K. Three isolated peaks appeared at low temperatures, suggesting that the CO state exists below 100 K, and spin-gap behavior was observed. By analyzing the chemical shift, the charges on the three sites were estimated as ˜+0.4e, ˜+0.6e, and ˜+1.0e. The ratio of peak intensity and unsymmetrical peak position suggest the CO state with some symmetry breaking. When pressure is applied, the splitting of the NMR peaks in the CO state is reduced. The salt finally exhibits superconductivity at 1.6 GPa, spin-gap behavior observed at (T1T)-1 below 1.3 GPa suddenly disappears, whereas the NMR spectrum predicts that charge disproportionation coexists with superconductivity. The suppression of the spin-singlet formation observed in (T1T)-1 at 1.6 GPa suggests the metallic state with the charge disproportionation and the CO instability with some symmetry breaking.

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

    PubMed

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

    2014-10-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2016-07-01

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

  1. Molecular dynamics of spider dragline silk fiber investigated by 2H MAS NMR.

    PubMed

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

    2015-03-09

    The molecular dynamics of the proteins that comprise spider dragline silk were investigated with solid-state (2)H magic angle spinning (MAS) NMR line shape and spin-lattice relaxation time (T1) analysis. The experiments were performed on (2)H/(13)C/(15)N-enriched N. clavipes dragline silk fibers. The silk protein side-chain and backbone dynamics were probed for Ala-rich regions (β-sheet and 31-helical domains) in both native (dry) and supercontracted (wet) spider silk. In native (dry) silk fibers, the side chains in all Ala containing regions undergo similar fast methyl rotations (>10(9) s(-1)), while the backbone remains essentially static (<10(2) s(-1)). When the silk is wet and supercontracted, the presence of water initiates fast side-chain and backbone motions for a fraction of the β-sheet region and 31-helicies. β-Sheet subregion 1 ascribed to the poly(Ala) core exhibits slower dynamics, while β-sheet subregion 2 present in the interfacial, primarily poly(Gly-Ala) region that links the β-sheets to disordered 31-helical motifs, exhibits faster motions when the silk is supercontracted. Particularly notable is the observation of microsecond backbone motions for β-sheet subregion 2 and 31-helicies. It is proposed that these microsecond backbone motions lead to hydrogen-bond disruption in β-sheet subregion 2 and helps to explain the decrease in silk stiffness when the silk is wet and supercontracted. In addition, water mobilizes and softens 31-helical motifs, contributing to the increased extensibility observed when the silk is in a supercontracted state. The present study provides critical insight into the supercontraction mechanism and corresponding changes in mechanical properties observed for spider dragline silks.

  2. Nanostructural effects on polymer and water dynamics in cellulose biocomposites: (2)h and (13)c NMR relaxometry.

    PubMed

    Terenzi, Camilla; Prakobna, Kasinee; Berglund, Lars A; Furó, István

    2015-05-11

    Improved moisture stability is desired in cellulose biocomposites. In order to clarify nanostructural effects, a new approach is presented where water and polymer matrix mobilities are characterized separately. Nanocomposites from cellulose nanofibers (CNF) in the xyloglucan (XG) biopolymer matrix are investigated at different hydration states. Films of XG, CNF, and CNF/XG composites are subjected to detailed (2)H and (13)C NMR relaxation studies. Since the (2)H NMR signal arises from heavy water and the (13)C signal from the polysaccharides, molecular water and polymer dynamics is for the first time investigated separately. In the neat components, (2)H transverse relaxation (T2) data are consistent with water clustering at the CNF fibril surfaces, but bulk spread of moisture in XG. The new method results in a description of water interaction with the nanoscale phases. At low hydration, water molecules at the CNF/XG interface exhibit higher water mobility than in neat CNF or XG, due to locally high water concentration. At the same time, CNF-associated interphase segments of XG show slower NMR-dynamics than that in neat XG.

  3. Structure vs. composition: A solid-state 1H and 29Si NMR study of quenched glasses along the Na 2O-SiO 2-H 2O join

    NASA Astrophysics Data System (ADS)

    Cody, George D.; Mysen, Bjorn O.; Lee, Sung Keun

    2005-05-01

    A suite of six hydrous (7 wt.% H 2O) sodium silicate glasses spanning sodium octasilicate to sodium disilicate in composition were analyzed using 29Si single pulse (SP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, 1H- 29Si cross polarization (CP) MAS NMR, and fast MAS 1H-NMR. From the 29Si SPMAS data it is observed that at low sodium compositions dissolved water significantly depolymerizes the silicate network. At higher sodium contents, however, dissolved H 2O does not affect a significant increase in depolymerization over that predicted based on the Na/Si ratio alone. The fast MAS 1H-NMR data reveal considerable complexity in proton environments in each of the glasses studied. The fast MAS 1H-NMR spectra of the highest sodium concentration glasses do not exhibit evidence of signficantly greater fractions of dissolved water as molecular H 2O than the lower sodium concentration glasses requiring that the decrease in polymerization at high sodium contents involves a change in sodium solution mechanism. Variable contact time 1H- 29Si cross polarization (CP) MAS NMR data reveal an increase in the rotating frame spin lattice relaxation rate constant ( T1ρ*) for various Q n species with increasing sodium content that correlates with a reduction in the average 1H- 29Si coupling strength. At the highest sodium concentration, however, T1ρ* drops significantly, consistent with a change in the Na 2O solution mechanism.

  4. Synthesis of (R)-[2-2H]isopentenyl diphosphate and determination of its enantiopurity by 2H NMR spectroscopy in a lyotropic medium.

    PubMed

    Leyes, A E; Poulter, C D

    1999-10-07

    [formula: see text] The synthesis of (R)-[2-2H]isopentenyl diphosphate from D-mannitol 1,2:5,6-bis-acetonide in 10 steps is reported. Stereospecific incorporation of the label is achieved by a BF3-catalyzed NaCNBD3 reduction of the enantiomerically pure (S)-isopropylidene oxirane intermediate. The enantiomeric excess of the penultimate precursor [2-2H]isopentenyl tosylate (> 95% ee) was determined by 2H NMR spectroscopy in a poly-gamma-benzyl-L-glutamate/CH2Cl2 liquid crystal at -50 degrees C.

  5. Mobility of core water in Bacillus subtilis spores by 2H NMR.

    PubMed

    Kaieda, Shuji; Setlow, Barbara; Setlow, Peter; Halle, Bertil

    2013-11-05

    Bacterial spores in a metabolically dormant state can survive long periods without nutrients under extreme environmental conditions. The molecular basis of spore dormancy is not well understood, but the distribution and physical state of water within the spore is thought to play an important role. Two scenarios have been proposed for the spore's core region, containing the DNA and most enzymes. In the gel scenario, the core is a structured macromolecular framework permeated by mobile water. In the glass scenario, the entire core, including the water, is an amorphous solid and the quenched molecular diffusion accounts for the spore's dormancy and thermal stability. Here, we use (2)H magnetic relaxation dispersion to selectively monitor water mobility in the core of Bacillus subtilis spores in the presence and absence of core Mn(2+) ions. We also report and analyze the solid-state (2)H NMR spectrum from these spores. Our NMR data clearly support the gel scenario with highly mobile core water (~25 ps average rotational correlation time). Furthermore, we find that the large depot of manganese in the core is nearly anhydrous, with merely 1.7% on average of the maximum sixfold water coordination. Copyright © 2013 Biophysical Society. Published by Elsevier Inc. All rights reserved.

  6. Mobility of Core Water in Bacillus subtilis Spores by 2H NMR

    PubMed Central

    Kaieda, Shuji; Setlow, Barbara; Setlow, Peter; Halle, Bertil

    2013-01-01

    Bacterial spores in a metabolically dormant state can survive long periods without nutrients under extreme environmental conditions. The molecular basis of spore dormancy is not well understood, but the distribution and physical state of water within the spore is thought to play an important role. Two scenarios have been proposed for the spore’s core region, containing the DNA and most enzymes. In the gel scenario, the core is a structured macromolecular framework permeated by mobile water. In the glass scenario, the entire core, including the water, is an amorphous solid and the quenched molecular diffusion accounts for the spore’s dormancy and thermal stability. Here, we use 2H magnetic relaxation dispersion to selectively monitor water mobility in the core of Bacillus subtilis spores in the presence and absence of core Mn2+ ions. We also report and analyze the solid-state 2H NMR spectrum from these spores. Our NMR data clearly support the gel scenario with highly mobile core water (∼25 ps average rotational correlation time). Furthermore, we find that the large depot of manganese in the core is nearly anhydrous, with merely 1.7% on average of the maximum sixfold water coordination. PMID:24209846

  7. A method for direct in vivo measurement of drug concentrations from a single 2H NMR spectrum.

    PubMed

    Evelhoch, J L; McCoy, C L; Giri, B P

    1989-03-01

    The use of 2H-labeled drugs provides a measure of drug concentration in situ directly from a single 2H NMR spectrum obtained with any antenna by correcting only for differential saturation effects. The limit of detection for a drug labeled with three equivalent deuterons is roughly 0.5 mM.

  8. Raftlike Mixtures of Sphingomyelin and Cholesterol Investigated by Solid-State 2H NMR Spectroscopy

    PubMed Central

    Bartels, Tim; Lankalapalli, Ravi S.; Bittman, Robert; Beyer, Klaus; Brown, Michael F.

    2009-01-01

    Sphingomyelin is a lipid that is abundant in the nervous systems of mammals, where it is associated with putative microdomains in cellular membranes and undergoes alterations due to aging or neurodegeneration. We investigated the effect of varying the concentration of cholesterol in binary and ternary mixtures with N-palmitoylsphingomyelin (PSM) and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) using deuterium nuclear magnetic resonance (2H NMR) spectroscopy in both macroscopically aligned and unoriented multilamellar dispersions. In our experiments, we used PSM and POPC perdeuterated on the N-acyl and sn-1 acyl chains, respectively. By measuring solid-state 2H NMR spectra of the two lipids separately in mixtures with the same compositions as a function of cholesterol mole fraction and temperature, we obtained clear evidence for the coexistence of two liquid-crystalline domains in distinct regions of the phase diagram. According to our analysis of the first moments M1 and the observed 2H NMR spectra, one of the domains appears to be a liquid-ordered phase. We applied a mean-torque potential model as an additional tool to calculate the average hydrocarbon thickness, the area per lipid, and structural parameters such as chain extension and thermal expansion coefficient in order to further define the two coexisting phases. Our data imply that phase separation takes place in raftlike ternary PSM/POPC/cholesterol mixtures over a broad temperature range but vanishes at cholesterol concentrations equal to or greater than a mole fraction of 0.33. Cholesterol interacts preferentially with sphingomyelin only at smaller mole fractions, above which a homogeneous liquid-ordered phase is present. The reasons for these phase separation phenomena seem to be differences in the effects of cholesterol on the configurational order of the palmitoyl chains in PSM-d31 and POPC-d31 and a difference in the affinity of cholesterol for sphingomyelin observed at low temperatures

  9. Limits of metastability in amorphous ices: 2H-NMR relaxation.

    PubMed

    Löw, Florian; Amann-Winkel, Katrin; Geil, Burkhard; Loerting, Thomas; Wittich, Carolin; Fujara, Franz

    2013-01-14

    The high-frequency reorientation dynamics of O-(2)H bonds is investigated in various amorphous ices including eHDA (expanded high density amorphous ice), LDA-II (low density amorphous ice II) and HGW (hyperquenched glassy water) using (2)H-NMR spin-lattice relaxation as a local probe. Both low density forms, HGW and LDA-II, show similar spin-lattice relaxation but differ in the thermal stability with respect to the transition into crystalline cubic ice I(c). HGW already transforms slightly above 135 K whereas LDA-II crystallizes at 150 K. eHDA is distinguishable from other high density amorphous ices in its thermal stability and spin-lattice relaxation. Its relaxation times are much larger compared to those of VHDA (very high density amorphous ice) and uHDA (unrelaxed high density amorphous ice). eHDA does not show annealing effects, transforms sharply into LDA-II above 123 K and provides higher thermal stability as compared to other high density forms.

  10. A new method for the identification of the origin of natural products. Quantitative /sup 2/H NMR at the natural abundance level applied to the characterization of anetholes

    SciTech Connect

    Martin, G.J.; Martin, M.L.; Mabon, F.; Bricont, J.

    1982-05-05

    We have shown by high-field /sup 2/H NMR spectrometry at the natural abundance level that very spectacular differences exist in the interal distribution of /sup 2/H in organic molecules. This phenomenon has been exemplified in particular by the case of ethyl and vinyl derivatives. We show in this study of various anethole samples the potential of this new method as a very powerful tool for the characterization and identification of natural products from different origins.

  11. Characterization of the myristoyl lipid modification of membrane-bound GCAP-2 by 2H solid-state NMR spectroscopy.

    PubMed

    Vogel, Alexander; Schröder, Thomas; Lange, Christian; Huster, Daniel

    2007-12-01

    Guanylate cyclase-activating protein-2 (GCAP-2) is a retinal Ca2+ sensor protein. It is responsible for the regulation of both isoforms of the transmembrane photoreceptor guanylate cyclase, a key enzyme of vertebrate phototransduction. GCAP-2 is N-terminally myristoylated and full activation of its target proteins requires the presence of this lipid modification. The structural role of the myristoyl moiety in the interaction of GCAP-2 with the guanylate cyclases and the lipid membrane is currently not well understood. In the present work, we studied the binding of Ca2+-free myristoylated and non-myristoylated GCAP-2 to phospholipid vesicles consisting of dimyristoylphosphatidylcholine or of a lipid mixture resembling the physiological membrane composition by a biochemical binding assay and 2H solid-state NMR. The NMR results clearly demonstrate the full-length insertion of the aliphatic chain of the myristoyl group into the membrane. Very similar geometrical parameters were determined from the 2H NMR spectra of the myristoyl group of GCAP-2 and the acyl chains of the host membranes, respectively. The myristoyl chain shows a moderate mobility within the lipid environment, comparable to the acyl chains of the host membrane lipids. This is in marked contrast to the behavior of other lipid-modified model proteins. Strikingly, the contribution of the myristoyl group to the free energy of membrane binding of GCAP-2 is only on the order of -0.5 kJ/mol, and the electrostatic contribution is slightly unfavorable, which implies that the main driving forces for membrane localization arises through other, mainly hydrophobic, protein side chain-lipid interactions. These results suggest a role of the myristoyl group in the direct interaction of GCAP-2 with its target proteins, the retinal guanylate cyclases.

  12. Structural water in carbonated hydroxylapatite and fluorapatite: confirmation by solid state (2)H NMR.

    PubMed

    Yoder, Claude H; Pasteris, Jill D; Worcester, Kimberly N; Schermerhorn, Demetra V

    2012-01-01

    Water is well recognized as an important component in bone, typically regarded as a constituent of collagen, a pore-filling fluid in bone, and an adsorbed species on the surface of bone crystallites. The possible siting and role of water within the structure of the apatite crystallites have not been fully explored. In our experiments, carbonated hydroxyl- and fluorapatites were prepared in D(2)O and characterized by elemental analysis, thermal gravimetric analysis, powder X-ray diffraction, and infrared and Raman spectroscopy. Two hydroxylapatites and two fluorapatites, with widely different amounts of carbonate were analyzed by solid state (2)H NMR spectroscopy using the quadrupole echo pulse sequence, and each spectrum showed one single line as well as a low-intensity powder pattern. The relaxation time of 7.1 ms for 5.9 wt% carbonated hydroxylapatite indicates that the single line is likely due to rapid, high-symmetry jumps in translationally rigid D(2)O molecules, indicative of structural incorporation within the lattice. Discrimination between structurally incorporated and adsorbed water is enhanced by the rapid exchange of surface D(2)O with atmospheric H(2)O. Moreover, a (2)H resonance was observed for samples dried under a variety of conditions, including in vacuo heating to 150°C. In contrast, a sample heated to 500°C produced no deuterium resonance, indicating that structural water had been released by that temperature. We propose that water is located in the c-axis channels. Because structural water is observed even for apatites with very low carbonate content, some of the water molecules must lie between the monovalent ions.

  13. Measurements of intracellular volumes by 59Co and 2H/1H NMR and their physiological applications.

    PubMed

    Askenasy, Nadir; Navon, Gil

    2005-04-01

    Determination of the intracellular water volumes using NMR spectroscopy was performed using the NMR-visible nuclei: 59Co and 2H or 1H. Accurate measurement of intracellular water in cell suspensions and perfused organs is an important physiological parameter in the context of electrolyte homeostasis and energy metabolism, in particular when these parameters are monitored by non-invasive NMR spectroscopy. Furthermore, repeated or continuous monitoring of intracellular water provided significant insights into the physiology of cardiac muscle and sarcolemmal membrane permeability and integrity.

  14. NMR relaxation rate studies of molecular motions in NaSn, the Laves-phase metal hydride C15-ZrCr(2)H(x) and carbon/epoxy composite materials

    NASA Astrophysics Data System (ADS)

    Stoddard, Ronald Dean

    Here I present studies of molecular motions in three very different systems: NaSn, which exhibits motion characteristic of both a superionic conductor and a rotor crystal; C15-ZrCrsb2Hsbx (x < 0.5), a metal hydride which exhibits unusual characteristics in its hydrogen motion; and, finally a study of the relationship between Tsb2 and the degree of cure of carbon/epoxy materials. NaSn is characterized by Nasp+ ions and stable (Snsb4)sp{4-} tetrahedra. At high temperatures NaSn displays a disordered solid phase (alpha-NaSn). The presence of Nasp+ ions suggests that alpha-NaSn may be a superionic conductor (translationally disordered) and the presence of stable Snsb4 tetrahedra suggests it may be a rotor crystal (organizationally disordered). The purpose of this study is to gain better understanding of the motions in alpha-NaSn by monitoring Na and Sn motion using sp{23}Na and sp{119}Sn NMR, respectively. C15-ZrCrsb2Hsbx (x < 0.5) is a Laves phase metal hydride which displays extremely rapid hydrogen motion and a Tsb1 peak which cannot be explained by a model employing a single correlation time for the motion. A model employing a Gaussian distribution of correlation times has been used to successfully fit Tsb1, but the origin of this distribution in a crystalline solid solution is not known. The purpose of this study is to better understand the low temperature hydrogen motions occurring in C15-ZrCrsb2Hsbx by extending the previous NMR measurements using Tsb1p and Tsb1D, experiments which effectively push the relaxation peak to lower temperatures. New techniques for manufacturing carbon/epoxy components are under development which require partial curing of the material. At present, no method for monitoring partial curing exists. Tsb2 is a promising monitor of degree of cure because of its sensitivity to changes rates of molecular motions. The purpose of this study is to demonstrate the sensitivity of Tsb2 to changes in molecular motion due to curing, and to find a

  15. (1)H-(2)H cross-polarization NMR in fast spinning solids by adiabatic sweeps.

    PubMed

    Wi, Sungsool; Schurko, Robert; Frydman, Lucio

    2017-03-14

    Cross-polarization (CP) experiments employing frequency-swept radiofrequency (rf) pulses have been successfully used in static spin systems for obtaining broadband signal enhancements. These experiments have been recently extended to heteronuclear I, S = spin-1/2 nuclides under magic-angle spinning (MAS), by applying adiabatic inversion pulses along the S (low-γ) channel while simultaneously applying a conventional spin-locking pulse on the I-channel ((1)H). This study explores an extension of this adiabatic frequency sweep concept to quadrupolar nuclei, focusing on CP from (1)H (I = 1/2) to (2)H spins (S = 1) undergoing fast MAS (νr = 60 kHz). A number of new features emerge, including zero- and double-quantum polarization transfer phenomena that depend on the frequency offsets of the swept pulses, the rf pulse powers, and the MAS spinning rate. An additional mechanism found operational in the (1)H-(2)H CP case that was absent in the spin-1/2 counterpart, concerns the onset of a pseudo-static zero-quantum CP mode, driven by a quadrupole-modulated rf/dipolar recoupling term arising under the action of MAS. The best CP conditions found at these fast spinning rates correspond to double-quantum transfers, involving weak (2)H rf field strengths. At these easily attainable (ca. 10 kHz) rf field conditions, adiabatic level-crossings among the {|1⟩,|0⟩,|-1⟩} mS energy levels, which are known to complicate the CP MAS of quadrupolar nuclei, are avoided. Moreover, the CP line shapes generated in this manner are very close to the ideal (2)H MAS spectral line shapes, facilitating the extraction of quadrupolar coupling parameters. All these features were corroborated with experiments on model compounds and justified using numerical simulations and average Hamiltonian theory models. Potential applications of these new phenomena, as well as extensions to higher spins S, are briefly discussed.

  16. 1H-2H cross-polarization NMR in fast spinning solids by adiabatic sweeps

    NASA Astrophysics Data System (ADS)

    Wi, Sungsool; Schurko, Robert; Frydman, Lucio

    2017-03-01

    Cross-polarization (CP) experiments employing frequency-swept radiofrequency (rf) pulses have been successfully used in static spin systems for obtaining broadband signal enhancements. These experiments have been recently extended to heteronuclear I, S = spin-1/2 nuclides under magic-angle spinning (MAS), by applying adiabatic inversion pulses along the S (low-γ) channel while simultaneously applying a conventional spin-locking pulse on the I-channel (1H). This study explores an extension of this adiabatic frequency sweep concept to quadrupolar nuclei, focusing on CP from 1H (I = 1/2) to 2H spins (S = 1) undergoing fast MAS (νr = 60 kHz). A number of new features emerge, including zero- and double-quantum polarization transfer phenomena that depend on the frequency offsets of the swept pulses, the rf pulse powers, and the MAS spinning rate. An additional mechanism found operational in the 1H-2H CP case that was absent in the spin-1/2 counterpart, concerns the onset of a pseudo-static zero-quantum CP mode, driven by a quadrupole-modulated rf/dipolar recoupling term arising under the action of MAS. The best CP conditions found at these fast spinning rates correspond to double-quantum transfers, involving weak 2H rf field strengths. At these easily attainable (ca. 10 kHz) rf field conditions, adiabatic level-crossings among the {|1 ⟩ ,|0 ⟩ ,|-1 ⟩ } mS energy levels, which are known to complicate the CP MAS of quadrupolar nuclei, are avoided. Moreover, the CP line shapes generated in this manner are very close to the ideal 2H MAS spectral line shapes, facilitating the extraction of quadrupolar coupling parameters. All these features were corroborated with experiments on model compounds and justified using numerical simulations and average Hamiltonian theory models. Potential applications of these new phenomena, as well as extensions to higher spins S, are briefly discussed.

  17. Critical behaviour in DOPC/DPPC/cholesterol mixtures: static (2)H NMR line shapes near the critical point.

    PubMed

    Davis, James H; Schmidt, Miranda L

    2014-05-06

    Static (2)H NMR spectroscopy is used to study the critical behavior of mixtures of 1,2-dioleoyl-phosphatidylcholine/1,2-dipalmitoyl-phosphatidylcholine (DPPC)/cholesterol in molar proportion 37.5:37.5:25 using either chain perdeuterated DPPC-d62 or chain methyl deuterated DPPC-d6. The temperature dependence of the first moment of the (2)H spectrum of the sample made with DPPC-d62 and of the quadrupolar splittings of the chain-methyl-labeled DPPC-d6 sample are directly related to the temperature dependence of the critical order parameter η, which scales as [Formula: see text] near the critical temperature. Analysis of the data reveals that for the chain perdeuterated sample, the value of Tc is 301.51 ± 0.1 K, and that of the critical exponent, βc = 0.391 ± 0.02. The line shape analysis of the methyl labeled (d6) sample gives Tc = 303.74 ± 0.07 K and βc = 0.338 ± 0.009. These values obtained for βc are in good agreement with the predictions of a three-dimensional Ising model. The difference in critical temperature between the two samples having nominally the same molar composition arises because of the lowering of the phase transition temperature that occurs due to the perdeuteration of the DPPC.

  18. Insights on the Interactions of Synthetic Amphipathic Peptides with Model Membranes as Revealed by 31P and 2H Solid-State NMR and Infrared Spectroscopies

    PubMed Central

    Ouellet, Marise; Bernard, Geneviève; Voyer, Normand; Auger, Michèle

    2006-01-01

    We studied the interaction between synthetic amphipathic peptides and model membranes by solid-state NMR and infrared spectroscopies. Peptides with 14 and 21 amino acids composed of leucines and phenylalanines modified by the addition of crown ethers were synthesized. The 14-mer and 21-mer peptides both possess a helical amphipathic structure. To shed light on their membrane interaction, 31P and 2H solid-state NMR experiments were performed on both peptides in interaction with dimyristoylphosphatidylcholine vesicles in the absence and presence of cholesterol, dimyristoylphosphatidylglycerol vesicles, and oriented bicelles. 31P NMR experiments on multilamellar vesicles reveal that the dynamics and/or orientation of the polar headgroups are weakly yet markedly affected by the presence of the peptides, whereas 31P NMR experiments on bicelles indicate no significant changes in the morphology and orientation of the bicelles. On the other hand, 2H NMR experiments on vesicles reveal that the acyl chain order is affected differently depending on the membrane lipidic composition and on the peptide hydrophobic length. Finally, infrared spectroscopy was used to study the interfacial region of the bilayer. Based on these studies, mechanisms of membrane perturbation are proposed for the 14-mer and 21-mer peptides in interaction with model membranes depending on the bilayer composition and peptide length. PMID:16533836

  19. Models of stratum corneum intercellular membranes: 2H NMR of macroscopically oriented multilayers.

    PubMed Central

    Fenske, D B; Thewalt, J L; Bloom, M; Kitson, N

    1994-01-01

    Deuterium NMR was used to characterize model membrane systems approximating the composition of the intercellular lipid lamellae of mammalian stratum corneum (SC). The SC models, equimolar mixtures of ceramide:cholesterol:palmitic acid (CER:CHOL:PA) at pH 5.2, were contrasted with the sphingomyelin:CHOL:PA (SPM:CHOL:PA) system, where the SPM differs from the CER only in the presence of a phosphocholine headgroup. The lipids were prepared both as oriented samples and as multilamellar dispersions, and contained either perdeuterated palmitic acid (PA-d31) or [2,2,3,4,6-2H5]CHOL (CHOL-d5). SPM:CHOL:PA-d31 formed liquid-ordered membranes over a wide range of temperatures, with a maximum order parameter of approximately 0.4 at 50 degrees C for positions C3-C10 (the plateau region). The quadrupolar splitting at C2 was significantly smaller, suggesting an orientational change at this position, possibly because of hydrogen bonding with water and/or other surface components. A comparison of the longitudinal relaxation times obtained at theta = 0 degrees and 90 degrees (where theta is the angle between the normal to the glass plates and the magnetic field) revealed a significant T1Z anisotropy for all positions. In contrast to the behavior observed with the SPM system, lipid mixtures containing CER exhibited a complex polymorphism. Between 20 and 50 degrees C, a significant portion of the entire membrane (as monitored by both PA-d31 and CHOL-d5) was found to exist as a solid phase, with the remainder either a gel or liquid-ordered phase. The proportion of solid decreased as the temperature was increased and disappeared entirely above 50 degrees C. Between 50 and 70 degrees C, the membrane underwent a liquid-ordered to isotropic phase transition. These transitions were reversible but displayed considerable hysteresis, especially the conversion from a fluid phase to solid. The order profiles, relaxation behavior, and angular dependence of these parameters suggest strongly that

  20. Rotational dynamics in a crystalline molecular gyroscope by variable-temperature 13C NMR, 2H NMR, X-ray diffraction, and force field calculations.

    PubMed

    Khuong, Tinh-Alfredo V; Dang, Hung; Jarowski, Peter D; Maverick, Emily F; Garcia-Garibay, Miguel A

    2007-01-31

    A combination of solid-state 13C CPMAS NMR, 2H NMR, X-ray-determined anisotropic displacement parameters (ADPs), and molecular mechanics calculations were used to analyze the rotational dynamics of 1,4-bis[3,3,3-tris(m-methoxyphenyl)propynyl]benzene (3A), a structure that emulates a gyroscope with a p-phenylene group acting as a rotator and two m-methoxy-substituted trityl groups acting as a stator. The line shape analysis of VT 13C CPMAS and broad-band 2H NMR data were in remarkable agreement with each other, with rotational barriers of 11.3 and 11.5 kcal/mol, respectively. The barriers obtained by analysis of ADPs obtained by single-crystal X-ray diffraction at 100 and 200 K, assuming a sinusoidal potential, were 10.3 and 10.1 kcal, respectively. A similar analysis of an X-ray structure solved from data acquired at 300 K suggested a barrier of only 8.0 kcal/mol. Finally, a rotational potential calculated with a finite cluster model using molecular mechanics revealed a symmetric but nonsinusoidal potential that accounts relatively well for the X-ray-derived values and the NMR experimental results. It is speculated that the discrepancy between the barriers derived from low and high-temperature X-ray data may be due to an increase in anharmonicity, or to disorder, at the higher temperature values.

  1. 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.

  2. Influence of the penetration enhancer isopropyl myristate on stratum corneum lipid model membranes revealed by neutron diffraction and (2)H NMR experiments.

    PubMed

    Eichner, Adina; Stahlberg, Sören; Sonnenberger, Stefan; Lange, Stefan; Dobner, Bodo; Ostermann, Andreas; Schrader, Tobias E; Hauß, Thomas; Schroeter, Annett; Huster, Daniel; Neubert, Reinhard H H

    2017-05-01

    The stratum corneum (SC) provides the main barrier properties in native skin. The barrier function is attributed to the intercellular lipids, forming continuous multilamellar membranes. In this study, SC lipid membranes in model ratios were enriched with deuterated lipids in order to investigate structural and dynamical properties by neutron diffraction and (2)H solid-state NMR spectroscopy. Further, the effect of the penetration enhancer isopropyl myristate (IPM) on the structure of a well-known SC lipid model membrane containing synthetically derived methyl-branched ceramide [EOS], ceramide [AP], behenic acid and cholesterol (23/10/33/33wt%) was investigated. IPM supported the formation of a single short-periodicity phase (SPP), in which we determined the molecular organization of CER[AP] and CER[EOS]-br for the first time. Furthermore, the thermotropic phase behavior of the lipid system was analyzed by additional neutron diffraction studies as well as by (2)H solid-state NMR spectroscopy, covering temperatures of 32°C (physiological skin temperature), 50°C, and 70°C with a subsequent cooldown back to skin temperature. Both techniques revealed a phase transition and a hysteresis effect. During the cooldown, Bragg peaks corresponding to a long-periodicity phase (LPP) appeared. Additionally, (2)H NMR revealed that the IPM molecules are isotopic mobile at all temperatures.

  3. 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

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

    PubMed

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

    2016-06-18

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

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

    PubMed

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

    2015-05-18

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

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

    NASA Astrophysics Data System (ADS)

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

    2015-09-01

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

  7. Fully automated high-quality NMR structure determination of small (2)H-enriched proteins.

    PubMed

    Tang, Yuefeng; Schneider, William M; Shen, Yang; Raman, Srivatsan; Inouye, Masayori; Baker, David; Roth, Monica J; Montelione, Gaetano T

    2010-12-01

    Determination of high-quality small protein structures by nuclear magnetic resonance (NMR) methods generally requires acquisition and analysis of an extensive set of structural constraints. The process generally demands extensive backbone and sidechain resonance assignments, and weeks or even months of data collection and interpretation. Here we demonstrate rapid and high-quality protein NMR structure generation using CS-Rosetta with a perdeuterated protein sample made at a significantly reduced cost using new bacterial culture condensation methods. Our strategy provides the basis for a high-throughput approach for routine, rapid, high-quality structure determination of small proteins. As an example, we demonstrate the determination of a high-quality 3D structure of a small 8 kDa protein, E. coli cold shock protein A (CspA), using <4 days of data collection and fully automated data analysis methods together with CS-Rosetta. The resulting CspA structure is highly converged and in excellent agreement with the published crystal structure, with a backbone RMSD value of 0.5 Å, an all atom RMSD value of 1.2 Å to the crystal structure for well-defined regions, and RMSD value of 1.1 Å to crystal structure for core, non-solvent exposed sidechain atoms. Cross validation of the structure with (15)N- and (13)C-edited NOESY data obtained with a perdeuterated (15)N, (13)C-enriched (13)CH(3) methyl protonated CspA sample confirms that essentially all of these independently-interpreted NOE-based constraints are already satisfied in each of the 10 CS-Rosetta structures. By these criteria, the CS-Rosetta structure generated by fully automated analysis of data for a perdeuterated sample provides an accurate structure of CspA. This represents a general approach for rapid, automated structure determination of small proteins by NMR.

  8. Hydrido-ruthenium cluster complexes as models for reactive surface hydrogen species of ruthenium nanoparticles. Solid-state 2H NMR and quantum chemical calculations.

    PubMed

    Gutmann, Torsten; Walaszek, Bernadeta; Yeping, Xu; Wächtler, Maria; del Rosal, Iker; Grünberg, Anna; Poteau, Romuald; Axet, Rosa; Lavigne, Guy; Chaudret, Bruno; Limbach, Hans-Heinrich; Buntkowsky, Gerd

    2010-08-25

    The (2)H quadrupolar interaction is a sensitive tool for the characterization of deuterium-metal binding states. In the present study, experimental solid-state (2)H MAS NMR techniques are used in the investigations of two ruthenium clusters, D(4)Ru(4)(CO)(12) (1) and D(2)Ru(6)(CO)(18) (2), which serve as model compounds for typical two-fold, three-fold, and octahedral coordination sites on metal surfaces. By line-shape analysis of the (2)H MAS NMR measurements of sample 1, a quadrupolar coupling constant of 67 +/- 1 kHz, an asymmetry parameter of 0.67 +/- 0.1, and an isotropic chemical shift of -17.4 ppm are obtained. In addition to the neutral complex, sample 2 includes two ionic clusters, identified as anionic [DRu(6)(CO)(18)](-) (2(-)) and cationic [D(3)Ru(6)(CO)(18)](+) (2(+)). By virtue of the very weak quadrupolar interaction (<2 kHz) and the strong low-field shift (+16.8 ppm) of 2(-), it is shown that the deuteron is located in the symmetry center of the octahedron spanned by the six ruthenium atoms. For the cationic 2(+), the quadrupolar interaction is similar to that of the neutral 2. Quantum chemical DFT calculations at different model structures for these ruthenium clusters were arranged in order to help in the interpretation of the experimental results. It is shown that the (2)H nuclear quadrupolar interaction is a sensitive tool for distinguishing the binding state of the deuterons to the transition metal. Combining the data from the polynuclear complexes with the data from mononuclear complexes, a molecular ruler for quadrupolar interactions is created. This ruler now permits the solid-state NMR spectroscopic characterization of deuterium adsorbed on the surfaces of catalytically active metal nanoparticles.

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

    PubMed

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

    2012-06-20

    The hydration properties of 2,3-O-hydroxypropylcellulose (HPC) and 2,3-O-hydroxyethylcellulose (HEC) were analyzed by multi-nuclear solid-state MAS NMR spectroscopy. By 13C single-pulse (SP) MAS and cross-polarization (CP) MAS NMR, differences between the immobile regions and all parts of the polysaccharides were detected as a function of hydration. Complementary information about the water environments was observed by 2H MAS NMR. By this approach it was demonstrated that side chains in 2,3-O-HPC and 2,3-O-HEC were easier to hydrate than the cellulose backbone. Furthermore the motion of water was more restricted (slower) in 2,3-O-HPC than in 2,3-O-HEC. For both polysaccharides the hydration could be explained by a two-step process: in step one increased ordering of the immobile regions occurs after which the entire polymer is hydrated in step two. Copyright © 2012 Elsevier Ltd. All rights reserved.

  10. Nuclear magnetic resonance studies of hydrogen motion in nanostructured Laves-phase hydrides ZrCr(2)H(x) and TaV(2)H(x).

    PubMed

    Soloninin, A V; Buzlukov, A L; Skripov, A V; Aleksashin, B A; Tankeyev, A P; Yermakov, A Ye; Mushnikov, N V; Uimin, M A; Gaviko, V S

    2008-07-09

    In order to study the mobility of hydrogen in nanostructured Laves-phase hydrides, we have measured the proton nuclear magnetic resonance (NMR) spectra and the proton spin-lattice and spin-spin relaxation rates in two nanostructured systems prepared by ball milling: ZrCr(2)H(3) and TaV(2)H(1+δ). The proton NMR measurements have been performed at the resonance frequencies of 14, 23.8 and 90 MHz over the temperature ranges 11-424 K (for coarse-grained samples) and 11-384 K (for nanostructured samples). Hydrogen mobility in the ball-milled ZrCr(2)H(3) is found to decrease strongly with increasing milling time. The experimental data suggest that this effect is related to the growth of the fraction of highly distorted intergrain regions where H mobility is much lower than in the crystalline grains. For the nanostructured TaV(2)H(1+δ) system, the ball milling is found to lead to a slight decrease in the long-range H mobility and to a suppression of the fast localized H motion in the crystalline grains.

  11. Solid-state NMR analysis of the PGLa peptide orientation in DMPC bilayers: structural fidelity of 2H-labels versus high sensitivity of 19F-NMR.

    PubMed

    Strandberg, Erik; Wadhwani, Parvesh; Tremouilhac, Pierre; Dürr, Ulrich H N; Ulrich, Anne S

    2006-03-01

    The structure and alignment of the amphipathic alpha-helical antimicrobial peptide PGLa in a lipid membrane is determined with high accuracy by solid-state 2H-NMR. Orientational constraints are derived from a series of eight alanine-3,3,3-d3-labeled peptides, in which either a native alanine is nonperturbingly labeled (4x), or a glycine (2x) or isoleucine (2x) is selectively replaced. The concentration dependent realignment of the alpha-helix from the surface-bound "S-state" to a tilted "T-state" by 30 degrees is precisely calculated using the quadrupole splittings of the four nonperturbing labels as constraints. The remaining, potentially perturbing alanine-3,3,3-d3 labels show only minor deviations from the unperturbed peptide structure and help to single out the unique solution. Comparison with previous 19F-NMR constraints from 4-CF3-phenylglycine labels shows that the structure and orientation of the PGLa peptide is not much disturbed even by these bulky nonnatural side chains, which contain CF3 groups that offer a 20-fold better NMR sensitivity than CD3 groups.

  12. Formation of Gel-like Nanodomains in Cholesterol-Containing Sphingomyelin or Phosphatidylcholine Binary Membrane As Examined by Fluorescence Lifetimes and (2)H NMR Spectra.

    PubMed

    Yasuda, Tomokazu; Matsumori, Nobuaki; Tsuchikawa, Hiroshi; Lönnfors, Max; Nyholm, Thomas K M; Slotte, J Peter; Murata, Michio

    2015-12-29

    In this study, we measured the time-resolved fluorescence of trans-parinaric acid (tPA), steady-state fluorescence anisotropy of diphenylhexatriene (DPH), and (2)H NMR of 10,10-d2-stearoyl lipids in stearoyl sphingomyelin with cholesterol (SSM/Chol) and l-palmitoyl-2-stearoyl-sn-glycero-3-phosphocholine with Chol (PSPC/Chol) binary membranes. The results suggest that the membrane order obtained from the fluorescence experiments shows a similar temperature dependency as those of the (2)H NMR data. More importantly, the time-resolved fluorescence data implied the presence of at least two types of domains, cholesterol-poor gel-like domains (CPGLD) and cholesterol-enriched liquid-ordered (Lo) domains. These domains appear on a nano-to-micro second time scale for both SSM-Chol and PSPC-Chol membranes. The relative size of the gel-like domain was also estimated from the temperature-dependent lifetime measurements and (2)H NMR spectral changes. The results imply that the size of the gel-like domains is very small, probably on the nanometer scale, and smaller in SSM-Chol membrane than those in PSPC-Chol bilayers, which could account for the higher thermal stability of SM-Chol membranes. The present study demonstrates that gel-like nanodomains occur in SM-Chol binary membrane even with Chol content of over 33 mol %, which has been thought to consist exclusively of Lo phase, implying that not only Lo domains but also gel-like nanodomains are important for formation of lipid-ordered phase in SM-Chol and PC-Chol membranes.

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

    SciTech Connect

    LeMaster, D.M.

    1994-12-01

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

  14. 13C NMR analysis of 3,6-dihydro-2H-pyrans: assignment of remote stereochemistry using axial shielding effects.

    PubMed

    Bartlett, Mark J; Northcote, Peter T; Lein, Matthias; Harvey, Joanne E

    2014-06-20

    The rational analysis of (13)C NMR axial shielding effects has enabled the assignment of remote relative stereochemistry in 3,6-oxygen-substituted 3,6-dihydro-2H-pyrans. Comparison of the (13)C NMR shifts of equivalent centers in cis- and trans-substituted 3,6-dihydro-2H-pyrans allows the relative configuration at the C3 and C6 positions to be defined in diastereoisomeric mixtures. Density functional calculations were used to validate this method and assess the conformational bias present in the ring system. Ultimately, the coupling of computational chemistry with this (13)C NMR-based method provided a reliable and convenient method for stereochemical assignment of a single diastereomer. This approach provides a facile and complementary alternative to the practices previously employed for determining the relative configuration in 3,6-dihydro-2H-pyrans.

  15. Theoretical study of the bonding of Nb(2+) to CH2, C2H2, and C2H4

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

    1991-01-01

    The bonding of Nb(2+) with CH2, C2H2, and C2H4 is studied by using electronic structure calculations that include high levels of electron correlation. The binding energy for NbCH2(2+) is in good agreement with the lower bound determined from the reaction with CH4 but is significantly smaller than the value determined from the binding energy and ionization potential of NbCH2(+). The calculations and a new interpretation of the experiment indicate that the larger value is in error primarily because the ionization potential of NbCH2(+) determined from bracketing charge-exchange reactions is too small. The computed binding energy of NbC2H2(2+) is in good agreement with experiment. The calculations show that the bonding is predominantly covalent in character for both NbCH2(2+) and NbC2H2(2+), whereas for NbC2H4(2+) the electronic states that are predominantly ionic and covalent are nearly degenerate. The trend in binding energies, CH2 greater than C2H2 greater than C2H4, is consistent with the energy required to prepare the ligands for bonding.

  16. Theoretical study of the bonding of Nb(2+) to CH2, C2H2, and C2H4

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.; Partridge, Harry

    1991-01-01

    The bonding of Nb(2+) with CH2, C2H2, and C2H4 is studied by using electronic structure calculations that include high levels of electron correlation. The binding energy for NbCH2(2+) is in good agreement with the lower bound determined from the reaction with CH4 but is significantly smaller than the value determined from the binding energy and ionization potential of NbCH2(+). The calculations and a new interpretation of the experiment indicate that the larger value is in error primarily because the ionization potential of NbCH2(+) determined from bracketing charge-exchange reactions is too small. The computed binding energy of NbC2H2(2+) is in good agreement with experiment. The calculations show that the bonding is predominantly covalent in character for both NbCH2(2+) and NbC2H2(2+), whereas for NbC2H4(2+) the electronic states that are predominantly ionic and covalent are nearly degenerate. The trend in binding energies, CH2 greater than C2H2 greater than C2H4, is consistent with the energy required to prepare the ligands for bonding.

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  18. Probing the role of the ceramide acyl chain length and sphingosine unsaturation in model skin barrier lipid mixtures by (2)H solid-state NMR spectroscopy.

    PubMed

    Stahlberg, Sören; Školová, Barbora; Madhu, Perunthiruthy K; Vogel, Alexander; Vávrová, Kateřina; Huster, Daniel

    2015-05-05

    We investigated equimolar mixtures of ceramides with lignoceric acid and cholesterol as models for the human stratum corneum by differential scanning calorimetry and (2)H solid-state NMR spectroscopy. Our reference system consisted of lignoceroyl sphingosine (Cer[NS24]), which represents one of the ceramides in the human stratum corneum. Furthermore, the effect of ceramide acyl chain truncation to 16 carbons as in Cer[NS16] and the loss of the C4 trans double bond as in dihydroceramide Cer[NDS24] were studied. Fully relaxed (2)H NMR spectra were acquired for each deuterated component of each mixture separately, allowing the quantitative determination of the individual lipid phases. At skin temperature, the reference system containing Cer[NS24] is characterized by large portions of each component of the mixture in a crystalline phase, which largely restricts the permeability of the skin lipid barrier. The loss of the C4 trans double bond in Cer[NDS24] leads to the replacement of more than 25% of the crystalline phase by an isotropic phase of the dihydroceramide that shows the importance of dihydroceramide desaturation in the formation of the skin lipid barrier. The truncated Cer[NS16] is mostly found in the gel phase at skin temperature, which may explain its negative effect on the transepidermal water loss in atopic dermatitis patients. These significant alterations in the phase behavior of all lipids are further reflected at elevated temperatures. The molecular insights of our study may help us to understand the importance of the structural parameters of ceramides in healthy and compromised skin barriers.

  19. Structure and Dynamics of the Myristoyl Lipid Modification of Src Peptides Determined by 2H Solid-State NMR Spectroscopy

    PubMed Central

    Scheidt, Holger A.; Huster, Daniel

    2009-01-01

    Lipid modifications of proteins are widespread in nature and play an important role in numerous biological processes. The nonreceptor tyrosine kinase Src is equipped with an N-terminal myristoyl chain and a cluster of basic amino acids for the stable membrane association of the protein. We used 2H NMR spectroscopy to investigate the structure and dynamics of the myristoyl chain of myr-Src(2–19), and compare them with the hydrocarbon chains of the surrounding phospholipids in bilayers of varying surface potentials and chain lengths. The myristoyl chain of Src was well inserted in all bilayers investigated. In zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine membranes, the myristoyl chain of Src was significantly longer and appears “stiffer” than the phospholipid chains. This can be explained by an equilibrium between the attraction attributable to the insertion of the myristoyl chain and the Born repulsion. In a 1,2-dimyristoyl-sn-glycero-3-phosphocholine/1,2-dimyristoyl-sn-glycero-3-[phospho-L-serine] membrane, where attractive electrostatic interactions come into play, the differences between the peptide and the phospholipid chain lengths were attenuated, and the molecular dynamics of all lipid chains were similar. In a much thicker 1,2-dipalmitoyl-sn-glycero-3-phosphocholine/1,2-dipalmitoyl-sn-glycero-3-[phospho-L-serine]/cholesterol membrane, the length of the myristoyl chain of Src was elongated nearly to its maximum, and the order parameters of the Src chain were comparable to those of the surrounding membrane. PMID:19413971

  20. Synthesis and complete assignment of the 1H and 13C NMR spectra of 6-substituted and 2,6-disubstituted pyridazin-3(2H)-ones.

    PubMed

    Besada, Pedro; Costas, Tamara; Vila, Noemi; Chessa, Carla; Terán, Carmen

    2011-07-01

    Several pyridazin-3(2H)-one derivatives were synthesized starting from alkyl furans using oxidation with singlet oxygen to give 4-methoxy or 4-hydroxybutenolides, key intermediates of the synthetic strategy followed. For all pyridazinones reported, a complete assignment of the (1)H and (13)C NMR spectra using one- and two-dimensional NMR spectroscopic methods, which included NOE, DEPT, COSY, HSQC and HMBC experiments, was accomplished. Correlations between the chemical shifts of the heterocyclic ring atoms and substituents at N-2 and C-6 were analyzed.

  1. Comparative analysis of the orientation of transmembrane peptides using solid-state (2)H- and (15)N-NMR: mobility matters.

    PubMed

    Grage, Stephan L; Strandberg, Erik; Wadhwani, Parvesh; Esteban-Martín, Santiago; Salgado, Jesús; Ulrich, Anne S

    2012-05-01

    Many solid-state nuclear magnetic resonance (NMR) approaches for membrane proteins rely on orientation-dependent parameters, from which the alignment of peptide segments in the lipid bilayer can be calculated. Molecules embedded in liquid-crystalline membranes, such as monomeric helices, are highly mobile, leading to partial averaging of the measured NMR parameters. These dynamic effects need to be taken into account to avoid misinterpretation of NMR data. Here, we compare two common NMR approaches: (2)H-NMR quadrupolar waves, and separated local field (15)N-(1)H polarization inversion spin exchange at magic angle (PISEMA) spectra, in order to identify their strengths and drawbacks for correctly determining the orientation and mobility of α-helical transmembrane peptides. We first analyzed the model peptide WLP23 in oriented dimyristoylphosphatidylcholine (DMPC) membranes and then contrasted it with published data on GWALP23 in dilauroylphosphatidylcholine (DLPC). We only obtained consistent tilt angles from the two methods when taking dynamics into account. Interestingly, the two related peptides differ fundamentally in their mobility. Although both helices adopt the same tilt in their respective bilayers (~20°), WLP23 undergoes extensive fluctuations in its azimuthal rotation angle, whereas GWALP23 is much less dynamic. Both alternative NMR methods are suitable for characterizing orientation and dynamics, yet they can be optimally used to address different aspects. PISEMA spectra immediately reveal the presence of large-amplitude rotational fluctuations, which are not directly seen by (2)H-NMR. On the other hand, PISEMA was unable to define the azimuthal rotation angle in the case of the highly dynamic WLP23, though the helix tilt could still be determined, irrespective of any dynamics parameters.

  2. Hysteresis effect of ammonium and water protons by 1H MAS NMR in (NH4)2CuBr4·2H2O

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran; Cho, Jiung

    2017-10-01

    The chemical shifts, linewidths, and spin-lattice relaxation times for ammonium and water protons in (NH4)2CuBr4·2H2O were investigated by 1H magic angle spinning nuclear magnetic resonance (MAS NMR) with a focus on the roles of NH4+ and H2O at high temperatures. The changes in the temperature dependence of the data near Td (=360 K) were related to variations of the H environments; the mechanism above Td was related to hydrogen-bond transfer involving breakage of the weak part of the hydrogen bond. The hysteresis effects for the ammonium and water protons in (NH4)2CuBr4·2H2O by MAS NMR were described with respect to heating and cooling.

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

    SciTech Connect

    Cinacchi, Giorgio; Domenici, Valentina

    2006-09-15

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

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

    SciTech Connect

    Zilm, K.W.

    1989-01-01

    This report covers the progress made on the title project during the past reporting 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 in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines the authors are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. The authors have been reinvestigating the prospects of using zero field NMR types of techniques for two dimensional NMR structural analysis of complex organic solids such as coals. Currently MAS spin rates are not sufficiently high to permit zero field in high field NMR for protons in typical organic solids, however they are compatible with {sup 13}C-{sup 13}C dipolar couplings. In collaboration with Dr. Robert Tycko of AT T Bell Laboratories, inventor of the zero field in high field NMR method, the authors have performed the first zero field in high field {sup 13}C NMR experiments. These results are described. 9 refs., 2 figs.

  5. Theoretical study on the rate constants for the C2H5 + HBr --> C2H6 + Br reaction.

    PubMed

    Sheng, Li; Li, Ze-Sheng; Liu, Jing-Yao; Xiao, Jing-Fa; Sun, Chia-Chung

    2004-02-01

    The reaction C(2)H(5) + HBr --> C(2)H(6) + Br has been theoretically studied over the temperature range from 200 to 1400 K. The electronic structure information is calculated at the BHLYP/6-311+G(d,p) and QCISD/6-31+G(d) levels. With the aid of intrinsic reaction coordinate theory, the minimum energy paths (MEPs) are obtained at the both levels, and the energies along the MEP are further refined by performing the single-point calculations at the PMP4(SDTQ)/6-311+G(3df,2p)//BHLYP and QCISD(T)/6-311++G(2df,2pd)//QCISD levels. The calculated ICVT/SCT rate constants are in good agreement with available experimental values, and the calculate results further indicate that the C(2)H(5) + HBr reaction has negative temperature dependence at T < 850 K, but clearly shows positive temperature dependence at T > 850 K. The current work predicts that the kinetic isotope effect for the title reaction is inverse in the temperature range from 200 to 482 K, i.e., k(HBr)/k(DBr) < 1.

