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Sample records for nmr spin-hamiltonian parameters

  1. Density functional theory (DFT) calculations of the proton nuclear magnetic resonance (NMR) spin-Hamiltonian parameters for serine

    1H nuclear magnetic resonance spin-Hamiltonian parameters: chemical shifts δ and indirect spin–spin coupling constants J, have been calculated for serine, a brain metabolite. Serine molecules in the gas-phase as well as in solution in water have been investigated using density functional theory. Solvent and conformer effects as well as zero-point vibrational corrections have been taken into account. For the non-vibrating molecule, the best agreement is obtained when solvent and conformer effects are included. Zero-point vibrational corrections improve the agreement with experimental values, leading to a root mean square deviation of 0.05 ppm for chemical shifts and 0.7 Hz for spin–spin coupling constants

  2. Effect of glass structure on spin Hamiltonian parameters: Cu doped tellurite glasses

    Cu-doped glasses with compositions [(70TeO2−(30−x)ZnO−xPbO)0.98− (CuO)0.02] (x = 5, 10, 15, 20) were prepared using the melt quenching technique and characterized by EPR. Cu2+ ions are found to be in distorted oxygen octahedral cage and their corresponding spin Hamiltonian (splitting) parameters are deduced for all glasses as a function of increasing PbO. Finally, effect of the matrix on spin Hamiltonian parameters of Cu2+ ions are correlated with the help of EPR and earlier Raman analysis

  3. Effect of glass structure on spin Hamiltonian parameters: Cu doped tellurite glasses

    Ramamoorthy, Raj Kumar, E-mail: rajrk37@gmail.com [School of Engineering Sciences and Technology, University of Hyderabad, Hyderabad-500046 (India); Bhatnagar, Anil K., E-mail: anilb42@gmail.com [School of Engineering Sciences and Technology, University of Hyderabad, Hyderabad-500046 (India); School of Physics, University of Hyderabad, Hyderabd-500046 (India)

    2015-06-24

    Cu-doped glasses with compositions [(70TeO{sub 2}−(30−x)ZnO−xPbO){sub 0.98}− (CuO){sub 0.02}] (x = 5, 10, 15, 20) were prepared using the melt quenching technique and characterized by EPR. Cu{sup 2+} ions are found to be in distorted oxygen octahedral cage and their corresponding spin Hamiltonian (splitting) parameters are deduced for all glasses as a function of increasing PbO. Finally, effect of the matrix on spin Hamiltonian parameters of Cu{sup 2+} ions are correlated with the help of EPR and earlier Raman analysis.

  4. Optical spectra and spin-Hamiltonian parameters of trivalent ytterbium in lead tungstate

    W-L Feng; X-M Li

    2011-01-01

    By using crystal-field theory, the optical spectra and spin-Hamiltonian parameters (abbr. SH parameters, i.e. the anisotropic factors $g_{\\|} g_{⊥}$, and hyperfine structure constants $A_{\\|}, A_{⊥}$) of 171Yb3+ and 173Yb3+ isotopes in the tetragonal PbWO4 are calculated. The theoretical results agree well with the experimental values. The crystal-field parameters and the signs of the hyperfine structure constants for both 171Yb3+ and 173Yb3+ isotopes are determined. The validities of the theoretical results are discussed.

  5. Density functional theory calculations of the nuclear magnetic resonance spin-Hamiltonian parameters for two polyamines of prostate tissue: spermidine and spermine

    1H nuclear magnetic resonance (NMR) spin-Hamiltonian parameters: chemical shifts δ and spin–spin coupling constants J have been calculated for the two polyamines: spermidine and spermine present in prostate tissue. Molecules in the gas phase as well as in solution in water have been investigated using density functional theory calculations. From calculated δ and J values, NMR spectra have been simulated and compared to the experimental ones we acquired at 400 MHz for each polyamine in solution in D2O. From these comparisons, reliable NMR parameters are proposed for spermidine and spermine, among which the J constants were until now unknown for these two molecules

  6. Theoretical studies of spin-Hamiltonian parameters of Mo5+ ion doped in K2SnCl6 crystal

    Fang, Wang; Yang, Da-Xiao; Chen, Heng-Jie; Tang, Hai-Yan

    2013-11-01

    The spin-Hamiltonian (SH) parameters (g factors g//, g⊥ and hyperfine structure constants A//, A⊥ ) of K2SnCl6: Mo5+ (4d1) crystal are theoretically studied by the use of two microscopic spin-Hamiltonian (SH) methods, the high-order perturbation theory method (PTM) and the complete diagonalization (of energy matrix) method (CDM) within the molecular orbital (MO) scheme. The contributions arising both from the crystal field and charge transfer excitations are taken into account. The investigations show that the charge transfer mechanism plays a decisive role in the understanding of the spin-Hamiltonian (SH) parameters for 4d1 ions in crystals with the strong coordinate covalence, especially for g//>g⊥ which cannot be explained in the frame work of traditional crystal field approximation (CFA). The local defect structure around Mo5+ impurity ion center is determined to be D4 h point group symmetry.

  7. Theoretical study for the cubic spin-Hamiltonian parameters of 3d ions

    Lei, Y.

    2009-08-01

    In this paper, the whole microscopic energy matrix elements of 3d3 and 3d7 within the molecular orbit scheme are obtained. Both the electrostatic parameters, the spin-orbit interaction of the central metal ion and the ligands, the crystal-field potential and the Tress correction, and the spin-spin interaction are considered. By means of the perturbation method, the cubic spin-Hamiltonian parameters g and u are investigated. Results show that the contribution to g due to the spin-spin interaction is negligible. However, the contribution to u due to the spin-spin interaction cannot be neglected. As some illustrations, the 3d7 energy matrix is used to study the cubic electronic paramagnetic resonance experiments of Co in ZnS and ZnSe crystals. The theoretical results agree well with the experimental findings.

  8. Theoretical studies of the local structure and spin Hamiltonian parameters for Rh{sup 2+}:ZnWO{sub 4}

    Ding, Chang-Chun, E-mail: ccding626@163.com; Wu, Shao-Yi; Kuang, Min-Quan; Cheng, Yong-Kun; Zhang, Li-Juan

    2014-10-15

    By establishing the perturbation formulas of the spin Hamiltonian parameters (anisotropic g factors and hyperfine structure constants) for a rhombically compressed 4d{sup 7} cluster, the EPR spectra and local structure are theoretically investigated for Rh{sup 2+}:ZnWO{sub 4}. Due to the Jahn–Teller effect, the impurity center shows slight axial compression of about 0.002 nm along the Z-axis and the perpendicular angular variation of about 6° for the planar impurity–ligand bonds. These lattice deformations transform the significant elongation (by about 0.031 nm) of host Zn{sup 2+} site into slight compression in the impurity center. The local distortion of the Jahn–Teller nature is discussed.

  9. Local structure distortion and spin Hamiltonian parameters of oxide-diluted magnetic semiconductor Mn-doped ZnO

    Yang Zi-Yuan

    2009-01-01

    The local structure distortion, the spin Hamiltonian (SH) parameters, and the electric fine structure of the ground state for Mn2+(3d5) ion in ZnO crystals are systematically investigated, where spin-spin (SS), spin-other-orbit (SOO) and orbit-orbit (OO) magnetic interactions, besides the well-known spin-orbit (SO) coupling, are taken into account for the first time, by using the complete diagonalization method. The theoretical results of the second-order zero-field splitting (ZFS) parameter D, the fourth-order ZFS parameter (a-F), the Zeeman p-factors: g// and g⊥ and the energy differences of the ground state: δ1 and δ2 for Mn2+ in Mn2+: ZnO are in good agreement with experimental measurements when the three O2- ions below the Mn2+ ion rotate by 1.085° away from the [111]-axis. Hence, the local structure distortion effect plays an important role in explaining the spectroscopic properties of Mn2+ ions in Mn2+: ZnO crystals. It is found for Mn2+ ions in Mn2+: ZnO crystals that although the SO mechanism is the most important one, the contributions to the SH parameters, made by other four mechanisms, i.e. SS, SOO, OO, and SO~SS~SOO~OO mechanisms, are significant and should not be omitted, especially for calculating ZFS parameter D.

  10. Theoretical Studies of the Spin Hamiltonian Parameters and Local Distortions for Cu2+ in Alkaline Earth Lead Zinc Phosphate Glasses

    Wang, Bo-Kun; Wu, Shao-Yi; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian; Teng, Bao-Hua; Wu, Ming-He

    2016-08-01

    The spin Hamiltonian parameters and local structures are theoretically studied for Cu2+-doped alkaline earth lead zinc phosphate (RPPZ, R=Mg, Ca, Sr, and Ba) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 cluster. The relative elongation ratios are found to be ρ≈3.2%, 4.4%, 4.6%, and 3.3% for R=Mg, Ca, Sr, and Ba, respectively, because of the Jahn-Teller effect. The whole decreasing crystal-field strength Dq and orbital reduction factor k from Mg to Sr are ascribed to the weakening electrostatic coulombic interactions and the increasing probability of productivity of nonbridge oxygen (and hence increasing Cu2+-O2- electron cloud admixtures) under PbO addition, respectively, with increasing alkali earth ionic radius. The anomalies (the largest Dq and the next highest k among the systems) for R=Ba are attributed to the cross linkage of this large cation in the network. The overall increasing order (Mg≤Ba

  11. Theoretical Studies of the Spin Hamiltonian Parameters and Local Distortions for Cu2+ in Alkaline Earth Lead Zinc Phosphate Glasses

    Wang, Bo-Kun; Wu, Shao-Yi; Yuan, Zi-Yi; Liu, Zi-Xuan; Jiang, Shi-Xin; Liu, Zheng; Yao, Zi-Jian; Teng, Bao-Hua; Wu, Ming-He

    2016-08-01

    The spin Hamiltonian parameters and local structures are theoretically studied for Cu2+-doped alkaline earth lead zinc phosphate (RPPZ, R=Mg, Ca, Sr, and Ba) glasses based on the high-order perturbation calculations for a tetragonally elongated octahedral 3d9 cluster. The relative elongation ratios are found to be ρ≈3.2%, 4.4%, 4.6%, and 3.3% for R=Mg, Ca, Sr, and Ba, respectively, because of the Jahn-Teller effect. The whole decreasing crystal-field strength Dq and orbital reduction factor k from Mg to Sr are ascribed to the weakening electrostatic coulombic interactions and the increasing probability of productivity of nonbridge oxygen (and hence increasing Cu2+-O2- electron cloud admixtures) under PbO addition, respectively, with increasing alkali earth ionic radius. The anomalies (the largest Dq and the next highest k among the systems) for R=Ba are attributed to the cross linkage of this large cation in the network. The overall increasing order (Mg≤Bacontaining copper dopants.

  12. Studies of the spin Hamiltonian parameters and defect structures for Ag2+ in NaF and CsCdF3 crystals

    Zhang, Li-Juan; Wu, Shao-Yi; Ding, Chang-Chun; Hu, Xian-Fen; He, Jia-Jun

    2016-03-01

    The spin Hamiltonian parameters (g factors g//, g⊥, hyperfine structure constants A//, A⊥ and superhyperfine parameters Az‧, Ax‧ and Ay‧) and defect structures for Ag2+ in NaF and CsCdF3 crystals are theoretically studied using the improved perturbation formulas of these quantities for a 4d9 ion in a tetragonally elongated octahedron. The contributions from both the crystal-field and charge transfer mechanisms are taken into account, and the relevant model parameters are quantitatively obtained from the cluster approach in a consistent way. The impurity centers are found to undergo the relative tetragonal elongations of about 9.4% and 8.2% for Ag2+ in NaF and CsCdF3, respectively, along the C4 axis due to the Jahn-Teller effect. By employing the few adjustable parameters, the calculated spin Hamiltonian parameters based on the above uniform formulas and the local tetragonal elongation distortions agree well with the experimental data. Despite dominant ionicity of the hosts, the charge transfer contributions are actually important to the spin Hamiltonian parameters (e.g., about 20% for the g-shifts) due to strong covalency of impurity Ag2+.

  13. Theoretical evaluation of the electron paramagnetic resonance spin Hamiltonian parameters for the impurity displacements for Fe3+ and Ru3+ in corundum

    Q Fu; S Y Wu; J Z Lin; J S Yao

    2007-03-01

    The impurity displacements for Fe3+ and Ru3+ in corundum (Al2O3) are theoretically studied using the perturbation formulas of the spin Hamiltonian parameters (zero-field splitting and anisotropic factors) for a 3d5 (with high spin = 5/2) and a 4d5 (with low spin = 1/2) ion in trigonal symmetry, respectively. According to the investigations, the nd5 ( = 3 and 4) impurity ions may not locate at the ideal Al3+ site but undergo axial displacements by about 0.132 Å and 0.170 Å for Fe3+ and Ru3+, respectively, away from the center of the ligand octahedron along the C3 axis. The calculated spin Hamiltonian parameters based on the above axial displacements show good agreement with the observed values. The validity of the results is discussed.

  14. Theoretical calculations of spin-Hamiltonian parameters for the square planer CuCl4 2 - cluster in Cs2ZrCl6 crystal

    Liu, Gang; Mei, Yang; Zhang, Xin-Xin; Zheng, Wen-Chen

    2015-05-01

    The high-order perturbation formulas based on a two-mechanism model (where in addition to the contributions from the crystal-field (CF) mechanism in the usually-applied CF theory, those from the generally-neglected charge-transfer (CT) mechanism are also contained) are employed to calculate the spin-Hamiltonian parameters (g factors g//, g⊥ and the hyperfine structure constants A//, A⊥) of the square planar CuCl4 2 - clusters in Cs2ZrCl6 crystal. The needed CF energy levels in the calculations are obtained from the observed optical spectra. The calculated results show reasonable agreement with the experimented values. The negative sign of A// and positive sign of A⊥ are proposed from the calculations. The calculations also suggest that one should take account of the contributions due to both the CF and CT mechanisms for the exact and rational calculations of spin-Hamiltonian parameters of Cu2+-Cl- combination in crystals.

  15. Theoretical calculations of spin-Hamiltonian parameters for the (MoOX5)2− (X=Cl, Br) metallic complexes in solution or frozen-glass

    The spin-Hamiltonian parameters (g factors g//, g⊥ and hyperfine structure constants A//, A⊥) of the (MoOX5)2− (X=Cl, Br) metallic complexes in solution or frozen-glass are calculated from the high-order perturbation formulas based on the two-mechanism model. In these formulas, the contributions to spin-Hamiltonian parameters due to both the widely-applied crystal-field (CF) mechanism and the charge-transfer (CT) mechanism (which is neglected in CF theory) are taken into account, and the needed CF and CT energy levels are obtained from the optical spectra. The calculated results with two adjustable parameters are in reasonable agreement with the experimental values. The calculations show that (i) the relative importance of CT mechanism in (MoOBr5)2− metallic complexes is larger than that in (MoOCl5)2− ones because of the stronger covalence of Mo5+–Br− combination, and (ii) in both (MoOCl5)2− and (MoOBr5)2− metallic complexes, the contributions to spin-Hamiltonian parameters due to CT mechanism should also be taken into account because of the high valence state of Mo5+ ion

  16. Theoretical calculations of spin-Hamiltonian parameters for the rhombic-like Mo5+ centers in KTiOPO4 crystal

    The spin-Hamiltonian parameters (g factors gi and hyperfine structure constants Ai, were i=x, y and z) for Mo5+ ion occupying the Ti(1) site with approximately rhombic symmetry in KTiOPO4 crystal are calculated from the high-order perturbation formulas based on the two-mechanism model. In the model, not only the contribution due to the conventional crystal-field (CF) mechanism, but also those due to the charge-transfer (CT) mechanism are included. The six calculated spin-Hamiltonian parameters with four adjustable parameters are in reasonable agreement with the experimental values. The calculations show that for more accurate calculations of spin-Hamiltonian parameters of the high valence dn ions (e.g., Mo5+ considered here) in crystals, the contribution from CT mechanism, which is ignored in the conventional crystal field theory, should be taken into account. The reasonable crystal field energy levels of Mo5+ in KTiOPO4 are also predicted from calculations

  17. Studies on the local angular distortion and spin Hamiltonian parameters for the trigonal Co2+ center in MgCl2

    The local angular distortion and spin Hamiltonian parameters (g factor g verticalstrokeverticalstroke, g perpendicularto and the hyperfine structure constants) for the trigonal Co2+ center in MgCl2 are theoretically studied by diagonalizing the 6 x 6 energy matrix of ground 4T1 state for a trigonally distorted octahedral 3d7 cluster. Based on the cluster approach, the contributions from the admixtures of various J (= 1/2, 3/2, 5/2) states and the ligand orbital and spin-orbit coupling interactions are taken into account in a uniform way. The local impurity-ligand bond angle in the Co2+ center is found to be about 3.44 larger than the host metal-ligand bond angle in the pure crystal due to substitution of smaller Mg2+ by bigger Co2+, inducing a further compressed ligand octahedron. The calculated spin Hamiltonian parameters using the above local angular distortion are in good agreement with the experimental data. The present studies on the local structure and the spin Hamiltonian parameters for Co2+ in MgCl2 are tentatively extended to a more general case by comparing the relevant impurity behaviours for Co2+ in various trigonal environments.

  18. Studies on the Local Angular Distortion and Spin Hamiltonian Parameters for the Trigonal Co2+ Center in MgCl2

    Hu, Xian-Fen; Wu, Shao-Yi; Kuang, Min-Quan; Li, Guo-Liang

    2014-11-01

    The local angular distortion and spin Hamiltonian parameters (g factors g||, g⊥ and the hyperfine structure constants) for the trigonal Co2+ center in MgCl2 are theoretically studied by diagonalizing the 6×6 energy matrix of ground 4T1 state for a trigonally distorted octahedral 3d7 cluster. Based on the cluster approach, the contributions from the admixtures of various J (= 1/2;3/2;5/2) states and the ligand orbital and spin-orbit coupling interactions are taken into account in a uniform way. The local impurity-ligand bond angle in the Co2+ center is found to be about 3.44° larger than the host metal-ligand bond angle in the pure crystal due to substitution of smaller Mg2+ by bigger Co2+, inducing a further compressed ligand octahedron. The calculated spin Hamiltonian parameters using the above local angular distortion are in good agreement with the experimental data. The present studies on the local structure and the spin Hamiltonian parameters for Co2+ in MgCl2 are tentatively extended to a more general case by comparing the relevant impurity behaviours for Co2+ in various trigonal environments.

  19. Research on the optical band positions, spin-Hamiltonian parameters and atom-position parameter of Co{sup 2+} ion in CdSe crystal

    Mei, Yang [School of Physics & Electronic Engineering, Mianyang Normal University, Mianyang 621000 (China); Research Center of Computational Physics, Mianyang Normal University, Mianyang 621000 (China); Zheng, Wen-Chen, E-mail: zhengwc1@163.com [Department of Material Science, Sichuan University, Chengdu 610064 (China); Peng, Ren-Ming; Wei, Cheng-Fu [School of Physics & Electronic Engineering, Mianyang Normal University, Mianyang 621000 (China)

    2015-10-01

    The optical band positions and EPR (or spin-Hamiltonian) parameters (g factors g{sub //}, g{sub ⊥} and zero-field splitting D) of Co{sup 2+} ion in the trigonally-distorted tetrahedral Cd{sup 2+} site of CdSe crystal are calculated simultaneously from the complete diagonalization (of energy matrix) method (CDM) based on the two-spin–orbit-parameter model. This model contains the contributions to the spectral data from both the spin–orbit parameters of central d{sup n} ion (i.e., one-spin–orbit-parameter model) in the conventional crystal-field theory and that of ligand ions via covalence effect. The calculated 12 optical band positions and three spin-Hamiltonian parameters using four adjustable parameters show reasonable agreement with the experimental values. The local atom-position parameter u{sub loc} (where the corresponding parameter u in the host CdSe crystal is unlikely) in the Co{sup 2+} center is also estimated from the calculations. The calculations of these spectral data from the CDM based on the conventional one-spin–orbit parameter model are also made for comparison. It is found that the calculated optical band positions are also close to the experimental values, but the calculated spin-Hamiltonian parameters are in poor agreement with the observed values. So, for the unified and reasonable calculations of optical and EPR data of d{sup n} ions in crystals (in particular, in the cases of ligand with large spin–orbit parameter), the CDM based on the two-spin–orbit-parameter model should be applied. - Highlights: • Fifteen optical and EPR data of Co{sup 2+} center in CdSe are calculated together. • Calculation is using the complete diagonalization (of energy matrix) method (CDM). • The CDM based on the two-spin–orbit-parameter model is more reasonable. • Local atom-position parameter in Co{sup 2+} center in CdSe is obtained from calculation.

  20. Local structure distortion and spin Hamiltonian parameters for Cr3+-VZn tetragonal defect centre in Cr3+ doped KZnF3 crystal

    Yang Zi-Yuan

    2011-01-01

    The quantitative relationship between the spin Hamiltonian parameters (D,g1l,Og) and the crystal structure parameters for the Cr3+-VZ,,tetragonal defect centre in a Cr3+:KZnF3 crystal is established by using the superposition model. On the above basis,the local structure distortion and the spin Hamiltonian parameter for the Cr3+-VZn tetragonal defect centre in the KZnF3 crystal are systematically investigated using the complete diagonalization method.It is found that the Vzn vacancy and the differences in mass,radius and charge between the Cr3+ and the Zn2+ ions induce the local lattice distortion of the Cr3+ centre ions in the KZnF3 crystal. The local lattice distortion is shown to give rise to the tetragonal crystal field,which in turn results in the tetragonal zero-field splitting parameter D and the anisotropic g factor △g. We find that the ligand F-ion along [001]and the other five F-ions move towards the central Cr3+ by distances of △l=0.0121 nm and △2=0.0026 nm,respectively. Our approach takes into account the spin-orbit interaction as well as the spin-spin,spin-other-orbit,and orbit-orbit interactions omitted in the previous studies. It is found that for the Cr3+ ions in the Cr3+:KZnF3 crystal,although the spin-orbit mechanism is the most important one,the contribution to the spin Hamiltonian parameters from the other three mechanisms,including spin-spin,spin-other-orbit,and orbit-orbit magnetic interactions,is appreciable and should not be omitted,especially for the zero-field splitting (ZFS) parameter D.

  1. Theoretical studies of the spin-Hamiltonian parameters for the orthorhombic Pr4+ centers in Sr2CeO4 crystals

    Wen-Lin Feng

    2008-04-01

    Theoretical studies of spin-Hamiltonian (SH) parameters associated with Pr4+ in Sr2CeO4 single crystals have been made by using the complete diagonalizing energy matrix method (CDM) for the 41 electronic configuration. The calculated results are in excellent agreement with the experimental data. The negative signs of the anisotropic -factors and hyperfine structure constants (where = || or ⊥) for the orthorhombic Pr4+ ion in Sr2CeO4 are suggested from the calculations. By comparing the results obtained by the CDM with the experimental data, one finds it is valid to interpret the SH parameters for 41 ions in crystals. The results are discussed.

  2. Theoretical research of the spin-Hamiltonian parameters for two rhombic W5+ centers in KTiOPO4 (KTP) crystal through a two-mechanism model

    Mei, Yang; Chen, Bo-Wei; Wei, Chen-Fu; Zheng, Wen-Chen

    2016-09-01

    The high-order perturbation formulas based on the two-mechanism model are employed to calculate the spin-Hamiltonian parameters (g factors gi and hyperfine structure constants Ai, where i=x, y, z) for two approximately rhombic W5+ centers in KTiOPO4 (KTP) crystal. In the model, both the widely-applied crystal-field (CF) mechanism concerning the interactions of CF excited states with the ground state and the generally-neglected charge-transfer (CT) mechanism concerning the interactions of CT excited states with the ground state are included. The calculated results agree with the experimental values, and the signs of constants Ai are suggested. The calculations indicate that (i) for the high valence state dn ions in crystals, the contributions to spin-Hamiltonian parameters should take into account both the CF and CT mechanisms and (ii) the large g-shifts |Δgi | (=|gi-ge |, where ge≈ 2.0023) for W5+ centers in crystals are due to the large spin-orbit parameter of free W5+ ion.

  3. Semi-empirical and ab initio DFT modeling of the spin-Hamiltonian parameters for Fe6+: K2MO4 (M = S, Cr, Se)

    In this paper we calculated the spin-Hamiltonian parameters (g factors g||, g⊥ and zero field splitting parameter D) for Fe6+ ions doped in K2MO4 (M = S, Cr, Se) crystals, taking into account the actual site symmetry of the Fe6+ impurity ion. The suggested method is based on the successful application of two different approaches: the crystal field theory (CFT) and density functional based (DFT). Within the CFT model we used the cluster approach and the perturbation theory method, based on the crystal field parameters, which were calculated in the superposition model. Within the DFT approach the calculations were done at the self-consistent field (SCF) by solving the coupled perturbed SCF equations. Comparison with experimental data shows that the obtained results are quite satisfactory, which proves applicability of the suggested calculating technique. (paper)

  4. Semi-empirical and ab initio DFT modeling of the spin-Hamiltonian parameters for Fe6+: K2MO4 (M = S, Cr, Se)

    Avram, N. M.; Brik, M. G.; Andreici, E.-L.

    2014-09-01

    In this paper we calculated the spin-Hamiltonian parameters (g factors {{g}||}, {{g}\\bot } and zero field splitting parameter D) for Fe6+ ions doped in K2MO4 (M = S, Cr, Se) crystals, taking into account the actual site symmetry of the Fe6+ impurity ion. The suggested method is based on the successful application of two different approaches: the crystal field theory (CFT) and density functional based (DFT). Within the CFT model we used the cluster approach and the perturbation theory method, based on the crystal field parameters, which were calculated in the superposition model. Within the DFT approach the calculations were done at the self-consistent field (SCF) by solving the coupled perturbed SCF equations. Comparison with experimental data shows that the obtained results are quite satisfactory, which proves applicability of the suggested calculating technique.

  5. Theoretical studies on the spin Hamiltonian parameters and local environment of Mn{sup 2+} in ZnO nanocrystal and bulk

    Li, Guo-Liang, E-mail: liguolianglq@163.com [Department of Applied Physics, School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054 (China); School of Physics and Engineering, Xingyi Normal University for Nationalities, Xingyi 562400 (China); Wu, Shao-Yi; Hu, Xian-Fen; Kuang, Min-Quan [Department of Applied Physics, School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054 (China)

    2015-06-15

    By employing the perturbation calculations, the spin Hamiltonian parameters (SHPs) and local structures are uniformly explored for Mn{sup 2+} in the ZnO nanocrystal and bulk. The EPR spectra are satisfactorily explained for both the systems, and the defect structure information is obtained, i.e., the substitutional impurity Mn{sup 2+} may undergo the axial displacements of 0.036 and 0.042 Å away from the oxygen triangles along the C{sub 3} axis in the ZnO nanocrystal and bulk, respectively. The similar SHPs for Mn{sup 2+} in the nanocrystal and bulk can be illustrated as the approximately identical covalency (equal covalency factor N) as well as the smaller axial displacement, the stronger crystal–field (CF) interactions (larger cubic CF parameter Dq) and Mn{sup 2+} 3d–3s orbital admixture (larger core polarization constant κ) in the former.

  6. An Investigation for the Spin Hamiltonian sParameters and the Local Structure for Co2+ in ZnWO4

    Ding Chang-Chun

    2016-01-01

    Full Text Available Based on the perturbation formulae of the spin Hamiltonian parameters (SHPs, i,e,. g factors gx, gy, gz, and hyperfine structure constants Ax, Ay, Az, for a 3d7 ion in rhombically distorted octahedra, the defect structure and the experimental EPR spectra are theoretically investigated for the rhombic Co2+ centre in ZnWO4. Due to the Jahn-Teller effect, the impurity ion Co2+ on host Zn2+ site is found to undergo the local rhombic elongation distortion, characterized by the axial elongation ΔZ (≈ 0.157 Å of the impurity-ligand bonds and the perpendicular distortion angle Δф (≈ 3.5° related to an ideal octahedron. Compared with host Zn2+ site in ZnWO4, the Co2+ centre exhibits a more regular oxygen octahedron. All the calculated SHPs show good agreement with the observed values. The present work may be helpful to understand the local structures and properties of metal tungstate with transition-metal dopants.

  7. Theoretical calculations of spin-Hamiltonian parameters for the (MoOX{sub 5}){sup 2−} (X=Cl, Br) metallic complexes in solution or frozen-glass

    Mei, Yang [School of Physics and Electronic Engineering, Mianyang Normal University, Mianyang 621000 (China); Research Center of Laser Fusion, CAEP, Mianyang 621900 (China); Research Center of Computational Physics, Mianyang Normal University, Mianyang 621000 (China); Zheng, Wen-Chen, E-mail: zhengwc1@163.com [Department of Material Science, Sichuan University, Chengdu 610064 (China); Zhang, Lin [Research Center of Laser Fusion, CAEP, Mianyang 621900 (China); Chen, Bo-Wei [School of Physics and Electronic Engineering, Mianyang Normal University, Mianyang 621000 (China); Research Center of Laser Fusion, CAEP, Mianyang 621900 (China); Research Center of Computational Physics, Mianyang Normal University, Mianyang 621000 (China)

    2014-11-01

    The spin-Hamiltonian parameters (g factors g{sub //}, g{sub ⊥} and hyperfine structure constants A{sub //}, A{sub ⊥}) of the (MoOX{sub 5}){sup 2−} (X=Cl, Br) metallic complexes in solution or frozen-glass are calculated from the high-order perturbation formulas based on the two-mechanism model. In these formulas, the contributions to spin-Hamiltonian parameters due to both the widely-applied crystal-field (CF) mechanism and the charge-transfer (CT) mechanism (which is neglected in CF theory) are taken into account, and the needed CF and CT energy levels are obtained from the optical spectra. The calculated results with two adjustable parameters are in reasonable agreement with the experimental values. The calculations show that (i) the relative importance of CT mechanism in (MoOBr{sub 5}){sup 2−} metallic complexes is larger than that in (MoOCl{sub 5}){sup 2−} ones because of the stronger covalence of Mo{sup 5+}–Br{sup −} combination, and (ii) in both (MoOCl{sub 5}){sup 2−} and (MoOBr{sub 5}){sup 2−} metallic complexes, the contributions to spin-Hamiltonian parameters due to CT mechanism should also be taken into account because of the high valence state of Mo{sup 5+} ion.

  8. Investigations on the local structure and the spin-Hamiltonian parameters for the tetragonal $Cu^{2+}$ centre in $ZnGeF_{6}·6H_{2}O$ crystal

    LI CHAO-YING; HUANG YING; ZHENG XUE MEI

    2016-08-01

    The spin-Hamiltonian parameters ($g$ factors $g_{||}, g{|perp}$ and hyperfine structure constants $A_{||}$, $A{|perp}$) and the local structure for the tetragonal $Cu^{2+}$ centre in trigonal $ZnGeF_{6}·6H_{2}O$ crystal are theoretically studied using the perturbation formulae of these parameters for a 3d9 ion in tetragonally elongated octahedra. In the calculations, the contributions to the spin-Hamiltonian parameters from ligand orbital and spin-orbit coupling are included on the basis of the cluster approach in view of moderate covalency of the studied systems, and the required crystal field parameters are obtained using the superposition model and the local structures of the studied $[Cu(H_{2}O)_{6}]^{2+}$ cluster. According to the calculations, the ligand octahedra around $Cu^{2+}$ suffer relative elongation$\\tau{\\sim 0.085 \\AA) along the [0 0 1] (or $C_4$) axis for the tetragonal $Cu^{2+}$ centres in $ZnGeF_{6}·6H_{2}O$ crystal, due to the Jahn--Teller effect. The calculated results show good agreement with the experimental data.

  9. Spin Hamiltonians for actinide ions

    The breakdown of Russel Saunders coupling for correlated f-levels of actinide ions is due to both spin orbit coupling and the crystalline electric field (CEF). Experiments on curium, an S-state ion in the metal for which the CEF is weak indicate a g-factor close to the Russel-Saunders value. Spin-orbit coupling is therefore too weak to produce jj coupling. This suggests a model for magnetic actinide ions in which the CEF ground multiplet is well separated from higher levels, completely determining thermodynamic magnetic properties. On this basis simplified spin Hamiltonians are derived for GAMMA1-GAMMA5 ground states in order to interpret thermodynamic measurements and ordering phenomena. (author)

  10. Assignments of the optical band positions and theoretical calculations of the spin-Hamiltonian parameters for the tetragonal W5+ octahedral clusters in tungsten oxide (WO3)-based glasses

    The optical band positions of W5+ octahedral clusters (WO6)7− in tungsten oxide (WO3)-based glasses are reassigned and suggested. Based on this, the spin-Hamiltonian parameters (g factors g//, g⊥ and hyperfine structure constants A//, A⊥) of these W5+ clusters are calculated from the high-order perturbation formulas based on the two-mechanism model. In the model, besides the contributions due to crystal-field (CF) mechanism in the extensively-used CF theory, the contributions owing to charge-transfer (CT) mechanism (which are often omitted) are also included. The calculated results are in reasonable agreement with the experimental values and the signs of hyperfine structure constants Ai are suggested. The results are discussed

  11. Assignments of the optical band positions and theoretical calculations of the spin-Hamiltonian parameters for the tetragonal W{sup 5+} octahedral clusters in tungsten oxide (WO{sub 3})-based glasses

    Peng, Ren-Ming [School of Physics & Electronic Engineering, Mianyang Normal University, Mianyang 621000 (China); Mei, Yang [School of Physics & Electronic Engineering, Mianyang Normal University, Mianyang 621000 (China); Research Center of Computational Physics, Mianyang Normal University, Mianyang 621000 (China); Zheng, Wen-Chen, E-mail: zhengwc1@163.com [Department of Material Science, Sichuan University, Chengdu 610064 (China); Wei, Cheng-Fu [School of Physics & Electronic Engineering, Mianyang Normal University, Mianyang 621000 (China)

    2015-03-15

    The optical band positions of W{sup 5+} octahedral clusters (WO{sub 6}){sup 7−} in tungsten oxide (WO{sub 3})-based glasses are reassigned and suggested. Based on this, the spin-Hamiltonian parameters (g factors g{sub //}, g{sub ⊥} and hyperfine structure constants A{sub //}, A{sub ⊥}) of these W{sup 5+} clusters are calculated from the high-order perturbation formulas based on the two-mechanism model. In the model, besides the contributions due to crystal-field (CF) mechanism in the extensively-used CF theory, the contributions owing to charge-transfer (CT) mechanism (which are often omitted) are also included. The calculated results are in reasonable agreement with the experimental values and the signs of hyperfine structure constants A{sub i} are suggested. The results are discussed.

  12. Studies on the spin Hamiltonian parameters and local angular distortions for the tetragonal Cu{sup 2+} centers in the ZnX (X=O and S) nanocrystals

    Li, Guo-Liang, E-mail: liguolianglq@163.com [Department of Applied Physics, School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054 (China); School of Physics and Engineering, Xingyi Normal University for Nationalities, Xingyi 562400 (China); Wu, Shao-Yi; Zhang, Zhi-Hong; Ding, Chang-Chun; Hu, Xian-Fen [Department of Applied Physics, School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054 (China)

    2015-01-15

    The spin Hamiltonian parameters (g factors and hyperfine structure constants) and local structures are theoretically studied for the tetragonal Cu{sup 2+} centers in the ZnX (X=O and S) nanocrystals from the perturbation formulas of these parameters for a 3d{sup 9} ion in tetragonally distorted tetrahedra. The ligand orbital and spin–orbit coupling contributions are considered in view of strong covalency. Due to the Jahn–Teller effect, the local Cu{sup 2+}‒X{sup 2−} bond angles between the four equivalent impurity-ligand bonds and the four-fold axis are found to be about 2.47° and 1.68° larger than that (≈54.74°) for an ideal tetrahedron. This induces tetragonally compressed [CuX{sub 4}]{sup 6−} clusters on tetrahedral substitutional Zn{sup 2+} sites, different from the assignments (i.e., Cu{sup 2+} on tetragonally elongated octahedral and tetrahedral substitutional sites in the ZnO and ZnS nanocrystals, respectively) in the previous works. The calculated g factors for both systems and the parallel component of the hyperfine structure constants for the ZnS:Cu{sup 2+} nanocrystals based on the above local angular distortions are in good agreement with the observed values. The validity of the present assignments for the local structures of the Cu{sup 2+} centers is analyzed.

  13. EPR study of Gd3+-doped RbR(SO4)2·4H2O (R=Pr,Nd,Sm,Eu) single crystals: Phase transitions and spin-Hamiltonian parameters

    Extensive EPR measurements were carried out in the temperature range 100 endash 300 K. The room-temperature data indicate that Gd3+ ions substitute equally for R3+ ions at the two magnetically inequivalent sites in the unit cell, and that the site symmetry of the Gd3+ ion is monoclinic. The Gd3+ room-temperature spin-Hamiltonian parameters and linewidths were estimated. The phase transition temperatures (Tc) were determined to be 175±1K (first order) in RbPr(SO4)2·4H2O, 178.5±1K (first order) in RbNd(SO4)2·4H2O, 232±0.5K (second order) in RbSm(SO4)2·4H2O, and 230.5±0.5K (second order) in RbEu(SO4)2·4H2O. In RbPr(SO4)2·4H2O and RbNd(SO4)2·4H2O, the occurrence of the first-order phase transitions was deduced from abrupt changes in the behavior of the linewidth, zero-field splitting, and line positions, and coexistence of lines observed below and above Tc. In addition, there were observed occurrences of two more phase transitions second order in nature in RbPr(SO4)2·4H2O (Tc1=261K, Tc2=207.5K) and in RbNd(SO4)2·4H2O (Tc1=250K, Tc2=219.5K); these were not as sharply defined as the preceding ones. Below Tc, for all the crystals, the symmetry of the crystals was found to be lower than monoclinic, the four ions in the unit cell becoming magnetically inequivalent from each other. The observed second-order phase transitions in the four crystals were found to be in agreement with Landau theory of second-order phase transitions; the critical exponent was determined to be β congruent 0.51. copyright 1997 The American Physical Society

  14. Gravitational spin Hamiltonians from the S matrix

    Vaidya, Varun

    2014-01-01

    We utilize generalized unitarity and recursion relations combined with effective field theory(EFT) techniques to compute spin dependent interaction terms for inspiralling binary systems in the post newtonian(PN) approximation. Using these methods offers great computational advantage over traditional techniques involving feynman diagrams, especially at higher orders in the PN expansion. As a specific example, we reproduce the spin-orbit interaction up to 2.5 PN order as also the leading order $S^2$(3PN) hamiltonian for an arbitrary massive object. We also obtain the unknown $S^3$(3.5PN) spin hamiltonian for an arbitrary massive object in terms of its low frequency linear response to gravitational perturbations, which was till now known only for a black hole. Furthermore, we derive the missing $S^4$ Hamiltonian at leading order(4PN) for an arbitrary massive object and establish that a minimal coupling of a massive elementary particle to gravity leads to a black hole structure. Finally, the Kerr metric is obtain...

  15. Investigations of the spin-Hamiltonian parameters and tetragonal distortion due to the Jahn-Teller effect for Cu(H{sub 2}O){sub 6}{sup 2+} clusters in C(NH{sub 2}){sub 3}Al(SO{sub 4}){sub 2}.6H{sub 2}O: Cu{sup 2+} crystal

    Feng Wenlin, E-mail: wenlinfeng@126.co [Department of Applied Physics, Chongqing University of Technology, Hong-Guang Street, Chongqing 400054 (China) and International Centre for Materials Physics, Chinese Academy of Sciences, Shengyang 110016 (China); Yang Weiqing [Department of Optics and Electronics, Chengdu University of Information Technology, Chengdu 610225 (China); Department of Material Science, Sichuan University, Chengdu 610064 (China); Zheng Wenchen [Department of Material Science, Sichuan University, Chengdu 610064 (China); International Centre for Materials Physics, Chinese Academy of Sciences, Shengyang 110016 (China); Liu Hongguang [Department of Material Science, Sichuan University, Chengdu 610064 (China)

    2010-04-15

    When Cu{sup 2+} ion occupies the trigonal Al{sup 3+} (II) site in guanidinium aluminium sulphate hexahydrate (GASH) (C(NH{sub 2}){sub 3}Al(SO{sub 4}){sub 2}.6H{sub 2}O) crystals, the trigonal Al(H{sub 2}O){sub 6}{sup 3+} octahedron in the host GASH crystal changes to the tetragonally-elongated Cu(H{sub 2}O){sub 6}{sup 2+} octahedron in the impurity center due to the Jahn-Teller effect. The tetragonal distortion (characterized by DELTAR=R{sub parallel} -R{sub perpendicular}, where R{sub parallel} and R{sub perpendicular} represent the metal-ligand distances parallel with and perpendicular to the C{sub 4} axis) of this Cu(H{sub 2}O){sub 6}{sup 2+} cluster is studied by calculating its spin-Hamiltonian parameters (g factors g{sub parallel} , g{sub perpendicular} and hyperfine structure constants A{sub parallel} and A{sub perpendicular}) from two theoretical methods, the complete diagonalization (of energy matrix) method (CDM) and the perturbation theory method (PTM). Both methods are based on the cluster approach in which the admixture between the d orbitals of 3d{sup n} ion and the p orbitals of ligand ion is considered. The calculated results show that both methods can be used to calculate the spin-Hamiltonian parameters and to determine the structure of 3d{sup 9} clusters in crystals. These results are discussed.

  16. On the energy landscape of 3D spin Hamiltonians with topological order

    Bravyi, Sergey

    2011-01-01

    We explore feasibility of a quantum self-correcting memory based on 3D spin Hamiltonians with topological quantum order in which thermal diffusion of topological defects is suppressed by macroscopic energy barriers. To this end we characterize the energy landscape of stabilizer code Hamiltonians with local bounded-strength interactions which have a topologically ordered ground state but do not have string-like logical operators. We prove that any sequence of local errors mapping a ground state of such Hamiltonian to an orthogonal ground state must cross an energy barrier growing at least as a logarithm of the lattice size. Our bound on the energy barrier is shown to be tight up to a constant factor for one particular 3D spin Hamiltonian.

  17. The dynamics of a spinning particle in a linear in spin Hamiltonian approximation

    Lukes-Gerakopoulos, Georgios; Patsis, Panos A; Seyrich, Jonathan

    2016-01-01

    We investigate for order and chaos the dynamical system of a spinning test particle of mass $m$ moving in the spacetime background of a Kerr black hole of mass M. This system is approximated in our investigation by the linear in spin Hamiltonian function provided in [E. Barausse, and A. Buonanno, Phys.Rev. D 81, 084024 (2010)]. We study the corresponding phase space by using 2D projections on a surface of section and the method of color and rotation on a 4D Poincar\\'e section. Various topological structures coming from the non-integrability of the linear in spin Hamiltonian are found and discussed. Moreover, an interesting result is that from the value of the dimensionless spin $S/(m M)=10^{-4}$ of the particle and below, the impact of the non-integrability of the system on the motion of the particle seems to be negligible.

  18. Rovibrational and temperature effects in theoretical studies of NMR parameters

    Faber, Rasmus; Kaminsky, Jakub; Sauer, Stephan P. A.

    2016-01-01

    resources. Highly sophisticated calculations including even relativistic effects are nowadays possible for these properties. However, NMR parameters depend not only on molecular structure and environment but also on molecular flexibility and temperature and the apparent success of theoretical predictions...

  19. Understanding visual map formation through vortex dynamics of spin Hamiltonian models

    Cho, M W; Cho, Myoung Won; Kim, Seunghwan

    2003-01-01

    We introduce a general method for cerebral cortical map generation and apply it to pattern formation in orientation and ocular dominance columns of the brain. From a known cortical structure, we build spin Hamiltonian models with long-range interactions of the Mexican hat type. These Hamiltonian models allow a coherent interpretation of the diverse phenomena in the map formation in the visual cortex with the help of relaxation dynamics of spins. In particular, we predict various phenomena of self-organization in orientation and ocular map formation including the pinwheel annihilation and its dependency on the columnar wave vector and boundary conditions.

  20. Spin Hamiltonian, order out of a Coulomb phase, and pseudocriticality in the frustrated pyrochlore Heisenberg antiferromagnet FeF3

    Sadeghi, Azam; Alaei, Mojtaba; Shahbazi, Farhad; Gingras, Michel J. P.

    2015-04-01

    FeF3, with its half-filled Fe3 +3 d orbital, hence zero orbital angular momentum and S =5 /2 , is often put forward as a prototypical highly frustrated classical Heisenberg pyrochlore antiferromagnet. By employing ab initio density functional theory, we obtain an effective spin Hamiltonian for this material. This Hamiltonian contains nearest-neighbor antiferromagnetic Heisenberg, biquadratic, and Dzyaloshinskii-Moriya interactions as dominant terms and we use Monte Carlo simulations to investigate the nonzero temperature properties of this minimal model. We find that upon decreasing temperature, the system passes through a Coulomb phase, composed of short-range correlated coplanar states, before transforming into an "all-in/all-out" (AIAO) state via a very weakly first-order transition at a critical temperature Tc≈22 K, in good agreement with the experimental value for a reasonable set of Coulomb interaction U and Hund's coupling JH describing the material. Despite the transition being first order, the AIAO order parameter evolves below Tc with a power-law behavior characterized by a pseudo "critical exponent" β ≈0.18 in accord with experiment. We comment on the origin of this unusual β value.

  1. Higher-order Zeeman and spin terms in the electron paramagnetic resonance spin Hamiltonian; their description in irreducible form using Cartesian, tesseral spherical tensor and Stevens' operator expressions.

    McGavin, Dennis G; Tennant, W Craighead

    2009-06-17

    In setting up a spin Hamiltonian (SH) to study high-spin Zeeman and high-spin nuclear and/or electronic interactions in electron paramagnetic resonance (EPR) experiments, it is argued that a maximally reduced SH (MRSH) framed in tesseral combinations of spherical tensor operators is necessary. Then, the SH contains only those terms that are necessary and sufficient to describe the particular spin system. The paper proceeds then to obtain interrelationships between the parameters of the MRSH and those of alternative SHs expressed in Cartesian tensor and Stevens operator-equivalent forms. The examples taken, initially, are those of Cartesian and Stevens' expressions for high-spin Zeeman terms of dimension BS(3) and BS(5). Starting from the well-known decomposition of the general Cartesian tensor of second rank to three irreducible tensors of ranks 0, 1 and 2, the decomposition of Cartesian tensors of ranks 4 and 6 are treated similarly. Next, following a generalization of the tesseral spherical tensor equations, the interrelationships amongst the parameters of the three kinds of expressions, as derived from equivalent SHs, are determined and detailed tables, including all redundancy equations, set out. In each of these cases the lowest symmetry, [Formula: see text] Laue class, is assumed and then examples of relationships for specific higher symmetries derived therefrom. The validity of a spin Hamiltonian containing mixtures of terms from the three expressions is considered in some detail for several specific symmetries, including again the lowest symmetry. Finally, we address the application of some of the relationships derived here to seldom-observed low-symmetry effects in EPR spectra, when high-spin electronic and nuclear interactions are present. PMID:21693947

  2. Modeling Ne-21 NMR parameters for carbon nanosystems

    Kupka, T.; Nieradka, M.; Kaminský, Jakub; Stobinski, L.

    2013-01-01

    Roč. 51, č. 10 (2013), s. 676-681. ISSN 0749-1581 R&D Projects: GA ČR GAP208/11/0105; GA MŠk(CZ) LH11033 Grant ostatní: AV ČR(CZ) M200551205 Institutional support: RVO:61388963 Keywords : Ne-21 NMR * GIAO NMR * molecular modeling * carbon nanostructures Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.559, year: 2013

  3. Ground-State Analysis for an Exactly Solvable Coupled-Spin Hamiltonian

    Eduardo Mattei

    2013-11-01

    Full Text Available We introduce a Hamiltonian for two interacting su(2 spins. We use a mean-field analysis and exact Bethe ansatz results to investigate the ground-state properties of the system in the classical limit, defined as the limit of infinite spin (or highest weight. Complementary insights are provided through investigation of the energy gap, ground-state fidelity, and ground-state entanglement, which are numerically computed for particular parameter values. Despite the simplicity of the model, a rich array of ground-state features are uncovered. Finally, we discuss how this model may be seen as an analogue of the exactly solvable p+ip pairing Hamiltonian.

  4. Theoretical and experimental determination of some complexing parameters of paramagnetic ions from NMR spectra

    Influence on the form of line in NMR spectrum of spin-spin interaction constant (J), limiting induced chemical shifts (Δi), relaxation time T2i and solution composition is studied. Solution composition proved the most essential factor. Experimental study of praseodymium(3) chloride complexing with cysteine indicated that accuracy of the complexing parameters obtained agrees with theoretical conclusions

  5. Magnetostructural correlations for Fe2+ ions at orthorhombic sites in FeCl2·4H2O and FeF2·4H2O crystals modeled by microscopic spin Hamiltonian approach

    Zając, Magdalena; Lipiński, Ignacy Eryk; Rudowicz, Czesław

    2016-03-01

    The microscopic spin Hamiltonian (MSH) theory developed up to the fourth-order perturbation theory for 3d4 and 3d6 ions with spin S=2 within the 5D approximation is employed to predict the zero field splitting (ZFS) parameters and the Zeeman electronic (Ze) ones. The SH parameters, measurable by electron magnetic resonance (EMR), are expressed in terms of the microscopic parameters, i.e. the spin-orbit (λ), spin-spin (ρ) coupling constants, and the crystal-field (ligands-field) energy levels (∆i) within the 5D multiplet. The energies, ∆i, are indirectly related with structural data, thus enabling investigation of magnetostructural correlations. As a case study Fe2+ (3d6; S=2) ions at orthorhombic sites in FeCl2·4H2O and FeF2·4H2O crystals are considered. Calculations of the ZFS and Ze parameters are carried out for wide ranges of values of the microscopic parameters using the package MSH/VBA. Dependence of the theoretically determined ZFS parameters bkq (in the Stevens notation) and the Zeeman factors gi on λ, ρ, and ∆i is examined and suitable graphs are presented. The absolute value of dominant ZFS parameter |b20| is predicted to be in the range from nearly 8.5 to 1.4 cm-1. Matching the theoretical SH parameters and the experimental ones enables determination of the suitable values of λ, ρ, and ∆i. The fourth-rank ZFS parameters and the ρ(spin-spin)-related contributions, considered for the first time here, are found important. The MSH predictions may be verified and fine-tuned by high-magnetic field and high-frequency EMR measurements. The method employed here and the present results may be also useful for other structurally related systems.

  6. Determination of Kinetic Parameters within a Single Nonisothermal On-Flow Experiment by Nanoliter NMR Spectroscopy.

    Gomez, M Victoria; Rodriguez, Antonio M; de la Hoz, Antonio; Jimenez-Marquez, Francisco; Fratila, Raluca M; Barneveld, Peter A; Velders, Aldrik H

    2015-10-20

    Conventional methods to determine the kinetic parameters for a certain reaction require multiple, separate isothermal experiments, resulting in time- and material-consuming processes. Here, an approach to determine the kinetic information within a single nonisothermal on-flow experiment is presented, consuming less than 10 μmol of reagents and having a total measuring time of typically 10 min. This approach makes use of a microfluidic NMR chip hyphenated to a continuous-flow microreactor and is based on the capabilities of the NMR chip to analyze subnanomole quantities of material in the 25 nL detection volume. Importantly, useful data are acquired from the microreactor platform in specific isothermal and nonisothermal frames. A model fitting the experimental data enables rapid determination of kinetic parameters, as demonstrated for a library of isoxazole and pyrazole derivatives. PMID:26383715

  7. Quantum model of a solid-state spin qubit: Ni cluster on a silicon surface by the generalized spin Hamiltonian and X-ray absorption spectroscopy investigations

    Farberovich, Oleg V. [School of Physics and Astronomy, Beverly and Raymond Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978 (Israel); Research Center for Nanoscale Structure of Matter, Southern Federal University, Zorge 5, 344090 Rostov-on-Don (Russian Federation); Voronezh State University, Voronezh 394000 (Russian Federation); Mazalova, Victoria L., E-mail: mazalova@sfedu.ru [Research Center for Nanoscale Structure of Matter, Southern Federal University, Zorge 5, 344090 Rostov-on-Don (Russian Federation); Soldatov, Alexander V. [Research Center for Nanoscale Structure of Matter, Southern Federal University, Zorge 5, 344090 Rostov-on-Don (Russian Federation)

    2015-11-15

    We present here the quantum model of a Ni solid-state electron spin qubit on a silicon surface with the use of a density-functional scheme for the calculation of the exchange integrals in the non-collinear spin configurations in the generalized spin Hamiltonian (GSH) with the anisotropic exchange coupling parameters linking the nickel ions with a silicon substrate. In this model the interaction of a spin qubit with substrate is considered in GSH at the calculation of exchange integrals J{sub ij} of the nanosystem Ni{sub 7}–Si in the one-electron approach taking into account chemical bonds of all Si-atoms of a substrate (environment) with atoms of the Ni{sub 7}-cluster. The energy pattern was found from the effective GSH Hamiltonian acting in the restricted spin space of the Ni ions by the application of the irreducible tensor operators (ITO) technique. In this paper we offer the model of the quantum solid-state N-spin qubit based on the studying of the spin structure and the spin-dynamics simulations of the 3d-metal Ni clusters on the silicon surface. The solution of the problem of the entanglement between spin states in the N-spin systems is becoming more interesting when considering clusters or molecules with a spectral gap in their density of states. For quantifying the distribution of the entanglement between the individual spin eigenvalues (modes) in the spin structure of the N-spin system we use the density of entanglement (DOE). In this study we have developed and used the advanced high-precision numerical techniques to accurately assess the details of the decoherence process governing the dynamics of the N-spin qubits interacting with a silicon surface. We have studied the Rabi oscillations to evaluate the N-spin qubits system as a function of the time and the magnetic field. We have observed the stabilized Rabi oscillations and have stabilized the quantum dynamical qubit state and Rabi driving after a fixed time (0.327 μs). The comparison of the energy

  8. Quantum model of a solid-state spin qubit: Ni cluster on a silicon surface by the generalized spin Hamiltonian and X-ray absorption spectroscopy investigations

    We present here the quantum model of a Ni solid-state electron spin qubit on a silicon surface with the use of a density-functional scheme for the calculation of the exchange integrals in the non-collinear spin configurations in the generalized spin Hamiltonian (GSH) with the anisotropic exchange coupling parameters linking the nickel ions with a silicon substrate. In this model the interaction of a spin qubit with substrate is considered in GSH at the calculation of exchange integrals Jij of the nanosystem Ni7–Si in the one-electron approach taking into account chemical bonds of all Si-atoms of a substrate (environment) with atoms of the Ni7-cluster. The energy pattern was found from the effective GSH Hamiltonian acting in the restricted spin space of the Ni ions by the application of the irreducible tensor operators (ITO) technique. In this paper we offer the model of the quantum solid-state N-spin qubit based on the studying of the spin structure and the spin-dynamics simulations of the 3d-metal Ni clusters on the silicon surface. The solution of the problem of the entanglement between spin states in the N-spin systems is becoming more interesting when considering clusters or molecules with a spectral gap in their density of states. For quantifying the distribution of the entanglement between the individual spin eigenvalues (modes) in the spin structure of the N-spin system we use the density of entanglement (DOE). In this study we have developed and used the advanced high-precision numerical techniques to accurately assess the details of the decoherence process governing the dynamics of the N-spin qubits interacting with a silicon surface. We have studied the Rabi oscillations to evaluate the N-spin qubits system as a function of the time and the magnetic field. We have observed the stabilized Rabi oscillations and have stabilized the quantum dynamical qubit state and Rabi driving after a fixed time (0.327 μs). The comparison of the energy pattern with the

  9. Filtering and parameter estimation of surface-NMR data using singular spectrum analysis

    Ghanati, Reza; Kazem Hafizi, Mohammad; Mahmoudvand, Rahim; Fallahsafari, Mahdi

    2016-07-01

    Ambient electromagnetic interferences at the site of investigation often degrade the signal quality of the Surface-NMR measurements leading to inaccurate estimation of the signal parameters. This paper proposes a new powerful de-noising method based on singular spectrum analysis (SSA), which is a nonparametric method for analyzing time series. SSA is a relatively simple method and can be understood using basic algebra notations. Singular value decomposition (SVD) plays a crucial role in SSA. As the length of recordings increases, the computational time required for computing SVD raises which restricts the usage of SSA in long-term time series. In order to overcome this drawback, we propose a randomized version of the singular value decomposition to accelerate the decomposition step of the algorithm. To evaluate the performance of the proposed strategy, the method is tested on synthetic signals corrupted by both simulated noise (including Gaussian white noise, spiky events and harmonic noise) and real noise recordings obtained from surface-NMR field surveys and a real data set. Our results show that the proposed algorithm can enhance the signal to noise ratio significantly, and gives an improvement in estimation of the surface-NMR signal parameters.

  10. Ab initio determination of spin Hamiltonians with anisotropic exchange interactions: The case of the pyrochlore ferromagnet Lu2V2O7

    Riedl, Kira; Guterding, Daniel; Jeschke, Harald O.; Gingras, Michel J. P.; Valentí, Roser

    2016-07-01

    We present a general framework for deriving effective spin Hamiltonians of correlated magnetic systems based on a combination of relativistic ab initio density functional theory calculations, exact diagonalization of a generalized Hubbard Hamiltonian on finite clusters, and spin projections onto the low-energy subspace. A key motivation is to determine anisotropic bilinear exchange couplings in materials of interest. As an example, we apply this method to the pyrochlore Lu2V2O7 where the vanadium ions form a lattice of corner-sharing spin-1/2 tetrahedra. In this compound, anisotropic Dzyaloshinskii-Moriya interactions (DMIs) play an essential role in inducing a magnon Hall effect. We obtain quantitative estimates of the nearest-neighbor Heisenberg exchange, the DMI, and the symmetric part of the anisotropic exchange tensor. Finally, we compare our results with experimental ones on the Lu2V2O7 compound.

  11. Thermal and solvent effects on NMR spectroscopy parameters of a prototypical Chagas disease drug

    NONE

    2011-07-01

    understood on the basis of semiclassical physics, J-coupling is a purely quantum- mechanical phenomenon. The present results provide evidence that hyperconjugative effects in solute molecules are not due to changes in geometric parameters upon solvation, but arise from the direct response of the electronic wave function to the presence of the solvent, which can be represented by discrete molecules and/or the dielectric bulk. We believe that our findings may be helpful to rationalize the relation between NMR parameters and the interactions in hydrogen-bonded complexes. Further applications along these lines are in progress. (author)

  12. Ab Initio Quality NMR Parameters in Solid-State Materials Using a High-Dimensional Neural-Network Representation.

    Cuny, Jérôme; Xie, Yu; Pickard, Chris J; Hassanali, Ali A

    2016-02-01

    Nuclear magnetic resonance (NMR) spectroscopy is one of the most powerful experimental tools to probe the local atomic order of a wide range of solid-state compounds. However, due to the complexity of the related spectra, in particular for amorphous materials, their interpretation in terms of structural information is often challenging. These difficulties can be overcome by combining molecular dynamics simulations to generate realistic structural models with an ab initio evaluation of the corresponding chemical shift and quadrupolar coupling tensors. However, due to computational constraints, this approach is limited to relatively small system sizes which, for amorphous materials, prevents an adequate statistical sampling of the distribution of the local environments that is required to quantitatively describe the system. In this work, we present an approach to efficiently and accurately predict the NMR parameters of very large systems. This is achieved by using a high-dimensional neural-network representation of NMR parameters that are calculated using an ab initio formalism. To illustrate the potential of this approach, we applied this neural-network NMR (NN-NMR) method on the (17)O and (29)Si quadrupolar coupling and chemical shift parameters of various crystalline silica polymorphs and silica glasses. This approach is, in principal, general and has the potential to be applied to predict the NMR properties of various materials. PMID:26730889

  13. The effects of fast molecular motions and nuclear delocalisation on NMR parameters

    Dračínský, Martin; Hodgkinson, P.

    Brno : Masaryk University, 2014 - (Novotný, J.; Foroutan -Nejad, C.; Marek, R.). C3 ISBN 978-80-86441-45-0. [NMR Valtice. Central European NMR Meeting /29./. 27.4.-30.4.2014, Valtice] Institutional support: RVO:61388963 Keywords : NMR spectroscopy * DFT molecular dynamics * nuclear quantum effects Subject RIV: CF - Physical ; Theoretical Chemistry

  14. Relationships between 1H NMR Relaxation Data and Some Technological Parameters of Meat: A Chemometric Approach

    Brown, Robert J. S.; Capozzi, Francesco; Cavani, Claudio; Cremonini, Mauro A.; Petracci, Massimiliano; Placucci, Giuseppe

    2000-11-01

    In this paper chemometrics (ANOVA and PCR) is used to measure unbiased correlations between NMR spin-echo decays of pork M. Longissimus dorsi obtained through Carr-Purcell-Meiboom-Gill (CPMG) experiments at low frequency (20 MHz) and the values of 14 technological parameters commonly used to assess pork meat quality. On the basis of the ANOVA results, it is also found that the CPMG decays of meat cannot be best interpreted with a "discrete" model (i.e., by expanding the decays in a series of a discrete number of exponential components, each with a different transverse relaxation time), but rather with a "continuous" model, by which a continuous distribution of T2's is allowed. The latter model also agrees with literature histological results.

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

    Internal backbone dynamic motions are essential for different protein functions and occur on a wide range of time scales, from femtoseconds to seconds. Molecular dynamic (MD) simulations and nuclear magnetic resonance (NMR) spin relaxation measurements are valuable tools to gain access to fast (nanosecond) internal motions. However, there exist few reports on correlation analysis between MD and NMR relaxation data. Here, backbone relaxation measurements of 15N-labeled SH3 (Src homology 3) domain proteins in aqueous buffer were used to generate general order parameters (S2) using a model-free approach. Simultaneously, 80 ns MD simulations of SH3 domain proteins in a defined hydrated box at neutral pH were conducted and the general order parameters (S2) were derived from the MD trajectory. Correlation analysis using the Gromos force field indicated that S2 values from NMR relaxation measurements and MD simulations were significantly different. MD simulations were performed on models with different charge states for three histidine residues, and with different water models, which were SPC (simple point charge) water model and SPC/E (extended simple point charge) water model. S2 parameters from MD simulations with charges for all three histidines and with the SPC/E water model correlated well with S2 calculated from the experimental NMR relaxation measurements, in a site-specific manner. - Highlights: • Correlation analysis between NMR relaxation measurements and MD simulations. • General order parameter (S2) as common reference between the two methods. • Different protein dynamics with different Histidine charge states in neutral pH. • Different protein dynamics with different water models

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

    Liu, Qing; Shi, Chaowei [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Yu, Lu [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui, 230031 (China); Zhang, Longhua [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Xiong, Ying, E-mail: yxiong73@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); Tian, Changlin, E-mail: cltian@ustc.edu.cn [Hefei National Laboratory for Physical Sciences at The Microscale and School of Life Sciences, University of Science and Technology of China, Hefei, Anhui, 230026 (China); High Magnetic Field Laboratory, Chinese Academy of Science, Hefei, Anhui, 230031 (China)

    2015-02-13

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

  17. Solid state NMR and bioequivalence comparison of the pharmacokinetic parameters of two formulations of clindamycin

    Al-Talla, Zeyad

    2011-01-01

    Objective: The purpose of this study was to compare the pharmacokinetic parameters and determine the bioequivalence of a generic formulation of clindamycin that is sold in the local markets in the Middle East (Clindox® 150 mg capsule; test) with a reference formulation (Dalacin C® 150 mg capsule) in healthy adult male volunteers. Methods: A single-dose, open-label, 2-period crossover study was conducted. Healthy male volunteers were randomly assigned to oral administration of a single treatment of the reference and test formulations. The same groups were given the alternate formulation. After dosing, serial blood samples were withdrawn for a period of 24 h. Serum harvested from the blood samples was analyzed for clindamycin by high performance liquid chromatography (HPLC) with ultraviolet detection. Pharmacokinetic parameters, including AUC0-∞, AUC 0-t, Cmax, Ke, tmax and t 1/2 were determined from the serum concentrations for both formulations (test and reference). The products were tested for bioequivalence after log-transformation of the data. Results: 24 healthy adult male volunteers from Jordan (mean [SD] age, 28.8 (7.7) years (range 19-45 years); height, 175.8 (10.6) cm (range 159.0-192.0 cm); weight, 75.6 (11.0) kg (range 58-101 kg); and body mass index, 24.4 (1.8) kg/m2 (range 21.3-28 kg/m2)) were enrolled in and completed the study. The 13C NMR spectra for both Dalacin C® and Clindox® showed 18 distinct lines associated with the 18 different carbon atoms. Conclusion: The statistical comparison suggested that Clindox® capsules are bioequivalent to Dalacin C® capsules. The 13C CPMAS results confirmed that the two drugs exhibit typical clindamycin spectra. ©2011 Dustri-Verlag Dr. K. Feistle.

  18. NMR parameters in RNA molecules and their correlation with molecular structure

    Vokáčová, Zuzana; Schneider, Bohdan; Sychrovský, Vladimír

    Wroclaw : -, 2006. L31. [Modeling & Design of Molecular Materials 2006. 10.09.2006-15.09.2006, Wroclaw] Institutional research plan: CEZ:AV0Z40550506 Keywords : dinukleoside monophosphate * RNA * NMR Subject RIV: CF - Physical ; Theoretical Chemistry

  19. Hunting for hydrogen: random structure searching and prediction of NMR parameters of hydrous wadsleyite.

    Moran, Robert F; McKay, David; Pickard, Chris J; Berry, Andrew J; Griffin, John M; Ashbrook, Sharon E

    2016-04-21

    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 Mg(2+) 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

  20. Calculations of Solid-State NMR Parameters of Isocytosine and Sesquiterpene Lactones

    Dračínský, Martin; Buděšínský, Miloš; Warzajtis, B.; Rychlewska, U.

    Ireland : University College Dublin, 2012. s. 243-243. [EUROMAR 2012. Magnetic Resonance Conference. 01.07.2012-05.07.2012, Dublin] Institutional research plan: CEZ:AV0Z40550506 Keywords : NMR * solid-state * DFT calculations * crystal packing Subject RIV: CC - Organic Chemistry

  1. The Effects of Fast Molecular Motions and Solvation on NMR Parameters

    Dračínský, Martin; Bouř, Petr; Exner, T.; Hodgkinson, P.

    Leipzig : European Science Foundation, 2013. s. 69-70. [CPMD - Leipzig 2013. Matter, life , light from ab initio molecular dynamics simulations. 02.09.2013-06.09.2013, Leipzig] Institutional support: RVO:61388963 Keywords : NMR spectroscopy * DFT calculations * molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry

  2. Effects of Quantum Nuclear Delocalisation on NMR Parameters from Path Integral Molecular Dynamics

    Dračínský, Martin; Hodgkinson, P.

    2014-01-01

    Roč. 20, č. 8 (2014), s. 2201-2207. ISSN 0947-6539 Grant ostatní: Seventh Framework Programme of the European Union(XE) FP7-299242 People Institutional support: RVO:61388963 Keywords : density functional calculations * isotope effects * NMR spectroscopy * nuclear delocalisation * path integral molecular dynamics Subject RIV: CC - Organic Chemistry Impact factor: 5.731, year: 2014

  3. The effects of fast molecular motions and nuclear delocalisation on NMR parameters

    Dračínský, Martin; Hodgkinson, P.

    Santiago : -, 2014. OP039. [WATOC 2014. Congress of the World Association of Theoretical and Computational Chemists /10./. 05.10.2014-10.10.2014, Santiago] R&D Projects: GA ČR GA13-24880S Institutional support: RVO:61388963 Keywords : NMR spectroscopy * molecular dynamics * DFT calculations Subject RIV: CF - Physical ; Theoretical Chemistry

  4. On the ability of molecular dynamics force fields to recapitulate NMR derived protein side chain order parameters.

    O'Brien, Evan S; Wand, A Joshua; Sharp, Kim A

    2016-06-01

    Molecular dynamics (MD) simulations have become a central tool for investigating various biophysical questions with atomistic detail. While many different proxies are used to qualify MD force fields, most are based on largely structural parameters such as the root mean square deviation from experimental coordinates or nuclear magnetic resonance (NMR) chemical shifts and residual dipolar couplings. NMR derived Lipari-Szabo squared generalized order parameter (O(2) ) values of amide NH bond vectors of the polypeptide chain were also often employed for refinement and validation. However, with a few exceptions, side chain methyl symmetry axis order parameters have not been incorporated into experimental reference sets. Using a test set of five diverse proteins, the performance of several force fields implemented in the NAMDD simulation package was examined. It was found that simulations employing explicit water implemented using the TIP3 model generally performed significantly better than those using implicit water in reproducing experimental methyl symmetry axis O(2) values. Overall the CHARMM27 force field performs nominally better than two implementations of the Amber force field. It appeared that recent quantum mechanics modifications to side chain torsional angles of leucine and isoleucine in the Amber force field have significantly hindered proper motional modeling for these residues. There remained significant room for improvement as even the best correlations of experimental and simulated methyl group Lipari-Szabo generalized order parameters fall below an R(2) of 0.8. PMID:26990788

  5. Temperature Dependence of NMR Parameters Calculated from Path Integral Molecular Dynamics Simulations.

    Dračínský, Martin; Bouř, Petr; Hodgkinson, Paul

    2016-03-01

    The influence of temperature on NMR chemical shifts and quadrupolar couplings in model molecular organic solids is explored using path integral molecular dynamics (PIMD) and density functional theory (DFT) calculations of shielding and electric field gradient (EFG) tensors. An approach based on convoluting calculated shielding or EFG tensor components with probability distributions of selected bond distances and valence angles obtained from DFT-PIMD simulations at several temperatures is used to calculate the temperature effects. The probability distributions obtained from the quantum PIMD simulations, which includes nuclear quantum effects, are significantly broader and less temperature dependent than those obtained with conventional DFT molecular dynamics or with 1D scans through the potential energy surface. Predicted NMR observables for the model systems were in excellent agreement with experimental data. PMID:26857802

  6. NMR Parameters Determination through ACE Committee Machine with Genetic Implanted Fuzzy Logic and Genetic Implanted Neural Network

    Asoodeh Mojtaba

    2015-06-01

    Full Text Available Free fluid porosity and rock permeability, undoubtedly the most critical parameters of hydrocarbon reservoir, could be obtained by processing of nuclear magnetic resonance (NMR log. Despite conventional well logs (CWLs, NMR logging is very expensive and time-consuming. Therefore, idea of synthesizing NMR log from CWLs would be of a great appeal among reservoir engineers. For this purpose, three optimization strategies are followed. Firstly, artificial neural network (ANN is optimized by virtue of hybrid genetic algorithm-pattern search (GA-PS technique, then fuzzy logic (FL is optimized by means of GA-PS, and eventually an alternative condition expectation (ACE model is constructed using the concept of committee machine to combine outputs of optimized and non-optimized FL and ANN models. Results indicated that optimization of traditional ANN and FL model using GA-PS technique significantly enhances their performances. Furthermore, the ACE committee of aforementioned models produces more accurate and reliable results compared with a singular model performing alone.

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

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

  8. Quantifying Lipari-Szabo modelfree parameters from 13CO NMR relaxation experiments

    It is proposed to obtain effective Lipari-Szabo order parameters and local correlation times for relaxation vectors of protein 13CO nuclei by carrying out a 13CO-R1 auto relaxation experiment, a transverse 13CO CSA/13CO-13C CSA/dipolar cross correlation and a transverse 13CO CSA/13CO-15N CSA/dipolar cross correlation experiment. Given the global rotational correlation time from 15N relaxation experiments, a new program COMFORD (CO-Modelfree Fitting Of Relaxation Data) is presented to fit the 13CO data to an effective order parameter SCO2, an effective local correlation time and the orientation of the CSA tensor with respect to the molecular frame. It is shown that the effective SCO2 is least sensitive to rotational fluctuations about an imaginary Cα-Cα axis and most sensitive to rotational fluctuations about an imaginary axis parallel to the NH bond direction. As such, the SCO2 information is fully complementary to the 15N relaxation order parameter, which is least sensitive to fluctuations about the NH axis and most sensitive to fluctuations about the Cα-Cα axis. The new paradigm is applied on data of Ca2+ saturated Calmodulin, and on available literature data for Ubiquitin. Our data indicate that the SCO2 order parameters rapport on slower, and sometimes different, motions than the 15N relaxation order parameters. The CO local correlation times correlate well with the calmodulin's secondary structure

  9. Multinuclear high-resolution NMR study of compounds from the ternary system NaF-CaF2-AlF3: from determination to modeling of NMR parameters.

    Martineau, C; Body, M; Legein, C; Silly, G; Buzaré, J-Y; Fayon, F

    2006-12-11

    27Al and 23Na NMR satellite transition spectroscopy and 3Q magic-angle-spinning spectra are recorded for three compounds from the ternary NaF-CaF2-AlF3 system. The quadrupolar frequency nuQ, asymmetry parameter etaQ, and isotropic chemical shift deltaiso are extracted from the spectrum reconstructions for five aluminum and four sodium sites. The quadrupolar parameters are calculated using the LAPW-based ab initio code WIEN2k. It is necessary to perform a structure optimization of all compounds to ensure a fine agreement between experimental and calculated parameters. By a comparison of experimental and calculated values, an attribution of all of the 27Al and 23Na NMR lines to the crystallographic sites is achieved. High-speed 19F NMR MAS spectra are recorded and reconstructed for the same compounds, leading to the determination of 18 isotropic chemical shifts. The superposition model developed by Bureau et al. is used, allowing a bijective assignment of the 19F NMR lines to the crystallographic sites. PMID:17140229

  10. Detecting pyramidal state of the glycosidic nitrogen in 8-oxo-2'-deoxyguanosine; theoretical study of 15N NMR parameters

    Šebera, Jakub; Dračínský, Martin; Nencka, Radim; Trantírek, L.; Tanaka, Y.; Sychrovský, Vladimír

    Brno : Masaryk University, 2014 - (Novotný, J.; Foroutan -Nejad, C.; Marek, R.). C7 ISBN 978-80-86441-45-0. [NMR Valtice. Central European NMR Meeting /29./. 27.4.-30.4.2014, Valtice] R&D Projects: GA ČR GA13-27676S Institutional support: RVO:61388963 Keywords : hOGG1 enzyme * OxoG * NMR Subject RIV: CF - Physical ; Theoretical Chemistry

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

    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 (CH3 and CD3) 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

  12. Compact NMR

    Bluemich, Bernhard; Haber-Pohlmeier, Sabina; Zia, Wasif [RWTH Aachen Univ. (Germany). Inst. fuer Technische und Makromolekulare Chemie (ITMC)

    2014-06-01

    Nuclear Magnetic Resonance (NMR) spectroscopy is the most popular method for chemists to analyze molecular structures, while Magnetic Resonance Imaging (MRI) is a non-invasive diagnostic tool for medical doctors that provides high-contrast images of biological tissue. In both applications, the sample (or patient) is positioned inside a large, superconducting magnet to magnetize the atomic nuclei. Interrogating radio-frequency pulses result in frequency spectra that provide the chemist with molecular information, the medical doctor with anatomic images, and materials scientist with NMR relaxation parameters. Recent advances in magnet technology have led to a variety of small permanent magnets to allow compact and low-cost instruments. The goal of this book is to provide an introduction to the practical use of compact NMR at a level nearly as basic as the operation of a smart phone.