  6. 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

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

    NASA Astrophysics Data System (ADS)

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

    2009-03-01

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

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

    PubMed

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

    2014-05-01

    It has been proposed that some neuropeptides may be anchored to the cell membranes prior to attaching to the adjacent active sites of transmembrane receptors. The three amphibian skin neuropeptides signiferin 1 [RLCIPYIIPC(OH)] (smooth muscle active and immunomodulator), riparin 1.1 [[RLCIPVIFPC(OH)] (immunomodulator) and rothein 1 [SVSNIPESIGF(OH)] (immunomodulator) act via CCK2 transmembrane receptors. A combination of (31)P and (2)H solid state NMR studies of each of these three peptides in eukaryotic phospholipid models at 25°C shows that rothein 1 does not interact with the membrane at all. In contrast, both of the cyclic disulfides signiferin 1 and riparin 1.1 interact with phospholipid head groups and partially penetrate into the upper leaflet of the model bilayer, but to different extents. These interactions are not sufficiently effective to cause disruption of the lipid bilayer since the peptides are not antimicrobial, anticancer, antifungal nor active against enveloped viruses. Copyright © 2014. Published by Elsevier Inc.

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

    SciTech Connect

    Zilm, K.W.

    1988-01-01

    This report covers the progress made on the title project during the current reporting 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 in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines we are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. This quarter we have focused on variable temperature spin lattice relaxation measurements for several of the Argonne coals. 5 figs.

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

    SciTech Connect

    Zilm, K.W.

    1988-01-01

    This report covers the progress made on the title project during the current reporting 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 in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines we are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. This quarter we have focussed on spin lattice relaxation measurements for several of the Argonne coals. 2 figs., 1 tab.

  11. Probing stereoselectivity and pro-chirality of hydride transfer during short-chain alcohol dehydrogenase activity: a combined quantitative 2H NMR and computational approach.

    PubMed

    Kwiecień, Renata A; Ayadi, Farouk; Nemmaoui, Youssef; Silvestre, Virginie; Zhang, Ben-Li; Robins, Richard J

    2009-02-01

    Different members of the alcohol oxidoreductase family can transfer the hydride of NAD(P)H to either the re- or the si-face of the substrate. The enantioselectivity of transfer is very variable, even for a range of substrates reduced by the same enzyme. Exploiting quantitative isotopic (2)H NMR to measure the transfer of (2)H from NAD(P)(2)H to ethanol, a range of enantiomeric excess between 0.38 and 0.98, depending on the origin of the enzyme and the nature of the cofactor, has been determined. Critically, in no case was only (R)-[1-(2)H]ethanol or (S)-[1-(2)H]ethanol obtained. By calculating the relative energies of the active site models for hydride transfer to the re- or si-face of short-chain aldehydes by alcohol dehydrogenase from Saccharomyces cerevisiae and Lactobacillus brevis, it is shown that the differences in the energy of the systems when the substrate is positioned with the alkyl group in one or the other pocket of the active site could play a role in determining stereoselectivity. These experiments help to provide insight into structural features that influence the potential catalytic flexibility of different alcohol dehydrogenase activities.

  12. 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.

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

    SciTech Connect

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

    1981-12-30

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

  14. Human organic cation transporter 2 (hOCT2): Inhibitor studies using S2-hOCT2 cells.

    PubMed

    Chiba, Shoetsu; Ikawa, Toru; Takeshita, Hiroshi; Kanno, Sanae; Nagai, Tomonori; Takada, Meri; Mukai, Toshiji; Wempe, Michael F

    2013-08-09

    Highly expressed in kidney and located on the basolateral membrane, human organic cation transporter 2 (hOCT2) can transport various compounds (i.e. drugs and toxins) into the proximal tubular cell. Using cultured proximal tubule cells stably expressing hOCT2 (i.e. S2-hOCT2 cells), we sought to probe different compound classes (e.g. analgesics, anti-depressants, anti-psychotics, disinfectant, herbicides, insecticides, local anesthetic, muscarinic acetylcholine receptor antagonist, sedatives, steroid hormone, stimulants and toxins) for their ability to inhibit (14)C-TEA uptake, a prototypical OCT2 substrate. Aconitine, amitriptyline, atropine, chlorpyrifos, diazepam, fenitrothion, haloperidol, lidocaine, malathion, mianserin, nicotine and triazolam significantly inhibited (14)C-TEA uptake; IC50 values were 59.2, 2.4, 2.0, 20.7, 32.3, 13.2, 32.5, 104.6, 71.1, 17.7, 52.8 and 65.5μM, respectively. In addition, aconitine, amitriptyline, atropine, chlorpyrifos, fenitrothion, haloperidol, lidocaine, and nicotine displayed competitive inhibition with Ki values of 145.6, 2.5, 2.4, 24.8, 16.9, 51.6, 86.8 and 57.7μM, respectively. These in vitro data support the notion that compounds pertaining to a wide variety of different drug classes have the potential to decrease renal clearance of drugs transported via hOCT2. Consequently, these data warrant additional studies to probe hOCT2 and its role to influence drug pharmacokinetics.

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

    SciTech Connect

    Zilm, K.W.

    1990-01-01

    This report covers the progress made on the title project and summarizes the accomplishments for the project period. Four major areas of inquiry have been pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines the authors are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. The authors have concentrated on a theoretical treatment of pairs of tightly coupled spin {1/2} nuclei under magic angle spinning conditions. The average Hamiltonian theory developed here is required for a quantitative understanding of two dimensional NMR experiments of such spin pairs in solids. These experiments in turn provide a means of determining connectivities between resonances in solid state NMR spectra. Development of these techniques will allow us to establish connectivities between functional components in coals. The complete description of these spin dynamics has turned out to be complex, and is necessary to provide a foundation upon which such experiments may be quantitatively interpreted in complex mixtures such as coals. 25 refs., 4 figs., 3 tabs.

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

    SciTech Connect

    Zilm, K.W.

    1989-01-01

    This report covers the progress made on the title project and summarizes the accomplishments for the project period. Four major areas of inquiry have been pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concern how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coals model. Along the same lines we are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. During the last quarter the authors have concentrated on improvements in cross polarization (CP) sequences with a goal of making the CP process insensitive to experimental conditions such as the magic angle spinning (MAS) rate. In order to be able to use fields the order of 7.0 T or higher, CP efficiency must be maintained at MAS rates of over 10 kHz. The standard sequences have severe limitations at these rates which lead to intensity distortions in {sup 13}C CPMAS spectra. Thus in order to be able to take advantage of the increases in sensitivity and resolution that accompany high field operation, improvements in the NMR methods are required. The new sequences the authors are developing will be especially important for quantitative analysis of coal structure by {sup 13}C solid state NMR at high field strengths. 13 refs., 7 figs., 2 tabs.

  17. Investigations of intramolecular hydrogen bonding in three types of Schiff bases by 2H and 3H NMR isotope effects.

    PubMed

    Schilf, Wojciech; Bloxsidge, James P; Jones, John R; Lu, Shui-Yu

    2004-06-01

    Hydrogen bonding within the structures of three Schiff bases (1-3), obtained by condensation of 4-methoxy-, 5-methoxy- and 4,6-dimethoxysalicylaldehyde with methylamine, was investigated by measuring deuterium and tritium NMR isotope effects. The primary deuterium and tritium isotope effects (delta(XH)-delta(XD/T)) and secondary one-bond nitrogen deuterium effect appear to be very useful parameters for defining the character of intramolecular hydrogen bonds. The tritium isotope effects were also determined for nitrogen-hydrogen one-bond coupling constants for both 4-methoxy and 4,6-dimethoxy derivatives. These parameters are seen to be highly sensitive to hydrogen bond characteristics and can be used to distinguish localized and tautomeric hydrogen bonds.

  18. 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.

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

    PubMed

    Xu, Jun; Sinelnikov, Regina; Huang, Yining

    2016-06-07

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

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

    SciTech Connect

    Zilm, K.W.

    1989-01-01

    This report covers the progress made on the title project and summarizes the accomplishments for the project period. Four major areas of inquiry have been pursued. Advanced solid state NMR methods are being developed to assay the distribution of the various important functional groups in coals that determine the reactivity of coals. Other methods are being developed which will also determine how these functional groups are linked together. A third area of investigation concerns how molecular mobility in coals impacts NMR relaxation times, which is important for interpretation of such data in terms of the mobile phase in coal models. Along the same lines the author are also using these studies to establish protocols for obtaining the best quantitative response from coals in solid state C-13 NMR spectra. The effects of very high MAS rates (>10 kHz) on cross polarization dynamics are also being investigated for similar reasons. During the last quarter the authors has concentrated on improvements in cross polarization (CP) sequences with a goal of making the CP process insensitive to experimental conditions such as the Hartmann-Hahn mismatch. It has been found that the usual theories of CP are incorrect, and that the CP process is very heterogeneous in nature. This has significant implications on methods typically used in quantifying {sup 13}C CPMAS spectra of coals. 19 refs., 11 figs.

  1. Ab initio study of {sup 2}H(d,{gamma}){sup 4}He, {sup 2}H(d,p){sup 3}H, and {sup 2}H(d,n){sup 4}He reactions and the tensor force

    SciTech Connect

    Arai, K.; Aoyama, S.; Suzuki, Y.; Descouvemont, P.; Baye, D.

    2012-11-12

    The {sup 2}H(d,p){sup 3}H, {sup 2}H(d,n){sup 3}He, and {sup 2}H(d,{gamma}){sup 4}He reactions at low energies are studied with realistic nucleon-nucleon interactions in an ab initio approach. The obtained astrophysical S-factors are all in very good agreement with experiment. The most important channels for both transfer and radiative capture are all found to dominate thanks to the tensor force.

  2. Synthesis, structural and spectroscopic studies of 2-oxoacenaphthylen-1(2H)-ylidene nicotinohydrazide.

    PubMed

    Henriques, M S C; Del Amparo, R; Pérez-Álvarez, D; Nogueira, B A; Rodríguez-Argüelles, M C; Paixão, J A

    2017-02-05

    The synthesis of a new hydrazone, 2-oxoacenaphthylen-1(2H)-ylidene nicotinohydrazide, and its structural and spectroscopic characterization is reported. The obtained powder was recrystallized from DMSO and ethanol that afforded small crystals used for single-crystal X-ray diffraction studies. The compound was found to crystallize in two polymorphs, depending on the crystallization conditions. One of the polymorphs (form I) crystallizes in the centrosymmetric P21/c monoclinic space group, the other (form II) crystallizes in the non-centrosymmetric, but achiral, orthorhombic space group P212121. Conformation of the molecules is similar in both polymorphs, but the network of weak intermolecular interactions determining the crystal packing is different. In form II an additional C-H⋯O bond connects molecules related by the screw-axis running parallel to the a-axis. Crystals of both polymorphs were also screened by FT-IR and Raman microscopy; a detailed analysis of the spectra and comparison with those of the isolated molecule calculated by ab-initio HF/MP2 and DFT/B3LYP methods using a correlation consistent cc-pVDZ basis set is presented. In addition, UV-vis and NMR studies were performed in solution.

  3. Synthesis, structural and spectroscopic studies of 2-oxoacenaphthylen-1(2H)-ylidene nicotinohydrazide

    NASA Astrophysics Data System (ADS)

    Henriques, M. S. C.; Del Amparo, R.; Pérez-Álvarez, D.; Nogueira, B. A.; Rodríguez-Argüelles, M. C.; Paixão, J. A.

    2017-02-01

    The synthesis of a new hydrazone, 2-oxoacenaphthylen-1(2H)-ylidene nicotinohydrazide, and its structural and spectroscopic characterization is reported. The obtained powder was recrystallized from DMSO and ethanol that afforded small crystals used for single-crystal X-ray diffraction studies. The compound was found to crystallize in two polymorphs, depending on the crystallization conditions. One of the polymorphs (form I) crystallizes in the centrosymmetric P21/c monoclinic space group, the other (form II) crystallizes in the non-centrosymmetric, but achiral, orthorhombic space group P212121. Conformation of the molecules is similar in both polymorphs, but the network of weak intermolecular interactions determining the crystal packing is different. In form II an additional C-H⋯O bond connects molecules related by the screw-axis running parallel to the a-axis. Crystals of both polymorphs were also screened by FT-IR and Raman microscopy; a detailed analysis of the spectra and comparison with those of the isolated molecule calculated by ab-initio HF/MP2 and DFT/B3LYP methods using a correlation consistent cc-pVDZ basis set is presented. In addition, UV-vis and NMR studies were performed in solution.

  4. Functional studies of split "Arabidopsis" Ca(2+)/H(+) exchangers

    USDA-ARS?s Scientific Manuscript database

    In plants, high capacity tonoplast cation/H (+) antiport is mediated in part by a family of cation exchanger (CAX) transporters. Functional association between CAX1 and CAX3 has previously been shown. In this study, we further examine the interactions between CAX protein domains using nonfunctional ...

  5. Functional studies of split Arabidopsis Ca2+/H+ exchangers.

    PubMed

    Zhao, Jian; Connorton, James M; Guo, YingQing; Li, Xiangkai; Shigaki, Toshiro; Hirschi, Kendal D; Pittman, Jon K

    2009-12-04

    In plants, high capacity tonoplast cation/H(+) antiport is mediated in part by a family of cation exchanger (CAX) transporters. Functional association between CAX1 and CAX3 has previously been shown. In this study we further examine the interactions between CAX protein domains through the use of nonfunctional halves of CAX transporters. We demonstrate that a protein coding for an N-terminal half of an activated variant of CAX1 (sCAX1) can associate with the C-terminal half of either CAX1 or CAX3 to form a functional transporter that may exhibit unique transport properties. Using yeast split ubiquitin, in planta bimolecular fluorescence complementation, and gel shift experiments, we demonstrate a physical interaction among the half proteins. Moreover, the half-proteins both independently localized to the same yeast endomembrane. Co-expressing variants of N- and C-terminal halves of CAX1 and CAX3 in yeast suggested that the N-terminal region mediates Ca(2+) transport, whereas the C-terminal half defines salt tolerance phenotypes. Furthermore, in yeast assays, auto-inhibited CAX1 could be differentially activated by CAX split proteins. The N-terminal half of CAX1 when co-expressed with CAX1 activated Ca(2+) transport, whereas co-expressing C-terminal halves of CAX variants with CAX1 conferred salt tolerance but no apparent Ca(2+) transport. These findings demonstrate plasticity through hetero-CAX complex formation as well as a novel means to engineer CAX transport.

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

    PubMed

    Felderhoff, Michael; Zibrowius, Bodo

    2011-10-14

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

  7. Nuclear magnetic resonance study of the ferroelastic phase transition of order-disorder type in [N(C2H5)4]2CdCl4

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran; Kim, Min Soo; Lim, Kye-Young

    2016-08-01

    This study uses nuclear magnetic resonance (NMR) techniques to examine the detailed changes in [N(C2H5)4]2CdCl4 around its phase transition at the temperature TC = 284 K. The chemical shifts and spin-lattice relaxation times in the rotating frame (T1ρ) were determined from 1H magic angle spinning (MAS) NMR and 13C cross-polarization (CP)/MAS NMR spectra. The two sets of inequivalent 1H and 13C nuclei in CH3 and CH2 were distinguished. A ferroelastic phase transition was observed at TC, without structural symmetry change. The phase transition is mainly attributed to the orientational ordering of the [N(C2H5)4]+ cations, and the spectral splitting at low temperature is associated with different ferroelastic domains.

  8. 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.

  9. 1H and 2H NMR spin-lattice relaxation probing water: PEG molecular dynamics in solution.

    PubMed

    Clop, Eduardo M; Perillo, María A; Chattah, Ana K

    2012-10-04

    Nuclear magnetic resonance spin-lattice relaxation times (T(1)) measurements were performed in aqueous solutions of poly(ethylene glycol) (PEG) of 6000 Da molecular mass to study the dynamical relation between PEG and water molecules at different solute concentrations. (1)H-T(1) experiments were carried on at a low magnetic field in the time domain (20 MHz) and at a high field (400 MHz) to obtain spectral resolution. Two contributing components were identified in each proton system, PEG and water, presenting values of T(1) with very different orders of magnitude. The approximate matching between the shorter (1)H-T(1) values associated with water and PEG has lead us to conclude that there exists a network of interactions (hydrogen bonds) between the solute and the solvent, which results in the presence of an ordered and dehydrated structure of PEG folded or self-assembled in equilibrium with a more flexible monomer structure. Dynamic light scattering results were consistent with the formation of PEG aggregates, showing a mean size between 40 and 100 nm.

  10. NMR Methods to Study Dynamic Allostery.

    PubMed

    Grutsch, Sarina; Brüschweiler, Sven; Tollinger, Martin

    2016-03-01

    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.

  11. 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

  12. Experimental and Modeling Study of the Temperature and Pressure Dependence of the Reaction C2H5 + O2 (+ M) → C2H5O2 (+ M).

    PubMed

    Fernandes, Ravi X; Luther, Klaus; Marowsky, Gerd; Rissanen, Matti P; Timonen, Raimo; Troe, Jürgen

    2015-07-16

    The reaction C2H5 + O2 (+ M) → C2H5O2 (+ M) was studied at 298 K at pressures of the bath gas M = Ar between 100 and 1000 bar. The transition from the falloff curve of an energy transfer mechanism to a high pressure range with contributions from the radical complex mechanism was observed. Further experiments were done between 188 and 298 K in the bath gas M = He at pressures in the range 0.7-2.0 Torr. The available data are analyzed in terms of unimolecular rate theory. An improved analytical representation of the temperature and pressure dependence of the rate constant is given for conditions where the chemical activation process C2H5 + O2 (+ M) → C2H4 + HO2 (+ M) is only of minor importance.

  13. Thermal hysteresis in the backbone and side-chain dynamics of the elastin mimetic peptide [VPGVG]3 revealed by 2H NMR.

    PubMed

    Ma, Xiang; Sun, Cheng; Huang, Jiaxin; Boutis, Gregory S

    2012-01-12

    We report on experimental measurements of the backbone and side-chain dynamics of the elastin mimetic peptide [VPGVG](3) by (2)H NMR echo spectroscopy and 2D T(1)-T(2) correlation relaxometry. The T(1) and T(2) relaxation times of the Gly α-deuterons and Val α-, β-, and γ-deuterons of a hydrated sample reveal a thermal hysteresis when the temperature is raised from -10 to 45 °C and then subsequently cooled back to -10 °C. In addition, near 30 °C we observe a reduction in the slope of the T(1)(T) and T(2)(T) heating curves, indicating a structural change that appears to be correlated well to the known inverse temperature transition of this peptide. The thermal dependence of the correlation times of the Gly α-deuterons are well fit by an Arrhenius Law, from which we measured E(act) = (20.0 ± 3.1) kJ/mol when the sample is heated and E(act) = (10.9 ± 2.8) kJ/mol when cooled. Molecular dynamics simulations support the notion that the measured activation energy is determined largely by the extent of localized water, which is observed to decrease with increasing temperature from approximately 25 to 42 °C.

  14. Concurrent quantification of tissue metabolism and blood flow via 2H/31P NMR in vivo. III. Alterations of muscle blood flow and metabolism during sepsis.

    PubMed

    Song, S K; Hotchkiss, R S; Karl, I E; Ackerman, J J

    1992-05-01

    In the conclusion of this series of reports, the application of 31P/2H NMR to investigate the pathophysiology of sepsis in rat hindlimb muscle is demonstrated. Sepsis decreased muscle [PCr] by 18%, 18 +/- 4 SD vs 22 +/- 4 SD mmol/kg tissue wet wt (P = 0.01) in control rats but [ATP] was unchanged, 6 mmol/kg tissue wet wt (P = 0.2). The derived free cytosolic [ADP] in the two groups was similar, [ADP]septic = 0.023 +/- 0.004 SD and [ADP]control = 0.021 +/- 0.003 SD mmol/kg tissue wet wt, and not statistically different (P = 0.14). Likewise [Pi] in the septic and control groups was not statistically different, [Pi]septic = 1.1 +/- 0.5 SD and [Pi]control = 1.2 +/- 0.4 SD mmol/kg tissue wet wt (P = 0.2). Septic rats presented the symptom of respiratory alkalosis evidenced by elevated blood pH. Sepsis decreased muscle blood flow by 33%, P = 0.003, but examination of individual subjects did not demonstrate a correlation with the reduction in [PCr]. Thus, a metabolic energy deficit caused by cellular ischemia/hypoxia is not a likely cause of cellular abnormality in rat hindlimb muscle during sepsis.

  15. Post-HTS case report and structural alert: Promiscuous 4-aroyl-1,5-disubstituted-3-hydroxy-2H-pyrrol-2-one actives verified by ALARM NMR.

    PubMed

    Dahlin, Jayme L; Nissink, J Willem M; Francis, Subhashree; Strasser, Jessica M; John, Kristen; Zhang, Zhiguo; Walters, Michael A

    2015-11-01

    Despite its wide use, not every high-throughput screen (HTS) yields chemical matter suitable for drug development campaigns, and seldom are 'go/no-go' decisions in drug discovery described in detail. This case report describes the follow-up of a 4-aroyl-1,5-disubstituted-3-hydroxy-2H-pyrrol-2-one active from a cell-free HTS to identify small-molecule inhibitors of Rtt109-catalyzed histone acetylation. While this compound and structural analogs inhibited Rtt109-catalyzed histone acetylation in vitro, further work on this series was halted after several risk mitigation strategies were performed. Compounds with this chemotype had a poor structure-activity relationship, exhibited poor selectivity among other histone acetyltransferases, and tested positive in a β-lactamase counter-screen for chemical aggregates. Furthermore, ALARM NMR demonstrated compounds with this chemotype grossly perturbed the conformation of the La protein. In retrospect, this chemotype was flagged as a 'frequent hitter' in an analysis of a large corporate screening deck, yet similar compounds have been published as screening actives or chemical probes versus unrelated biological targets. This report-including the decision-making process behind the 'no-go' decision-should be informative for groups engaged in post-HTS triage and highlight the importance of considering physicochemical properties in early drug discovery. Copyright © 2015 Elsevier Ltd. All rights reserved.

  16. 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.

  17. Indirect Approach To The {sup 2}H(d,p){sup 3}H Reaction Study

    SciTech Connect

    Sparta, R.; Pizzone, R. G.; Spitaleri, C.; Cherubini, S.; Crucilla, V.; Gulino, M.; La Cognata, M.; Lamia, L.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Aliotta, M.; Burjan, V.; Hons, Z.; Kroha, V.; Mrazek, J.; Kiss, G.; McCleskey, M.; Trache, L.

    2010-11-24

    In order to understand primordial and stellar nucleosynthesis, we have studied {sup 2}H(d,p){sup 3}H reaction at 0.4 MeV down to astrophysical energies. Knowledge of its S-factor is interesting also to plan reactions for fusion reactors to produce energy. The {sup 2}H(d,p)H reaction has been studied through the Trojan Horse Method applied to the three-body reaction {sup 2}H(He,pt)H, at beam energy of 17 MeV. Once selection of protons and tritons detected in coincidence and the selection of quasi-free events, the obtained S-factor is compared with direct measurements. Such data are in agreement with the direct ones and a pole invariance test has been obtained comparing the present results with another {sup 2}H(d,p){sup 3}H THM measurements, where a different spectator particle was employed.

  18. 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.

  19. Structure, phase transitions, dielectric and spectroscopic studies of the 2-aminopyrimidinium salts: [(2-NH 2C 4N 2H 3) 2H][ClO 4] and [2-NH 2C 4N 2H 4][BF 4

    NASA Astrophysics Data System (ADS)

    Czupiński, O.; Wojtaś, M.; Ciunik, Z.; Jakubas, R.

    2006-01-01

    Crystal structure of the 2-aminopyrimidinium derivatives: [(2-NH 2C 4N 2H 3) 2H][ClO 4] (I) and [2-NH 2C 4N 2H 4][BF 4] (II) has been determined at 100 K (I) and 293 K (II) by means of single crystal X-ray diffraction as monoclinic space group, P2/c and P2/n, respectively. The asymmetric part of the unit cell of (I) contains two symmetry independent 2-aminopyrimidine forming one dimeric cation and one disordered perchlorate anion. The structure of (II) consists of 2-aminopyrimidinium cation, [2-NH 2C 4N 2H 4] +, protonated at a pyrimidine ring-N atom and [BF 4] - anion. Differential scanning calorimetry (DSC) on perchlorate derivative ( 1:1), [2-NH 2C 4N 2H 3][ClO 4] (III)—being isomorphic to tetrafluoroborate one (I) at room temperature, reveals two phase transitions of first order: at 250/275 K and 390/410 K (cooling-heating, respectively), whereas the analog (II) only one transition at high temperatures—343/385 K. The dielectric studies in the frequency range 75 kHz - 10 MHz disclose relaxation process at high temperatures in salt (I). Infrared spectra of polycrystalline [2-NH 2C 4N 2H 4][BF 4] have been studied in the temperature range 300-420 K. Substantial changes in the temperature evolution of frequencies of internal modes of the 2-aminopyrimidinium cations and [BF 4] - anions near 390 K are due to the variations in the motion of both moieties and hydrogen bond configuration. The experimental studies indicate that all phase transitions taking place in studied 2-aminopyrimidinium derivatives are classified as an order-disorder.

  20. A density functional theory study of phenyl formation initiated by ethynyl radical (C2H*) and ethyne (C2H2).

    PubMed

    Santiago, Romero M; Indarto, Antonius

    2008-12-01

    An ab initio computational density functional theory (DFT) was used to study the formation of the first cyclic molecule (phenyl) initiated by the ethynyl radical (C(2)H*). The study covers a competition reaction between the addition reactions of C(2)H* with ethyne (C(2)H(2)) and some molecular re-arrangement schemes. The minimum energy paths of the preferred cyclic formation route were characterized. A thorough thermochemical analysis was performed by evaluating the differences in the energy of activation (DeltaE), enthalpy (DeltaH), and Gibb's free energy (DeltaG) of the optimized stable and transition state (TS) molecules. The reaction temperatures were set to normal (T = 298 K) and combustion (T = 1,200 K) conditions.

  1. Tensor Force Manifestations in Ab Initio Study of the {sup 2}H(d,{gamma}){sup 4}He, {sup 2}H(d,p){sup 3}H, and {sup 2}H(d,n){sup 3}He Reactions

    SciTech Connect

    Arai, K.; Aoyama, S.; Suzuki, Y.; Descouvemont, P.; Baye, D.

    2011-09-23

    The {sup 2}H(d,p){sup 3}H, {sup 2}H(d,n){sup 3}He, and {sup 2}H(d,{gamma}){sup 4}He reactions are studied at low energies in a multichannel ab initio model that takes into account the distortions of the nuclei. The internal wave functions of these nuclei are given by the stochastic variational method with the AV8{sup '} realistic interaction and a phenomenological three-body force included to reproduce the two-body thresholds. The obtained astrophysical S factors are all in very good agreement with the experiment. The most important channels for both transfer and radiative capture are identified by comparing to calculations with an effective central force. They are all found to dominate thanks to the tensor force.

  2. 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.

  3. 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.

  4. Laboratory studies of 2H evaporator scale dissolution in dilute nitric acid

    SciTech Connect

    Oji, L.

    2014-09-23

    The rate of 2H evaporator scale solids dissolution in dilute nitric acid has been experimentally evaluated under laboratory conditions in the SRNL shielded cells. The 2H scale sample used for the dissolution study came from the bottom of the evaporator cone section and the wall section of the evaporator cone. The accumulation rate of aluminum and silicon, assumed to be the two principal elemental constituents of the 2H evaporator scale aluminosilicate mineral, were monitored in solution. Aluminum and silicon concentration changes, with heating time at a constant oven temperature of 90 deg C, were used to ascertain the extent of dissolution of the 2H evaporator scale mineral. The 2H evaporator scale solids, assumed to be composed of mostly aluminosilicate mineral, readily dissolves in 1.5 and 1.25 M dilute nitric acid solutions yielding principal elemental components of aluminum and silicon in solution. The 2H scale dissolution rate constant, based on aluminum accumulation in 1.5 and 1.25 M dilute nitric acid solution are, respectively, 9.21E-04 ± 6.39E-04 min{sup -1} and 1.07E-03 ± 7.51E-05 min{sup -1}. Silicon accumulation rate in solution does track the aluminum accumulation profile during the first few minutes of scale dissolution. It however diverges towards the end of the scale dissolution. This divergence therefore means the aluminum-to-silicon ratio in the first phase of the scale dissolution (non-steady state conditions) is different from the ratio towards the end of the scale dissolution. Possible causes of this change in silicon accumulation in solution as the scale dissolution progresses may include silicon precipitation from solution or the 2H evaporator scale is a heterogeneous mixture of aluminosilicate minerals with several impurities. The average half-life for the decomposition of the 2H evaporator scale mineral in 1.5 M nitric acid is 12.5 hours, while the half-life for the decomposition of the 2H evaporator scale in 1.25 M nitric acid is 10

  5. Nuclear Quadrupole Coupling Tensors of 2H in the a-Alum RbAl(SO4)2 · 12D2O and the Dynamical Behaviour of the D2O Molecules. An Investigation by NMR and IR

    NASA Astrophysics Data System (ADS)

    Ramakrishna, J.; Weiden, Norbert; Weiss, Alarich

    1990-04-01

    By single crystal NMR the nuclear quadrupole coupling constants eQΦzz h-1 (2H), the asymmetry parameters η(2H) and the direction cosines of the principal axes of the electric field gradient tensors of the 2H atoms of the two kinds of D2O molecules have been determined at 295 K in RbAl(SO4)2 · 12D2O. The results show that the D2O molecules surrounding the ion Al3+ are "static" within the time scale of the 2H nuclear quadrupole interaction while the D2O belonging to the octahedron around the Rb+ undergoes fast reorientations around the twofold molecular axis. For the two kinds of D2O in the alum we found: eQΦzz(1)h-1 (2H) = 186.5 kHz, η(1),(2H) = 0.1234; eQΦzz(2)h-1 (2H) = 169.7 kHz,η (2)(2H) = 0.1297; eQΦzz(3)h-1(2H) = 122.1 kHz, (2H) = 0.8087. eQΦzz(1) and eQΦzz(2) belong to the "static" D2O molecules and an assignment to the two different 2H atoms has been performed. The IR spectra of RbAl(SO4)2 · 12(H1-xDx)2O have been investigated, and for the O - D stretching frequencies values of 2145 cm-1 , 2235 cm-1 , 2470 cm-1 and 2525 cm -1 have been obtained. They agree well with the relations between ṽOD and eQΦzz h-1(2H) given in the literature.

  6. 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.

  7. Primary and secondary relaxation process in plastically crystalline cyanocyclohexane studied by 2H nuclear magnetic resonance. II. Quantitative analysis

    NASA Astrophysics Data System (ADS)

    Micko, B.; Kruk, D.; Rössler, E. A.

    2013-02-01

    We analyze the results of our previously reported 2H nuclear magnetic resonance (NMR) experiments in the plastically crystalline (PC) phase of cyanocyclohexane (Part I of this work) to study the fast secondary relaxation (or β-process) in detail. Both, the occurrence of an additional minimum in the spin-lattice relaxation T1 and the pronounced effects arising in the solid-echo spectrum above the glass transition temperature Tg = 134 K, allow for a direct determination of the restricting geometry of the β-process in terms of the "wobbling-in-a-cone" model. Whereas at temperatures below Tg the reorientation is confined to rather small solid angles (below 10°), the spatial restriction decreases strongly with temperature above Tg, i.e., the distribution of cone angles shifts continuously towards higher values. The β-process in the PC phase of cyanocyclohexane proceeds via the same mechanism as found in structural glass formers. This is substantiated by demonstrating the very similar behavior (for T < Tg) of spin-lattice relaxation, stimulated echo decays, and spectral parameters when plotted as a function of ⟨log τβ⟩ (taken from dielectric spectroscopy). We do, however, not observe a clear-cut relation between the relaxation strength of the β-process observed by NMR (calculated within the wobbling-in-a-cone model) and dielectric spectroscopy.

  8. 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.

  9. 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

  10. Solid state NMR studies of materials for energy technology

    NASA Astrophysics Data System (ADS)

    Nambukara Kodiweera Arachchilage, Chandana K.

    Presented in this dissertation are NMR investigations of the dynamical and structural properties of materials for energy conversion and storage devices. 1H and 2H NMR was used to study water and methanol transportation in sulfonated poly(arylene ether ketone) based membranes for direct methanol fuel cells (DMFC). These results are presented in chapter 3. The amount of liquid in the membrane and ion exchange capacity (IEC) are two main factors that govern the dynamics in these membranes. Water and methanol diffusion coefficients also are comparable. Chapters 4 and 5 are concerned with 31P and 1H NMR in phosphoric acid doped PBI membranes (para-PBI and 2OH-PBI) as well as PBI membranes containing ionic liquids (H3PO4/PMIH2PO4/PBI). These membranes are designed for higher-temperature fuel cell operation. In general, stronger short and long range interactions were observed in the 2OH-PBI matrix, yielding reduced proton transport compared to that of para-PBI. In the case of H3PO4/PMIH2PO 4/PBI, both conductivity and diffusion are higher for the sample with molar ratio 2/4/1. Finally, chapter 6 is devoted to the 31P NMR MAS study of phosphorus-containing structural groups on the surfaces of micro/mesoporous activated carbons. Two spectral features were observed and the narrow feature identifies surface phosphates while the broad component identifies heterogeneous subsurface phosphorus environments including phosphate and more complex structure multiple P-C, P-N and P=N bonds.

  11. Theoretical study of the C-H bond dissociation energy of C2H

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1990-01-01

    A theoretical study of the convergence of the C-H bond dissociation energy D(0) in C2H with respect to both the one- and n-particle spaces is presented. The calculated C-H bond energies of C2H2 and C2H4, which are in excellent agreement with experiment, are used for calibration. The best estimate for D(0) of 112.4 + or - 2.0 kcal/mol is slightly below the recent experimental value of 116.3 + or - 2.6 kcal/mol, but substantially above a previous theoretical estimate of 102 kcal/mol. The remaining discrepancy with experiment may reflect primarily the uncertainty in the experimental D(0) value of C2 required in the analysis.

  12. Studies of Molecular Dynamics by Solid State Deuterium NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhao, Baiyi

    The rotational dynamics of molecules in a number of solid systems were followed by variable temperature deuterium (^2H), nuclear magnetic resonance (NMR) spectroscopy via changes in the spectral lineshapes and spin-lattice relaxation times (T _1). First the pure solid trimethylamine-borane adduct, (CH_3)_3NBH_3, was studied. For a methyl deuterated sample, T _1 measurements yielded two T_1 minima, 6.9 ms and 4.3 ms corresponding to the slowing of methyl and trimethyl rotation, respectively, with decreasing temperature. Activation energies for methyl and trimethyl rotation, obtained from fitting the T _1 curve as a function of temperature, were 32.8 and 15.0 kJ/mol, respectively; simulations of the spectral lineshapes gave 26.6 and 18.9 kT/mol, respectively. Fitting of the ^2H T_1 curve for the borane deuterated sample gave a BH _3 rotation activation energy of 14.1 kT/mol and a ^2H quadrupolar coupling constant, chi, of 101 kHz. The activation energy for BH_3 rotation obtained from the spectral lineshape simulations gave 12.6 kT/mol. A series of deuterated organic chalcogen cations: (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, were ion exchanged into the cavities of sodium Mordenite LZ-M5 and the dynamics of these guests within the hydrated zeolite were followed by ^2H NMR. All three undergo isotropic motion above about -80 to -90^circC. Below this temperature two superimposed ^2H powder spectra appear; the broad lineshape is consistent with only methyl rotation in a hindered, coordinated site, and the other narrow lineshape is due to both methyl and trimethyl rotation in a less hindered, uncoordinated site. As the temperature is lowered the population of the lower energy coordinated site increases. Relative peak areas yield adsorption enthalpies of 6.7, 7.8 and 10.0 kJ/mol for (CH_3)_3S^+, (CH_3)_3Se^+ and (CH_3)_3Te^+, respectively. The series of methyl deuterated ammonium and phosphonium cations: (CH_3)NH_3^+ , (CH_3)_2NH^+ , (CH_3)_3NH^+ and (CH_3)_4P^+ , were

  13. NMR studies of protein structure and dynamics

    NASA Astrophysics Data System (ADS)

    Kay, Lewis E.

    2011-12-01

    Recent advances in solution NMR spectroscopy have significantly extended the spectrum of problems that can now be addressed with this technology. In particular, studies of proteins with molecular weights on the order of 100 kDa are now possible at a level of detail that was previously reserved for much smaller systems. An example of the sort of information that is now accessible is provided in a study of malate synthase G, a 723 residue enzyme that has been a focal point of research efforts in my laboratory. Details of the labeling schemes that have been employed and optimal experiments for extraction of structural and dynamics information on this protein are described. NMR studies of protein dynamics, in principle, give insight into the relation between motion and function. A description of deuterium-based spin relaxation methods for the investigation of side chain dynamics is provided. Examples where millisecond (ms) time scale dynamics play an important role and where relaxation dispersion NMR spectroscopy has been particularly informative, including applications involving the membrane enzyme PagP and mutants of the Fyn SH3 domain that fold on a ms time scale, are presented.

  14. Direct ab initio study of the C6H6 + CH3/C2H5 = C6H5 + CH4/C2H6 reactions

    NASA Astrophysics Data System (ADS)

    Mai, Tam V.-T.; Ratkiewicz, Artur; Duong, Minh v.; Huynh, Lam K.

    2016-02-01

    A kinetic study of the reactions C6H6 + CH3/C2H5 = C6H5 + CH4/C2H6 was carried out in the temperature range of 300-2500 K using high levels of electronic structure theory, namely, CCSD(T)/CBS//BH&HLYP/cc-pVDZ, and canonical variational transition state theory (CVT) with corrections for small curvature tunneling (SCT) and hindered internal rotation (HIR) treatments. It is found that variational effect is not important and both SCT and HIR corrections noticeably affect the rate constants. Being in good agreement with literature data, the calculated results provide solid basis information for the investigation of the polyaromatic hydrocarbon (PAH) + alkyl radical reaction, an important class in combustion and soot formation.

  15. 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.

  16. Polymeric proanthocyanidins 13C NMR studies of procyanidins

    Treesearch

    Lawrence J. Porter; Roger H. Newman; Lai Yeap Foo; Herbert Wong; Richard W. Hemingway

    1982-01-01

    Proanthocyanidin polymers have been shown to consist entirely of flavan-3-ol units by a combination of techniques including 13C n.m.r. spectroscopy. The 13C n.m.r. spectra of the polymers and related molecules are now considered in more detail. Prior to this study UC n.m.r. data has been published of procyanidins and...

  17. HPLC & NMR-based forced degradation studies of ifosfamide: The potential of NMR in stability studies.

    PubMed

    Salman, D; Peron, J-M R; Goronga, T; Barton, S; Swinden, J; Nabhani-Gebara, S

    2016-03-01

    The aim of this study is to conduct a forced degradation study on ifosfamide under several stress conditions to investigate the robustness of the developed HPLC method. It also aims to provide further insight into the stability of ifosfamide and its degradation profile using both HPLC and NMR. Ifosfamide solutions (20mg/mL; n=15, 20mL) were stressed in triplicate by heating (70°C), under acidic (pH 1 & 4) and alkaline (pH 10 & 12) conditions. Samples were analysed periodically using HPLC and FT-NMR. Ifosfamide was most stable under weakly acidic conditions (pH 4). NMR results suggested that the mechanism of ifosfamide degradation involves the cleavage of the PN bond. For all stress conditions, HPLC was not able to detect ifosfamide degradation products that were detected by NMR. These results suggest that the developed HPLC method for ifosfamide did not detect the degradation products shown by NMR. It is possible that degradation products co-elute with ifosfamide, do not elute altogether or are not amenable to the detection method employed. Therefore, investigation of ifosfamide stability requires additional techniques that do not suffer from the aforementioned shortcomings. Copyright © 2015 Académie Nationale de Pharmacie. Published by Elsevier Masson SAS. All rights reserved.

  18. Kinetics Studies of Radical-Radical Reactions: The NO2 + N2H3 System

    DTIC Science & Technology

    2013-10-01

    investigating the kinetics of this elementary reaction . 15. SUBJECT TERMS 16. SECURITY CLASSIFICATION OF: 17. LIMITATION OF ABSTRACT 18. NUMBER OF PAGES...Viewgraph 3. DATES COVERED (From - To) September 2013- October 2013 4. TITLE AND SUBTITLE Kinetics Studies of Radical-Radical Reactions (I): The NO2...characteristics in relevant operating environments. Here we report theoretical results obtained on the prototypical radical- radical reaction : NO2 + N2H3

  19. Laboratory IR Studies and Astrophysical Implications of C2H2-Containing Binary Ices

    NASA Technical Reports Server (NTRS)

    Knez, C.; Moore, M.; Ferrante, R.; Hudson, R.

    2012-01-01

    Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C2H2) cannot be matched by chemical models without the inclusion of C2H2 molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C2H2 in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and water (H2O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's nu5-band position (743 cm-1, 13.46 micrometers) and FWHM on temperature. Our results show that the nu5 feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO2, and CH4, than in mixtures dominated by H2O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.

  20. Laboratory IR Studies and Astrophysical Implications of C2H2-Containing Binary Ices

    NASA Technical Reports Server (NTRS)

    Knez, C.; Moore, M.; Ferrante, R.; Hudson, R.

    2012-01-01

    Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C2H2) cannot be matched by chemical models without the inclusion of C2H2 molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C2H2 in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO2), methane (CH4), and water (H2O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's nu5-band position (743 cm-1, 13.46 micrometers) and FWHM on temperature. Our results show that the nu5 feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO2, and CH4, than in mixtures dominated by H2O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.

  1. Unfolding the Quantum Nature of Proton Bound Symmetric Dimers of (MeOH)2H+ and (Me2O)2H+: a Theoretical Study

    NASA Astrophysics Data System (ADS)

    Tan, Jake Acedera; Kuo, Jer-Lai

    2014-06-01

    A proton under a tug of war between two competing Lewis bases is a common motif in biological systems and proton transfer processes. Over the past decades, model compounds for such motifs can be prepared by delicate stoichiometric control of salt solutions. Unfortunately, condensed phase studies, which aims to identify the key vibrational signatures are complicated to analyze. As a result, gas-phase studies do provide promising insights on the behavior of the shared proton. This study attempts to understand the quantum nature of the shared proton under theoretical paradigms. Proton bound symmetric dimers of (MeOH)2H+ and (Me2O)2H+ are chosen as the model compounds. The simulation is performed using Density Functional Theory (DFT) at the B3LYP level with 6-311+G(d,p) as the basis set. It was found out that stretching mode of shared proton couples with several other normal modes and its corresponding oscillator strength do distribute to other normal modes. J.R. Roscioli, L.R. McCunn and M.A. Johnson. Science 2007, 316, 249 T.E. DeCoursey. Physiol. Rev., 2003, 83, 475 E.S. Stoyanov. Psys. Chem. Phys., 2000,2,1137

  2. 2H Stable Isotope Analysis of Tooth Enamel: A Pilot Study

    NASA Astrophysics Data System (ADS)

    Holobinko, Anastasia; Kemp, Helen; Meier-Augenstein, Wolfram; Prowse, Tracy; Ford, Susan

    2010-05-01

    Stable isotope analysis of biogenic tissues such as tooth enamel and bone mineral has become a well recognized and increasingly important method for determining provenance of human remains, and has been used successfully in bioarchaeological studies as well as forensic investigations (Lee-Thorp, 2008; Meier-Augenstein and Fraser, 2008). Particularly, 18O and 2H stable isotopes are well established proxies as environmental indicators of climate (temperature) and source water and are therefore considered as indicators of geographic life trajectories of animals and humans (Hobson et al., 2004; Schwarcz and Walker, 2006). While methodology for 2H analysis of human hair, fingernails, and bone collagen is currently used to determine geographic origin and identify possible migration patterns, studies involving the analysis of 2H in tooth enamel appear to be nonexistent in the scientific literature. The apparent lack of research in this area is believed to have two main reasons. (1) Compared to the mineral calcium hydroxylapatite Ca10(PO4)6(OH)2, in tooth enamel forming bio-apatite carbonate ions replace some of the hydroxyl ions at a rate of one CO32 replacing two OH, yet published figures for the degree of substitution vary (Wopenka and Pasteris, 2005). (2) Most probably due to the aforementioned no published protocols exist for sample preparation and analytical method to obtain δ2H-values from the hydroxyl fraction of tooth enamel. This dilemma has been addressed through a pilot study to establish feasibility of 2H stable isotope analysis of ground tooth enamel by continuous-flow isotope ratio mass spectrometry (IRMS) coupled on-line to a high-temperature conversion elemental analyzer (TC/EA). An array of archaeological and modern teeth has been analyzed under different experimental conditions, and results from this pilot study are being presented. References: Lee-Thorp, J.A. (2008) Archaeometry, 50, 925-950 Meier-Augenstein, W. and Fraser, I. (2008) Science & Justice

  3. Direct dynamics study on the hydrogen abstraction reactions N2H4+R→N2H3+RH (R=NH2,CH3)

    NASA Astrophysics Data System (ADS)

    Li, Qian Shu; Zhang, Xin

    2006-08-01

    We present a direct ab initio dynamics study on the hydrogen abstraction reactions N2H4+R→N2H3+RH (R=NH2,CH3), which are predicted to have six possible reaction channels for NH2 abstraction and four for CH3 abstraction caused by the different N2H4 isomers and various attacking orientations of foreign radical to N2H4. The structures and frequencies at the stationary points and the points along the minimum energy paths (MEPs) of all reaction channels are obtained at the UMP2(full)/6-31+G(d,p) level of theory. Energetic information of stationary points and the points along the MEPs is further refined by means of MC-QCISD method. The rate constants of these channels are calculated using the improved canonical variational transition-state theory with the small-curvature tunneling correction (ICVT/SCT) method. The calculated results show that the favorable reaction channels are channels (n1) and (n4) as well as (c1) and (c3) (refer to Scheme 1) in the whole temperature range. The total ICVT/SCT rate constants of all channels for the two reactions at the MC-QCISD //UMP2(full)/6-31+G(d,p) level are both in good agreement with the available experimental data, and corresponding three-parameter expressions of kICVT /SCT in 220-3000K are fitted as 6.46×10-15(T/298)3.60exp(-386/T)cm3mol-1s-1 for NH2 abstraction and 1.04×10-14 (T/298)4.00exp(-2037/T)cm3mol-1s-1 for CH3 abstraction. Additionally, the long range interaction between the H atom of X -H bond in foreign radicals and the lone pair on the nonreactive N atom of the transition states is further discussed to explain the various transition-state numbers of the two similar hydrogen abstraction reactions.

  4. Laser-induced fluorescence studies of excited Sr reactions: II. Sr(3P1)+CH3F, C2H5F, C2H4F2

    NASA Astrophysics Data System (ADS)

    Teule, J. M.; Janssen, M. H. M.; Bulthuis, J.; Stolte, S.

    1999-06-01

    The vibrational and rotational energy distributions of ground state SrF(X 2Σ) formed in the reactions of electronically excited Sr(3P1) with methylfluoride, ethylfluoride, and 1,1-difluoroethane have been studied by laser-induced fluorescence. Although the reactions of ground state Sr with these reactants are exothermic, no SrF products are observed for those reactions in this study. The fraction of available energy disposed into the sum of rotational and vibrational energy of the SrF(X 2Σ) product is approximately the same for all three reactions, i.e., 40%. The reaction of Sr(3P1) with CH3F results in very low vibrational excitation in the SrF reaction product. The product vibration increases in going to C2H5F and C2H4F2. It is concluded that the alkyl group influences the energy disposal mechanism in these reactions, and some suggestions are given for a partial explanation of the observations.

  5. NMR study of magnetism and superparamagnetism

    NASA Astrophysics Data System (ADS)

    Yuan, Shaojie

    The research described in this dissertation is concerned with two different types of magnetic materials. Both types of systems involve competing interactions between transition metal ions. New approaches involving magnetic resonance in the large hyperfine fields at nuclear sites have been developed. The interactions responsible for the properties that have been investigated in the materials studied are geometric frustration in an insulator and ferromagnetic and antiferromagnetic interactions in a metal alloy. Further details are given below. The extended kagome frustrated system YBaCo4O7 has 2D kagome and triangular lattices of Co ions stacked along the c-axis. Antiferromagnetic (AF) ordering accompanied by a structural transition has been reported in the literature. From a zero field (ZF) NMR single crystal rotation experiment, we have obtained the Co spin configurations for both the kagome and triangular layers. A 'spin-flop' configuration between the spins on the kagome layer and the spins on the triangular layer is indicated by our results. Our NMR findings are compared with neutron scattering results for this intriguing frustrated AF spin system. The non-stoichiometric oxygenated sister compound YBaCo4O7.1 has application potential for oxygen storage. While, its' magnetic properties are quite different from those of the stoichiometric compound, in spite of their similar structures of alternating kagome and triangular Co layers. Various techniques, including ZF NMR have been used to investigate the spin dynamics and spin configuration in a single crystal of YBaCo4O7.1. A magnetic transition at 80 K is observed, which is interpreted as the freezing out of spins in the triangular layers. At low temperatures (below 50 K), the spin dynamics persists and a fraction of spins in the kagome layers form a viscous spin liquid. Below 10 K, a glass-like spin structure forms and a large distribution of spin correlation times are suggested by nuclear spin lattice relaxation

  6. Experimental, DFT and molecular docking studies on 2-(2-mercaptophenylimino)-4-methyl-2H-chromen-7-ol

    NASA Astrophysics Data System (ADS)

    Singh, Ashok Kumar; Singh, Ravindra Kumar

    2016-10-01

    A new coumarin derivative 2-(2-mercaptophenylimino)-4-methyl-2H-chromen-7-ol (COMSB) was synthesized and characterized with the help of 1H,13C NMR, FT-IR, FT-Raman and mass spectrometry. All quantum calculations were performed at DFT level of theory using B3LYP functional and 6-31G (d,p) as basis set. The UV-Vis spectrum studied by TD-DFT theory, with a hybrid exchange-correlation functional using Coulomb-attenuating method (CAM-B3LYP) in solvent phase gives similar pattern of bands, at energies and is consistent with that of experimental findings. The detailed analysis of vibrational (IR and Raman) spectra and their assignments has been done by computing Potential Energy Distribution (PED) using Gar2ped. Intra-molecular interactions were analyzed by 'Atoms in molecule' (AIM) approach. Computed first static hyperpolarizability (β0 = 8.583 × 10-30 esu) indicates non-linear optical (NLO) response of the molecule. Molecular docking studies show that the title molecule may act as potential acetylcholine esterase (AChE) inhibitor.

  7. Computational and spectral studies of 6-phenylazo-3-(p-tolyl)-2H-chromen-2-one

    NASA Astrophysics Data System (ADS)

    Manimekalai, A.; Vijayalakshmi, N.