  13. Compact NMR

    Nuclear Magnetic Resonance (NMR) spectroscopy is the most popular method for chemists to analyze molecular structures, while Magnetic Resonance Imaging (MRI) is a non-invasive diagnostic tool for medical doctors that provides high-contrast images of biological tissue. In both applications, the sample (or patient) is positioned inside a large, superconducting magnet to magnetize the atomic nuclei. Interrogating radio-frequency pulses result in frequency spectra that provide the chemist with molecular information, the medical doctor with anatomic images, and materials scientist with NMR relaxation parameters. Recent advances in magnet technology have led to a variety of small permanent magnets to allow compact and low-cost instruments. The goal of this book is to provide an introduction to the practical use of compact NMR at a level nearly as basic as the operation of a smart phone.

  14. Calculation of average molecular parameters, functional groups, and a surrogate molecule for heavy fuel oils using 1H and 13C NMR spectroscopy

    Abdul Jameel, Abdul Gani

    2016-04-22

    Heavy fuel oil (HFO) is primarily used as fuel in marine engines and in boilers to generate electricity. Nuclear Magnetic Resonance (NMR) is a powerful analytical tool for structure elucidation and in this study, 1H NMR and 13C NMR spectroscopy were used for the structural characterization of 2 HFO samples. The NMR data was combined with elemental analysis and average molecular weight to quantify average molecular parameters (AMPs), such as the number of paraffinic carbons, naphthenic carbons, aromatic hydrogens, olefinic hydrogens, etc. in the HFO samples. Recent formulae published in the literature were used for calculating various derived AMPs like aromaticity factor 〖(f〗_a), C/H ratio, average paraffinic chain length (¯n), naphthenic ring number 〖(R〗_N), aromatic ring number〖 (R〗_A), total ring number〖 (R〗_T), aromatic condensation index (φ) and aromatic condensation degree (Ω). These derived AMPs help in understanding the overall structure of the fuel. A total of 19 functional groups were defined to represent the HFO samples, and their respective concentrations were calculated by formulating balance equations that equate the concentration of the functional groups with the concentration of the AMPs. Heteroatoms like sulfur, nitrogen, and oxygen were also included in the functional groups. Surrogate molecules were finally constructed to represent the average structure of the molecules present in the HFO samples. This surrogate molecule can be used for property estimation of the HFO samples and also serve as a surrogate to represent the molecular structure for use in kinetic studies.

  15. Exact NMR simulation of protein-size spin systems using tensor train formalism

    Savostyanov, D V; Werner, J M; Kuprov, Ilya

    2014-01-01

    We introduce a new method, based on alternating optimization, for compact representation of spin Hamiltonian, and solution of linear systems in the tensor train format. We demonstrate its utility by simulating, without significant approximations, a 15N NMR spectrum of ubiquitin --- protein containing several hundred interacting nuclear spins. Existing simulation algorithms for the spin system and the NMR experiment in question either require significant approximations or scale exponentially with the system size. We compare the proposed method to the Spinach package that uses heuristic restricted state space (RSS) techniques to achieve polynomial complexity scaling. When the spin system topology is close to a linear chain (e.g. for backbone of a protein), the tensor train representation of a Hamiltonian is more compact and can be computed faster than the sparse representation using the RSS.

  16. A molecular dynamics study of the effects of fast molecular motions on solid-state NMR parameters

    Dračínský, Martin; Hodgkinson, P.

    2013-01-01

    Roč. 15, č. 43 (2013), s. 8705-8712. ISSN 1466-8033 Grant ostatní: Seventh Framework Programme of the European Union(XE) FP7-299242 People Institutional support: RVO:61388963 Keywords : molecular dynamics * DFT calculations * NMR spectroscopy Subject RIV: CC - Organic Chemistry Impact factor: 3.858, year: 2013

  17. Gravitational spin Hamiltonians from the S matrix

    Vaidya, Varun

    2014-01-01

    We utilize generalized unitarity and recursion relations combined with effective field theory(EFT) techniques to compute spin dependent interaction terms for inspiralling binary systems in the post newtonian(PN) approximation. Using these methods offers great computational advantage over traditional techniques involving feynman diagrams, especially at higher orders in the PN expansion. As a specific example, we reproduce the spin-orbit interaction up to 2.5 PN order as also the leading order ...

  18. Dft Study on 4(5-Imidazole-Carbaldehyde-N(5-Phenylthiosemicarbazone (Imtph: Nmr Shielding Tensors, Thermodynamic Parameters, Nbo Analysis, Molecular Electrostatic Potential (Mep, Homo and Lumo Studies

    Masoome Sheikhi

    2014-03-01

    Full Text Available The density functional theory (DFT calculations at the level of B3LYP/6-31G was carried out on the structure 4(5-Imidazole-carbaldehyde-N(5-phenylthiosemicarbazone (ImTPh in gas phase using Gaussian 03. Dipole moment (Debye, energy of structure formation (HF; kcal/mol and point group, NMR parameters such as isotropic shielding (σiso and anisotropic shielding (σaniso, σ11, σ22 and σ33 obtained. Also thermodynamic properties and natural bond orbitals (NBO were calculated. Besides, the frontier molecular orbital (FMO analysis and the molecular electrostatic potential (MEP of the compound were investigated by theoretical calculations.

  19. Multiple quantum NMR of spin-carrying molecules in nanopores: high order corrections to the two-spin/two-quantum Hamiltonian

    Doronina, Sergei I; Fel’dmana, Edward B; Zenchuka, Alexander I

    2010-01-01

    This paper is devoted to the multiple-quantum (MQ) NMR spectroscopy in nanopores filled by a gas of spin-carrying molecules (s=1/2) in the strong external magnetic field. It turned out that the high symmetry of the spin system in nanopores yields a possibility to overcome the problem of the exponential growth of the Hilbert space dimension with an increase in a number of spins and to investigate MQ NMR dynamics in systems consisting of several hundreds of spins. We investigate the dependence of the MQ coherence intensities on their order (the profile of the MQ coherence intensities) for the spin system governed by the standard MQ NMR Hamiltonian (the nonsecular two-quantum/two-spin Hamiltonian) together with the second order correction of the average Hamiltonian theory. It is shown that the profile depends on the value of this correction and varies from the exponential to the logarithmic one.

  20. Optimisation of NMR dynamic models II. A new methodology for the dual optimisation of the model-free parameters and the Brownian rotational diffusion tensor

    Finding the dynamics of an entire macromolecule is a complex problem as the model-free parameter values are intricately linked to the Brownian rotational diffusion of the molecule, mathematically through the autocorrelation function of the motion and statistically through model selection. The solution to this problem was formulated using set theory as an element of the universal set U-the union of all model-free spaces (d'Auvergne EJ and Gooley PR (2007) Mol BioSyst 3(7), 483-494). The current procedure commonly used to find the universal solution is to initially estimate the diffusion tensor parameters, to optimise the model-free parameters of numerous models, and then to choose the best model via model selection. The global model is then optimised and the procedure repeated until convergence. In this paper a new methodology is presented which takes a different approach to this diffusion seeded model-free paradigm. Rather than starting with the diffusion tensor this iterative protocol begins by optimising the model-free parameters in the absence of any global model parameters, selecting between all the model-free models, and finally optimising the diffusion tensor. The new model-free optimisation protocol will be validated using synthetic data from Schurr JM et al. (1994) J Magn Reson B 105(3), 211-224 and the relaxation data of the bacteriorhodopsin (1-36)BR fragment from Orekhov VY (1999) J Biomol NMR 14(4), 345-356. To demonstrate the importance of this new procedure the NMR relaxation data of the Olfactory Marker Protein (OMP) of Gitti R et al. (2005) Biochem 44(28), 9673-9679 is reanalysed. The result is that the dynamics for certain secondary structural elements is very different from those originally reported

  1. Correlation of tryptophan fluorescence intensity decay parameters with sup 1 H NMR-determined rotamer conformations: (tryptophan sup 2 )oxytocin

    Ross, J.B.A.; Schwartz, G.P.; Laws, W.R. (Mount Sinai, New York, NY (United States)); Wyssbrod, H.R.; Porter, R.A. (Univ. of Louisville, KY (United States)); Michaels, C.A. (Swarthmore Coll., PA (United States))

    1992-02-18

    While the fluorescence decay kinetics of tyrosine model compounds can be explained in terms of heterogeneity derived from the three ground-state {chi}{sup 1} rotamers, a similar correlation has yet to be directly observed for a tryptophan residue. In addition, the asymmetric indole ring might also lead to heterogeneity from {chi}{sup 2} rotations. In this paper, the time-resolved and steady-state fluorescence properties of (tryptophan{sup 2})oxytocin at pH 3 are presented and compared with {sup 1}H NMR results. According to the unrestricted analyses of individual fluorescence decay curves taken as a function of emission wavelength-independent decay constants, only three exponential terms are required. In addition, the preexponential weighting factors (amplitudes) have the same relative relationship (weights) as the {sup 1}H NMR-determined {chi}{sup 1} rotamer populations of the indole side chain. {sup 15}N was used in heteronuclear coupling experiments to confirm the rotamer assignments. Inclusion of a linked function restricting the decay amplitudes to the {chi}{sup 1} rotamer populations in the individual decay curve analyses and in the global analysis confirms this correlation. According to qualitative nuclear Overhauser data, there are two {chi}{sup 2} populations.

  2. NMR determination of dynamic parameters of CH3 groups in P(CH3)4SbCl6.

    Medycki, W; Jakubas, R

    1999-11-01

    The longitudinal relaxation time T1 and the second moment M2 of 1H NMR line in a wide temperature range have been measured for P(CH3)4SbCl6. It was found that two different methyl groups in each tetramethylphosphonium cation perform two different rates of C3 motions. The reduction of the proton second moment M2 just below the temperature of the phase transition Tc2 = 350 K may suggest that the isotropic tumbling of the whole cation [P(CH3)4]+ is involved in the structural change of the crystal lattice induced by the movements of the [SbCl6]- anion. PMID:10670898

  3. Vibrational studies, NMR analysis, modeling of electronic and thermodynamical parameters of 1,3-bis(4-benzamido)triazene

    Ghalebsaz-Jeddi, N.; Vessally, E.

    2016-07-01

    The optimized geometry, vibrational wavenumbers, 1H and 13C chemical shift values of 1,3-bis(4-benzamido)triazene, BBT, in the ground state were computed with the Hartree-Fock (HF) and density functional theory method (PBE1PBE) with 6-311+G(2 d, p) basis set. The harmonic vibrational wavenumbers of BBT were calculated and the scaled values were compared with the experimental FT-IR spectra. A detailed interpretation of the NMR spectra of BBT was reported. The calculated data are in reasonably good agreement with experimental measurements. Moreover, the log P value was estimated with ChemBioOffice Ultra 11.0, ACD/LogP, and ALOGPS programs.

  4. (1)H NMR z-spectra of acetate methyl in stretched hydrogels: quantum-mechanical description and Markov chain Monte Carlo relaxation-parameter estimation.

    Shishmarev, Dmitry; Chapman, Bogdan E; Naumann, Christoph; Mamone, Salvatore; Kuchel, Philip W

    2015-01-01

    The (1)H NMR signal of the methyl group of sodium acetate is shown to be a triplet in the anisotropic environment of stretched gelatin gel. The multiplet structure of the signal is due to the intra-methyl residual dipolar couplings. The relaxation properties of the spin system were probed by recording steady-state irradiation envelopes ('z-spectra'). A quantum-mechanical model based on irreducible spherical tensors formed by the three magnetically equivalent spins of the methyl group was used to simulate and fit experimental z-spectra. The multiple parameter values of the relaxation model were estimated by using a Bayesian-based Markov chain Monte Carlo algorithm. PMID:25486634

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

    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.

  6. 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.

    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

  7. Rheo-NMR - how nuclear magnetic resonance is providing new insight regarding complex fluid rheology

    Over the past five decades, NMR has revolutionised chemistry, and has found widespread application in condensed matter physics, in molecular biology, in medicine and in food technology. Most recently NMR has made a significant impact in chemical engineering, where it is being extensively used for the non-invasive study of dispersion and flow in porous media. One of the most recent applications of NMR in materials science concerns its use in the study of the mechanical properties of complex fluids. This particular aspect of NMR has been extensively developed in research carried out at Massey University in New Zealand. In this short article, some of the ideas behind this work and the applications which have resulted, will be described. These examples provide a glimpse of possible applications of Nuclear Magnetic Resonance to the study of complex fluid rheology. While this is a very new field of research in which only a handful of groups presently participate, the potential exists for a substantial increase in Rheo-NMR research activity. Systems studied to date include polymer melts and semi-dilute solutions, thermotropic and lyotropic liquid crystals and liquid crystalline polymers, micellar solutions, food materials and colloidal suspensions. Rheo-NMR suffers in a number of respects by comparison with optical methods. It is expensive, it is difficult to use, it suffers from poor signal-to-noise ratios and the effective interpretation of spectra often depends on familiarity with the nuclear spin Hamiltonian and the associated effects of spin dynamics. Nonetheless NMR offers some unique advantages, including the ability to work with opaque materials, the ability to combine velocimetry with localised spectroscopy, and the ability to access a wide range of molecular properties relating to organisation, orientation and dynamics. Rheo-NMR has been able to provide a direct window on a variety of behaviours, including slip, shear-thinning, shear banding, yield stress

  8. The automatic NMR gaussmeter

    The paper describes the automatic gaussmeter operating according to the principle of nuclear magnetic resonance. There have been discussed the operating principle, the block diagram and operating parameters of the meter. It can be applied to measurements of induction in electromagnets of wide-line radio-spectrometers EPR and NMR and in calibration stands of magnetic induction values. Frequency range of an autodyne oscillator from 0,6 up to 86 MHz for protons is corresponding to the field range from 0.016 up to 2T. Applicaton of other nuclei, such as 7Li and 2D is also foreseen. The induction measurement is carried over automatically, and the NMR signal and value of measured induction are displayed on a monitor screen. (author)

  9. NMR spectroscopy

    The book reviews the applications of NMR-spectroscopy in medicine and biology. The first chapter of about 40 pages summarizes the history of development and explains the chemical and physical fundamentals of this new and non-invasive method in an easily comprehensible manner. The other chapters summarize diagnostic results obtained with this method in organs and tissues, so that the reader will find a systematic overview of the available findings obtained in the various organ systems. It must be noted, however, that ongoing research work and new insight quite naturally will necessitate corrections to be done, as is the case here with some biochemical interpretations which would need adjustment to latest research results. NMR-spectroscopy is able to measure very fine energy differences on the molecular level, and thus offers insight into metabolic processes, with the advantage that there is no need of applying ionizing radiation in order to qualitatively or quantitatively analyse the metabolic processes in the various organ systems. (orig./DG) With 40 figs., 4 tabs

  10. Methyl tunnelling sidebands in the low-field NMR spectrum of 3-pentanone: Driving A-E transitions using rf irradiation.

    Zhang, Bo; Horsewill, Anthony J

    2015-09-01

    Using magnetic field-cycling at cryogenic temperatures, low-field dipole-dipole driven NMR spectra have been recorded on 3-pentanone (CH3CH2C(O)CH2CH3). The spectra are characterised by tunnelling sidebands arising from the quantum dynamics of the methyl (CH3) rotors. From the sideband frequencies, the CH3 tunnelling frequency is determined to be νt=3.05±0.01MHz. The tunnelling sidebands are characterised by A-E transitions in nuclear spin-symmetry, involving simultaneous changes in tunnelling and nuclear spin states. To gain further insight, a theoretical analysis of the spin Hamiltonian matrix has been used to calculate the sideband transition probabilities. These are subsequently used in a thermodynamic model to simulate the low-field NMR spectrum which is compared with experiment. The level-crossings encountered as part of the magnetic field-cycling NMR sequence are found to play an essential role in determining the tunnelling sideband intensities. PMID:26183303

  11. NMR espectroscopic parameters of HX and Si (Sn)X{sub 4} (X = H, F, Cl, Br and I) and SnBr{sub 4-n}I{sub n} model compounds

    Maldonado, Alejandro F.; Gimenez, Carlos A. [Physics Department, Natural and Exact Science Faculty, Northeastern University of Argentina and Institute of Modelling and Innovation on Technology, IMIT Avda Libertad 5460, W3404AAS Corrientes (Argentina); Aucar, Gustavo A., E-mail: gaa@unne.edu.ar [Physics Department, Natural and Exact Science Faculty, Northeastern University of Argentina and Institute of Modelling and Innovation on Technology, IMIT Avda Libertad 5460, W3404AAS Corrientes (Argentina)

    2012-02-20

    Graphical abstract: Optimized fully relativistic calculations of NMR J-couplings (HBr, HI), chemical shifts (Si, Sn) and absolute shielding for reference compounds of heavy atoms (Si, Sn) are given. Highlights: Black-Right-Pointing-Pointer In this article we show a procedure to get accurate NMR {sigma}{sup Ref} of Si and Sn. Black-Right-Pointing-Pointer Calculations of {sigma} on more than three heavy-atom-containing molecules are given. Black-Right-Pointing-Pointer Our results are closer to {delta}{sup exp} than previous calculations for SnX{sub 4} (X = H, Cl, Br, I). Black-Right-Pointing-Pointer Optimized basis sets were considered for full R and NR calculations of NMR J and {sigma}. Black-Right-Pointing-Pointer Relativistic effects enlarge electron correlation effects on J-couplings. - Abstract: The NMR spectroscopic parameters are largely influenced by relativistic effects. They are highly dependent on the electronic behavior inside the spatial regions occupied by nuclei. Full relativistic calculations of indirect nuclear spin-spin couplings at random phase level of approach (RPA) in the title compounds with reoptimized Dyall cVTZ basis sets are given. A comparison with the results of calculations with other basis sets that are mostly used within the non-relativistic (NR) domain is presented. We analyzed the dependence of that couplings with the speed of light over the whole range of values, from the full relativistic to the NR regimes. Within this last regime, calculations at the second-order level of approach (SOPPA) indicated that electron correlation effects may not be as important for nuclear magnetic shieldings, but they must be included with care for J-coupling calculations. From these calculations, we determined that relativity enlarges the electron correlation effects of the J-couplings of HBr and HI. Because the results of nuclear magnetic shielding calculations within polarization propagators at the RPA level were reliable, we were able to show a new

  12. Minimalist Relativistic Force Field: Prediction of Proton-Proton Coupling Constants in (1)H NMR Spectra Is Perfected with NBO Hybridization Parameters.

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-05-15

    We previously developed a reliable method for multiparametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. We now report that utilization of NBO hybridization coefficients for carbon atoms in the involved C-H bonds allows for a significant simplification of this parametric scheme, requiring only four general types of SSCCs: geminal, vicinal, 1,3-, and long-range constants. The method is optimized for inexpensive B3LYP/6-31G(d) molecular geometries. A new DU8 basis set, based on a training set of 475 experimental spin-spin coupling constants, is developed for hydrogen and common non-hydrogen atoms (Li, B, C, N, O, F, Si, P, S, Cl, Se, Br, I) to calculate Fermi contacts. On a test set of 919 SSCCs from a diverse collection of natural products and complex synthetic molecules the method gave excellent accuracy of 0.29 Hz (rmsd) with the maximum unsigned error not exceeding 1 Hz. PMID:25885091

  13. On domain wall boundary conditions for the XXZ spin Hamiltonian

    Orlando, Domenico; Reffert, Susanne; Reshetikhin, Nicolai

    In this note, we derive the spectrum of the infinite quantum XXZ spin chain with domain wall boundary conditions. The eigenstates are constructed as limits of Bethe states for the finite XXZ spin chain with quantum sl(2) invariant boundary conditions.......In this note, we derive the spectrum of the infinite quantum XXZ spin chain with domain wall boundary conditions. The eigenstates are constructed as limits of Bethe states for the finite XXZ spin chain with quantum sl(2) invariant boundary conditions....

  14. DFT study of NH3 adsorption on the (5,0), (8,0), (5,5) and (6,6) single-walled carbon nanotubes. Calculated binding energies, NMR and NQR parameters

    Behavior of a single NH3 molecule adsorbed on external surface of H-capped (5,5), (6,6), (5,0), and (8,0) single-walled carbon nanotubes (SWCNTs) is studied via DFT calculations. Binding energies clearly exhibit adsorption dependence on tube diameter. 13C, 15N and 1H chemical shielding tensors are calculated at the B3LYP level using GIAO method. NMR calculations reveal that 13C chemical shielding of (8,0) is more sensitive to NH3 adsorption compared to (5,5), (6,6) and (5,0) tubes. 15N and 1H chemical shielding correlate noticeably with diameter of the nanotubes. 14N and 2H nuclear quadrupole coupling constants, CQ, and asymmetry parameter, η, reveal the remarkable effect of NH3 adsorption on electronic structure of the SWCNTs.

  15. NMR and dynamics of biopolymers

    Several basic experimental analytical NMR techniques that are frequently used for the qualitative and quantitative analysis of dynamic and exchange processes, focusing on proteins systems, are described: chemical exchange (slow exchange, fast exchange, intermediate exchange), heteronuclear relaxation measurements (relaxation parameters, strategy of relaxation data analysis, experimental results and examples, motional model interpretation of relaxation data, homonuclear relaxation); slow large-scale exchange and hydrogen-deuterium exchange are also studied: mechanisms of hydrogen exchange in a native protein, methods for measuring amide exchange rates by NMR, interpretation of amide exchange rates. 9 fig., 3 tab., 56 ref

  16. Ligand-receptor Interactions by NMR Spectroscopy

    Novak. P.

    2008-04-01

    Full Text Available Today NMR spectroscopy is a method of choice for elucidation of interactions between biomolecules and the potential ligands. Knowledge on these interactions is an essential prerequisite for the rational drug design. The most important contribution of NMR to drug design a few years ago was the 3D structure determination of proteins. Besides delivering the 3D structures of the free proteins as a raw material for the modeling studies on ligand binding, NMR can directly yield valuable experimental data on the biologically important protein-ligand complexes. In addition to X-ray diffraction, NMR spectroscopy can provide information on the internal protein dynamics ordynamics of intermolecular interactions. Changes in NMR parameters allow us to detect ("SAR by NMR" and quantitatively determine binding affinities (titration, diffusion NMR experiments, etc. of potential ligands. Also, it is possible to determine the binding site and conformations of ligands, receptors and receptor-ligand complexes with the help of NMR methods such as tr-NOESY. Epitopes or functional groups responsible for binding of ligands to the receptor can be identified by employing STD or WaterLOGSY experiments. In this review are described some of the most frequent NMR methods for the characterization of the interactions between biomolecules and ligands, together with their advantages and disadvantages.

  17. NMR studies of metabolism

    In this paper, the authors present applications of NMR to the study of different aspects of metabolism. The authors begin with a brief outline of localization methods that are commonly used to obtain in vivo NMR spectra. The authors then describe in more detail metabolic information recently obtained by NMR of perfused organs, intact animals, and humans. Previous reviews have already covered the applications of NMR to the study of metabolism in microorganisms, isolated or cultivated cells, and tumors. NMR spectroscopy of the brain, and human in vivo NMR spectroscopy have also been reviewed

  18. Spectroscopic (FT-IR, FT-Raman and UV-Visible) investigations, NMR chemical shielding anisotropy (CSA) parameters of 2,6-Diamino-4-chloropyrimidine for dye sensitized solar cells using density functional theory.

    Gladis Anitha, E; Joseph Vedhagiri, S; Parimala, K

    2014-10-24

    The molecular structure, geometry optimization, vibrational frequencies of organic dye sensitizer 2,6-Diamino-4-chloropyrimidine (DACP) were studied based on Hartree-Fock (HF) and density functional theory (DFT) using B3LYP methods with 6-311++G(d,p) basis set. Ultraviolet-Visible (UV-Vis) spectrum was investigated by time dependent DFT (TD-DFT). Features of the electronic absorption spectrum in the UV-Visible regions were assigned based on TD-DFT calculation. The absorption bands are assigned to transitions. The interfacial electron transfer between semiconductor TiO2 electrode and dye sensitizer DACP is due to an electron injection process from excited dye to the semiconductor's conduction band. The observed and the calculated frequencies are found to be in good agreement. The energies of the frontier molecular orbitals (FMOS) have also been determined. The chemical shielding anisotropic (CSA) parameters are calculated from the NMR analysis, Stability of the molecule arising from hyperconjugative interactions and charge delocalization has been analyzed using natural bond orbital (NBO) analysis. PMID:25459717

  19. NMR analysis of biodiesel

    Biodiesel is usually analyzed by the various methods called for in standards such as ASTM D6751 and EN 14214. Nuclear magnetic resonance (NMR) is not one of these methods. However, NMR, with 1H-NMR commonly applied, can be useful in a variety of applications related to biodiesel. These include monit...

  20. NMR studies of multiphase flows II

    Altobelli, S.A.; Caprihan, A.; Fukushima, E. [Lovelace Institutes, Albuquerque, NM (United States)] [and others

    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.

  1. An introduction to biological NMR spectroscopy

    NMR spectroscopy is a powerful tool for biologists interested in the structure, dynamics, and interactions of biological macromolecules. This review aims at presenting in an accessible manner the requirements and limitations of this technique. As an introduction, the history of NMR will highlight how the method evolved from physics to chemistry and finally to biology over several decades. We then introduce the NMR spectral parameters used in structural biology, namely the chemical shift, the J-coupling, nuclear Overhauser effects, and residual dipolar couplings. Resonance assignment, the required step for any further NMR study, bears a resemblance to jigsaw puzzle strategy. The NMR spectral parameters are then converted into angle and distances and used as input using restrained molecular dynamics to compute a bundle of structures. When interpreting a NMR-derived structure, the biologist has to judge its quality on the basis of the statistics provided. When the 3D structure is a priori known by other means, the molecular interaction with a partner can be mapped by NMR: information on the binding interface as well as on kinetic and thermodynamic constants can be gathered. NMR is suitable to monitor, over a wide range of frequencies, protein fluctuations that play a crucial role in their biological function. In the last section of this review, intrinsically disordered proteins, which have escaped the attention of classical structural biology, are discussed in the perspective of NMR, one of the rare available techniques able to describe structural ensembles. This Tutorial is part of the International Proteomics Tutorial Programme (IPTP 16 MCP). (authors)

  2. NMR at 900 MHz

    2002-01-01

    @@ An important factor in the development of solutionstate NMR has always been th e ability to produce stable and homogeneous magnetic fields. As higher and higher field strengths are reached the pressure is growing on manufacturers to produce NMR systems with greatly improved spectral resolution and signal to noise ratio. The introduction of the Varian 900 MHz INOVA system in August 2000 featuring Oxford Instruments 21.1 T magnet represents the latest pioneering development in NMR technology.

  3. Theoretical studies of the local structure and electron paramagnetic resonance parameters for tetragonal VO{sup 2+} in C{sub 6}H{sub 7}KO{sub 7}

    Zhou, Ping [Chongqing Jiaotong Univ. (China). School of Science; Li, Ling [Sichuan University of Arts and Science, Dazhou (China). Dept. of Maths and Finance-Economics

    2015-07-01

    The optical spectra, electron paramagnetic resonance parameters (i.e., the spin Hamiltonian parameters, including paramagnetic g factors and the hyperfine structure constants A{sub i}) and the local distortion structure for the tetragonal VO{sup 2+} in C{sub 6}H{sub 7}KO{sub 7} are theoretically studied based on the crystal-field theory and three-order perturbation formulas of a 3d{sup 1} centre in tetragonal site. The magnitude of orbital reduction factor, core polarisation constant κ, and local structure parameters are obtained by fitting the calculated optical spectra and electron paramagnetic resonance parameters to the experimental values. The theoretical results are in reasonable agreement with the experimental values.

  4. Lectures on pulsed NMR

    These lectures discuss some recent developments in pulsed NMR, emphasizing fundamental principles with selected illustrative applications. Major topics covered include multiple-quantum spectroscopy, spin decoupling, the interaction of spins with a quantized field, adiabatic rapid passage, spin temperature and statistics of cross-polarization, coherent averaging, and zero field NMR. 32 refs., 56 figs

  5. Lectures on pulsed NMR

    These lectures discuss some recent developments in pulsed NMR, emphasizing fundamental principles with selected illustrative applications. Major topics covered include multiple-quantum spectroscopy, spin decoupling, the interaction of spins with a quantized field, adiabatic rapid passage, spin temperature and statistics of cross-polarization, coherent averaging, and zero field NMR. 55 figs

  6. Dynamics in solids studied by NMR crystalography and MD simulations

    Dračínský, Martin; Šála, Michal; Hodgkinson, P.

    Baveno : -, 2015. s. 20-21. [SMASH 2015. Small Molecule NMR Conference. 20.09.2015-23.09.2015, Baveno] R&D Projects: GA ČR GA15-11223S; GA ČR GA13-24880S Institutional support: RVO:61388963 Keywords : molecular dynamics * calculations of NMR parameters * path integral molecular dynamics Subject RIV: CF - Physical ; Theoretical Chemistry

  7. Optimization and practical implementation of ultrafast 2D NMR experiments

    Luiz H. K. Queiroz Júnior

    2013-01-01

    Full Text Available Ultrafast 2D NMR is a powerful methodology that allows recording of a 2D NMR spectrum in a fraction of second. However, due to the numerous non-conventional parameters involved in this methodology its implementation is no trivial task. Here, an optimized experimental protocol is carefully described to ensure efficient implementation of ultrafast NMR. The ultrafast spectra resulting from this implementation are presented based on the example of two widely used 2D NMR experiments, COSY and HSQC, obtained in 0.2 s and 41 s, respectively.

  8. Optimization and practical implementation of ultrafast 2D NMR experiments

    Queiroz Junior, Luiz H. K., E-mail: professorkeng@gmail.com [Universidade Federal de Sao Carlos (UFSC), SP (Brazil). Departamento de Quimica; Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Inst. de Quimica; Ferreira, Antonio G. [Universidade Federal de Sao Carlos (UFSC), SP (Brazil). Departamento de Quimica; Giraudeau, Patrick [Universite de Nantes (France). CNRS, Chimie et Interdisciplinarite: Synthese, Analyse, Modelisation

    2013-09-01

    Ultrafast 2D NMR is a powerful methodology that allows recording of a 2D NMR spectrum in a fraction of second. However, due to the numerous non-conventional parameters involved in this methodology its implementation is no trivial task. Here, an optimized experimental protocol is carefully described to ensure efficient implementation of ultrafast NMR. The ultrafast spectra resulting from this implementation are presented based on the example of two widely used 2D NMR experiments, COSY and HSQC, obtained in 0.2 s and 41 s, respectively. (author)

  9. EPR Properties of Concentrated NdVO4 Single Crystal System

    Kaczmarek, S.M.; Fuks, H.; Berkowski, M.; Głowacki, M.; Bojanowski, B.

    2015-01-01

    Single crystals of NdVO4 were grown by the Czochralski method under ambient pressure in a nitrogen atmosphere. Obtained crystals were transparent with strong violet coloring. Temperature and angular dependences of electron paramagnetic resonance (EPR) spectra of the samples in the 3–103 K temperature range were analyzed applying Dyson like lineshape typically used for concentrated magnetic system. EPR-NMR program was used to find local symmetry and spin-Hamiltonian parameters of neodymium ion...

  10. Functional studies using NMR

    This volume is based on a series of lectures delivered at a one-day teaching symposium on functional and metabolic aspects of NMR measurements held at the Middlesex Hospital Medical School on 1st September 1985 as a part of the European Nuclear Medicine Society Congress. Currently the major emphasis in medical NMR in vivo is on its potential to image and display abnormalities in conventional radiological images, providing increased contrast between normal and abnormal tissue, improved definition of vasculature, and possibly an increased potential for differential diagnosis. Although these areas are undeniably of major importance, it is probable that NMR will continue to complement conventional measurement methods. The major potential benefits to be derived from in vivo NMR measurements are likely to arise from its use as an instrument for functional and metabolic studies in both clinical research and in the everyday management of patients. It is to this area that this volume is directed

  11. Rapid prediction of multi-dimensional NMR data sets

    Gradmann, Sabine; Ader, Christian [Utrecht University, Faculty of Science, Bijvoet Center for Biomolecular Research (Netherlands); Heinrich, Ines [Max Planck Institute for Molecular Physiology, Department of Physical Biochemistry (Germany); Nand, Deepak [Utrecht University, Faculty of Science, Bijvoet Center for Biomolecular Research (Netherlands); Dittmann, Marc [Max Planck Institute for Molecular Physiology, Department of Physical Biochemistry (Germany); Cukkemane, Abhishek; Dijk, Marc van; Bonvin, Alexandre M. J. J. [Utrecht University, Faculty of Science, Bijvoet Center for Biomolecular Research (Netherlands); Engelhard, Martin [Max Planck Institute for Molecular Physiology, Department of Physical Biochemistry (Germany); Baldus, Marc, E-mail: m.baldus@uu.nl [Utrecht University, Faculty of Science, Bijvoet Center for Biomolecular Research (Netherlands)

    2012-12-15

    We present a computational environment for Fast Analysis of multidimensional NMR DAta Sets (FANDAS) that allows assembling multidimensional data sets from a variety of input parameters and facilitates comparing and modifying such 'in silico' data sets during the various stages of the NMR data analysis. The input parameters can vary from (partial) NMR assignments directly obtained from experiments to values retrieved from in silico prediction programs. The resulting predicted data sets enable a rapid evaluation of sample labeling in light of spectral resolution and structural content, using standard NMR software such as Sparky. In addition, direct comparison to experimental data sets can be used to validate NMR assignments, distinguish different molecular components, refine structural models or other parameters derived from NMR data. The method is demonstrated in the context of solid-state NMR data obtained for the cyclic nucleotide binding domain of a bacterial cyclic nucleotide-gated channel and on membrane-embedded sensory rhodopsin II. FANDAS is freely available as web portal under WeNMR (http://www.wenmr.eu/services/FANDAShttp://www.wenmr.eu/services/FANDAS).

  12. Rapid prediction of multi-dimensional NMR data sets

    We present a computational environment for Fast Analysis of multidimensional NMR DAta Sets (FANDAS) that allows assembling multidimensional data sets from a variety of input parameters and facilitates comparing and modifying such “in silico” data sets during the various stages of the NMR data analysis. The input parameters can vary from (partial) NMR assignments directly obtained from experiments to values retrieved from in silico prediction programs. The resulting predicted data sets enable a rapid evaluation of sample labeling in light of spectral resolution and structural content, using standard NMR software such as Sparky. In addition, direct comparison to experimental data sets can be used to validate NMR assignments, distinguish different molecular components, refine structural models or other parameters derived from NMR data. The method is demonstrated in the context of solid-state NMR data obtained for the cyclic nucleotide binding domain of a bacterial cyclic nucleotide-gated channel and on membrane-embedded sensory rhodopsin II. FANDAS is freely available as web portal under WeNMR (http://www.wenmr.eu/services/FANDAShttp://www.wenmr.eu/services/FANDAS).

  13. Renal transplant NMR

    The preliminary results of NMR evaluation of renal transplants (Txs) are reported including correlation with nuclear medicine (NM) and ultrasound (US). Thirteen Txs (8 cadaver (Cd), 5 living related doner (LRD) in 13 patients (6M, 7F) ranging in age from 25-47 (x 35) were evaluated by NM (32), NMR (15) and US (5). Clinical diagnoses included: rejection (8), ATN (2), infarction (1), and normal (2). Of the 8 patients with rejection (5) Cd; 3 LRD) pathologic proof was obtained in 3. An experimental 0.12 T resistive magnet (GE) was used with a partial saturation technique with repetition time (TR) of 143 and 286 msec to provide T1 weighting. T2 weighted information was obtained with a spin echo technique with echo times (TE) of 20, 40, 60 and 80 msec. The NMR appearance of normal Txs consisted of a uniform signal intensity (Tx> pelvic musculature), well-defined internal architecture with good cortical medullary differentiation and normal appearing vessels. The NMR appearance of abnormal transplants consisted of a heterogeneous or overall decrease in signal intensity (kidney muscle) with poor cortical medullary differentiation with or without a halo of decreased signal intensity. Although NMR was able to differentiate normal from abnormal, it was unable to clearly discriminate between ATN and rejection. Advantages of NMR included the ability to demonstrate regional anatomy, vasculature, post operative fluid collections and hematomas, and associated avascular necrosis of the hips

  14. Combining solid-state NMR spectroscopy with first-principles calculations - a guide to NMR crystallography.

    Ashbrook, Sharon E; McKay, David

    2016-06-01

    Recent advances in the application of first-principles calculations of NMR parameters to periodic systems have resulted in widespread interest in their use to support experimental measurement. Such calculations often play an important role in the emerging field of "NMR crystallography", where NMR spectroscopy is combined with techniques such as diffraction, to aid structure determination. Here, we discuss the current state-of-the-art for combining experiment and calculation in NMR spectroscopy, considering the basic theory behind the computational approaches and their practical application. We consider the issues associated with geometry optimisation and how the effects of temperature may be included in the calculation. The automated prediction of structural candidates and the treatment of disordered and dynamic solids are discussed. Finally, we consider the areas where further development is needed in this field and its potential future impact. PMID:27117884

  15. Molecular dynamics simulations on PGLa using NMR orientational constraints

    NMR data obtained by solid state NMR from anisotropic samples are used as orientational constraints in molecular dynamics simulations for determining the structure and dynamics of the PGLa peptide within a membrane environment. For the simulation the recently developed molecular dynamics with orientational constraints technique (MDOC) is used. This method introduces orientation dependent pseudo-forces into the COSMOS-NMR force field. Acting during a molecular dynamics simulation these forces drive molecular rotations, re-orientations and folding in such a way that the motional time-averages of the tensorial NMR properties are consistent with the experimentally measured NMR parameters. This MDOC strategy does not depend on the initial choice of atomic coordinates, and is in principle suitable for any flexible and mobile kind of molecule; and it is of course possible to account for flexible parts of peptides or their side-chains. MDOC has been applied to the antimicrobial peptide PGLa and a related dimer model. With these simulations it was possible to reproduce most NMR parameters within the experimental error bounds. The alignment, conformation and order parameters of the membrane-bound molecule and its dimer were directly derived with MDOC from the NMR data. Furthermore, this new approach yielded for the first time the distribution of segmental orientations with respect to the membrane and the order parameter tensors of the dimer systems. It was demonstrated the deuterium splittings measured at the peptide to lipid ratio of 1/50 are consistent with a membrane spanning orientation of the peptide

  16. Molecular dynamics simulations on PGLa using NMR orientational constraints

    Sternberg, Ulrich, E-mail: ulrich.sternberg@partner.kit.edu; Witter, Raiker [Tallinn University of Technology, Technomedicum (Estonia)

    2015-11-15

    NMR data obtained by solid state NMR from anisotropic samples are used as orientational constraints in molecular dynamics simulations for determining the structure and dynamics of the PGLa peptide within a membrane environment. For the simulation the recently developed molecular dynamics with orientational constraints technique (MDOC) is used. This method introduces orientation dependent pseudo-forces into the COSMOS-NMR force field. Acting during a molecular dynamics simulation these forces drive molecular rotations, re-orientations and folding in such a way that the motional time-averages of the tensorial NMR properties are consistent with the experimentally measured NMR parameters. This MDOC strategy does not depend on the initial choice of atomic coordinates, and is in principle suitable for any flexible and mobile kind of molecule; and it is of course possible to account for flexible parts of peptides or their side-chains. MDOC has been applied to the antimicrobial peptide PGLa and a related dimer model. With these simulations it was possible to reproduce most NMR parameters within the experimental error bounds. The alignment, conformation and order parameters of the membrane-bound molecule and its dimer were directly derived with MDOC from the NMR data. Furthermore, this new approach yielded for the first time the distribution of segmental orientations with respect to the membrane and the order parameter tensors of the dimer systems. It was demonstrated the deuterium splittings measured at the peptide to lipid ratio of 1/50 are consistent with a membrane spanning orientation of the peptide.

  17. Dynamics of a truncated prion protein, PrP(113–231), from 15N NMR relaxation: Order parameters calculated and slow conformational fluctuations localized to a distinct region

    O'Sullivan, Denis B D; Jones, Christopher E; Abdelraheim, Salama R; Brazier, Marcus W; Toms, Harold; Brown, David R; Viles, John H.

    2009-01-01

    Prion diseases are associated with the misfolding of the prion protein (PrPC) from a largely α-helical isoform to a β-sheet rich oligomer (PrPSc). Flexibility of the polypeptide could contribute to the ability of PrPC to undergo the conformational rearrangement during PrPC–PrPSc interactions, which then leads to the misfolded isoform. We have therefore examined the molecular motions of mouse PrPC, residues 113–231, in solution, using 15N NMR relaxation measurements. A truncated fragment has b...

  18. A hybrid inversion method of (T2 ,D) 2D NMR logging and observation parameters effects%(T2,D)二维核磁共振测井混合反演方法与参数影响分析

    谭茂金; 邹友龙

    2012-01-01

    一维核磁共振(1D NMR)测井技术在流体识别中具有一定的局限性.二维核磁共振(2D NMR)测井能同时测量到多孔介质中横向弛豫时间(T2)和扩散系数(D)等信息,利用这两个参数区分流体性质,较一维核磁共振测井技术具有明显的优越性.针对梯度场下的2D NMR测井弛豫机理和数学模型,提出了适用于求解大型稀疏矩阵方程的反演方法—基于非负最小二乘法(LSQR)和截断奇异值分解(TSVD)法的混合算法.为验证方法的有效性,先根据多回波观测模式合成回波串数据,然后再用混合反演算法进行反演,反演得到横向弛豫时间(T2)和扩散系数(D),并构建T2-D二维谱图.结果对比表明,该混合反演算法得到的T2-D二维谱与流体模型一致性好,计算精度均比单一反演方法有较大改善,表明该混合反演方法可用于油气储集层2D NMR测井的反演和流体识别.此外,分别对油水同层和气水同层模型进行了正演模拟和反演实验,系统考察了不同磁场梯度、不同回波间隔组合对反演效果的影响,为2D NMR参数设计提供依据.%One dimensional nuclear magnetic resonance (ID NMR) logging technology is limited for fluid typing. Two dimensional nuclear magnetic resonance (2D NMR) logging can provide more parameters including transverse relaxation time (T2) and diffusion coefficient (D) in multi-pore media, and the fluid typing is realized successfully according to the fluid properties of NMR. So, 2D NMR logging is more advantageous than ID NMR logging. Point to the relaxation mechanism of 2D NMR at gradient field, the echo simulation and inversion of 2D NMR are discussed in detail. And a hybrid inversion algorithm is proposed, which is based on a dampingleast squares method (LSQR) and truncated singular value decomposition (TSVD). For verifying the hybrid inversion method, a series of spin echo trains in an ideal fluid model are firstly simulated with multiple echo spacing

  19. NMR Aerosolomics: Novel NMR Method for Organic Aerosol Analysis

    Horník, Štěpán; Schwarz, Jaroslav; Sýkora, Jan

    - : -, 2015, s. 162. ISBN N. [Small Molecule NMR Conference - SMASH 2015. Baveno (IT), 20.09.2015-23.09.2015] Institutional support: RVO:67985858 Keywords : aerosol * analysis * NMR Subject RIV: CC - Organic Chemistry

  20. NMR imaging technique

    This invention provides a method that can be adapted to existing NMR tomographic scanners of producing spectra of any given point in the image of the specimen slice, the intensity distribution of a selected resonance within an area of the image of the specimen slice, or an entire NMR spectrum of the given area. The method comprises acquiring n projections of the specimen slice, where n is greater than 1. Each of the projections is then shifted by Δ f for the point (the frequency offset of the signal arising from the point, from the true chemical shift)

  1. NMR studies of oriented molecules

    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.

  2. NMR a substitute for CT

    The possibility that NMR (Nuclear Magnetic Resonance) can be a substitute for CT (Computerized Tomography), is described. NMR focus on the nuclei in the atoms of certain elements, for example hydrogen

  3. International symposium on NMR spectroscopy

    The publication consists of 32 papers and presentations from the field of NMR spectroscopy applications submitted to the International Symposium on NMR Spectroscopy held at Smolenice between 29 Sep and 3 Oct, 1980. (B.S.)

  4. NMR crystallography of polylactide

    Czernek, Jiří

    Prague : Institute of Macromolecular Chemistry AS CR, v. v. i, 2013. s. 60. ISBN 978-80-85009-77-4. [European Symposium on Polymer Spectroscopy /19./ - ESOPS19. Prague Meeting on Macromolecules /77./. 07.07.2013-11.07.2013, Prague] Institutional support: RVO:61389013 Keywords : NMR crystallography * polylactide Subject RIV: CD - Macromolecular Chemistry

  5. Soils, Pores, and NMR

    Pohlmeier, Andreas; Haber-Pohlmeier, Sabina; Haber, Agnes; Sucre, Oscar; Stingaciu, Laura; Stapf, Siegfried; Blümich, Bernhard

    2010-05-01

    Within Cluster A, Partial Project A1, the pore space exploration by means of Nuclear Magnetic Resonance (NMR) plays a central role. NMR is especially convenient since it probes directly the state and dynamics of the substance of interest: water. First, NMR is applied as relaxometry, where the degree of saturation but also the pore geometry controls the NMR signature of natural porous systems. Examples are presented where soil samples from the Selhausen, Merzenhausen (silt loams), and Kaldenkirchen (sandy loam) test sites are investigated by means of Fast Field Cycling Relaxometry at different degrees of saturation. From the change of the relaxation time distributions with decreasing water content and by comparison with conventional water retention curves we conclude that the fraction of immobile water is characterized by T1 samples (Haber-Pohlmeier et al. 2010). Third, relaxometric information forms the basis of understanding magnetic resonance imaging (MRI) results. The general difficulty of imaging in soils are the inherent fast T2 relaxation times due to i) the small pore sizes, ii) presence of paramagnetic ions in the solid matrix, and iii) diffusion in internal gradients. The last point is important, since echo times can not set shorter than about 1ms for imaging purposes. The way out is either the usage of low fields for imaging in soils or special ultra-short pulse sequences, which do not create echoes. In this presentation we will give examples on conventional imaging of macropore fluxes in soil cores (Haber-Pohlmeier et al. 2010), and the combination with relaxometric imaging, as well as the advantages and drawbacks of low-field and ultra-fast pulse imaging. Also first results on the imaging of soil columns measured by SIP in Project A3 are given. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Waterflow Monitored by Tracer Transport in Natural Porous Media Using MRI." Vadose Zone J.: submitted. Haber-Pohlmeier, S., S. Stapf, et al. (2010). "Relaxation in a

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

    Hirasaki, George J.; Mohanty, Kishore K.

    2003-02-10

    The objective of this project was to characterize the fluid properties and fluid-rock interactions which are needed for formation evaluation by NMR well logging. NMR well logging is finding wide use in formation evaluation. The formation parameters commonly estimated were porosity, permeability, and capillary bound water. Special cases include estimation of oil viscosity, residual oil saturation, location of oil/water contact, and interpretation on whether the hydrocarbon is oil or gas.

  7. Solid state NMR study of cumbaru flour

    The polysaccharide obtained by seed of Dipteryx alata Vog, has been characterised by 13C solid state, using the basic routine techniques, like MAS and CPMAS and by the proton spin-lattice relaxation time in the rotating frame parameter (T1Hρ). Knowing that the chemical structure and molecular dynamic are extremely necessary route to obtain information on the polysaccharides, this work contributes to the classification of the seed containing in the cumbaru fruit to get response on its application. To obtain the initial responses for our purposes some solid state NMR techniques were chosen. The CPMAS 13C NMR spectrum of the polysaccharide was investigated to know if it has some crystallinity. The MAS 13C NMR spectrum showed the presence of domains with distinct molecular mobility, because these domains will differ basically in the distribution size and chain packing. The variable contact time experiment was used to analyse the distribution form of 13C decays, which give us more information about sample heterogeneity. The T1HρHr values were obtained from the variable contact time and by delayed contact time experiment, because these parameter indicate the order of polysaccharides. From the values of this parameter, we found that this polysaccharide is completely non-ordered. (author)

  8. NMR of unfolded proteins

    Amarnath Chtterjee; Ashutosh Kumar; Jeetender Chugh; Sudha Srivastava; Neel S Bhavesh; Ramakrishna V Hosur

    2005-01-01

    In the post-genomic era, as more and more genome sequences are becoming known and hectic efforts are underway to decode the information content in them, it is becoming increasingly evident that flexibility in proteins plays a crucial role in many of the biological functions. Many proteins have intrinsic disorder either wholly or in specific regions. It appears that this disorder may be important for regulatory functions of the proteins, on the one hand, and may help in directing the folding process to reach the compact native state, on the other. Nuclear magnetic resonance (NMR) has over the last two decades emerged as the sole, most powerful technique to help characterize these disordered protein systems. In this review, we first discuss the significance of disorder in proteins and then describe the recent developments in NMR methods for their characterization. A brief description of the results obtained on several disordered proteins is presented at the end.

  9. Some exercises in quantitative NMR imaging

    The articles represented in this thesis result from a series of investigations that evaluate the potential of NMR imaging as a quantitative research tool. In the first article the possible use of proton spin-lattice relaxation time T1 in tissue characterization, tumor recognition and monitoring tissue response to radiotherapy is explored. The next article addresses the question whether water proton spin-lattice relaxation curves of biological tissues are adequately described by a single time constant T1, and analyzes the implications of multi-exponentiality for quantitative NMR imaging. In the third article the use of NMR imaging as a quantitative research tool is discussed on the basis of phantom experiments. The fourth article describes a method which enables unambiguous retrieval of sign information in a set of magnetic resonance images of the inversion recovery type. The next article shows how this method can be adapted to allow accurate calculation of T1 pictures on a pixel-by-pixel basis. The sixth article, finally, describes a simulation procedure which enables a straightforward determination of NMR imaging pulse sequence parameters for optimal tissue contrast. (orig.)

  10. NMR, water and plants

    This thesis describes the application of a non-destructive pulsed proton NMR method mainly to measure water transport in the xylem vessels of plant stems and in some model systems. The results are equally well applicable to liquid flow in other biological objects than plants, e.g. flow of blood and other body fluids in human and animals. The method is based on a pulse sequence of equidistant π pulses in combination with a linear magnetic field gradient. (Auth.)

  11. Extracting protein dynamics information from overlapped NMR signals using relaxation dispersion difference NMR spectroscopy

    Protein dynamics plays important roles in many biological events, such as ligand binding and enzyme reactions. NMR is mostly used for investigating such protein dynamics in a site-specific manner. Recently, NMR has been actively applied to large proteins and intrinsically disordered proteins, which are attractive research targets. However, signal overlap, which is often observed for such proteins, hampers accurate analysis of NMR data. In this study, we have developed a new methodology called relaxation dispersion difference that can extract conformational exchange parameters from overlapped NMR signals measured using relaxation dispersion spectroscopy. In relaxation dispersion measurements, the signal intensities of fluctuating residues vary according to the Carr-Purcell-Meiboon-Gill pulsing interval, whereas those of non-fluctuating residues are constant. Therefore, subtraction of each relaxation dispersion spectrum from that with the highest signal intensities, measured at the shortest pulsing interval, leaves only the signals of the fluctuating residues. This is the principle of the relaxation dispersion difference method. This new method enabled us to extract exchange parameters from overlapped signals of heme oxygenase-1, which is a relatively large protein. The results indicate that the structural flexibility of a kink in the heme-binding site is important for efficient heme binding. Relaxation dispersion difference requires neither selectively labeled samples nor modification of pulse programs; thus it will have wide applications in protein dynamics analysis

  12. Extracting protein dynamics information from overlapped NMR signals using relaxation dispersion difference NMR spectroscopy

    Konuma, Tsuyoshi [Icahn School of Medicine at Mount Sinai, Department of Structural and Chemical Biology (United States); Harada, Erisa [Suntory Foundation for Life Sciences, Bioorganic Research Institute (Japan); Sugase, Kenji, E-mail: sugase@sunbor.or.jp, E-mail: sugase@moleng.kyoto-u.ac.jp [Kyoto University, Department of Molecular Engineering, Graduate School of Engineering (Japan)

    2015-12-15

    Protein dynamics plays important roles in many biological events, such as ligand binding and enzyme reactions. NMR is mostly used for investigating such protein dynamics in a site-specific manner. Recently, NMR has been actively applied to large proteins and intrinsically disordered proteins, which are attractive research targets. However, signal overlap, which is often observed for such proteins, hampers accurate analysis of NMR data. In this study, we have developed a new methodology called relaxation dispersion difference that can extract conformational exchange parameters from overlapped NMR signals measured using relaxation dispersion spectroscopy. In relaxation dispersion measurements, the signal intensities of fluctuating residues vary according to the Carr-Purcell-Meiboon-Gill pulsing interval, whereas those of non-fluctuating residues are constant. Therefore, subtraction of each relaxation dispersion spectrum from that with the highest signal intensities, measured at the shortest pulsing interval, leaves only the signals of the fluctuating residues. This is the principle of the relaxation dispersion difference method. This new method enabled us to extract exchange parameters from overlapped signals of heme oxygenase-1, which is a relatively large protein. The results indicate that the structural flexibility of a kink in the heme-binding site is important for efficient heme binding. Relaxation dispersion difference requires neither selectively labeled samples nor modification of pulse programs; thus it will have wide applications in protein dynamics analysis.

  13. Rhodopsin-lipid interactions studied by NMR.

    Soubias, Olivier; Gawrisch, Klaus

    2013-01-01

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

  14. NMR molecular photography

    Khitrin, Anatoly K.; Ermakov, Vladimir L.; Fung, B M

    2002-01-01

    A procedure is described for storing a 2D pattern consisting of 32x32 = 1024 bits in a spin state of a molecular system and then retrieving the stored information as a stack of NMR spectra. The system used is a nematic liquid crystal, the protons of which act as spin clusters with strong intramolecular interactions. The technique used is a programmable multi-frequency irradiation with low amplitude. When it is applied to the liquid crystal, a large number of coherent long-lived 1H response si...

  15. Some nitrogen-14 NMR studies in solids

    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.

  16. DNA oligonucleotide conformations: high resolution NMR studies

    The present work describes a DNA double-helix model, which is well comparable with the models derived from fibre-diffraction studies. The model has a mononucleotide repeat with torsion angles in accordance with average geometries as derived from 1H NMR studies. Special attention was paid to reduce the number of short H-H nonbonding contacts, which are abundantly present in the 'classical' fibre-diffraction models. Chapter 3 describes the first complete assignment of a 1H NMR spectrum of a DNA tetramer, d(TAAT). Preliminary conformational data derived from the spectral parameters recorded at 27 0C are given. A more detailed analysis employing temperature-dependence studies is given in Chapter 4. (Auth.)

  17. Fully automated system for pulsed NMR measurements

    A system is described which places many of the complex, tedious operations for pulsed NMR experiments under computer control. It automatically optimizes the experiment parameters of pulse length and phase, and precision, accuracy, and measurement speed are improved. The hardware interface between the computer and the NMR instrument is described. Design features, justification of the choices made between alternative design strategies, and details of the implementation of design goals are presented. Software features common to all the available experiments are discussed. Optimization of pulse lengths and phases is performed via a sequential search technique called Uniplex. Measurements of the spin-lattice and spin-spin relaxation times and of diffusion constants are automatic. Options for expansion of the system are explored along with some of the limitations of the system

  18. Some nitrogen-14 NMR studies in solids

    The first order quadrupolar perturbation of the 14N NMR spectrum yields information regarding the static and dynamic properties of the surrounding electronic environment. Signal to noise problems caused by long 14N longitudinal relaxation times (T1) and small equilibrium polarizations are reduced by rotating frame cross polarization (CP) experiments between 14N and 1H. Using quadrupolar echo and CP techniques, the 14N quadrupolar coupling constants (e2qQ/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 14N NMR powder patterns exhibit the effects of anisotropic molecular motion, while choline bromide spectra show no such effects

  19. Exploiting periodic first-principles calculations in NMR spectroscopy of disordered solids

    Ashbrook, Sharon Elizabeth Marie; Dawson, Daniel McLean

    2013-01-01

    Much of the information contained within solid-state nuclear magnetic resonance (NMR) spectra remains unexploited because of the challenges in obtaining high-resolution spectra and the difficulty in assigning those spectra. Recent advances that enable researchers to accurately and efficiently determine NMR parameters in periodic systems have revolutionized the application of density functional theory (DFT) calculations in solid-state NMR spectroscopy. These advances are particularly useful fo...

  20. Phenomenological simulation and density functional theory prediction of 57Fe Mössbauer parameters: application to magnetically coupled diiron proteins

    The use of phenomenological spin Hamiltonians and of spin density functional theory for the analysis and interpretation of Mössbauer spectra of antiferromagnetic or ferromagnetic diiron centers is briefly discussed. The spectroscopic parameters of the hydroxylase component of methane monooxygenase (MMOH), an enzyme that catalyzes the conversion of methane to methanol, have been studied. In its reduced diferrous state (MMOHRed) the enzyme displays 57Fe Mössbauer and EPR parameters characteristic of two ferromagnetically coupled high spin ferrous ions. However, Mössbauer spectra recorded for MMOHRed from two different bacteria, Methylococcus capsulatus (Bath) and Methylosinus trichosporium OB3b, display slightly different electric quadrupole splittings (ΔEQ) in apparent contradiction to their essentially identical active site crystallographic structures and biochemical functions. Herein, the Mössbauer spectral parameters of MMOHRed have been predicted and studied via spin density functional theory. The somewhat different ΔEQ recorded for the two bacteria have been traced to the relative position of an essentially unbound water molecule within their diiron active sites. It is shown that the presence or absence of the unbound water molecule mainly affects the electric field gradient at only one iron ion of the binuclear active sites.

  1. NMR spectrometers as "magnetic tongues"

    Malmendal, Anders; Amoresano, Claudia; Trotta, Roberta;

    2011-01-01

    the analyzed samples based on their chemical composition. We were able to correlate the NMR metabolomic fingerprints recorded for canned tomato samples to the sensory descriptors bitterness, sweetness, sourness, saltiness, tomato and metal taste, redness, and density, suggesting that NMR might be a very useful...

  2. NMR in pulsed magnetic field

    Abou-Hamad, Edy

    2011-09-01

    Nuclear magnetic resonance (NMR) experiments in pulsed magnetic fields up to 30.4 T focused on 1H and 93Nb nuclei are reported. Here we discuss the advantage and limitation of pulsed field NMR and why this technique is able to become a promising research tool. © 2011 Elsevier Inc. All Rights Reserved.

  3. Structural Biology: Practical NMR Applications

    Teng, Quincy

    2005-01-01

    This textbook begins with an overview of NMR development and applications in biological systems. It describes recent developments in instrument hardware and methodology. Chapters highlight the scope and limitation of NMR methods. While detailed math and quantum mechanics dealing with NMR theory have been addressed in several well-known NMR volumes, chapter two of this volume illustrates the fundamental principles and concepts of NMR spectroscopy in a more descriptive manner. Topics such as instrument setup, data acquisition, and data processing using a variety of offline software are discussed. Chapters further discuss several routine stategies for preparing samples, especially for macromolecules and complexes. The target market for such a volume includes researchers in the field of biochemistry, chemistry, structural biology and biophysics.

  4. Fundamentals of Protein NMR Spectroscopy

    Rule, Gordon S

    2006-01-01

    NMR spectroscopy has proven to be a powerful technique to study the structure and dynamics of biological macromolecules. Fundamentals of Protein NMR Spectroscopy is a comprehensive textbook that guides the reader from a basic understanding of the phenomenological properties of magnetic resonance to the application and interpretation of modern multi-dimensional NMR experiments on 15N/13C-labeled proteins. Beginning with elementary quantum mechanics, a set of practical rules is presented and used to describe many commonly employed multi-dimensional, multi-nuclear NMR pulse sequences. A modular analysis of NMR pulse sequence building blocks also provides a basis for understanding and developing novel pulse programs. This text not only covers topics from chemical shift assignment to protein structure refinement, as well as the analysis of protein dynamics and chemical kinetics, but also provides a practical guide to many aspects of modern spectrometer hardware, sample preparation, experimental set-up, and data pr...

  5. Constants of NMR spectra

    The NMR (nuclear magnetic resonance) spectroscopy is a method for studying matter. It has been developed in a lot of fields of physics, physical chemistry, chemistry and biology. It concerns both the solid state and the liquid state. The study in solution of synthesis organic molecules or of organic molecules of natural origin and of biological molecules is particularly stressed on but it is also possible to study inorganic molecules. The originality of this method is to give both data on each atoms of the studied structure, on the atoms sequence in this structure, on the conformation and on the related configurations. It allows to reveal the interactions between separate molecules too. It is also a precious tool for the analysis of molecular movements. The development of this method for the study of condensed phases is particularly studied nowadays and the data obtained are for a lot of fields as acute as those obtained at the liquid state. (O.M.)

  6. NMR-based screening of membrane protein ligands.

    Yanamala, Naveena; Dutta, Arpana; Beck, Barbara; van Vliet, Bart; van Fleet, Bart; Hay, Kelly; Yazbak, Ahmad; Ishima, Rieko; Doemling, Alexander; Klein-Seetharaman, Judith

    2010-03-01

    Membrane proteins pose problems for the application of NMR-based ligand-screening methods because of the need to maintain the proteins in a membrane mimetic environment such as detergent micelles: they add to the molecular weight of the protein, increase the viscosity of the solution, interact with ligands non-specifically, overlap with protein signals, modulate protein dynamics and conformational exchange and compromise sensitivity by adding highly intense background signals. In this article, we discuss the special considerations arising from these problems when conducting NMR-based ligand-binding studies with membrane proteins. While the use of (13)C and (15)N isotopes is becoming increasingly feasible, (19)F and (1)H NMR-based approaches are currently the most widely explored. By using suitable NMR parameter selection schemes independent of or exploiting the presence of detergent, (1)H-based approaches require least effort in sample preparation because of the high sensitivity and natural abundance of (1)H in both, ligand and protein. On the other hand, the (19)F nucleus provides an ideal NMR probe because of its similarly high sensitivity to that of (1)H and the lack of natural (19)F background in biologic systems. Despite its potential, the use of NMR spectroscopy is highly underdeveloped in the area of drug discovery for membrane proteins. PMID:20331645

  7. NMR Logging to Estimate Hydraulic Conductivity in Unconsolidated Aquifers.

    Knight, Rosemary; Walsh, David O; Butler, James J; Grunewald, Elliot; Liu, Gaisheng; Parsekian, Andrew D; Reboulet, Edward C; Knobbe, Steve; Barrows, Mercer

    2016-01-01

    Nuclear magnetic resonance (NMR) logging provides a new means of estimating the hydraulic conductivity (K) of unconsolidated aquifers. The estimation of K from the measured NMR parameters can be performed using the Schlumberger-Doll Research (SDR) equation, which is based on the Kozeny-Carman equation and initially developed for obtaining permeability from NMR logging in petroleum reservoirs. The SDR equation includes empirically determined constants. Decades of research for petroleum applications have resulted in standard values for these constants that can provide accurate estimates of permeability in consolidated formations. The question we asked: Can standard values for the constants be defined for hydrogeologic applications that would yield accurate estimates of K in unconsolidated aquifers? Working at 10 locations at three field sites in Kansas and Washington, USA, we acquired NMR and K data using direct-push methods over a 10- to 20-m depth interval in the shallow subsurface. Analysis of pairs of NMR and K data revealed that we could dramatically improve K estimates by replacing the standard petroleum constants with new constants, optimal for estimating K in the unconsolidated materials at the field sites. Most significant was the finding that there was little change in the SDR constants between sites. This suggests that we can define a new set of constants that can be used to obtain high resolution, cost-effective estimates of K from NMR logging in unconsolidated aquifers. This significant result has the potential to change dramatically the approach to determining K for hydrogeologic applications. PMID:25810149

  8. Two dimensional solid state NMR

    This thesis illustrates, by discussing some existing and newly developed 2D solid state experiments, that two-dimensional NMR of solids is a useful and important extension of NMR techniques. Chapter 1 gives an overview of spin interactions and averaging techniques important in solid state NMR. As 2D NMR is already an established technique in solutions, only the basics of two dimensional NMR are presented in chapter 2, with an emphasis on the aspects important for solid spectra. The following chapters discuss the theoretical background and applications of specific 2D solid state experiments. An application of 2D-J resolved NMR, analogous to J-resolved spectroscopy in solutions, to natural rubber is given in chapter 3. In chapter 4 the anisotropic chemical shift is mapped out against the heteronuclear dipolar interaction to obtain information about the orientation of the shielding tensor in poly-(oxymethylene). Chapter 5 concentrates on the study of super-slow molecular motions in polymers using a variant of the 2D exchange experiment developed by us. Finally chapter 6 discusses a new experiment, 2D nutation NMR, which makes it possible to study the quadrupole interaction of half-integer spins. 230 refs.; 48 figs.; 8 tabs

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

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

    2011-03-01

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

  10. Flow units from integrated WFT and NMR data

    Kasap, E.; Altunbay, M.; Georgi, D.

    1997-08-01

    Reliable and continuous permeability profiles are vital as both hard and soft data required for delineating reservoir architecture. They can improve the vertical resolution of seismic data, well-to-well stratigraphic correlations, and kriging between the well locations. In conditional simulations, permeability profiles are imposed as the conditioning data. Variograms, covariance functions and other geostatistical indicators are more reliable when based on good quality permeability data. Nuclear Magnetic Resonance (NMR) logging and Wireline Formation Tests (WFT) separately generate a wealth of information, and their synthesis extends the value of this information further by providing continuous and accurate permeability profiles without increasing the cost. NMR and WFT data present a unique combination because WFTs provide discrete, in situ permeability based on fluid-flow, whilst NMR responds to the fluids in the pore space and yields effective porosity, pore-size distribution, bound and moveable fluid saturations, and permeability. The NMR permeability is derived from the T{sub 2}-distribution data. Several equations have been proposed to transform T{sub 2} data to permeability. Regardless of the transform model used, the NMR-derived permeabilities depend on interpretation parameters that may be rock specific. The objective of this study is to integrate WFT permeabilities with NMR-derived, T{sub 2} distribution-based permeabilities and thereby arrive at core quality, continuously measured permeability profiles. We outlined the procedures to integrate NMR and WFT data and applied the procedure to a field case. Finally, this study advocates the use of hydraulic unit concepts to extend the WFT-NMR derived, core quality permeabilities to uncored intervals or uncored wells.

  11. NMR for chemists and biologists

    Carbajo, Rodrigo J

    2013-01-01

    This book intends to be an easy and concise introduction to the field of nuclear magnetic resonance or NMR, which has revolutionized life sciences in the last twenty years. A significant part of the progress observed in scientific areas like Chemistry, Biology or Medicine can be ascribed to the development experienced by NMR in recent times. Many of the books currently available on NMR deal with the theoretical basis and some of its main applications, but they generally demand a strong background in Physics and Mathematics for a full understanding. This book is aimed to a wide scientific audie

  12. Annual reports on NMR spectroscopy

    Webb, Graham A; McCarthy, M J

    1995-01-01

    Over recent years, no other technique has grown to such importance as that of NMR spectroscopy. It is used in all branches of science where precise structural determination is required and where the nature of interactions and reactions in solution is being studied. Annual Reports on NMR Spectroscopy has established itself as a means for the specialist and non-specialist alike to become familiar with new applications of the technique in all branches of chemistry, including biochemistry, and pharmaceutics. This volume focuses on theoretical aspects of NMR nuclear shielding and on applications of

  13. Conventions and nomenclature for double diffusion encoding NMR and MRI

    Shemesh, Noam; Jespersen, Sune N; Alexander, Daniel C;

    2015-01-01

    , such as double diffusion encoding (DDE) NMR and MRI, may provide novel quantifiable metrics that are less easily inferred from conventional diffusion acquisitions. Despite the growing interest on the topic, the terminology for the pulse sequences, their parameters, and the metrics that can be derived...

  14. 25 T high resolution NMR magnet program and technology

    Markiewicz, W.D.; Dixon, I.R.; Eyssa, Y.M.; Schwartz, J.; Swenson, C.A.; Van Sciver, S.; Schneider-Muntau, H.J. [National High Magnetic Field Lab., Tallahassee, FL (United States)

    1996-07-01

    The program at the National High Magnetic Field Laboratory for the design and development of 1 GHz class NMR magnets is described. The parameters are given for a 1.066 GHz magnet incorporating an HTS inner coil. The design of the related wide bore 900 MHz conventional superconductor magnet is described. Aspects of the technology development program supporting these designs are presented.

  15. Integrative NMR for biomolecular research.

    Lee, Woonghee; Cornilescu, Gabriel; Dashti, Hesam; Eghbalnia, Hamid R; Tonelli, Marco; Westler, William M; Butcher, Samuel E; Henzler-Wildman, Katherine A; Markley, John L

    2016-04-01

    NMR spectroscopy is a powerful technique for determining structural and functional features of biomolecules in physiological solution as well as for observing their intermolecular interactions in real-time. However, complex steps associated with its practice have made the approach daunting for non-specialists. We introduce an NMR platform that makes biomolecular NMR spectroscopy much more accessible by integrating tools, databases, web services, and video tutorials that can be launched by simple installation of NMRFAM software packages or using a cross-platform virtual machine that can be run on any standard laptop or desktop computer. The software package can be downloaded freely from the NMRFAM software download page ( http://pine.nmrfam.wisc.edu/download_packages.html ), and detailed instructions are available from the Integrative NMR Video Tutorial page ( http://pine.nmrfam.wisc.edu/integrative.html ). PMID:27023095

  16. Optical pumping and xenon NMR

    Raftery, M.D.

    1991-11-01

    Nuclear Magnetic Resonance (NMR) spectroscopy of xenon has become an important tool for investigating a wide variety of materials, especially those with high surface area. The sensitivity of its chemical shift to environment, and its chemical inertness and adsorption properties make xenon a particularly useful NMR probe. This work discusses the application of optical pumping to enhance the sensitivity of xenon NMR experiments, thereby allowing them to be used in the study of systems with lower surface area. A novel method of optically-pumping [sup 129]Xe in low magnetic field below an NMR spectrometer and subsequent transfer of the gas to high magnetic field is described. NMR studies of the highly polarized gas adsorbed onto powdered samples with low to moderate surface areas are now possible. For instance, NMR studies of optically-pumped xenon adsorbed onto polyacrylic acid show that xenon has a large interaction with the surface. By modeling the low temperature data in terms of a sticking probability and the gas phase xenon-xenon interaction, the diffusion coefficient for xenon at the surface of the polymer is determined. The sensitivity enhancement afforded by optical pumping also allows the NMR observation of xenon thin films frozen onto the inner surfaces of different sample cells. The geometry of the thin films results in interesting line shapes that are due to the bulk magnetic susceptibility of xenon. Experiments are also described that combine optical pumping with optical detection for high sensitivity in low magnetic field to observe the quadrupoler evolution of 131 Xe spins at the surface of the pumping cells. In cells with macroscopic asymmetry, a residual quadrupolar interaction causes a splitting in the [sup 131]Xe NMR frequencies in bare Pyrex glass cells and cells with added hydrogen.

  17. Optical pumping and xenon NMR

    Raftery, M.D.

    1991-11-01

    Nuclear Magnetic Resonance (NMR) spectroscopy of xenon has become an important tool for investigating a wide variety of materials, especially those with high surface area. The sensitivity of its chemical shift to environment, and its chemical inertness and adsorption properties make xenon a particularly useful NMR probe. This work discusses the application of optical pumping to enhance the sensitivity of xenon NMR experiments, thereby allowing them to be used in the study of systems with lower surface area. A novel method of optically-pumping {sup 129}Xe in low magnetic field below an NMR spectrometer and subsequent transfer of the gas to high magnetic field is described. NMR studies of the highly polarized gas adsorbed onto powdered samples with low to moderate surface areas are now possible. For instance, NMR studies of optically-pumped xenon adsorbed onto polyacrylic acid show that xenon has a large interaction with the surface. By modeling the low temperature data in terms of a sticking probability and the gas phase xenon-xenon interaction, the diffusion coefficient for xenon at the surface of the polymer is determined. The sensitivity enhancement afforded by optical pumping also allows the NMR observation of xenon thin films frozen onto the inner surfaces of different sample cells. The geometry of the thin films results in interesting line shapes that are due to the bulk magnetic susceptibility of xenon. Experiments are also described that combine optical pumping with optical detection for high sensitivity in low magnetic field to observe the quadrupoler evolution of 131 Xe spins at the surface of the pumping cells. In cells with macroscopic asymmetry, a residual quadrupolar interaction causes a splitting in the {sup 131}Xe NMR frequencies in bare Pyrex glass cells and cells with added hydrogen.