    2015-02-01

    6-Phenylazo-3-(p-tolyl)-2H-chromen-2-one 4 was prepared and characterized by IR, 1H, and 13C NMR spectral studies. The optimized structure of the chromen-2-one 4 was investigated by the Gaussian 03 B3LYP density functional method calculations at 6-31G(d,p) basis set. The gauge-independent atomic orbital (GIAO) 13C and 1H chemical shift calculations for the synthesized chromen-2-one in CDCl3 were also made by the same method. The computed IR frequencies of the chromen-2-one and the corresponding vibrational assignments were analyzed by means of potential energy distribution (PED%) calculation using vibrational energy distribution analysis (VEDA) program. The first order hyperpolarizability (βtot), polarizability (α) and dipole moment (μ) were calculated using 6-311G(d,p) basis set and the nonlinear optical (NLO) properties are also addressed theoretically. Stability of the chromen-2-one 4 molecule has been analyzed by calculating the intramolecular charge transfer using natural bond order (NBO) analysis. The molecular electrostatic potentials, HOMO-LUMO energy gap and geometrical parameters were also computed. Topological properties of the electronic charge density in chromen-2-one 4 were analyzed employing the Bader's Atoms in Molecule (AIM) theory which indicated the presence of intramolecular hydrogen bond in the molecule.

  8. Computational and spectral studies of 6-phenylazo-3-(p-tolyl)-2H-chromen-2-one.

    PubMed

    Manimekalai, A; Vijayalakshmi, N

    2015-02-05

    6-Phenylazo-3-(p-tolyl)-2H-chromen-2-one 4 was prepared and characterized by IR, (1)H, and (13)C NMR spectral studies. The optimized structure of the chromen-2-one 4 was investigated by the Gaussian 03 B3LYP density functional method calculations at 6-31G(d,p) basis set. The gauge-independent atomic orbital (GIAO) (13)C and (1)H chemical shift calculations for the synthesized chromen-2-one in CDCl3 were also made by the same method. The computed IR frequencies of the chromen-2-one and the corresponding vibrational assignments were analyzed by means of potential energy distribution (PED%) calculation using vibrational energy distribution analysis (VEDA) program. The first order hyperpolarizability (βtot), polarizability (α) and dipole moment (μ) were calculated using 6-311G(d,p) basis set and the nonlinear optical (NLO) properties are also addressed theoretically. Stability of the chromen-2-one 4 molecule has been analyzed by calculating the intramolecular charge transfer using natural bond order (NBO) analysis. The molecular electrostatic potentials, HOMO-LUMO energy gap and geometrical parameters were also computed. Topological properties of the electronic charge density in chromen-2-one 4 were analyzed employing the Bader's Atoms in Molecule (AIM) theory which indicated the presence of intramolecular hydrogen bond in the molecule.

  9. Theoretical study of the C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O

    NASA Technical Reports Server (NTRS)

    Bauschlicher, Charles W., Jr.; Langhoff, Stephen R.

    1991-01-01

    The successive C-H bond dissociation energies of CH4, C2H2, C2H4, and H2C2O (ketene) are determined using large-basis sets and a high level of correlation treatment. For CH4, C2H2, and C2H4 the computed values are in excellent agreement with experiment. Using these results, the values 107.9 + or - 2.0 and 96.7 + or - 2.0 kcal/mol are recommended for the C-H bond dissociation energies of H2C2O and HC2O, respectively.

  10. Ion-neutral reaction of the C2H2N+ cation with C2H2: An experimental and theoretical study

    NASA Astrophysics Data System (ADS)

    Fathi, P.; Geppert, W. D.; Kaiser, A.; Ascenzi, D.

    2016-03-01

    The ion-neutral reactions of the C2H2N+ cation with C2H2 have been investigated using a Guided Ion Beam Mass Spectrometer (GIB-MS). The following ionic products were observed: CH3+, C2H2+, C2H3+, HNC+ /HCN+ , HCNH+, C3H+ , C2N+ , C3H3+, HCCN+ and C4H2N+ . Theoretical calculations have been carried out to propose reaction pathways leading to the observed products. These processes are of relevance for the generation of long chain nitrogen-containing species and they may be of interest for the chemistry of Titan's ionosphere or circumstellar envelopes.

  11. Phase equilibria and molecular packing in the N,N-dimethyldodecylamine oxide/gramicidin D/water system studied by 2H nuclear magnetic resonance spectroscopy.

    PubMed Central

    Orädd, G; Lindblom, G; Arvidson, G; Gunnarsson, K

    1995-01-01

    A partial phase diagram of the system N,N-dimethyldodecylamine oxide (DDAO)/water/gramicidin D was determined by 2H-NMR. Both 2H2O and perdeuterated DDAO (DDAO-d31) were studied by solid state NMR techniques. Addition of gramicidin D to the micellar (L1), normal hexagonal (HI) and cubic (I) phases of DDAO induces phase separations, giving two-phase regions, which all contain a lamellar (L alpha) phase. The L alpha phase containing gramicidin is characterized by larger order parameters for DDAO-d31 compared with the corresponding order parameters in the L alpha and HI phases of DDAO-d31/H2O. The L alpha phase may stay in equilibrium with any other phase in the phase diagram. The DDAO exchange between the coexisting phases is slow on the NMR timescale, which is why the recorded NMR spectrum consists of superimposed spectra from the different phases occurring in the sample. Gramicidin D can be solubilized in appreciable quantities only in the lamellar phase of DDAO-d31. Increasing amounts of gramicidin in the liquid crystalline phases result in a continuous increase in the molecular ordering up to about 5 mol% gramicidin, where a plateau is reached. This is consistent with a recent theoretical model describing the influence on the ordering of lipids by a membrane protein with larger hydrophobic thickness than the lipid bilayer. The solvent used for dissolving gramicidin at the incorporation of the peptide in the lipid aggregates has no effect on the 2H-NMR lineshapes of DDAO-d31. It is concluded that gramicidin is solubilized in the L alpha phase and that it always adopts the channel conformation independent of a particular solvent. The channel conformation is also supported by CD studies. In some of the samples, macroscopic orientation of the lipid aggregates is observed. It is concluded that DDAO-d31 in the binary system favors an orientation with the long axis of the hydrocarbon chain perpendicular to the magnetic field, whereas when gramicidin D is present the

  12. Detection of platinum dihydride bisphosphine complexes and studies of their reactivity through para-hydrogen-enhanced NMR methods.

    PubMed

    Godard, Cyril; López-Serrano, Joaquín; Gálvez-López, María-Dolores; Roselló-Merino, Marta; Duckett, Simon B; Khazal, Iman; Lledós, Agustí; Whitwood, Adrian C

    2008-01-01

    In-situ NMR studies on the reactions of Pt{CH2 = CHSi(Me)2}2O)(PCy3) with phosphines, HSiEt3 and--hydrogen or Pt(L)(L')(Me)(2) alone enable the detection of cis-Pt(L)(L')(H)2 [L = PCy3 and L' = PCy2H, PPh3 or PCy3] which then undergo hydride site interchange and H2 reductive elimination on the NMR timescale.

  13. Microslot NMR probe for metabolomics studies.

    PubMed

    Krojanski, Hans Georg; Lambert, Jörg; Gerikalan, Yilmaz; Suter, Dieter; Hergenröder, Roland

    2008-11-15

    A NMR microprobe based on microstrip technology suitable for investigations of volume-limited samples in the low nanoliter range was designed. NMR spectra of sample quantities in the 100 pmol range can be obtained with this probe in a few seconds. The planar geometry of the probe is easily adaptable to the size and geometry requirements of the samples.

  14. Mechanistic Study of the Stereoselective Hydroxylation of [2-(2) H1 ,3-(2) H1 ]Butanes Catalyzed by Cytochrome P450 BM3 Variants.

    PubMed

    Yang, Chung-Ling; Lin, Cheng-Hung; Luo, Wen-I; Lee, Tsu-Lin; Ramu, Ravirala; Ng, Kok Yaoh; Tsai, Yi-Fang; Wei, Guor-Tzo; Yu, Steve S-F

    2017-02-21

    Engineered bacterial cytochrome P450s are noted for their ability in the oxidation of inert small alkanes. Cytochrome P450 BM3 L188P A328F (BM3 PF) and A74E L188P A328F (BM3 EPF) variants are able to efficiently oxidize n-butane to 2-butanol. Esterification of the 2-butanol derived from this reaction mediated by the aforementioned two mutants gives diastereomeric excesses (de) of -56±1 and -52±1 %, respectively, with the preference for the oxidation occurring at the C-HS bond. When tailored (2R,3R)- and (2S,3S)-[2-(2) H1 ,3-(2) H1 ]butane probes are employed as substrates for both variants, the obtained de values from (2R,3R)-[2-(2) H1 ,3-(2) H1 ]butane are -93 and -92 % for BM3 PF and EPF, respectively; whereas the obtained de values from (2S,3S)-[2-(2) H1 ,3-(2) H1 ]butane are 52 and 56 % in the BM3 PF and EPF systems, respectively. The kinetic isotope effects (KIEs) for the oxidation of (2R,3R)-[2-(2) H1 ,3-(2) H1 ]butane are 7.3 and 7.8 in BM3 PF and EPF, respectively; whereas KIEs for (2S,3S)-[2-(2) H1 ,3-(2) H1 ]butanes are 18 and 25 in BM3 PF and EPF, respectively. The discrepancy in KIEs obtained from the two substrates supports the two-state reactivity (TSR) that is proposed for alkane oxidation in cytochrome P450 systems. Moreover, for the first time, experimental evidence for tunneling in the oxidation mediated by P450 is given through the oxidation of the C-HR bond in (2S,3S)-[2-(2) H1 ,3-(2) H1 ]butane. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  15. Study of C2H2 optic-fiber monitoring system on spectrum absorption

    NASA Astrophysics Data System (ADS)

    Wang, Yutian; Li, Xiao-Xin; Wang, Zhong-Dong

    2005-02-01

    We report our research on the development of optical fiber trace gas sensors for environmental applications. A novel optical fiber sensor for monitoring acetylene (C2H2) gases is described. Through studying the measure theory, we use the Beer-Lambert law to monitor the gas. And after analyzing the C2H2 spectrum, we select Distributed Feedback Laser Diode (DFB LD) as light source. Comparing many kinds" sensor detection head, the gas absorbing cell with tail fiber can have good coupling with optical fiber and improve the coupling stability. In the data processing system, signals are distilled by lock-in amplifiers and then harmonic measure technology processes that distilled faint signals. After the all, the electronic signals are transmitted into computer to process, alarm and display. We design the instrument who can remote and on-line measuring acetylene. Through theory analysis and system experiment, the design of the system is practicable, and has a better precision and some apply foreground.

  16. 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.

  17. First-principles studies of complex hydride YMn2H6 and its synthesis from metal hydride YMn2H4.5

    NASA Astrophysics Data System (ADS)

    Matsuo, Motoaki; Miwa, Kazutoshi; Semboshi, Satoshi; Li, Hai-Wen; Kano, Mika; Orimo, Shin-ichi

    2011-05-01

    First-principles calculations were performed for a complex hydride YMn2H6 to investigate its electronic structure and thermodynamic stability. The results indicated that an Y atom and one of two Mn atoms were ionized as Y3+ and Mn2+, respectively, and another Mn atom bound covalently to H atoms to form a [MnH6]5- complex anion. Based on the enthalpy change of -65 kJ/mol estimated from the calculation, we experimentally verified a possible low-pressure synthesis of YMn2H6 from a metal hydride YMn2H4.5. X-ray diffractometry confirmed the formation of YMn2H6 after hydrogenation below 5 MPa, much lower than the previously reported value of 170 MPa.

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

    USDA-ARS?s Scientific Manuscript database

    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...

  19. A classical trajectory study of the dissociation and isomerization of C2H5.

    PubMed

    Wagner, Albert F; Rivera-Rivera, Luis A; Bachellerie, Damien; Perry, Jamin W; Thompson, Donald L

    2013-11-21

    Motivated by photodissociation experiments in which non-RRKM nanosecond lifetimes of the ethyl radical were reported, we have performed a classical trajectory study of the dissociation and isomerization of C2H5 over the energy range 100-150 kcal/mol. We used a customized version of the AIREBO semiempirical potential (Stuart, S. J.; et al. J. Chem. Phys. 2000, 112, 6472-6486) to more accurately describe the gas-phase decomposition of C2H5. This study constitutes one of the first gas-phase applications of this potential form. At each energy, 10,000 trajectories were run and all underwent dissociation in less than 100 ps. The calculated dissociation rate constants are consistent with RRKM models; no evidence was found for nanosecond lifetimes. An analytic kinetics model of isomerization/dissociation competition was developed that incorporated incomplete mode mixing through a postulated divided phase space. The fits of the model to the trajectory data are good and represent the trajectory results in detail through repeated isomerizations at all energies. The model correctly displays single exponential decay at lower energies, but at higher energies, multiexponential decay due to incomplete mode mixing becomes more apparent. At both ends of the energy range, we carried out similar trajectory studies on CD2CH3 to examine isotopic scrambling. The results largely support the assumption that a H or a D atom is equally likely to dissociate from the mixed-isotope methyl end of the molecule. The calculated fraction of products that have the D atom dissociation is ∼20%, twice the experimental value available at one energy within our range. The calculated degree of isotopic scrambling is non-monotonic with respect to energy due to a non-monotonic ratio of the isomerization to dissociation rate constants.

  20. Solution structure of (Cr/sup III/(L)(O-O))/sup n/ complexes (L = nitrilotriacetate, N,N-. beta. -alaninediacetate; O-O = malonate, oxalate, acetylacetonate, 2H/sub 2/O) and characterization of (Cr(nta)(OH))/sub 2//sup 2 -/ by deuteron NMR spectroscopy

    SciTech Connect

    Koine, N.; Bianchini, R.J.; Legg, J.I.

    1986-07-30

    The complexes (Cr/sup III/(L)(O-O))/sup n/ (L = nitrilotriacetate (nta), N,N-..beta..-alaninediacetate (..beta..-alada); O-O = malonate (mal), oxalate (ox), acetylacetonate (acac), 2H/sub 2/O) have been synthesized, chromatographically purified, and characterized by deuteron NMR, infrared and electronic absorption spectroscopy. The two possible isomers, symmetrical (sym) and unsymmetrical (unsym), for (Cr(..beta..-alada)(acac))/sup -/ and (Cr(..beta..-alada)(mal))/sup 2 -/ were isolated, but only the unsym isomer for (Cr(..beta..-alada)(ox))/sup 2 -/ was found. The starting materials for the synthesis of these complexes, (Cr(nta)(OH))/sub 2//sup 2 -/ and unsym-(Cr(..beta..-alada)(H/sub 2/O)/sub 2/), were also characterized. Both species were shown to be in equilibrium with the corresponding monomer and dimer, respectively. The chemistry of the various species investigated differs, to some extent, from what has been previously reported. The recent availability of a readily applicable NMR technique for the study of Cr(III) chemistry (/sup 2/H NMR) has greatly facilitated these studies.

  1. Ethanol perturbs lipid organization in models of stratum corneum membranes: An investigation combining differential scanning calorimetry, infrared and (2)H NMR spectroscopy.

    PubMed

    Kwak, Sungjong; Brief, Elana; Langlais, Denis; Kitson, Neil; Lafleur, Michel; Thewalt, Jenifer

    2012-05-01

    Ethanol is used in a variety of topical products. It is known to enhance the permeability of the skin by altering the ability of the stratum corneum (SC) intercellular membranes to form an effective barrier. In addition, ethanol and other alcohols are key components of antiseptic gels currently used for hand wash. Using infrared and deuterium NMR spectroscopy as well as calorimetry, we have investigated the effect of ethanol on a model membrane composed of lipids representing the three classes of SC lipids, an equimolar mixture of N-palmitoylsphingosine (ceramide), palmitic acid and cholesterol. Ethanol is found to influence the membrane in a dose dependent manner, disrupting packing and increasing lipid motion at low concentrations and selectively extracting lipids at moderate concentrations.

  2. 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.

  3. 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.

  4. 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.

  5. ENDOR/HYSCORE Studies of the Common Intermediate Trapped During Nitrogenase Reduction of N2H2, CH3N2H, and N2H4 Support an Alternating Reaction Pathway for N2 Reduction

    PubMed Central

    Lukoyanov, Dmitriy; Dikanov, Sergei A.; Yang, Zhi-Yong; Barney, Brett M.; Samoilova, Rimma I.; Narasimhulu, Kuppala V.; Dean, Dennis R.; Seefeldt, Lance C.; Hoffman, Brian M.

    2011-01-01

    Enzymatic N2 reduction proceeds along a reaction pathway comprised of a sequence of intermediate states generated as a dinitrogen bound to the active-site iron-molybdenum cofactor (FeMo-co) of the nitrogenase MoFe protein undergoes six steps of hydrogenation (e−/H+ delivery). There are two competing proposals for the reaction pathway, and they invoke different intermediates. In the ‘Distal’ (D) pathway, a single N of N2 is hydrogenated in three steps until the first NH3 is liberated, then the remaining nitrido-N is hydrogenated three more times to yield the second NH3. In the ‘Alternating’ (A) pathway, the two N’s instead are hydrogenated alternately, with a hydrazine-bound intermediate formed after four steps of hydrogenation and the first NH3 liberated only during the fifth step. A recent combination of X/Q-band EPR and 15N, 1,2H ENDOR measurements suggested that states trapped during turnover of the α-70Ala/α-195Gln MoFe protein with diazene or hydrazine as substrate correspond to a common intermediate (here denoted I) in which FeMo-co binds a substrate-derived [NxHy] moiety, and measurements reported here show that turnover with methyldiazene generates the same intermediate. In the present report we describe X/Q-band EPR and 14/15N, 1,2H ENDOR/-HYSCORE/ESEEM measurements that characterize the N-atom(s) and proton(s) associated with this moiety. The experiments establish that turnover with N2H2, CH3N2H, and N2H4 in fact generates a common intermediate, I, and show that the N-N bond of substrate has been cleaved in I. Analysis of this finding leads us to conclude that nitrogenase reduces N2H2, CH3N2H, and N2H4 via a common A reaction pathway, and that the same is true for N2 itself, with Fe ion(s) providing the site of reaction. PMID:21744838

  6. 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.

  7. Dynamics and ferroelectric phase transition of (C3N2H5)5Bi2Br11 by means of ac calorimetry and 1H NMR relaxometry

    NASA Astrophysics Data System (ADS)

    Przesławski, J.; Medycki, W.; Piecha, A.; Jakubas, R.; Kruk, D.

    2013-01-01

    A quite uncommon type of heat anomaly has been disclosed by calorimetric experiments in ferroelectric crystal (C3N2H5)5Bi2Br11 close to the paraelectric-ferroelectric transition. Thermal parameters (such as the excess enthalpy (ΔH) and the excess entropy (ΔS)) of the continuous ferroelectric phase transition at ca. 155 K have been estimated and discussed. The entropy transition accompanying the ferroelectric phase transition (PT) of the order of 35 J/mol K confirms an 'order-disorder' mechanism. The ferroelectric-paraelectric PT has been described by the Landau model using the specific heat data.1H spin-lattice relaxation at 25 MHz has been measured for this crystal in a very broad temperature range 90-420 K, covering two phase transitions (at 155 and 355 K). The relaxation data have been interpreted in terms of different dynamical properties of imidazolium cations put in structurally different environments.

  8. A Classical Trajectory Study of the Dissociation and Isomerization of C2H5

    DTIC Science & Technology

    2013-01-01

    C2H5) plays an important role in combustion chemistry. Because the reverse reactions constitute the addition of a hydrogen atom to a stable molecule...primary reaction zones of premixed flames. The hydrogen atom thus produced acts to promote chain branching through the H + O2 ⇌ OH + O reaction . Thus...calculations of reaction paths on the electronically excited-state potential energy surfaces (PESs) of C2H5 14 predict that the nonclassical bridge structure is

  9. Dynamics of Antibody Domains Studied by Solution NMR

    PubMed Central

    Vu, Bang K.; Walsh, Joseph D.; Dimitrov, Dimiter S.; Ishima, Rieko

    2012-01-01

    Information on local dynamics of antibodies is important to evaluate stability, to rationally design variants, and to clarify conformational disorders at the epitope binding sites. Such information may also be useful for improved understanding of antigen recognition. NMR can be used for characterization of local protein dynamics at the atomic level through relaxation measurements. Due to the complexity of the NMR spectra, an extensive use of this method is limited to small protein molecules, for example, antibody domains and some scFv. Here, we describe a protocol that was used to study the dynamics of an antibody domain in solution using NMR. We describe protein preparation for NMR studies, NMR sample optimization, signal assignments, and dynamics experiments. PMID:19252840

  10. High-resolution, high-pressure NMR studies of proteins.

    PubMed Central

    Jonas, J; Ballard, L; Nash, D

    1998-01-01

    Advanced high-resolution NMR spectroscopy, including two-dimensional NMR techniques, combined with high pressure capability, represents a powerful new tool in the study of proteins. This contribution is organized in the following way. First, the specialized instrumentation needed for high-pressure NMR experiments is discussed, with specific emphasis on the design features and performance characteristics of a high-sensitivity, high-resolution, variable-temperature NMR probe operating at 500 MHz and at pressures of up to 500 MPa. An overview of several recent studies using 1D and 2D high-resolution, high-pressure NMR spectroscopy to investigate the pressure-induced reversible unfolding and pressure-assisted cold denaturation of lysozyme, ribonuclease A, and ubiquitin is presented. Specifically, the relationship between the residual secondary structure of pressure-assisted, cold-denatured states and the structure of early folding intermediates is discussed. PMID:9649405

  11. Low-temperature NMR studies of Zn tautomerism and hindered rotations in solid zincocene derivatives.

    PubMed

    Lopez del Amo, Juan Miguel; Buntkowsky, Gerd; Limbach, Hans-Heinrich; Resa, Irene; Fernandez, Rafael; Carmona, Ernesto

    2008-04-24

    Using a combination of NMR methods we have detected and studied fluxional motions in the slip-sandwich structure of solid decamethylzincocene (I, [(eta5-C5Me5)Zn(eta1-C5Me5)]). For comparison, we have also studied the solid iminoacyl derivative [(eta5-C5Me5)Zn(eta1-C(NXyl)C5Me5)] (II). The variable temperature 13C CPMAS NMR spectra of I indicate fast rotations of both Cp* rings in the molecule down to 156 K as well as the presence of an order-disorder phase transition around 210 K. The disorder is shown to be dynamic arising from a fast combined Zn tautomerism and eta1/eta5 reorganization of the Cp* rings between two degenerate states A and B related by a molecular inversion. In the ordered phase, the degeneracy of A and B is lifted; that is, the two rings X and Y are inequivalent, where X exhibits a larger fraction of time in the eta5 state than Y. However, the interconversion is still fast and characterized by a reaction enthalpy of DeltaH = 2.4 kJ mol-1 and a reaction entropy of DeltaS = 4.9 J K-1 mol-1. In order to obtain quantitative kinetic information, variable temperature 2H NMR experiments were performed on static samples of I-d6 and II-d6 between 300 and 100 K, where in each ring one CH3 is replaced by one CD3 group. For II-d6, the 2H NMR line shapes indicate fast CD3 group rotations and a fast "eta5 rotation", corresponding to 72 degrees rotational jumps of the eta5 coordinated Cp* ring. The latter motion becomes slow around 130 K. By line shape analysis, an activation energy of the eta5 rotation of about 21 kJ mol-1 was obtained. 2H NMR line shapes analysis of I-d6 indicates fast CD3 group rotations at all temperatures. Moreover, between 100 and 150 K, a transition from the slow to the fast exchange regime is observed for the 5-fold rotational jumps of both Cp* rings, exhibiting an activation energy of 18 kJ mol-1. This value was corroborated by 2H NMR relaxometry from which additionally the activation energies 6.3 kJ mol-1 and 11.2 kJ mol-1 for the CD3

  12. Full CI calibration of model hamiltonian, large basis set studies of the H 2-H 2 van der Waals interaction.

    NASA Astrophysics Data System (ADS)

    Burton, P. G.

    1983-08-01

    The non-variational CEPA2 PNO ansatz, recently employed in detailed studies of the H 2-H 2 van der Waals interaction by Burton and Senff and the full CI extrapolation studies on the same system by Burton are discussed in relation to the explicit full CI study of Harrison and Handy for the planar T configuration of H 2-H 2 ( R = 6.5 ao) in a basis of 80 functions.

  13. 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.

  14. Satellite observations of ethylene (C2H4) from the Aura Tropospheric Emission Spectrometer: A scoping study

    NASA Astrophysics Data System (ADS)

    Dolan, Wayana; Payne, Vivienne H.; Kualwik, Susan S.; Bowman, Kevin W.

    2016-09-01

    We present a study focusing on detection and initial quantitative estimates of ethylene (C2H4) in observations from the Tropospheric Emission Spectrometer (TES), a Fourier transform spectrometer aboard the Aura satellite that measures thermal infrared radiances with high spectral resolution (0.1 cm-1). We analyze observations taken in support of the 2008 Arctic Research of the Composition of the Troposphere from Aircraft and Satellites (ARCTAS) mission and demonstrate the feasibility of future development of C2H4 into a TES standard product. In the Northern Hemisphere, C2H4 is commonly associated with boreal fire plumes, motor vehicle exhaust and petrochemical emissions. It has a short lifetime (∼14-32 h) in the troposphere due to its reaction with OH and O3. Chemical destruction of C2H4 in the atmosphere leads to the production of ozone and other species such as carbon monoxide (CO) and formaldehyde. Results indicate a correlation between C2H4 and CO in boreal fire plumes. Quantitative C2H4 estimates are sensitive to assumptions about the plume height and width. We find that C2H4 greater than 2-3 ppbv can be detected in a single TES observation (for a fire plume at 3 km altitude and 1.5 km width). Spatial averaging will be needed for surface-peaking profiles where TES sensitivity is lower.

  15. Deuterium Magic Angle Spinning NMR Used to Study the Dynamics of Peptides Adsorbed onto Polystyrene and Functionalized Polystyrene Surfaces

    PubMed Central

    Breen, Nicholas F.; Li, Kun; Olsen, Gregory L.; Drobny, Gary P.

    2011-01-01

    LKα14 is a 14 amino acid peptide with a periodic sequence of leucine and lysine residues consistent with an amphipathic α-helix. This “hydrophobic periodicity” has been found to result in an α-helical secondary structure at air-water interfaces and on both polar and non-polar solid polymer surfaces. In this paper the dynamics of LKα14 peptides, selectively deuterated at a single leucine and adsorbed onto polystyrene and carboxylated polystyrene beads, are studied using 2H Magic Angle Spinning (MAS) solid state NMR over a 100 degree temperature range. We first demonstrate the sensitivity enhancement possible with 2H MAS techniques, which in turn enables us to obtain high quality 2H NMR spectra for selectively deuterated peptides adsorbed onto solid polymer surfaces. An extensive literature shows that the dynamics of leucine side chains are sensitive to the local structural environment of the protein. Therefore the degree to which the dynamics of leucine side chains and the backbone of the peptide LKα14 are influenced by surface proximity and surface chemistry is studied as a function of temperature with 2H MAS NMR. It is found that the dynamics of the leucine side chains in LKα14 depend strongly upon the orientation of the polymer on the surface, which in turn depends on whether the LKα14 peptide adsorbs onto a polar or non-polar surface. 2H MAS line shapes therefore permit probes of surface orientation over a wide temperature range. PMID:21650191

  16. Deuterium magic angle spinning NMR used to study the dynamics of peptides adsorbed onto polystyrene and functionalized polystyrene surfaces.

    PubMed

    Breen, Nicholas F; Li, Kun; Olsen, Gregory L; Drobny, Gary P

    2011-08-04

    LKα14 is a 14 amino acid peptide with a periodic sequence of leucine and lysine residues consistent with an amphipathic α-helix. This "hydrophobic periodicity" has been found to result in an α-helical secondary structure at air-water interfaces and on both polar and nonpolar solid polymer surfaces. In this paper, the dynamics of LKα14 peptides, selectively deuterated at a single leucine and adsorbed onto polystyrene and carboxylated polystyrene beads, are studied using (2)H magic angle spinning (MAS) solid state NMR over a 100 °C temperature range. We first demonstrate the sensitivity enhancement possible with (2)H MAS techniques, which in turn enables us to obtain high-quality (2)H NMR spectra for selectively deuterated peptides adsorbed onto solid polymer surfaces. The extensive literature shows that the dynamics of leucine side chains are sensitive to the local structural environment of the protein. Therefore, the degree to which the dynamics of leucine side chains and the backbone of the peptide LKα14 are influenced by surface proximity and surface chemistry is studied as a function of temperature with (2)H MAS NMR. It is found that the dynamics of the leucine side chains in LKα14 depend strongly upon the orientation of the polymer on the surface, which in turn depends on whether the LKα14 peptide adsorbs onto a polar or nonpolar surface. (2)H MAS line shapes therefore permit probes of surface orientation over a wide temperature range.

  17. NMR study of n-dodecane adsorbed on graphite.

    PubMed

    Alba, M D; Castro, M A; Clarke, S M; Perdigón, A C

    2003-05-01

    In this brief contribution we demonstrate that 1H and 2H NMR spectroscopy can be an effective method of investigating adsorption from liquids at the solid-liquid interface. The method is illustrated here with the adsorption of a simple alkane adsorbed on graphite, in particular the system n-dodecane and graphite at coverages of 1 and 5 monolayers. Static single-pulse proton nuclear magnetic resonance and static quadrupolar echo deuterium nuclear magnetic resonance spectra were recorded for both coverages. The experimental NMR results presented here show features clearly consistent with earlier calorimetric and neutron scattering work and demonstrate the formation of solid adsorbed layers that coexist with the bulk adsorbate with both isotopes. This ability to probe both deuterated and protonated materials simultaneously illustrates that this experimental approach can be readily extended to investigate the adsorption behaviour of multicomponent mixtures.

  18. NMR contributions to structural dynamics studies of intrinsically disordered proteins☆

    PubMed Central

    Konrat, Robert

    2014-01-01

    Intrinsically disordered proteins (IDPs) are characterized by substantial conformational plasticity. Given their inherent structural flexibility X-ray crystallography is not applicable to study these proteins. In contrast, NMR spectroscopy offers unique opportunities for structural and dynamic studies of IDPs. The past two decades have witnessed significant development of NMR spectroscopy that couples advances in spin physics and chemistry with a broad range of applications. This article will summarize key advances in basic physical-chemistry and NMR methodology, outline their limitations and envision future R&D directions. PMID:24656082

  19. 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.

  20. First principles study of CrH and CrM2H

    NASA Astrophysics Data System (ADS)

    Kanagaprabha, S.; Santhosh, M.; Rajeswarapalanichamy, R.; Iyakutti, K.

    2013-06-01

    First principles calculation were performed using Tight-binding LMTO method with Local density approximation (LDA) and Atomic sphere approximation (ASA) to understand the electronic properties of CrH. A pressure induced structural phase transition from cubic to hexagonal structure of CrH is predicted. The stability of CrM2H is analyzed.

  1. Synthesis, experimental spectra (IR & Raman and NMR), vibrational analysis and theoretical DFT investigations of N-(5-(4-methylbenzoyl)-2-oxo-4-(4-methylphenyl)pyrimidine-1(2H)-yl)-4-methylbenzamide.

    PubMed

    Aydın, Lütfiye; Şahan, Emine; Önal, Zülbiye; Özpozan, Talat

    2014-08-14

    The title molecule, N-(5-(4-methylbenzoyl)-2-oxo-4-(4-methylphenyl)pyrimidine-1(2H)-yl)-4-methylbenzamide (C27H23N3O3), was synthesized and characterized by elemental analysis, IR, Raman, (1)H and (13)C NMR spectral data. To determine conformational flexibility, potential energy surfaces of the title compound were obtained by DFT regarding the selected degree of torsional freedom, which was varied from 0° to 360° in 6° and 20° steps. The ten conformers of the title compound were determined and it was found that the conformer 1 basis the most stable one. All conformers were also optimized by using the density functional theory (DFT/B3LYP) method with the 6-31G(d,p), 6-311G(d,p) and cc-pVDZ basis sets in the ground state. Potential energy distribution was calculated with the 6-31G(d,p) basis set. The vibrational spectra were recorded in solid phase IR and Raman spectra were compared based on the results of the theoretical calculations. The formation of hydrogen bonds was explained using natural bond orbital (NBO) analysis and spectroscopic analysis. NMR analysis and frontier molecular orbitals (FMOs) were also investigated by DFT.

  2. 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.

  3. 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.

  4. 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

  5. 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.

  6. 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.

  7. Synthesis, spectral, thermal, fluorescence, antimicrobial, anthelmintic and DNA cleavage studies of mononuclear metal chelates of bi-dentate 2H-chromene-2-one Schiff base.

    PubMed

    Prabhakara, Chetan T; Patil, Sangamesh A; Kulkarni, Ajaykumar D; Naik, Vinod H; Manjunatha, M; Kinnal, Shivshankar M; Badami, Prema S

    2015-07-01

    The Co(II), Ni(II) and Cu(II) complexes have been synthesized with Schiff base (HL), derived from 8-formyl-7-hydroxy-4-methylcoumarin with benzylamine. The Schiff base and its metal complexes were structurally characterized based on IR, (1)H NMR, (13)C NMR, UV-visible, ESR, magnetic, thermal, fluorescence, mass and ESI-MS studies. The complexes are completely soluble in DMF and DMSO. The molar conductance values indicate that, all synthesized metal complexes are non-electrolytic in nature. Elemental analysis reveals [ML2(H2O)2] stoichiometry, here MCo(II), Ni(II) and Cu(II), L=deprotonated ligand. The coordination between metal ion and Schiff base was supported by IR data, through deprotonation of phenolic oxygen of coumarin and azomethine nitrogen atoms. Solution electronic spectral results unveiled that all the synthesized complexes posses six coordinated geometry around metal ion. Thermal studies suggest the presence of coordinated water molecules. The Schiff base and its metal complexes have been screened for their antibacterial (Escherichia coli, Pseudomonas aureginosa, Klebsiella pneumoniae and Staphylococcus aureus) and antifungal (Penicillium chrysogenum and Aspergillus niger), anthelmintic (Pheretima posthuma) and DNA cleavage (Calf Thymus DNA) activities. Copyright © 2015 Elsevier B.V. All rights reserved.

  8. ETM and ANN study for polysubstituted 2H-pyran-2-ones.

    PubMed

    Saracoglu, Murat; Basaran, Murat Alper; Thul, Pallavi; Sayiner, Hakan; Kandemirli, Sedat Giray; Gupta, Ved Prakash; Kandemirli, Fatma

    2013-09-01

    The structure glutamate pyruvate transaminase (GPT), glutamate oxaloacetate transaminase (GOT), acid phosphatase (ACP), alkaline phosphatase (ALP) and glutamate dehydrogenase (GlDH) activity relationships of 2H-pyran-2- ones polysubstitutes being a new class of hepatoprotective agents have been investigated by means of the Electronic- Topological Method (ETM) and two Statistical Analysis. Molecular fragments specific for active compounds were calculated for 2H-pyran-2-ones polysubstitutes by applying the ETM. QSAR descriptors such as molecular weight, EHOMO, ELUMO, ΔE, chemical potential, softness, electrophilicity index, dipole moment, etc were calculated. In order to examine the relationship between independent and dependent variables, both Partial Least Squares Regression and ANNs are employed to determine the relationship since the data set consists of highly nonlinearity and multicolinearity. It is observed that ANN has surpassed both PLS2 and PLS1 in terms of better modeling and validation.

  9. Interfaces in polymer nanocomposites – An NMR study

    SciTech Connect

    Böhme, Ute; Scheler, Ulrich

    2016-03-09

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

  10. Diamond Deposition and Defect Chemistry Studied via Solid State NMR

    DTIC Science & Technology

    1994-06-30

    same integrated NMR signal, regardless of its chemical environment, provided complete spin-lattice relaxation occurs between averages 3 . Gem -quality...occurs between averages, and broadening from years, a large research effort has been devoted to the study paramagnetic centers is insignificant. Gem ...information on the distribution and motion mond’s durability very attractive. However, while gem - of hydrogen can be obtained from the solid-state NMR

  11. 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

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

    NASA Astrophysics Data System (ADS)

    Tang, J. H.

    1981-11-01

    The theoretical background of spin Hamiltonians, the density matrix formalism of multiple quantum NMR are discussed as well as creation and detection of multiple quantum coherence by multiple pulse sequence. 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 considered. An oriented methyl group relaxed by paramagnetic impurities is examined and possible correlated motion between two coupled methyl groups is investigated by multiple quantum NMR. 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 spin lattice dynamics of orienting or tunneling methyl groups (CH3 and CD3) at low temperatures and the anisotropic spin lattice relaxation of deuterated hexamethylbenzene, caused by the sixfold reorientation of the molecules are described as well as NMR spectrometers.

  13. Quantifying cholesterol synthesis in vivo using 2H2O: enabling back-to-back studies in the same subject

    PubMed Central

    Previs, Stephen F.; Mahsut, Ablatt; Kulick, Alison; Dunn, Keiana; Andrews-Kelly, Genevieve; Johnson, Christopher; Bhat, Gowri; Herath, Kithsiri; Miller, Paul L.; Wang, Sheng-Ping; Azer, Karim; Xu, Jing; Johns, Douglas G.; Hubbard, Brian K.; Roddy, Thomas P.

    2011-01-01

    The advantages of using 2H2O to quantify cholesterol synthesis include i) homogeneous precursor labeling, ii) incorporation of 2H via multiple pathways, and iii) the ability to perform long-term studies in free-living subjects. However, there are two concerns. First, the t1/2 of tracer in body water presents a challenge when there is a need to acutely replicate measurements in the same subject. Second, assumptions are made regarding the number of hydrogens (n) that are incorporated during de novo synthesis. Our primary objective was to determine whether a step-based approach could be used to repeatedly study cholesterol synthesis a subject. We observed comparable changes in the 2H-labeling of plasma water and total plasma cholesterol in African-Green monkeys that received five oral doses of 2H2O, each dose separated by one week. Similar rates of cholesterol synthesis were estimated when comparing data in the group over the different weeks, but better reproducibility was observed when comparing replicate determinations of cholesterol synthesis in the same nonhuman primate during the respective dosing periods. Our secondary objective was to determine whether n depends on nutritional status in vivo; we observed n of ∼25 and ∼27 in mice fed a high-carbohydrate (HC) versus carbohydrate-free (CF) diet, respectively. We conclude that it is possible to acutely repeat studies of cholesterol synthesis using 2H2O and that n is relatively constant. PMID:21498887

  14. High-Resolution NMR Studies of Human Tissue Factor

    PubMed Central

    Nuzzio, Kristin M.; Watt, Eric D.; Boettcher, John M.; Gajsiewicz, Joshua M.; Morrissey, James H.; Rienstra, Chad M.

    2016-01-01

    In normal hemostasis, the blood clotting cascade is initiated when factor VIIa (fVIIa, other clotting factors are named similarly) binds to the integral membrane protein, human tissue factor (TF). The TF/fVIIa complex in turn activates fX and fIX, eventually concluding with clot formation. Several X-ray crystal structures of the soluble extracellular domain of TF (sTF) exist; however, these structures are missing electron density in functionally relevant regions of the protein. In this context, NMR can provide complementary structural information as well as dynamic insights into enzyme activity. The resolution and sensitivity for NMR studies are greatly enhanced by the ability to prepare multiple milligrams of protein with various isotopic labeling patterns. Here, we demonstrate high-yield production of several isotopically labeled forms of recombinant sTF, allowing for high-resolution NMR studies both in the solid and solution state. We also report solution NMR spectra at sub-mM concentrations of sTF, ensuring the presence of dispersed monomer, as well as the first solid-state NMR spectra of sTF. Our improved sample preparation and precipitation conditions have enabled the acquisition of multidimensional NMR data sets for TF chemical shift assignment and provide a benchmark for TF structure elucidation. PMID:27657719

  15. A neutron scattering study of hydrogen dynamics in coarse-grained and nanostructured ZrCr2H3

    NASA Astrophysics Data System (ADS)

    Skripov, A. V.; Udovic, T. J.; Rush, J. J.; Uimin, M. A.

    2011-02-01

    The vibrational spectra of hydrogen and parameters of H diffusion in the coarse-grained C15-type system ZrCr2H3 and in nanostructured ZrCr2H3 have been studied by means of inelastic and quasielastic neutron scattering. It is found that the diffusive motion of hydrogen in coarse-grained ZrCr2H3 can be described in terms of at least two jump processes: a fast localized H motion with the jump rate τl - 1 over the hexagons formed by interstitial Zr2Cr2 sites and a slower process with the rate τd - 1 associated with H jumps leading to long-range diffusion. While τd - 1(T) in the range 250-380 K follows the Arrhenius law with the activation energy of 142 ± 4 meV, the temperature dependence of τl - 1 deviates from Arrhenius behavior. The nanostructured ZrCr2H3 samples prepared by ball milling consist of C15-type grains and strongly distorted (amorphous-like) regions. H atoms in the strongly distorted regions are found to be immobile on the time scale of our experiments. The microscopic picture of H jump motion in the C15-type grains of the nanostructured samples is similar to that in coarse-grained ZrCr2H3; however, the ball milling leads to a considerable decrease in the jump rate τd - 1.

  16. a Rotational Study of 2H-3H-PERFLUOROPENTANE and its Isotopologues

    NASA Astrophysics Data System (ADS)

    Duong, Chinh H.; Obenchain, Daniel A.; Novick, Stewart E.; Cooke, S. A.

    2012-06-01

    The chirped pulse Fourier transform microwave spectrum of 2H-3H-perfluoropentane has been observed and assigned. Given a racemic mixture sample of the four available structural isomers, only the (S,S) structure was observed in the broadband spectrum. Attempts at observing the 13C isotopologues on a Balle-Flygare cavity type spectrometer and their assignments will be discussed, along with an examination of the theoretical predictions for the structure and rotational constants of the molecule against their experimental values. Structural results of the monomer will also be compared with those of the helical structure of C2 perfluoropentane. Joseph A. Fournier, Robert K. Bohn, John A. Montgomery Jr., Masao Onda. J. Phys. Chem. 114 (1118), 2010.

  17. Study of cultured fibroblasts in vivo using NMR

    SciTech Connect

    Karczmar, G.S.

    1984-08-01

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

  18. Influence of anthraquinone scaffold on E/Z isomer distribution of two thiosemicarbazone derivatives. 2D NMR and DFT studies

    NASA Astrophysics Data System (ADS)

    Marković, Violeta; Joksović, Milan D.; Marković, Svetlana; Jakovljević, Ivan

    2014-01-01

    A distribution of possible isomeric and tautomeric forms of two tautomerizable anthraquinone-thiosemicarbazones with pronounced cytotoxic potential was investigated using 2D NMR and DFT studies. Conformational analysis of the E and Z isomers of both thiosemicarbazones was performed to find out the most stable conformation for each molecule. It was found that superior stability of E-isomers results from ten-membered intramolecular hydrogen bond between thiosemicarbazone N2H and anthraquinone carbonyl group. This hydrogen bond is stronger than that between thiosemicarbazone N2H and ester oxygen, owing to the large partial negative charge on the anthraquinone oxygen.

  19. Supramolecular order and structural dynamics: A STM study of 2H-tetraphenylporphycene on Cu(111)

    SciTech Connect

    Stark, Michael; Träg, Johannes; Ditze, Stefanie; Steinrück, Hans-Peter; Marbach, Hubertus; Brenner, Wolfgang; Jux, Norbert

    2015-03-14

    The adsorption of 2H-tetraphenylporphycene (2HTPPc) on Cu(111) was investigated by scanning tunneling microscopy (STM). At medium coverages, supramolecular ordered islands are observed. The individual 2HTPPc molecules appear as two pairs of intense protrusions which are separated by an elongated depression. In the islands, the molecules are organized in rows oriented along one of the close packed Cu(111) substrate rows; the structure is stabilized by T-type interactions of the phenyl substituents of neighboring molecules. Two types of rows are observed, namely, highly ordered rows in which all molecules exhibit the same orientation, and less ordered rows in which the molecules exhibit two perpendicular orientations. Altogether, three different azimuthal orientations of 2HTPPc are observed within one domain, all of them rotated by 15° ± 1° relative to one closed packed Cu direction. The highly ordered rows are always separated by either one or two less ordered rows, with the latter structure being the thermodynamically more stable one. The situation in the islands is highly dynamic, such that molecules in the less ordered rows occasionally change orientation, also complete highly ordered rows can move. The supramolecular order and structural dynamics are discussed on the basis of the specific molecule-substrate and molecule-molecule interactions.

  20. The chemistry of 5-(tetrazol-1-yl)-2H-tetrazole: an extensive study of structural and energetic properties.

    PubMed

    Fischer, Niko; Izsák, Dániel; Klapötke, Thomas M; Stierstorfer, Jörg

    2013-07-01

    5-(Tetrazol-1-yl)-2H-tetrazole (1), or 1,5'-bistetrazole, was synthesized by the cyclization of 5-amino-1H-tetrazole, sodium azide and triethyl orthoformate in glacial acetic acid. A derivative of 1, 2-methyl-5-(tetrazol-1-yl)tetrazole (2) can be obtained by this method starting from 5-amino-2-methyl-tetrazole. Furthermore, selected salts of 1 with nitrogen-rich and metal (alkali and transition metal) cations, including hydroxylammonium (4), triaminoguanidinium (5), copper(I) (8) and silver (9), as well as copper(II) complexes of both 1 and 2 were prepared. An intensive characterization of the compounds is given, including vibrational (IR, Raman) and multinuclear NMR spectroscopy, mass spectrometry, DSC and single-crystal X-ray diffraction. Their sensitivities towards physical stimuli (impact, friction, electrostatic) were determined according to Bundesamt für Materialforschung (BAM) standard methods. Energetic performance (detonation velocity, pressure, etc.) parameters were calculated with the EXPLO5 program, based on predicted heats of formation derived from enthalpies computed at the CBS-4M level of theory and utilizing the atomization energy method. From the analytical and calculated data, their potential as energetic materials in different applications was evaluated and discussed.

  1. Solution NMR Spectroscopy for the Study of Enzyme Allostery

    PubMed Central

    Lisi, George P.; Loria, J. Patrick

    2016-01-01

    Allostery is a ubiquitous biological regulatory process in which distant binding sites within a protein or enzyme are functionally and thermodynamically coupled. Allosteric interactions play essential roles in many enzymological mechanisms, often facilitating formation of enzyme-substrate complexes and/or product release. Thus, elucidating the forces that drive allostery is critical to understanding the complex transformations of biomolecules. Currently, a number of models exist to describe allosteric behavior, taking into account energetics as well as conformational rearrangements and fluctuations. In the following review, we discuss the use of solution NMR techniques designed to probe allosteric mechanisms in enzymes. NMR spectroscopy is unequaled in its ability to detect structural and dynamical changes in biomolecules, and the case studies presented herein demonstrate the range of insights to be gained from this valuable method. We also provide a detailed technical discussion of several specialized NMR experiments that are ideally suited for the study of enzymatic allostery. PMID:26734986

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

    PubMed Central

    Sobolev, Anatoly P.; Capitani, Donatella; Giannino, Donato; Nicolodi, Chiara; Testone, Giulio; Santoro, Flavio; Frugis, Giovanna; Iannelli, Maria A.; Mattoo, Autar K.; Brosio, Elvino; Gianferri, Raffaella; D’Amico, Irene; Mannina, Luisa

    2010-01-01

    The 1H-NMR methodology used in the study of genetically modified (GM) foods is discussed. Transgenic lettuce (Lactuca sativa cv "Luxor") over-expressing the ArabidopsisKNAT1 gene is presented as a case study. Twenty-two water-soluble metabolites (amino acids, organic acids, sugars) present in leaves of conventional and GM lettuce were monitored by NMR and quantified at two developmental stages. The NMR spectra did not reveal any difference in metabolite composition between the GM lettuce and the wild type counterpart. Statistical analyses of metabolite variables highlighted metabolism variation as a function of leaf development as well as the transgene. A main effect of the transgene was in altering sugar metabolism. PMID:22253988

  3. Self-metalation of 2H-tetraphenylporphyrin on Cu(111): an x-ray spectroscopy study.

    PubMed

    Diller, K; Klappenberger, F; Marschall, M; Hermann, K; Nefedov, A; Wöll, Ch; Barth, J V

    2012-01-07

    The bonding and the temperature-driven metalation of 2H-tetraphenylporphyrin (2H-TPP) on the Cu(111) surface under ultrahigh vacuum conditions were investigated by a combination of x-ray photoelectron spectroscopy (XPS) and near-edge x-ray absorption fine structure (NEXAFS) spectroscopy with density functional theory calculations. Thin films were prepared by organic molecular beam epitaxy and subsequent annealing. Our systematic study provides an understanding of the changes of the spectroscopic signature during adsorption and metalation. Specifically, we achieved a detailed peak assignment of the 2H-TPP multilayer data of the C1s and the N1s region. After annealing to 420 K both XPS and NEXAFS show the signatures of a metalloporphyrin, which indicates self-metalation at the porphyrin-substrate interface, resulting in Cu-TPP. Furthermore, for 2H-TPP monolayer samples we show how the strong influence of the copper surface is reflected in the spectroscopic signatures. Adsorption results in a strongly deformed macrocycle and a quenching of the first NEXAFS resonance in the nitrogen edge suggesting electron transfer into the LUMO. For Cu-TPP the spectroscopic data indicate a reduced interaction of first-layer molecules with the substrate as demonstrated by the relaxed macrocycle geometry.

  4. Relaxation dispersion NMR spectroscopy for the study of protein allostery.

    PubMed

    Farber, Patrick J; Mittermaier, Anthony

    2015-06-01

    Allosteric transmission of information between distant sites in biological macromolecules often involves collective transitions between active and inactive conformations. Nuclear magnetic resonance (NMR) spectroscopy can yield detailed information on these dynamics. In particular, relaxation dispersion techniques provide structural, dynamic, and mechanistic information on conformational transitions occurring on the millisecond to microsecond timescales. In this review, we provide an overview of the theory and analysis of Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion NMR experiments and briefly describe their application to the study of allosteric dynamics in the homeodomain from the PBX transcription factor (PBX-HD). CPMG NMR data show that local folding (helix/coil) transitions in one part of PBX-HD help to communicate information between two distant binding sites. Furthermore, the combination of CPMG and other spin relaxation data show that this region can also undergo local misfolding, reminiscent of conformational ensemble models of allostery.

  5. NMR STUDY OF MOLECULAR REFORIENTATION UNDER FIVEFOLD SYMMETRY SOLID PERMETHYLFERROCENE

    SciTech Connect

    Wemmer, D.E.; Ruben, D.J.; Pines, A.

    1980-08-01

    The ring reorientation in permethylferrocene has been studied using high resolution solid state {sup 13}C NMR. The constraints which symmetry places upon the number and types of motional parameters which may be determined from the NMR spectrum are discussed. From comparison of the experimental lineshapes in the slow reorientation temperatures range with theoretical models for random rotations and symmetry related jumps, it is concluded that the reorientation occurs as jumps between symmetry related orientations with jumps of 2{pi}/5 highly favored over 4{pi}/5. The activation energy derived for the jump process is 13.5 kjoules/mole.