  18. Optical pumping and xenon NMR

    Nuclear Magnetic Resonance (NMR) spectroscopy of xenon has become an important tool for investigating a wide variety of materials, especially those with high surface area. The sensitivity of its chemical shift to environment, and its chemical inertness and adsorption properties make xenon a particularly useful NMR probe. This work discusses the application of optical pumping to enhance the sensitivity of xenon NMR experiments, thereby allowing them to be used in the study of systems with lower surface area. A novel method of optically-pumping 129Xe in low magnetic field below an NMR spectrometer and subsequent transfer of the gas to high magnetic field is described. NMR studies of the highly polarized gas adsorbed onto powdered samples with low to moderate surface areas are now possible. For instance, NMR studies of optically-pumped xenon adsorbed onto polyacrylic acid show that xenon has a large interaction with the surface. By modeling the low temperature data in terms of a sticking probability and the gas phase xenon-xenon interaction, the diffusion coefficient for xenon at the surface of the polymer is determined. The sensitivity enhancement afforded by optical pumping also allows the NMR observation of xenon thin films frozen onto the inner surfaces of different sample cells. The geometry of the thin films results in interesting line shapes that are due to the bulk magnetic susceptibility of xenon. Experiments are also described that combine optical pumping with optical detection for high sensitivity in low magnetic field to observe the quadrupoler evolution of 131 Xe spins at the surface of the pumping cells. In cells with macroscopic asymmetry, a residual quadrupolar interaction causes a splitting in the 131Xe NMR frequencies in bare Pyrex glass cells and cells with added hydrogen

  19. Carbon-13 NMR studies of liquid crystals

    High resolution, proton decoupled 13C nmr are observed for a series of neat nematic liquid crystals, the p-alkoxyazoxybenzenes, and a smectic-A liquid crystal, diethylazoxydibenzoate in a magnetic field of 23 kG. The (uniaxial) order parameters S = less than P2(costheta) greater than are found to be about 0.4 and 0.9 for the nematic and smectic-A phase respectively at the clearing points. The order parameter increases with decreasing temperature in the nematic phase but is constant, or nearly so, with temperature in the smectic-A phase. In the nematic series studied, the ordering exhibits an even-odd alternation along the series and qualitative agreement with a recent theory due to Marcelja is found. In both phases, the spectra show that the molecule rotates rapidly about its long axis. Tentative conclusions about molecular conformational motion and 14N spin relaxation are presented for both nematic and smectic-A phases. In the smectic-A phase, the sample is rotated about an axis perpendicular to H0 and the resulting spectra are dicusssed. The theory of observed chemical shifts in liquid crystals is discussed and equations are derived which relate the nmr spectra of liquid-crystals to the order parameters. A model for the smectic-C phase due to Luz and Meiboom and Doane is described and lineshapes are determined on the basis of this model for special cases. The dependence of the order parameters on the molecular potential which give rise to the various degrees of order in the different liquid crystalline phases is examined. To a good approximation the functional dependence of the order parameters on the molecular potential is shown to be a simple one in the limit of small tilt angle in the smectic-C phase

  20. NMR studies of the mechanism of enzyme action

    No single technique can fully elucidate an enzyme mechanism. The authors' laboratory has therefore been using a number of methods, including NMR, to study two broad classes of enzyme-catalyzed reactions that are ubiquitous in biochemistry, namely, nucleophilic substitutions on phosphorus and the polarization of carbonyl groups. In this chapter the authors first discuss those parameters of NMR spectroscopy that are most useful in studying enzyme mechanisms. They then consider, with specific examples, the mechanisms of enzyme-catalyzed nucleophilic substitution on phosphorus, and enzyme-catalyzed carbonyl polarization reactions, including reactions of biotin

  1. Deriving NMR surface relaxivities, pore size distributions and water retention curves by NMR relaxation experiments on partially de-saturated rocks

    Mohnke, O.; Nordlund, C. L.; Klitzsch, N.

    2013-12-01

    Nuclear magnetic resonance (NMR) is a method used over a wide field of geophysical applications to non-destructively determine transport and storage properties of rocks and soils. In NMR relaxometry signal amplitudes correspond directly to the rock's fluid (water, oil) content. On the other hand the NMR relaxation behavior, i.e. the longitudinal (T1) and transverse (T2) NMR relaxation times, can be used to derive pore sizes and permeability as it is linearly linked to the pore's surface-to-volume-ratio and physiochemical properties of the rock-fluid interface by the surface relaxivity ρ_s This parameter, however, is dependent on the type and mineral constituents of the investigated rock sample and thus has to be determined and calibrated prior to estimating pore sizes from NMR relaxometry measurements. Frequently used methods to derive surface relaxivity to calibrate NMR pore sizes comprise mercury injection, pulsed field gradients (PFG-NMR) or grain size analysis. This study introduces an alternative approach to jointly estimate NMR surface relaxivity and pore radii distributions using NMR relaxation data obtained from partially de-saturated rocks. In this, inverse modeling is carried on a linked Young Laplace equation for capillary bundles and the Brownstein and Tarr equations. Subsequently, this approach is used to predict water retention curves of the investigated rocks. The method was tested and validated on simulated and laboratory transverse NMR data. Calculated inverse models are generally in a good agreement with results obtained from mercury injection and drainage measurements. Left: Measured and predicted water retention (pF) curves. Center: NMR relaxometry data, fit and error. Right: Mercury injection data (HgPor, dashed line) and jointly derived pore radii distributions and surface relaxivity by joint inverse modelling

  2. Medical applications of NMR imaging and NMR spectroscopy with stable isotopes. Summary

    The current status of NMR imaging and NMR spectroscopy are summarized. For the most part examples from the March 1983 Puerto Rico symposium are used to illustrate the utility of NMR in medicine. 18 refs., 5 figs

  3. Ligand screening by saturation-transfer difference (STD) NMR spectroscopy.

    Krishnan, V V

    2005-04-26

    NMR based methods to screen for high-affinity ligands have become an indispensable tool for designing rationalized drugs, as these offer a combination of good experimental design of the screening process and data interpretation methods, which together provide unprecedented information on the complex nature of protein-ligand interactions. These methods rely on measuring direct changes in the spectral parameters, that are often simpler than the complex experimental procedures used to study structure and dynamics of proteins. The goal of this review article is to provide the basic details of NMR based ligand-screening methods, with particular focus on the saturation transfer difference (STD) experiment. In addition, we provide an overview of other NMR experimental methods and a practical guide on how to go about designing and implementing them.

  4. Variable-temperature NMR and conformational analysis of Oenothein B

    Santos, Suzana C.; Carvalho, Ariadne G.; Fortes, Gilmara A.C.; Ferri, Pedro H.; Oliveira, Anselmo E. de, E-mail: suzana.quimica.ufg@hotmail.com [Universidade Federal de Goias (UFGO), Goiania, GO (Brazil). Instituto de Quimica

    2014-02-15

    Oenothein B is a dimeric hydrolyzable tannin with a wide range of biological activities, such as antitumour, anti-inflammatory and antiviral. Its nuclear magnetic resonance (NMR) at room temperature show duplications and broadening of signals. Experiments of 1D and 2D NMR at lower temperatures were useful for the complete NMR assignments of all hydrogens and carbons. The 3D structure of the most stable conformer was determined for the first time by nuclear Overhauser effect spectroscopy (NOESY) experiment (-20 deg C) and density functional theory (DFT)(B3LYP/6-31G)/ polarizable continuum model (PCM) quantum chemical calculations. The favoured conformation showed a highly compacted geometry and a lack of symmetry, in which the two valoneoyl groups showed distinct conformational parameters and stabilities. (author)

  5. NMRFx Processor: a cross-platform NMR data processing program.

    Norris, Michael; Fetler, Bayard; Marchant, Jan; Johnson, Bruce A

    2016-08-01

    NMRFx Processor is a new program for the processing of NMR data. Written in the Java programming language, NMRFx Processor is a cross-platform application and runs on Linux, Mac OS X and Windows operating systems. The application can be run in both a graphical user interface (GUI) mode and from the command line. Processing scripts are written in the Python programming language and executed so that the low-level Java commands are automatically run in parallel on computers with multiple cores or CPUs. Processing scripts can be generated automatically from the parameters of NMR experiments or interactively constructed in the GUI. A wide variety of processing operations are provided, including methods for processing of non-uniformly sampled datasets using iterative soft thresholding. The interactive GUI also enables the use of the program as an educational tool for teaching basic and advanced techniques in NMR data analysis. PMID:27457481

  6. NMR Dynamic Studies in Living Systems

    闫永彬; 范明杰; 罗雪春; 张日清

    2002-01-01

    Nuclear magnetic resonance (NMR) can noninvasively monitor the intracellular concentrations and kinetic properties of numerous inorganic and organic compounds. These characteristics have made NMR a useful tool for dynamic studies of living systems. Applications of NMR to living systems have successfully extended to many areas, including studies of metabolic regulation, ion transport, and intracellular reaction rates in vivo. The major purpose of this review is to summarize the results that can be obtained by modern NMR techniques in living systems. With the advances of new techniques, NMR measurements of various nuclides have been performed for specific physiological purposes. Although some technical problems still remain and there are still discrepancies between NMR and traditional biochemical results, the abundant and unique information obtained from NMR spectra suggests that NMR will be more extensively applied in future studies of living systems. The fast development of these new techniques is providing many new NMR applications in living systems, as well as in structural biology.

  7. Application of Solution NMR Spectroscopy to Study Protein Dynamics

    Christoph Göbl

    2012-03-01

    Full Text Available Recent advances in spectroscopic methods allow the identification of minute fluctuations in a protein structure. These dynamic properties have been identified as keys to some biological processes. The consequences of this structural flexibility can be far‑reaching and they add a new dimension to the structure-function relationship of biomolecules. Nuclear Magnetic Resonance (NMR spectroscopy allows the study of structure as well as dynamics of biomolecules in a very broad range of timescales at atomic level. A number of new NMR methods have been developed recently to allow the measurements of time scales and spatial fluctuations, which in turn provide the thermodynamics associated with the biological processes. Since NMR parameters reflect ensemble measurements, structural ensemble approaches in analyzing NMR data have also been developed. These new methods in some instances can even highlight previously hidden conformational features of the biomolecules. In this review we describe several solution NMR methods to study protein dynamics and discuss their impact on important biological processes.

  8. NMR signal analysis to attribute the components to the solid/liquid phases present in mixes and ice creams

    Mariette, F.; Lucas, T.

    2005-01-01

    The NMR relaxation signals from complex products like ice cream are hard to interpret because of the multi-exponential behaviour of the relaxation signal and the difficulty of attributing the NMR relaxation components to specific molecule fractions. An attribution of the NMR relaxation parameters is proposed, however, based on an approach that combines quantitative analysis of the spin-spin and spin-lattice relaxation times and the signal intensities with characterization of the ice cream com...

  9. Two-dimensional NMR spectrometry

    This article is the second in a two-part series. In part one (ANALYTICAL CHEMISTRY, May 15) the authors discussed one-dimensional nuclear magnetic resonance (NMR) spectra and some relatively advanced nuclear spin gymnastics experiments that provide a capability for selective sensitivity enhancements. In this article and overview and some applications of two-dimensional NMR experiments are presented. These powerful experiments are important complements to the one-dimensional experiments. As in the more sophisticated one-dimensional experiments, the two-dimensional experiments involve three distinct time periods: a preparation period, t0; an evolution period, t1; and a detection period, t2

  10. Advanced NMR characterization of zeolite catalysts

    Welsh, L. B.

    1985-04-01

    The program discussed in this report is a two-year two-phase joint UOP-University of Illinois study of the application of improved high resolution solid state nuclear magnetic resonance (NMR) techniques to the characterization of zeolite catalysts. During the first phase of this program very pure, and in some cases isotopically enriched faujasites will be prepared and studied by magic angle sample spinning NMR (MASS NMR) and variable engine sample spinning NMR (VASS NMR) on 500 and 360 MHz (proton frequency) NMR spectrometers. The NMR techniques that will be emphasized are the measurement and analysis of the (17)O NMR properties, (27)Al NMR intensity quantitation, and (27)Al and (29)Si NMR relaxation rates. During the second phase of this program these NMR techniques will be used to study the effects of impurity concentration, dealumination treatments and cation exchange on the NMR properties of faujasites. The initial emphasis of this program during Phase I is on the preparation and measurement of the NMR properties of (17)O enriched Na-Y faujasties.

  11. Pulsed zero field NMR of solids and liquid crystals

    This work describes the development and applications to solids and liquid crystals of zero field nuclear magnetic resonance (NMR) experiments with pulsed dc magnetic fields. Zero field NMR experiments are one approach for obtaining high resolution spectra of amorphous and polycrystalline materials which normally (in high field) display broad featureless spectra. The behavior of the spin system can be coherently manipulated and probed in zero field with dc magnetic field pulses which are employed in a similar manner to radiofrequency pulses in high field NMR experiments. Nematic phases of liquid crystalline systems are studied in order to observe the effects of the removal of an applied magnetic field on sample alignment and molecular order parameters. In nematic phases with positive and negative magnetic susceptibility anisotropies, a comparison between the forms of the spin interactions in high and low fields is made. High resolution zero field NMR spectra of unaligned smectic samples are also obtained and reflect the symmetry of the liquid crystalline environment. These experiments are a sensitive measure of the motionally induced asymmetry in biaxial phases. Homonuclear and heteronuclear solute spin systems are compared in the nematic and smectic phases. Nonaxially symmetric dipolar couplings are reported for several systems. The effects of residual fields in the presence of a non-zero asymmetry parameter are discussed theoretically and presented experimentally. Computer programs for simulations of these and other experimental results are also reported. 179 refs., 75 figs

  12. NMR relaxation times of trabecular bone—reproducibility, relationships to tissue structure and effects of sample freezing

    Prantner, Viktória; Isaksson, Hanna; Närväinen, Johanna; Lammentausta, Eveliina; Nissi, Mikko J.; Avela, Janne; Gröhn, Olli H. J.; Jurvelin, Jukka S.

    2010-12-01

    Nuclear magnetic resonance (NMR) spectroscopy provides a potential tool for non-invasive evaluation of the trabecular bone structure. The objective of this study was to determine the reproducibility of the NMR relaxation parameters (T2, Carr-Purcel-T2, T1ρ) for fat and water and relate those to the structural parameters obtained by micro-computed tomography (μCT). Especially, we aimed to evaluate the effect of freezing on the relaxation parameters. For storing bone samples, freezing is the standard procedure during which the biochemical and cellular organization of the bone marrow may be affected. Bovine trabecular bone samples were stored at -20 °C for 7 days and measured by NMR spectroscopy before and after freezing. The reproducibility of NMR relaxation parameters, as expressed by the coefficient of variation, ranged from 3.1% to 27.9%. In fresh samples, some correlations between NMR and structural parameters (Tb.N, Tb.Sp) were significant (e.g. the relaxation rate for T2 of fat versus Tb.Sp: r = -0.716, p NMR relaxation times but the correlations between relaxation parameters and the μCT structural parameters were not statistically significant after freezing, suggesting some nonsystematic alterations of the marrow structure. Therefore, the use of frozen bone samples for NMR relaxation studies may provide inferior information about the trabecular bone structure.

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

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

    1999-01-01

    The possibilities for application of low-field H-1 nuclear magnetic resonance (NMR) as a rapid method for simultaneous assessment of basic quality parameters in fish were explored. In a first experiment, 200 salmon (Salmo salar) samples mapping the variation over an entire fish were measured by NMR...... and subsequently analysed for oil or water content by standard chemical methods. In a second experiment, 58 differently thawed cod (Gadus morhua) samples were measured by NMR and subsequently analysed for water-holding capacity. Correlations between chemical data and NMR data were evaluated using.......9% for oil and water content in fresh salmon flesh and water-holding capacity in thawed cod flesh respectively. Thus rapid, non-invasive low- field NMR can be used to simultaneously determine both oil and water content of fish flesh. Furthermore, it can predict water- holding capacity of cod flesh, with...

  14. Dynamic NMR of nano- and microstructured materials

    Olaru, Maria Alexandra

    2013-07-01

    double quantum filtered SD experiments and including a series of bonds for and minimizing uncertainties in the estimation of essential parameters. Recently developed cement-in-polymer dispersions (c/p) with different compositions and cement to polymer ratios are investigated in Chapters 3 and 4, by a vast array of NMR techniques, that probe, on different length scales, the structure of the investigated specimens, as well as the dynamics of water transport inside the materials. Chapter 3 presents the results obtained using multinuclear solid state magic angle spinning NMR to probe, at nanometer level, the structure of cement-in-polymer dispersions. The hydration effects and crystallization of the inorganic matrix are probed by {sup 29}Si NMR while the chemical reactions of the organic phase are quantified by {sup 13}C cross-polarization; the results are correlated with data offered by other analysis techniques. The study of hydrated c/p is continued in Chapter 4, where proton NMR imaging is employed to obtain information about the microstructural changes which take place upon exposure to water at different temperatures. The water transport in the c/p matrix is monitored on line and the hydration phenomenon, together with information about the physical suffered by the samples are discussed with regard to polymer type, amount and curing conditions. A simple mathematical model of diffusion in a cylindrical system, involving time dependent diffusion coefficients and variable surface concentrations, is used to predict the manner in which the water amount inside the organic/cementitious pastes evolves in time. Further on, the effects of diffusive and advective transport in model and natural porous media are systematically investigated in Chapters 5 and 6. NMR exchange relaxometry is known as a very powerful tool for probing the structure and dynamics of fully or partially hydrated porous systems, but, until know, no information existed on how the effects of slow advective

  15. Radiofrequency and magnet technology in medical NMR

    Nuclear magnetic resonance (NMR) is briefly described, particularly its rf and magnet aspects. Particular attention is given to the duplexer, the rf coils, and new kinds of magnets for remote sensing NMR

  16. Push-through Direction Injectin NMR Automation

    Nuclear magnetic resonance (NMR) and mass spectrometry (MS) are the two major spectroscopic techniques successfully used in metabolomics studies. The non-invasive, quantitative and reproducible characteristics make NMR spectroscopy an excellent technique for detection of endogeno...

  17. A web-based database for EPR centers in semiconductors

    Umeda, T. [Graduate School of Library, Information, and Media Studies, Research Center for Knowledge Communities, University of Tsukuba, Tsukuba 305-8550 (Japan)]. E-mail: umeda@slis.tsukuba.ac.jp; Hagiwara, S. [Graduate School of Library, Information, and Media Studies, Research Center for Knowledge Communities, University of Tsukuba, Tsukuba 305-8550 (Japan); Katagiri, M. [Graduate School of Library, Information, and Media Studies, Research Center for Knowledge Communities, University of Tsukuba, Tsukuba 305-8550 (Japan); Mizuochi, N. [Graduate School of Library, Information, and Media Studies, Research Center for Knowledge Communities, University of Tsukuba, Tsukuba 305-8550 (Japan); Isoya, J. [Graduate School of Library, Information, and Media Studies, Research Center for Knowledge Communities, University of Tsukuba, Tsukuba 305-8550 (Japan)

    2006-04-01

    We develop a web-based database system for electron paramagnetic resonance (EPR) centers in semiconductors. This database is available to anyone at http://www.kc.tsukuba.ac.jp/div-media/epr/. It currently has more than 300 records of the spin-Hamiltonian parameters for major known EPR centers. One can upload own new records to the database or can use simulation tools powered by EPR-NMR(C). Here, we describe the features and objectives of this database, and mention some future plans.

  18. Growth and EPR properties of ErVO4 single crystals

    Leniec Grzegorz

    2015-07-01

    Full Text Available Single crystals of ErVO4 were grown by the Czochralski method under ambient pressure in a nitrogen atmosphere. Obtained crystals were transparent with strong pink coloring. Electron paramagnetic resonance (EPR spectra were recorded as a function of the applied magnetic field. Temperature and angular dependences of the EPR spectra of the samples in the 3–300 K temperature range were analyzed applying both Lorentzian––Gauss approximation for diluted medium and Dyson for dense magnetic medium. EPR-NMR program was done to find local symmetry and spin Hamiltonian parameters of erbium ions.

  19. High resolution NMR theory and chemical applications

    Becker, Edwin D

    1969-01-01

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

  20. Cancer metastasis detected by NMR

    A narrow NMR line originating from the plasma membrane of a cancer cell is unexpected. The behaviour of these lines is explained in terms of fundamental physics and chemistry. There is biochemical evidence to support the presence of neutral lipid domains in the plasma membrane. T2 relaxation and clinical implications are briefly discussed

  1. 95Mo nuclear magnetic resonance parameters of molybdenum hexacarbonyl from density functional theory: appraisal of computational and geometrical parameters.

    Cuny, Jérôme; Sykina, Kateryna; Fontaine, Bruno; Le Pollès, Laurent; Pickard, Chris J.; Gautier, Régis

    2011-01-01

    Solid-state (95)Mo nuclear magnetic resonance (NMR) properties of molybdenum hexacarbonyl have been computed using density functional theory (DFT) based methods. Both quadrupolar coupling and chemical shift parameters were evaluated and compared with parameters of high precision determined using single-crystal (95)Mo NMR experiments. Within a molecular approach, the effects of major computational parameters, i.e. basis set, exchange-correlation functional, treatment of relativity, have been e...

  2. Study of a Conformational Equilibrium of Lisinopril by HPLC, NMR, and DFT

    Bouabdallah, Sondes; Ben Dhia, Med Thaieb; Driss, Med Rida

    2014-01-01

    The isomerization of lisinopril has been investigated using chromatographic, NMR spectroscopic, and theoretical calculations. The NMR data, particularly the NOEDIFF experiments, show that the major species that was eluted first is the trans form. The proportion was 77% and 23% for the trans and cis, respectively. The thermodynamic parameters (ΔH, ΔS, and ΔG) were determined by varying the temperature in the NMR experiments. The interpretations of the experimental data were further supported by DFT/B3LYP calculations. PMID:24707291

  3. Mössbauer and NMR study of novel Tin(IV)-lactames

    N-tributylstannylated 2-pyrrolidinone was reacted with tributyltin triflate in different molar ratios and the complex formation monitored using 1H-NMR, 13C-NMR and 119Sn Mössbauer spectroscopy. Comparing the carbon NMR and tin Mössbauer results, a reaction scheme is suggested for the complexation which assumes the formation of a simultaneously O- and N-tributylstannylated pyrrolidinone cation. The formation of the only O-stannylated pyrrolidinone is also assumed to account for the non-constant Mössbauer parameters of the two tin environments in the distannylated pyrrolidinone cation when the ratio of tributyltin triflate is increased in the reaction.

  4. An AMBER/DYANA/MOLMOL Phosphorylated Amino Acid Library Set and Incorporation into NMR Structure Calculations

    Protein structure determination using Nuclear Magnetic Resonance (NMR) requires the use of molecular dynamics programs that incorporate both NMR experimental and implicit atomic data. Atomic parameters for each amino acid type are encoded in libraries used by structure calculation programs such as DYANA and AMBER. However, only a few non-standard amino acid library sets are included in these programs or the molecular visualization program MOLMOL. Our laboratory is calculating the phosphorylated and non-phosphorylated states of peptides and proteins using NMR methods. To calculate chemically correct structures, we have extended the available molecular libraries for these programs to include the modified amino acids phosphoserine, phosphothreonine, and phosphotyrosine

  5. Application progress of solid 29Si, 27Al NMR in the research of cement-based materials

    Background: The solid-state Nuclear Magnetic Resonance (NMR) is an effective method for the research of cement-based materials. Now it focuses on using solid 29Si and 27Al NMR to research the hydration structure of the cement-based materials in cement chemistry. Purpose: A theoretical guidance is proposed for solid 29Si and 27Al NMR technology used in cement chemistry research. Methods: We reviewed the application of solid 29Si and 27Al NMR in the cement-based materials and analyzed the problem among the researches. Results: This paper introduced an fundamental, relevant-conditions and basic parameters of NMR, and studied the technical parameters of solid 29Si and 27Ai NMR together with the relationship among the hydration structure of cement based material. Moreover, this paper reviewed the related domestic and overseas achievements in the research of hydration structure of the cement-based materials using solid 29Si and 27Al NMR. Conclusion: There were some problems in the research on cement-based materials by technology of solid 29Si and 27Al NMR. NMR will promote the Hydration theory of cement-based material greatly. (authors)

  6. New methodological approaches in solid-state NMR

    Full text: Spectacular advances in solid-state NMR methodology, instrumentation and sample preparation have made possible studies of structure and dynamics on increasingly complex molecular systems, such as proteins that cannot be investigated by X-ray, or solution-state NMR (amyloid fibrils, membrane proteins embedded in native environments, protein aggregates), other large biomolecular systems (DNA, RNA, carbohydrates), functionalized polymeric materials, selfassembled and inclusion molecular complexes, molecular nano-devices, etc. Many of these applications rely on the development of solid-state NMR techniques tailored to specifically address characteristic structural and dynamical features of larger and larger molecules, where often the dynamics of abundant spins, for instance, 1H, or 13C(15N) in uniformly labeled samples, represents a major challenge. To account for a broad range of multi-spin processes in such systems that may influence the efficiency of the proposed experimental scheme, or the reliability of the extracted parameters from the measured data, adequate theoretical tools are also highly desirable. In this context, here, we present some of our recent developments that address exactly these issues, namely: (i) elaboration of viable approaches for symbolic algebra computation of dynamics in extended spin networks, within a framework called SD-CAS (Spin Dynamics by Computer Algebra System), and (ii) development of new solid-state NMR methods for structural investigation of complex molecular systems. (author)

  7. NMR spin relaxation rates in the Heisenberg bilayer

    Mendes, Tiago; Curro, Nicholas; Scalettar, Richard; Paiva, Thereza; Dos Santos, Raimundo R.

    One of the striking features of heavy fermions is the fact that in the vicinity of a quantum phase transition these systems exhibit the breakdown of Fermi-liquid behavior and superconductivity. Nuclear magnetic resonance (NMR) expirements play an important role in the study of these phenomena. Measurements of NMR spin relaxation rates and Knight shift, for instance, can be used to probe the electronic spin susceptibility of these systems. Here we studied the NMR response of the Heisenberg bilayer model. In this model, it is well known that the increase of the interplane coupling between the planes, Jperp, supresses the antiferromagnetic order at a quantum critical point (QCP). We use stochastic series expansion (SSE) and the maximum-entropy analytic continuation method to calculate the NMR spin lattice relaxation rate 1 /T1 and the spin echo decay 1 /T2 G as function of Jperp. The spin echo decay, T2 G increases for small Jperp, due to the increase of the order parameter, and then vanishes abruptly in the QCP. The effects of Jperp dilution disorder in the QCP and the relaxation rates are also discussed. This research was supported by the NNSA Grant Number DE-NA 0002908, and Ciência sem fronteiras program/CNPQ.

  8. NMR Studies of Inclusion Compounds

    Nikkhou Aski, Sahar

    2008-01-01

    This thesis presents the application of some of the NMR methods in studying host-guest complexes, mainly in solution. The general focus of the work is on investigating the reorientational dynamics of some small molecules that are bound inside cavities of larger moieties. In the current work, these moieties belong to two groups: cryptophanes and cyclodextrins. Depending on the structure of the cavities, properties of the guest molecules and the formed complexes vary. Chloroform and dichloromet...

  9. Measurement of deformations by NMR

    Bytchenkoff, Dimitri; Rodts, Stéphane

    2015-12-01

    Two NMR data acquisition protocols together with corresponding data processing algorithms for locating macroscopic objects, measuring distances between them or monitoring their displacements or deformations with microscopic precision are presented and discussed. The performance of the methods is demonstrated by applying them to the measurement of deformations of a freely supported beam under loading. We believe that our methods will find their applications in mechanics, civil engineering and medicine.

  10. RECENT PROGRESS IN BIOMOLECULAR NMR

    2002-01-01

    @@ Structural genomics and proteomics were born from the understanding that functions of a protein are dictated by its 3D structure and dynamics. To understand protein functions on a genomic scale, we must know protein structures on a genomic scale. High resolution NMR can be used for this purpose. Traditional multidimensional NMR structure determination protocols become ineffective for structural genomics since to obtain a structure of a small protein of 15kD requires many months of painstaking spectral analysis and modeling. Recent advances in magnet and probe technology and in experimental methods have expanded the range of proteins amenable to structure determination and make the large scale structure determination possible. These advances are (1) effective expression systems for protein production, (2) introduction of cryoprobe, (3) structure determination with the use of the minimal amount of structural restraints obtained from the chemical shifts, residual dipolar couplings, NOEs, and computer modeling. In this talk,Iwill briefly outline these developments and related works done in our NMR lab.

  11. NMR-Based Milk Metabolomics

    Hanne C. Bertram

    2013-04-01

    Full Text Available Milk is a key component in infant nutrition worldwide and, in the Western parts of the world, also in adult nutrition. Milk of bovine origin is both consumed fresh and processed into a variety of dairy products including cheese, fermented milk products, and infant formula. The nutritional quality and processing capabilities of bovine milk is closely associated to milk composition. Metabolomics is ideal in the study of the low-molecular-weight compounds in milk, and this review focuses on the recent nuclear magnetic resonance (NMR-based metabolomics trends in milk research, including applications linking the milk metabolite profiling with nutritional aspects, and applications which aim to link the milk metabolite profile to various technological qualities of milk. The metabolite profiling studies encompass the identification of novel metabolites, which potentially can be used as biomarkers or as bioactive compounds. Furthermore, metabolomics applications elucidating how the differential regulated genes affects milk composition are also reported. This review will highlight the recent advances in NMR-based metabolomics on milk, as well as give a brief summary of when NMR spectroscopy can be useful for gaining a better understanding of how milk composition is linked to nutritional or quality traits.

  12. NMR-Based Milk Metabolomics.

    Sundekilde, Ulrik K; Larsen, Lotte B; Bertram, Hanne C

    2013-01-01

    Milk is a key component in infant nutrition worldwide and, in the Western parts of the world, also in adult nutrition. Milk of bovine origin is both consumed fresh and processed into a variety of dairy products including cheese, fermented milk products, and infant formula. The nutritional quality and processing capabilities of bovine milk is closely associated to milk composition. Metabolomics is ideal in the study of the low-molecular-weight compounds in milk, and this review focuses on the recent nuclear magnetic resonance (NMR)-based metabolomics trends in milk research, including applications linking the milk metabolite profiling with nutritional aspects, and applications which aim to link the milk metabolite profile to various technological qualities of milk. The metabolite profiling studies encompass the identification of novel metabolites, which potentially can be used as biomarkers or as bioactive compounds. Furthermore, metabolomics applications elucidating how the differential regulated genes affects milk composition are also reported. This review will highlight the recent advances in NMR-based metabolomics on milk, as well as give a brief summary of when NMR spectroscopy can be useful for gaining a better understanding of how milk composition is linked to nutritional or quality traits. PMID:24957988

  13. Structural proteomics by NMR spectroscopy.

    Shin, Joon; Lee, Woonghee; Lee, Weontae

    2008-08-01

    Structural proteomics is one of the powerful research areas in the postgenomic era, elucidating structure-function relationships of uncharacterized gene products based on the 3D protein structure. It proposes biochemical and cellular functions of unannotated proteins and thereby identifies potential drug design and protein engineering targets. Recently, a number of pioneering groups in structural proteomics research have achieved proof of structural proteomic theory by predicting the 3D structures of hypothetical proteins that successfully identified the biological functions of those proteins. The pioneering groups made use of a number of techniques, including NMR spectroscopy, which has been applied successfully to structural proteomics studies over the past 10 years. In addition, advances in hardware design, data acquisition methods, sample preparation and automation of data analysis have been developed and successfully applied to high-throughput structure determination techniques. These efforts ensure that NMR spectroscopy will become an important methodology for performing structural proteomics research on a genomic scale. NMR-based structural proteomics together with x-ray crystallography will provide a comprehensive structural database to predict the basic biological functions of hypothetical proteins identified by the genome projects. PMID:18761469

  14. Measurements of Boar Spermatozoa Motility Using PFG NMR Method

    The evaluation of spermatozoa motility, viability and morphology is an essential parameter in the examination of sperm quality and in the establishment of correlations between sperm quality and fertility. Until now, assessment of sperm quality has been based on subjective evaluation of parameters, such as motility and viability, and on objective parameters, such as semen concentration and morphology abnormalities. When subjective optical microscopic evaluation was used in humans and animals, variations of 30 to 60% have been reported in the estimation of the motility parameters of the same ejaculates. To overcome this variability, different systems have been proposed such as turbidimetry, laser-Doppler spectroscopy, and photometric methods. Other accurate techniques, such as flow cytometry, which allows the evaluation of concentration, and cellulose-acetate/nitrate filter measure only a single semen parameter. The more recent track semen analysis system, based on individual spermatozoon evaluation, offers an accurate calculation of different semen parameters. Although some interesting results have already been obtained, many questions remain, which have to be answered to allow for further development in veterinary medicine, clinical fertility settings, physiological, and toxicology research activities. Pulsed field gradient nuclear magnetic resonance (PFG NMR) techniques have been presented demonstrating the potential to study flow and transport processes in complex systems. By PFG NMR, the molecular displacement can be measured that occurs during a time interval D, between two consecutive magnetic field gradient pulses. In this poster we present the results of PFG-NMR obtained for a number of samples of boar spermatozoa with varying motility and discuss whether this method can be useful for fast and reliable spermatozoa motility evaluation. (author)

  15. Insight into sodium silicate glass structural organization by multinuclear NMR combined with first-principles calculations

    Short and medium range order of silica and sodium silicate glasses have been investigated from a quantitative analysis of 29Si MAS NMR and 23Na, 17O MQMAS NMR spectra. The method described enables the extraction of the underlying 17O NMR parameter distributions of bridging oxygens (BOs) and non-bridging oxygens (NBOs), and yields site populations which are confirmed by 29Si NMR data. The extracted NMR parameter distributions and their variations with respect to the glass chemical composition can then be analyzed in terms of local structural features (bond angles and bond lengths, coordination numbers) with the help of molecular dynamics simulations combined with first-principles calculations of NMR parameters. Correlations of relevant structural parameters with 23Na, 29Si and 17O NMR interactions (isotropic chemical shift δ(iso), quadrupolar coupling constant C(Q) and quadrupolar asymmetry parameter ηQ are re-examined and their applicability is discussed. These data offer better insights into the structural organization of the glass network, including both chemical and topological disorder. Adding sodium to pure silica significantly diminishes the Si-O-Si bond angles and leads to a longer mean Si-O bond length with a slight decrease of the mean Na-O bond length. Moreover, the present data are in favor of a homogeneous distribution of Na around both oxygen species in the silicate network. Finally, our approach was found to be sensitive enough to investigate the effect of addition of a small quantity of molybdenum oxide (about 1 mol%) on the 17O MAS spectrum, opening new possibilities for investigating the Mo environment in silicate glasses. (authors)

  16. A theoretical study of the stationary structures of the methane surface with special emphasis on NMR properties

    Alkorta, Ibon; Elguero, José

    2010-04-01

    The seven stationary points of the methane hypersurface were first explored concerning geometries and energies to check previous data. On these geometries, absolute 1H and 13C NMR shieldings as well as 1J(CH) and 2J(HH) coupling constants were calculated. The results show important variations in the NMR parameters depending on the stationary point considered. Relationships have been found between the 1H and 13C shieldings and between these NMR parameters and the relative energy of the different species.

  17. Computational Analysis of Solvent Effects in NMR Spectroscopy.

    Dračínský, Martin; Bouř, Petr

    2010-01-12

    Solvent modeling became a standard part of first principles computations of molecular properties. However, a universal solvent approach is particularly difficult for the nuclear magnetic resonance (NMR) shielding and spin-spin coupling constants that in part result from collective delocalized properties of the solute and the environment. In this work, bulk and specific solvent effects are discussed on experimental and theoretical model systems comprising solvated alanine zwitterion and chloroform molecules. Density functional theory computations performed on larger clusters indicate that standard dielectric continuum solvent models may not be sufficiently accurate. In some cases, more reasonable NMR parameters were obtained by approximation of the solvent with partial atomic charges. Combined cluster/continuum models yielded the most reasonable values of the spectroscopic parameters, provided that they are dynamically averaged. The roles of solvent polarizability, solvent shell structure, and bulk permeability were investigated. NMR shielding values caused by the macroscopic solvent magnetizability exhibited the slowest convergence with respect to the cluster size. For practical computations, however, inclusion of the first solvation sphere provided satisfactory corrections of the vacuum values. The simulations of chloroform chemical shifts and CH J-coupling constants were found to be very sensitive to the molecular dynamics model used to generate the cluster geometries. The results show that computationally efficient solvent modeling is possible and can reveal fine details of molecular structure, solvation, and dynamics. PMID:26614339

  18. Quality assessment of protein NMR structures

    Rosato A.; Montelione G.T.; Tejero R.

    2013-01-01

    Biomolecular NMR structures are now routinely used in biology, chemistry, and bioinformatics. Methods and metrics for assessing the accuracy and precision of protein NMR structures are beginning to be standardized across the biological NMR community. These include both knowledge-based assessment metrics, parameterized from the database of protein structures, and model versus data assessment metrics. On line servers are available that provide comprehensive protein structure quality assessment ...

  19. NMR INVESTIGATIONS OF HYDROGENATED AMORPHOUS SILICON

    J. Reimer

    1981-01-01

    A review is presented of the N.M.R. (Nuclear Magnetic Resonance) studies to date of hydrogenated amorphous silicon-hydrogen films. Structural features of proton N.M.R. lineshapes, dynamics of hydrogen containing defect sites, and the promise of quantitative determinations of local silicon-hydrogen bonding environments are discussed in detail. Finally, some comments are given on future directions for N.M.R. studies of hydrogenated thin films.