  6. Experimental and theoretical studies of charge transfer and deuterium ion transfer between D2O+ and C2H4

    NASA Astrophysics Data System (ADS)

    Liu, Li; Cai, Xiaohui; Li, Yue; Richards O'Grady, Elizabeth; Farrar, James M.

    2004-08-01

    The charge transfer and deuterium ion transfer reactions between D2O+ and C2H4 have been studied using the crossed beam technique at relative collision energies below one electron volt and by density functional theory (DFT) calculations. Both direct and rearrangement charge transfer processes are observed, forming C2H4+ and C2H3D+, respectively. Independent of collision energy, deuterium ion transfer accounts for approximately 20% of the reactive collisions. Between 22 and 36 % of charge transfer collisions occur with rearrangement. In both charge transfer processes, comparison of the internal energy distributions of products with the photoelectron spectrum of C2H4 shows that Franck-Condon factors determine energy disposal in these channels. DFT calculations provide evidence for transient intermediates that undergo H/D migration with rearrangement, but with minimal modification of the product energy distributions determined by long range electron transfer. The cross section for charge transfer with rearrangement is approximately 103 larger than predicted from the Rice-Ramsperger-Kassel-Marcus isomerization rate in transient complexes, suggesting a nonstatistical mechanism for H/D exchange. DFT calculations suggest that reactive trajectories for deuterium ion transfer follow a pathway in which a deuterium atom from D2O+ approaches the π-cloud of ethylene along the perpendicular bisector of the C-C bond. The product kinetic energy distributions exhibit structure consistent with vibrational motion of the D-atom in the bridged C2H4D+ product perpendicular to the C-C bond. The reaction quantitatively transforms the reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the deuterium ion is transferred in a configuration in which both the breaking and the forming bonds are extended.

  7. Application of a Pyroprobe-Deuterium NMR System: Deuterium Tracing and Mechanistic Study of Upgrading Process for Lignin Model Compounds

    SciTech Connect

    Ben, Haoxi; Jarvis, Mark W.; Nimlos, Mark R.; Gjersing, Erica L.; Sturgeon, Matthew R.; Foust, Thomas D.; Ragauskas, Arthur J.; Biddy, Mary J.

    2016-04-21

    In this study, a pyroprobe-deuterium (2H) NMR system has been used to identify isotopomer products formed during the deuteration and ring opening of lignin model compounds. Several common model compounds for lignin and its upgraded products, including guaiacol, syringol, toluene, p-xylene, phenol, catechol, cyclohexane, methylcyclohexane, and methylcyclopentane, have been examined for selective ring opening. Similar pathways for upgrading of toluene and p-xylene has been found, which will undergo hydrogenation, methyl group elimination, and ring opening process, and benzene, cyclohexane, and methylcyclohexane have been found as major intermediates before ring opening. Very interestingly, the 2H NMR analysis for the deuterium-traced ring opening of catechol on Ir/..gamma..-Al2O3 is almost identical to the ring opening process for phenol. The ring opening processes for guaiacol and syringol appeared to be very complicated, as expected. Benzene, phenol, toluene, cyclohexane, and methylcyclohexane have been determined to be the major products.

  8. Theoretical study of electronic and tribological properties of h-BNC2/graphene, h-BNC2/h-BN and h-BNC2/h-BNC2 bilayers.

    PubMed

    Ansari, Narjes; Nazari, Fariba; Illas, Francesc

    2015-05-21

    Density functional theory based methods are used to investigate the interlayer sliding energy landscape (ISEL), binding energy and interlayer spacing between h-BNC2/graphene (I), h-BNC2/h-BN (II) and h-BNC2/h-BNC2 (III) bilayer structures for three, six and fourteen different stacking patterns, respectively. Our results show that, in the studied cases, increasing the atomic variety of the ingredient monolayers leads to an ISEL corrugation increase as well. For the studied bilayers the ISEL is obtained by means of the registry index. For sufficiently large flakes of h-BNC2 on graphene sheets with the largest incommensurability and the least monolayer anisotropy, a robust superlubricity occurs regardless of the relative interlayer orientation. On the other hand, for the h-BNC2/h-BNC2 bilayer exhibiting the least incommensurability and the most monolayer anisotropy, the occurrence of robust superlubricity depends on the relative interlayer orientation.

  9. NMR study of a membrane protein in detergent-free aqueous solution.

    PubMed

    Zoonens, Manuela; Catoire, Laurent J; Giusti, Fabrice; Popot, Jean-Luc

    2005-06-21

    One of the major obstacles to membrane protein (MP) structural studies is the destabilizing effect of detergents. Amphipols (APols) are short amphipathic polymers that can substitute for detergents to keep MPs water-soluble under mild conditions. In the present work, we have explored the feasibility of studying the structure of APol-complexed MPs by NMR. As a test MP, we chose the 171-residue transmembrane domain of outer MP A from Escherichia coli (tOmpA), whose x-ray and NMR structures in detergent are known. 2H,15N-labeled tOmpA was produced as inclusion bodies, refolded in detergent solution, trapped with APol A8-35, and the detergent removed by adsorption onto polystyrene beads. The resolution of transverse relaxation-optimized spectroscopy-heteronuclear single-quantum correlation spectra of tOmpA/A8-35 complexes was found to be close to that of the best spectra obtained in detergent solutions. The dispersion of chemical shifts indicated that the protein had regained its native fold and retained it during the exchange of surfactants. MP-APol interactions were mapped by substituting hydrogenated for deuterated A8-35. The resulting dipolar broadening of amide proton linewidths was found to be limited to the beta-barrel region of tOmpA, indicating that A8-35 binds specifically to the hydrophobic transmembrane surface of the protein. The potential of this approach to MP studies by solution NMR is discussed.

  10. A detailed quantum mechanical and quasiclassical trajectory study on the dynamics of the H+ + H2 --> H2 + H+ exchange reaction.

    PubMed

    González-Lezana, Tomás; Roncero, Octavio; Honvault, Pascal; Launay, Jean-Michel; Bulut, Niyazi; Aoiz, F Javier; Bañares, Luis

    2006-09-07

    The H+ + H2 exchange reaction has been studied theoretically by means of a different variety of methods as an exact time independent quantum mechanical, approximate quantum wave packet, statistical quantum, and quasiclassical trajectory approaches. Total and state-to-state reaction probabilities in terms of the collision energy for different values of the total angular momentum obtained with these methods are compared. The dynamics of the reaction is extensively studied at the collision energy of E(coll)=0.44 eV. Integral and differential cross sections and opacity functions at this collision energy have been calculated. In particular, the fairly good description of the exact quantum results provided by the statistical quantum method suggests that the dynamics of the process is governed by an insertion mechanism with the formation of a long-lived collision complex.

  11. Solid state synthesis, spectroscopic and X-ray studies of metal complexes of 2-picolinic acid and vapochromic behavior of [Co(Pic)2(H2O)2]·2H2O

    NASA Astrophysics Data System (ADS)

    Tella, Adedibu C.; Oladipo, Adetola C.; Adeyemi, Olalere G.; Oluwafemi, Oluwatobi S.; Oguntoye, Stephen O.; Alimi, Lukman O.; Ajayi, Joseph T.; Degni, Sylvestre K.

    2017-06-01

    Three compounds, [Cu(Pic)2(H2O)] (1a), [M(Pic)2(H2O)2]·2H2O] (M=Co (2a), Zn (3a), Pic = 2-picolinic acid) were obtained by solvent-free synthesis through grinding of metal acetate salt with 2-picolinic acid. Favorable comparison of solvent-free with solution based method of 1b, 2b and 3b was observed. Good resemblance of identity of compounds obtained through the two methods was confirmed by elemental analysis, spectroscopic techniques (UV-Vis and FTIR), TGA and PXRD. The single crystal diffraction data for [Co(Pic)2(H2O)2]·2H2O obtained from the Cambridge structure database (CSD), its PXRD simulated patterns closely matched that of complex 2a by solvent-free synthesis. Vapochromic behavior of this complex was studied using colour change, FT-IR, TGA, PXRD and solid state UV-visible spectroscopies. This complex generated specific colour which is also evident in the shifting of the vibrational frequencies (νO-H and ν C=O bands). The resulting inclusion compounds have different colours depending on the solvent used. In addition, exposure of the resultant inclusion compounds to ambient environment or heating for a few minutes regenerate the original material without degradation even after exposure/heating cycles as evident from TGA/DTG thermograms.

  12. 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.

  13. 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.

  14. Lanthanide Chelates as Bilayer Alignment Tools in NMR Studies of Membrane-Associated Peptides

    NASA Astrophysics Data System (ADS)

    Prosser, R. S.; Bryant, H.; Bryant, R. G.; Vold, Regitze R.

    1999-12-01

    Theequimolar complex, consisting of the lipid-like, amphiphilic chelating agent 1,11-bis[distearylamino]-diethylenetriamine pentaacetic acid (DTPA-18) and Tm3+, is shown by deuterium (2H) NMR to be useful in aligning bicelle-like model membranes, consisting of dimyristoylphosphatidylcholine (DMPC) and dihexanoylphosphatidylcholine (DHPC). As shown previously (1996, R. S. Prosser et al., J. Am. Chem. Soc. 118, 269-270), in the absence of chelate, the lanthanide ions bind loosely with the lipid phosphate groups and confer the membrane with a sufficient positive magnetic anisotropy to result in parallel alignment (i.e., average bilayer normal along the field). Apparently, DTPA-18 sequesters the lanthanide ions and inserts into the phospholipid bilayer in such a manner that bilayer morphology is preserved over a wide temperature range (35-70°C). The inherent paramagnetic shifts and line broadening effects are illustrated by 2H NMR spectra of the membrane binding peptide, Leu-enkephalin (Lenk-d2, Tyr-(Gly-d2)-Gly-Phe-Leu-OH), in the presence of varying concentrations of Tm3+, and upon addition of DTPA-18. Two conclusions could be drawn from this study: (1) The addition of Tm3+ to the bicelle system is consistent with a conformational change in the surface associated peptide, and this effect is shown to be reversed by addition of the chelate, and (2) The paramagnetic shifts are shown to be significantly reduced by addition of chelate.

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

    PubMed

    Lerche, Mathilde H; Meier, Sebastian; Jensen, Pernille R; Baumann, Herbert; Petersen, Bent O; Karlsson, Magnus; Duus, Jens Ø; Ardenkjaer-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 (13)C NMR ligand binding studies at natural isotopic abundance of (13)C gets feasible in this way. Resultant screens are easy to interpret and can be performed at (13)C concentrations below muM. 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. Copyright (c) 2009 Elsevier Inc. All rights reserved.

  16. Studies of Transition Metal Complexes Using Dynamic NMR Techniques.

    NASA Astrophysics Data System (ADS)

    Coston, Timothy Peter John

    Available from UMI in association with The British Library. This Thesis is primarily concerned with the quantitative study of fluxional processes in, predominantly platinum(IV) complexes, with the ligands 1,1,2,2-tetrakis(methylthio)ethane (MeS)_2CHCH(SMe)_2 , and 1,1,2,2-tetrakis(methylthio)ethene (MeS) _2C=C(SMe)_2. Quantitative information relating to the energetics of these processes has been obtained by a combination of one- and two-dimensional NMR techniques. Chapter One provides an introduction to the background of fluxional processes in transition metal complexes together with data concerning the energetics of the processes that have already been studied by NMR techniques. Chapter Two provides a thorough grounding in NMR techniques, in particular those concerned with the quantitative measurement of rates involved in chemical exchange processes. A description of the use of 2D EXSY NMR spectroscopy in obtaining rate data is given. The properties of the magnetic isotope of platinum are given in Chapter Three. A general survey is also given of some additional compounds that have already been studied by platinum-195 spectroscopy. Chapter Four is concerned with the quantitative study of low temperature (<293 K) fluxionality (sulphur inversion) in the complexes (PtXMe_3 (MeS)_2CHCH(SMe) _2) (X = Cl, Br, I). These complexes were studied by dynamic nuclear magnetic resonance and the information regarding the rates of sulphur inversion was obtained by complete band-shape analysis. Chapter Five is concerned with high temperature (>333 K) fluxionality, of the previous complexes, as studied by a combination of one- and two -dimensional NMR techniques. Aside from obtaining thermodynamic parameters for all the processes, a new novel mechanism is proposed. Chapter Six is primarily concerned with the NMR investigation of the new dinuclear complexes ((PtXMe _3)_2(MeS) _2CHCH(SMe)_2) (X = Cl, Br, I). The solution properties have been established and thermo-dynamic parameters

  17. Solid-state NMR studies of the dynamics and structure of mouse keratin intermediate filaments

    SciTech Connect

    Mack, J.W.; Torchia, D.A.; Steinert, P.M.

    1988-07-26

    The molecular dynamics and structural organization of mouse epidermal keratin intermediate filaments (IF) have been studied via solid-state nuclear magnetic resonance (NMR) experiments performed on IF labeled both in vivo and in vitro with isotopically enriched amino acids. As a probe of the organization of the peripheral glycine-rich end domains of the IF, carbon-13 NMR experiments have been performed on subfilamentous forms (prekeratin) and on IF reassembled in vitro that had been labeled with either (1-/sup 13/C)glycine or (2-/sup 13/C)glycine, as more than 90% of the glycines of the keratins are located in the end domains. Measurements of carbon relaxation times, nuclear Overhauser enhancements, and signal intensities show that the motions of the peptide backbone in the end domains are effectively isotropic. These results indicate that the end domains of IF are remarkably flexible and have little or no structural order. To probe the structural organization of the coiled-coil rod domains of the IF, separate samples of native keratin IF, raised in primary tissue culture, were labeled with L-(1-/sup 13/C)leucine, L-(/sup 2/H/sub 10/)leucine, or L-(2,3,3-/sup 2/H/sub 3/)leucine, as greater than 90% of the leucyl residues of the keratin IF types studied are located in the coiled coils which form the central core of IF. Deuterium NMR experiments performed on IF labeled with deuteriated leucines indeed reveal a marked degree of peptide backbone rigidity within the coiled coils, confirming the initial conclusions of the carbon-13 data. These data, demonstrating relative peptide backbone rigidity yet side-chain flexibility, are interpreted to mean that the coiled coils of these keratin IF are not tightly packed together but rather form a somewhat looser structure which permits a significant degree of side-chain mobility.

  18. The PAW/GIPAW approach for computing NMR parameters: a new dimension added to NMR study of solids.

    PubMed

    Charpentier, Thibault

    2011-07-01

    In 2001, Mauri and Pickard introduced the gauge including projected augmented wave (GIPAW) method that enabled for the first time the calculation of all-electron NMR parameters in solids, i.e. accounting for periodic boundary conditions. The GIPAW method roots in the plane wave pseudopotential formalism of the density functional theory (DFT), and avoids the use of the cluster approximation. This method has undoubtedly revitalized the interest in quantum chemical calculations in the solid-state NMR community. It has quickly evolved and improved so that the calculation of the key components of NMR interactions, namely the shielding and electric field gradient tensors, has now become a routine for most of the common nuclei studied in NMR. Availability of reliable implementations in several software packages (CASTEP, Quantum Espresso, PARATEC) make its usage more and more increasingly popular, maybe indispensable in near future for all material NMR studies. The majority of nuclei of the periodic table have already been investigated by GIPAW, and because of its high accuracy it is quickly becoming an essential tool for interpreting and understanding experimental NMR spectra, providing reliable assignments of the observed resonances to crystallographic sites or enabling a priori prediction of NMR data. The continuous increase of computing power makes ever larger (and thus more realistic) systems amenable to first-principles analysis. In the near future perspectives, as the incorporation of dynamical effects and/or disorder are still at their early developments, these areas will certainly be the prime target.

  19. Study of cultured fibroblasts in vivo using NMR

    SciTech Connect

    Karczmar, G.S.

    1984-01-01

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

  20. 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.

  1. LABORATORY IR STUDIES AND ASTROPHYSICAL IMPLICATIONS OF C{sub 2}H{sub 2}-CONTAINING BINARY ICES

    SciTech Connect

    Knez, C.; Moore, M. H.; Hudson, R. L.; Ferrante, R. F.

    2012-04-01

    Studies of molecular hot cores and protostellar environments have shown that the observed abundance of gas-phase acetylene (C{sub 2}H{sub 2}) cannot be matched by chemical models without the inclusion of C{sub 2}H{sub 2} molecules subliming from icy grain mantles. Searches for infrared (IR) spectral features of solid-phase acetylene are under way, but few laboratory reference spectra of C{sub 2}H{sub 2} in icy mixtures, which are needed for spectral fits to observational data, have been published. Here, we report a systematic study of the IR spectra of condensed-phase pure acetylene and acetylene in ices dominated by carbon monoxide (CO), carbon dioxide (CO{sub 2}), methane (CH{sub 4}), and water (H{sub 2}O). We present new spectral data for these ices, including band positions and intrinsic band strengths. For each ice mixture and concentration, we also explore the dependence of acetylene's {nu}{sub 5}-band position (743 cm{sup -1}, 13.46 {mu}m) and FWHM on temperature. Our results show that the {nu}{sub 5} feature is much more cleanly resolved in ices dominated by non-polar and low-polarity molecules, specifically CO, CO{sub 2}, and CH{sub 4}, than in mixtures dominated by H{sub 2}O-ice. We compare our laboratory ice spectra with observations of a quiescent region in Serpens.

  2. 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.

  3. Solid State NMR Studies of Energy Conversion and Storage Materials

    NASA Astrophysics Data System (ADS)

    Jankuru Hennadige, Sohan Roshel De Silva

    NMR (Nuclear magnetic resonance) spectroscopy is utilized to study energy conversion and storage materials. Different types of NMR techniques including Magic Angle Spinning, Cross-polarization and relaxation measurement experiments were employed. Four different projects are discussed in this dissertation. First, three types of CFx battery materials were investigated. Electrochemical studies have demonstrated different electrochemical performances by one type, delivering superior performance over the other two. 13C and 19F MAS NMR techniques are employed to identify the atomic/molecular structural factors that might account for differences in electrochemical performance among different types. Next as the second project, layered polymer dielectrics were investigated by NMR. Previous studies have shown that thin film capacitors are improved by using alternate layers of two polymers with complementary properties: one with a high breakdown strength and one with high dielectric constant as opposed to monolithic layers. 13C to 1H cross-polarization techniques were used to investigate any inter-layer properties that may cause the increase in the dielectric strength. The third project was to study two types of thermoelectric materials. These samples were made of heavily doped phosphorous and boron in silicon by two different methods: ball-milled and annealed. These samples were investigated by NMR to determine the degree of disorder and obtain insight into the doping efficiency. The last ongoing project is on a lithium-ion battery system. The nature of passivating layers or the solid electrolyte interphase (SEI) formed on the electrodes surface is important because of the direct correlation between the SEI and the battery life time/durability. Multinuclear (7Li, 19F, 31P) techniques are employed to identify the composition of the SEI formation of both positive and negative electrodes.

  4. 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

    2007-06-05

    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.

  5. Multinuclear NMR studies of gaseous and liquid sevoflurane

    NASA Astrophysics Data System (ADS)

    Macięga, E.; Makulski, W.; Jackowski, K.; Blicharska, B.

    2006-03-01

    For the first time, a small amount of sevoflurane ((CF 3) 2CHOCH 2F) in carbon dioxide and xenon as the gaseous solvents has been studied using 19F and 1H NMR spectra. Density-dependent 19F and 1H nuclear magnetic shielding was observed when the pressure of each solvent was increased. After extrapolation of the results to the zero-density limit it was possible to determine the appropriate shielding constants free from intermolecular interactions, σ0(F) and σ0(H). Similar procedure has also been applied for the investigation of fluorine-proton spin-spin couplings and the 2J 0(FH) and 3J 0(FH) constants of an isolated (CF 3) 2CHOCH 2F molecule were also obtained. Additionally, high-resolution 1H, 13C, 17O and 19F NMR spectra of pure liquid sevoflurane were also recorded and all the 1H- 13C, 1H- 19F and 19F- 13C spin-spin coupling constants and NMR chemical shifts were measured. It is shown that the experimental NMR parameters are suitable for comparison with the results of recent quantum-chemical calculations.

  6. Multinuclear NMR study of silica fiberglass modified with zirconia.

    PubMed

    Lapina, O B; Khabibulin, D F; Terskikh, V V

    2011-01-01

    Silica fiberglass textiles are emerging as uniquely suited supports in catalysis, which offer unprecedented flexibility in designing advanced catalytic systems for chemical and auto industries. During manufacturing fiberglass materials are often modified with additives of various nature to improve glass properties. Glass network formers, such as zirconia and alumina, are known to provide the glass fibers with higher strength and to slow down undesirable devitrification processes. In this work multinuclear (1)H, (23)Na, (29)Si, and (91)Zr NMR spectroscopy was used to characterize the effect of zirconia on the molecular-level fiberglass structure. (29)Si NMR results help in understanding why zirconia-modified fiberglass is more stable towards devitrification comparing with pure silica glass. Internal void spaces formed in zirconia-silica glass fibers after acidic leaching correlate with sodium and water distributions in the starting bulk glass as probed by (23)Na and (1)H NMR. These voids spaces are important for stabilization of catalytically active species in the supported catalysts. Potentials of high-field (91)Zr NMR spectroscopy to study zirconia-containing glasses and similarly disordered systems are illustrated. Copyright © 2011 Elsevier Inc. All rights reserved.

  7. Studies on supramolecular gel formation using DOSY NMR.

    PubMed

    Nonappa; Šaman, David; Kolehmainen, Erkki

    2015-04-01

    Herein, we present the results obtained from our studies on supramolecular self-assembly and molecular mobility of low-molecular-weight gelators (LMWGs) in organic solvents using pulsed field gradient (PFG) diffusion ordered spectroscopy (DOSY) NMR. A series of concentration-dependent DOSY NMR experiments were performed on selected LMWGs to determine the critical gelation concentration (CGC) as well as to understand the behaviour of the gelator molecules in the gel state. In addition, variable-temperature DOSY NMR experiments were performed to determine the gel-to-sol transition. The PFG NMR experiments performed as a function of gradient strength were further analyzed using monoexponential DOSY processing, and the results were compared with the automated Bayesian DOSY transformation to obtain 2D plots. Our results provide useful information on the stepwise self-assembly of small molecules leading to gelation. We believe that the results obtained from these experiments are applicable in determining the CGC and gel melting temperatures of supramolecular gels.

  8. Theoretical study on structures and infrared spectroscopy of Cu2+(H2O)Ar n ( n = 1-4)

    NASA Astrophysics Data System (ADS)

    Song, Xiudan; Li, Shuxia; Jiang, Zishi; Zhang, Yongzhi

    2017-09-01

    The binding energy of Cu2+(H2O) is computed to be 98.4 kcal/mol and thus one-photon photodissociation is not possible in the 3400-3800 cm-1 (9.7-10.9 kcal/mol) region. To study whether the infrared photodissociation processes of Cu2+(H2O) can occur by multiple argon atoms tagging technique, density functional and CCSD(T) methods are used to investigate the geometries, OH stretching frequencies and the argon atom binding energies of Cu2+(H2O)Ar n ( n = 1-4) complexes. Various isomers are found resulting from the different coordination sites of argon atoms. The OH stretches in these complexes are shifted to lower frequencies than those of the free water molecule, and the corresponding vibrational red shifts are progressively smaller as more argon atom is added to Cu2+ while binding an argon atom to an OH site should lead to additional sizable red shift to the OH stretching vibrations.

  9. Developing interaction potential for H (2H) → Cu(1 1 1) interaction system: A numerical study

    NASA Astrophysics Data System (ADS)

    Vurdu, Can D.; Güvenç, Ziya B.

    2010-03-01

    In this study, we have used London-Eyring-Polanyi-Sato (LEPS) functional form as an interaction potential energy function to simulate H (2H) → Cu(1 1 1) interaction system. The parameters of the LEPS function are determined in order to analyze reaction dynamics via molecular dynamics computer simulations of the Cu(1 1 1) surface and H/(2H) system. Nonlinear least-squares method is used to find the LEPS parameters. For this purpose, we use the energy points which were calculated by a density-functional theory method with the generalized gradient approximation including exchange-correlation energy for various configurations of one and two hydrogen atoms on the Cu(1 1 1) surface. After the fitting procedures, two different parameters sets are obtained that the calculated root-mean-square values are close to each other. Using these sets, contour plots of the potential energy surfaces are analyzed for H → Cu(1 1 1) and 2H → Cu(1 1 1) interactions systems. In addition, sticking, penetration, and scattering sites on the surface are analyzed by using these sets.

  10. Free energies of CO2/H-2 capture by p-tert-butylcalix[4]arene. A molecular dynamics study

    SciTech Connect

    Daschbach, John L.; Thallapally, Praveen K.; Atwood, Jerry L.; McGrail, B. Peter; Dang, Liem X.

    2007-09-14

    The interactions of CO2/H2 with p-tert-butylcalix[4]arene (TBC4) were studied using potential of mean force (PMF) and free energy perturbation approaches. The computed PMFs for the interaction of CO2/H2 with a single TBC4 molecule establish that the interaction of CO2 with the open end of the cage structure is attractive while interaction with H2 is not. Free energy perturbation calculations were performed for the same two guest molecules with a pair of facing TBC4 molecules used as a representative model as found in the TBC4 molecular solid. At low temperature both CO2/H2 have favorable interactions with the TBC4 pair with the CO2 interaction considerably larger. These results are in agreement with recent experimental data showing considerable CO2 uptake by TBC4 at moderate pressures. This work was performed at the Pacific Northwest National Laboratory (PNNL) and was supported by the Division of Chemical Sciences, Office of Basic Energy Sciences, U.S. Department of Energy (DOE). PNNL is operated by Battelle for the DOE.

  11. An experimental study of the reaction kinetics of C 2(X 1Σ g+) with hydrocarbons (CH 4, C 2H 2, C 2H 4, C 2H 6 and C 3H 8) over the temperature range 24-300 K: Implications for the atmospheres of Titan and the Giant Planets

    NASA Astrophysics Data System (ADS)

    Canosa, André; Páramo, Alejandra; Le Picard, Sébastien D.; Sims, Ian R.

    2007-04-01

    The reactivity of C 2(X 1Σ +g) with simple saturated (CH 4, C 2H 6 and C 3H 8) and unsaturated (C 2H 2 and C 2H 4) hydrocarbons has been studied in the gas phase over the temperature range 24-300 K using the CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in a Uniform Supersonic Flow) technique. All reactions have been found to be very rapid in this temperature range and the rate coefficients are typically ⩾10 -10 cm 3 molecule -1 s -1 with the exception of methane for which the rate coefficient is one order of magnitude lower: ˜10 -11 cm 3 molecule -1 s -1. These results have been analyzed in terms of potential destruction sources of C 2(X 1Σ +g) in the atmospheres of Titan and the Giant Planets. It appears that the rate coefficient of the reaction 1C 2 + CH 4 should be updated with our new data and that reactions with C 2H 2, C 2H 4 and C 2H 6 should also be included in the existing photochemical models.

  12. Theoretical study of collinear Be + FH/nu1/ yields BeF/nu2/ + H

    NASA Technical Reports Server (NTRS)

    Schor, H.; Chapman, S.; Green, S.; Zare, R. N.

    1978-01-01

    The potential energy surface for collinear Be + FH yields BeF + H was studied at various levels of ab initio approximation. A final surface was obtained from a first order configuration interaction wave function, using the iterative orbital method and a medium-sized basis of Slater atomic functions. The exothermicity is computed to be 6 kcal/mole; the barrier height is predicted to be about 28 kcal/mole at a geometry where both internuclear separations are extended by about 0.4 bohr from their asymptotic equilibrium values. This surface differs qualitatively from simple LEPS models.

  13. 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)

  14. 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)

  15. 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.

  16. 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

  17. Experimental study of the 2p-2h band in {sup 111}Sn

    SciTech Connect

    Ganguly, S.; Banerjee, P.; Ray, I.; Kshetri, R.; Raut, R.; Bhattacharya, S.; Saha-Sarkar, M.; Goswami, A.; Basu, S. K.

    2008-09-15

    The {delta}I=2 intruder band in {sup 111}Sn, built upon the 4074.3 keV state, was studied. The states were populated in the {sup 100}Mo({sup 20}Ne, {alpha}5n) reaction at a beam energy of 136 MeV. Mean lifetimes of five states up to 8737.2 keV (spin 43/2{sup -}) have been measured for the first time using the Doppler shift attenuation method. In addition, an upper limit of mean lifetime has been estimated for the 9860.0 keV (spin 47/2{sup -}) state. The B(E2) values, derived from the present lifetime results, indicate a quadrupole deformation of {beta}{sub 2}=0.28{+-}0.02 for the 31/2{sup -} state and decrease progressively with spin, suggesting a reduction in collectivity. The dynamic moment of inertia for the band also decreases continuously up to the highest observed frequencies. These results, along with the predictions of a total Routhian surface calculation, suggest that the {delta}I=2 band in {sup 111}Sn undergoes a change of shape from collective prolate to triaxial with increase in spin and possibly terminates in a noncollective oblate state at a high spin.

  18. NMR Studies of Some Plasma Proteins.

    NASA Astrophysics Data System (ADS)

    Lawrence, Mark P.

    Available from UMI in association with The British Library. Requires signed TDF. The work reported in this thesis consists of a study of the solution structure of a domain of protein structure found in some of the enzymes involved in blood coagulation. These domains, known as kringles, are of between 78 and 82 residues and contain three conserved disulphide bridges in their primary sequence. The study attempts to elucidate the nature of the lysine-binding site of the fourth kringle of human plasminogen to probe its physiological action, and a theory is developed to explain the overall fold of the protein in terms of its physiological role. The protein structure is found to contain only one small region of secondary structure, an antiparallel beta-sheet of about 8 residues, which provides the support for the binding site. The binding site itself consists of a hydrophobic channel provided by the aromatic residues at positions 61, 63, 71 and 73 in the beta-sheet and a negatively charged site at one end of this channel provided by the aspartic acid residues at positions 54 and 56. The beta-sheet appears to become more tightly defined on binding the kringle with alpha,omega -amino acids which are analogues of lysine and exhibit known anti-fibrinolytic properties. The rest of the solution structure appears to be less clearly defined and relies mainly on the three disulphide bridges and some rather isolated hydrogen bonding for maintenance of the fold. An explanation for this structure with a rigid binding site and a more flexible region for the remainder of the domain is proposed. Shorter studies are reported on the second kringle of bovine prothrombin and the first of human plasminogen which suggest strongly that the kringle fold is conserved.

  19. 1H NMR relaxometry, viscometry, and PFG NMR studies of magnetic and nonmagnetic ionic liquids.

    PubMed

    Daniel, Carla I; Chávez, Fabián Vaca; Feio, Gabriel; Portugal, Carla A M; Crespo, João G; Sebastião, Pedro J

    2013-10-03

    A study is presented of the molecular dynamics and of the viscosity in pure [Aliquat][Cl] ionic liquid and in a mixture of [Aliquat][Cl] with 1% (v/v) of [Aliquat][FeCl4]. The (1)H spin-lattice relaxation rate, R1, was measured by NMR relaxometry between 8 and 300 MHz. In addition, the translation self-diffusion, D, was measured by pulse field gradient NMR. The ILs' viscosity was measured as a function of an applied magnetic field, B, and it was found that the IL mixture's viscosity decreased with increasing B, whereas the [Aliquat][Cl] viscosity is independent of B. All experimental results were analyzed taking into account the viscosity's magnetic field dependence, assuming a modified Stokes-Einstein diffusion/viscosity relation. The main difference between the relaxation mechanisms responsible for R1 in the two IL systems is related to the additional paramagnetic relaxation contribution associated with the (1)H spins-[FeCl4] paramagnetic moments' interactions. Cross-relaxation cusps in the R1 dispersion, associated with (35)Cl and (1)H nuclear spins in the IL systems, were detected. The R1 model considered was successfully fitted to the experimental results, and it was possible to estimate the value of D at zero field in the case of the IL mixture which was consistent with the values of D measured at 7 and 14.1 T and with the magnetic field dependence estimated from the viscosity measurements. It was observed that a small concentration of [Aliquat][FeCl4] in the [Aliquat][Cl] was enough to produce a "superparamagnetic"-like effect and to change the IL mixture's molecular dynamics and viscosity and to allow for their control with an external magnetic field.

  20. Studying skin penetration by NMR imaging

    NASA Astrophysics Data System (ADS)

    Burg, J. M.; Voelker, M.; Schlupp, P.; Schmidts, T.; Maeder, U.; Bergmann, T.; Runkel, F.; Heverhagen, J. T.; Fiebich, M.

    2011-03-01

    Skin penetration studies are an important part for the development of dermal drug carrier systems. As a novel approach a 7-tesla Magnetic Resonance Imaging (MRI) Scanner was used to obtain information about the penetration of agents into the skin. The main advantage of this method is, that the properties of the skin does not influence the signals. Compared to optical assessments the MRI method is not limited to imaging depth. Furthermore, it is possible to analyze fat and water components of the skin separately. The aim of this work was to evaluate, if this method is a promising analysis tool for the visualization of the transport of substances across the skin. Gadobutrol (Gadovist®1.0), respresenting a coventional contrast agent in MRI, was used as a model drug for the visualization of the skin penetration. These first promising results showed that Gadobutrol, incorporated in an oil-in-water emulsion, could be detected across the skin tissue compared to an aqueous solution. After 24 hours, the pixel intensity value was increased about 4-fold compared to an untreated tissue.

  1. Experimental study of exclusive $^2$H$(e,e^\\prime p)n$ reaction mechanisms at high $Q^2$

    SciTech Connect

    Kim Egiyan; Gegham Asryan; Nerses Gevorgyan; Keith Griffioen; Jean Laget; Sebastian Kuhn; Gary Adams; Moscov Amaryan; Pawel Ambrozewicz; Marco Anghinolfi; Gerard Audit; Harutyun AVAKIAN; Harutyun Avakian; Hovhannes Baghdasaryan; Nathan Baillie; Jacques Ball; Nathan Baltzell; Steve Barrow; Vitaly Baturin; Marco Battaglieri; Ivan Bedlinski; Ivan Bedlinskiy; Mehmet Bektasoglu; Matthew Bellis; Nawal Benmouna; Barry Berman; Angela Biselli; Lukasz Blaszczyk; Sylvain Bouchigny; Sergey Boyarinov; Robert Bradford; Derek Branford; William Briscoe; William Brooks; Stephen Bueltmann; Volker Burkert; Cornel Butuceanu; John Calarco; Sharon Careccia; Daniel Carman; Antoine Cazes; Shifeng Chen; Philip Cole; Patrick Collins; Philip Coltharp; Dieter Cords; Pietro Corvisiero; Donald Crabb; Volker Crede; John Cummings; Natalya Dashyan; Rita De Masi; Raffaella De Vita; Enzo De Sanctis; Pavel Degtiarenko; Haluk Denizli; Lawrence Dennis; Alexandre Deur; Kahanawita Dharmawardane; Richard Dickson; Chaden Djalali; Gail Dodge; Joseph Donnelly; David Doughty; Michael Dugger; Steven Dytman; Oleksandr Dzyubak; Hovanes Egiyan; Lamiaa Elfassi; Latifa Elouadrhiri; Paul Eugenio; Renee Fatemi; Gleb Fedotov; Gerald Feldman; Robert Feuerbach; Robert Fersch; Michel Garcon; Gagik Gavalian; Gerard Gilfoyle; Kevin Giovanetti; Francois-Xavier Girod; John Goetz; Atilla Gonenc; Christopher Gordon; Ralf Gothe; Michel Guidal; Matthieu Guillo; Hayko Guler; Lei Guo; Vardan Gyurjyan; Cynthia Hadjidakis; Kawtar Hafidi; Hayk Hakobyan; Rafael Hakobyan; Charles Hanretty; John Hardie; F. Hersman; Kenneth Hicks; Ishaq Hleiqawi; Maurik Holtrop; Charles Hyde-Wright; Yordanka Ilieva; David Ireland; Boris Ishkhanov; Eugeny Isupov; Mark Ito; David Jenkins; Hyon-Suk Jo; Kyungseon Joo; Henry Juengst; Narbe Kalantarians; James Kellie; Mahbubul Khandaker; Wooyoung Kim; Andreas Klein; Franz Klein; Alexei Klimenko; Mikhail Kossov; Zebulun Krahn; Laird Kramer; V. Kubarovsky; Joachim Kuhn; Sergey Kuleshov; Jeff Lachniet; Jorn Langheinrich; David Lawrence; Ji Li; Kenneth Livingston; Haiyun Lu; Marion MacCormick; Claude Marchand; Nikolai Markov; Paul Mattione; Simeon McAleer; Bryan McKinnon; John McNabb; Bernhard Mecking; Surik Mehrabyan; Joseph Melone; Mac Mestayer; Curtis Meyer; Tsutomu Mibe; Konstantin Mikhaylov; Ralph Minehart; Marco Mirazita; Rory Miskimen; Viktor Mokeev; Kei Moriya; Steven Morrow; Maryam Moteabbed; James Mueller; Edwin Munevar Espitia; Gordon Mutchler; Pawel Nadel-Turonski; Rakhsha Nasseripour; Silvia Niccolai; Gabriel Niculescu; Maria-Ioana Niculescu; Bogdan Niczyporuk; Megh Niroula; Rustam Niyazov; Mina Nozar; Grant O'Rielly; Mikhail Osipenko; Alexander Ostrovidov; Kijun Park; Evgueni Pasyuk; Craig Paterson; Sergio Pereira; Joshua Pierce; Nikolay Pivnyuk; Dinko Pocanic; Oleg Pogorelko; Sergey Pozdnyakov; Barry Preedom; John Price; Yelena Prok; Dan Protopopescu; Brian Raue; Gregory Riccardi; Giovanni Ricco; Marco Ripani; Barry Ritchie; Federico Ronchetti; Guenther Rosner; Patrizia Rossi; Franck Sabatie; Julian Salamanca; Carlos Salgado; Joseph Santoro; Vladimir Sapunenko; Reinhard Schumacher; Vladimir Serov; Youri Sharabian; Nikolay Shvedunov; Alexander Skabelin; Elton Smith; Lee Smith; Daniel Sober; Daria Sokhan; Aleksey Stavinskiy; Samuel Stepanyan; Stepan Stepanyan; Burnham Stokes; Paul Stoler; Steffen Strauch; Mauro Taiuti; David Tedeschi; Ulrike Thoma; Avtandil Tkabladze; Svyatoslav Tkachenko; Luminita Todor; Clarisse Tur; Maurizio Ungaro; Michael Vineyard; Alexander Vlassov; Daniel Watts; Lawrence Weinstein; Dennis Weygand; M. Williams; Elliott Wolin; Michael Wood; Amrit Yegneswaran; Lorenzo Zana; Jixie Zhang; Bo Zhao; Zhiwen Zhao

    2007-06-01

    The reaction {sup 2}H(e,e{prime} p)n has been studied with full kinematic coverage for photon virtuality 1.75 < 5.5 {approx} GeV{sup 2}. Comparisons of experimental data with theory indicate that for very low values of neutron recoil momentum (p{sub n} < 100 MeV/c) the neutron is primarily a spectator and the reaction can be described by the plane-wave impulse approximation. For 100 < 750 MeV/c proton-neutron rescattering dominates the cross section, while {Delta} production followed by the N{Delta} {yields} NN transition is the primary contribution at higher momenta.

  2. Experimental study of exclusive 2H(e,e'p)n reaction mechanisms at high Q2.

    PubMed

    Egiyan, K S; Asryan, G; Gevorgyan, N; Griffioen, K A; Laget, J M; Kuhn, S E; Adams, G; Amaryan, M J; Ambrozewicz, P; Anghinolfi, M; Audit, G; Avakian, H; Bagdasaryan, H; Baillie, N; Ball, J P; Baltzell, N A; Barrow, S; Batourine, V; Battaglieri, M; Bedlinskiy, I; Bektasoglu, M; Bellis, M; Benmouna, N; Berman, B L; Biselli, A S; Blaszczyk, L; Bouchigny, S; Boiarinov, S; Bradford, R; Branford, D; Briscoe, W J; Brooks, W K; Bültmann, S; Burkert, V D; Butuceanu, C; Calarco, J R; Careccia, S L; Carman, D S; Cazes, A; Chen, S; Cole, P L; Collins, P; Coltharp, P; Cords, D; Corvisiero, P; Crabb, D; Crede, V; Cummings, J P; Dashyan, N; De Masi, R; De Vita, R; De Sanctis, E; Degtyarenko, P V; Denizli, H; Dennis, L; Deur, A; Dharmawardane, K V; Dickson, R; Djalali, C; Dodge, G E; Donnelly, J; Doughty, D; Dugger, M; Dytman, S; Dzyubak, O P; Egiyan, H; El Fassi, L; Elouadrhiri, L; Eugenio, P; Fatemi, R; Fedotov, G; Feldman, G; Feuerbach, R J; Fersch, R; Garçon, M; Gavalian, G; Gilfoyle, G P; Giovanetti, K L; Girod, F X; Goetz, J T; Gonenc, A; Gordon, C I O; Gothe, R W; Guidal, M; Guillo, M; Guler, N; Guo, L; Gyurjyan, V; Hadjidakis, C; Hafidi, K; Hakobyan, H; Hakobyan, R S; Hanretty, C; Hardie, J; Hersman, F W; Hicks, K; Hleiqawi, I; Holtrop, M; Hyde-Wright, C E; Ilieva, Y; Ireland, D G; Ishkhanov, B S; Isupov, E L; Ito, M M; Jenkins, D; Jo, H S; Joo, K; Juengst, H G; Kalantarians, N; Kellie, J D; Khandaker, M; Kim, W; Klein, A; Klein, F J; Klimenko, A V; Kossov, M; Krahn, Z; Kramer, L H; Kubarovsky, V; Kuhn, J; Kuleshov, S V; Lachniet, J; Langheinrich, J; Lawrence, D; Li, Ji; Livingston, K; Lu, H Y; Maccormick, M; Marchand, C; Markov, N; Mattione, P; McAleer, S; McKinnon, B; McNabb, J W C; Mecking, B A; Mehrabyan, S; Melone, J J; Mestayer, M D; Meyer, C A; Mibe, T; Mikhailov, K; Minehart, R; Mirazita, M; Miskimen, R; Mokeev, V; Moriya, K; Morrow, S A; Moteabbed, M; Mueller, J; Munevar, E; Mutchler, G S; Nadel-Turonski, P; Nasseripour, R; Niccolai, S; Niculescu, G; Niculescu, I; Niczyporuk, B B; Niroula, M R; Niyazov, R A; Nozar, M; O'Rielly, G V; Osipenko, M; Ostrovidov, A I; Park, K; Pasyuk, E; Paterson, C; Anefalos Pereira, S; Pierce, J; Pivnyuk, N; Pocanic, D; Pogorelko, O; Pozdniakov, S; Preedom, B M; Price, J W; Prok, Y; Protopopescu, D; Raue, B A; Riccardi, G; Ricco, G; Ripani, M; Ritchie, B G; Ronchetti, F; Rosner, G; Rossi, P; Sabatié, F; Salamanca, J; Salgado, C; Santoro, J P; Sapunenko, V; Schumacher, R A; Serov, V S; Sharabian, Y G; Shvedunov, N V; Skabelin, A V; Smith, E S; Smith, L C; Sober, D I; Sokhan, D; Stavinsky, A; Stepanyan, S S; Stepanyan, S; Stokes, B E; Stoler, P; Strauch, S; Taiuti, M; Tedeschi, D J; Thoma, U; Tkabladze, A; Tkachenko, S; Todor, L; Tur, C; Ungaro, M; Vineyard, M F; Vlassov, A V; Watts, D P; Weinstein, L B; Weygand, D P; Williams, M; Wolin, E; Wood, M H; Yegneswaran, A; Zana, L; Zhang, J; Zhao, B; Zhao, Z W

    2007-06-29

    The reaction 2H(e,e'p)n has been studied with full kinematic coverage for photon virtuality 1.75NN transition is the primary contribution at higher momenta.

  3. Muon spin relaxation study of Zr(H2PO4)(PO4).2H2O.

    PubMed

    Clayden, Nigel J; Cottrell, Stephen P

    2006-07-14

    Muon spin relaxation has been used to study the muon dynamics in the layered zirconium phosphate Zr(H(2)PO(4))(PO(4)).2H(2)O as a function of temperature. Radiofrequency decoupling was used to establish the origin of the local dipolar field as coupling with (1)H spins. Muons were trapped at two sites, one identified as HMuO and the other consistent with PO-Mu on the basis of their zero-field second moments. Although a small decrease in the local nuclear dipolar field was seen with temperature, the muons remained essentially static over the temperature range 20-300 K.

  4. Review of NMR studies of nanoscale molecular magnets composed of geometrically frustrated antiferromagnetic triangles

    DOE PAGES

    Furukawa, Yuji

    2016-10-01

    This paper presents a comprehensive review of nuclear magnetic resonance (NMR) studies performed on three nanoscale molecular magnets with different novel configurations of geometrically frustrated antiferromagnetic (AFM) triangles: (1) the isolated single AFM triangle K6[V15As6O42(H2O)]·8H2O (in short V15), (2) the spin ball [Mo72Fe30O252(Mo2O7(H2O))2(Mo2O8H2(H2O)) (CH3COO)12(H2O)91]·150H2O (in short Fe30 spin ball), and (3) the twisted triangular spin tube [(CuCl2tachH)3Cl]Cl2 (in short Cu3 spin tube). In V15t, from 51V NMR spectra, the local spin configurations were directly determined in both the nonfrustrated total spin ST = 3/2 state at higher magnetic fields (H ge; 2.7 T) and the two nearly degenerate ST =more » 1/2 ground states at lower magnetic fields (H ≤ 2.7 T). The dynamical magnetic properties of V15 were investigated by proton spin-lattice relaxation rate (1/T1) measurements. In the ST = 3/2 state, 1/T1 shows thermally activated behaviour as a function of temperature. On the other hand, the temperature independent behaviour of 1/T1 at very low temperatures is observed in the frustrated ST = 1/2 ground state. Possible origins for the peculiar behaviour of 1/T1 will be discussed in terms of magnetic fluctuations due to spin frustrations. In Fe30, static and dynamical properties of Fe3+ (s = 5/2) have been investigated by proton NMR spectra and 1/T1 measurements. From the temperature dependence of 1/T1, the fluctuation frequency of the Fe3+ spins is found to decrease with decreasing temperature, indicating spin freezing at low temperatures. The spin freezing is also evidenced by the observation of a sudden broadening of 1H NMR spectra below 0.6 K. Finally, 1H NMR data in Cu3 will be described. An observation of magnetic broadening of 1H NMR spectra at low temperatures below 1 K directly revealed a gapless ground state. The 1/T1 measurements revealed a usual slow spin dynamics in the Cu3 spin tube.« less

  5. 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.

  6. Achieving Reversible H2/H+ Interconversion at Room Temperature with Enzyme-Inspired Molecular Complexes: A Mechanistic Study

    SciTech Connect

    Priyadarshani, Nilusha; Dutta, Arnab; Ginovska-Pangovska, Bojana; Buchko, Garry W.; O'Hagan, Molly J.; Raugei, Simone; Shaw, Wendy J.

    2016-09-02

    Inspired by the contribution of the protein scaffold to the efficiency with which enzymes function, we report the first molecular complex that is reversible for electrocatalytic H2 production/oxidation at room temperature in methanol. [Ni(PCy2NPhe2)2]2+ (CyPhe; PR2NR’2 = 1,5-diaza-3,7-diphosphacyclooctane, Cy=cyclohexyl, Phe=phenylalanine), shows reversible behavior in acidic methanol with peripheral phenylalanine groups providing key contributions to the catalytic behavior. The importance of the aromatic rings is implicated in achieving reversibility, based on the lack of reversibility of similar complexes, [Ni(PCy2NAmino Acid2)2]2+, containing arginine (CyArg) or glycine (CyGly). A complex with an added OH group on the ring, (CyTyr; Tyr=Tyrosine), also shows similar behavior. NMR studies reveal a significantly slower rate of chair-boat isomerization for the CyPhe relative to other derivatives, suggesting that the aromatic groups provide structural control by interacting with each other, an observation supported by molecular dynamics studies. NMR studies also show extremely fast proton movement, with a proton pathway from the Ni-H through the pendant amine to the –COOH group. Further, studies of acomplex without the –COOH group, [Ni(PCy2NTym2)2]2+ (CyTym; Tym=Tyramine), are not reversible and have slow proton movement from the pendant amine, demonstrating the essential nature of the –COOH group in achieving reversibility. Finally, methanol is demonstrated to play a critical contributing role. The influence of multiple factors on reversibility for this synthetic catalyst is a demonstration of the intricate interplay between the first, second, and outer coordination spheres and resembles the complexity observed in metalloenzymes.

  7. Low energy crossed beam studies of OD+ and D2O+ with C2H4: covalent and electrostatic complexes

    NASA Astrophysics Data System (ADS)

    Liu, Li; Li, Yue; Cai, Xiaohui; Richards, Elizabeth S.; Farrar, James M.

    2007-09-01

    Density functional theory (DFT) calculations are used in conjunction with low-energy crossed beam studies of the ion-molecule reactions of D2O+ and OD+ with C2H4 to probe collision dynamics, particularly the role that electrostatic and covalent intermediates play. In the D+-transfer reaction initiated with D2O+, an electrostatic complex formed when the transferred species approaches the perpendicular bisector of the C=C bond plays an important role. Observation of C2H4D+ products with excitation in the ν10 stretching mode, in which the bridging D-atom moves along the perpendicular bisector, provides support for this complex. In the OD+ reaction, evidence for the occurrence of reaction on the ground singlet surface following internal conversion comes from the observation of a transient complex living ~100 fs. The DFT calculations show that the rate-limiting step corresponds to ring-opening and H/D exchange initiated in an ethylene oxide species with D+ bound to the oxygen atom. Computed lifetimes are in agreement with experiment. This study provides an example of how high-resolution crossed beam studies in conjunction with quantum chemical calculations, can provide a detailed understanding of collision dynamics in systems of moderate complexity. New experimental developments, including the application of velocity space imaging methods, as well as the production of beams of free radicals, will lead to a greater understanding of energy and angular momentum disposal in systems of chemical relevance.

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

    SciTech Connect

    Jelinek, Raz

    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. 27Al and 23Na 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 27Al 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+ cations are directly involved in adsorption processes and reactions in zeolite cavities.

  9. 1H NMR Studies of MgH2

    NASA Astrophysics Data System (ADS)

    Itoh, Yutaka; Kado, Ryoichi

    We report on 1H NMR studies of commercially available powder MgH2 exposed to air and maybe humidity, which has been believed to be a promising material for hydrogen storage. The Fourier transform of the free-induction decay of the protons indicatesd superposition of broad and narrow components in the NMR spectrum, while the Fourier transform of the 1H nuclear spin-echo reproduced the narrow component. With cooling down below room temperature, the ratio of the narrow peak to the broad spectrum decreased. The broad spectrum is associated with direct dipolar coupled protons on an inhomogeneous rigid lattice. The narrow peak is associated with interstitial protons with more inhomogeneous surroundings.

  10. a Study of Molecular Dynamics in Water-Cellulose Systems Using NMR

    NASA Astrophysics Data System (ADS)

    Waana, Charles Musannyana

    This thesis presents the application of Nuclear Magnetic Resonance (NMR) to the study of the water dynamics in water-cellulose systems. Both H_2O and D_2O were used in polycrystalline Sigmacell 50 cellulose and in cellulose acetate films. Both the spectral lineshapes and various spin relaxation times were studied as functions of temperature and moisture content of the samples. ^1H and ^2 H NMR spectra of rm H_2O and rm D_2O absorbed in cellulose acetate films were observed while changing the angle between the plane of the film and the static magnetic field. ^1H-NMR spectra show dipolar splittings that vary depending on the angle. The splitting has a maximum when the surface of the film is perpendicular to the magnetic field. From the angular dependence of the dipolar splittings, it is deduced that the motionally averaged axis of the dipole moments is perpendicular to the film surface. ^2H NMR spectra show quadrupolar splittings which indicate that the motionally averaged axis of the electric quadrupole interaction is oriented perpendicular to the film. A number of NMR parameters were determined as a function of moisture content at 20^circ C for water adsorbed on Sigmacell 50 cellulose. The NMR parameters indicate that the cellulose swells as the water is added. Ninety-two percent of the cellulose is in crystalline domains and undergoes very little swelling indicating that it is largely inaccessible to water, whereas the remaining 8% is in paracrystalline or amorphous domains which are accessible to water and undergo considerable swelling. A three state model is applied for the protons in these samples, consisting of cellulose protons, water in intimate contact with these cellulose portons, and water which is not in intimate contact. Exchange and/or cross relaxation occurs between the three different proton groups. All the data are consistent with this model. An NMR relaxation study of water dynamics in hydrated Sigmacell 50 cellulose and cellulose acetate films has

  11. A study on the distribution of 37 well conserved families of C2H2 zinc finger genes in eukaryotes.

    PubMed

    Seetharam, Arun; Stuart, Gary W

    2013-06-24

    The C2H2 zinc-finger (ZNF) containing gene family is one of the largest and most complex gene families in metazoan genomes. These genes are known to exist in almost all eukaryotes, and they constitute a major subset of eukaryotic transcription factors. The genes of this family usually occur as clusters in genomes and are thought to have undergone a massive expansion in vertebrates by multiple tandem duplication events (BMC Evol Biol 8:176, 2008). In this study, we combined two popular approaches for homolog detection, Reciprocal Best Hit (RBH) (Proc Natl Acad Sci USA 95:6239-6244, 1998) and Hidden-Markov model (HMM) profiles search (Bioinformatics 14:755-763, 1998), on a diverse set of complete genomes of 124 eukaryotic species ranging from excavates to humans to identify all detectable members of 37 C2H2 ZNF gene families. We succeeded in identifying 3,890 genes as distinct members of 37 C2H2 gene families. These 37 families are distributed among the eukaryotes as progressive additions of gene blocks with increasing complexity of the organisms. The first block featuring the protists had 7 families, the second block featuring plants had 2 families, the third block featuring the fungi had 2 families (one of which was also present in plants) and the final block consisted of metazoans with 25 families. Among the metazoans, the simpler unicellular metazoans had just 15 of the 25 families while most of the bilaterians had all 25 families making up a total of 37 families. Multiple potential examples of lineage-specific gene duplications and gene losses were also observed. Our hybrid approach combines features of the both RBH and HMM methods for homolog detection. This largely automated technique is much faster than manual methods and is able to detect homologs accurately and efficiently among a diverse set of organisms. Our analysis of the 37 evolutionarily conserved C2H2 ZNF gene families revealed a stepwise appearance of ZNF families, agreeing well with the

  12. Hydrogen jump diffusion in C14-type ZrMn2H3 : Quasielastic neutron scattering study

    NASA Astrophysics Data System (ADS)

    Skripov, A. V.; Udovic, T. J.; Rush, J. J.

    2007-09-01

    In order to study the mechanism and parameters of hydrogen diffusion in the hexagonal (C14-type) Laves-phase ZrMn2 , we have performed quasielastic neutron scattering measurements for ZrMn2H3 over the temperature range 10-390K . It is found that the diffusive motion of hydrogen in this system can be described in terms of at least two jump processes: a fast localized H motion with the jump rate τl-1 and a slower process with the rate τd-1 associated with H jumps leading to long-range diffusion. The temperature dependence of τd-1 in the range 225-390K follows the Arrhenius law with the activation energy of 124±4meV . In the same range, the temperature dependence of τl-1 deviates from the Arrhenius behavior and is considerably weaker than that of τd-1 . The Q dependence of the elastic incoherent structure factor (studied up to Qmax≈3.8Å-1 ) suggests that the fast localized H motion in ZrMn2H3 corresponds to two-site jumps within pairs of closely spaced interstitial Zr2Mn2 sites.

  13. NMR Structural Studies of Antimicrobial Peptides: LPcin Analogs

    PubMed Central

    Jeong, Ji-Ho; Kim, Ji-Sun; Choi, Sung-Sub; Kim, Yongae

    2016-01-01

    Lactophoricin (LPcin), a component of proteose peptone (113–135) isolated from bovine milk, is a cationic amphipathic antimicrobial peptide consisting of 23 amino acids. We designed a series of N- or C-terminal truncated variants, mutated analogs, and truncated mutated analogs using peptide-engineering techniques. Then, we selected three LPcin analogs of LPcin-C8 (LPcin-YK1), LPcin-T2WT6W (LPcin-YK2), and LPcin-T2WT6W-C8 (LPcin-YK3), which may have better antimicrobial activities than LPcin, and successfully expressed them in E. coli with high yield. We elucidated the 3D structures and topologies of the three LPcin analogs in membrane environments by conducting NMR structural studies. We investigated the purity of the LPcin analogs and the α-helical secondary structures by performing 1H-15N 2D HSQC and HMQC-NOESY liquid-state NMR spectroscopy using protein-containing micelle samples. We measured the 3D structures and tilt angles in membranes by conducting 15N 1D and 2D 1H-15N SAMMY type solid-state NMR spectroscopy with an 800 MHz in-house-built 1H-15N double-resonance solid-state NMR probe with a strip-shield coil, using protein-containing large bicelle samples aligned and confirmed by molecular-dynamics simulations. The three LPcin analogs were found to be curved α-helical structures, with tilt angles of 55–75° for normal membrane bilayers, and their enhanced activities may be correlated with these topologies. PMID:26789765

  14. Folding of the KIX domain: characterization of the equilibrium analog of a folding intermediate using 15N/13C relaxation dispersion and fast 1H/2H amide exchange NMR spectroscopy.

    PubMed

    Schanda, Paul; Brutscher, Bernhard; Konrat, Robert; Tollinger, Martin

    2008-07-18

    The KIX domain of the transcription co-activator CBP is a three-helix bundle protein that folds via rapid accumulation of an intermediate state, followed by a slower folding phase. Recent NMR relaxation dispersion studies revealed the presence of a low-populated (excited) state of KIX that exists in equilibrium with the natively folded form under non-denaturing conditions, and likely represents the equilibrium analog of the folding intermediate. Here, we combine amide hydrogen/deuterium exchange measurements using rapid NMR data acquisition techniques with backbone (15)N and (13)C relaxation dispersion experiments to further investigate the equilibrium folding of the KIX domain. Residual structure within the folding intermediate is detected by both methods, and their combination enables reliable quantification of the amount of persistent residual structure. Three well-defined folding subunits are found, which display variable stability and correspond closely to the individual helices in the native state. While two of the three helices (alpha(2) and alpha(3)) are partially formed in the folding intermediate (to approximately 50% and approximately 80%, respectively, at 20 degrees C), the third helix is disordered. The observed helical content within the excited state exceeds the helical propensities predicted for the corresponding peptide regions, suggesting that the two helices are weakly mutually stabilized, while methyl (13)C relaxation dispersion data indicate that a defined packing arrangement is unlikely. Temperature-dependent experiments reveal that the largest enthalpy and entropy changes along the folding reaction occur during the final transition from the intermediate to the native state. Our experimental data are consistent with a folding mechanism where helices alpha(2) and alpha(3) form rapidly, although to different extents, while helix alpha(1) consolidates only as folding proceeds to complete the native state-structure.

  15. NMR Studies of Molecular Orientation and Dynamics in Spider silk

    NASA Astrophysics Data System (ADS)

    Michal, Carl; Eles, Philip

    2004-05-01

    Spider dragline silk has a unique combination of strength and extensibility that has been difficult to achieve in synthetic polymer fibres and has inspired industrial efforts to produce genetically engineered analogues. In light of these efforts elsewhere, we describe solid-state NMR experiments that elucidate the molecular structure and dynamics of this remarkable material. These experiments include the use of a 2-D exchange NMR experiment known as DECODER in which the sample is reoriented through a discrete angle during the mixing time. This experiment allows a reconstruction of the orientation distribution of the protein backbone. Our data is well described by a two-component distribution where the protein backbones of both components are preferentially aligned along the silk fibre. This experiment is also sensitive to molecular motion on a wide range of time-scales, and is employed to study changes in the silk as a function of fibre extension and hydration. Hydrated silk undergoes a remarkable phenomena known as supercontraction where fibres shrink by up to 50% in length while swelling in diameter. DECODER NMR of fully and partially supercontracted silk reveals that supercontraction occurs through a process of local phase transitions where water disrupts inter- and intra-chain hydrogen bonds.

  16. 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.

  17. Theoretical study of radiative electron attachment to CN, C{sub 2}H, and C{sub 4}H radicals

    SciTech Connect

    Douguet, Nicolas; Fonseca dos Santos, S.; Orel, Ann E.; Raoult, Maurice; Dulieu, Olivier

    2015-06-21

    A first-principle theoretical approach to study the process of radiative electron attachment is developed and applied to the negative molecular ions CN{sup −}, C{sub 4}H{sup −}, and C{sub 2}H{sup −}. Among these anions, the first two have already been observed in the interstellar space. Cross sections and rate coefficients for formation of these ions by direct radiative electron attachment to the corresponding neutral radicals are calculated. For the CN molecule, we also considered the indirect pathway, in which the electron is initially captured through non-Born-Oppenheimer coupling into a vibrationally resonant excited state of the anion, which then stabilizes by radiative decay. We have shown that the contribution of the indirect pathway to the formation of CN{sup −} is negligible in comparison to the direct mechanism. The obtained rate coefficients for the direct mechanism at 30 K are 7 × 10{sup −16} cm{sup 3}/s for CN{sup −}, 7 × 10{sup −17} cm{sup 3}/s for C{sub 2}H{sup −}, and 2 × 10{sup −16} cm{sup 3}/s for C{sub 4}H{sup −}. These rates weakly depend on temperature between 10 K and 100 K. The validity of our calculations is verified by comparing the present theoretical results with data from recent photodetachment experiments.

  18. Laboratory Studies on the Formation of Three C2H4O Isomers-Acetaldehyde (CH3CHO), Ethylene Oxide (c-C2H4O), and Vinyl Alcohol (CH2CHOH)-in Interstellar and Cometary Ices

    NASA Astrophysics Data System (ADS)

    Bennett, Chris J.; Osamura, Yoshihiro; Lebar, Matt D.; Kaiser, Ralf I.

    2005-11-01

    Laboratory experiments were conducted to unravel synthetic routes to form three C2H4O isomers-acetaldehyde (CH3CHO), ethylene oxide (c-C2H4O), and vinyl alcohol (CH2CHOH)-in extraterrestrial ices via electronic energy transfer processes initiated by electrons in the track of MeV ion trajectories. Here we present the results of electron irradiation on a 2:1 mixture of carbon dioxide (CO2) and ethylene (C2H4). Our studies suggest that suprathermal oxygen atoms can add to the carbon-carbon π bond of an ethylene molecule to form initially an oxirene diradical (addition to one carbon atom) and the cyclic ethylene oxide molecule (addition to two carbon atoms) at 10 K. The oxirene diradical can undergo a [1, 2]-H shift to the acetaldehyde molecule. Both the ethylene oxide and the acetaldehyde isomers can be stabilized in the surrounding ice matrix. To a minor amount, suprathermal oxygen atoms can insert into a carbon-hydrogen bond of the ethylene molecule, forming vinyl alcohol. Once these isomers have been synthesized inside the ice layers of the coated grains in cold molecular clouds, the newly formed molecules can sublime as the cloud reaches the hot molecular core stage. These laboratory investigations help to explain astronomical observations by Nummelin et al. and Ikeda et al. toward massive star-forming regions and hot cores, where observed fractional abundances of these isomers are higher than can be accounted for by gas-phase reactions alone. Similar synthetic routes could help explain the formation of acetaldehyde and ethylene oxide in comet C/1995 O1 (Hale-Bopp) and also suggest a presence of both isomers in Titan's atmosphere.

  19. 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

    2015-04-07

    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.

  20. Electron paramagnetic resonance spectral study of [Mn(acs)2(2-pic)2(H2O)2] single crystals

    NASA Astrophysics Data System (ADS)

    Kocakoç, Mehpeyker; Tapramaz, Recep

    2016-03-01

    Acesulfame potassium salt is a synthetic and non-caloric sweetener. It is also important chemically for its capability of being ligand in coordination compounds, because it can bind over Nitrogen and Oxygen atoms of carbonyl and sulfonyl groups and ring oxygen. Some acesulfame containing transition metal ion complexes with mixed ligands exhibit solvato and thermo chromic properties and these properties make them physically important. In this work single crystals of Mn+2 ion complex with mixed ligand, [Mn(acs)2(2-pic)2(H2O)2], was studied with electron paramagnetic resonance (EPR) spectroscopy. EPR parameters were determined. Zero field splitting parameters indicated that the complex was highly symmetric. Variable temperature studies showed no detectable chance in spectra.

  1. A low-temperature NMR study of the structure of the ionic complexes of phosphoryl compounds with a hydrogen bond

    SciTech Connect

    Golubov, N.S.; Denisov, G.S.; Matrosov, E.I.; Kabachnik, M.I.

    1982-04-01

    In the present work, low-temperature /sup 1/H NMR spectroscopy was used to study two types of complexes in which the phosphoryl group is part of either the acid or basic part of the molecule. Ionic complexes of trifluoromethylsulfonic acid with phosphoryl bases: (C/sub 8/H/sub 17/)/sub 3/P=O (1), (C/sub 2/H/sub 5/)/sub 2/PON(C/sub 2/H/sub 5/)/sub 2/ (2), and the dioxide (C/sub 2/H/sub 5/)/sub 2/P(O)CH/sub 2/CH/sub 2/P(O)(C/sub 2/H/sub 5/)/sub 2/ (3), and complexes of diethylphosphoric acid with dimethylformamide (4), dimethylsulfoxide (5), THF (6), and other ionic complexes of the type (C/sub 2/H/sub 5/O/sub 2/PO/sub 2/)/sub 2//sup -/HX/sup +/ with a homoconjugated anion, where X = N(C/sub 4/H/sub 9/) or (CD/sub 3/)/sub 3/ /sup 15/NH were studied.

  2. 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

  3. Solution deuterium NMR quadrupolar relaxation study of heme mobility in myoglobin

    SciTech Connect

    Johnson, R.D.; La Mar, G.N.; Smith, K.M.; Parish, D.W.; Langry, K.C. )

    1989-01-18

    NMR spectroscopy has been used to monitor the quadrupolar relaxation and motional dynamics of {sup 2}H selectively incorporated into skeletal and side chain positions of the heme in sperm whale myoglobin. The hyperfine shifts of the heme resonances in paramagnetic states of myoglobin allow resolution of the signals of interest, and paramagnetic contributions to the observed line widths are shown to be insignificant. The {sup 2}H line widths for the skeletal positions of deuterohemin-reconstituted myoglobin yield a correlation time identical with that of overall protein tumbling (9 ns at 30{degree}C) and hence reflect an immobile heme group. The {sup 2}H NMR line widths of heme methyl groups exhibit motional narrowing indicative of very rapid internal rotation. Hence the methyl rotation is effectively decoupled from the overall protein tumbling, and the residual quadrupolar line width can be used directly to determine the protein tumbling rate. The {sup 2}H NMR lines from heme vinyl groups were found narrower than those from the heme skeleton. However, the range of quadrupolar coupling constants for sp{sup 2} hybridized C-{sup 2}H bonds does not permit an unequivocal interpretation in terms of mobility. 48 refs., 4 figs.

  4. NMR study of a membrane protein in detergent-free aqueous solution

    PubMed Central

    Zoonens, Manuela; Catoire, Laurent J.; Giusti, Fabrice; Popot, Jean-Luc

    2005-01-01

    One of the major obstacles to membrane protein (MP) structural studies is the destabilizing effect of detergents. Amphipols (APols) are short amphipathic polymers that can substitute for detergents to keep MPs water-soluble under mild conditions. In the present work, we have explored the feasibility of studying the structure of APol-complexed MPs by NMR. As a test MP, we chose the 171-residue transmembrane domain of outer MP A from Escherichia coli (tOmpA), whose x-ray and NMR structures in detergent are known. 2H,15N-labeled tOmpA was produced as inclusion bodies, refolded in detergent solution, trapped with APol A8-35, and the detergent removed by adsorption onto polystyrene beads. The resolution of transverse relaxation-optimized spectroscopy–heteronuclear single-quantum correlation spectra of tOmpA/A8-35 complexes was found to be close to that of the best spectra obtained in detergent solutions. The dispersion of chemical shifts indicated that the protein had regained its native fold and retained it during the exchange of surfactants. MP–APol interactions were mapped by substituting hydrogenated for deuterated A8-35. The resulting dipolar broadening of amide proton linewidths was found to be limited to the β-barrel region of tOmpA, indicating that A8-35 binds specifically to the hydrophobic transmembrane surface of the protein. The potential of this approach to MP studies by solution NMR is discussed. PMID:15956183

  5. Deuterium NMR study of structural and dynamic properties of horseradish peroxidase

    SciTech Connect

    La Mar, G.N.; Thanabal, V.; Johnson, R.D.; Smith, K.M.; Parish, D.W.

    1989-04-05

    High field deuterium NMR spectra have been recorded for various horseradish peroxidase complexes reconstituted with hemins possessing specific 2H labels. The line width of the 2H NMR signals of deuteroheme reconstituted-horseradish peroxidase (HRP) and its cyano complex for the immobilized skeletal 2-2H and 4-2H labels yield the overall protein rotational correlation time (22 ms at 55 degrees C), which is consistent with expectations based on molecular weight. Meso-2H4 labels yield broad (1.3 kHz) signals just upfield from the diamagnetic protein envelope for HRP, and in the central portion of the protein envelope for the CN- ligated resting state HRP. Meso-2H4-labeled mesohemin-reconstituted HRP exhibits a similar signal but shifted further upfield by approximately 10 ppm. The net upfield meso-H hyperfine shifts confirm a five-coordinate structure for resting state HRP. 2Ha resonances for essentially rotationally immobile vinyl groups were detected in both resting state HRP and CN- ligated resting state HRP. Heme methyl-2H-labeling yields relatively narrow lines (approximately 80 Hz) indicative of effective averaging of the quadrupolar relaxation by rapid methyl rotation. Thus the 2H line width of rapidly rotating methyls in hemoproteins can be used effectively to determine the overall protein tumbling rate. Preliminary 2H experiments in meso-2H4-labeled compound I do not support large pi spin density at these positions on the porphyrin cation radical, and argue for a a1u rather than a a2u orbital ground state.

  6. Experimental Study on Dynamics of 2H2/O2/2Ar Detonations with a Constant Mass Divergence

    NASA Astrophysics Data System (ADS)

    Xiao, Qiang; Chang, Jiaxin; Fleche, Maxime La; Radulescu, Matei I.

    2016-11-01

    Very recently, Borzou and Radulescu (2016) formulated a novel solution allowing for an easy and precise quantification of loss effects during detonation propagation involving an exponentially shaped channel. They found that the detonation dynamics departed from the ZND model predictions, particularly for very unstable detonations. The question arises if the ZND model can predict the dynamics of much less unstable mixtures, in spite of the presence of a cellular structure. The present study focuses on a more stable mixture of 2H2/O2/2Ar with better known reaction kinetics. The results obtained experimentally for the velocity deficit in terms of the amount of mass divergence were found in excellent agreement with the predictions made with the ZND model, in spite of the detonation reaction zone being organized in strong cellular structures with reactive transverse waves.

  7. A vibrational spectroscopic study of the phosphate mineral churchite (REE)(PO(4))⋅2H(2)O.

    PubMed

    Frost, Ray L; López, Andrés; Scholz, Ricardo; Xi, Yunfei; Filho, Mauro Cândido

    2014-06-05

    Vibrational spectroscopy has been used to study the rare earth mineral churchite of formula (REE)(PO4)⋅2H2O. The mineral contains a range of rare earth metals including yttrium depending on the locality. The Raman spectra of churchite-(REE) are characterized by an intense sharp band at 984cm(-1) assigned to the ν1(PO4(3-)) symmetric stretching mode. A lower intensity band observed at around 1067cm(-1) is attributed to the ν3(PO4(3-)) antisymmetric stretching mode. The (PO4(3-)) bending modes are observed at 497cm(-1) (ν2) and 565cm(-1)(ν4). Raman bands at 649 and 681cm(-1) are assigned to water librational modes. Vibrational spectroscopy enables aspects of the structure of churchite to be ascertained. Copyright © 2014 Elsevier B.V. All rights reserved.

  8. Quantum Dynamics Scattering Study of AB+CDE Reactions: A Seven Dimensional Treatment for the H2+C2H Reaction

    NASA Technical Reports Server (NTRS)

    Wang, Dunyou

    2003-01-01

    A time-dependent wave-packet approach is presented for the quantum dynamics study of the AB+CDE reaction system for zero total angular momentum. A seven-degree-of-freedom calculation is employed to study the chemical reaction of H2+C2H yields H + C2H2 by treating C2H as a linear molecule. Initial state selected reaction probabilities are presented for various initial ro-vibrational states. This study shows that vibrational excitation of H2 enhances the reaction probability, whereas the excitation of C2H has only a small effect on the reactivity. An integral cross section is also reported for the initial ground states of H2 and C2H. The theoretical and experimental results agree with each other very well when the calculated seven dimensional results are adjusted to account for the lower transition state barrier heights found in recent ab initio calculations.

  9. Solid-state NMR and TGA studies of silver reduction in chabazite.

    PubMed

    Chen, Fu; Liu, Yan; Wasylishen, Roderick E; Xu, Zhenghe; Kuznicki, Steven M

    2012-03-01

    Silver-exchanged molecular sieves have shown great promise in applications ranging from antimicrobial materials to the adsorption of xenon and iodide, two key contaminants emitted from nuclear reactors. In this work, solid-state 27Al and 29Si MAS NMR and TGA were used to study silver reduction in silver-exchanged chabazite under various thermal conditions. The solid-state NMR results for both 27Al and 29Si show that there are no major changes in the chabazite during silver reduction in an argon stream; however a progressive structural change does take place in the hydrogen stream. The structural change likely involves breaking the silicon oxygen bond of the Si-O-AI fragment of chabazite, leading to the formation of extra-framework aluminum oxide. The TGA results at temperatures up to 600 degrees C indicate that silver reduction is less complete in an argon stream than in a hydrogen stream. In this paper we propose that silver reduction occurs via the following reactions: 2(Ag + ZO-)+H2O --> 1/2O2+2Ag0 + 2ZOH and nAg + mAg = Ag(m+n)n+ (in an argon stream); and Ag(+) + ZO(-) + 1/2H2 = Ag0 + ZOH and 2ZOH = ZO(-) + Z(+) + H2O (in a hydrogen stream).

  10. 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.

  11. 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.

  12. Oxovanadium alkoxides: Structure, reactivity, and sup 51 V NMR characteristics. Crystal and molecular structures of VO(OCH sub 2 CH sub 2 Cl) sub 3 and VOCl sub 2 (THF) sub 2 H sub 2 O

    SciTech Connect

    Priebsch, W.; Rehder, D. )

    1990-08-08

    The vanadyl esters VO(OR){sub 3} (R = Me, Et, Pr, iPr, sBu, tBu, CH{sub 2}CH{sub 2}F, CH{sub 2}CH{sub 2}Cl, CH{sub 2}CCl{sub 3}) have been prepared and their association properties in pentane investigated by {sup 51}V NMR. Limiting (low concentration) {delta}({sup 51}V) values depend on the bulk of R (highest {sup 51}V shielding for tBu). Shielding decreases with increasing concentration (more pronounced for small R groups), owing to the formation of oligomers, probably connected by {mu}-OR groups. The X-ray diffraction study of VO(OCH{sub 2}CH{sub 2}Cl){sub 3} reveals dimer association of molecules belonging to adjacent unit cells via long V-OR bonds (226.1 (2) pm), and a trigonal-bipyramidal geometry for each monomeric unit. From the reaction between VOCl{sub 3} and diols (glycol, 1,3-propanediol, 1,2-, 2,3-, 1,3-, and 1,4-butanediol), complexes are obtained that contain the {l brace}VOCl(OR){sub 2}{r brace} and {l brace}VOCl{sub 2}OR{r brace} moieties and the alcohol coordinated in the monofunctional or bifunctional (chelating and bridging) mode. The {sup 51}V NMR spectrum of VOCl{sub 2}OCH(Me)CH(Me)OH exhibits resolved {sup 51}V-{sup 35,37}Cl coupling: J({sup 51}V-{sup 35}Cl) = 100 Hz; J({sup 51}V-{sup 37}Cl) = 83 Hz. V{sup V}OCl{sub 2}(OCH{sub 2}CH{sub 2}CH{sub 2}OH) reacts with 1,4-butanediol to form V{sup IV}OCl{sub 2}(THF){sub 2}(OH{sub 2}). In the presence of COCL{sub 3}, THF undergoes ether splitting, chlorination, and coordination to vanadium to yield VOCl{sub 2}(OCH{sub 2}CH{sub 2}CH{sub 2}CH{sub 2}Cl). 35 refs., 7 figs., 7 tabs.

  13. Solid-state NMR relaxation studies of Australian spider silks.

    PubMed

    Kishore, A I; Herberstein, M E; Craig, C L; Separovic, F

    Solid-state NMR techniques were used to study two different types of spider silk from two Australian orb-web spider species, Nephila edulis and Argiope keyserlingi. A comparison of (13)C-T(1) and (1)H-T(1rho) solid-state NMR relaxation data of the Ala Calpha, Ala Cbeta, Gly Calpha, and carbonyl resonances revealed subtle differences between dragline and cocoon silk. (13)C-T(1rho) and (1)H-T(1) relaxation experiments showed significant differences between silks of the two species with possible structural variations. Comparison of our data to previous (13)C-T(1) relaxation studies of silk from Nephila clavipes (A. Simmons et al., Macromolecules, 1994, Vol. 27, pp. 5235-5237) also supports the finding that differences in molecular mobility of dragline silk exist between species. Interspecies differences in silk structure may be due to different functional properties. Relaxation studies performed on wet (supercontracted) and dry silks showed that the degree of hydration affects relaxation properties, and hence changes in molecular mobility are correlated with functional properties of silk. Copyright 2002 Wiley Periodicals, Inc.

  14. NMR Study of Organic Counterion Binding to Perfluorinated Micellar Structures

    NASA Astrophysics Data System (ADS)

    Bossev, Dobrin; Matsumoto, Mustuo; Nakahara, Masaru

    2008-03-01

    In this study we have applied our previously developed NMR method to study the adsorption of tetramethylammonium (TMA^+) and tetraethylammonium (TEA^+) counterions to micelles formed by perfluorooctylsulfonate (FOS^-) surfactant in water at 30 C. These two counterions induce formation of threadlike surfactant structures that result in well pronounced viscoelastic properties of the solution. To selectively probe the degree of counterion binding we have used ^1H and ^19F NMR chemical shifts and self-diffusion coefficients that are sensitive to the Stern and diffuse double layers, respectively. The competitive adsorption of TMA^+ and TEA^+ was examined as a function of the TMA^+/TEA^+ ratio at a constant FOS^- concentration of 100 mM. The two counterions were found to form Stern layer around the FOS^- micelles with comparable packing; about one counterion per two micellized FOS molecules. When mixed at intermediate proportions, however, the TEA^+ counterion shows preferential binding; the concentration of TEA^+ in the Stern layer is found to be twice higher than that of TMA^+ at equal total respective concentrations in the solution. These results are discussed in terms of counterion size and hydrophobicity and presented in parallel with those that involved the smaller and more hydrophilic lithium counterion.

  15. Tricritical point in ferroelastic ammonium titanyl fluoride: NMR study

    SciTech Connect

    Kavun, V.Ya.; Kozlova, S.G.; Laptash, N.M; Tkachenko, I.A.; Gabuda, S.P

    2010-09-15

    Ionic mobility and phase transitions in ammonium titanyl pentafluoride (NH{sub 4}){sub 3}TiOF{sub 5} were studied using the {sup 19}F and {sup 1}H NMR data. The high-temperature phase (I) is characterized by spherically symmetric (isotropic) reorientation of [TiOF{sub 5}]{sup 3-} anions and by uniaxial reorientation of these anions in the ferroelastic phase II. A previously unknown second-order phase transition to the low-temperature modification (NH{sub 4}){sub 3}TiOF{sub 5}(III) was found at 205 K. The transition is accompanied by hindering of uniaxial rotations of [TiOF{sub 5}]{sup 3-} anions and by noticeable change of {sup 19}F magnetic shielding tensor associated with the influence of pseudo-Jahn-Teller effect. A pressure-induced tricritical point with coordinates p{sub TCR{approx}}2 kbar and T{sub TCR{approx}}170 K is estimated on the base of {sup 19}F NMR chemical shift data, and previously studied p-T diagram of (NH{sub 4}){sub 3}TiOF{sub 5}. - Graphical abstract: p-T phase diagram of (NH{sub 4}){sub 3}TiOF{sub 5}.

  16. Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

    NASA Technical Reports Server (NTRS)

    Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C.

    2000-01-01

    The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

  17. Rate Constant and RRKM Product Study for the Reaction Between CH3 and C2H3 at T = 298K

    NASA Technical Reports Server (NTRS)

    Thorn, R. Peyton, Jr.; Payne, Walter A., Jr.; Chillier, Xavier D. F.; Stief, Louis J.; Nesbitt, Fred L.; Tardy, D. C.

    2000-01-01

    The total rate constant k1 has been determined at P = 1 Torr nominal pressure (He) and at T = 298 K for the vinyl-methyl cross-radical reaction CH3 + C2H3 yields products. The measurements were performed in a discharge flow system coupled with collision-free sampling to a mass spectrometer operated at low electron energies. Vinyl and methyl radicals were generated by the reactions of F with C2H4 and CH4, respectively. The kinetic studies were performed by monitoring the decay of C2H3 with methyl in excess, 6 < |CH3|(sub 0)/|C2H3|(sub 0) < 21. The overall rate coefficient was determined to be k1(298 K) = (1.02 +/- 0.53)x10(exp -10) cubic cm/molecule/s with the quoted uncertainty representing total errors. Numerical modeling was required to correct for secondary vinyl consumption by reactions such as C2H3 + H and C2H3 + C2H3. The present result for k1 at T = 298 K is compared to two previous studies at high pressure (100-300 Torr He) and to a very recent study at low pressure (0.9-3.7 Torr He). Comparison is also made with the rate constant for the similar reaction CH3 + C2H5 and with a value for k1 estimated by the geometric mean rule employing values for k(CH3 + CH3) and k(C2H3 + C2H3). Qualitative product studies at T = 298 K and 200 K indicated formation of C3H6, C2H2, and C2H5 as products of the combination-stabilization, disproportionation, and combination-decomposition channels, respectively, of the CH3 + C2H3 reaction. We also observed the secondary C4H8 product of the subsequent reaction of C3H5 with excess CH3; this observation provides convincing evidence for the combination-decomposition channel yielding C3H5 + H. RRKM calculations with helium as the deactivator support the present and very recent experimental observations that allylic C-H bond rupture is an important path in the combination reaction. The pressure and temperature dependencies of the branching fractions are also predicted.

  18. Phenol-formaldehyde resins: A quantitative NMR study of molecular structure and molecular dynamics

    NASA Astrophysics Data System (ADS)

    Ottenbourgs, Benjamin Tony

    criteria to follow the curing evolution. FT-Raman spectroscopy showed to be complementary to 13C NMR for the determination of the degree of polymerization and of conversion in PF prepolymers or in cured PF resins. In the last part of this work it was shown that 1H wideline and 13C CP/MAS solid-state NMR relaxometry provides interesting information concerning the molecular dynamics of cured novolak resins and resole/novolak copolymers. The relaxation times investigated were the spin-lattice relaxation time (T 1H), the spin-lattice relaxation time in the rotating frame (T 1pH), and the spin-spin relaxation time (T 2H). It was noticed that these relaxation times of the PF resins, at temperatures below the glass transition temperature, were ascertained not only by dynamic phenomena, but also a contribution from the spin diffusion mechanism should be implemented. Measurements as a function of the temperature indicated for a reversible hydrogen bond deformation, confirmed by FT-IR measurements. 13C CP/MAS and 1H wideline NMR can be applied as complementary techniques in order to investigate phenol-formaldehyde resins in the solid state. The chemical structure and the molecular dynamics of these resins can be studied in an adequate manner. Correlations can be made between their relaxation times, their chemical structure and their macroscopic properties.

  19. Entangled Polymer Melt Dynamics Studied By Low-Field NMR

    NASA Astrophysics Data System (ADS)

    Vaca Chavez, Fabian; Huebsch, Patrick; Zirbs, Ronald; Binder, Wolfgang; Saalwaechter, Kay

    2009-03-01

    Proton Multiple-Quantum (MQ) NMR is a powerful technique to investigate polymer dynamics due to its sensitivity to molecular motions on very different timescales. Entangled melts exhibit dynamic processes that cover a wide range of timescales, starting from fast ps-scale segmental reorientation up to diffusive and cooperative motions on the ms-s-scale. In this work, we apply MQ NMR to linear poly(cis-1,4-isoprene) and poly(isobutylene) of different molecular weight above the glass transition over suitable ranges of temperature, in order to establish the dynamic regimes predicted by the tube model, and, for the first time, to extract actual time scale information. This directly complements many neutron scattering studies, which are restricted to the sub-μs-timescale. Measurements on PIB-grafted silica particles with different molecular weights and different chain densities on the surface of the particle are also shown. The data is analyzed by establishing scaling laws which can be directly associated with different dynamic regimes predicted by the tube/reptation model. Full analytical analyses based on a correlation function which explicitly includes segmental, Rouse, and reptation dynamics are discussed.

  20. Effects of nucleotide binding to LmrA: A combined MAS-NMR and solution NMR study.

    PubMed

    Hellmich, Ute A; Mönkemeyer, Leonie; Velamakanni, Saroj; van Veen, Hendrik W; Glaubitz, Clemens

    2015-12-01

    ABC transporters are fascinating examples of fine-tuned molecular machines that use the energy from ATP hydrolysis to translocate a multitude of substrates across biological membranes. While structural details have emerged on many members of this large protein superfamily, a number of functional details are still under debate. High resolution structures yield valuable insights into protein function, but it is the combination of structural, functional and dynamic insights that facilitates a complete understanding of the workings of their complex molecular mechanisms. NMR is a technique well-suited to investigate proteins in atomic resolution while taking their dynamic properties into account. It thus nicely complements other structural techniques, such as X-ray crystallography, that have contributed high-resolution data to the architectural understanding of ABC transporters. Here, we describe the heterologous expression of LmrA, an ABC exporter from Lactococcus lactis, in Escherichia coli. This allows for more flexible isotope labeling for nuclear magnetic resonance (NMR) studies and the easy study of LmrA's multidrug resistance phenotype. We use a combination of solid-state magic angle spinning (MAS) on the reconstituted transporter and solution NMR on its isolated nucleotide binding domain to investigate consequences of nucleotide binding to LmrA. We find that nucleotide binding affects the protein globally, but that NMR is also able to pinpoint local dynamic effects to specific residues, such as the Walker A motif's conserved lysine residue.

  1. Application of chirally-deuterated (S)-D-(6-2H1)glucose to conformational studies

    USDA-ARS?s Scientific Manuscript database

    Deuterated sugars are widely used to elucidate mechanisms of biosynthesis and of chemical reactions, and to confirm assignments of complex NMR or mass spectra. To date, however, there are few reported syntheses for regio and stereospecifically deuterated pyranoses. Chirally-deuterated (S)-D-(6-**2...

  2. Thermal decomposition of (UO2)O2(H2O)2·2H2O: Influence on structure, microstructure and hydrofluorination

    NASA Astrophysics Data System (ADS)

    Thomas, R.; Rivenet, M.; Berrier, E.; de Waele, I.; Arab, M.; Amaraggi, D.; Morel, B.; Abraham, F.

    2017-01-01

    The thermal decomposition of uranyl peroxide tetrahydrate, (UO2)O2(H2O)2.2H2O, was studied by combining high temperature powder X-ray diffraction, scanning electron microscopy, thermal analyses and spectroscopic techniques (Raman, IR and 1H NMR). In situ analyses reveal that intermediates and final uranium oxides obtained upon heating are different from that obtained after cooling at room temperature and that the uranyl precursor used to synthesize (UO2)O2(H2O)2·2H2O, sulfate or nitrate, has a strong influence on the peroxide thermal behavior and morphology. The decomposition of (UO2)O2(H2O)2·2H2O ex sulfate is pseudomorphic and leads to needle-like shaped particles of metastudtite, (UO2)O2(H2O)2, and UO3-x(OH)2x·zH2O, an amorphous phase found in air in the following of (UO2)O2(H2O)2 dehydration. (UO2)O2(H2O)2·2H2O and the compounds resulting from its thermal decomposition are very reactive towards hydrofluorination as long as their needle-like morphology is kept.

  3. ESR study of p-type natural 2H-polytype MoS2 crystals: The As acceptor activity

    NASA Astrophysics Data System (ADS)

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

    2016-10-01

    Low-temperature (T = 1.7-77 K) multi frequency electron spin resonance (ESR) study on p-type 2H-polytype geological MoS2 crystals reveals p-type doping predominantly originating from As atoms substituting for S sites in densities of (2.4 ± 0.2) × 1017 cm-3. Observation of a "half field"(g ˜ 3.88) signal firmly correlating with the central Zeeman As accepter signal indicates the presence of spin S > ½ As agglomerates, which together with the distinct multicomponent makeup of the Zeeman signal points to manifest non-uniform As doping; only ˜13% of the total As response originates from individual decoupled As dopants. From ESR monitoring the latter vs. T, an activation energy Ea = (0.7 ± 0.2) meV is obtained. This unveils As as a noticeable shallow acceptor dopant, appropriate for realization of effective p-type doping in targeted 2D MoS2-based switching devices.

  4. Ordered and Disordered Phases Coexist in Plasma Membrane Vesicles of RBL-2H3 Mast Cells. An ESR Study

    PubMed Central

    Ge, Mingtao; Gidwani, Arun; Brown, H. Alex; Holowka, David; Baird, Barbara; Freed, Jack H.

    2003-01-01

    Four chain spin labels and a spin-labeled cholestane were used to study the dynamic structure of plasma membrane vesicles (PMV) prepared from RBL-2H3 mast cells at temperatures ranging from 22°C to 45°C. Analysis shows that the spectra from most labels consist of two components. The abundant spectral components exhibit substantial ordering that is intermediate between that of a liquid-ordered (Lo) phase, and that of a liquid-crystalline (Lc) phase as represented by model membranes. Also, rotational diffusion rates of the spin labels are comparable to those in the Lo phase. In contrast, the ordering for the less abundant components is much lower. These results indicate that a Lo-like region or phase (the abundant component) and an Lc-like region or phase (the less abundant component) coexist in the PMV. In contrast, membranes reconstituted from extracted lipids exhibit the more ordered phase only. This suggests that membrane-associated proteins are important for the coexistence of Lo-like and Lc-like regions in the plasma membrane. In addition, binding of the myristoylated protein, ARF6 to PMV, leads to a new spectral component for a headgroup lipid spin label that indicates the formation of plasma membrane defects by this low molecular weight GTPase. PMID:12885671

  5. Synthesis, antimicrobial activity and QSAR studies of new 2,3-disubstituted-3,3a,4,5,6,7-hexahydro-2H-indazoles.

    PubMed

    Minu, Maninder; Thangadurai, Ananda; Wakode, Sharad Ramesh; Agrawal, Shyam Sundar; Narasimhan, Balasubramanian

    2009-06-01

    Antimicrobial activity of synthesized 2,3-disubstituted-3,3a,4,5,6,7-hexahydro-2H-indazole derivatives indicated that 3-(4-chlorophenyl)-2-(4-nitrophenylsulfonyl)-3,3a,4,5,6,7-hexahydro-2H-indazole (6) and 3-(4-fluorophenyl)-2-(4-nitrophenylsulfonyl)-3,3a,4,5,6,7-hexahydro-2H-indazole (20) were the most active compounds. Further, the results of QSAR studies indicated the importance of topological parameters (2)chi and (2)chi(v) in defining the antimicrobial activity of hexahydroindazoles.

  6. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations.

    PubMed

    Cao, Jun

    2015-06-28

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π(*) transition induces a cleavage of the C-N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π(*) excitation of the imine chromophore results in a cleavage of the C-C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N-O bond cleavages on both S1((1)ππ(*)) and S2((1)nNπ(*)) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  7. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    NASA Astrophysics Data System (ADS)

    Cao, Jun

    2015-06-01

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π* transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π* excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S1(1ππ*) and S2(1nNπ*) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  8. Photoinduced reactions of both 2-formyl-2H-azirine and isoxazole: A theoretical study based on electronic structure calculations and nonadiabatic dynamics simulations

    SciTech Connect

    Cao, Jun

    2015-06-28

    In the present work, the combined electronic structure calculations and dynamics simulations have been performed to explore photocleavages of 2-formyl-2H-azirine and isoxazole in the gas phase and the subsequent rearrangement reactions. The carbonyl n → π{sup *} transition induces a cleavage of the C—N single bond of 2-formyl-2H-azirine to yield β-formylvinylnitrene in open-shell singlet state. However, the n → π{sup *} excitation of the imine chromophore results in a cleavage of the C—C single bond, producing a nitrile ylide intermediate through an internal conversion to the ground state. β-formylvinylnitrene and nitrile ylide with the carbonyl group are easily transformed into 2-formyl-2H-azirine and oxazole, respectively. The N—O bond cleavages on both S{sub 1}({sup 1}ππ{sup *}) and S{sub 2}({sup 1}n{sub N}π{sup *}) of isoxazole are ultrafast processes, and they give products of 2-formyl-2H-azirine, 3-formylketenimine, HCN + CHCHO, and HCO + CHCHN. Both 2H-azirines and ketenimines were suggested to be formed from the triplet vinylnitrenes by intersystem crossing in the previous studies. However, our calculations show that the singlet β-formylvinylnitrene is responsible for the formation of 2-formyl-2H-azirine and 3-formylketenimine, and the singlet vinylnitrenes can play a key role in the photoinduced reactions of both 2H-azirines and isoxazoles.

  9. UV/vis, 1H, and 13C NMR spectroscopic studies to determine mangiferin pKa values.

    PubMed

    Gómez-Zaleta, Berenice; Ramírez-Silva, María Teresa; Gutiérrez, Atilano; González-Vergara, Enrique; Güizado-Rodríguez, Marisol; Rojas-Hernández, Alberto

    2006-07-01

    The acid constants of mangiferin (a natural xanthonoid) in aqueous solution were determined through an UV/vis spectroscopic study employing the SQUAD program as a computational tool. A NMR study complements the pK(a) values assignment and evidences a H-bridge presence on 1-C. The chemical model used was consistent with the experimental data obtained. The pK(a) values determined with this procedure were as follows: H(4)(MGF)=H(3)(MGF)(-)+H(+), pKa1 (6-H)=6.52+/-0.06; H(3)(MGF)(-)=H(2)(MGF)(2-)+H(+), pKa2 (3-H)=7.97+/-0.06; H(2)(MGF)(2-)=H(MGF)(3-)+H(+), pKa3 (7-H)=9.44+/-0.04; H(MGF)(3-)=(MGF)(4-)+H(+), pKa4 (1-H)=12.10+/-0.01; where it has been considered mangiferin C(19)H(18)O(11) as H(4)(MGF). Mangiferin UV/vis spectral behavior, stability study in aqueous solution as well as NMR spectroscopy studies: one-dimensional (1)H,(13)C, 2D correlated (1)H/(13)C performed by (g)-HSQC and (g)-HMBC methods; are also presented. pK(a) values determination of H(4)(MGF) in aqueous solution is a necessary contribution to subsequent pharmacokinetic study, and a step towards the understanding of its biological effects.

  10. NMR structural studies of PECVD amorphous silicon films

    NASA Astrophysics Data System (ADS)

    Cull, Thomas Sidley, Jr.

    The properties of plasma enhanced chemical vapor deposition (PECVD) amorphous semiconductor films vary depending upon preparation conditions and doping. Hydrogenated amorphous silicon films (a-Si:H) have some properties that make these films desirable for use in solar cells and photoreceptor devices. Maximizing electronic and structural properties of such films is key to their success. Nuclear magnetic resonance, and in particular deuterium magnetic resonance (DMR) for a-Si:H,D films, is a useful means to study the morphology of such samples. The location and motions of hydrogen and the chemically equivalent deuterium within an amorphous semiconductor film can be observed with NMR. The information from the NMR studies can be correlated with electronic properties studies to determine whether a given sample would make a successful photovoltaic device. This thesis focuses on three aspects of study: comparison of two samples that differ in the bias applied to the substrate upon which the amorphous films were grown; derivation of relaxation parameters for covalently bonded deuterium; development of a new pulse sequence "incremental spin echo double resonance (SEDOR)" to study the number of unlike spins that contribute to the local field of a given nuclei. Four significant conclusions can be drawn. First, the electronic quality as measured by the photoresponse product etamutau correlates with the broad Gaussian DMR spectral feature which arises from molecular hydrogen in sites that restrict motion. Second, the relaxation of nuclear magnetization under extreme inhomogeneous broadening can be modeled very well as the relaxation without spin diffusion to faster relaxing species within a sample. Third, incremental SEDOR has either a quantum mechanical or classical behavior depending upon the length of the pulse spacing in comparison to the spin-spin relaxation time. Fourth, the local field at the hydrogen of an HD pair within an a-Si:H,D sample is determined on average by

  11. 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.

  12. Unilateral NMR study of a XVI century wall painted

    NASA Astrophysics Data System (ADS)

    Proietti, N.; Capitani, D.; Rossi, E.; Cozzolino, S.; Segre, A. L.

    2007-06-01

    Wall paintings in the XVI century Serra Chapel in the "Chiesa di Nostra Signora del Sacro Cuore" Rome, have been studied using unilateral NMR. In order to map the distribution of moisture content in the wall painted, a large number of Hahn echo measurements, covering large areas of the wall painting were performed. Because the intensity of the Hahn echo is proportional to the amount of moisture in the area under study, the experimental data were transformed into 2D gradient colour maps which allowed an easy visualization of the moisture content of the wall. The state of conservation of the wall painting was monitored using T2 measurements specially with regards to outcropping salt.

  13. 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.

  14. The {sup 2}H(d,p){sup 3}H Reaction At Astrophysical Energies Studied Via The Trojan Horse Method And Pole Approximation Validity Test

    SciTech Connect

    Sparta, R.; Pizzone, R. G.; Spitaleri, C.; Cherubini, S.; Crucilla, V.; Gulino, M.; La Cognata, M.; Lamia, L.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.; Aliotta, M.; Burjan, V.; Hons, Z.; Kroha, V.; Mrazek, J.; Kiss, G.; McCleskey, M.; Trache, L.

    2010-03-01

    In order to understand primordial and stellar nucleosynthesis, we have studied {sup 2}H(d,p){sup 3}H reaction at 0, 4 MeV down to astrophysical energies. Knowledge of this S-factor is interesting also to plan reactions for fusion reactors to produce energy. {sup 2}H(d,p){sup 3}H has been studied through the Trojan Horse Method applied to the three-body reaction {sup 2}H({sup 3}He,pt)H, at a beam energy of 17 MeV. Once protons and tritons are detected in coincidence and the quasi-free events are selected, the obtained S-factor has been compared with direct reactions results. Such data are in agreement with the direct ones, and a pole invariance test has been obtained comparing the present result with another {sup 2}H(d,p){sup 3}H THM one, performed with a different spectator particle (see fig. 1).

  15. NMR Studies of Protein Hydration and Protein-Ligand Interactions

    NASA Astrophysics Data System (ADS)

    Chong, Yuan

    Water on the surface of a protein is called hydration water. Hydration water is known to play a crucial role in a variety of biological processes including protein folding, enzymatic activation, and drug binding. Although the significance of hydration water has been recognized, the underlying mechanism remains far from being understood. This dissertation employs a unique in-situ nuclear magnetic resonance (NMR) technique to study the mechanism of protein hydration and the role of hydration in alcohol-protein interactions. Water isotherms in proteins are measured at different temperatures via the in-situ NMR technique. Water is found to interact differently with hydrophilic and hydrophobic groups on the protein. Water adsorption on hydrophilic groups is hardly affected by the temperature, while water adsorption on hydrophobic groups strongly depends on the temperature around 10 C, below which the adsorption is substantially reduced. This effect is induced by the dramatic decrease in the protein flexibility below 10 C. Furthermore, nanosecond to microsecond protein dynamics and the free energy, enthalpy, and entropy of protein hydration are studied as a function of hydration level and temperature. A crossover at 10 C in protein dynamics and thermodynamics is revealed. The effect of water at hydrophilic groups on protein dynamics and thermodynamics shows little temperature dependence, whereas water at hydrophobic groups has stronger effect above 10 C. In addition, I investigate the role of water in alcohol binding to the protein using the in-situ NMR detection. The isotherms of alcohols are first measured on dry proteins, then on proteins with a series of controlled hydration levels. The free energy, enthalpy, and entropy of alcohol binding are also determined. Two distinct types of alcohol binding are identified. On the one hand, alcohols can directly bind to a few specific sites on the protein. This type of binding is independent of temperature and can be

  16. ¹H NMR and hyperpolarized ¹³C NMR assays of pyruvate-lactate: a comparative study.

    PubMed

    Hill, Deborah K; Jamin, Yann; Orton, Matthew R; Tardif, Nicolas; Parkes, Harold G; Robinson, Simon P; Leach, Martin O; Chung, Yuen-Li; Eykyn, Thomas R

    2013-10-01

    Pyruvate-lactate exchange is mediated by the enzyme lactate dehydrogenase (LDH) and is central to the altered energy metabolism in cancer cells. The measurement of exchange kinetics using hyperpolarized (13) C NMR has provided a biomarker of response to novel therapeutics. However, the observable signal is restricted to the exchanging hyperpolarized (13) C pools and the endogenous pools of (12) C-labelled metabolites are invisible in these measurements. In this study, we investigated an alternative in vitro (1) H NMR assay, using [3-(13) C]pyruvate, and compared the measured kinetics with a hyperpolarized (13) C NMR assay, using [1-(13) C]pyruvate, under the same conditions in human colorectal carcinoma SW1222 cells. The apparent forward reaction rate constants (kPL ) derived from the two assays showed no significant difference, and both assays had similar reproducibility (kPL  = 0.506 ± 0.054 and kPL  = 0.441 ± 0.090 nmol/s/10(6) cells; mean ± standard deviation; n = 3); (1) H, (13) C assays, respectively). The apparent backward reaction rate constant (kLP ) could only be measured with good reproducibility using the (1) H NMR assay (kLP  = 0.376 ± 0.091 nmol/s/10(6) cells; mean ± standard deviation; n = 3). The (1) H NMR assay has adequate sensitivity to measure real-time pyruvate-lactate exchange kinetics in vitro, offering a complementary and accessible assay of apparent LDH activity.