  20. An Inversion Recovery NMR Kinetics Experiment

    Williams, Travis J.; Kershaw, Allan D.; Li, Vincent; Wu, Xinping

    2011-01-01

    A convenient laboratory experiment is described in which NMR magnetization transfer by inversion recovery is used to measure the kinetics and thermochemistry of amide bond rotation. The experiment utilizes Varian spectrometers with the VNMRJ 2.3 software, but can be easily adapted to any NMR platform. The procedures and sample data sets in this article will enable instructors to use inversion recovery as a laboratory activity in applied NMR classes and provide research students with a conveni...

  1. NMR studies of isotopically labeled RNA

    Pardi, A. [Univ. of Colorado, Boulder, CO (United States)

    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.

  2. NMR exposure sensitizes tumor cells to apoptosis.

    Ghibelli, L; Cerella, C; Cordisco, S; Clavarino, G; Marazzi, S; De Nicola, M; Nuccitelli, S; D'Alessio, M; Magrini, A; Bergamaschi, A; Guerrisi, V; Porfiri, L M

    2006-03-01

    NMR technology has dramatically contributed to the revolution of image diagnostic. NMR apparatuses use combinations of microwaves over a homogeneous strong (1 Tesla) static magnetic field. We had previously shown that low intensity (0.3-66 mT) static magnetic fields deeply affect apoptosis in a Ca2+ dependent fashion (Fanelli et al., 1999 FASEBJ., 13;95-102). The rationale of the present study is to examine whether exposure to the static magnetic fields of NMR can affect apoptosis induced on reporter tumor cells of haematopoietic origin. The impressive result was the strong increase (1.8-2.5 fold) of damage-induced apoptosis by NMR. This potentiation is due to cytosolic Ca2+ overload consequent to NMR-promoted Ca2+ influx, since it is prevented by intracellular (BAPTA-AM) and extracellular (EGTA) Ca2+ chelation or by inhibition of plasma membrane L-type Ca2+ channels. Three-days follow up of treated cultures shows that NMR decrease long term cell survival, thus increasing the efficiency of cytocidal treatments. Importantly, mononuclear white blood cells are not sensitised to apoptosis by NMR, showing that NMR may increase the differential cytotoxicity of antitumor drugs on tumor vs normal cells. This strong, differential potentiating effect of NMR on tumor cell apoptosis may have important implications, being in fact a possible adjuvant for antitumor therapies. PMID:16528477

  3. Spin-Exchange Pumped NMR Gyros

    Walker, Thad G

    2016-01-01

    We present the basic theory governing spin-exchange pumped NMR gyros. We review the basic physics of spin-exchange collisions and relaxation as they pertain to precision NMR. We present a simple model of operation as an NMR oscillator and use it to analyze the dynamic response and noise properties of the oscillator. We discuss the primary systematic errors (differential alkali fields, quadrupole shifts, and offset drifts) that limit the bias stability, and discuss methods to minimize them. We give with a brief overview of a practical implementation and performance of an NMR gyro built by Northrop-Grumman Corporation, and conclude with some comments about future prospects.

  4. Advance reservoir evaluation by using NMR logging

    Based on brief explanation of the measurement principle for nuclear magnetic resonance (NMR) logging, this paper illustrates the importance of NMR logging in reservoir evaluation through typical case examples. These case examples include: Reservoir characterization and productivity evaluation by using NMR logging, determination of reservoir porosity in complex lithology, identification of oil, water and gas zones under complex reservoir conditions where resistivity log data give poor indication, guiding the implementation of completion and drilling programs, etc. Excellent application results indicate that NMR logging has its special features and advantages in comparison with conventional logging techniques. It is a very practical and very promising logging technology

  5. NMR characterization of pituitary tumors

    Twelve patients (5 male, 7 female, mean age 37.9 +- 20) with pituitary tumors were extensively evaluated with NMR imaging using a 1.5K gauss resistive magnet. Saturation recovery (SR), inversion recovery (IR) and spin echo (SE) pulse sequences were used for qualitative characterization of the lesions. T/sub 1/ calculations were also performed for brain and pituitary. Tumor histology and endocrine status were correlated with NMR data. All tumors were large with suprasellar extension (6 with prolactin secretion, 6 without). Pituitary T/sub 1/'s ranged from .2 to .64, the mean T/sub 1/ being longer than that of brain (Brain = .4 +- .04; Pit = .48 +- .14). 3 patients with histological evidence of homogeneous adenomas had long T/sub 1/'s (0.58 +- .05). 3 patients with evidence of recent or old hemorhage into the pituitary had much shorter T/sub 1/'s (0.29 +- .12). There was no relationship between prolactin secretion and T/sub 1/. Qualitative T/sub 1/ and T/sub 2/ information can be obtained by using a combination of SR, IR, and SE images. Using this method in the patients, homogeneous adenomas had similar T/sub 1/'s and longer T/sub 2/'s compared to the brain, while patients with bleeds had shorter T/sub 1/'s and T/sub 2/'s. Image T/sub 1/ characteristics correlated well with the calculated T/sub 1/ values. The range of T/sub 1/ (and potentially T/sub 2/) values which occur in apparently similar lesions are most likely due to anatomical and pathophysiological variations in these lesions. It may be ultimately possible to separate different types of pathological processes based on NMR image T/sub 1/ and T/sub 2/ characteristics after careful comparative studies of NMR and histological data are completed. The combination of calculated T/sub 1/ and T/sub 2/ with image T/sub 1/ and T/sub 2/ information may also be useful in further characterization of lesions

  6. NMR investigation of Ag nanoparticles

    Son, Kwanghyo; Jang, Zeehoon

    2013-01-01

    109Ag nuclear magnetic resonance (NMR) and relaxation measurements have been performed on two powder samples of Ag nanoparticles with average sizes of 20 nm and 80 nm. The measurements have been done in an external field of 9.4 T and in the temperature range 10 K Knight shift ( K) and the nuclear spin-lattice relaxation rate (1/ T 1) are observed to be almost identical to the values reported for the bulk Ag metal, whereby the Korringa ratio R(= K 2 T 1 T/S) is found to be 2.0 for both samples in the investigated temperature range.

  7. 13C NMR studies of the molecular flexibility of antidepressants

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

  8. The fluorescence properties and NMR analysis of protopine and allocryptopine

    The fluorescence properties of protopine and allocryptopine in aqueous and organic environments are described for the first time. The fluorescence of alkaloids and their pH-dependent interconversion to cationic forms (transannular interaction) were studied using steady-state and time-resolved fluorescence techniques. For the analysis of tricyclic base and cis/trans tetracyclic cations of the alkaloids, NMR and X-ray crystallography were used. - Highlights: → We describe fundamental fluorescence characteristics of alkaloids protopine and allocryptopine. → We analyzed the pH-dependent transitions and cis/trans isomerization. → These two alkaloids can be better distinguished by their fluorescence decay characteristics. → The fluorescence parameters are related to the NMR and crystallographic structural data.

  9. The fluorescence properties and NMR analysis of protopine and allocryptopine

    Kubala, Martin, E-mail: mkubala@prfnw.upol.c [Department of Biophysics, Faculty of Science, Palacky University, tr. 17. listopadu 12, CZ-77146 Olomouc (Czech Republic); Vacek, Jan [Department of Medical Chemistry and Biochemistry, Faculty of Medicine and Dentistry, Palacky University, Hnevotinska 3, CZ-77515 Olomouc (Czech Republic); Popa, Igor [Department of Inorganic Chemistry, Faculty of Science, Palacky University, tr. 17. listopadu 12, CZ-77146 Olomouc (Czech Republic); Janovska, Marika [Department of Biophysics, Faculty of Science, Palacky University, tr. 17. listopadu 12, CZ-77146 Olomouc (Czech Republic); Kosina, Pavel; Ulrichova, Jitka [Department of Medical Chemistry and Biochemistry, Faculty of Medicine and Dentistry, Palacky University, Hnevotinska 3, CZ-77515 Olomouc (Czech Republic); Travnicek, Zdenek [Department of Inorganic Chemistry, Faculty of Science, Palacky University, tr. 17. listopadu 12, CZ-77146 Olomouc (Czech Republic); Simanek, Vilim [Department of Medical Chemistry and Biochemistry, Faculty of Medicine and Dentistry, Palacky University, Hnevotinska 3, CZ-77515 Olomouc (Czech Republic)

    2011-07-15

    The fluorescence properties of protopine and allocryptopine in aqueous and organic environments are described for the first time. The fluorescence of alkaloids and their pH-dependent interconversion to cationic forms (transannular interaction) were studied using steady-state and time-resolved fluorescence techniques. For the analysis of tricyclic base and cis/trans tetracyclic cations of the alkaloids, NMR and X-ray crystallography were used. - Highlights: {yields} We describe fundamental fluorescence characteristics of alkaloids protopine and allocryptopine. {yields} We analyzed the pH-dependent transitions and cis/trans isomerization. {yields} These two alkaloids can be better distinguished by their fluorescence decay characteristics. {yields} The fluorescence parameters are related to the NMR and crystallographic structural data.

  10. Field Experiment Provides Ground Truth for Surface NMR Measurement

    Knight, R. J.; Abraham, J. D.; Cannia, J. C.; Dlubac, K. I.; Grau, B.; Grunewald, E. D.; Irons, T.; Song, Y.; Walsh, D.

    2010-12-01

    Effective and sustainable long-term management of fresh water resources requires accurate information about the availability of water in groundwater aquifers. Proton Nuclear Magnetic Resonance (NMR) can provide a direct link to the presence of water in the pore space of geological materials through the detection of the nuclear magnetization of the hydrogen nuclei (protons) in the pore water. Of interest for groundwater applications is the measurement of the proton-NMR relaxation time constant, referred to as T2. This parameter is sensitive to the geometry of the water-filled pore space and can be related to the hydraulic conductivity. NMR logging instruments, which have been available since the 1980’s, provide direct measurements of T2 in boreholes. Surface NMR (SNMR) is a non-invasive geophysical method that uses a loop of wire on the surface to probe the NMR properties of groundwater aquifers to a depth of ~100 m, without the need for the drilling of boreholes. SNMR provides reliable measurements of a different NMR time constant referred to as T2*, that is related to, but not necessarily equivalent to, T2. The relationship between T2* and T2 is likely to depend upon the physical environment and the composition of the sampled material. In order to advance the use of SNMR as a non-invasive means of characterizing groundwater aquifers, we must answer the fundamental question: When probing a groundwater aquifer, what information is provided by T2*, the time constant measured with SNMR? Our approach was to conduct a field experiment in Nebraska, in an area underlain by the Quaternary Alluvium and Tertiary Ogallala aquifers. We first used SNMR to obtain a 1D profile of T2* to a depth of ~60 m. We then drilled a well inside the area of the SNMR loop, to a depth of ~150 m, and used the drill cuttings to describe the composition of the geologic material at the site. The borehole was kept open for 2 days to acquire logging NMR T2 measurements over the total depth. Three

  11. EPR spectroscopy of a family of Cr(III) 7M(II) (M = Cd, Zn, Mn, Ni) "wheels": studies of isostructural compounds with different spin ground states

    Piligkos, Stergios; Weihe, Høgni; Bill, Eckhard;

    2009-01-01

    Spinning wheels: The presented highly resolved multifrequency continuous wave EPR spectra (e.g., see figure) of the heterooctametalic "wheels" Cr(7)M provide rare examples of high nuclearity polymetallic systems where detailed information on the spin-Hamiltonian parameters of the ground and excit...... to 10(5) by use of the Davidson algorithm. We show that transferability of spin-Hamiltonian parameters across complexes of the Cr(7)M family is possible and that the spin-Hamiltonian parameters of Cr(7)M do not have sharply defined values, but are rather distributed around a mean value....

  12. A Guided Inquiry Approach to NMR Spectroscopy

    Parmentier, Laura E.; Lisensky, George C.; Spencer, Brock

    1998-04-01

    We present a novel way to introduce NMR spectroscopy into the general chemistry curriculum as part of a week-long aspirin project in our one-semester introductory course. Aspirin is synthesized by reacting salicylic acid and acetic anhydride. Purity is determined by titration and IR and NMR spectroscopy. Students compare IR and NMR spectra of their aspirin product to a series of reference spectra obtained by the class. Students are able to interpret the IR spectra of their aspirin using IR data from previous experiments. NMR is introduced by having students collect 1H NMR spectra of a series of reference compounds chosen to include some of the structural features of aspirin and compare spectra and structures of the reference compounds to develop a correlation chart for chemical shifts. This process is done in small groups using shared class data and is guided by a series of questions designed to relate the different kinds of hydrogen atoms to number and position of peaks in the NMR spectrum. Students then identify the peaks in the NMR spectrum of their aspirin product and relate percent purity by titration with spectral results and percent yield. This is an enjoyable project that combines the synthesis of a familiar material with a guided inquiry-based introduction to NMR spectroscopy.

  13. NMR spectra of phosphorus 17O esters

    By the 17O NMR method the authors investigated methyl, ethyl, isopropyl, tert-butyl, and phenyl ethylene phosphites; methyl, ethyl, and isopropyl trimethylene phosphites; and methyl, ethyl, isopropyl, and tert-butyl o-phenylene phosphites. They also determined the 13C and 31P NMR spectra of these compounds

  14. 2D NMR studies of biomolecules

    The work described in this thesis comprises two related subjects. The first part describes methods to derive high-resolution structures of proteins in solution using two-dimensional (2-D) NMR. The second part describes 2-D NMR studies on the interaction between proteins and DNA. (author). 261 refs.; 52 figs.; 23 tabs

  15. NMR Spectroscopy and Its Value: A Primer

    Veeraraghavan, Sudha

    2008-01-01

    Nuclear magnetic resonance (NMR) spectroscopy is widely used by chemists. Furthermore, the use of NMR spectroscopy to solve structures of macromolecules or to examine protein-ligand interactions is popular. Yet, few students entering graduate education in biological sciences have been introduced to this method or its utility. Over the last six…

  16. An Inversion Recovery NMR Kinetics Experiment

    Williams, Travis J.; Kershaw, Allan D.; Li, Vincent; Wu, Xinping

    2011-01-01

    A convenient laboratory experiment is described in which NMR magnetization transfer by inversion recovery is used to measure the kinetics and thermochemistry of amide bond rotation. The experiment utilizes Varian spectrometers with the VNMRJ 2.3 software, but can be easily adapted to any NMR platform. The procedures and sample data sets in this…

  17. Using Cloud Storage for NMR Data Distribution

    Soulsby, David

    2012-01-01

    An approach using Google Groups as method for distributing student-acquired NMR data has been implemented. We describe how to configure NMR spectrometer software so that data is uploaded to a laboratory section specific Google Group, thereby removing bottlenecks associated with printing and processing at the spectrometer workstation. Outside of…

  18. Early history of NMR at Los Alamos

    Nuclear magnetic resonance (NMR) spectroscopy has developed into an important research tool in chemistry. More recently, NMR imaging and in vivo spectroscopy promise to produce a revolution in medicine and biochemistry. Early experiments at Los Alamos led to DOE programs involving stable isotopes of importance to biology and to medicine. These events are briefly recounted. 2 refs

  19. Carbon-13 NMR spectroscopy of biological systems

    Beckmann, Nicolau

    1995-01-01

    This book is intended to provide an in-depth understanding of 13C NMR as a tool in biological research. 13C NMR has provided unique information concerning complex biological systems, from proteins and nucleic acids to animals and humans. The subjects addressed include multidimensional heteronuclear techniques for structural studies of molecules in the liquid and solid states, the investigation of interactions in model membranes, the elucidation of metabolic pathwaysin vitro and in vivo on animals, and noninvasive metabolic studies performed on humans. The book is a unique mix of NMR methods and biological applications which makes it a convenient reference for those interested in research in this interdisciplinary area of physics, chemistry, biology, and medicine.Key Features* An interdisciplinary text with emphasis on both 13C NMR methodology and the relevant biological and biomedical issues* State-of-the-art 13C NMR techniques are described; Whenever possible, their advantages over other approaches are empha...

  20. Parameter Estimation

    Sales-Cruz, Mauricio; Heitzig, Martina; Cameron, Ian;

    2011-01-01

    In this chapter the importance of parameter estimation in model development is illustrated through various applications related to reaction systems. In particular, rate constants in a reaction system are obtained through parameter estimation methods. These approaches often require the application...... of optimisation techniques coupled with dynamic solution of the underlying model. Linear and nonlinear approaches to parameter estimation are investigated. There is also the application of maximum likelihood principles in the estimation of parameters, as well as the use of orthogonal collocation to...... generate a set of algebraic equations as the basis for parameter estimation.These approaches are illustrated using estimations of kinetic constants from reaction system models....

  1. Applications of NMR spectroscopy to systems biochemistry.

    Fan, Teresa W-M; Lane, Andrew N

    2016-02-01

    The past decades of advancements in NMR have made it a very powerful tool for metabolic research. Despite its limitations in sensitivity relative to mass spectrometric techniques, NMR has a number of unparalleled advantages for metabolic studies, most notably the rigor and versatility in structure elucidation, isotope-filtered selection of molecules, and analysis of positional isotopomer distributions in complex mixtures afforded by multinuclear and multidimensional experiments. In addition, NMR has the capacity for spatially selective in vivo imaging and dynamical analysis of metabolism in tissues of living organisms. In conjunction with the use of stable isotope tracers, NMR is a method of choice for exploring the dynamics and compartmentation of metabolic pathways and networks, for which our current understanding is grossly insufficient. In this review, we describe how various direct and isotope-edited 1D and 2D NMR methods can be employed to profile metabolites and their isotopomer distributions by stable isotope-resolved metabolomic (SIRM) analysis. We also highlight the importance of sample preparation methods including rapid cryoquenching, efficient extraction, and chemoselective derivatization to facilitate robust and reproducible NMR-based metabolomic analysis. We further illustrate how NMR has been applied in vitro, ex vivo, or in vivo in various stable isotope tracer-based metabolic studies, to gain systematic and novel metabolic insights in different biological systems, including human subjects. The pathway and network knowledge generated from NMR- and MS-based tracing of isotopically enriched substrates will be invaluable for directing functional analysis of other 'omics data to achieve understanding of regulation of biochemical systems, as demonstrated in a case study. Future developments in NMR technologies and reagents to enhance both detection sensitivity and resolution should further empower NMR in systems biochemical research. PMID:26952191

  2. NMR-based milk metabolomics

    Sundekilde, Ulrik; Larsen, Lotte Bach; Bertram, Hanne Christine S.

    2013-01-01

    Milk is a key component in infant nutrition worldwide and, in the Western parts of the world, also in adult nutrition. Milk of bovine origin is both consumed fresh and processed into a variety of dairy products including cheese, fermented milk products, and infant formula. The nutritional quality...... and processing capabilities of bovine milk is closely associated to milk composition. Metabolomics is ideal in the study of the low-molecular-weight compounds in milk, and this review focuses on the recent nuclear magnetic resonance (NMR)-based metabolomics trends in milk research, including...... applications linking the milk metabolite profiling with nutritional aspects, and applications which aim to link the milk metabolite profile to various technological qualities of milk. The metabolite profiling studies encompass the identification of novel metabolites, which potentially can be used as biomarkers...

  3. NMR of small solutes in liquid crystals and molecular sieves

    Ylihautala, Mika Petri

    The present thesis deals with the nuclear magnetic resonance (NMR) spectroscopy of small solutes applied to the studies of liquid crystals and molecular sieves. In this method, changes induced by the investigated environment to the static spectral parameters (i.e. nuclear shielding, indirect and direct spin-spin coupling and quadrupole coupling) of the solute are measured. The nuclear shielding of dissolved noble gases is utilized for the studies of thermotropic liquid crystals. The relation between the symmetry properties of mesophases and the nuclear shielding is described. The different interaction mechanisms perturbing the observed noble gas nuclear shielding are discussed, particularly, the role of long-range attractive van der Waals interactions is brought out. The suitability of the noble gas NMR spectroscopy to the studies of Iyotropic liquid crystals is investigated in terms of nuclear shielding and quadrupole coupling interactions. In molecular sieve systems, the effect of inter- and intracrystalline motions of solutes on their NMR spectra is discussed. A novel method for the measurement of the intracrystalline motions is developed. The distinctions in the 13C shielding of methane adsorbed in AlPO4-11 and SAPO-11, two structurally similar molecular sieves differing in composition, are indicated.

  4. 1H NMR spectroscopic identification of a glue sniffing biomarker.

    Kwon, Bobae; Kim, Siwon; Kim, Sosun; Lee, Dong-Kye; Park, Yu-Jin; Kim, Myung-Duck; Lee, Jae-Shin; Kim, Suhkmann

    2011-06-15

    Organic solvent abuse typically involves sniffing organic solvents to experience the mind-altering conditions they induce. In Republic of Korea, organic solvent abuse is a serious social problem, especially among teenagers. Several studies have addressed the effects of organic solvent abuse on mind and body, but there are no simple methods by which such abuse can be positively identified. In this report, we describe a method for analyzing toluene metabolites (toluene is the main ingredient of glue) in glue-sniffers' urine using (1)H NMR spectroscopy. Toluene is a commonly used solvent in the rubber, paint, plastics, leather, printing, and chemical industries. Inhaled toluene is metabolized to hippuric acid in the liver and excreted in the urine. Hippuric acid is known as a good biomarker for biological monitoring of toluene exposure. We have scanned hippuric acid and other toluene metabolites by NMR spectroscopy and performed statistical multivariate analysis of the data. Based on this analysis, we sought to determine parameters by which glue-sniffing (toluene inhalation) behavior may be verified. We also demonstrate the use of a pattern recognition method for accurate and efficient analysis of NMR data. In comparison to conventional methods, such as mass spectroscopy coupled with liquid chromatography or gas chromatography, nuclear magnetic resonance spectroscopy has several advantages, including simple sample preparation, non-destructive sampling, accuracy, short acquisition time, and reproducibility in the determination of urinary hippuric acid. PMID:21316881

  5. Image reconstruction by NMR Fresnel diffractive imaging technique

    A new approach to MR angiography, the NMR diffractive imaging technique, has been investigated. The expression for NMR signals obtained in the NMR diffractive imaging technique is similar to the equation for Fresnel diffraction in light waves or sound waves. Therefore, it is possible to reconstruct an image focusing on any plane in the depth direction from data scanned two-dimensionally by changing an imaging parameter in the reconstruction step. To support this imaging technique, a coil system composed of six coils was designed. Experiments were performed using an ultra-low-field MRI scanner to acquire two-dimensional data in the proposed technique. Even though blurred images outside the focus are superimposed on the image in the focal plane, the three-dimensional distribution of the object can be recognized by moving the focal plane in the depth direction. To obtain supplemental information for the object, acquiring images from different angles is helpful for recognizing the spatial distribution of the object more precisely. Although the image obtained contains blurred images outside the focus the proposed imaging technique is expected to be useful in MR fast angiography. (author)

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

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

    2016-08-18

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

  7. Microscale simulations of NMR relaxation in porous media

    Mohnke, Oliver; Klitzsch, Norbert

    2010-05-01

    In petrophysical applications of nuclear magnetic resonance (NMR), the measured relaxation signals originate from the fluid filled pore space. Hence, in rocks or sediments the water content directly corresponds to the initial amplitude of the recorded NMR relaxation signals. The relaxation rate (longitudinal/transversal decay time T1, T2) is sensitive to pore sizes and physiochemical properties of rock-fluid interfaces (surface relaxivity), as well as the concentration of paramagnetic ions in the fluid phases (bulk relaxivity). In the subproject A2 of the TR32 we aim at improving the basic understanding of these processes at the pore scale and thereby advancing the interpretation of NMR data by reducing the application of restrictive approximated interpretation schemes, e.g. for deriving pore size distributions, connectivity or permeability. In this respect we numerically simulate NMR relaxation data at the micro sale to study the impact of physical and hydrological parameters such as internal field gradients or pore connectivities on NMR signals. Joint numerical simulations of the NMR relaxation behavior (Bloch equations) in the presence of internal gradients (Ampere's law) and fluid flow (Navier-Stokes) on a pore scale dimension have been implemented in a finite element (FE) model using Comsol Multiphysics. Processes governing the time and spatial behavior of the nuclear magnetization density in a porous medium are diffusion and surface interactions at the rock-fluid interface. Based on Fick's law of diffusive motion Brownstein and Tarr (1979) introduced differential equations that describe the relaxation behavior of the Spin magnetization in single isolated pores and derived analytical solutions for simple geometries, i.e. spherical, cylindrical and planar. However, by numerically solving these equations in a general way using a FE algorithm this approach can be applied to study and simulate coupled complex pore systems, e.g. derived from computer tomography (CT

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

    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.

  9. NMR in solid ionic and nanoionics

    Full text: Nuclear Magnetic Resonance (NMR) is a spectroscopic technique which employs magnetic nuclei to study, among others, the dynamics of condensed matter at the atomic level. Thus, NMR has been and still is a successful instrument in the research field of solid electrolytes also known as solid ionics. This paper presents the typical NMR experiments performed in solid ionics together with some examples from nanoionics. The experiments to be discussed comprise: (i) measurements of the diffusion coefficient employing the pulsed-field gradient and the static fringe-field method; (ii) the experimentally related NMR imaging; (iii) double resonance experiments like spin-echo double resonance (SEDOR) and two-dimensional Fourier transform NMR (2D-FT NMR); (iv) various types of nuclear relaxation, in particular spin-lattice relaxation. The NMR techniques yield information on topics like the following: type and number of mobile atoms and defects, diffusion pathways (e.g. dimensionality restrictions), atomic jump frequencies, activation energy and activation volume of these movements, diffusion coefficient with activation energy and prefactor, correlation effects in atomic movements, space correlation factor, cooperative phenomena, symmetry of atomic sites, behavior at phase transitions. These applications will be illustrated by giving examples from crystals, glasses, and polymers. (author)

  10. Graphical programming for pulse automated NMR experiments

    We describe a software program designed to control a broadband pulse Nuclear Magnetic Resonance (NMR) spectrometer used in zero-field NMR studies of magnetic metals. The software is written in the graphical language LabVIEW. This type of programming allows modifications and the inclusion of new routines to be easily made by the non-specialist, without changing the basic structure of the program. The program corrects for differences in the gain of the two acquisition channels [U (phase) and V (quadrature)], and automatic baseline subtraction. We present examples of measurements of NMR spectra, spin-echo decay (T2), and quadrupolar oscillations, performed in magnetic intermetallic compounds. (author)

  11. NMR imaging of the brain: initial impressions

    An NMR imaging system designed and built by Thorn-EMI Ltd was installed at Hammersmith Hospital in March 1981. In the first year of operation 180 patients and 40 volunteers have had cranial examinations and initial impressions bases on this experience are presented. Patients with a wide variety of neurological diseases have been studied to provide a basis for diagnostic interpretation, to define distinctive features, and to evaluate different types of scanning sequences. NMR imaging appears to be of considerable value in neurological diagnosis and has a number of advantages over CT. The detailed evaluation of NMR imaging will require much more work but the initial results are very promising

  12. Solid-state NMR of polymers

    Mirau, P

    2001-07-01

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

  13. Solid-state NMR of polymers

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

  14. Median Modified Wiener Filter for nonlinear adaptive spatial denoising of protein NMR multidimensional spectra

    Cannistraci, Carlo Vittorio

    2015-01-26

    Denoising multidimensional NMR-spectra is a fundamental step in NMR protein structure determination. The state-of-the-art method uses wavelet-denoising, which may suffer when applied to non-stationary signals affected by Gaussian-white-noise mixed with strong impulsive artifacts, like those in multi-dimensional NMR-spectra. Regrettably, Wavelet\\'s performance depends on a combinatorial search of wavelet shapes and parameters; and multi-dimensional extension of wavelet-denoising is highly non-trivial, which hampers its application to multidimensional NMR-spectra. Here, we endorse a diverse philosophy of denoising NMR-spectra: less is more! We consider spatial filters that have only one parameter to tune: the window-size. We propose, for the first time, the 3D extension of the median-modified-Wiener-filter (MMWF), an adaptive variant of the median-filter, and also its novel variation named MMWF*. We test the proposed filters and the Wiener-filter, an adaptive variant of the mean-filter, on a benchmark set that contains 16 two-dimensional and three-dimensional NMR-spectra extracted from eight proteins. Our results demonstrate that the adaptive spatial filters significantly outperform their non-adaptive versions. The performance of the new MMWF* on 2D/3D-spectra is even better than wavelet-denoising. Noticeably, MMWF* produces stable high performance almost invariant for diverse window-size settings: this signifies a consistent advantage in the implementation of automatic pipelines for protein NMR-spectra analysis.

  15. NMR data-driven structure determination using NMR-I-TASSER in the CASD-NMR experiment

    NMR-I-TASSER, an adaption of the I-TASSER algorithm combining NMR data for protein structure determination, recently joined the second round of the CASD-NMR experiment. Unlike many molecular dynamics-based methods, NMR-I-TASSER takes a molecular replacement-like approach to the problem by first threading the target through the PDB to identify structural templates which are then used for iterative NOE assignments and fragment structure assembly refinements. The employment of multiple templates allows NMR-I-TASSER to sample different topologies while convergence to a single structure is not required. Retroactive and blind tests of the CASD-NMR targets from Rounds 1 and 2 demonstrate that even without using NOE peak lists I-TASSER can generate correct structure topology with 15 of 20 targets having a TM-score above 0.5. With the addition of NOE-based distance restraints, NMR-I-TASSER significantly improved the I-TASSER models with all models having the TM-score above 0.5. The average RMSD was reduced from 5.29 to 2.14 Å in Round 1 and 3.18 to 1.71 Å in Round 2. There is no obvious difference in the modeling results with using raw and refined peak lists, indicating robustness of the pipeline to the NOE assignment errors. Overall, despite the low-resolution modeling the current NMR-I-TASSER pipeline provides a coarse-grained structure folding approach complementary to traditional molecular dynamics simulations, which can produce fast near-native frameworks for atomic-level structural refinement

  16. NMR data-driven structure determination using NMR-I-TASSER in the CASD-NMR experiment

    Jang, Richard [Huazhong University of Science and Technology, School of Software Engineering (China); Wang, Yan [Huazhong University of Science and Technology, School of Life Science and Technology (China); Xue, Zhidong, E-mail: zdxue@hust.edu.cn [Huazhong University of Science and Technology, School of Software Engineering (China); Zhang, Yang, E-mail: zhng@umich.edu [University of Michigan, Department of Computational Medicine and Bioinformatics (United States)

    2015-08-15

    NMR-I-TASSER, an adaption of the I-TASSER algorithm combining NMR data for protein structure determination, recently joined the second round of the CASD-NMR experiment. Unlike many molecular dynamics-based methods, NMR-I-TASSER takes a molecular replacement-like approach to the problem by first threading the target through the PDB to identify structural templates which are then used for iterative NOE assignments and fragment structure assembly refinements. The employment of multiple templates allows NMR-I-TASSER to sample different topologies while convergence to a single structure is not required. Retroactive and blind tests of the CASD-NMR targets from Rounds 1 and 2 demonstrate that even without using NOE peak lists I-TASSER can generate correct structure topology with 15 of 20 targets having a TM-score above 0.5. With the addition of NOE-based distance restraints, NMR-I-TASSER significantly improved the I-TASSER models with all models having the TM-score above 0.5. The average RMSD was reduced from 5.29 to 2.14 Å in Round 1 and 3.18 to 1.71 Å in Round 2. There is no obvious difference in the modeling results with using raw and refined peak lists, indicating robustness of the pipeline to the NOE assignment errors. Overall, despite the low-resolution modeling the current NMR-I-TASSER pipeline provides a coarse-grained structure folding approach complementary to traditional molecular dynamics simulations, which can produce fast near-native frameworks for atomic-level structural refinement.

  17. Assessment of structural changes of human teeth by low-field nuclear magnetic resonance (NMR)

    A technique of low-field pulsed proton nuclear magnetic resonance (NMR) spin relaxation is described for assessment of age-related structural changes (dentin and pulp) of human teeth in vitro. The technique involves spin–spin relaxation measurement and inversion spin–spin spectral analysis methods. The spin–spin relaxation decay curve is converted into a T2 distribution spectrum by a sum of single exponential decays. The NMR spectra from the extracted dentin-portion-only and dental pulp-cells-only were compared with the whole extracted teeth spectra, for the dentin and pulp peak assignments. While dentin and pulp are highly significant parameters in determining tooth quality, variations in these parameters with age can be used as an effective tool for estimating tooth quality. Here we propose an NMR calibration method—the ratio of the amount of dentin to the amount of pulp obtained from NMR T2 distribution spectra can be used for measuring the age-related structural changes in teeth while eliminating any variations in size of teeth. Eight teeth (third molars) extracted from humans, aged among 17–67 years old, were tested in this study. It is found that the intensity ratio of dentin to pulp sensitively changes from 0.48 to 3.2 approaching a linear growth with age. This indicates that age-related structural changes in human teeth can be detected using the low-field NMR technique

  18. Numerical simulation of ( T 2, T 1) 2D NMR and fluid responses

    Tan, Mao-Jin; Zou, You-Long; Zhang, Jin-Yan; Zhao, Xin

    2012-12-01

    One-dimensional nuclear magnetic resonance (1D NMR) logging technology is limited for fluid typing, while two-dimensional nuclear magnetic resonance (2D NMR) logging can provide more parameters including longitudinal relaxation time ( T 1) and transverse relaxation time ( T 2) relative to fluid types in porous media. Based on the 2D NMR relaxation mechanism in a gradient magnetic field, echo train simulation and 2D NMR inversion are discussed in detail. For 2D NMR inversion, a hybrid inversion method is proposed based on the damping least squares method (LSQR) and an improved truncated singular value decomposition (TSVD) algorithm. A series of spin echoes are first simulated with multiple waiting times ( T W s) in a gradient magnetic field for given fluid models and these synthesized echo trains are inverted by the hybrid method. The inversion results are consistent with given models. Moreover, the numerical simulation of various fluid models such as the gas-water, light oil-water, and vicious oil-water models were carried out with different echo spacings ( T E s) and T W s by this hybrid method. Finally, the influences of different signal-to-noise ratios (SNRs) on inversion results in various fluid models are studied. The numerical simulations show that the hybrid method and optimized observation parameters are applicable to fluid typing of gas-water and oil-water models.

  19. CoNSEnsX: an ensemble view of protein structures and NMR-derived experimental data

    Perczel András

    2010-10-01

    Full Text Available Abstract Background In conjunction with the recognition of the functional role of internal dynamics of proteins at various timescales, there is an emerging use of dynamic structural ensembles instead of individual conformers. These ensembles are usually substantially more diverse than conventional NMR ensembles and eliminate the expectation that a single conformer should fulfill all NMR parameters originating from 1016 - 1017 molecules in the sample tube. Thus, the accuracy of dynamic conformational ensembles should be evaluated differently to that of single conformers. Results We constructed the web application CoNSEnsX (Consistency of NMR-derived Structural Ensembles with eXperimental data allowing fast, simple and convenient assessment of the correspondence of the ensemble as a whole with diverse independent NMR parameters available. We have chosen different ensembles of three proteins, human ubiquitin, a small protease inhibitor and a disordered subunit of cGMP phosphodiesterase 5/6 for detailed evaluation and demonstration of the capabilities of the CoNSEnsX approach. Conclusions Our results present a new conceptual method for the evaluation of dynamic conformational ensembles resulting from NMR structure determination. The designed CoNSEnsX approach gives a complete evaluation of these ensembles and is freely available as a web service at http://consensx.chem.elte.hu.

  20. Metabolic flux in carbohydrate biosynthesis. New methods using stable isotopes, mass spectrometry, and NMR

    Structural analysis of carbohydrates involves three parameters: composition, linkage, and conformation, and tends to rely on the various forms of two techniques; mass spectrometry (MS) and nuclear magnetic resonance (NMR) spectroscopy. These techniques are enhanced and extended by the use of stable...

  1. Interfaces in polymer nanocomposites - An NMR study

    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.

  2. Bayesian Peak Picking for NMR Spectra

    Cheng, Yichen

    2014-02-01

    Protein structure determination is a very important topic in structural genomics, which helps people to understand varieties of biological functions such as protein-protein interactions, protein–DNA interactions and so on. Nowadays, nuclear magnetic resonance (NMR) has often been used to determine the three-dimensional structures of protein in vivo. This study aims to automate the peak picking step, the most important and tricky step in NMR structure determination. We propose to model the NMR spectrum by a mixture of bivariate Gaussian densities and use the stochastic approximation Monte Carlo algorithm as the computational tool to solve the problem. Under the Bayesian framework, the peak picking problem is casted as a variable selection problem. The proposed method can automatically distinguish true peaks from false ones without preprocessing the data. To the best of our knowledge, this is the first effort in the literature that tackles the peak picking problem for NMR spectrum data using Bayesian method.