  17. NMR studies on an oligodeoxynucleotide containing 2-aminopurine opposite adenine

    SciTech Connect

    Fazakerley, G.V.; Sowers, L.C.; Eritja, R.; Kaplan, B.E.; Goodman, M.F.

    1987-09-08

    A heteroduplex containing the mismatch 2-aminopurine (AP)-adenine has been synthesized and studied by proton NMR. The mismatch was incorporated into the sequence d(CGG(AP)GGC) x d-(GCCACCG). One-dimensional nuclear Overhauser effect measurements in H/sub 2/O and two-dimensional nuclear Overhauser effect spectra in D/sub 2/O show AP x A base pairs in a wobble structure in which both bases are in the anti conformation. The adenine is stacked well in the helix, but the helix twist between the adenine and neighboring cytosine in the 3' direction is unusually small. As a result, the aminopurine on the opposite strand is somewhat pushed out of the helix. From the measurements of the imino proton line widths, the two adjacent G x C base pairs are not found to be significantly destabilized by the presence of the purine-purine wobble pair.

  18. Ion transport in porous media studied by NMR.

    PubMed

    Pel, L; Huinink, H P; Kopinga, K; Rijniers, L A; Kaasschieter, E F

    2001-01-01

    Moisture and salt transport in masonry can give rise to damages. Therefore a detailed knowledge of the moisture and salt transport is essential for understanding the durability of masonry. A special NMR apparatus has been made allowing quasi-simultaneous measurements of both moisture and Na profiles in porous building materials. Using this apparatus both the absorption of a 4 M NaCl solution in a calcium silicate brick and the drying of a 3 M NaCl capillary saturated fired-clay brick have been studied. It was found that during the absorption process the Na ions clearly stay behind, which this is caused by adsorption of these ions to the pore surface. For the drying it was found that at the beginning of the drying process the ions accumulate near the surface. As the drying rate decreases, diffusion becomes dominant and the ion profile levels off again.

  19. NMR and molecular mechanics study of pyrethrins I and II.

    PubMed

    Rugutt, J K; Henry, C W; Franzblau, S G; Warner, I M

    1999-08-01

    Bioassay-directed fractionation of the organic extract of the Kenyan pyrethrum flowers (Chrysanthemum cinerariaefolium Vissiani) resulted in the isolation of two natural pyrethrin esters, pyrethrin I (PI) and pyrethrin II (PII) as the major constituents. These esters elicited inhibition of the multiple drug resistant (MDR) Mycobacterium tuberculosis. The high-field (1)H and (13)C nuclear magnetic resonance (NMR) chemical shifts of PI and PII were unequivocally assigned using modern two-dimensional (2D) proton-detected heteronuclear multiple-quantum coherence (HMQC) and heteronuclear multiple-bond correlation (HMBC) experiments. The conformations of both esters were deduced from (1)H-(1)H vicinal coupling constants and confirmed by 2D nuclear Overhauser effect spectroscopy (NOESY). Computer molecular modeling (MM) studies revealed that PI and PII molecules adopt a "love-seat" conformation in chloroform (CDCl(3)) solution.

  20. Mass transfer in chromatographic columns studied by PFG NMR.

    PubMed

    Tallarek, U; van Dusschoten, D; Van As, H; Guiochon, G; Bayer, E

    1998-01-01

    Pulsed field gradient (PFG) nuclear magnetic resonance (NMR) is applied to study convective and diffusional transport in chromatographic columns packed with totally porous support particles. Here stagnant zones exist in the particle pores, and diffusional mass-transfer limitations between fluid molecules diffusing in the intraparticle pore network and flowing in the interparticle void space are detected quantitatively. Axial displacement probability distributions were measured for water over a range of Peclet numbers and observation times, with diffusion lengths between 0.15 and 0.91 times the average support particle diameter. The transition towards complete diffusional exchange is demonstrated, thereby also revealing the development of the classical convective dispersion process in a packed bed of (porous) particles.

  1. Ultra-broadband NMR probe: numerical and experimental study of transmission line NMR probe.

    PubMed

    Kubo, Atsushi; Ichikawa, Shinji

    2003-06-01

    We have reinvestigated a transmission line NMR probe first published by Lowe and co-workers in 1970s [Rev. Sci. Instrum. 45 (1974) 631; 48 (1977) 268] numerically and experimentally. The probe is expected to be ultra-broadband, thus might enable new types of solid-state NMR experiments. The NMR probe consists of a coil and capacitors which are connected to the coil at regular intervals. The circuit is the same as a cascaded LC low-pass filter, except there are nonzero mutual inductances between different coil sections. We evaluated the mutual inductances by Neumann's formula and calculated the electrical characteristics of the probe as a function of a carrier frequency. We found that they were almost the same as those of a cascaded LC low-pass filter, when the inductance L of a section was estimated from the inductance of the whole coil divided by the number of the sections, and if C was set to the capacitance in a section. For example, the characteristic impedance of a transmission line coil is given by Z=(L/C)(1/2). We also calculated the magnitude and the distribution of RF magnetic field inside the probe. The magnitude of RF field decreases when the carrier frequency is increased because the phase delay between neighboring sections is proportional to the carrier frequency. For cylindrical coils, the RF field is proportional to (pinu/2nu(d))(1/2)exp(-nu/nu(d)), where the decay frequency nu(d) is determined by the dimensions of the coil. The observed carrier frequency thus must be much smaller than the decay frequency. This condition restricts the size of transmission line coils. We made a cylindrical coil for a 1H NMR probe operating below 400 MHz. It had a diameter 2.3mm and a pitch 1.2mm. Five capacitors of 6pF were connected at every three turns. The RF field strength was 40 and 60 kHz at the input RF power 100 W by a calculation and by experiments, respectively. The calculations showed that the RF field inhomogeneity along the coil axis was caused by a

  2. A theoretical study of the CH[sub 3]+C[sub 2]H[sub 2] reaction

    SciTech Connect

    Diau, E.W.; Lin, M.C. ); Melius, C.F. )

    1994-09-01

    The rate constants for the formation of various products in the CH[sub 3]+C[sub 2]H[sub 2] reaction have been computed by multichannel RRKM calculations using the molecular and transition-state parameters predicted by the BAC-MP4 method. The results of the calculations agree quantitatively with experimental data obtained under varying conditions: [ital T]=300--2200 K, [ital P]=30--2500 Torr. At low temperatures ([ital T][lt]1300 K), the CH[sub 3]+C[sub 2]H[sub 2] reaction is dominated by the addition-stabilization process producing CH[sub 3]C[sub 2]H[sub 2]. Under high-temperature ([ital T][gt]1400 K) and atmospheric-pressure conditions, the reaction occurs primarily by the CH[sub 3]-for-H displacement process producing CH[sub 3]C[sub 2]H, a likely source of the C[sub 3]H[sub 3] radical (which has recently been shown to be a key precursor of C[sub 6]H[sub 6] in hydrocarbon combustion reactions).

  3. Theoretical study of the potential energy surface governing the stereochemistry in ClC sub 2 H sub 4 reactions

    SciTech Connect

    Engels, B.; Peyerimhoff, S.D. ); Skell, P.S. )

    1990-02-22

    Large-scale multireference configuration interaction calculations in a double-{xi}-type AO basis including polarization functions are carried out for the potential surface of the ClC{sub 2}H{sub 4} system. The charge distribution for various extreme points of the surface is discussed. The absolute minimum is found for an asymmetric ClC{sub 2}H{sub 4} structure. The symmetrical bridged nuclear conformation is also found to be stable with respect to dissociation into Cl + C{sub 2}H{sub 4}. The activation energy for rotation about the C-C axis is calculated to be around 18 kJ/mol, which is comparable to that for the 1,2 migration (around 26 kJ mol). The stereochemistry is governed by the fact that addition of Cl to C{sub 2}H{sub 4} (or dissociation) is a two-step reaction proceeding through a symmetrical intermediate. The direct addition pathway possesses a small barrier of about 8 kJ/mol.

  4. 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

  5. Magnetic Shielding Studies of C2 and C2 H2 Support Higher than Triple Bond Multiplicity in C2.

    PubMed

    Karadakov, Peter B; Kirsopp, Josh

    2017-07-17

    The carbon-carbon bonds in the ground states of C2 and C2 H2 , at their equilibrium geometries, are compared by analysing the changes in the off-nucleus magnetic shielding tensor within the space surrounding each of these molecules. A wide range of quantum-chemical approaches, including full-valence CASSCF-GIAO, CCSD(T)-GIAO and CCSDT-GIAO, all with the cc-pVQZ basis set, as well as HF-GIAO and MP2-GIAO, with the cc-pVQZ, cc-pV5Z and cc-pV6Z basis sets, show that the surroundings of the carbon-carbon bond in C2 are more shielded than those of the carbon-carbon bond in C2 H2 . The additional shielding of the carbon-carbon bond in C2 is found to be due to a larger paramagnetic contribution to the component of the shielding tensor which is perpendicular to the molecular axis. The analysis of the off-nucleus shielding data indicates that the carbon-carbon bond in C2 is "bulkier" and, therefore, of a higher multiplicity, but weaker than the corresponding bond in C2 H2 . According to the results of the shielding calculations, the carbon nuclei in C2 should be much more shielded than those in C2 H2 , with (13) C isotropic magnetic shieldings in the ranges of around 224-227 ppm and around 123-125 ppm for C2 and C2 H2 , respectively. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  6. Freezing point depression of water in phospholipid membranes: a solid-state NMR study.

    PubMed

    Lee, Dong-Kuk; Kwon, Byung Soo; Ramamoorthy, Ayyalusamy

    2008-12-02

    Lipid-water interaction plays an important role in the properties of lipid bilayers, cryoprotectants, and membrane-associated peptides and proteins. The temperature at which water bound to lipid bilayers freezes is lower than that of free water. Here, we report a solid-state NMR investigation on the freezing point depression of water in phospholipid bilayers in the presence and absence of cholesterol. Deuterium NMR spectra at different temperatures ranging from -75 to + 10 degrees C were obtained from fully (2)H2O-hydrated POPC (1-palmitoyl-2-oleoylphosphatidylcholine) multilamellar vesicles (MLVs), prepared with and without cholesterol, to determine the freezing temperature of water and the effect of cholesterol on the freezing temperature of water in POPC bilayers. Our 2H NMR experiments reveal the motional behavior of unfrozen water molecules in POPC bilayers even at temperatures significantly below 0 degrees C and show that the presence of cholesterol further lowered the freezing temperature of water in POPC bilayers. These results suggest that in the presence of cholesterol the fluidity and dynamics of lipid bilayers can be retained even at very low temperatures as exist in the liquid crystalline phase of the lipid. Therefore, bilayer samples prepared with a cryoprotectant like cholesterol should enable the performance of multidimensional solid-state NMR experiments to investigate the structure, dynamics, and topology of membrane proteins at a very low temperature with enhanced sample stability and possibly a better sensitivity. Phosphorus-31 NMR data suggest that lipid bilayers can be aligned at low temperatures, while 15N NMR experiments demonstrate that such aligned samples can be used to enhance the signal-to-noise ratio of is 15N chemical shift spectra of a 37-residue human antimicrobial peptide, LL-37.

  7. Freezing Point Depression of Water in Phospholipid Membranes — A Solid-State NMR Study

    PubMed Central

    Lee, Dong-Kuk; Kwon, ByungSoo; Ramamoorthy, Ayyalusamy

    2009-01-01

    Lipid-water interaction plays an important role in the properties of lipid bilayers, cryoprotectants, and membrane-associated peptides and proteins. The temperature at which water bound to lipid bilayers freezes is lower than that of free water. Here, we report a solid-state NMR investigation on the freezing point depression of water in phospholipid bilayers in the presence and absence of cholesterol. Deuterium NMR spectra at different temperatures ranging from -75 to +10°C were obtained from fully 2H2O-hydrated POPC (1-palmitoyl-2-oleoyl-phosphatidylcholine) multilamellar vesicles (MLVs), prepared with and without cholesterol, to determine the freezing temperature of water and the effect of cholesterol on the freezing temperature of water in POPC bilayers. Our 2H NMR experiments reveal the motional behavior of unfrozen water molecules in POPC bilayers even at temperatures significantly below 0°C and show that the presence of cholesterol further lowered the freezing temperature of water in POPC bilayers. These results suggest that in the presence of cholesterol the fluidity and dynamics of lipid bilayers can be retained even at very low temperatures as exist in the liquid crystalline phase of the lipid. Therefore, bilayer samples prepared with a cryoprotectant like cholesterol should enable the performance of multidimensional solid-state NMR experiments to investigate the structure, dynamics, and topology of membrane proteins at a very low temperature with enhanced sample stability and possibly a better sensitivity. Phosphorus-31 NMR data suggest that lipid bilayers can be aligned at low temperatures, while 15N NMR experiments demonstrate that such aligned samples can be used to enhance the signal-to-noise ratio of 15N chemical shift spectra of a 37-residue human antimicrobial peptide, LL-37. PMID:18991419

  8. 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.

  9. Homo-C-nucleoside analogs III. Studies on the base-catalyzed dehydrative cyclization of 4-(d-manno-pentitol-1-yl)-2-phenyl-2H-1,2,3-triazole.

    PubMed

    Sallam, Mohammed A E

    2010-10-13

    Treatment of 4-(d-manno-pentitol-1-yl)-2-phenyl-2H-1,2,3-triazole with one molar equivalent of 2,4,6-triisopropylbenzenesulfonyl chloride (TIBSCl) in pyridine solution afforded the homo-C-nucleoside analog; 4-(2,5-anhydro-d-manno-pentitol-1-yl)-2-phenyl-2H-1,2,3-triazole in 54% yield and 4-(α-d-arabinopyranosyl)-2-phenyl-2H1,2,3-triazole analog in 3% yield. The 4-(5-O-triisopropylbenzenesulfonyl)-d-manno-pentitol-1-yl)-2-phenyl-2H-1,2,3-triazole analog was isolated as an intermediate and identified as its tetra-O-acetyl derivative. The 4-(5-chloro-5-deoxy-d-manno-pentitol-1-yl)-2-phenyl-2H-1,2,3-triazole analog was isolated as a byproduct. The structure and anomeric configuration of the products were determined by acylation, NMR spectroscopy, and mass spectrometry.

  10. Beneficial associations of physical activity with 2-h but not fasting blood glucose in Australian adults: the AusDiab study.

    PubMed

    Healy, Genevieve N; Dunstan, David W; Shaw, Jonathan E; Zimmet, Paul Z; Owen, Neville

    2006-12-01

    We examined the associations of physical activity with fasting plasma glucose (FPG) and with 2-h postload plasma glucose (2-h PG) in men and women with low, moderate, and high waist circumference. The Australian Diabetes, Obesity and Lifestyle (AusDiab) study provided data on a population-based cross-sectional sample of 4,108 men and 5,106 women aged >or=25 years without known diabetes or health conditions that could affect physical activity. FPG and 2-h PG were obtained from an oral glucose tolerance test. Self-reported physical activity level was defined according to the current public health guidelines as active (>or=150 min/week across five or more sessions) or inactive (<150 min/week and/or less than five sessions). Sex-specific quintiles of physical activity time were used to ascertain dose response. Being physically active and total physical activity time were independently and negatively associated with 2-h PG. When physical activity level was considered within each waist circumference category, 2-h PG was significantly lower in active high-waist circumference women (beta -0.30 [95% CI -0.59 to -0.01], P = 0.044) and active low-waist circumference men (beta -0.25 [-0.49 to -0.02], P = 0.036) compared with their inactive counterparts. Considered across physical activity and waist circumference categories, 2-h PG levels were not significantly different between active moderate-waist circumference participants and active low-waist circumference participants. Associations between physical activity and FPG were nonsignificant. There are important differences between 2-h PG and FPG related to physical activity. It appears that 2-h PG is more sensitive to the beneficial effects of physical activity, and these benefits occur across the waist circumference spectrum.

  11. Theoretical and Laboratory Studies on the Interaction of Cosmic-Ray Particles with Interstellar Ices. III. Suprathermal Chemistry-Induced Formation of Hydrocarbon Molecules in Solid Methane (CH4), Ethylene (C2H4), and Acetylene (C2H2)

    NASA Astrophysics Data System (ADS)

    Kaiser, R. I.; Roessler, K.

    1998-08-01

    Methane, ethylene, and acetylene ices are irradiated in a ultra high vacuum vessel at 10 K with 9.0 MeV α-particles and 7.3 MeV protons to elucidate mechanisms to form hydrocarbon molecules upon interaction of Galactic cosmic-ray particles with extraterrestrial, organic ices. Theoretical calculations focus on computer simulations of ion-induced collision cascades in irradiated targets. Our experimental and computational investigations reveal that each MeV particle transfers its kinetic energy predominantly through inelastic encounters to the target leading to electronic excitation and ionization of the target molecules. Here electronically excited CH4 species can fragment to mobile H atoms and nonmobile CH3 radicals. The potential energy stored in Coulomb interaction of the CH+4 ions release energetic H and C atoms not in thermal equilibrium with the 10 K target (suprathermal species). Moderated to 1-10 eV kinetic energy, these carbon atoms and those triggered by the elastic energy transfer of the MeV projectile to the target are found to abstract up to two H atoms to yield suprathermal CH and CH2 species. C and CH, as well as CH2, can insert into a CH bond of a CH4 molecule to form methylcarbene (HCCH3), the ethyl radical (C2H5), and ethane (C2H6). HCCH3 either loses H2/2H to form acetylene, C2H2, rearranges to ethylene, C2H4, or adds two H atoms to form ethane, C2H6. C2H5 can abstract or lose an H atom, giving ethane and ethylene, respectively. C2H2 and C2H4 are found to react with suprathermal H atoms to form C2H3 and C2H5, respectively. Overlapping cascades and an increasing MeV ion exposure transforms C2Hx (x = 2, ..., 6) to even more complex alkanes up to C14H30. These elementary reactions of suprathermal species to insert, abstract, and add in/to bonds supply a powerful pathway to form new molecules in icy grain mantles condensed on interstellar grains or in hydrocarbon rich bodies in our solar system even at temperatures as low as 10 K.

  12. Study of the C2H4/Si(100)-(2×1) Interface by Derivative Photoelectron Holography

    NASA Astrophysics Data System (ADS)

    Xu, S. H.; Wu, H. S.; Tong, S. Y.; Keeffe, M.; Lapeyre, G. J.; Rotenberg, E.

    The k derivative spectra (KDS) transform is used for construction of the three-dimensional atomic structure of the C2H4/Si(100)-(2×1) system from photoelectron diffraction data. The image function obtained by the KDS transform clearly observes the second-layer Si atoms and the C emitters apart from the first-layer Si atoms. The observations of the second-layer Si atoms and the C emitters make it easy to measure the C-C bond length correctly. Then a conclusive adsorption model — the di-σ model — for the C2H4/Si(100)-(2×1) system is established. In comparison with the KDS transform, the normal small-cone transform hardly measures the C-C bond length. The ability to observe more scatterers of a photoelectron emitter by the KDS transform expands the applicability of holographic imaging.

  13. High-resolution NMR study of a synthetic DNA-RNA hybrid dodecamer containing the consensus Pribnow promoter sequence

    SciTech Connect

    Chou, S.H.; Flynn, P.; Reid, B. )

    1989-03-21

    The nonsymmetrical double-helical hybrid dodecamer d(CGTTATAATGCG){center dot}r(CGCAUUAUAACG) was synthesized with solid-phase phosphoramidite methods and studied by high-resolution 2D-NMR. The imino protons were assigned by one-dimensional nuclear Overhauser methods. All the base protons and H1', H2', H2'', H3', and H4' sugar protons of the DNA strand and the base protons, H1', H2', and most of the H3'-H4' protons of the RNA strand were assigned by 2D NMR techniques. The well-resolved spectra allowed a qualitative analysis of relative proton-proton distances in both strands of the dodecamer. The chemical shifts of the hybrid duplex were compared to those of the pure DNA double helix with the same sequence. The intrastrand and cross-strand NOEs from adenine H2 to H1' resonances of neighboring base pairs exhibited characteristic patterns that were very useful for checking the spectral assignments, and their highly nonsymmetric nature reveals that the conformations of the two strands are quite different. Detailed analysis of the NOESY and COSY spectra, as well as the chemical shift data, indicate that the RNA strand assumes a normal A-type conformation (C3'-endo) whereas the DNA strand is in the general S domain but not exactly in the normal C2'-endo conformation.

  14. Application of a pyroprobe–deuterium NMR system: Deuterium tracing and mechanistic study of upgrading process for lignin model compounds

    DOE PAGES

    Ben, Haoxi; Jarvis, Mark W.; Nimlos, Mark R.; ...

    2016-03-03

    In this study, a pyroprobe–deuterium (2H) NMR system has been used to identify isotopomer products formed during the deuteration and ring opening of lignin model compounds. Several common model compounds for lignin and its upgraded products, including guaiacol, syringol, toluene, p-xylene, phenol, catechol, cyclohexane, methylcyclohexane, and methylcyclopentane, have been examined for selective ring opening. Similar pathways for upgrading of toluene and p-xylene has been found, which will undergo hydrogenation, methyl group elimination, and ring opening process, and benzene, cyclohexane, and methylcyclohexane have been found as major intermediates before ring opening. Very interestingly, the 2H NMR analysis for the deuterium-traced ringmore » opening of catechol on Ir/γ-Al2O3 is almost identical to the ring opening process for phenol. The ring opening processes for guaiacol and syringol appeared to be very complicated, as expected. As a result, benzene, phenol, toluene, cyclohexane, and methylcyclohexane have been determined to be the major products.« less

  15. Computational study of the rovibrational spectra of CO2-C2H2 and CO2-C2D2

    NASA Astrophysics Data System (ADS)

    Donoghue, Geoff; Wang, Xiao-Gang; Dawes, Richard; Carrington, Tucker

    2016-12-01

    An intermolecular potential energy surface and rovibrational transition frequencies are computed for CO2-C2H2. An interpolating moving least squares method is used to fit ab initio points at the explicitly correlated coupled-cluster level. The rovibrational Schrödinger equation is solved with a symmetry-adapted Lanczos algorithm. The computed disrotatory and torsion vibrational levels of both CO2-C2H2 and CO2-C2D2 differ from those obtained by experimentalists by less than 0.5 cm-1. CO2-C2H2 has two equivalent minima with the monomers perpendicular to the inter-monomer axis. In contrast to many other Van der Waals dimers there is no disrotatory path that connects the minima. The tunnelling path follows the torsional coordinate over a high barrier and the splitting is therefore tiny. Using vibrational parent analysis we are able to fit and thus obtain rotational constants and centrifugal distortion constants. Calculated rotational constants differ from their experimental counterparts by less than 0.001 cm-1.

  16. Permutationally invariant fitting of intermolecular potential energy surfaces: A case study of the Ne-C2H2 system

    NASA Astrophysics Data System (ADS)

    Li, Jun; Guo, Hua

    2015-12-01

    The permutation invariant polynomial-neural network (PIP-NN) approach is extended to fit intermolecular potential energy surfaces (PESs). Specifically, three PESs were constructed for the Ne-C2H2 system. PES1 is a full nine-dimensional PIP-NN PES directly fitted to ˜42 000 ab initio points calculated at the level of CCSD(T)-F12a/cc-pCVTZ-F12, while the other two consist of the six-dimensional PES for C2H2 [H. Han, A. Li, and H. Guo, J. Chem. Phys. 141, 244312 (2014)] and an intermolecular PES represented in either the PIP (PES2) or PIP-NN (PES3) form. The comparison of fitting errors and their distributions, one-dimensional cuts and two-dimensional contour plots of the PESs, as well as classical trajectory collisional energy transfer dynamics calculations shows that the three PESs are very similar. We conclude that full-dimensional PESs for non-covalent interacting molecular systems can be constructed efficiently and accurately by the PIP-NN approach for both the constituent molecules and intermolecular parts.

  17. Segmental dynamics of polyethylene-alt-propylene studied by NMR spin echo techniques

    NASA Astrophysics Data System (ADS)

    Lozovoi, A.; Mattea, C.; Hofmann, M.; Saalwaechter, K.; Fatkullin, N.; Stapf, S.

    2017-06-01

    Segmental dynamics of a highly entangled melt of linear polyethylene-alt-propylene with a molecular weight of 200 kDa was studied with a novel proton nuclear magnetic resonance (NMR) approach based upon 1H → 2H isotope dilution as applied to a solid-echo build-up function ISE(t), which is constructed from the NMR spin echo signals arising from the Hahn echo (HE) and two variations of the solid-echo pulse sequence. The isotope dilution enables the separation of inter- and intramolecular contributions to this function and allows one to extract the segmental mean-squared displacements in the millisecond time range, which is hardly accessible by other experimental methods. The proposed technique in combination with time-temperature superposition yields information about segmental translation in polyethylene-alt-propylene over 6 decades in time from 10-6 s up to 1 s. The time dependence of the mean-squared displacement obtained in this time range clearly shows three regimes of power law with exponents, which are in good agreement with the tube-reptation model predictions for the Rouse model, incoherent reptation and coherent reptation regimes. The results at short times coincide with the fast-field cycling relaxometry and neutron spin echo data, yet, significantly extending the probed time range. Furthermore, the obtained data are verified as well by the use of the dipolar-correlation effect on the Hahn echo, which was developed before by the co-authors. At the same time, the amplitude ratio of the intermolecular part of the proton dynamic dipole-dipole correlation function over the intramolecular part obtained from the experimental data is not in agreement with the predictions of the tube-reptation model for the regimes of incoherent and coherent reptation.

  18. A solid-state NMR study of phospholipid-cholesterol interactions: sphingomyelin-cholesterol binary systems.

    PubMed

    Guo, Wen; Kurze, Volker; Huber, Thomas; Afdhal, Nezam H; Beyer, Klaus; Hamilton, James A

    2002-09-01

    We used solid-state NMR techniques to probe the interactions of cholesterol (Chol) with bovine brain sphingomyelin (SM) and for comparison of the interactions of Chol with dipalmitoylphosphatidylcholine (DPPC), which has a similar gel-to-liquid crystalline transition temperature. (1)H-, (31)P-, and (13)C-MASNMR yielded high-resolution spectra from multilamellar dispersions of unlabeled brain SM and Chol for analysis of chemical shifts and linewidths. In addition, (2)H-NMR spectra of oriented lipid membranes with specific deuterium labels gave information about membrane ordering and mobility. Chol disrupted the gel-phase of pure SM and increased acyl chain ordering in the liquid crystalline phase. As inferred from (13)C chemical shifts, the boundaries between the ordered and disordered liquid crystalline phases (L and L) were similar for SM and DPPC. The solubility limit of Chol in SM was ~50 mol %, the same value as previously reported for DPPC membranes. We found no evidence for specific H-bonding between Chol and the amide group of SM. The order parameters of a probe molecule, d31-sn1-DPPC, in SM were slightly higher than in DPPC for all carbons except the terminal groups at 30 mol % but were not significantly different at 5 and 60 mol % Chol. These studies show a general similarity with some subtle differences in the way Chol interacts with DPPC and SM. In the environment of a typical biomembrane, the higher proportion of saturated fatty acyl chains in SM compared to other phospholipids may be the most significant factor influencing interactions with Chol.

  19. X-ray, NMR and DFT studies on benzo[h]thiazolo[2,3-b]quinazoline derivatives

    NASA Astrophysics Data System (ADS)

    Gupta, Richa; Chaudhary, R. P.

    2013-10-01

    4-Phenyl-3,4,5,6-tetrahydrobenzo[h]quinazoline-2(1H)-thione 3, obtained by the condensation of 2-Benzylidene-3,4-dihydronapthalen-1(2H)-one 2 with thiourea, on reaction with chloroacetic acid and 1,2-dibromoethane furnish compounds 4 and 5 and not their possible isomers 7 and 8 respectively. The regiochemistry of the cyclized products and their structure is established by elemental analysis, 1H NMR, 13C NMR, IR and mass spectral data. Density functional theory (DFT) calculations have been carried out for compounds 4, 5 and their isomers 7 and 8 with Jaguar version 6.5112 using B3LYP density functional method and 6-31G∗∗ basis set. X-ray diffraction technique indicates that compound 4 crystallizes in the triclinic space group P-1, with Z = 2 and cell parameters a = 6.3404 (11) Å, b = 9.997 (3) Å, c = 13.560 (2) Å, α = 107.532(19)°, β = 94.108(14)°, γ = 97.469(17)°. 1H and 13C NMR of compounds 4, 5, 7 and 8 have been calculated and correlated with experimental results. 2-Arylidene derivatives of 4 were obtained by two routes and their structure was established by spectral data. The lowest energy optimized geometry of the compound 4 in gas phase is consistent with that obtained by X-ray crystallographic studies.

  20. In-Cell Solid-State NMR: An Emerging Technique for the Study of Biological Membranes

    PubMed Central

    Warnet, Xavier L.; Arnold, Alexandre A.; Marcotte, Isabelle; Warschawski, Dror E.

    2015-01-01

    Biological molecular processes are often studied in model systems, which simplifies their inherent complexity but may cause investigators to lose sight of the effects of the molecular environment. Information obtained in this way must therefore be validated by experiments in the cell. NMR has been used to study biological cells since the early days of its development. The first NMR structural studies of a protein inside a cell (by solution-state NMR) and of a membrane protein (by solid-state NMR) were published in 2001 and 2011, respectively. More recently, dynamic nuclear polarization, which has been used to enhance the signal in solid-state NMR, has also been applied to the study of frozen cells. Much progress has been made in the past 5 years, and in this review we take stock of this new technique, which is particularly appropriate for the study of biological membranes. PMID:26682804

  1. 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.

  2. The Surface of Nanoparticle Silicon as Studied by Solid-State NMR

    PubMed Central

    Faulkner, Rebecca A.; DiVerdi, Joseph A.; Yang, Yuan; Kobayashi, Takeshi; Maciel, Gary E.

    2012-01-01

    The surface structure and adjacent interior of commercially available silicon nanopowder (np-Si) was studied using multinuclear, solid-state NMR spectroscopy. The results are consistent with an overall picture in which the bulk of the np-Si interior consists of highly ordered (“crystalline”) silicon atoms, each bound tetrahedrally to four other silicon atoms. From a combination of 1H, 29Si and 2H magic-angle-spinning (MAS) NMR results and quantum mechanical 29Si chemical shift calculations, silicon atoms on the surface of “as-received” np-Si were found to exist in a variety of chemical structures, with apparent populations in the order (a) (Si–O–)3Si–H > (b) (Si–O–)3SiOH > (c) (HO–)nSi(Si)m(–OSi)4−m−n ≈ (d) (Si–O–)2Si(H)OH > (e) (Si–O–)2Si(–OH)2 > (f) (Si–O–)4Si, where Si stands for a surface silicon atom and Si represents another silicon atom that is attached to Si by either a Si–Si bond or a Si–O–Si linkage. The relative populations of each of these structures can be modified by chemical treatment, including with O2 gas at elevated temperature. A deliberately oxidized sample displays an increased population of (Si–O–)3Si–H, as well as (Si–O–)3SiOH sites. Considerable heterogeneity of some surface structures was observed. A combination of 1H and 2H MAS experiments provide evidence for a substantial population of silanol (Si–OH) moieties, some of which are not readily H-exchangeable, along with the dominant Si–H sites, on the surface of “as-received” np-Si; the silanol moieties are enhanced by deliberate oxidation. An extension of the DEPTH background suppression method is also demonstrated that permits measurement of the T2 relaxation parameter simultaneously with background suppression. PMID:28809292

  3. 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.

  4. PFG NMR study of hydrodynamic dispersion in porous media

    NASA Astrophysics Data System (ADS)

    Ding, Aimin

    We have studied hydrodynamic dispersion in plastic bead packs using the pulsed field gradient (PFG) NMR technique. The bead diameter was varied from 15 to 138 mum and the Peclet number Pe varied from 0 to 10sp3 (the Peclet number is a dimensionless measure of the flow velocity). We studied the time dependence of both the longitudinal dispersion coefficient Dsb{||} and the transverse dispersion coefficient Dsb{⊥}. We observed transitions from decreasing with time at low Pe to increasing with time at high Pe for both Dsb{||} and Dsb{⊥}. We used our data to find the transition time tsb0 the time required for dispersion coefficient to reach its long time value. For both Dsb{||} and Dsb{⊥}, we found a power-law dependence of tsb0 on Pe, as has been predicted by Koch and Brady. The Pe dependence of tsb0 provides information on the operative dispersion mechanisms. Our results show that both convection dispersion and boundary layer dispersion contribute to longitudinal dispersion in our experiments. However, the Pe dependence of tsb0 for transverse dispersion does not agree with the theoretical prediction of Koch and Brady. We measured Dsb{||} and Dsb{⊥} as a function of Pe. Our experimental results are consistent with previous results measured using conventional methods. We found that the results for longitudinal dispersion agree with Saffman's capillary tube model in our observation range. The results for transverse dispersion agree with Koch and Brady's fixed bed model to some extent, but at low Pe, the disagreement is significant. We obtained the wave-number and frequency dependent nonlocal dispersion coefficient {buildrel{≈}/{D}}sb{| |,⊥}(q,omega) from our PFG NMR data. In the local (long time and distance) limit, our results agree with previous results obtained with conventional methods and for no flow they agree with a simple model of restricted diffusion. Our results for nonlocal dispersion with flow are in reasonable agreement with Koch and Brady

  5. 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.

  6. Protein NMR Studies of substrate binding to human blood group A and B glycosyltransferases.

    PubMed

    Peters, Thomas; Grimm, Lena Lisbeth; Weissbach, Sophie; Flügge, Friedemann; Begemann, Nora; Palcic, Monica

    2017-03-03

    Donor and acceptor substrate binding to human blood group A and B glycosyltransferases (GTA, GTB) has been studied by a variety of protein NMR experiments. Prior crystallographic studies have shown these enzymes to adopt an open conformation in the absence of substrates. Binding of either the donor substrate UDP-Gal, or of UDP induces a semi-closed conformation. In the presence of both, donor- and acceptor substrates, the enzymes shift towards a closed conformation with ordering of an internal loop and the C-terminal residues, which then completely cover the donor-binding pocket. Chemical shift titrations of uniformly 2H,15N labeled GTA or GTB with UDP affected about 20% of all cross peaks in 1H,15N-TROSY-HSQC spectra reflecting substantial plasticity of the enzymes. On the other hand, it is this conformational flexibility that impedes NH backbone assignments. Chemical shift perturbation experiments using 1-13C-methyl Ile labeled samples revealed two Ile residues, Ile123 at the bottom of the UDP binding pocket, and Ile192 as part of the internal loop that were significantly disturbed upon stepwise addition of UDP and H-disaccharide, also revealing long-range perturbations. Finally, methyl TROSY based relaxation dispersion experiments do not reveal s to ms time scale motions. Although this study reveals substantial conformational plasticity of GTA and GTB it remains enigmatic how binding of substrates shifts the enzymes into catalytically competent states.

  7. NMR study of strontium binding by a micaceous mineral.

    PubMed

    Bowers, Geoffrey M; Ravella, Ramesh; Komarneni, Sridhar; 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 Na(4)Mg(6)Al(4)Si(4)O(20)F(4). Thermogravimetric analysis, X-ray diffraction analysis, and NMR evidence supports that heat treatment at 500 degrees 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 (1)H-(87)Sr transfer of populations by double resonance NMR experiment. We conclude that the strontium cations in the proton-free interlayer are observable by (87)Sr NMR and bound through electrostatic interactions as nine coordinate inner-sphere complexes sitting in the ditrigonal holes. Partially hydrated strontium cations invisible to direct (87)Sr 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.

  8. 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.

  9. Fundamental studies of supported bimetallic catalysts by NMR spectroscopy

    SciTech Connect

    Savargaonkar, Nilesh

    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.

  10. NMR study of small molecule adsorption in MOF-74-Mg

    NASA Astrophysics Data System (ADS)

    Lopez, M. G.; Canepa, Pieremanuele; Thonhauser, T.

    2013-04-01

    We calculate the carbon nuclear magnetic resonance (NMR) shielding for CO2 and the hydrogen shieldings for both H2 and H2O inside the metal organic framework MOF-74-Mg. Our ab initio calculations are at the density functional theory level using the van der Waals including density functional vdW-DF. The shieldings are obtained while placing the small molecules throughout the structure, including the calculated adsorption site for various loading scenarios. We then explore relationships between loading, rotational and positional characteristics, and the NMR shieldings for each adsorbate. Our NMR calculations show a change in the shielding depending on adsorbate, position, and loading in a range that is experimentally observable. We further provide a simple model for the energy and the NMR shieldings throughout the cavity of the MOF. By providing this mapping of shielding to position and loading for these adsorbates, we argue that NMR probes could be used to provide additional information about the position at which these small molecules bind within the MOF, as well as the loading of the adsorbed molecule.

  11. NMR study of small molecule adsorption in MOF-74-Mg.

    PubMed

    Lopez, M G; Canepa, Pieremanuele; Thonhauser, T

    2013-04-21

    We calculate the carbon nuclear magnetic resonance (NMR) shielding for CO2 and the hydrogen shieldings for both H2 and H2O inside the metal organic framework MOF-74-Mg. Our ab initio calculations are at the density functional theory level using the van der Waals including density functional vdW-DF. The shieldings are obtained while placing the small molecules throughout the structure, including the calculated adsorption site for various loading scenarios. We then explore relationships between loading, rotational and positional characteristics, and the NMR shieldings for each adsorbate. Our NMR calculations show a change in the shielding depending on adsorbate, position, and loading in a range that is experimentally observable. We further provide a simple model for the energy and the NMR shieldings throughout the cavity of the MOF. By providing this mapping of shielding to position and loading for these adsorbates, we argue that NMR probes could be used to provide additional information about the position at which these small molecules bind within the MOF, as well as the loading of the adsorbed molecule.

  12. [Cryogenic Raman spectroscopic studies in the system of NaCl-MgCl2-H2O].

    PubMed

    Yang, Dan; Xu, Wen-Yi

    2010-03-01

    In the present paper, the best experimental conditions for producing hydrates in the NaCl-H2O and MgCl2-H2O systems were found through the cryogenic Raman spectroscopy. This experimental condition is rapidly cooling to -180 degrees C and slowly warming to observe hydrate formation process (that is manifested as a darkening of the vision in the microscope), and finally, rapidly cooling down to -180 degrees C. Moreover, a qualitative or semiquantitative analytical method for NaCl-MgCl2-H2O system was established. This method is that 3 537 cm(-1) may instruct the existence of NaCl hydrates, 3 514 cm(-1) may instruct the existence of MgCl2 hydrates, and comparison of the intensity of 3 537 and 3 514 cm(-1) peaks can be used to estimate the ratio of NaCl and MgCl2 in the system. All these are the foundations for quantifying the components of natural fluid inclusions. The author supports Samson's idea through observing the phenomenon of experiments in the controversy of the meta-stable eutectics formation model, that is ice forms on initial cooling, leaving a residual, interstitial, hypersaline liquid. On warming, the salt hydrates crystallize from this liquid.

  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. Copyright © 2015 John Wiley & Sons, Ltd.

  14. 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.

  15. Vibrational and NMR probe studies of S Az-1 montmorillonite

    SciTech Connect

    Johnston, C.T.; Erickson, C.; Earl, W.L.

    1992-09-01

    This paper reports a study of the interactions of exchangeable metal cations with mineral surfaces using a combined spectroscopic/macroscopic approach. Objectives were to examine the use of water molecules and metal cations as molecular probes of smectite water interactions. The {nu}{sub 2} mode of water is used as a diagnostic vibrational band. An FTIR-gravimetric cell is used to examine the FTIR spectra of water on homoionic smectites. The {sup 23}Na NMR resonance is used to probe metal-water interactions on the surface. Results show that there are strong changes in both position and absorption coefficient of the H-O-H bending mode of water sorbed on SAz-1 montmorillonite as a function of water content. These changes are attributed to strong electrostatic forces and mobility changes that occur when the water in the interlammelar space is associated with the metal ion. The clay surface is viewed as having at least two distinct sites to which a hydrated Na{sup +} can bind. 32 refs, 5 figs. (DLC)

  16. Vibrational and NMR probe studies of S Az-1 montmorillonite

    SciTech Connect

    Johnston, C.T.; Erickson, C. . Dept. of Soil Science); Earl, W.L. )

    1992-01-01

    This paper reports a study of the interactions of exchangeable metal cations with mineral surfaces using a combined spectroscopic/macroscopic approach. Objectives were to examine the use of water molecules and metal cations as molecular probes of smectite water interactions. The {nu}{sub 2} mode of water is used as a diagnostic vibrational band. An FTIR-gravimetric cell is used to examine the FTIR spectra of water on homoionic smectites. The {sup 23}Na NMR resonance is used to probe metal-water interactions on the surface. Results show that there are strong changes in both position and absorption coefficient of the H-O-H bending mode of water sorbed on SAz-1 montmorillonite as a function of water content. These changes are attributed to strong electrostatic forces and mobility changes that occur when the water in the interlammelar space is associated with the metal ion. The clay surface is viewed as having at least two distinct sites to which a hydrated Na{sup +} can bind. 32 refs, 5 figs. (DLC)

  17. NMR studies of the conformational interconversion of butaclamol in solution.

    PubMed

    Casarotto, M G; Craik, D J; Lloyd, E J

    1991-07-01

    1H NMR experiments at 300 MHz have been carried out to determine the identity and study the interconversion of two conformations of butaclamol in solution. The hydrochloride salt in DMSO exists as an equilibrium mixture of two conformations, which differ in their stereochemistry about the ring junction that contains the single nitrogen atom in butaclamol. The trans form has a relative population of 80% and the cis I form 20%. In CDCl3 only the trans form is observed, while in CDCl3-DMSO mixtures, both forms are detected in a ratio (trans:cis I) that decreases as the percentage of CDCl3 decreases. For the free base in either CD2Cl2 or DMSO, only a single set of resonances is observed at room temperature, but as temperature is lowered, peaks from methine protons H4a and H13b near the ring junction broaden and (for samples in CD2Cl2) eventually split into two resonances corresponding to the cis and trans forms. It is suggested that nitrogen inversion is the dynamic process responsible for the interconversion of the two forms. Line shape analysis as a function of temperature yielded an energy barrier of 9.6 +/- 0.5 kcal/mol for the interconversion, in good agreement with values obtained from saturation transfer experiments. In the hydrochloride salt, the barrier in DMSO was somewhat higher, i.e., 17.3 +/- 0.9 kcal/mol, as determined by saturation transfer and variable-temperature measurements.

  18. A first principles study on the solvation and structure of SO{sub 4}{sup 2-}(H{sub 2}O){sub n}, n=6-12

    SciTech Connect

    Gao Bing; Liu Zhifeng

    2004-11-01

    The structures of hydrated sulfate clusters, SO{sub 4}{sup 2-}(H{sub 2}O){sub n} with n=6-12, are obtained by density functional theory calculations. For SO{sub 4}{sup 2-}(H{sub 2}O){sub 12}, two structures with symmetric distribution of H{sub 2}O molecules around the sulfate group are favored in energy. The structures for the smaller clusters, SO{sub 4}{sup 2-}(H{sub 2}O){sub n} with n=6-11, are obtained by taking away one H{sub 2}O molecule successively from the two symmetric SO{sub 4}{sup 2-}(H{sub 2}O){sub 12} isomers. The hydrogen bonding between the sulfate O atoms and H{sub 2}O molecules are strong. So are the hydrogen bonds among H{sub 2}O molecules, which are facilitated by the structure of the polyatomic sulfate group. The solvation energy is quite large (often exceeding 15 kcal/mol). The patterns for structural and energy changes as the cluster size increases are very different from the well studied hydrated halide ions, although the competition between solute-solvent and solvent-solvent interactions is again an important factor. Ab initio molecular dynamics simulations also show 'crowding' effects in the first solvation of SO{sub 4}{sup 2-}(H{sub 2}O){sub 12} at raised temperature.

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

    PubMed

    Elamurugu Porchelvi, E; Muthu, S

    2014-04-05

    The Fourier-Transform Infrared and Fourier-Transform Raman spectra of 6-Chloro-3,4dihydro-2H-1,2,4-benzothiazine-7sulphonamide1,1-dioxide(6CDBSD) was recorded in the region 4000-450cm(-1) and 4000-100cm(-1)respectively. Quantum chemical calculations of energies, geometrical structure and vibrational wave numbers of 6CDBSD were carried out by HF and DFT (B3LYP) method with 6-31G (d,p) basis set. The difference between the observed and scaled wavenumber value of most of the fundamentals is very small. The assignments of the vibrational spectra have been carried out with the aid of normal coordinate analysis (NCA) following the scaled quantum mechanical force field methodology (SQMFF). The linear polariazability (α) and the first order hyperpolarizability (βtot) values of the investigated molecule have been computed using HF and DFT with 6-31G (d,p) basis set. Stability of the molecule arising from hyper conjugative interaction and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. The (1)H and (13)C Nuclear Magnetic Resonance (NMR) chemical shifts of the molecules were calculated using the Gauge-Invariant Atomic orbital (GIAO) method, confirms with the experimental values. The calculated HOMO and LUMO energies also confirm that charge transfer occurs within the molecule. Thermal stability of 6CDBSD was studied by thermo gravimetric analysis (TGA). Next Fukui functions was calculated to identify changes in the reactivity of molecule. Finally molecular electrostatic potential (MEP) and other molecular properties were performed. Copyright © 2013 Elsevier B.V. All rights reserved.

  20. NMR study of black-phase in SmS

    NASA Astrophysics Data System (ADS)

    Koyama, T.; Yamada, H.; Ueda, K.; Mito, T.; Haga, Y.

    2015-03-01

    We report the result of the 33S nuclear magnetic resonance (NMR) measurement on the nonmagnetic semiconductor SmS at ambient pressure. For this measurement, the 33S isotope enriched powder sample of SmS was prepared to increase the 33S NMR intensity. We have attempted 33S NMR measurement on SmS and successfully observed the signal of it. With decreasing temperature, the spectrum measured at the constant magnetic field shifted to lower frequency and became weakly temperature dependent below 50 K. The presence of the energy gap was microscopically established by the rapid decrease in the nuclear spin-lattice relaxation rate 1/T1. The activation energy was deduced to be 625 K from an Arrhenius plot of T1.

  1. Al NMR study of molten aluminum oxide compounds and mixtures, measured at ultra high temperatures.

    NASA Astrophysics Data System (ADS)

    Piwowarczyk, J.; Marzke, R. F.; Wolf, G. H.; Petuskey, W. T.; Takulapalli, B.

    2002-10-01

    The technique of ultra high-temperature nuclear magnetic resonance (NMR) has provided insight into the chemical structure and properties of molten aluminum-bearing refractory ceramics, at temperatures in excess of 2000 ^oC. Through application of standard NMR measurements we have studied molten aluminum-bearing ceramics via ^27Al NMR. We have measured spin-lattice (T_1) and spin-spin (T_2) relaxation times, have studied Al-O-P chemical bonding within molten aluminua-monazite (Al_2O3 + LaPO_4) samples and have begun to measure Al diffusivity as a function of temperature and composition. To overcome the limitations of standard NMR heating systems a specially designed NMR probe was developed. Application of levitation technology and a laser heating system permit controlled, containerless heating of samples over a wide range of temperatures. Supported by NSF DMR 0116361, DMR 9818133 and by Research Corp. RA 0276

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

    PubMed Central

    Kolehmainen, E.

    2016-01-01

    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. 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.

  4. 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.

  5. Chemical Kinetic Studies Using Ultraviolet Cavity Ring-Down=20 Spectroscopic Detection: Self-Reaction of Ethyl and Ethylperoxy Radicals=20 and the Reaction, O2 + C_2H_5arrow C_2H_5O_2

    NASA Astrophysics Data System (ADS)

    Atkinson, Dean B.; Hudgens, Jeffrey W.

    1997-04-01

    A laser-photolysis reactor that uses cavity ring-down spectroscopic (CRDS) detection was characterized and used to measure the rate coefficients of three benchmark reactions of known importance to ethane oxidation. At 295 K and approximately 700 Pa (5.5 torr) total pressure we obtained the self-reaction rate coefficients of k =3D 1.99(±0.44)×10-11=A0cm^3s-1 for C_2H5 + C_2H5 and k =3D 7.26(±2.4)×10-14=A0cm^3s-1 for C_2H_5O2 + C_2H_5O_2. We obtained k =3D 2.7(±0.3)×10-12=A0cm^3s-1 for the pseudo-first order association reaction, O2 + C_2H5 + Ar. We also measured the absorption cross-sections of the ethyl radical, σ _220 =3D 252(±42)×10-20 cm^2 and σ _222 =3D 206(±42)×10-20 cm^2. Stated uncertainties are ±2σ. The new rate coefficients agree with those obtained previously by other methods. The agreement confirms that ultraviolet CRDS detection is a viable tool for experimental determinations of gas-phase radical-radical and radical-molecule reaction rate coefficients.

  6. Energetics and kinetics of phase transition between a 2H and a 1T MoS2 monolayer-a theoretical study.

    PubMed

    Zhao, Wen; Ding, Feng

    2017-02-09

    Phase transitions between semiconducting 2H and metallic 1T (or 1T') molybdenum disulphides (MoS2) are explored comprehensively by first-principles calculations. The nucleation of a 1T (or 1T') nucleus in a 2H MoS2 lattice, the formation of the 2H-1T (1T') interfaces and the kinetics of interface propagation during phase transition were thoroughly investigated in this study. It was found that, among various potential interface structures between the two phases, Mo-rich and two S-rich zigzag (ZZ) boundaries are energetically more preferable than others. Therefore, triangular or hexagonal 1T MoS2 domains with the three types of ZZ boundaries are expected to be the equilibrium structures of the 1T nucleus in a 2H lattice. Further exploration reveals a very high nucleation energy of the 1T phase which suggests that the nucleation may start from a defect site or the edge of the 2H phase. Besides, the kinetics of 2H-1T (1T') boundary propagation show that the growth rate of the ZZ boundaries is significantly slower than the armchair (AC) ones'. Therefore, the ZZ-boundary dominated domains are expected to be observed during the growth of the 1T phase while the rounded domains with various high-index edges are expected to be seen throughout shrinkage. This study reveals both the energetics and the kinetics of the phase transition of transition metal dichalcogenide materials and also sheds light on other 2D materials.

  7. Determination of membrane immersion depth with O(2): a high-pressure (19)F NMR study.

    PubMed Central

    Prosser, R S; Luchette, P A; Westerman, P W; Rozek, A; Hancock, R E

    2001-01-01

    Oxygen is known to partition with an increasing concentration gradient toward the hydrophobic membrane interior. At partial pressures (P(O2)) of 100 Atm or more, this concentration gradient is sufficient to induce paramagnetic effects that depend sensitively on membrane immersion depth. This effect is demonstrated for the fluorine nucleus by depth-dependent paramagnetic shifts and spin-lattice relaxation rates, using a fluorinated detergent, CF3(CF(2))(5)C(2)H(4)-O-maltose (TFOM), reconstituted into a lipid bilayer model membrane system. To interpret the spin-lattice relaxation rates (R) in terms of a precise immersion depth, two specifically fluorinated cholesterol species (6-fluorocholesterol and 25-fluorocholesterol), whose membrane immersion depths were independently estimated, were studied by (19)F NMR. The paramagnetic relaxation rates, R, of the cholesterol species were then used to parameterize a Gaussian profile that directly relates R to immersion depth z. This same Gaussian curve could then be used to determine the membrane immersion depth of all six fluorinated chain positions of TFOM and of two adjacent residues of specifically fluorinated analogs of the antibacterial peptide indolicidin. The potential of this method for determination of immersion depth and topology of membrane proteins is discussed. PMID:11222301

  8. Raman studies of phase transitions in ferroelectric [C2H5NH3]2ZnCl4

    NASA Astrophysics Data System (ADS)

    Ben Mohamed, C.; Karoui, K.; Bulou, A.; Ben Rhaiem, A.

    2017-03-01

    The present paper accounted for the synthesis, differential scanning calorimetric and vibrational spectroscopy of [C2H5NH3]2ZnCl4grown at room temperature. Differential scanning calorimetric (DSC) disclosed five phase transitions at T1=231 K, T2=234 K, T3=237 K, T4=247 K and T5=312 K. The temperature dependence of the dielectric constant at different temperatures proved that this compound is ferroelectric below 238 K. Raman spectra as function temperature have been used to characterize these transitions and their nature, which indicates a change of the some peak near the transitions phase. The analysis of the wavenumber and the line width based on the order-disorder model allowed to obtain information relative to the thermal coefficient and the activation energy near the transitions phase.

  9. Structure and bonding studies of ClX-C 2H 4 (X = H or Br) van der Waals complexes

    NASA Astrophysics Data System (ADS)

    Lin, Zhenyang; Bytheway, Ian

    1995-07-01

    High-quality ab initio calculations at the MP n ( n = 2, 3 or 4) levels for the π-donor complex formed by HCl and ethene, and the recently characterized ClBr-ethene complex are presented. Interaction energies were calculated with the inclusion of both basis-set superposition error and zero-point energy corrections, resulting in values of about 1 kcal mol -1 for both complexes. The total charge densities for both complexes yielded molecular graphs indicative of the weak binding in these molecules, and correspondingly, calculated charges showed that the XCl moiety has an overall slightly negative charge, while the ethene moiety is slightly positive. Analysis of the Laplacian of the charge density showed that the geometry of the ClBr- C 2H 4 complex may be understood in terms of the VSEPR model as an example of an AXYE 3 molecule.

  10. NMR-based simulation studies of Pf1 coat protein in explicit membranes.

    PubMed

    Cheng, Xi; Jo, Sunhwan; Marassi, Francesca M; Im, Wonpil

    2013-08-06

    As time- and ensemble-averaged measures, NMR observables contain information about both protein structure and dynamics. This work represents a computational study to extract such information for membrane proteins from orientation-dependent NMR observables: solid-state NMR chemical shift anisotropy and dipolar coupling, and solution NMR residual dipolar coupling. We have performed NMR-restrained molecular dynamics simulations to refine the structure of the membrane-bound form of Pf1 coat protein in explicit lipid bilayers using the recently measured chemical shift anisotropy, dipolar coupling, and residual dipolar coupling data. From the simulations, we have characterized detailed protein-lipid interactions and explored the dynamics. All simulations are stable and the NMR restraints are well satisfied. The C-terminal transmembrane (TM) domain of Pf1 finds its optimal position in the membrane quickly (within 6 ns), illustrating efficient solvation of TM domains in explicit bilayer environments. Such rapid convergence also leads to well-converged interaction patterns between the TM helix and the membrane, which clearly show the interactions of interfacial membrane-anchoring residues with the lipids. For the N-terminal periplasmic helix of Pf1, we identify a stable, albeit dynamic, helix orientation parallel to the membrane surface that satisfies the amphiphatic nature of the helix in an explicit lipid bilayer. Such detailed information cannot be obtained solely from NMR observables. Therefore, the present simulations illustrate the usefulness of NMR-restrained MD refinement of membrane protein structure in explicit membranes.

  11. Acyl chain orientational order in large unilamellar vesicles: comparison with multilamellar liposomes: a 2H and 31P nuclear magnetic resonance study.

    PubMed Central

    Fenske, D B; Cullis, P R

    1993-01-01

    Large unilamellar vesicles (LUVs) composed of 1-[2H31]palmitoyl-2-oleoyl phosphatidylcholine (POPC-d31), with diameters of approximately 117 +/- 31 and 180 +/- 44 nm, were prepared by extrusion through polycarbonate filters with pore sizes of 0.1 and 0.2 microns, respectively. The 2H nuclear magnetic resonance (NMR) spectra obtained at 21 degrees C contain two components: a broad component (approximately 17 kHz linewidth) corresponding to the methylene groups and a narrower component originating from the methyl groups. Spectra with increasing powder pattern characteristics were obtained by reducing the rate of phospholipid reorientations by addition of glycerol (to increase the solvent viscosity) and by lowering the temperature. Full powder spectra, characteristic of liquid-crystalline bilayers, were obtained for both LUV samples at 0 degrees C in the presence of 50 wt% glycerol. Individual quadrupolar splittings were not resolved in these spectra, due to broader linewidths in the LUVs, which have significantly shorter values for spin-spin relaxation time T2 measured from the decay of the quadrupolar echo (90 microseconds) than the multilmellar vesicles (MLVs; 540 microseconds). Smoothed order parameter profiles (OPPs) were obtained for these samples by integration of the dePaked spectra. The OPPs were very similar to the OPP of POPC-d31 MLVs in 50 wt% glycerol at the same temperature, indicating that orientational order in MLVs and LUVs with a diameter of > or = 100 nm is essentially the same. The presence of 80 wt% glycerol was found to have a disordering effect on the vesicles. PMID:8324185

  12. Selectively labeling the heterologous protein in Escherichia coli for NMR studies: a strategy to speed up NMR spectroscopy.

    PubMed

    Almeida, F C; Amorim, G C; Moreau, V H; Sousa, V O; Creazola, A T; Américo, T A; Pais, A P; Leite, A; Netto, L E; 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 (1)H/(15)N heteronuclear correlation two-dimensional NMR spectrum (HMQC) of the selective (15)N-labeled thioredoxin without any purification is remarkably similar to the spectrum of the purified protein. The method has high yields and a good (1)H/(15)N 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 (15)N-edited spectrum of Opaque 2 LZ showed only the resonances of the protein of heterologous expression (Opaque 2 LZ) while the (1)H 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. 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.

  14. NMR Studies of Biomass and its Reaction Products

    USDA-ARS?s Scientific Manuscript database

    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...

  15. 129Xe NMR studies of biochar made from biobased materials

    USDA-ARS?s Scientific Manuscript database

    Biochar is created by pyrolysis of biobased materials under controlled oxidative environments. The product is charcoal-like and can be used as filtration medium, sequestrant for metallic ions, soil conditioner, and other applications. In our work we have found 129Xe NMR to be an excellent technique...

  16. Application of lanthanide-induced shifts in solution NMR studies of coordinated extractants. [Dibutylbutylphosphonate; butyldibutylphosphinate

    SciTech Connect

    Kalina, D.G.; Horwitz, E.P.

    1983-01-01

    A NMR study was conducted to study the coordination of monofunctional extractants (TBP, dibutylbutylphosphonate, and butyldibutylphosphinate) and bifunctional extractants (DHDECMP). Pr, Eu, and Yb ions were used as solution structural probes. (DLC)

  17. Multidimensional HRMAS NMR: a platform for in vivo studies using intact bacterial cells.

    PubMed

    Li, Wei

    2006-07-01

    In vivo analysis in whole cell bacteria, especially the native tertiary structures of the bacterial cell wall, remains an unconquered frontier. The current understanding of bacterial cell wall structures has been based on destructive analysis of individual components. These in vitro results may not faithfully reflect the native structural and conformational information. Multidimensional High Resolution Magic Angle Spinning NMR (HRMAS NMR) has evolved to be a powerful technique in a variety of in vivo studies, including live bacterial cells. Existing studies of HRMAS NMR in bacteria, technical consideration of its successful application, and current limitations in studying true human pathogens are briefly reviewed in this report.

  18. Large Area, High Resolution N2H+ studies of dense gas in the Perseus and Serpens Molecular Clouds

    NASA Astrophysics Data System (ADS)

    Storm, Shaye; Mundy, Lee

    2014-07-01

    Star formation in molecular clouds occurs over a wide range of spatial scales and physical densities. Understanding the origin of dense cores thus requires linking the structure and kinematics of gas and dust from cloud to core scales. The CARMA Large Area Star Formation Survey (CLASSy) is a CARMA Key Project that spectrally imaged five diverse regions of the Perseus and Serpens Molecular Clouds in N2H+ (J=1-0), totaling over 800 square arcminutes. The observations have 7’’ angular resolution (~0.01 pc spatial resolution) to probe dense gas down to core scales, and use combined interferometric and single-dish data to fully recover line emission up to parsec scales. CLASSy observations are complete, and this talk will focus on three science results. First, the dense gas in regions with existing star formation has complex hierarchical structure. We present a non-binary dendrogram analysis for all regions and show that dense gas hierarchy correlates with star formation activity. Second, well-resolved velocity information for each dendrogram-identified structure allows a new way of looking at linewidth-size relations in clouds. Specifically, we find that non-thermal line-of-sight velocity dispersion varies weakly with structure size, while rms variation in the centroid velocity increases strongly with structure size. We argue that the typical line-of-sight depth of a cloud can be estimated from these relations, and that our regions have depths that are several times less than their extent on the plane of the sky. This finding is consistent with numerical simulations of molecular cloud turbulence that show that high-density sheets are a generic result. Third, N2H+ is a good tracer of cold, dense gas in filaments; we resolve multiple beams across many filaments, some of which are narrower than 0.1 pc. The centroid velocity fields of several filaments show gradients perpendicular to their major axis, which is a common feature in filaments formed from numerical

  19. NMR studies of coupled low- and high-barrier hydrogen bonds in pyridoxal-5'-phosphate model systems in polar solution.

    PubMed

    Sharif, Shasad; Denisov, Gleb S; Toney, Michael D; Limbach, Hans-Heinrich

    2007-05-16

    The 1H and 15N NMR spectra of several 15N-labeled pyridoxal-5'-phosphate model systems have been measured at low temperature in various aprotic and protic solvents of different polarity, i.e., dichloromethane-d2, acetonitrile-d3, tetrahydrofuran-d8, freon mixture CDF3/CDClF2, and methanol. In particular, the 15N-labeled 5'-triisopropyl-silyl ether of N-(pyridoxylidene)-tolylamine (1a), N-(pyridoxylidene)-methylamine (2a), and the Schiff base with 15N-2-methylaspartic acid (3a) and their complexes with proton donors such as triphenylmethanol, phenol, and carboxylic acids of increasing strength were studied. With the use of hydrogen bond correlation techniques, the 1H/15N chemical shift and scalar coupling data could be associated with the geometries of the intermolecular O1H1N1 (pyridine nitrogen) and the intramolecular O2H2N2 (Schiff base) hydrogen bonds. Whereas O1H1N1 is characterized by a series of asymmetric low-barrier hydrogen bonds, the proton in O2H2N2 faces a barrier for proton transfer of medium height. When the substituent on the Schiff base nitrogen is an aromatic ring, the shift of the proton in O1H1N1 from oxygen to nitrogen has little effect on the position of the proton in the O2H2N2 hydrogen bond. By contrast, when the substituent on the Schiff base nitrogen is a methyl group, a proton shift from O to N in O1H1N1 drives the tautomeric equilibrium in O2H2N2 from the neutral O2-H2...N2 to the zwitterionic O2-...H2-N(2+) form. This coupling is lost in aqueous solution where the intramolecular O2H2N2 hydrogen bond is broken by solute-solvent interactions. However, in methanol, which mimics hydrogen bonds to the Schiff base in the enzyme active site, the coupling is preserved. Therefore, the reactivity of Schiff base intermediates in pyridoxal-5'-phosphate enzymes can likely be tuned to the requirements of the reaction being catalyzed by differential protonation of the pyridine nitrogen.

  20. Crossed-beams and theoretical studies of the O((3)P) + H(2)O --> HO(2) + H reaction excitation function.

    PubMed

    Brunsvold, Amy L; Zhang, Jianming; Upadhyaya, Hari P; Minton, Timothy K; Camden, Jon P; Paci, Jeffrey T; Schatz, George C

    2007-11-01

    Hyperthermal collisions of ground-state atomic oxygen with H2O have been investigated, with special attention paid to the H-atom elimination reaction, O((3)P) + H(2)O(X (1)A(1)) --> HO(2)((2)A') + H((2)S). This reaction was observed in a crossed-beams experiment, and the relative excitation function in the region around its energy threshold (50-80 kcal mol(-1)) was measured. Direct dynamics calculations were also performed at two levels of theory, B3LYP/6-31G(d,p) and MP2/6-31G(d,p). The shape of the B3LYP excitation function closely matches that of the experiment. The calculations provided a detailed description of the dynamics and revealed a striking dependence of the reaction mechanism on collision energy, where the cross section rises from a threshold near 60 kcal mol(-1) to a peak at approximately 115 kcal mol(-1) and then decreases at higher energies as secondary dissociation of the internally excited HO(2) product becomes dominant. The calculations show that the cross section for H-atom elimination (O + H(2)O --> HO(2) + H) is about 10-25% that of the H-atom abstraction (O + H(2)O --> OH + OH) cross section for collision energies in the 70-160 kcal mol(-1) range.

  1. Study on photoacoustic phase spectrum of rare earth complex: Pr(HFA) 3·2H 2O

    NASA Astrophysics Data System (ADS)

    Qinglu, Mao; Qingde, Su; Guiwen, Zhao

    1996-06-01

    The β-diketone rare earth complex: Pr(HFA) 3·2H 2O was synthesized and its amplitude and phase photoacoustic spectra in the range of 300-700 nm were reported. It was observed that the phase angle depends variously on the relaxation time τ and the optical absorption coefficient β with the incident light wavelength λ. A model of a homogeneous powder sample containing multiple optical absorption bands based on the Mandelis work was introduced to interpret the phase spectrum. It is shown that this model is very suitable for explaining the phase data associated with the π-π∗ transition and tf-tf transitions of the title complex. The phase angle ψ is mainly related to τ for the π-π∗ transition while it is determined by β for the tf-tf transition at relatively low chopping frequencies. Furthermore, the dependence of amplitude and phase information on the chopping frequency was also investigated.

  2. A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C2H3

    NASA Astrophysics Data System (ADS)

    Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

    2017-06-01

    We report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C2H3. The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C2H3. All well converged 158 vibrational bands up to 3200 cm-1 are determined, together with a comparison to previous calculations and experimental results. Results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from that of previous reduced dimensional calculations. The rotational constants of the fundamental vibrational bands of C2H3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. In addition, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C2H3 without the requirement of explicit wavefunctions.

  3. Theoretical and kinetic studies of the reactions of CF2HCFHCF2H and CF3CFHCFH2 with hydroxyl radicals

    NASA Astrophysics Data System (ADS)

    Gao, Hong; Liu, Jing-yao; Sun, Chia-chung

    2009-06-01

    The hydrogen abstraction reactions of fluoroalkane isomers CF2HCFHCF2H and CF3CFHCFH2 with the OH radicals have been studied theoretically by a dual-level direct dynamics method. Optimized geometries and frequencies of all the stationary points and extra points along the minimum-energy path are obtained at the BB1K/6-31+G(d,p) level of theory, and then the energy profiles are refined at G3(MP2) level of theory. Using the improved canonical variational transition-state theory (ICVT) with the small-curvature tunneling correction (SCT), the rate constants for each channel are calculated over a wide temperature range of 200-1000 K. Our results show that the tunneling correction plays an important role in the rate constant calculation in the low temperature range. The calculated ICVT/SCT rate constants are consistent with available experimental data. Our calculations indicate the contribution of the abstraction from the -CFH- group of isomeric compounds CF2HCFHCF2H and CF3CFHCFH2 to the overall reactions is quite different over the whole temperature range due to the effect of different groups at both sides of -CFH- group. Furthermore, to further reveal the thermodynamic properties, the enthalpies of formation of the two reactants CF2HCFHCF2H, and CF3CFHCFH2, and the product radicals CF2HCFCF2H, CF2HCFHCF2, CF3CFCFH2, and CF3CFHCFH are obtained by using isodesmic reactions.

  4. An experimental and numerical study of the high-temperature oxidation of 1,1,1-C[sub 2]H[sub 3]Cl[sub 3

    SciTech Connect

    Thomson, M.J.; Koshland, C.P.; Sawyer, R.F. ); Lucas, D. . Energy and Environment Div.); Wu, Y.P.; Bozzelli, J.W. )

    1994-07-01

    Gaseous 1,1,1-trichloroethane (1,1,1-C[sub 2]H[sub 3]Cl[sub 3]) is injected into the postflame region of a turbulent combustor with equivalence ratios, residence times and temperatures in the range of those encountered in the postflame regions of hazardous waste incinerators. Measured concentrations and are compared with a detailed chemical kinetic mechanism, which is presented with the sources of the reaction rate constants. Each rate is based on literature evaluation of experimental data, or if it is estimated, on fundamental principles of thermochemical kinetics and molecular thermodynamic properties. By basing the mechanism on fundamental principles, its applicability should extend beyond the experimental conditions for which it was developed. The model and the experimental data show reasonable agreement for all temperatures. A study of the important destruction pathways indicates that 1,1,1-C[sub 2]H[sub 3]Cl[sub 3] undergoes unimolecular decomposition to form 1,1,-C[sub 2]H[sub 2]Cl[sub 2]. Reacting with either Cl or OH, the 1,1-C[sub 2]H[sub 2]Cl[sub 2] forms the 1,1-dichlorinated vinyl radical CCl[sub 2]CH. This radical reacts via competing routes CCl[sub 2]CH = C[sub 2]HCl + Cl, CCl[sub 2]CH + O[sub 2] = COCl[sub 2] + HCO, to form chloroacetylene or phosgene.

  5. Study of ketone body kinetics in children by a combined perfusion of /sup 13/C and /sup 2/H3 tracers

    SciTech Connect

    Bougneres, P.F.; Ferre, P.

    1987-11-01

    Ketone body kinetics were quantified in six children (3-5 yr old), who were fasted for 13-22 h, by a combined perfusion of (3-/sup 13/C)acetoacetate ((/sup 13/C)AcAc) and D-(-)-beta-(4,4,4-/sup 2/H3)hydroxybutyrate (beta-(/sup 2/H3)OHB) and gas chromatography-mass spectrometry analysis. Results were analyzed according to the single-pool (combined enrichments) or the two-accessible pools models. After 20-22 h of fasting, ketone body turnover rate was 30-50 mumol.kg-1.min-1, a rate achieved after several days of fasting in adults. At low ketosis, acetoacetate was the ketone body preferentially synthesized de novo and utilized irreversibly. When ketosis increased, acetoacetate irreversible disposal was not enhanced, since it was largely converted into beta-OHB, whereas beta-OHB irreversible disposal was very much increased. The single-pool and two-pool models gave similar ketone body turnover rates when (/sup 13/C)AcAc was the tracer, whereas the use of beta-(/sup 2/H3)OHB gave some more divergent results, especially at low ketosis. These studies demonstrate that ketogenesis is very active in short-term fasted children and that the use of a combined infusion of (/sup 13/C)AcAc and beta-(/sup 2/H3)OHB is a convenient way to give insight into individual ketone body kinetics.

  6. A rigorous full-dimensional quantum dynamics study of tunneling splitting of rovibrational states of vinyl radical C 2 H 3

    DOE PAGES

    Yu, Hua-Gen; Song, Hongwei; Yang, Minghui

    2017-06-12

    Here, we report a rigorous quantum mechanical study of the rovibrational energy levels of vinyl radical C2H3. The calculations are carried out using a real two-component multi-layer Lanczos algorithm in a set of orthogonal polyspherical coordinates based on a recently developed accurate ab initio potential energy surface of C2H3. All well converged 158 vibrational bands up to 3200 cm-1 are determined, together with a comparison to previous calculations and experimental results. Our results show a remarkable multi-dimensional tunneling effect on the vibrational spectra of the radical. The vibrational tunneling splitting is substantially different from that of previous reduced dimensional calculations.more » The rotational constants of the fundamental vibrational bands of C2H3 are also given. It was found that the rovibrational states are strongly coupled, especially among those bending vibrational modes. Additionally, the perturbative iteration approach of Gruebele has been extended to assign the rovibrational energy levels of C2H3 without the requirement of explicit wavefunctions.« less

  7. 125Te NMR study of IrTe 2

    NASA Astrophysics Data System (ADS)

    Mizuno, Kiyoshi; Magishi, Ko-ichi; Shinonome, Yasuaki; Saito, Takahito; Koyama, Kuniyuki; Matsumoto, Nobuhiro; Nagata, Shoichi

    2002-03-01

    We have measured 125Te NMR of IrTe2 in order to elucidate the origin of the anomalous behaviors in electrical and magnetic properties around 270 K. In high-temperature region, the NMR spectrum exhibits a sharp line. On the other hand, in low-temperature region, the spectrum shifts to higher magnetic field and splits into three lines. Also, the nuclear spin-lattice relaxation rate, 1/T1, is proportional to the temperature in both temperature sides; Korringa-like behavior which is characteristic of a metallic state. From the T dependences of the spectrum and 1/T1 around 270 K, it is suggested that these anomalous behaviors may not be due to the charge density wave formation but be caused by a kind of lattice distortion at low temperature.

  8. NMR study of mesomorphic solutions of cellulose derivatives

    SciTech Connect

    Dayan, S.; Fried, F.; Gilli, J.M.; Sixou, P.

    1983-01-01

    Highly concentrated solutions of hydroxypropylcellulose and cellulose acetate give mesomorphic phases in a precise range of temperatures and concentrations. The existence of an orientational anisotropy in such solutions induces typical parameters of the high-resolution NMR spectra (chemical shift, splitting) that are similar to those of liquid crystal spectra. In the present work, the high-resolution NMR spectra of nuclei belonging to the solute molecules (D/sub 2/O and trifluoroacetic acid) were recorded as a function of various physical parameters such as temperature, concentration, and temporal change of the solutions. The specific variation of the orientational degree of order for each mesophase is described. In the case of the cellulose acetate/trifluoroacetic acid solution, an order parameter is calculated and a model for the orientational organization of the solution is described. 34 references, 10 figures, 1 table.

  9. Multiwavelength study of RX J2015.6+3711: a magnetic cataclysmic variable with a 2-h spin period

    NASA Astrophysics Data System (ADS)

    Coti Zelati, F.; Rea, N.; Campana, S.; de Martino, D.; Papitto, A.; Safi-Harb, S.; Torres, D. F.

    2016-02-01

    The X-ray source RX J2015.6+3711 was discovered by ROSAT in 1996 and recently proposed to be a cataclysmic variable (CV). Here, we report on an XMM-Newton observation of RX J2015.6+3711 performed in 2014, where we detected a coherent X-ray modulation at a period of 7196 ± 11 s and discovered other significant (>6σ) small-amplitude periodicities which we interpret as the CV spin period and the sidebands of a possible ˜12-h periodicity, respectively. The 0.3-10 keV spectrum can be described by a power law (Γ = 1.15 ± 0.04) with a complex absorption pattern, a broad emission feature at 6.60 ± 0.01 keV, and an unabsorbed flux of (3.16 ± 0.05) × 10-12 erg cm-2 s-1. We observed a significant spectral variability along the spin phase, which can be ascribed mainly to changes in the density of a partial absorber and the power law normalization. Archival X-ray observations carried out by the Chandra satellite, and two simultaneous X-ray and UV/optical pointings with Swift, revealed a gradual fading of the source in the soft X-rays over the last 13 yr, and a rather stable X-ray-to-optical flux ratio (FX/FV ≈ 1.4-1.7). Based on all these properties, we identify this source with a magnetic CV, most probably of the intermediate polar type. The 2-h spin period makes RX J2015.6+3711, the second slowest rotator of the class, after RX J0524+4244 (`Paloma'; Pspin ˜ 2.3 h). Although we cannot unambiguously establish the true orbital period with these observations, RX J2015.6+3711 appears to be a key system in the evolution of magnetic CVs.

  10. 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.

  11. Phase Separation in Polyurethanes - A Deuterium NMR Study.

    DTIC Science & Technology

    1985-02-18

    from the diphenylmethane diisocyanate (MDI) or the soft segment polyol residues. The deuteriunm NMR spectra’ 9 for these four samples are shown in...other decays more slowly and is assigned to the polyester soft segments. With proton spin diffusion as an experimental probe, Assink and Wilkes3 4 35...evaluated phase mixing in a series of MDI- polyester polyurethanes. Their data require the presence of both short and long range degrees of mixing

  12. Study of an organogelator by diffusion-ordered NMR spectroscopy.

    PubMed

    Dama, Murali; Berger, Stefan

    2013-05-09

    The low-molecular weight organogelator 2,3-di-n-decyloxyanthracene was synthezised and dissolved in dimethyl sulfoxide. With diffusion-ordered NMR spectroscopy, the temperature dependence of the diffusion coefficients was measured and a clear hysteresis of the gelation was observed between 320 and 330 K. This hysteresis was interpreted with respect to different entanglement behavior on heating and cooling. No alignment of the gelator with respect to the magnetic field was found despite its 14 π-electrons.

  13. NMR studies of molecules in liquid crystals and graphite

    SciTech Connect

    Rosen, Mark Edward

    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.

  14. 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.

  15. 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.

  16. Molecular Mobility of the Interface in a Model Composite: A NMR Study

    DTIC Science & Technology

    1992-07-15

    liquid recovered. This product was analyzed without separation by 1H and 13C NMR to be 2-(N’-butylamino)-N-methylmaleimide. The reaction in acetone...TITLE AND SUBTITLE 5. FUNDING NUMBERS Molecular Mbility of the Interface in a Model Composite: A NMR Study N00014-91-J-1274 6. AUTHOR(S) Joan E. Gamblgi...Maximum 200 worus) The interface of a model polymer composite has been probed using solid-state NMR techniques. The adsorption of aminoalkylsilane

  17. 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.

  18. Conformational studies by 1H and 13C NMR of lisinopril

    NASA Astrophysics Data System (ADS)

    Sakamoto, Yohko; Ishi, Tomoko

    1993-10-01

    Lisinopril, N-N-[( s-1-carboxy-3-phenylpropyl]- L-lysyl- L-proline) (MK-521), is an inhibitor of angiotensin-converting enzyme and a new drug for the treatment of hypertension. 1H and 13C NMR studies have shown that the s-cis equilibrium about the amide bond is strongly dependent on the configuration of the chiral centres. Vicinal coupling constants of stereochemical significance were obtained in deuterated solvent using NMR techniques. Comparison with values calculated for lisinopril using potential energy calculations and NMR show that lisinopril exists in preferred optimum conformation in solution.

  19. 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.

  20. Investigation of structural information for boron-rich solids and aluminates via NMR and NQR studies

    SciTech Connect

    Lee, D.

    1991-01-01

    Along with NMR, Nuclear Quadrupole Resonance (NQR) has become important recently for obtaining structural information from oxide glasses. The NQR studies prove in this thesis that they provide more accurate structural information than the NMR studies have done. This study presents boron and aluminum NMR, and NQR studies for some borate glasses and compounds, icosahedral boron-rich solids, some crystalline aluminosilicates. Various borates were employed to acquire structural information as well as to determine the quadrupole parameters (the quadrupole coupling constant Qcc and the asymmetry parameter {eta}) using NQR under a guidance of NMR or vice versa. By NQR a previously unknown boron site was observed for vitreous Li{sub 2}O{center dot}B{sub 2}O{sub 3}. The NMR and NQR studies were performed on some icosachedral boron-rich solids: {alpha}-rhombohedral boron (B{sub 12}), {beta}-boron (B{sub 105}) and boron carbide (B{sub 12}C{sub 3}). Three different forms of crystalline aluminosilicate (Al{sub 2}SiO{sub 5}) were studied by NQR. The NQR study yielded more accurate values of the quadrupole parameters for {sup 27}Al than the previous NMR single crystal study did.

  1. Benchmark Theoretical and Experimental Study on (15)N NMR Shifts of Oxidatively Damaged Guanine.

    PubMed

    Dračínský, Martin; Šála, Michal; Klepetářová, Blanka; Šebera, Jakub; Fukal, Jiří; Holečková, Veronika; Tanaka, Yoshiyuki; Nencka, Radim; Sychrovský, Vladimír

    2016-02-11

    The (15)N NMR shifts of 9-ethyl-8-oxoguanine (OG) were calculated and measured in liquid DMSO and in crystal. The OG molecule is a model for oxidatively damaged 2'-deoxyguanosine that occurs owing to oxidative stress in cell. The DNA lesion is repaired with human 8-oxoguanine glycosylase 1 (hOGG1) base-excision repair enzyme, however, the exact mechanism of excision of damaged nucleobase with hOGG1 is currently unknown. This benchmark study on (15)N NMR shifts of OG aims their accurate structural interpretation and calibration of the calculation protocol utilizable in future studies on mechanism of hOGG1 enzyme. The effects of NMR reference, DFT functional, basis set, solvent, structure, and dynamics on calculated (15)N NMR shifts were first evaluated for OG in crystal to calibrate the best performing calculation method. The effect of large-amplitude motions on (15)N NMR shifts of OG in liquid was calculated employing molecular dynamics. The B3LYP method with Iglo-III basis used for B3LYP optimized geometry with 6-311++G(d,p) basis and including effects of solvent and molecular dynamic was the calculation protocol used for calculation of (15)N NMR shifts of OG. The NMR shift of N9 nitrogen of OG was particularly studied because the atom is involved in an N-glycosidic bond that is cleaved with hOGG1. The change of N9 NMR shift owing to oxidation of 9-ethylguanine (G) measured in liquid was -27.1 ppm. The calculated N9 NMR shift of OG deviated from experiment in crystal and in liquid by 0.45 and 0.65 ppm, respectively. The calculated change of N9 NMR shift owing to notable N9-pyramidalization of OG in one previously found polymorph was 20.53 ppm. We therefore assume that the pyramidal geometry of N9 nitrogen that could occur for damaged DNA within hOGG1 catalytic site might be detectable with (15)N NMR spectroscopy. The calculation protocol can be used for accurate structural interpretation of (15)N NMR shifts of oxidatively damaged guanine DNA residue.

  2. From precursors to non-oxide ceramics: Pyrolytic mechanisms studied by NMR

    SciTech Connect

    Sigmund, W.M.; Aldinger, F.; Feike, M.; Spiess, H.W.

    1996-12-31

    The pyrolysis of a poly ethylsilazane was studied using a CO{sub 2}-laser beam heated solid state MAS-NMR probe head. Chemical structures of the intermediate stages could be identified. The analogy of the pyrolysis evolution for the following two different methods could be shown: (A) in an inert gas furnace conventionally prepared and (B) laser irradiated in the NMR probe head under magic-angle spinning (MAS) conditions. Samples prepared by method A were studied by {sup 29}Si MAS-NMR and samples prepared by method B were studied with an appropriate cross polarization time by {sup 29}Si CP-MAS-NMR. Both experiments showed the same mechanisms for the pyrolysis as the polymer is transformed into a Si{sub 3}N{sub 4}/C ceramic.

  3. An experimental study iof the diffusion of C and O in calcite in mixed Co2-H2O fluids.

    SciTech Connect

    Labotka, Theodore C.; Cole, David; Fayek, Mostafa; Chacko, Thomas {nmn}

    2011-01-01

    The diffusivity of C and O in calcite in mixed CO2-H2O fluid was determined over the range in xCO2 from 1.0 to about 0.2 at 700 C, 100 MPa, with selected experiments conducted at pressures to 250 MPa and temperatures of 600 and 800 C. The diffusivity of C, DC, varies little with xCO2, although there is some evidence for a slight increase in DC from 5 10 18 to 5 10 17 cm2/s with decreasing xCO2. Our data and those of others are consistent with a model for DC 1/fCO2. Despite the large uncertainty, we observed that the diffusivity of O, DO, increases from 2 10 16 to 5 10 14 cm2/s with xCO2 decreasing from 1.0 to 0. There is a good correlation at 700 C between log DO and log fH2O regardless of the total pressure, matching the observations of previous workers. The data are consistent with a simple two-component model for the diffusion of O in calcite, one component for diffusion in the presence of CO2 and one in the presence of H2O: DO = DOCO2 + DOH2O aH2O. The activity of H2O is relative to the fugacity at 100 MPa, 700 C. DOCO2 is 3.45 10 16, and DOH2O is 3.8 10 14 cm2/s. The data indicate that the rate of diffusion of C and O in calcite is controlled by reactions at the surface of calcite. Adsorption of H2O and the creation of vacancies at the surface account for the dependence of the diffusivity on the fugacity of the fluid components. There is little evidence that H itself diffuses into calcite. With this model and the values of DO in pure CO2 (Labotka et al. 2000) and in pure H2O (Farver 1994), the value of DO is predicted over the temperature range 600 800 C and pH2O up to 300 MPa, the range of the data. Calculated closure temperatures for diffusive exchange of O between calcite and fluid are reduced by about 150 C in the presence of an aqueous fluid.

  4. Comparative study of the degradation of real textile effluents by photocatalytic reactions involving UV/TiO2/H2O2 and UV/Fe2+/H2O2 systems.

    PubMed

    Garcia, J C; Oliveira, J L; Silva, A E C; Oliveira, C C; Nozaki, J; de Souza, N E

    2007-08-17

    This work investigated the treatability of real textile effluents using several systems involving advanced oxidation processes (AOPs) such as UV/H2O2, UV/TiO2, UV/TiO2/H2O2, and UV/Fe2+/H2O2. The efficiency of each technique was evaluated according to the reduction levels observed in the UV absorbance of the effluents, COD, and organic nitrogen reduction, as well as mineralization as indicated by the formation of ammonium, nitrate, and sulfate ions. The results indicate the association of TiO2 and H2O2 as the most efficient treatment for removing organic pollutants from textile effluents. In spite of their efficiency, Fenton reactions based treatment proved to be slower and exhibited more complicated kinetics than the ones using TiO2, which are pseudo-first-order reactions. Decolorization was fast and effective in all the experiments despite the fact that only H2O2 was used.

  5. Recent progress in solid-state NMR studies of drugs confined within drug delivery systems.

    PubMed

    Skorupska, Ewa; Jeziorna, Agata; Kazmierski, Slawomir; Potrzebowski, Marek J

    2014-01-01

    Recent progress in the application of solid-state NMR (SS NMR) spectroscopy in structural studies of active pharmaceutical ingredients (APIs) embedded in different drug carriers is detailed. This article is divided into sections. The first part reports short characterization of the nanoparticles and microparticles that can be used as drug delivery systems (DDSs). The second part shows the applicability of SS NMR to study non-steroidal anti-inflammatory drugs (NSAIDs). In this section, problems related to API-DDS interactions, morphology, local molecular dynamics, nature of inter- or intramolecular connections, and pore filling are reviewed for different drug carriers (e.g. mesoporous silica nanoparticles (MSNs), cyclodextrins, polymeric matrices and others). The third and fourth sections detail the recent applications of SS NMR for searching for antibiotics and anticancer drugs confined in zeolites, MSNs, amorphous calcium phosphate and other carriers.

  6. Low-temperature IR and NMR studies of the interaction of group 8 metal dihydrides with alcohols.

    PubMed

    Gutsul, Evgenii I; Belkova, Natalia V; Sverdlov, Maria S; Epstein, Lina M; Shubina, Elena S; Bakhmutov, Vladimir I; Gribanova, Tatiana N; Minyaev, Ruslan M; Bianchini, Claudio; Peruzzini, Maurizio; Zanobini, Fabrizio

    2003-05-23

    The reactions of the octahedral dihydrido complexes [MH(2)(PP(3))] [M=Fe, Ru, Os; PP(3)=P(CH(2)CH(2)PPh(2))(3)] with a variety of weak ROH acids have been studied by IR and NMR methods in either CH(2)Cl(2) or THF in the temperature range from 190 to 290 K. This study has allowed the determination of the spectral and thermodynamic properties associated with the formation of dihydrogen bonds (DHB) between the terminal hydrides and the OH group. Both the DHB enthalpy values and the hydride basicity factors (E(j)) have been found to increase in the order Fe < Ru < Os. The proton transfer process, leading to the DHB complexes, and eventually to eta(2)-H(2) products, has been found to depend on the acidic strength of the alcohol as well as the nature of the solvent. Low temperature IR and NMR techniques have been used to trace the complete energy profile of the proton transfer process involving the osmium complex [OsH(2)(PP(3))] with trifluoroethanol.

  7. A comparative adsorption study of C2H4 and SO2 on clinoptilolite-rich tuff: effect of acid treatment.

    PubMed

    Erdoğan Alver, Burcu

    2013-11-15

    In this study, ethylene (C2H4) and sulphur dioxide (SO2) adsorption properties of clinoptilolite tuff from Gördes, Turkey and that of acid treated forms were studied at 293K using volumetric apparatus up to 38 and 100 kPa, respectively. In order to consider the effect of acid treatment on structural and gas adsorption properties of zeolite, clinoptilolite mineral was modified with 0.1, 0.5, 1.0 and 2.0M HCl solutions at 70 °C during 3h. XRD, XRF, TG/DTG, DTA and N2 adsorption methods were employed for thermal and structural characterization of clinoptilolite samples before and after the acid treatment. SO2 adsorption capacities (2.356-2.739 mmol/g) of the clinoptilolite samples were superior to those of the C2H4 adsorptions (0.619-1.219 mmol/g).

  8. 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.

  9. 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.

  10. An NMR probe for the study of aerobic suspensions of cells and organelles

    SciTech Connect

    Balaban, R.S.; Gadian, D.G.; Radda, G.K.; Wong, G.G.

    1981-09-15

    The construction of an NMR probe and cell chamber with good mixing, pH buffering, and oxygenation characteristics, which can be used for relatively dilute cell and organelle suspension is described. The /sup 31/P NMR spectra of acceptable signal-to-noise ratios are obtained from approximately 200 mg (protein) of tissues, and kinetic studies of mitochondrial oxidative phosphorylation are demonstrated. Representative spectra from rabbit kidney cortical tubules and rabbit kidney cortical mitochondria are presented.

  11. 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.

  12. NMR studies on the flexibility of nucleoside diphosphate kinase.

    PubMed

    Xu, Y; Lecroisey, A; Veron, M; Delepierre, M; Janin, J

    1997-06-01

    Human NDP kinase B, product of the nm23-H2 gene, binds DNA. It has been suggested that a helix hairpin on the protein surface, part of the nucleotide substrate binding site, could accommodate DNA binding by swinging away. The presence of flexible regions was therefore investigated by 1H NMR dynamic filtering. Although TOCSY peaks could be assigned to five residues at the N terminus of Dictyostelium NDP kinase, no flexible region was detected in the human enzyme. These data favor the idea that the protein offers different binding sites to mono- and polynucleotides.

  13. NMR study of seven coumarins from mammea siamensis.

    PubMed

    Prachyawarakorn, V; Mahidol, C; Ruchirawat, S

    2000-01-01

    Seven known mammea coumarins, mammea A/AA cyclo D ( 1 ), mammea A/AD cyclo D ( 2 ), mammea A/AB cyclo D ( 3 ), mammea A/AC cyclo F ( 4 ), mam-mea A/AB cyclo F ( 5 ), mammea A/AA cyclo F ( 6 ), mammea B/AC cyclo F ( 7 ), were isolated for the first time from the hexane extract of Mammea siamensis . A detailed analysis of both 1D and 2D NMR spectral data of these compounds was made.

  14. An ab initio study of the C2H2-HF, C2H(CH3)-HF and C2(CH3)2-HF hydrogen-bonded complexes.

    PubMed

    Ramos, Mozart N; Lopes, Kelson C; Silva, Washington L V; Tavares, Alessandra M; Castriani, Fátima A; do Monte, Silmar A; Ventura, Elizete; Araújo, Regiane C M U

    2006-02-01

    MP2/6-31++G** and B3LYP/6-31++G** ab initio molecular orbital calculations have been performed in order to obtain molecular geometries, binding energies and vibrational properties of the C2H2-HF, C2H(CH3)-HF and C2(CH3)2-HF H-bonded complexes. As expected, the more pronounced effects on the structural properties of the isolated molecules due to complexation was verified for the C[triple bond]C and H-F bond lengths, which are directly involved in the H-bond formation. These bond distances increased after complexation. BSSE uncorrected B3LYP binding energies are always lower than the corresponding MP2 values. However, the opposite trend has been verified after BSSE correction by the counterpoise method since it is much lower at B3LYP than at MP2 level. The binding energies for these complexes as well as for the HF acid submolecule modes (the HF stretching and vibrational frequency modes) showed an increasing hydrogen-bonding strength with increasing methyl substitution. The splitting in the HF in-plane and out-of-plane bending modes reflects the anisotropy in the hydrogen-bonding interaction with the pi system of the C[triple bond]C bond. The H-F stretching frequency is shifted downward after complexation and it increases with the methyl substitution. The IR intensities of the HF acid submolecule fundamentals are adequately interpreted through the atomic polar tensor of the hydrogen atom using the charge-charge flux-overlap model. The skeletal stretching modes of the Alkyne submolecule are decreased in the complex. The new vibrational modes arising from complexation show several interesting features.

  15. NMR studies on the temperature-dependent dynamics of confined water.

    PubMed

    Sattig, Matthias; Reutter, Stefan; Fujara, Franz; Werner, Mayke; Buntkowsky, Gerd; Vogel, Michael

    2014-09-28

    We use (2)H NMR to study the rotational motion of supercooled water in silica pores of various diameters, specifically, in the MCM-41 materials C10, C12, and C14. Combination of spin-lattice relaxation, line-shape, and stimulated-echo analyses allows us to determine correlation times in very broad time and temperature ranges. For the studied pore diameters, 2.1-2.9 nm, we find two crossovers in the temperature-dependent correlation times of liquid water upon cooling. At 220-230 K, a first kink in the temperature dependence is accompanied by a solidification of a fraction of the confined water, implying that the observed crossover is due to a change from bulk-like to interface-dominated water dynamics, rather than to a liquid-liquid phase transition. Moreover, the results provide evidence that α process-like dynamics is probed above the crossover temperature, whereas β process-like dynamics is observed below. At 180-190 K, we find a second change of the temperature dependence, which resembles that reported for the β process of supercooled liquids during the glass transition, suggesting a value of Tg ≈ 185 K for interface-affected liquid water. In the high-temperature range, T > 225 K, the temperature dependence of water reorientation is weaker in the smaller C10 pores than in the larger C12 and C14 pores, where it is more bulk-like, indicating a significant effect of the silica confinement on the α process of water in the former 2.1 nm confinement. By contrast, the temperature dependence of water reorientation is largely independent of the confinement size and described by an Arrhenius law with an activation energy of Ea ≈ 0.5 eV in the low-temperature range, T < 180 K, revealing that the confinement size plays a minor role for the β process of water.

  16. Theoretical studies of UO2(H2O)n2+,NpO2(H2O)n+, and PuO2(H2O)n2+ complexes (n=4-6) in aqueous solution and gas phase

    NASA Astrophysics Data System (ADS)

    Cao, Zhiji; Balasubramanian, K.

    2005-09-01

    Extensive ab initio calculations both in gas phase and solution have been carried out to study the equilibrium structure, vibrational frequencies, and bonding characteristics of various actinyl (UO22+,NpO2+, and PuO22+) and their hydrated forms, AnO2(H2O)nz + (n =4, 5, and 6). Bulk solvent effects were studied using a continuum method. The geometries were fully optimized at the coupled-cluster singles + doubles (CCSD), density-functional theory (DFT), and Møller-Plesset (MP2) level of theories. In addition vibrational frequencies have been obtained at the CCSD as well as MP2/DFT levels. The results show that both the short-range and long-range solvent effects are important. The combined discrete-continuum model, in which the ionic solute and the solvent molecules in the first and second solvation shells are treated quantum mechanically while the solvent is simulated by a continuum model, can predict accurately the bonding characteristics. Moreover, our values of solvation free energies suggest that five- and six-coordinations are equally preferred for UO22+, and five-coordinated species are preferred for NpO2+ and PuO22+. On the basis of combined quantum-chemical and continuum treatments of the hydrated complexes, we are able to determine the optimal cavity radii for the solvation models. The coupled-cluster computations with large basis sets were employed for the vibrational spectra and equilibrium geometries both of which compare quite favorably with experiment. Our most accurate computations reveal that both five- and six-coordination complexes are important for these species.

  17. Indirect use of deuterium in solution NMR studies of protein structure and hydrogen bonding.

    PubMed

    Tugarinov, Vitali

    2014-02-01

    A description of the utility of deuteration in protein NMR is provided with an emphasis on quantitative evaluation of the effects of deuteration on a number of NMR parameters of proteins: (1) chemical shifts, (2) scalar coupling constants, (3) relaxation properties (R1 and R2 rates) of nuclei directly attached to one or more deuterons as well as protons of methyl groups in a highly deuterated environment, (4) scalar relaxation of 15N and 13C nuclei in 15N-D and 13C-D spin systems as a measure of hydrogen bonding strength, and (5) NOE-based applications of deuteration in NMR studies of protein structure. The discussion is restricted to the 'indirect' use of deuterium in the sense that the description of NMR parameters and properties of the nuclei affected by nearby deuterons (15N, 13C, 1H) is provided rather than those of deuterium itself. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. NMR and NQR studies of URu2Si2 and isostructural nonmagnetic references

    NASA Astrophysics Data System (ADS)

    Emi, Naoya; Hamabata, Ryosuke; Koyama, Takehide; Ueda, Koichi; Mito, Takeshi; Kohori, Yoh; Matsumoto, Yuji; Haga, Yoshinori; Yamamoto, Etsuji; Fisk, Zachary

    2017-06-01

    The non-f compound ThRu2Si2 has been studied as an isostructural nonmagnetic reference for URu2Si2 using nuclear magnetic resonance (NMR) measurement. The temperature dependences of Knight shifts measured by 29Si-NMR and 99Ru-NMR are independent of temperature. The results are consistent with data previously reported on the susceptibility. 101Ru-NQR frequency 101 ν Q was also estimated from the 99Ru-NMR measurement. 101 ν Q of ThRu2Si2 is close to that of URu2Si2, especially at high temperatures, suggesting that U ions in URu2Si2 are in a nearly tetravalent state.

  19. A density functional study of (17)O, (14)N and (2)H electric field gradient tensors in the real crystalline structure of alpha-glycine.

    PubMed

    Behzadi, Hadi; Hadipour, Nasser L; Mirzaei, Mahmoud

    2007-01-01

    A density functional theory (DFT) study was carried out to calculate (17)O, (14)N and (2)H electric field gradient (EFG) tensors in accurate neutron diffraction structures of alpha-glycine at 288 and 427 K. B3LYP is the used method and 6-311+G(*) and 6-311++G(**) are the basis sets in the calculations of EFG tensors at the sites of (17)O, (14)N and (2)H nuclei in the monomer and the octameric cluster of alpha-glycine at two temperatures. Quadrupole coupling constants and asymmetry parameters are the converted parameters of calculated EFG tensors to experimentally measurable ones. The calculated results of monomer and the target molecule in octameric cluster reveal that hydrogen-bonding interactions play an important role in the crystalline structure of alpha-glycine where the results of the target molecule in octameric cluster are in good agreement with the experiments.

  20. 1H, 13C NMR and DFT Study of Hydrogen Bonding in Imidazolium-based Ionic Liquids.

    PubMed

    Balevičius, Vytautas; Gdaniec, Zofia; Džiaugys, Lukas; Kuliešius, Feliksas; Maršalka, Arūnas

    2011-09-01

    The ionic liquid 1-decyl-3-methyl-imidazolium bromide [C10mim][Br], the neat material, and also dissolved (~0.01 mole fraction) in various dielectric media (acetonitrile, benzene, chloroform, dichloromethane, methanol, 2-butanol and H2O) was studied using 1H and 13C NMR spectroscopy. The most important interaction in this compound is considered to be the Br-...H-C2+ hydrogen bond, which is formed between the anions and cations. The obtained results show that dielectric medium influence mostly the behavior of the Br-...H-C2+ bridge proton. The changes observed in 1H and 13C NMR spectra of [C10mim][Br] with increasing solvents polarity and temperature can be explained applying the model of the lengthening of the H2...Br- bond with the accompanying thickening of the solvation shell of bromine anion and C2-H bond contraction. The short-range order effects related to the configuration of neighboring dipoles of solvent molecules are more important for the solvation ability of small anions than the bulk solvent field effect. However, the solvents, molecules of which tend to associate via hydrogen bonding, can significantly affect the dynamics of anions.

  1. Further Studies on 2-Arylacetamide Pyridazin-3(2H)-ones: Design, Synthesis and Evaluation of 4,6-Disubstituted Analogues as Formyl Peptide Receptors (FPRs) Agonists

    PubMed Central

    Giovannoni, Maria Paola; Schepetkin, Igor A.; Cilibrizzi, Agostino; Crocetti, Letizia; Khlebnikov, Andrei I.; Dahlgren, Claes; Graziano, Alessia; Piaz, Vittorio Dal; Kirpotina, Liliya N.; Zerbinati, Serena; Vergelli, Claudia; Quinn, Mark T.

    2013-01-01

    Formyl peptide receptors (FPRs) play an essential role in the regulation of endogenous inflammation and immunity. In the present studies, a large series of pyridazin-3(2H)-one derivatives bearing an arylacetamide chain at position 2 was synthesized and tested for FPR agonist activity. The pyridazin-3(2H)-one ring was confirmed to be an appropriate scaffold to support FPR agonist activity, and its modification at the 4 and 6 positions led to the identification of additional active agonists, which induced intracellular Ca2+ flux in HL-60 cells transfected with either FPR1, FPR2, or FPR3. Seven formyl peptide receptor 1 (FPR1)-specific and several mixed FPR1/FPR2 dual agonists were identified with low micromolar EC50 values. Furthermore, these agonists also activated human neutrophils, inducing intracellular Ca2+ flux and chemotaxis. Finally, molecular docking studies indicated that the most potent pyridazin-3(2H)-ones overlapped in their best docking poses with fMLF and WKYMVM peptides in the FPR1 and FPR2 ligand binding sites, respectively. Thus, pyridazinone-based compounds represent potential lead compounds for further development of selective and/or potent FPR agonists. PMID:23685570

  2. Isolation, purification and characterization of novel antimicrobial compound 7-methoxy-2,2-dimethyl-4-octa-4',6'-dienyl-2H-napthalene-1-one from Penicillium sp. and its cytotoxicity studies.

    PubMed

    Kaur, Harpreet; Onsare, Jemimah Gesare; Sharma, Vishal; Arora, Daljit Singh

    2015-12-01

    Fungus isolated from soil has been evaluated for its antimicrobial activity which showed broad spectrum antimicrobial activity against all the pathogenic microorganisms used. Optimization was done by response surface methodology (RSM) to further optimize the medium which could further enhance the antimicrobial activity by 1.1-1.9 folds. Column chromatography was used to isolate the active compound which was characterized to be by various spectroscopic techniques such NMR, IR and LCMS and it was found to be apparently novel compound 7-methoxy-2,2-dimethyl-4-octa-4',6'-dienyl-2 H -napthalene-1-one. MIC of the active compound ranged from (0.5-15 µg/mL which was found to be comparable with the standard antibiotics. Viable cell count studies of the active compound showed it to be bactericidal in nature. Further, the compound when tested for its biosafety was found neither to be cytotoxic nor mutagenic. Cytotoxicity studies of the compound on cancer cell lines showed a valuable cytotoxic potential against all tested human cancer cell lines. Further, the compound induces apoptosis in lung cancer (A549) cells reveled by increase the distribution of nuclear DNA in Sub G1 phase as observed in flow cytometry. The study demonstrated that an apparently novel compound isolated from Penicillium sp. seems to be a stable and potent antimicrobial.