  3. Characterization of Hydrogenated Fullerenes by NMR Spectroscopy

    Hedenström, Mattias; Wågberg, Thomas; Johnels, Dan

    NMR spectroscopy is so far the only analytical technique that has been used to get a detailed structural characterization of hydrogenated fullerenes. A substantial amount of information derived from different NMR experiments can thus be found in the literature for a number of fullerenes hydrogenated to various degrees. These studies have benefitted from the fact that chemical shifts of 1H and 13C and in some cases also 3He can be used to obtain structural information of these compounds. Such results, together with discussions about different NMR experiments and general considerations regarding sample preparations, are summarized in this chapter. The unique information, both structural and physicochemical, that can be derived from different NMR experiments ensures that this technique will continue to be of central importance in characterization of hydrogenated fullerenes.

  4. NMR spectroscopy assists synthetic fuels research

    Cookson, D.J.; Smith, B.E.

    1983-01-01

    NMR spectroscopy has proved to be a useful and versatile technique for the study of synthetic fuels feedstocks, catalysts, process intermediates and final products. Some applications of the technique to coal and gas conversion research are illustrated and discussed.

  5. NMR studies of cerebral metabolism in vivo

    The nature and extent of the potential synergism between PET and NMR methods is not yet well appreciated in the biomedical community. The long-range interest of medical neurobiology will be well served by efforts of PET and NMR scientists to follow each others' work so that opportunities for productive interchange can be efficiently exploited. Appreciation of the synergism by the rest of the biomedical community will follow naturally. PET is said by the people doing it to be still in its infancy, for they are more concerned with advancing their discipline than with admiring its already impressive achievements. On the scale of the same developmental metaphor, many NMR methods for studying the living human brain are still in utero. The best way to provide the reader a sense of the current status and future course of NMR research in medical neurobiology is by discussion of published in vivo studies. Such a discussion, adapted from another article is what follows

  6. NMR study of hydride systems

    The hydrides of thorium (ThH2, Th4H15 and Th4D15) and the intermetallic compound system (Zr(Vsub(1-x)Cosub(x))2 and its hydrides were investigated using the nuclear magnetic resonance (NMR) technique. From the results for the thorium hydride samples it was concluded that the density of states at the Fermi level n(Esub(f)) is higher in Th4H15 than in ThH2; there is an indirect reaction between the protons and the d electrons belonging to the Th atoms in Th4H15; n(E) has a sharp structure near Esub(f). It was also found that the hydrogen diffusion mechanism changes with temperature. From the results for the intermetallic compound system conclusions were drawn concerning variations in the electronic structure, which explain the behavior of the system. In hydrogen diffusion studies in several samples it was found that Co atoms slow the diffusion rate. Quadrupole spectra obtained at low temperatures show that the H atoms preferably occupy tetrahedral sites formed by three V atoms and one Z atom. (H.K.)

  7. Rheology of Blood by NMR

    Han, Song-I.; Marseille, Oliver; Gehlen, Christa; Blümich, Bernhard

    2001-09-01

    Pipe flow of blood in tubes of 1 and 7 mm inner diameter, respectively, was investigated employing two-dimensional NMR velocity imaging and PFG propagator measurements at different Reynolds numbers between 10 and 3500. The results are compared to flow of a water/glycerol mixture of matching viscosity under identical conditions. The transition from laminar to turbulent flow is observed by both a flattening of the velocity profile and a change of the propagator shape. For blood flow this transition is found to be shifted toward higher Reynolds numbers as compared to the transition of the water/glycerol mixture. This observation is in agreement with predictions from hydraulic measurements and is a consequence of the non-Newtonian flow characteristics of blood as a suspension of erythrocytes and plasma. Likewise, a deviation from the laminar flow condition is observed for blood at low Reynolds numbers between 10 and 100. This phenomenon is unknown for Newtonian liquids and is explained by the onset of a geometrical arrangement of the erythrocytes, the so-called rouleaux effect.

  8. Observation of supramolecular aggregation by dosy NMR

    Šaman, David; Wimmer, Zdeněk; Kolehmainen, E.

    Tatranská Lomnica : Slovak National NMR Centre. Slovak Chemical Society, 2011 - (Liptaj, T.; Imrich, J.; Kovaľaková, M.; Olčák, D.). s. 56-56 ISBN 978-80-89284-77-1. [Magnetic Moments in Central Europe. 16.03.2011-20.03.2011, Tatranská Lomnica] R&D Projects: GA MŠk 2B06024 Institutional research plan: CEZ:AV0Z40550506 Keywords : difusion * NMR Subject RIV: CC - Organic Chemistry

  9. NMR Investigation of the Quantum Piegonhole Effect

    S., Anjusha V.; Hegde, Swathi S.; Mahesh, T. S.

    2015-01-01

    Quantum simulators based on nuclear spin-systems controlled by NMR techniques have been used for studying various quantum phenomena. In this work, using a four-qubit NMR quantum simulator, we investigate the recently postulated quantum pigeon-hole effect. In mathematics, the pigeonhole effect is described by a set of three objects being allocated with only two containers. Classically, one would expect at least one container to accommodate more than one object. However, recently it was predict...

  10. NMR of Membrane Proteins: Beyond Crystals.

    Rajesh, Sundaresan; Overduin, Michael; Bonev, Boyan B

    2016-01-01

    Membrane proteins are essential for the flow of signals, nutrients and energy between cells and between compartments of the cell. Their mechanisms can only be fully understood once the precise structures, dynamics and interactions involved are defined at atomic resolution. Through advances in solution and solid state NMR spectroscopy, this information is now available, as demonstrated by recent studies of stable peripheral and transmembrane proteins. Here we highlight recent cases of G-protein coupled receptors, outer membrane proteins, such as VDAC, phosphoinositide sensors, such as the FAPP-1 pleckstrin homology domain, and enzymes including the metalloproteinase MMP-12. The studies highlighted have resulted in the determination of the 3D structures, dynamical properties and interaction surfaces for membrane-associated proteins using advanced isotope labelling strategies, solubilisation systems and NMR experiments designed for very high field magnets. Solid state NMR offers further insights into the structure and multimeric assembly of membrane proteins in lipid bilayers, as well as into interactions with ligands and targets. Remaining challenges for wider application of NMR to membrane structural biology include the need for overexpression and purification systems for the production of isotope-labelled proteins with fragile folds, and the availability of only a few expensive perdeuterated detergents.Step changes that may transform the field include polymers, such as styrene maleic acid, which obviate the need for detergent altogether, and allow direct high yield purification from cells or membranes. Broader demand for NMR may be facilitated by MODA software, which instantly predicts membrane interactive residues that can subsequently be validated by NMR. In addition, recent developments in dynamic nuclear polarization NMR instrumentation offer a remarkable sensitivity enhancement from low molarity samples and cell surfaces. These advances illustrate the current

  11. Frontiers of NMR in Molecular Biology

    NONE

    1999-08-25

    NMR spectroscopy is expanding the horizons of structural biology by determining the structures and describing the dynamics of blobular proteins in aqueous solution, as well as other classes of proteins including membrane proteins and the polypeptides that form the aggregates diagnostic of prion and amyloid diseases. Significant results are also emerging on DNA and RNA oligomers and their complexes with proteins. This meeting focused attention on key structural questions emanating from molecular biology and how NMR spectroscopy can be used to answer them.

  12. Applications of 1H-NMR relaxometry in experimental liver studies

    Purpose of this study was to investigate applications of proton nuclear magnetic resonance (1H-NMR) relaxometry in experimental medicine. Relaxometry was performed by measurements of spin-lattice (T1) and spin-spin (T2) relaxation time parameters on liver biopsies up to four hours after biopsy excision. Variations of relaxation times due to species and strain, different sample handling and different liver damage models, ethionine fatty liver and paracetamol liver necrosis, were investigated. Cell integrity effects were studied on homogenized liver samples. Relaxation time parameters, especially 'main' components T1A and T2A of biexponential model fit, were identified to react very sensitive after tissue damages as well as to cell viability. Thus, investigation of stored liver grafts was performed in order to evaluate the possibility of a rapid liver graft viability testing method for human liver transplantation surgery by 1H-NMR relaxometry. Another series of measurements was performed to investigate the applicability of isoflurane anesthesia for in vivo NMR experiments. This study proved the good appropriateness of isoflurane for that purpose provided that physiological monitoring and individual adjustment of anesthesia are performed. In these investigations it could be revealed that mainly T1A and T2A are influenced by tissue condition and that different information is inherent in these two parameters, with T2A reflecting tissue viability and changes of tissue conditions very sensitively but rather unspecifically in respect to the damage applied. Based on these results the following future applications of 1H-NMR relaxometry are suggested : (1) model investigations, (2) investigation of given pathologies, (3) investigation of basic requirements for in vivo NMR and (4) application in a liver graft viability testing protocol, which seems to be the most important future application of 1H-NMR relaxometry in medicine. (author)

  13. A new laboratory approach to shale analysis using NMR relaxometry

    Washburn, Kathryn E.; Birdwell, Justin E.

    2013-01-01

    kerogen, thermally degraded kerogen, and char. Integrated peak areas from the LF-NMR results representative of kerogen and bitumen were found to be well correlated with S1 and S2 parameters from Rock-Eval programmed pyrolysis. This study demonstrates that LFNMR relaxometry can provide a wide range of information on shales and other reservoir rocks that goes well beyond porosity and pore-fluid analysis.

  14. 33S NMR cryogenic probe for taurine detection

    Hobo, Fumio; Takahashi, Masato; Maeda, Hideaki

    2009-03-01

    With the goal of a S33 nuclear magnetic resonance (NMR) probe applicable to in vivo NMR on taurine-biological samples, we have developed the S33 NMR cryogenic probe, which is applicable to taurine solutions. The NMR sensitivity gain relative to a conventional broadband probe is as large as 3.5. This work suggests that improvements in the preamplifier could allow NMR measurements on 100 μM taurine solutions, which is the level of sensitivity necessary for biological samples.

  15. Benchmarks for the 13C NMR chemical shielding tensors in peptides in the solid state

    Czernek, Jiří; Pawlak, Tomasz; Potrzebowski, Marek J.

    2012-02-01

    The benchmark set is proposed, which comprises 126 principal elements of chemical shielding tensors, and the respective isotropic chemical shielding values, of all 42 13C nuclei in crystalline Tyr-D-Ala-Phe and Tyr-Ala-Phe tripeptides with known, but highly dissimilar structures. These data are obtained by both the NMR measurements and the density functional theory in the pseudopotential plane-wave scheme. Using the CASTEP program, several computational strategies are employed, for which the level of agreement between calculations and experiment is established. This set is mainly intended for the validation of methods capable of predicting the 13C NMR parameters in solid-state systems.

  16. Grape juice quality control by means of ¹H nmr spectroscopy and chemometric analyses

    Caroline Werner Pereira da Silva Grandizoli

    2014-01-01

    Full Text Available This work shows the application of ¹H NMR spectroscopy and chemometrics for quality control of grape juice. A wide range of quality assurance parameters were assessed by single ¹H NMR experiments acquired directly from juice. The investigation revealed that conditions and time of storage should be revised and indicated on all labels. The sterilization process of homemade grape juices was efficient, making it possible to store them for long periods without additives. Furthermore, chemometric analysis classified the best commercial grape juices to be similar to homemade grape juices, indicating that this approach can be used to determine the authenticity after adulteration.

  17. Validation of quantitative 1H NMR method for the analysis of pharmaceutical formulations

    The need for effective and reliable quality control in products from pharmaceutical industries renders the analyses of their active ingredients and constituents of great importance. This study presents the theoretical basis of ¹H NMR for quantitative analyses and an example of the method validation according to Resolution RE N. 899 by the Brazilian National Health Surveillance Agency (ANVISA), in which the compound paracetamol was the active ingredient. All evaluated parameters (selectivity, linearity, accuracy, repeatability and robustness) showed satisfactory results. It was concluded that a single NMR measurement provides structural and quantitative information of active components and excipients in the sample. (author)

  18. 1H NMR spectroscopic determination of deterioration marker compounds in fats and oils

    Skiera, Christina

    2013-01-01

    In food and pharmaceutical analysis, the classical indices peroxide value (PV), acid value (AV) and p-anisidine value (ANV) still play an important role as quality and authenticity control parameters of fats and oils. These indices are sum parameters for certain deterioration products (PV for hydroperoxides, AV for free fatty acids, ANV for aldehydes) and are obtained using volumetric or UV/VIS spectroscopic analytical approaches. 1H NMR spectroscopy provides a fast and simple alternative to ...

  19. Carbon-13 NMR characterization of actinyl(VI) carbonate complexes in aqueous solution

    Clark, D.L.; Hobart, D.E.; Palmer, P.D. [Los Alamos National Lab., NM (United States); Sullivan, J.C. [Argonne National Lab., IL (United States); Stout, B.E. [Cincinnati Univ., OH (United States). Dept. of Chemistry

    1992-07-01

    The uranyl(VI) carbonate system has been re-examined using {sup 13}C NMR of 99.9% {sup 13}C-enriched U{sup VI}O{sub 2} ({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} in millimolar concentrations. By careful control of carbonate ion concentration, we have confirmed the existence of the trimer, and observed dynamic equilibrium between the monomer and the timer. In addition, the ligand exchange reaction between free and coordinated carbonate on Pu{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} and Am{sup VI}O{sub 2}({sup 13}CO{sub 3}){sub 3}{sup 4{minus}} systems has been examined by variable temperature {sup 13}C NMR line-broadening techniques {sup 13}C NMR line-broadening techniques. A modified Carr-Purcell-Meiboom-Gill NMR pulse sequence was written to allow for experimental determination of ligand exchange parameters for paramagnetic actinide complexes. Preliminary Eyring analysis has provided activation parameters of {Delta}G{sup {double_dagger}}{sub 295} = 56 kJ/M, {Delta}H{sup {double_dagger}} = 38 kJ/M, and {Delta}S{sup {double_dagger}} = {minus}60 J/M-K for the plutonyl triscarbonate system, suggesting an associative transition state for the plutonyl (VI) carbonate complex self-exchange reaction. Experiments for determination of the activation parameters for the americium (VI) carbonate system are in progress.

  20. Uniform procedure of (1)H NMR analysis of rat urine and toxicometabonomics Part II: comparison of NMR profiles for classification of hepatotoxicity.

    Schoonen, Willem G E J; Kloks, Cathelijne P A M; Ploemen, Jan-Peter H T M; Smit, Martin J; Zandberg, Pieter; Horbach, G Jean; Mellema, Jan-Remt; Thijssen-Vanzuylen, Carol; Tas, Albert C; van Nesselrooij, Joop H J; Vogels, Jack T W E

    2007-07-01

    A procedure of nuclear magnetic resonance (NMR) urinalysis using pattern recognition is proposed for early detection of toxicity of investigational compounds in rats. The method is applied to detect toxicity upon administration of 13 toxic reference compounds and one nontoxic control compound (mianserine) in rats. The toxic compounds are expected to induce necrosis (bromobenzene, paracetamol, carbon tetrachloride, iproniazid, isoniazid, thioacetamide), cholestasis (alpha-naphthylisothiocyanate (ANIT), chlorpromazine, ethinylestradiol, methyltestosterone, ibuprofen), or steatosis (phenobarbital, tetracycline). Animals were treated daily for 2 or 4 days except for paracetamol and bromobenzene (1 and 2 days) and carbon tetrachloride (1 day only). Urine was collected 24 h after the first and second treatment. The animals were sacrificed 24 h after the last treatment, and NMR data were compared with liver histopathology as well as blood and urine biochemistry. Pathology and biochemistry showed marked toxicity in the liver at high doses of bromobenzene, paracetamol, carbon tetrachloride, ANIT, and ibuprofen. Thioacetamide and chlorpromazine showed less extensive changes, while the influences of iproniazid, isoniazid, phenobarbital, ethinylestradiol, and tetracycline on the toxic parameters were marginal or for methyltestosterone and mianserine negligible. NMR spectroscopy revealed significant changes upon dosing in 88 NMR biomarker signals preselected with the Procrustus Rotation method on principal component discriminant analysis (PCDA) plots. Further evaluation of the specific changes led to the identification of biomarker patterns for the specific types of liver toxicity. Comparison of our rat NMR PCDA data with histopathological changes reported in humans and/or rats suggests that rat NMR urinalysis can be used to predict hepatotoxicity. PMID:17420222

  1. Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy, a new approach to study humic material?

    Knicker, Heike; Lange, Sascha; van Rossum, Barth; Oschkinat, Hartmut

    2016-04-01

    Compared to solution NMR spectroscopy, solid-state NMR spectra suffer from broad resonance lines and low resolution. This could be overcome by the use of 2-dimenstional solid-state NMR pulse sequences. Until recently, this approach has been unfeasible as a routine tool in soil chemistry, mainly because of the low NMR sensitivity of the respective samples. A possibility to circumvent those sensitivity problems represents high-field Dynamic Nuclear Polarization (DNP) solid-state NMR spectroscopy (Barnes et al., 2008), allowing considerable signal enhancements (Akbey et al., 2010). This is achieved by a microwave-driven transfer of polarization from a paramagnetic center to nuclear spins. Application of DNP to MAS spectra of biological systems (frozen solutions) showed enhancements of the factor 40 to 50 (Hall et al., 1997). Enhancements of this magnitude, thus may enable the use of at least some of the 2D solid-state NMR techniques that are presently already applied for pure proteins but are difficult to apply to soil peptides in their complex matrix. After adjusting the required acquisition parameters to the system "soil organic matter", lower but still promising enhancement factors were achieved. Additional optimization was performed and allowed the acquisition of 2D 13C and 15N solid-state NMR spectra of humified 13C and 15N enriched plant residues. Within the present contribution, the first solid-state DNP NMR spectra of humic material are presented. Those data demonstrate the great potential of this approach which certainly opens new doors for a better understanding of biochemical processes in soils, sediments and water. Akbey, Ü., Franks, W.T., Linden, A., Lange, S., Griffin, R.G., van Rossum, B.-J., Oschkinat, H., 2010. Dynamic nuclear polarization of deuterated proteins. Angewandte Chemie International Edition 49, 7803-7806. Barnes, A.B., De Paëpe, G., van der Wel, P.C.A., Hu, K.N., Joo, C.G., Bajaj, V.S., Mak-Jurkauskas, M.L., Sirigiri, J.R., Herzfeld, J

  2. Use of NMR and NMR Prediction Software to Identify Components in Red Bull Energy Drinks

    Simpson, Andre J.; Shirzadi, Azadeh; Burrow, Timothy E.; Dicks, Andrew P.; Lefebvre, Brent; Corrin, Tricia

    2009-01-01

    A laboratory experiment designed as part of an upper-level undergraduate analytical chemistry course is described. Students investigate two popular soft drinks (Red Bull Energy Drink and sugar-free Red Bull Energy Drink) by NMR spectroscopy. With assistance of modern NMR prediction software they identify and quantify major components in each…

  3. HPLC-NMR revisited: Using time-slice HPLC-SPE-NMR with database assisted dereplication

    Johansen, Kenneth; Wubshet, Sileshi Gizachew; Nyberg, Nils

    2013-01-01

    Time based trapping of chromatographically separated compounds on to solid-phase extraction cartridges (SPE) and subsequent elution to NMR-tubes was done to emulate the function of HPLC–NMR for dereplication purposes. Sufficient mass sensitivity was obtained by the use of a state-of-the-art HPLC...

  4. Epr of Mn2+ Impurities in Calcite: A Detailed Study Pertinent to Marble Provenance Determination

    Weihe, H.; Piligkos, S.; Barra, A.L.;

    2009-01-01

    We demonstrate that the electron paramagnetic resonance spectrum of Mn2+ impurities in calcite, and therefore also in marble, may be accurately reproduced by a traditional spin Hamiltonian formalism. The success of such a treatment, however, very much depends on the spin Hamiltonian parameters...... having the correct signs as well as magnitudes. We present data that determine the sign of the axial anisotropy parameter and thereby facilitate future quantum mechanical characterizations of marble electron paramagnetic resonance spectra that supplement provenance determination...

  5. EPR OF Mn2+ IMPURITIES IN CALCITE: A DETAILED STUDY PERTINENT TO MARBLE PROVENANCE DETERMINATION

    Weihe, H.; Piligkos, S.; Barra, A.L.;

    2009-01-01

    We demonstrate that the electron paramagnetic resonance spectrum of Mn2+ impurities in calcite, and therefore also in marble, may be accurately reproduced by a traditional spin Hamiltonian formalism. The success of such a treatment, however, very much depends on the spin Hamiltonian parameters...... having the correct signs as well as magnitudes. We present data that determine the sign of the axial anisotropy parameter and thereby facilitate future quantum mechanical characterizations of marble electron paramagnetic resonance spectra that supplement provenance determination....

  6. Solid-state NMR in the analysis of drugs and naturally occurring materials.

    Paradowska, Katarzyna; Wawer, Iwona

    2014-05-01

    This article presents some of the solid-state NMR (SSNMR) techniques used in the pharmaceutical and biomedical research. Solid-state magic angle spinning (MAS) NMR provides structural information on powder amorphous solids for which single-crystal diffraction structures cannot be obtained. NMR is non-destructive; the powder sample may be used for further studies. Quantitative results can be obtained, although solid-state NMR spectra are not normally quantitative. As compared with other techniques, MAS NMR is insensitive and requires a significant amount of the powder sample (2-100mg) to fill the 1.3-7 mm ZrO2 rotor. This is its main drawback, since natural compounds isolated from plants, microorganisms or cell cultures are difficult to obtain in quantities higher than a few milligrams. Multinuclear MAS NMR routinely uses (1)H and (13)C nuclei, less frequently (15)N, (19)F, (31)P, (77)Se, (29)Si, (43)Ca or (23)Na. The article focuses on the pharmaceutical applications of SSNMR, the studies were aimed to control over manufacturing processes (e.g. crystallization and milling) investigation of chemical and physical stability of solid forms both as pure drug and in a formulated product. SSNMR is used in combination with some other analytical methods (DSC, XRD, FT-IR) and theoretical calculations of NMR parameters. Biologically active compounds, such as amino acids and small peptides, steroids and flavonoids were studied by SSNMR methods (part 4) providing valuable structural information. The SSNMR experiments performed on biopolymers and large natural products like proteins, cellulose and lipid layers are commented upon briefly in part 5. PMID:24173236

  7. AEM and NMR: Tools for the Future of Groundwater Management

    Abraham, J. D.; Cannia, J. C.; Lawrie, K.

    2012-12-01

    Within the world, understanding groundwater resources and their management are growing in importance to society as groundwater resources are stressed by drought and continued development. To minimize conflicts, tools and techniques need to be applied to support knowledge-based decisions and management. Airborne electromagnetic (AEM) surveys provide high-quality subsurface data not available from any other source for building the complex hydrogeologic frameworks needed by water-resource managers for effective groundwater management. Traditionally, point data, such as borehole logs, borehole geophysics, surface geophysics, and aquifer tests were interpolated over long distances to create hydrogeologic frameworks. These methods have enjoyed a long history of being the best available technology to inform our understanding of groundwater and how it moves. The AEM techniques proivde pathway for geoscientists to follow to develop more accurate descriptions of the hydrogeological framework. However, the critical and challenging measurements in characterizing aquifers include effective porosity and hydraulic conductivity. These parameters are not reliable derived from AEM. Typically, values for effective porosity and hydraulic conductivity are derived by lithological comparisons with published data; direct measurements of hydraulic conductivity acquired by a few constant head aquifer tests or slug tests; and expensive and time consuming laboratory measurements of cores which can be biased by sampling and the difficulty of making measurements on unconsolidated materials. Aquifer tests are considered to be the best method to gather information on hydraulic conductivity but are rare because of cost and difficult logistics. Also they are unique in design and interpretation from site to site. Nuclear Magnetic Resonance (NMR) can provide a direct measurement of the presence of water in the pore space of aquifer materials. Detection and direct measurement is possible due to the

  8. NMR Studies on the Internal Structure of High- T c Superconductors and Other Anorganic Compounds

    Kumagai, K.; Kakuyanagi, K.; Saitoh, M.; Matsuda, Y.; Hasegawa, M.; Takashima, S.; Nohara, M.; Takagi, H.

    2004-12-01

    Spatially-resolved NMR is used to probe internal structures in highly correlated superconductors of optimally-doped {text{Tl}}2 {text{Ba}}2 {text{CuO}}_{{6 + δ }} ( T c = 85 K) and a heavy fermion superconductor CeCoIn5 ( T c = 2.3 K). The characteristic change of the properties of 205Tl-NMR in the vortex state provides a clear evidence of the antiferromagnetic order in the vortex cores below 20 K in {text{Tl}}2 {text{Ba}}2 {text{CuO}}_{{6 + δ }} . We also obtain anomalous 115In-NMR spectra of CeCoIn5, which provides a microscopic evidence for the occurrence of a spatially-modulated superconducting order parameter expected in a Fulde Ferrel Larkin Ovchinnkov (FFLO) state.

  9. NMR-Based Multi Parametric Quality Control of Fruit Juices: SGF Profiling

    Fang Fang

    2009-11-01

    Full Text Available With SGF Profiling™ we introduce an NMR-based screening method for the quality control of fruit juices. This method has been developed in a joint effort by Bruker BioSpin GmbH and SGF International e.V. The system is fully automated with respect to sample transfer, measurement, data analysis and reporting and is set up on an Avance 400 MHz flow-injection NMR spectrometer. For each fruit juice a multitude of parameters related to quality and authenticity are evaluated simultaneously from a single data set acquired within a few minutes. This multimarker/multi-aspect NMR screening approach features low cost-per-sample and is highly competitive with conventional and targeted fruit juice quality control methods.

  10. Identifying Stereoisomers by ab-initio Calculation of Secondary Isotope Shifts on NMR Chemical Shieldings

    Karl-Heinz Böhm

    2014-04-01

    Full Text Available We present ab-initio calculations of secondary isotope effects on NMR chemical shieldings. The change of the NMR chemical shift of a certain nucleus that is observed if another nucleus is replaced by a different isotope can be calculated by computing vibrational corrections on the NMR parameters using electronic structure methods. We demonstrate that the accuracy of the computational results is sufficient to even distinguish different conformers. For this purpose, benchmark calculations for fluoro(2-2Hethane in gauche and antiperiplanar conformation are carried out at the HF, MP2 and CCSD(T level of theory using basis sets ranging from double- to quadruple-zeta quality. The methodology is applied to the secondary isotope shifts for 2-fluoronorbornane in order to resolve an ambiguity in the literature on the assignment of endo- and exo-2-fluoronorbornanes with deuterium substituents in endo-3 and exo-3 positions, also yielding insight into mechanistic details of the corresponding synthesis.

  11. NMR standard probe for precision measurement of the free proton NMR frequency

    The authors have designed and constructed a special NMR standard probe using a spehrical pure water sample to determine the free proton NMR frequency fp at high field and an accuracy of 0.04 ppm has been achieved. Since the proton gyromagnetic ratio γp is less well known (∼0.1 ppm), the free proton NMR frequency measured by the probe may serve as a calibration standard for the magnetic field B. The standard probe can be used at various magnetic field values without introducing any additional magnetic perturbations. The probe is designed in such a way that a cylindrical sample or a small NMR probe can be inserted to replace the 1 cm diameter spherical water sample for systematic studies. Other NMR probes can be calibrated easily against the standard probe using a calibration form. Results will be presented and discussed

  12. BOOK REVIEW: NMR Imaging of Materials

    Blümich, Bernhard

    2003-09-01

    Magnetic resonance imaging (MRI) of materials is a field of increasing importance. Applications extend from fundamental science like the characterization of fluid transport in porous rock, catalyst pellets and hemodialysers into various fields of engineering for process optimization and product quality control. While the results of MRI imaging are being appreciated by a growing community, the methods of imaging are far more diverse for materials applications than for medical imaging of human beings. Blümich has delivered the first book in this field. It was published in hardback three years ago and is now offered as a paperback for nearly half the price. The text provides an introduction to MRI imaging of materials covering solid-state NMR spectroscopy, imaging methods for liquid and solid samples, and unusual MRI in terms of specialized approaches to spatial resolution such as an MRI surface scanner. The book represents an excellent and thorough treatment which will help to grow research in materials MRI. Blümich developed the treatise over many years for his research students, graduates in chemistry, physics and engineering. But it may also be useful for medical students looking for a less formal discussion of solid-state NMR spectroscopy. The structure of this book is easy to perceive. The first three chapters cover an introduction, the fundamentals and methods of solid-state NMR spectroscopy. The book starts at the ground level where no previous knowledge about NMR is assumed. Chapter 4 discusses a wide variety of transformations beyond the Fourier transformation. In particular, the Hadamard transformation and the 'wavelet' transformation are missing from most related books. This chapter also includes a description of noise-correlation spectroscopy, which promises the imaging of large objects without the need for extremely powerful radio-frequency transmitters. Chapters 5 and 6 cover basic imaging methods. The following chapter about the use of relaxation and

  13. Nuclear magnetic resonance (NMR): principles and applications

    The basis for the phenomenon of nuclear magnetic resonance (NMR) is the ability of certain nuclei possessing both intrinsic angular momentum or ''spin'' I and magnetic moment to absorb electromagnetic energy in the radio frequency range. In principle, there are approximately 200 nuclei which may be investigated using the NMR technique. The NMR spectrum consists of intensity peaks along an axis calibrated in terms of the steady magnetic field or the frequency of the radiofrequency electromagnetic radiation. Analysis of the number, spacing, position and intensity of the lines in an NMR spectrum consists of intensity peaks along an axis calibrated in terms of the steady magnetic field or the frequency of the radiofrequency electromagnetic radiation. Analysis of the number, spacing, position and intensity of the lines in an NMR spectrum provides a variety of qualitative and quantitative analytical applications. The most obvious applications consist of the measurements of nuclear properties, such as spin number and nuclear magnetic moment. In liquids, the fine structure of resonance spectra provides a tool for chemical identification and molecular structure analysis. Other applications include the measurements of self-diffusion coefficients, magnetic fields and field homogeneity, inter-nuclear distances, and, in some cases, the water content of biological materials. (author)

  14. Wine analysis to check quality and authenticity by fully-automated 1H-NMR

    Spraul Manfred

    2015-01-01

    Full Text Available Fully-automated high resolution 1H-NMR spectroscopy offers unique screening capabilities for food quality and safety by combining non-targeted and targeted screening in one analysis (15–20 min from acquisition to report. The advantage of high resolution 1H-NMR is its absolute reproducibility and transferability from laboratory to laboratory, which is not equaled by any other method currently used in food analysis. NMR reproducibility allows statistical investigations e.g. for detection of variety, geographical origin and adulterations, where smallest changes of many ingredients at the same time must be recorded. Reproducibility and transferability of the solutions shown are user-, instrument- and laboratory-independent. Sample prepara- tion, measurement and processing are based on strict standard operation procedures which are substantial for this fully automated solution. The non-targeted approach to the data allows detecting even unknown deviations, if they are visible in the 1H-NMR spectra of e.g. fruit juice, wine or honey. The same data acquired in high-throughput mode are also subjected to quantification of multiple compounds. This 1H-NMR methodology will shortly be introduced, then results on wine will be presented and the advantages of the solutions shown. The method has been proven on juice, honey and wine, where so far unknown frauds could be detected, while at the same time generating targeted parameters are obtained.

  15. NMR Evidence for the Topologically Nontrivial Nature in a Family of Half-Heusler Compounds

    Zhang, Xiaoming

    2016-03-16

    Spin-orbit coupling (SOC) is expected to partly determine the topologically nontrivial electronic structure of heavy half-Heusler ternary compounds. However, to date, attempts to experimentally observe either the strength of SOC or how it modifies the bulk band structure have been unsuccessful. By using bulk-sensitive nuclear magnetic resonance (NMR) spectroscopy combined with first-principles calculations, we reveal that 209Bi NMR isotropic shifts scale with relativity in terms of the strength of SOC and average atomic numbers, indicating strong relativistic effects on NMR parameters. According to first-principles calculations, we further claim that nuclear magnetic shieldings from relativistic p1/2 states and paramagnetic contributions from low-lying unoccupied p3/2 states are both sensitive to the details of band structures tuned by relativity, which explains why the hidden relativistic effects on band structure can be revealed by 209Bi NMR isotropic shifts in topologically nontrivial half-Heusler compounds. Used in complement to surface-sensitive methods, such as angle resolved photon electron spectroscopy and scanning tunneling spectroscopy, NMR can provide valuable information on bulk electronic states.

  16. Spin Choreography: Basic Steps in High Resolution NMR (by Ray Freeman)

    Minch, Michael J.

    1998-02-01

    There are three orientations that NMR courses may take. The traditional molecular structure course focuses on the interpretation of spectra and the use of chemical shifts, coupling constants, and nuclear Overhauser effects (NOE) to sort out subtle details of structure and stereochemistry. Courses can also focus on the fundamental quantum mechanics of observable NMR parameters and processes such a spin-spin splitting and relaxation. More recently there are courses devoted to the manipulation of nuclear spins and the basic steps of one- and two-dimensional NMR experiments. Freeman's book is directed towards the latter audience. Modern NMR methods offer a myriad ways to extract information about molecular structure and motion by observing the behavior of nuclear spins under a variety of conditions. In Freeman's words: "We can lead the spins through an intricate dance, carefully programmed in advance, to enhance, simplify, correlate, decouple, edit or assign NMR spectra." This is a carefully written, well-illustrated account of how this dance is choreographed by pulse programming, double resonance, and gradient effects. Although well written, this book is not an easy read; every word counts. It is recommended for graduate courses that emphasize the fundamentals of magnetic resonance. It is not a text on interpretation of spectra.

  17. NMR Evidence for the Topologically Nontrivial Nature in a Family of Half-Heusler Compounds

    Zhang, Xiaoming; Hou, Zhipeng; Wang, Yue; Xu, Guizhou; Shi, Chenglong; Liu, Enke; Xi, Xuekui; Wang, Wenhong; Wu, Guangheng; Zhang, Xi-Xiang

    2016-03-01

    Spin-orbit coupling (SOC) is expected to partly determine the topologically nontrivial electronic structure of heavy half-Heusler ternary compounds. However, to date, attempts to experimentally observe either the strength of SOC or how it modifies the bulk band structure have been unsuccessful. By using bulk-sensitive nuclear magnetic resonance (NMR) spectroscopy combined with first-principles calculations, we reveal that 209Bi NMR isotropic shifts scale with relativity in terms of the strength of SOC and average atomic numbers, indicating strong relativistic effects on NMR parameters. According to first-principles calculations, we further claim that nuclear magnetic shieldings from relativistic p1/2 states and paramagnetic contributions from low-lying unoccupied p3/2 states are both sensitive to the details of band structures tuned by relativity, which explains why the hidden relativistic effects on band structure can be revealed by 209Bi NMR isotropic shifts in topologically nontrivial half-Heusler compounds. Used in complement to surface-sensitive methods, such as angle resolved photon electron spectroscopy and scanning tunneling spectroscopy, NMR can provide valuable information on bulk electronic states.

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

    Fridjonsson, E.O.

    2015-04-20

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

  19. Determination of relative natural isotopic abundance of 2H using NMR spectroscopy and application in food analysis

    The basic relations are defined for determining the content of deuterium in compound CXHP. Hydrogen atoms 1H and 2H are distributed among the individual diastereotopic points in the molecule which is either monodeuterized or non deuterized. The SNIF-NMR parameter is derived from these assumptions. Procedures are presented for preparing samples for NMR experiments. For measuring NMR spectra of 2H the effects are considered of relaxation times and the total time of measurement. Relaxation times of deuterium in small molecules are of the order of 1 second. The possibilities are shown of using 2H NMR spectroscopy for the study of deuterium transfer during chemical and biochemical reactions, for the determination of isotope purity, the determination of the origin of the sample and for the surveillance of technological processes. Examples of the applications are given. (E.S.). 3 figs., 8 tabs., 42 refs

  20. Optimization of CPMG sequences for NMR borehole measurements

    M. Ronczka

    2012-07-01

    Full Text Available Nuklear Magnetic Resonance (NMR can provide key information such as porosity and permeability for hydrological characterization of geological material. Especially the NMR transverse relaxation time T2 is used to estimate permeability since it reflects a pore-size dependent relaxation process. The measurement sequence (CPMG usually used consists of several thousands of electromagnetic pulses to densely record the relaxation process. These pulses are equidistantly spaced by a time constant τ. In NMR borehole applications the use of CPMG sequences for measuring the transverse relaxation time T2 is limited due to requirements on energy consumption. It is state of the art to conduct at least two sequences with different echo spacings (τ for recording fast and slow relaxing processes that correspond to different pore-sizes. For the purpose to reduce the amount of energy used for conducting CPMG sequences and to obtain both, slow and fast, decaying components within one sequence we tested the usage of CPMG sequences with an increasing τ and a decreasing number of pulses. A synthetic study as well as laboratory measurements on samples of glass beads and granulate of different grain size spectra were conducted to evaluate the effects of of an increasing τ spacing, e.g. an enhanced relaxation due to diffusion processes. The results are showing broadened T2 distributions if the number of pulses is decreasing and the mean grain size is increasing, which is mostly an effect of a significantly shortened acquisition time. The shift of T2 distributions to small decay times in dependence of the τ spacing and the mean grain size distribution is observable. We found that it is possible to conduct CPMG sequences with an increased τ spacing. According to the acquisition time and enhanced diffusion the sequence parameters (number of pulses and τmax has to be chosen carefully. Otherwise the underestimated relaxation time (T2 will lead to misinterpretations.