  3. Dynamical properties of confined supercooled water: an NMR study

    NASA Astrophysics Data System (ADS)

    Mallamace, Francesco; Broccio, Matteo; Corsaro, Carmelo; Faraone, Antonio; Liu, Li; Mou, Chung-Yuan; Chen, Sow-Hsin

    2006-09-01

    We report a set of dynamical data of confined water measured in a very deeply supercooled regime (290-190 K). Water is contained in silica matrices (MCM-41-S) which consist of 1D cylindrical pores with diameters d = 14,18 and 24 Å. When confined in these tubular pores, water does not crystallize, and can be supercooled well below 200 K. We use the NMR technique to obtain the characteristic proton relaxation time-constants (the spin-lattice relaxation time-constant T1 and the spin-spin relaxation time-constant T2) and a direct measurement of the self-diffusion coefficient in the whole temperature range. We give evidence of the existence of a fragile-to-strong dynamic crossover (FSC) at TL = 225 K from the temperature dependence of the self-diffusion coefficient. A combination of the NMR self-diffusion coefficient with the average translational relaxation time, as measured by quasi-elastic neutron scattering, shows a well defined decoupling of transport coefficients, i.e. the breakdown of the Stokes-Einstein relation, on approaching the crossover temperature TL.

  4. Cell-free protein production for NMR studies.

    PubMed

    Takeda, Mitsuhiro; Kainosho, Masatsune

    2012-01-01

    The cell-free expression system using an Escherichia coli extract is a practical method for producing isotope-labeled proteins. The advantage of the cell-free system over cellular expression is that any isotope-labeled amino acid can be incorporated into the target protein with minimal scrambling, thus providing opportunities for advanced isotope labeling of proteins. We have modified the standard protocol for E. coli cell-free expression to cope with two problems specific to NMR sample preparation. First, endogenous amino acids present in the E. coli S30 extract lead to dilution of the added isotope. To minimize the content of the remaining amino acids, a gel filtration step is included in the preparation of the E. coli extract. Second, proteins produced by the cell-free system are not necessarily homogeneous due to incomplete processing of the N-terminal formyl-methionine residue, which complicates NMR spectra. Therefore, the protein of interest is engineered to contain a cleavable N-terminal histidine-tag, which generates a homogeneous protein after the digestion of the tag. Here, we describe the protocol for modified E. coli cell-free expression.

  5. 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.

  6. NMR study of CeTe at low temperatures

    NASA Astrophysics Data System (ADS)

    Hinderer, J.; Weyeneth, S. M.; Weller, M.; Gavilano, J. L.; Felder, E.; Hulliger, F.; Ott, H. R.

    2006-05-01

    We present 125Te NMR measurements on CeTe powder at temperatures between 1 and 150 K and in magnetic fields between 5 and 8 T. CeTe is a rocksalt-type intermetallic compound. It orders antiferromagnetically at TN≈2.2 K with a much reduced ordered moment [H.R. Ott, J.K. Kjems, F. Hulliger, Phys. Rev. Lett. 42 20 (1979) 1378]. From our low-temperature NMR spectra we infer the presence of at least three inequivalent Te sites at low temperatures. Considering the crystal structure this result is completely unexpected. The linewidths and the Knight shifts of the individual lines are significantly different and increase substantially with decreasing temperature. They follow the temperature dependence of the magnetic susceptibility above 20 K. Above TN, hyperfine fields of 1.6, 0.8 and 0.0 T at the three Te sites per Bohr magneton of Ce moment are deduced from Knight shift vs. magnetic susceptibility data. These values are typical for transferred hyperfine fields via conduction electrons.

  7. Positional isotope exchange studies on enzyme using NMR spectroscopy

    SciTech Connect

    Matsunaga, T.O.

    1987-01-01

    The isotopically enriched compounds, /sup 18/O-..beta..,..gamma..-ATP and /sup 18/O bridge-labeled pyrophosphate, synthesized previously in this laboratory, were used to investigate and measure the exchange vs. turnover of substrates and products from their central complexes in four selected enzyme systems. Using hi-field /sup 31/P NMR, we were able to differentiate between /sup 18/O labeled in the bridge vs. the non-bridge positions by virtue of the isotope shift upon the phosphorus nuclei. The bridge to non-bridge scrambling of the label was quantitated and the exchange vs. turnover ratios under a variety of conditions was determined. Using the substrate inhibitor carboxycreatinine, PIX experiments with /sup 18/O-..beta..,..gamma..-ATP and creatine kinase were conducted. It was shown that carboxycreatinine and creatine kinase promoted exchange of the /sup 18/O label as determined by NMR. We have concluded that carboxycreatinine is either a substrate that catalyzes very slow turnover or it catalyzes exchange by a dissociative (SN/sub 1//sub P/) type of mechanism

  8. 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

  9. 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.

  10. 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.

  11. A Field Study of NMR Logging to Quantify Petroleum Contamination in Subsurface Sediments

    NASA Astrophysics Data System (ADS)

    Fay, E. L.; Knight, R. J.; Grunewald, E. D.

    2016-12-01

    Nuclear magnetic resonance (NMR) measurements are directly sensitive to hydrogen-bearing fluids including water and petroleum products. NMR logging tools can be used to detect and quantify petroleum hydrocarbon contamination in the sediments surrounding a well or borehole. An advantage of the NMR method is that data can be collected in both cased and uncased holes. In order to estimate the volume of in-situ hydrocarbon, there must be sufficient contrast between either the relaxation times (T2) or the diffusion coefficients (D) of water and the contaminant. In a field study conducted in Pine Ridge, South Dakota, NMR logging measurements were used to investigate an area of hydrocarbon contamination from leaking underground storage tanks. A contaminant sample recovered from a monitoring well at the site was found to be consistent with a mixture of gasoline and diesel fuel. NMR measurements were collected in two PVC-cased monitoring wells; D and T2 measurements were used together to detect and quantify contaminant in the sediments above and below the water table at both of the wells. While the contrast in D between the fluids was found to be inadequate for fluid typing, the T2 contrast between the contaminant and water in silt enabled the estimation of the water and contaminant volumes. This study shows that NMR logging can be used to detect and quantify in-situ contamination, but also highlights the importance of sediment and contaminant properties that lead to a sufficiently large contrast in T2 or D.

  12. 13C-NMR relation study of heparin-disaccharide interactions with tripeptides GRG and GKG.

    PubMed Central

    Mikhailov, D; Mayo, K H; Pervin, A; Linhardt, R J

    1996-01-01

    Heparin is a polydisperse sulphated copolymer consisting mostly of 1-->4 linked glucosamine and uronic acid residues, i.e. 2-deoxy-2-sulphamido-D-glucopyranose 6-sulphate and L-idopyranosyluronic acid 2-sulphate. 13C NMR has been used to study the interactions of heparinase-derived and purified heparin disaccharide with N- and C-terminally-blocked tripeptides GRG and GKG. Titration of the disaccharide with peptide indicates that GRG binds the disaccharide more strongly than does GKG, with interactions in either case being stronger at uronate ring positions. In the presence of GRG, a carboxylate pKa depression suggests electrostatic interactions between the arginine guanidinium group and the uronate carboxylate group. 13C relaxation data have been acquired for all disaccharide and peptide carbons in the presence and absence of GRG and GKG. 13C relaxation rates for the disaccharide are significantly faster in the presence of peptide, especially with GRG. Analysis of these relaxation data has been done in terms of molecular diffusion constants, D [symbol: see text] and D parallel, and an angle alpha between D parallel and a molecular frame defined by the moment of inertia tensor calculated for an internally rigid disaccharide. Disaccharide conformational space in these calculations has been sampled for both uronate half-chair forms (2H1 and 1H2) and over a range of glycosidic bond angles defined by motional order parameters and inter-residue nuclear Overhauser effects (+/- 30 degree from the average). In the absence of peptide, the ratio D [symbol: see text] /D parallel falls between 0.4 and 0.7; therefore molecular diffusion occurs preferentially about D parallel, which runs through both disaccharide rings. In the presence of peptide, D [symbol: see text] /D parallel is decreased, indicating that GRG is oriented along D parallel and proximal to the uronic acid ring. A model for this is shown. PMID:8615813

  13. Study of the Reaction Cl + Ethyl Formate at 700-950 Torr and 297 to 435 K: Product Distribution and the Kinetics of the Reaction C2H5OC(═O) → CO2 + C2H5.

    PubMed

    Kaiser, E W

    2016-05-26

    The kinetics and mechanism of the reaction of atomic chlorine with ethyl formate [Cl + CH3CH2O(C═O)H, reaction 1] have been examined. These experiments were performed at pressures of 760-950 Torr and temperatures from 297 to 435 K. Reactants and products were quantified by gas chromatography-flame ionization detector (GC/FID) analysis. The initial mixture contained ethyl formate, Cl2, and N2. Cl atoms were generated by UV photolysis of this initial mixture at 360 nm, which dissociates Cl2. The rate constant of reaction 1 was measured at 297 K relative to that of the reaction Cl + C2H5Cl (reaction 2), yielding the rate constant ratio k1/k2 = 1.09 ± 0.05. The final products formed from reaction 1 are ethyl chloroformate, 1-chloroethyl formate, and 2-chloroethyl formate. These products result from the reactions with Cl2 of the three free radicals formed by H atom abstraction from ethylformate in reaction 1. Based on the molar yields of these three chlorinated products, the yields of the three radicals formed from reaction 1 at 297 K are (25 ± 3) mole percent of CH3CH2O(C═O); (67 ± 5) mole percent of CH3CHO(C═O)H; and (8 ± 2) mole percent of CH2CH2O(C═O)H. A second phase of this experiment measured the rate constant of the decarboxylation of the ethoxy carbonyl radical [CH3CH2O(C═O) → CO2 + C2H5, reaction 4] relative to the rate constant of its reaction with Cl2 [CH3CH2O(C═O) + Cl2 → CH3CH2O(C═O)Cl + Cl, reaction 3a]. Over the temperature range 297 to 404 K at 1 atm total pressure, this ratio can be expressed by k4/k3a = 10(23.56±0.22) e(-(12700±375)/RT) molecules cm(-3). Estimating the value of k3a (which has not been measured) based on similar reactions, the expression k4 = 5.8 × 10(12) e(-(12700)/RT) s(-1) is obtained. The estimated error of this rate constant is ± a factor of 2 over the experimental temperature range. This rate expression is compared with recent ab initio calculations of the decarboxylation of the analogous methoxy

  14. Theoretical study of the dynamics of AR collisions with C2H6 and C2F6 at hyperthermal energy.

    PubMed

    Tasić, Uros; Hein, Pyae; Troya, Diego

    2007-05-10

    We present a classical-trajectory study of the dynamics of high-energy (5-12 eV) collisions between Ar atoms and the C2H6 and C2F6 molecules. We have constructed the potential-energy surfaces for these systems considering separately the Ar-molecule interactions (intermolecular potential) and the interactions within the molecule (intramolecular potential). The intermolecular surfaces consist of pairwise empirical potentials derived from high-accuracy ab initio calculations. The intramolecular potentials for C2H6 and C2F6 are described using specific-reaction-parameters semiempirical Hamiltonians and are calculated "on the fly", i.e., while the trajectories are evolving. Trajectory analysis shows that C2F6 absorbs more energy than C2H6 and is more susceptible to collision-induced dissociation (CID). C-C bond-breakage processes are more important than C-H or C-F bond breakage at the energies explored in this work. Analysis of the reaction mechanism for CID processes indicates that, although C-C breakage is mostly produced by side-on collisions, head-on collisions are more efficient in producing C-F or C-H dissociation. Our results suggest that high-energy collisions between closed-shell species of the natural low-Earth-orbit environment and spacecraft can contribute to the observed degradation of polymers that coat spacecraft surfaces.

  15. Contrast and Raman spectroscopy study of single- and few-layered charge density wave material: 2H-TaSe2

    PubMed Central

    Hajiyev, Parviz; Cong, Chunxiao; Qiu, Caiyu; Yu, Ting

    2013-01-01

    In this article, we report the first successful preparation of single- and few-layers of tantalum diselenide (2H-TaSe2) by mechanical exfoliation technique. Number of layers is confirmed by white light contrast spectroscopy and atomic force microscopy (AFM). Vibrational properties of the atomically thin layers of 2H-TaSe2 are characterized by micro-Raman spectroscopy. Room temperature Raman measurements demonstrate MoS2-like spectral features, which are reliable for thickness determination. E1g mode, usually forbidden in backscattering Raman configuration is observed in the supported TaSe2 layers while disappears in the suspended layers, suggesting that this mode may be enabled because of the symmetry breaking induced by the interaction with the substrate. A systematic in-situ low temperature Raman study, for the first time, reveals the existence of incommensurate charge density wave phase transition in single and double-layered 2H-TaSe2 as reflected by a sudden softening of the second-order broad Raman mode resulted from the strong electron-phonon coupling (Kohn anomaly). PMID:24005335

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

    PubMed

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

    2012-04-01

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

  17. Double-quantum-filtered 23Na NMR study of intracellular sodium in the perfused liver.

    PubMed Central

    Lyon, R C; McLaughlin, A C

    1994-01-01

    We acquired double-quantum-filtered 23Na NMR spectra from perfused liver, using a range of tau values from 0.2 to 24 ms, where tau is the separation between the first and second pi/2 pulses in the radio-frequency pulse sequence. For each tau value we compared the amplitude of the double-quantum-filtered 23Na NMR signal acquired from intracellular sodium ions when the liver was perfused with buffer containing the "shift reagent" Dy(PPP)2 to the amplitude of the total double-quantum-filtered 23Na NMR signal acquired when the liver was perfused with buffer containing no Dy(PPP)2. For tau < or = 4 ms, the average ratio of the two amplitudes was 0.98 +/- 0.03 (mean +/- SEM). For tau > or = 8 ms, the average ratio was significantly less than 1. These results demonstrate that double-quantum-filtered 23Na NMR signals acquired from perfused liver using short tau values arise almost exclusively from intracellular sodium ions, but double-quantum-filtered 23Na NMR signals acquired from perfused liver using long tau values contain contributions from both intracellular and extracellular sodium ions. This conclusion suggests that multiple-quantum-filtered 23Na NMR spectroscopy will be useful in studying intracellular sodium levels in the perfused liver, and possibly in the intact liver in vivo. PMID:7919009

  18. Protein folding and unfolding studied at atomic resolution by fast two-dimensional NMR spectroscopy.

    PubMed

    Schanda, Paul; Forge, Vincent; Brutscher, Bernhard

    2007-07-03

    Atom-resolved real-time studies of kinetic processes in proteins have been hampered in the past by the lack of experimental techniques that yield sufficient temporal and atomic resolution. Here we present band-selective optimized flip-angle short transient (SOFAST) real-time 2D NMR spectroscopy, a method that allows simultaneous observation of reaction kinetics for a large number of nuclear sites along the polypeptide chain of a protein with an unprecedented time resolution of a few seconds. SOFAST real-time 2D NMR spectroscopy combines fast NMR data acquisition techniques with rapid sample mixing inside the NMR magnet to initiate the kinetic event. We demonstrate the use of SOFAST real-time 2D NMR to monitor the conformational transition of alpha-lactalbumin from a molten globular to the native state for a large number of amide sites along the polypeptide chain. The kinetic behavior observed for the disappearance of the molten globule and the appearance of the native state is monoexponential and uniform along the polypeptide chain. This observation confirms previous findings that a single transition state ensemble controls folding of alpha-lactalbumin from the molten globule to the native state. In a second application, the spontaneous unfolding of native ubiquitin under nondenaturing conditions is characterized by amide hydrogen exchange rate constants measured at high pH by using SOFAST real-time 2D NMR. Our data reveal that ubiquitin unfolds in a gradual manner with distinct unfolding regimes.

  19. A DFT study of the mechanism of copper-catalyzed synthesis of 2H-indazoles from aryl azide.

    PubMed

    Li, Juan; Zhang, Qi; Wu, Caihong; Gu, Honghong; Yan, Bo

    2014-01-07

    DFT calculations have been performed to study the reaction mechanism of N-N bond formation from aryl azide catalyzed by the copper(I) iodide complex. We studied various activation modes for the azide group, and found that the azide group is activated by the Cu(μ-I)2Cu(TMEDA) dimer coordinating to the N-atom of phenyl imine and the internal N-atom of azide.

  20. Changes in triglycerides and high-density lipoprotein cholesterol may precede peripheral insulin resistance, with 2-h insulin partially mediating this unidirectional relationship: a prospective cohort study.

    PubMed

    Han, Tianshu; Cheng, Yu; Tian, Shuang; Wang, Li; Liang, Xi; Duan, Wei; Na, Lixin; Sun, Changhao

    2016-11-04

    Results of longitudinal researches regarding the temporal relationship between dyslipidemia and insulin resistance (IR) are inconsistent. This study assessed temporal relationships of blood lipids with IR and determined whether there are any mediating effects existed in these temporal relationships. This study examined a longitudinal cohort of 3325 subjects aged 20-74 years from China with an average of 4.2 years follow-up. Measurements of fasting blood lipids, as well as fasting and 2-h serum glucose and insulin, were obtained at two time points. The Gutt index and HOMA-IR were calculated as indicators of peripheral IR and hepatic IR. A cross-lagged path analysis was performed to examine the temporal relationships between blood lipids and IR. A mediation analysis was used to examine mediating effect. After adjusting for covariates, the cross-lagged path coefficients from baseline TG and HDL-C to follow-up Gutt index were significantly greater than those from baseline Gutt index to follow-up TG and HDL-C (β1 = -0.131 vs β2 = -0.047, P < 0.001 for TG; β1 = 0.134 vs β2 = 0.023, P < 0.001 for HDL-C). The path coefficients from baseline TG and HDL-C to follow-up 2-h insulin were significantly greater than those from baseline 2-h insulin to follow-up TG and HDL-C (β1 = 0.125 vs β2 = 0.040, P < 0.001 for TG; β1 = -0.112 vs β2 = -0.026, P < 0.001 for HDL-C). 2-h insulin partially mediated the effect of TG/HDL-C on Gutt index with a 59.3% mediating effect for TG and 61.0% for HDL-C. These findings provide strong evidence that dyslipidemia probably precede peripheral IR and that 2-h insulin partially mediates this unidirectional temporal relationship.

  1. Molecular dynamics of solid cortisol studied by NMR

    NASA Astrophysics Data System (ADS)

    Andrew, E. R.

    Polycrystalline cortisol (hydrocortisone; 11β,17α,21-trihydroxy-4-preg- nene-3,20-dione; C21H30O5) has been investigated by continuous and pulse proton NMR methods between 78 and 400 K at Larmor frequencies of 7, 25 and 60 MHz. A reduced value of second moment was found above 90 K and is ascribed to reorientation of two methyl groups. A single asymmetric minimum was found in the temperature dependence of the spin-lattice relaxation times and this also is attributed to reorientation of two methyl groups. The asymmetry suggests an asymmetric distribution of correlation times of the motion. Using the Cole-Davidson distribution, the best computer fit yields the following parameters characterizing the motion: Ea = 11ṡ8 ± 0ṡ1 kJ mol-1, τ0 = 4ṡ6 ± 0ṡ4) x 10-13s, distribution parameter δ = 0ṡ62.

  2. Antimalarial drugs and heme in detergent micelles: An NMR study.

    PubMed

    Casabianca, Leah B; Kallgren, Joye B; Natarajan, Jayakumar K; Alumasa, John N; Roepe, Paul D; Wolf, Christian; de Dios, Angel C

    2009-05-01

    Proton nuclear magnetic resonance relaxation times were measured for the protons of micelles formed by the detergents sodium dodecyl sulfate, dodecyltrimethyl ammonium bromide, and polyethylene glycol sorbitan monolaureate in the presence of ferriprotoporphyrin IX and the antimalarial drugs chloroquine, 7-chloro-4-quinolyl 4-N,N-diethylaminobutyl sulfide, and primaquine. Diffusion coefficients were extracted from pulsed gradient NMR experiments to evaluate the degree of association of these drugs with the detergent micelles. Results indicate that at low or neutral pH when the quinolyl N is protonated, chloroquine does not associate with neutral or cationic detergent micelles. For this reason, chloroquine's interaction with heme perturbs the partitioning of heme between the aqueous medium and detergent micelles.

  3. Pulsed NMR study of the curing process of epoxy resin.

    PubMed

    Kimoto, Hiroki; Tanaka, Chikako; Yaginuma, Michiko; Shinohara, Emi; Asano, Atsushi; Kurotsu, Takuzo

    2008-07-01

    To analyze a curing process of epoxy resin in terms of molecular motion, we adapted a pulsed NMR method. Three kinds of (1)H spin-spin relaxation times (T(2L) (long), T(2S) (short) and T(2M) (intermediate)) were estimated from observed solid echo train signals as the curing process proceeded. A short T(2S) value below 20 micros suggests the existence of a motion-restricted chain, that is, cured elements of resin, and its fraction, P(S), sigmoidally increased with the curing time. On the other hand, the fraction of T(2L), P(L), decreased with the reaction time reciprocally against P(S), suggesting the disappearance of highly mobile molecules raised from pre-cured resin. The spin-lattice relaxation time, T(1), was also measured to check another aspect of molecular motion in the process. T(1) of the mixed epoxy resin and curing agent gradually increased just after mixing both of them. This corresponds to an increment of a less-mobile fraction, of which the correction time is more than 10(-6) s, and also means that the occurrence of a network structure whose mobility is strongly restricted by chemically bonded bridges between the epoxy resin and curing agent. The time courses of these parameters coincided with those of IR peaks pertinent to the curing reaction. Therefore, pulsed NMR is a useful tool to monitor the hardening process of epoxy resin in real time non-distractively in terms of the molecular motion of protons.

  4. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  5. A laser flash photolysis kinetics study of the reaction OH + H2O2 yields HO2 + H2O

    NASA Technical Reports Server (NTRS)

    Wine, P. H.; Semmes, D. H.; Ravishankara, A. R.

    1981-01-01

    Absolute rate constants for the reaction are reported as a function of temperature over the range 273-410 K. OH radicals are produced by 266 nm laser photolysis of H2O2 and detected by resonance fluorescence. H2O2 concentrations are determined in situ in the slow flow system by UV photometry. The results confirm the findings of two recent discharge flow-resonance fluorescence studies that the title reaction is considerably faster, particularly at temperatures below 300 K, than all earlier studies had indicated. A table giving kinetic data from the reaction is included.

  6. HK97 maturation studied by crystallography and H/2H exchange reveals the structural basis for exothermic particle transitions.

    PubMed

    Gertsman, Ilya; Komives, Elizabeth A; Johnson, John E

    2010-03-26

    HK97 is an exceptionally amenable system for characterizing major conformational changes associated with capsid maturation in double-stranded DNA bacteriophage. HK97 undergoes a capsid expansion of approximately 20%, accompanied by major subunit rearrangements during genome packaging. A previous 3.44-A-resolution crystal structure of the mature capsid Head II and cryo-electron microscopy studies of other intermediate expansion forms of HK97 suggested that, primarily, rigid-body movements facilitated the maturation process. We recently reported a 3.65-A-resolution structure of the preexpanded particle form Prohead II (P-II) and found that the capsid subunits undergo significant refolding and twisting of the tertiary structure to accommodate expansion. The P-II study focused on major twisting motions in the P-domain and on refolding of the spine helix during the transition. Here we extend the crystallographic comparison between P-II and Head II, characterizing the refolding events occurring in each of the four major domains of the capsid subunit and their effect on quaternary structure stabilization. In addition, hydrogen/deuterium exchange, coupled to mass spectrometry, was used to characterize the structural dynamics of three distinct capsid intermediates: P-II, Expansion Intermediate, and the nearly mature Head I. Differences in the solvent accessibilities of the seven quasi-equivalent capsid subunits, attributed to differences in secondary and quaternary structures, were observed in P-II. Nearly all differences in solvent accessibility among subunits disappear after the first transition to Expansion Intermediate. We show that most of the refolding is coupled to this transformation, an event associated with the transition from asymmetric to symmetric hexamers.

  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. A Raman spectroscopic study of the basic carbonate mineral callaghanite Cu2Mg2(CO3)(OH)6·2H2O.

    PubMed

    Čejka, Jiří; Sejkora, Jiří; Jebavá, Ivana; Xi, Yunfei; Couperthwaite, Sara J; Frost, Ray L

    2013-05-01

    Raman spectrum of callaghanite, Cu2Mg2(CO3)(OH)6·2H2O, was studied and compared with published Raman spectra of azurite, malachite and hydromagnesite. Stretching and bending vibrations of carbonate and hydroxyl units and water molecules were tentatively assigned. Approximate O-H…O hydrogen bond lengths were inferred from the spectra. Because of the high content of hydroxyl ions in the crystal structure in comparison with low content of carbonate units, callaghanite should be better classified as a carbonatohydroxide than a hydroxycarbonate. Copyright © 2013 Elsevier B.V. All rights reserved.

  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.

  10. 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.

  11. Compost effect on soil humic acid: A NMR study.

    PubMed

    Adani, Fabrizio; Genevini, Pierluigi; Tambone, Fulvia; Montoneri, Enzo

    2006-11-01

    The humic acid (HA) fraction of a food and vegetable residues compost (CM) was taken as indicator to trace the fate of CM organic matter in four years CM amended soil. (1)H and (13)C NMR spectroscopy were used to investigate the nature of the HA isolates from CM, control soil (S(4)) and amended soil. The result indicated a significant structural difference between CM HA and S(4) HA, and supported the presence of both HA fractions in soil at the end of the amendment trials. However, the nature and content of CM HA in soil did not fully explain the increase of soil cation exchange capacity (CEC) after amendment. All CM humic fractions (i.e., fulvic acid, humic acid and humin) were found to contribute to the change of the soil organic matter composition. It is concluded that although CM HA is a suitable indicator of the survival of compost organic matter in soil during amendment, all three humic fractions should be monitored and analyzed to fully understand changes in the composition and properties of amended soil.

  12. 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.

  13. NMR studies of molecular structure in fruit cuticle polyesters.

    PubMed

    Fang, X; Qiu, F; Yan, B; Wang, H; Mort, A J; Stark, R E

    2001-07-01

    The cuticle of higher plants functions primarily as a protective barrier for the leaves and fruits, controlling microbial attack as well as the diffusion of water and chemicals from the outside environment. Its major chemical constituents are waxes (for waterproofing) and cutin (a structural support polymer). However, the insolubility of cutin has hampered investigations of its covalent structure and domain architecture, which are viewed as essential for the design of crop protection strategies and the development of improved synthetic waterproofing materials. Recently developed strategies designed to meet these investigative challenges include partial depolymerization using enzymatic or chemical reagents and spectroscopic examination of the intact polyesters in a solvent-swelled form. The soluble oligomers from degradative treatments of lime fruit cutin are composed primarily of the expected 10,16-dihydroxyhexadecanoic and 16-hydroxy-10-oxo-hexadecanoic acids; low-temperature HF treatments also reveal sugar units that are covalently attached to the hydroxyfatty acids. Parallel investigations of solvent-swollen cutin using 2D NMR spectroscopy assisted by magic-angle spinning yield well-resolved spectra that permit detailed comparisons to be made among chemical moieties present in the intact biopolymer, the soluble degradation products, and the unreacted solid residue.

  14. Coupling δ2H and δ18O biomarker results yields information on relative humidity and isotopic composition of precipitation - a climate transect validation study

    NASA Astrophysics Data System (ADS)

    Tuthorn, M.; Zech, R.; Ruppenthal, M.; Oelmann, Y.; Kahmen, A.; del Valle, H. F.; Eglinton, T.; Rozanski, K.; Zech, M.

    2015-06-01

    The hydrogen isotopic composition (δ2H) of leaf waxes, especially of n-alkanes (δ2Hn-alkanes), is increasingly used for paleohydrological and paleoclimate reconstructions. However, it is challenging to disentangle past changes in the isotopic composition of precipitation and changes in evapotranspirative enrichment of leaf water, which are both recorded in leaf wax δ2H values. In order to overcome this limitation, Zech M. et al. (2013) proposed a coupled δ2Hn-alkanes-δ18Osugar biomarker approach. This coupled approach allows for calculating (i) biomarker-based "reconstructed" δ2Hδ18O values of leaf water (δ2Hδ18Oleaf water), (ii) biomarker-based reconstructed deuterium excess (d-excess) of leaf water, which mainly reflects evapotranspirative enrichment and which can be used to reconstruct relative air humidity (RH) and (iii) biomarker-based reconstructed δ2Hδ18Oprecipitation values. Here we present a climate transect validation study by coupling new results from δ2H analyses of n-alkanes and fatty acids in topsoils along a climate transect in Argentina with previously measured δ18O results obtained for plant-derived sugars. Accordingly, both the reconstructed RH and δ2Hδ18Oprecipitation values correlate highly significantly with actual RH and δ2Hδ18Oprecipitation values. We conclude that compared to single δ2Hn-alkane or δ18Osugar records, the proposed coupled δ2Hn-alkane-δ18Osugar biomarker approach will allow more robust δ2Hδ18Oprecipitation reconstructions in future paleoclimate research. Additionally, the proposed coupled δ2Hn-alkane-δ18Osugar biomarker approach allows for the establishment of a "paleohygrometer", more specifically, the reconstruction of mean summer daytime RH changes/history.

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

    PubMed Central

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

    2016-01-01

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

  16. N-H...F hydrogen bonds in fluorinated benzanilides: NMR and DFT study.

    PubMed

    Manjunatha Reddy, G N; Vasantha Kumar, M V; Guru Row, T N; Suryaprakash, N

    2010-10-28

    Using (19)F and (1)H-NMR (with (14)N decoupling) spectroscopic techniques together with density functional theoretical (DFT) calculations, we have investigated weak molecular interactions in isomeric fluorinated benzanilides. Simultaneous presence of through space nuclear spin-spin couplings ((1h)J(N-HF)) of diverse strengths and feeble structural fluctuations are detected as a function of site specific substitution of fluorine atoms within the basic identical molecular framework. The transfer of hydrogen bonding interaction energies through space is established by perturbing their strengths and monitoring the effect on NMR parameters. Multiple quantum (MQ) excitation, up to the highest possible MQ orders of coupled protons, is utilized as a tool for accurate (1)H assignments. Results of NMR studies and DFT calculations are compared with the relevant structural parameters taken from single crystal X-ray diffraction studies.

  17. Practical applications of hydrostatic pressure to refold proteins from inclusion bodies for NMR structural studies.

    PubMed

    Ogura, Kenji; Kobashigawa, Yoshihiro; Saio, Tomohide; Kumeta, Hiroyuki; Torikai, Shinnosuke; Inagaki, Fuyuhiko

    2013-06-01

    Recently, the hydrostatic pressure refolding method was reported as a practical tool for solubilizing and refolding proteins from inclusion bodies; however, there have been only a few applications for protein structural studies. Here, we report the successful applications of the hydrostatic pressure refolding method to refold proteins, including the MOE-2 tandem zinc-finger, the p62 PB1 domain, the GCN2 RWD domain, and the mTOR FRB domain. Moreover, the absence of aggregation and the correct folding of solubilized protein samples were evaluated with size exclusion chromatography and NMR experiments. The analyses of NMR spectra for MOE-2 tandem zinc-finger and GCN2 RWD further led to the determination of tertiary structures, which are consistent with those from soluble fractions. Overall, our results indicate that the hydrostatic pressure method is effective for preparing samples for NMR structural studies.

  18. 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.

  19. Surface structure of bulk 2H-MoS 2 (0001) and exfoliated suspended monolayer MoS 2 : A selected area low energy electron diffraction study

    DOE PAGES

    Dai, Zhongwei; Jin, Wencan; Grady, Maxwell; ...

    2017-02-10

    Here, we used selected area low energy electron diffraction intensity-voltage (μLEED-IV) analysis to investigate the surface structure of crystalline 2H molybdenum disulfide (MoS2) and mechanically exfoliated and suspended monolayer MoS2. Our results show that the surface structure of bulk 2H-MoS2 is distinct from its bulk and that it has a slightly smaller surface relaxation at 320 K than previously reported at 95 K. We concluded that suspended monolayer MoS2 shows a large interlayer relaxation compared to the MoS2 sandwich layer terminating the bulk surface. The Debye temperature of MoS2 was concluded to be about 600 K, which agrees with amore » previous theoretical study. Our work has shown that the dynamical μLEED-IV analysis performed with a low energy electron microscope (LEEM) is a powerful technique for determination of the local atomic structures of currently extensively studied two-dimensional (2-D) materials.« less

  20. Kinetic study of IO radical with RO2 (R = CH(3), C2H5, and CF3) using cavity ring-down spectroscopy.

    PubMed

    Enami, Shinichi; Yamanaka, Takashi; Hashimoto, Satoshi; Kawasaki, Masahiro; Nakano, Yukio; Ishiwata, Takashi

    2006-08-17

    The reactions of iodine monoxide radical, IO, with alkyl peroxide radicals, RO(2) (R = CH(3), C(2)H(5), and CF(3)), have been studied using cavity ring-down spectroscopy. The rate constant of the reaction of IO with CH(3)O(2) was determined to be (7.0 +/- 3.0) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K and 100 Torr of N(2) diluent. The quoted uncertainty is two standard deviations. No significant pressure dependence of the rate constant was observed at 30-130 Torr total pressure of N(2) diluent. The temperature dependence of the rate constants was also studied at 213-298 K. The upper limit of the branching ratio of OIO radical formation from IO + CH(3)O(2) was estimated to be <0.1. The reaction rate constants of IO + C(2)H(5)O(2) and IO + CF(3)O(2) were determined to be (14 +/- 6) x 10(-11) and (6.3 +/- 2.7) x 10(-11) cm(3) molecule(-1) s(-1) at 298 K, 100 Torr of N(2) diluent, respectively. The upper limit of the reaction rate constant of IO with CH(3)I was <4 x 10(-14) cm(3) molecule(-1) s(-1).

  1. Study of the A(e,e'$\\pi^+$) Reaction on $^1$H, $^2$H, $^{12}$C, $^{27}$Al, $^{63}$Cu and $^{197}$Au

    SciTech Connect

    Qian, X; Clasie, B; Arrington, J; Asaturyan, R; Benmokhtar, F; Boeglin, W; Bosted, P; Bruell, A; Christy, M E; Chudakov, E; Dalton, M M; Daniel, A; Day, D; Dutta, D; El Fassi, L; Ent, R; Fenker, H C; Ferrer, J; Fomin, N; Gao, H; Garrow, K; Gaskell, D; Gray, C; Huber, G M; Jones, M K; Kalantarians, N; Keppel, C E; Kramer, K; Li, Y; Liang, Y; Lung, A F; Malace, S; Markowitz, P; Matsumura, A; Meekins, D G; Mertens, T; Miyoshi, T; Mkrtchyan, H; Monson, R; Navasardyan, T; Niculescu, G; Niculescu, I; Okayasu, Y; Opper, A K; Perdrisat, C; Punjabi, V; Rauf, A W; Rodriquez, V M; Rohe, D; Seely, J; Segbefia, E; Smith, G R; Sumihama, M; Tadevosyan, V; Tang, L; Villano, A; Vulcan, W F; Wesselmann, F R; Wood, S A; Yuan, L; Zheng, X

    2010-05-01

    Cross sections for the p($e,e'\\pi^{+}$)n process on $^1$H, $^2$H, $^{12}$C, $^{27}$Al, $^{63}$Cu and $^{197}$Au targets were measured at the Thomas Jefferson National Accelerator Facility (Jefferson Lab) in order to extract the nuclear transparencies. Data were taken for four-momentum transfers ranging from $Q^2$=1.1 to 4.8 GeV$^2$ for a fixed center of mass energy of $W$=2.14 GeV. The ratio of $\\sigma_L$ and $\\sigma_T$ was extracted from the measured cross sections for $^1$H, $^2$H, $^{12}$C and $^{63}$Cu targets at $Q^2$ = 2.15 and 4.0 GeV$^2$ allowing for additional studies of the reaction mechanism. The experimental setup and the analysis of the data are described in detail including systematic studies needed to obtain the results. The results for the nuclear transparency and the differential cross sections as a function of the pion momentum at the different values of $Q^2$ are presented. Global features of the data are discussed and the data are compared with the results of model calculations for the p($e,e'\\pi^{+}$)n reaction from nuclear targets.

  2. A systematic computational study of the reactions of HO2 with RO2: the HO2 + C2H5O2 reaction.

    PubMed

    Hou, Hua; Li, Jicun; Song, Xinli; Wang, Baoshan

    2005-12-15

    The reaction of HO2 with C2H5O2 has been studied using the density functional theory (B3LYP) and the coupled-cluster theory [CCSD(T)]. The reaction proceeds on the triplet potential energy surface via hydrogen abstraction to form ethyl hydroperoxide and oxygen. On the singlet potential energy surface, the addition-elimination mechanism is revealed. Variational transition state theory is used to calculate the temperature-dependent rate constants in the range 200-1000 K. At low temperatures (e.g., below 300 K), the reaction takes place predominantly on the triplet surface. The calculated low-temperature rate constants are in good agreement with the experimental data. As the temperature increases, the singlet reaction mechanism plays more and more important role, with the formation of OH radical predominantly. The isotope effect of the reaction (DO2 + C2D5O2 vs HO2 + C2H5O2) is negligible. In addition, the triplet abstraction energetic routes for the reactions of HO2 with 11 alkylperoxy radicals (CnHmO2) are studied. It is shown that the room-temperature rate constants have good linear correlation with the activation energies for the hydrogen abstraction.

  3. Surface structure of bulk 2H-MoS2(0001) and exfoliated suspended monolayer MoS2: A selected area low energy electron diffraction study

    NASA Astrophysics Data System (ADS)

    Dai, Zhongwei; Jin, Wencan; Grady, Maxwell; Sadowski, Jerzy T.; Dadap, Jerry I.; Osgood, Richard M.; Pohl, Karsten

    2017-06-01

    We have used selected area low energy electron diffraction intensity-voltage (μLEED-IV) analysis to investigate the surface structure of crystalline 2H molybdenum disulfide (MoS2) and mechanically exfoliated and suspended monolayer MoS2. Our results show that the surface structure of bulk 2H-MoS2 is distinct from its bulk and that it has a slightly smaller surface relaxation at 320 K than previously reported at 95 K. We concluded that suspended monolayer MoS2 shows a large interlayer relaxation compared to the MoS2 sandwich layer terminating the bulk surface. The Debye temperature of MoS2 was concluded to be about 600 K, which agrees with a previous theoretical study. Our work has shown that the dynamical μLEED-IV analysis performed with a low energy electron microscope (LEEM) is a powerful technique for determination of the local atomic structures of currently extensively studied two-dimensional (2-D) materials.

  4. Mechanical Behavior of Polymer Gels for RDCs and RCSAs Collection: NMR Imaging Study of Buckling Phenomena.

    PubMed

    Hellemann, Erich; Teles, Rubens R; Hallwass, Fernando; Barros, W; Navarro-Vázquez, Armando; Gil, Roberto R

    2016-11-07

    Anisotropic NMR parameters, such as residual dipolar couplings (RDCs), residual chemical shift anisotropies (RCSAs) and residual quadrupolar couplings (RQCs or ΔνQ ), appear in solution-state NMR when the molecules under study are subjected to a degree of order. The tunable alignment by reversible compression/relaxation of gels (PMMA and p-HEMA) is an easy, user-friendly, and very affordable method to measure them. When using this method, a fraction of isotropic NMR signals is observed in the NMR spectra, even at a maximum degree of compression. To explain the origin of these isotropic signals we decided to investigate their physical location inside the NMR tube using deuterium 1D imaging and MRI micro-imaging experiments. It was observed that after a certain degree of compression the gels start to buckle and they generate pockets of isotropic solvent, which are never eliminated. The amount of buckling depends on the amount of cross-linker and the length of the gel.

  5. 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.

  6. Calcium binding by phosphatidylserine headgroups. Deuterium NMR study.

    PubMed Central

    Roux, M; Bloom, M

    1991-01-01

    The binding of calcium to headgroup deuterated 1-palmitoyl, 2-oleoyl-sn-glycero-3-phosphoserine (POPS) was investigated by using deuterium magnetic resonance in pure POPS membranes and in mixed 1-palmitoyl, 2-oleoyl-sn-glycero-3-phosphocholine (POPC)/POPS 5:1 (m:m) bilayers. Addition of CaCl2 to pure POPS bilayers led to two component spectra attributed, respectively, to liquid-crystallin POPS (less than 15 kHz) and POPS molecules in the calcium-induced dehydrated phase (cochleate) (approximately 120 kHz). The liquid-crystalline component has nearly disappeared at a Ca2+ to POPS ratio of 0.5, indicating that, under such conditions, most of the POPS molecules are in the precipitated cochleate phase. After dilution of the POPS molecules in zwitterionic POPC membranes (POPC/POPS 5:1 m:m), single component spectra characteristic of POPS in the liquid-crystalline state were observed in the presence of Molar concentrations of calcium ions (Ca2+ to POPS ratio greater than 50), showing that the amount of dehydrated cochleate PS-Ca2+ phase, if any, was low (less than 5%) under such conditions. Deuterium NMR data obtained in the 15-50 degrees C temperature range with the mixed PC/PS membranes, either in the absence or the presence of Ca2+ ions, indicate that the serine headgroup undergoes a temperature-induced conformational change, independent of the presence of Ca2+. This is discussed in relation to other headgroup perturbations such as that observed upon change of the membrane surface charge density. PMID:1883944

  7. 1H NMR, 13C NMR and mass spectral studies of some Schiff bases derived from 3-amino-1,2,4-triazole.

    PubMed

    Issa, Y M; Hassib, H B; Abdelaal, H E

    2009-11-01

    Heterocyclic Schiff bases derived from 3-amino-1,2,4-triazole and different substituted aromatic aldehydes are prepared and subjected to (1)H NMR, (13)C NMR and mass spectral analyses. (1)H NMR spectra in DMSO exhibit a sharp singlet within the 9.35-8.90ppm region which corresponds to the azomethine proton. The position of this signal is largely dependent on the nature of the substituents on the benzal moiety. It is observed that the shape, position and the integration value of the signal of the aromatic proton of the triazole ring ((5)C) are clearly affected by the rate of exchange, relaxation time, concentration of solution as well as the solvent used. (13)C NMR is taken as substantial support for the results reached from (1)H NMR studies. The mass spectral results are taken as a tool to confirm the structure of the investigated compounds. The base peak (100%), mostly the M-1 peak, indicates the facile loss of hydrogen radical. The fragmentation pattern of the unsubstituted Schiff base is taken as the general scheme. Differences in the other schemes result from the effect of the electronegativity of the substituents attached to the aromatic ring.

  8. 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...

  9. 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...

  10. Lamellar structures formed by stratum corneum lipids in vitro: a deuterium nuclear magnetic resonance (NMR) study.

    PubMed

    Abraham, W; Downing, D T

    1992-11-01

    Hydrated lipid mixtures consisting of stratum corneum ceramides, cholesterol, specifically deuterated palmitic acid, and cholesteryl sulfate were investigated by solid-state 2H NMR spectroscopy at different temperatures. The mole ratio of cholesterol to ceramides was varied from 1 to 0. 2H NMR spectra from these mixtures showed powder patterns with quadrupolar splittings smaller than those obtained from control mixtures containing dipalmitoylphosphatidylcholine (DPPC) instead of the ceramides. This result is attributed to the rigid amide group of the ceramides, with a planar configuration, which could prevent close packing of the alpha-methylenes of the acyl chains. There was a gradual loss of symmetry in the powder pattern as the amount of cholesterol was decreased and the amount of ceramides (or DPPC) was increased concomitantly. The loss was more pronounced in the ceramide-containing samples. This phenomenon is interpreted as a decrease in the axial reorientation rate of the alpha-deuterated palmitic acid in the bilayers, presumably caused by the increased hydrogen bonding resulting from the high amount of hydroxyl-bearing ceramides. Spectra obtained at temperatures above 60 degrees C indicated the formation of a hexagonal phase (HII) by the ceramide-containing mixtures. Spectra of the omega-deuterated palmitic acid in the mixture containing 76 mol% ceramides and no cholesterol indicated phase separation into a more rigid phase and a more mobile phase in the temperature range of 25 to 60 degrees C. The bilayer configuration of lipids at 25 degrees C was confirmed by thin-section electron microscopy.

  11. Ab initio study of the reaction pathways for OH + C/sub 2/H/sub 4/. -->. HOCH/sub 2/CH/sub 2/. -->. products

    SciTech Connect

    Sosa, C.; Schlegel, H.B.

    1987-11-11

    The energetically favorable reaction paths for the unimolecular decomposition of the primary addition product of OH + C/sub 2/H/sub 4/ have been studied with ab initio techniques. Equilibrium geometries and transition structures were fully optimized with 3-21G and 6-31G* basis sets at the Hartree-Fock level. Heats of reaction and barrier heights have been computed with Moeller-Plesset perturbation theory up to fourth order, with and without annihilation of spin contamination. At the MP4 level barrier heights are lowered by 2-7 kcal/mol when the largest spin contaminant is removed. After the addition of OH + C/sub 2/H/sub 4/ to form the 2-hydroxyethyl radical, the most favorable reaction path (other than decomposition to reactants) is the (1,3)-hydrogen shift to form ethoxy radical followed by a dissociation into CH/sub 3/ + CH/sub 2/O. Other slightly higher energy paths include dissociation of ethoxy into H + CH/sub 3/CHO and decomposition of the 2-hydroxyethyl radical into H + HOCHCH/sub 2/.

  12. Mechanistic Studies of Wacker-Type Amidocyclization of Alkenes Catalyzed by (IMes)Pd(TFA)2(H2O): Kinetic and Stereochemical Implications of Proton Transfer†

    PubMed Central

    Ye, Xuan; White, Paul B.

    2012-01-01

    The stereochemical course of the amidopalladation of alkenes has important implications for the development of enantioselective Pd-catalyzed “Wacker-type” oxidative amination of alkenes. We have recently shown that the addition of base (Na2CO3) can alter the stereochemical course of amidopalladation in the (IMes)Pd(TFA)2(H2O)-catalyzed aerobic oxidative amidation of alkene. In this study, the mechanism of (IMes)Pd(TFA)2(H2O)-catalyzed oxidative heterocyclization of (Z)-4-hexenyltosylamide was investigated in the presence and absence of exogenous base Na2CO3. The results reveal two parallel pathways in the absence of base: a cis-amidopalladation pathway with turnover-limiting deprotonation of the sulfonamide nucleophile, and a trans-amidopalladation pathway with turnover-limiting nucleophilic attack of sulfonamide on the coordinated alkene. The addition of base (Na2CO3) lowers the energy barrier associated with the proton transfer, leading to an overall faster turnover rate and exclusive cis-amidopalladation of alkene. PMID:23157332

  13. Mechanistic studies of Wacker-type amidocyclization of alkenes catalyzed by (IMes)Pd(TFA)2(H2O): kinetic and stereochemical implications of proton transfer.

    PubMed

    Ye, Xuan; White, Paul B; Stahl, Shannon S

    2013-03-01

    The stereochemical course of the amidopalladation of alkenes has important implications for the development of enantioselective Pd-catalyzed "Wacker-type" oxidative amidation of alkenes. We have recently shown that the addition of base (Na2CO3) can alter the stereochemical course of amidopalladation in the (IMes)Pd(TFA)2(H2O)-catalyzed aerobic oxidative amidation of alkene. In this study, the mechanism of (IMes)Pd(TFA)2(H2O)-catalyzed oxidative heterocyclization of (Z)-4-hexenyltosylamide was investigated in the presence and absence of exogenous base Na2CO3. The results reveal two parallel pathways in the absence of base: a cis-amidopalladation pathway with turnover-limiting deprotonation of the sulfonamide nucleophile and a trans-amidopalladation pathway with turnover-limiting nucleophilic attack of sulfonamide on the coordinated alkene. The addition of base (Na2CO3) lowers the energy barrier associated with the proton transfer, leading to an overall faster turnover rate and exclusive cis-amidopalladation of alkene.

  14. 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.

  15. Solid-state NMR studies of form I of atorvastatin calcium.

    PubMed

    Wang, Wei David; Gao, Xudong; Strohmeier, Mark; Wang, Wei; Bai, Shi; Dybowski, Cecil

    2012-03-22

    Solid-state (13)C, (19)F, and (15)N magic angle spinning NMR studies of Form I of atorvastatin calcium are reported, including chemical shift tensors of all resolvable carbon sites and fluorine sites. The complete (13)C and (19)F chemical shift assignments are given based on an extensive analysis of (13)C-(1)H HETCOR and (13)C-(19)F HETCOR results. The solid-state NMR data indicate that the asymmetric unit of this material contains two atorvastatin molecules. A possible structure of Form I of atorvastatin calcium (ATC-I), derived from solid-state NMR data and density functional theory calculations of various structures, is proposed for this important active pharmaceutical ingredient (API).

  16. 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.

  17. 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. Copyright © 2014 Elsevier B.V. All rights reserved.

  18. Crystal structure and dynamic NMR studies of octaacetyl-tetra(propyl)calix[4]resorcinarene

    NASA Astrophysics Data System (ADS)

    Velásquez-Silva, Astrid; Cortés, Brian; Rivera-Monroy, Zuly J.; Pérez-Redondo, Adrián; Maldonado, Mauricio

    2017-06-01

    The reaction between C-tetra(propyl)calix[4]resorcinarene (1) and acetic anhydride in pyridine results in the formation of octaacetyl-tetra(propyl)calix[4]resorcinarene (2). The structure was determined using FT-IR, 1H-NMR and 13C-NMR. The dynamic 1H-NMR of acetylated resorcinarene was studied by means of variable temperature in a CDCl3 solution and revealed that two conformers are formed in the solution. Boat conformations for acetylated resorcinarene exhibited a rapid interconversion at low temperatures, and the activation barrier for the pseudorotation was determined (54.72 kJmol-1). The acetylated resorcinarene 2 was also characterized by an X-ray crystal structure determination. This analysis indicated a boat configuration for the macrocycle skeleton in the solid state. Csbnd H⋯O hydrogen bonding interactions were observed in the packing of compound.

  19. 125Te and 139La NMR Studies of Single Crystal LaTe3

    NASA Astrophysics Data System (ADS)

    Chudo, Hiroyuki; Michioka, Chishiro; Itoh, Yutaka; Yoshimura, Kazuyoshi

    2007-12-01

    We report 125Te and 139La NMR studies for single crystals of LaTe3 between 10 and 160 K under an applied field of H = 7.4841 T. We observed the broad 125Te(1) NMR signals of metallic Te(1) sheets with a superlattice modulation and the sharp 125Te(2) and 139La NMR signals of LaTe(2) bi-layers. Temperature dependence of 125Te(1) nuclear spin-lattice relaxation times of the modulated Te(1) sheets obeys a modified Korringa relation. The results indicate that the electronic state on the Te(1) sheets is a Landau-Fermi liquid on a misfit superlattice or a Tomonaga-Luttinger liquid in a two-dimensional charge-density wave ordering state.