  1. Bomb parameters

    The reconstruction of neutron and gamma-ray doses at Hiroshima and Nagasaki begins with a determination of the parameters describing the explosion. The calculations of the air transported radiation fields and survivor doses from the Hiroshima and Nagasaki bombs require knowledge of a variety of parameters related to the explosions. These various parameters include the heading of the bomber when the bomb was released, the epicenters of the explosions, the bomb yields, and the tilt of the bombs at time of explosion. The epicenter of a bomb is the explosion point in air that is specified in terms of a burst height and a hypocenter (or the point on the ground directly below the epicenter of the explosion). The current reassessment refines the energy yield and burst height for the Hiroshima bomb, as well as the locations of the Hiroshima and Nagasaki hypocenters on the modern city maps used in the analysis of the activation data for neutrons and TLD data for gamma rays. (J.P.N.)

  2. Characterization by NMR of ozonized methyl linoleate

    Diaz, Maritza F. [National Center for Scientific Research, Havana (Cuba). Ozone Research Center. Dept. of Ozonized Substances]. E-mail: maritza.diaz@cnic.edu.cu; Gavin, Jose A. [University of the Laguna, Tenerife (Spain)

    2007-07-01

    In the present study ozonized methyl linoleate with peroxide index of 1,800 mmol-equiv kg{sup -1} was chemically characterized. Ozonation of methyl linoleate produced hydroperoxides, ozonides and aldehydes which were identified by {sup 1}H and {sup 13}C NMR two-dimensional. The standard methyl linoleate and ozonized methyl linoleate shown very similar {sup 1}H NMR spectra except for the signals at {delta} 9.7 and {delta} 9.6 that correspond to aldehydic hydrogen, {delta} 5.7 and {delta} 5.5 (olefinic signals from hydroperoxides) and {delta} 5.2 ppm (multiplet from ozonides methynic hydrogen). Other resonance assignments are based on the connectivities provided by the hydrogen scalar coupling constants. These results indicate that NMR spectroscopy can provide valuable information about the amount of formed oxygenated compounds in the ozonized methyl linoleate in order to use it to follow up ozone therapy and chemistry of ozonized vegetable oil. (author)

  3. Remote tuning of NMR probe circuits.

    Kodibagkar, V D; Conradi, M S

    2000-05-01

    There are many circumstances in which the probe tuning adjustments cannot be located near the rf NMR coil. These may occur in high-temperature NMR, low-temperature NMR, and in the use of magnets with small diameter access bores. We address here circuitry for connecting a fixed-tuned probe circuit by a transmission line to a remotely located tuning network. In particular, the bandwidth over which the probe may be remotely tuned while keeping the losses in the transmission line acceptably low is considered. The results show that for all resonant circuit geometries (series, parallel, series-parallel), overcoupling of the line to the tuned circuit is key to obtaining a large tuning bandwidth. At equivalent extents of overcoupling, all resonant circuit geometries have nearly equal remote tuning bandwidths. Particularly for the case of low-loss transmission line, the tuning bandwidth can be many times the tuned circuit's bandwidth, f(o)/Q. PMID:10783273

  4. A modularized pulse programmer for NMR spectroscopy

    A modularized pulse programmer for a NMR spectrometer is described. It consists of a networked PCI-104 single-board computer and a field programmable gate array (FPGA). The PCI-104 is dedicated to translate the pulse sequence elements from the host computer into 48-bit binary words and download these words to the FPGA, while the FPGA functions as a sequencer to execute these binary words. High-resolution NMR spectra obtained on a home-built spectrometer with four pulse programmers working concurrently demonstrate the effectiveness of the pulse programmer. Advantages of the module include (1) once designed it can be duplicated and used to construct a scalable NMR/MRI system with multiple transmitter and receiver channels, (2) it is a totally programmable system in which all specific applications are determined by software, and (3) it provides enough reserve for possible new pulse sequences

  5. Deuterium NMR, induced and intrinsic cholesteric lyomesophases

    Induced and intrinsic cholesteric lyotropic mesophases were studied. Induced cholesteric lyomesophases based on potassium laurate (KL) system, with small amounts of cholesterol added, were studied by deuterium NMR and by polarizing microscopy. Order profiles obtained from deuterium NMR of KL perdenderated chains in both induced cholesteric and normal mesophases were compared. The intrinsic cholesteric lyotropic mesophases were based on the amphiphile potassium N-lauroyl serinate (KLNS) in the resolved levo form. The study of the type I intrinsic cholesteric mesophase was made by optical microscopy under polarized light and the type II intrinsic cholesteric lyomesophase was characterized by deuterium NMR. The new texture was explained by the use of the theory of disclinations developed for thermotropic liquid crystals, specially for cholesteric type. (M.J.C.)

  6. Handbook of tritium NMR spectroscopy and applications

    Following a brief introduction, highlighting the importance of 3H nmr spectroscopy for tritium tracer studies, Chapter 1 deals with the theory of the method, the interpretation of spectra and other experimental aspects, emphasizing the importance of careful sample preparation and the special relationship of 3H nmr spectral detail to the wealth of published data for proton spectra. Chapter 2 reviews the current methods for labelling compounds with tritium and the relationship of observed patterns of labelling to these methods. Chapter 3 describes applications of 3H nmr spectroscopy to research in the life sciences which illustrate the power of the technique. Studies employing this analytical tool have revealed numerous interesting and indeed unexpected results in the behaviour of tritium atoms in labelled molecules. These studies have included applications of tritiated compounds in analytical and biochemical problems, in problems of catalysis and reaction mechanisms, and in other areas of scientific research. (author)

  7. Chemical applications of 99Tc NMR spectroscopy: preparation of novel Tc(VII) species and their characterization by multinuclear NMR spectroscopy

    The 99Tc NMR parameters of a number of Tc(VII) and one Tc(V) species have been determined. The anion TcO4- (ω = 22.508 311 MHz in H2O) was chosen as the standard for 99Tc NMR spectroscopy. A 99Tc-17O coupling constant of 131.4 Hz was obtained from a 17O- and 18O-enriched sample of TcO4- whose 99Tc spectrum also showed an isotopic shift of 0.22 ppm/mass number arising from a statistical distribution of 16O/17O/18O isotopic isomers. Technetium-99 and proton NMR provided definitive proof for the existence of the stereochemically nonrigid TcH92- anion. Both TcO3F and the novel TcO3+ cation were synthesized and characterized by 99Tc, 17O, and 19F NMR spectroscopy. Preliminary results on two new technetium(VII) oxyfluorides tentatively identified as F2O2TcOTcO2F2 and TcO2F3 are also reported. The diagmagnetic d2 anion, TcO2(CN)43-, represents the most deshielded 99Tc environment encountered in the present study

  8. NMR Microscopy - Micron-Level Resolution.

    Kwok, Wing-Chi Edmund

    1990-01-01

    Nuclear Magnetic Resonance Imaging (MRI) has been developed into a powerful and widely used diagnostic tool since the invention of techniques using linear magnetic field gradients in 1973. The variety of imaging contrasts obtainable in MRI, such as spin density, relaxation times and flow rate, gives MRI a significant advantage over other imaging techniques. For common diagnostic applications, image resolutions have been in the order of millimeters with slice thicknesses in centimeters. For many research applications, however, resolutions in the order of tens of microns or smaller are needed. NMR Imaging in these high resolution disciplines is known as NMR microscopy. Compared with conventional microscopy, NMR microscopy has the advantage of being non-invasive and non-destructive. The major obstacles of NMR microscopy are low signal-to-noise ratio and effects due to spin diffusion. To overcome these difficulties, more sensitive RF probes and very high magnetic field gradients have to be used. The most effective way to increase sensitivity is to build smaller probes. Microscope probes of different designs have been built and evaluated. Magnetic field gradient coils that can produce linear field gradients up to 450 Gauss/cm were also assembled. In addition, since microscope probes often employ remote capacitors for RF tuning, the associated signal loss in the transmission line was studied. Imaging experiments have been carried out in a 2.1 Tesla small bore superconducting magnet using the typical two-dimensional spin warp imaging technique. Images have been acquired for both biological and non-biological samples. The highest resolution was obtained in an image of a nerve bundle from the spinal cord of a racoon and has an in-plane resolution of 4 microns. These experiments have demonstrated the potential application of NMR microscopy to pathological research, nervous system study and non -destructive testings of materials. One way to further improve NMR microscopy is

  9. The Quiet Renaissance of Protein NMR

    Barrett, Paul J.; Chen, Jiang; Cho, Min-Kyu; Kim, Ji-Hun; Lu, Zhenwei; Mathew, Sijo; Peng, Dungeng; Song, Yuanli; Van Horn, Wade D.; Zhuang, Tiandi; Sönnichsen, Frank D.; Sanders, Charles R.

    2013-01-01

    From roughly 1985 through the start of the new millennium, the cutting edge of solution protein nuclear magnetic resonance (NMR) spectroscopy was to a significant extent driven by the aspiration to determine structures. Here we survey recent advances in protein NMR that herald a renaissance in which a number of its most important applications reflect the broad problem-solving capability displayed by this method during its classical era during the 1970s and early 80s. “Without receivers fitted and kept in order, the air may tingle and thrill with the message, but it will not reach my spirit and consciousness.” Mary Slessor, Calabar, circa 1910 PMID:23368985

  10. Application of site-specific natural isotope fractionation (SNIF-NMR) of hydrogen to the characterization of European beers

    Martin, G.J.; Benbernou, M.; Lantier, F. (Nantes Univ., 44 (France))

    More than one hundred samples of European beers have been investigated by the new SNIF-NMR method which is based on 2H NMR at the natural abundance level and enables site-specific natural isotope fractionation factors in ethanol to be determined. The relative (R) and absolute (D/H)sub(i) parameters are shown to be characteristic of the country where the beers are brewed and the observed variations are explained in terms of cereal composition, water resource, and manufacturing processing (fermentation, yeast, temperature cycle). These new parameters find analytical and mechanistic applications in the identification of a beer and in the investigation of a fermentation process.

  11. Application of site-specific natural isotope fractionation (SNIF-NMR) of hydrogen to the characterization of European beers

    More than one hundred samples of European beers have been investigated by the new SNIF-NMR method which is based on 2H NMR at the natural abundance level and enables site-specific natural isotope fractionation factors in ethanol to be determined. The relative (R) and absolute (D/H)sub(i) parameters are shown to be characteristic of the country where the beers are brewed and the observed variations are explained in terms of cereal composition, water resource, and manufacturing processing (fermentation, yeast, temperature cycle). These new parameters find analytical and mechanistic applications in the identification of a beer and in the investigation of a fermentation process. (author)

  12. NMR-based metabolomics of mammalian cell and tissue cultures

    NMR spectroscopy was used to evaluate growth media and the cellular metabolome in two systems of interest to biomedical research. The first of these was a Chinese hamster ovary cell line engineered to express a recombinant protein. Here, NMR spectroscopy and a quantum mechanical total line shape analysis were utilized to quantify 30 metabolites such as amino acids, Krebs cycle intermediates, activated sugars, cofactors, and others in both media and cell extracts. The impact of bioreactor scale and addition of anti-apoptotic agents to the media on the extracellular and intracellular metabolome indicated changes in metabolic pathways of energy utilization. These results shed light into culture parameters that can be manipulated to optimize growth and protein production. Second, metabolomic analysis was performed on the superfusion media in a common model used for drug metabolism and toxicology studies, in vitro liver slices. In this study, it is demonstrated that two of the 48 standard media components, choline and histidine are depleted at a faster rate than many other nutrients. Augmenting the starting media with extra choline and histidine improves the long-term liver slice viability as measured by higher tissues levels of lactate dehydrogenase (LDH), glutathione and ATP, as well as lower LDH levels in the media at time points out to 94 h after initiation of incubation. In both models, media components and cellular metabolites are measured over time and correlated with currently accepted endpoint measures.

  13. Conventions and nomenclature for double diffusion encoding NMR and MRI.

    Shemesh, Noam; Jespersen, Sune N; Alexander, Daniel C; Cohen, Yoram; Drobnjak, Ivana; Dyrby, Tim B; Finsterbusch, Jurgen; Koch, Martin A; Kuder, Tristan; Laun, Fredrik; Lawrenz, Marco; Lundell, Henrik; Mitra, Partha P; Nilsson, Markus; Özarslan, Evren; Topgaard, Daniel; Westin, Carl-Fredrik

    2016-01-01

    Stejskal and Tanner's ingenious pulsed field gradient design from 1965 has made diffusion NMR and MRI the mainstay of most studies seeking to resolve microstructural information in porous systems in general and biological systems in particular. Methods extending beyond Stejskal and Tanner's design, such as double diffusion encoding (DDE) NMR and MRI, may provide novel quantifiable metrics that are less easily inferred from conventional diffusion acquisitions. Despite the growing interest on the topic, the terminology for the pulse sequences, their parameters, and the metrics that can be derived from them remains inconsistent and disparate among groups active in DDE. Here, we present a consensus of those groups on terminology for DDE sequences and associated concepts. Furthermore, the regimes in which DDE metrics appear to provide microstructural information that cannot be achieved using more conventional counterparts (in a model-free fashion) are elucidated. We highlight in particular DDE's potential for determining microscopic diffusion anisotropy and microscopic fractional anisotropy, which offer metrics of microscopic features independent of orientation dispersion and thus provide information complementary to the standard, macroscopic, fractional anisotropy conventionally obtained by diffusion MR. Finally, we discuss future vistas and perspectives for DDE. PMID:26418050

  14. Performance of the WeNMR CS-Rosetta3 web server in CASD-NMR

    van der Schot, Gijs; Bonvin, Alexandre M. J. J.

    2016-01-01

    We present here the performance of the WeNMR CS-Rosetta3 web server in CASD-NMR, the critical assessment of automated structure determination by NMR. The CS-Rosetta server uses only chemical shifts for structure prediction, in combination, when available, with a post-scoring procedure based on unassigned NOE lists (Huang et al. in J Am Chem Soc 127:1665–1674, 2005b, doi:10.1021/ja047109h). We compare the original submissions using a previous version of the server based on Rosetta version 2.6 ...

  15. Theory of mirrored time domain sampling for NMR spectroscopy

    Ghosh, Arindam; Wu, Yibing; He, Yunfen; Szyperski, Thomas

    2011-12-01

    A generalized theory is presented for novel mirrored hypercomplex time domain sampling (MHS) of NMR spectra. It is the salient new feature of MHS that two interferograms are acquired with different directionality of time evolution, that is, one is sampled forward from time t = 0 to the maximal evolution time tmax, while the second is sampled backward from t = 0 to - tmax. The sampling can be accomplished in a (semi) constant time or non constant-time manner. Subsequently, the two interferograms are linearly combined to yield a complex time domain signal. The manifold of MHS schemes considered here is defined by arbitrary settings of sampling phases ('primary phase shifts') and amplitudes of the two interferograms. It is shown that, for any two given primary phase shifts, the addition theorems of trigonometric functions yield the unique linear combination required to form the complex signal. In the framework of clean absorption mode (CAM) acquisition of NMR spectra being devoid of residual dispersive signal components, 'secondary phase shifts' represent time domain phase errors which are to be eliminated. In contrast, such secondary phase shifts may be introduced by experimental design in order to encode additional NMR parameters, a new class of NMR experiments proposed here. For generalization, it is further considered that secondary phase shifts may depend on primary phase shifts and/or sampling directionality. In order to compare with MHS theory, a correspondingly generalized theory is derived for widely used hypercomplex ('States') sampling (HS). With generalized theory it is shown, first, that previously introduced 'canonical' schemes, characterized by primary phases being multiples of π/4, afford maximal intensity of the desired absorptive signals in the absence of secondary phase shifts, and second, how primary phases can be adjusted to maximize the signal intensity provided that the secondary phase shifts are known. Third, it is demonstrated that theory

  16. Benzhydroximic Acids - NMR Study of Trimethylsilyl Derivatives

    Schraml, Jan; Kvíčalová, Magdalena; Soukupová, Ludmila; Blechta, Vratislav; Exner, Otto

    2000-01-01

    Roč. 597, 1-2 (2000), s. 200-205. ISSN 0022-328X R&D Projects: GA AV ČR IAA4072605; GA MŠk LB98233 Keywords : trimethylsilyl derivatives * substituted benzhydroximic acids * NMR chemical shifts Subject RIV: CC - Organic Chemistry Impact factor: 1.632, year: 2000

  17. Responsibilities of NMR application in research

    NMR investigations in clinical and/or scientific studies may be covered by different radiation protection regulations and legal liability responsibilities. The following topics are discussed: incidental findings, applicability to the situation in radiological hospitals, explicit abandonment of probands/patients, liability of the clinic, liability with respect to contrast agent administration, creation of additional imaging, attendance of radiologists, information requirements.

  18. NMR study of multiferroic iron niobate perovskites

    Kouřil, K.; Chlan, V.; Štěpánková, H.; Řezníček, R.; Laguta, Valentyn; Raevski, I. P.

    Warszawa : Polish Academy of Sciences, 2015, s. 234-236. ISSN 0587-4246. [The European Conference PHYSICS OF MAGNETISM 2014/PM'14/. Poznań (PL), 23.06.2014-27.06.2014] R&D Projects: GA ČR GA13-11473S Institutional support: RVO:68378271 Keywords : multiferroics * magnetism * NMR Subject RIV: BM - Solid Matter Physics ; Magnetism

  19. The bar coil for NMR tomograph

    The bar coil (bi-planar) for the NMR tomograph, designed for medical diagnostics, has been described. The tests of coil shown that it generates good homogenous magnetic field in a big volume what results in improving of the signal-to-noise ratio

  20. Molecular dynamics - NMR experiments and simulations

    Dračínský, Martin; Hodgkinson, P.; Kessler, Jiří; Bouř, Petr

    Brno : Masaryk University Press, 2015 - (Sklenář, V.). s. 277-278 ISBN 978-80-210-7890-1. [EUROMAR 2015. 05.07.2015-10.07.2015, Praha] Institutional support: RVO:61388963 Keywords : molecular dynamics * NMR spectroscopy * MD simulations Subject RIV: CF - Physical ; Theoretical Chemistry

  1. 3D Reconstruction of NMR Images

    Peter Izak; Milan Smetana; Libor Hargas; Miroslav Hrianka; Pavol Spanik

    2007-01-01

    This paper introduces experiment of 3D reconstruction NMR images scanned from magnetic resonance device. There are described methods which can be used for 3D reconstruction magnetic resonance images in biomedical application. The main idea is based on marching cubes algorithm. For this task was chosen sophistication method by program Vision Assistant, which is a part of program LabVIEW.

  2. Novel NMR Method for Organic Aerosol Analysis

    Horník, Štěpán

    Prague: Institute of Chemical Process Fundamental of the CAS, v. v. i, 2015 - (Bendová, M.; Wagner, Z.), s. 20-21 ISBN 978-80-86186-70-2. [Bažant Postgraduate Conference 2015. Prague (CZ)] Institutional support: RVO:67985858 Keywords : nmr method * organic aerosol composition * analysis Subject RIV: CF - Physical ; Theoretical Chemistry

  3. Novel NMR Method for Organic Aerosol Analysis

    Horník, Štěpán

    Prague : Institute of Chemical Process Fundamental of the CAS, v. v. i, 2015 - (Bendová, M.; Wagner, Z.), s. 20-21 ISBN 978-80-86186-70-2. [Bažant Postgraduate Conference 2015. Prague (CZ)] Institutional support: RVO:67985858 Keywords : nmr method * organic aerosol composition * analysis Subject RIV: CF - Physical ; Theoretical Chemistry

  4. Hyperpolarized NMR Probes for Biological Assays

    Sebastian Meier

    2014-01-01

    Full Text Available During the last decade, the development of nuclear spin polarization enhanced (hyperpolarized molecular probes has opened up new opportunities for studying the inner workings of living cells in real time. The hyperpolarized probes are produced ex situ, introduced into biological systems and detected with high sensitivity and contrast against background signals using high resolution NMR spectroscopy. A variety of natural, derivatized and designed hyperpolarized probes has emerged for diverse biological studies including assays of intracellular reaction progression, pathway kinetics, probe uptake and export, pH, redox state, reactive oxygen species, ion concentrations, drug efficacy or oncogenic signaling. These probes are readily used directly under natural conditions in biofluids and are often directly developed and optimized for cellular assays, thus leaving little doubt about their specificity and utility under biologically relevant conditions. Hyperpolarized molecular probes for biological NMR spectroscopy enable the unbiased detection of complex processes by virtue of the high spectral resolution, structural specificity and quantifiability of NMR signals. Here, we provide a survey of strategies used for the selection, design and use of hyperpolarized NMR probes in biological assays, and describe current limitations and developments.

  5. SQUID detected NMR in microtesla magnetic fields

    Matlachov, Andrei N.; Volegov, Petr L.; Espy, Michelle A.; George, John S.; Kraus, Robert H.

    2004-09-01

    We have built an NMR system that employs a superconducting quantum interference device (SQUID) detector and operates in measurement fields of 2-25 μT. The system uses a pre-polarizing field from 4 to 30 mT generated by simple room-temperature wire-wound coils that are turned off during measurements. The instrument has an open geometry with samples located outside the cryostat at room-temperature. This removes constraints on sample size and allows us to obtain signals from living tissue. We have obtained 1H NMR spectra from a variety of samples including water, mineral oil, and a live frog. We also acquired gradient encoded free induction decay (FID) data from a water-plastic phantom in the μT regime, from which simple projection images were reconstructed. NMR signals from samples inside metallic containers have also been acquired. This is possible because the penetration skin depth is much greater at the low operating frequencies of this system than for conventional systems. Advantages to ultra-low field NMR measurements include lower susceptibility artifacts caused by high strength polarizing and measurement fields, and negligible line width broadening due to measurement field inhomogeneity, reducing the burden of producing highly homogeneous fields.

  6. e-NMR gLite grid enabled infrastructure

    Ferreira, N.L.; Wassenaar, T.A.; de Vries, S.J.; van Dijk, M.; van der Schot, G.; van der Zwan, J.; Boelens, R.; Bonvin, A.M.J.J.; Giachetti, A.; Carotenuto, D.; Rosato, A.; Bertini, I.; Herrmann, T.; Bagaria, A.; Zharavin, V.; Jonker, H.R.A.; Güntert, P.; Schwalbe, H.; Vranken, W.F.

    2010-01-01

    The e-NMR project is an European e-infrastructure that aims at providing the bio-NMR community with a software platform integrating and streamlining computational approaches necessary for NMR data analysis. The infrastructure is grid enabled with fteen gLite based partners sharing computational reso

  7. Several Applications of NMR in Organic Chemistry Research

    CUI yuxin; LIU xuehui; XU hao

    2001-01-01

    @@ Modem NMR techniques, especially 2D-NMR have presented their powerful application in organic chemistry. Not only in structural determination, mechanism investigation, but also in solution conformation study for natural products. In this paper, various pulse field gradient NMR techniques such as COSY, NOESY, HMBC and HMQC were combined to study these problems.

  8. Petrophysical properties of greensand as predicted from NMR measurements

    Hossain, Zakir; Grattoni, Carlos A.; Solymar, Mikael;

    2011-01-01

    ABSTRACT: Nuclear magnetic resonance (NMR) is a useful tool in reservoir evaluation. The objective of this study is to predict petrophysical properties from NMR T2 distributions. A series of laboratory experiments including core analysis, capillary pressure measurements, NMR T2 measurements and i...

  9. Performance of the WeNMR CS-Rosetta3 web server in CASD-NMR

    We present here the performance of the WeNMR CS-Rosetta3 web server in CASD-NMR, the critical assessment of automated structure determination by NMR. The CS-Rosetta server uses only chemical shifts for structure prediction, in combination, when available, with a post-scoring procedure based on unassigned NOE lists (Huang et al. in J Am Chem Soc 127:1665–1674, 2005b, doi: 10.1021/ja047109h 10.1021/ja047109h ). We compare the original submissions using a previous version of the server based on Rosetta version 2.6 with recalculated targets using the new R3FP fragment picker for fragment selection and implementing a new annotation of prediction reliability (van der Schot et al. in J Biomol NMR 57:27–35, 2013, doi: 10.1007/s10858-013-9762-6 10.1007/s10858-013-9762-6 ), both implemented in the CS-Rosetta3 WeNMR server. In this second round of CASD-NMR, the WeNMR CS-Rosetta server has demonstrated a much better performance than in the first round since only converged targets were submitted. Further, recalculation of all CASD-NMR targets using the new version of the server demonstrates that our new annotation of prediction quality is giving reliable results. Predictions annotated as weak are often found to provide useful models, but only for a fraction of the sequence, and should therefore only be used with caution

  10. Solid-state NMR studies of supercapacitors.

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

    2016-01-01

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

  11. Lithological control on gas hydrate saturation as revealed by signal classification of NMR logging data

    Bauer, Klaus; Kulenkampff, Johannes; Henninges, Jan; Spangenberg, Erik

    2015-09-01

    In this paper, nuclear magnetic resonance (NMR) downhole logging data are analyzed with a new strategy to study gas hydrate-bearing sediments in the Mackenzie Delta (NW Canada). In NMR logging, transverse relaxation time (T2) distribution curves are usually used to determine single-valued parameters such as apparent total porosity or hydrocarbon saturation. Our approach analyzes the entire T2 distribution curves as quasi-continuous signals to characterize the rock formation. We apply self-organizing maps, a neural network clustering technique, to subdivide the data set of NMR curves into classes with a similar and distinctive signal shape. The method includes (1) preparation of data vectors, (2) unsupervised learning, (3) cluster definition, and (4) classification and depth mapping of all NMR signals. Each signal class thus represents a specific pore size distribution which can be interpreted in terms of distinct lithologies and reservoir types. A key step in the interpretation strategy is to reconcile the NMR classes with other log data not considered in the clustering analysis, such as gamma ray, hydrate saturation, and other logs. Our results defined six main lithologies within the target zone. Gas hydrate layers were recognized by their low signal amplitudes for all relaxation times. Most importantly, two subtypes of hydrate-bearing shaly sands were identified. They show distinct NMR signals and differ in hydrate saturation and gamma ray values. An inverse linear relationship between hydrate saturation and clay content was concluded. Finally, we infer that the gas hydrate is not grain coating, but rather, pore filling with matrix support is the preferred growth habit model for the studied formation.

  12. Non-uniform sampling of NMR relaxation data

    Schwarz-Linnet, Troels; Teilum, Kaare

    2016-01-01

    The use of non-uniform sampling of NMR spectra may give significant reductions in the data acquisition time. For quantitative experiments such as the measurement of spin relaxation rates, non-uniform sampling is however not widely used as inaccuracies in peak intensities may lead to errors...... in the extracted dynamic parameters. By systematic reducing the coverage of the Nyquist grid of (15)N Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion datasets for four different proteins and performing a full data analysis of the resulting non-uniform sampled datasets, we have compared the performance...... reconstructs the non-uniform sampled spectra with high accuracy. For two of the four analyzed datasets, a coverage of only 20 % results in essentially the same results as the fully sampled data. As exemplified by other data, such a low coverage is in general not enough to produce reliable results. We find...

  13. Pulsed NMR experiments in superfluid 3He confined in aerogel

    Pulsed NMR experiments have been performed in both B and supercooled A phases of superfluid 3He in aerogel. Dependencies of spin precession frequency on tipping angle in B-phase of superfluid 3He in aerogel are found to be different for pure 3He and for the cell preplated with 4He. A sharp increase of the frequency for tipping angles greater than 104 deg. was observed in low temperature superfluid phase of 3He in 4He preplated aerogel as it is expected for the B-phase structure of the order parameter. Dependencies of the frequency on the tipping angle in supercooled A-phase are similar for both pure 3He and 4He preplated aerogel

  14. NMR Constraints Analyser: a web-server for the graphical analysis of NMR experimental constraints.

    Heller, Davide Martin; Giorgetti, Alejandro

    2010-07-01

    Nuclear magnetic resonance (NMR) spectroscopy together with X-ray crystallography, are the main techniques used for the determination of high-resolution 3D structures of biological molecules. The output of an NMR experiment includes a set of lower and upper limits for the distances (constraints) between pairs of atoms. If the number of constraints is high enough, there will be a finite number of possible conformations (models) of the macromolecule satisfying the data. Thus, the more constraints are measured, the better defined these structures will be. The availability of a user-friendly tool able to help in the analysis and interpretation of the number of experimental constraints per residue, is thus of valuable importance when assessing the levels of structure definition of NMR solved biological macromolecules, in particular, when high-quality structures are needed in techniques such as, computational biology approaches, site-directed mutagenesis experiments and/or drug design. Here, we present a free publicly available web-server, i.e. NMR Constraints Analyser, which is aimed at providing an automatic graphical analysis of the NMR experimental constraints atom by atom. The NMR Constraints Analyser server is available from the web-page http://molsim.sci.univr.it/constraint. PMID:20513646

  15. From crystalline to glassy gallium fluoride materials: an NMR study of 69Ga and 71Ga quadrupolar nuclei.

    Bureau, B; Silly, G; Buzaré, J Y; Legein, C; Massiot, D

    1999-11-01

    Owing to the implementation of acquisition techniques specific for nuclei with very large quadrupolar interaction (full shifted echo and variable offset cumulative spectra (VOCS)), NMR spectra of 69Ga and 71Ga are obtained in crystallised (PbGaF5, Pb3Ga2F12, Pb9Ga2F24 and CsZnGaF6) and glassy (PbF2-ZnF2-GaF3) gallium fluorides. Simulations of both static (full echo or VOCS) and 15 kHz MAS spectra allow to obtain consistent determinations of isotropic chemical shifts and very large quadrupolar parameters (nuQ up to 14 MHz). In the crystalline compounds whose structures are unknown, the number and the local symmetry of the different gallium sites are tentatively worked out. For the glassy systems, a continuous Czjzek's distribution of the NMR quadrupolar parameters accounts for the particular shape of the NMR spectrum. PMID:10670905

  16. Comparative study of models for predicting permeability from nuclear magnetic resonance (NMR) logs in two Chinese tight sandstone reservoirs

    Xiao, Liang; Liu, Xiao-Peng; Zou, Chang-Chun; Hu, Xiao-Xin; Mao, Zhi-Qiang; Shi, Yu-Jiang; Guo, Hao-Peng; Li, Gao-Ren

    2014-02-01

    Based on the analysis of mercury injection capillary pressure (MICP) and nuclear magnetic resonance (NMR) experimental data for core plugs, which were drilled from two Chinese tight sandstone reservoirs, permeability prediction models, such as the classical SDR, Timur-Coates, the Swanson parameter, the Capillary Parachor, the R10 and R35 models, are calibrated to estimating permeabilities from field NMR logs, and the applicabilities of these permeability prediction models are compared. The processing results of several field examples show that the SDR model is unavailable in tight sandstone reservoirs. The Timur-Coates model is effective once the optimal T 2cutoff can be acquired to accurately calculate FFI and BVI from field NMR logs. The Swanson parameter model and the Capillary Parachor model are not always available in tight sandstone reservoirs. The R35 based model cannot effectively work in tight sandstone reservoirs, while the R10 based model is optimal in permeability prediction.

  17. Physiological parameters

    The physiological characteristics of man depend on the intake, metabolism and excretion of stable elements from food, water, and air. The physiological behavior of natural radionuclides and radionuclides from nuclear weapons testing and from the utilization of nuclear energy is believed to follow the pattern of stable elements. Hence information on the normal physiological processes occurring in the human body plays an important role in the assessment of the radiation dose received by man. Two important physiological parameters needed for internal dose determination are the pulmonary function and the water balance. In the Coordinated Research Programme on the characterization of Asian population, five participants submitted data on these physiological characteristics - China, India, Japan, Philippines and Viet Nam. During the CRP, data on other pertinent characteristics such as physical and dietary were simultaneously being collected. Hence, the information on the physiological characteristics alone, coming from the five participants were not complete and are probably not sufficient to establish standard values for the Reference Asian Man. Nonetheless, the data collected is a valuable contribution to this research programme

  18. NMR Data Analysis: A Time-Domain Parametric Approach Using Adaptive Subband Decomposition

    Djermoune E.-H.

    2013-03-01

    Full Text Available This paper presents a fast time-domain data analysis method for one- and two-dimensional Nuclear Magnetic Resonance (NMR spectroscopy, assuming Lorentzian lineshapes, based on an adaptive spectral decomposition. The latter is achieved through successive filtering and decimation steps ending up in a decomposition tree. At each node of the tree, the parameters of the corresponding subband signal are estimated using some high-resolution method. The resulting estimation error is then processed through a stopping criterion which allows one to decide whether the decimation should be carried on or not. Thus the method leads to an automated selection of the decimation level and consequently to a signal-adaptive decomposition. Moreover, it enables one to reduce the processing time and makes the choice of usual free parameters easier, comparatively to the case where the whole signal is processed at once. The efficiency of the method is demonstrated using 1-D and 2-D 13C NMR signals.

  19. Solution conformation and dynamics of a tetrasaccharide related to the LewisX antigen deduced by NMR relaxation measurements

    1H-NMR cross-relaxation rates and nonselective longitudinal relaxation times have been obtained at two magnetic fields (7.0 and 11.8 T) and at a variety of temperatures for the branched tetrasaccharide methyl 3-O-α-N-acetyl-galactosaminyl-β-galactopyranosyl-(1→4)[3-O-α-fucosyl] -glucopyranoside (1), an inhibitor of astrocyte growth. In addition, 13C-NMR relaxation data have also been recorded at both fields. The 1H-NMR relaxation data have been interpreted using different motional models to obtain proton-proton correlation times. The results indicate that the GalNAc and Fuc rings display more extensive local motion than the two inner Glc and Gal moieties, since those present significantly shorter local correlation times. The13C-NMR relaxation parameters have been interpreted in terms of the Lipari-Szabo model-free approach. Thus, order parameters and internal motion correlation times have been deduced. As obtained for the1H-NMR relaxation data, the two outer residues possess smaller order parameters than the two inner rings. Internal correlation times are in the order of 100 ps. The hydroxymethyl groups have also different behaviour,with the exocyclic carbon on the glucopyranoside unit showing the highestS2. Molecular dynamics simulations using a solvated system have also been performed and internal motion correlation functions have been deduced from these calculations. Order parameters and interproton distances have been compared to those inferred from the NMR measurements. The obtained results are in fair agreement with the experimental data

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

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

    1997-07-15

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

  1. Squid detected NMR and MRI at ultralow fields

    Clarke, John; Pines, Alexander; McDermott, Robert F.; Trabesinger, Andreas H.

    2008-12-16

    Nuclear magnetic resonance (NMR) signals are detected in microtesla fields. Prepolarization in millitesla fields is followed by detection with an untuned dc superconducting quantum interference device (SQUID) magnetometer. Because the sensitivity of the SQUID is frequency independent, both signal-to-noise ratio (SNR) and spectral resolution are enhanced by detecting the NMR signal in extremely low magnetic fields, where the NMR lines become very narrow even for grossly inhomogeneous measurement fields. MRI in ultralow magnetic field is based on the NMR at ultralow fields. Gradient magnetic fields are applied, and images are constructed from the detected NMR signals.

  2. Solid state NMR of biopolymers and synthetic polymers

    Solid state NMR has been invaluable in evaluating the structure, phase separation, and dynamics of polymers. Because polymers are generally used in the solid state, solid state NMR is especially powerful because it provides information about the materials in their native state. This review gives a general overview of solid state NMR, concentrating on solid state 13 C and 2 H NMR. It then focuses on two examples: the biopolymer spider silka and the engineering material polyurethane. It illustrates how solid state NMR can provide new information about synthetic and bio-polymers. (author)

  3. Inadequate-1D and dynamic NMR of mesoion 3-phenyl-1-thio-2,3,4-triazole-5-methylides; INADEQUATE-1D i dynamiczny NMR mezojonowych 3-fenylo-1-tio-2,3,4-triazolo-5-metylidow

    Bocian, W.; Stefaniak, L. [Inst. Chemii Organicznej, Polska Akademia Nauk, Warsaw (Poland)

    1994-12-31

    The chemical shifts and coupling constants have been measured in series of mesoionic triazoles by means of inadequate atoms and dynamic NMR techniques. The electronic structure and other parameters of C5-C6 chemical bond in different derivatives of mesoionic 3-phenyl-1-thio-2,3,4-triazole-5 methyls have been determined. 14 refs, 3 figs, 2 tabs.

  4. Lithological controls on gas hydrate saturation: Insights from signal classification of NMR downhole data

    Bauer, Klaus; Kulenkampff, Johannes; Henninges, Jan; Spangenberg, Erik

    2016-04-01

    Nuclear magnetic resonance (NMR) downhole data are analyzed with a new strategy to study gas hydrate-bearing sediments in the Mackenzie Delta (NW Canada). NMR logging is a powerful tool to study geological reservoir formations. The measurements are based on interactions between the magnetic moments of protons in geological formation water and an external magnetic field. Inversion of the measured raw data provides so-called transverse relaxation time (T2) distribution curves or spectra. Different parts of the T2 curve are related with distinct pore radii and corresponding fluid components. A common practice in the analysis of T2 distribution curves is to extract single-valued parameters such as apparent total porosity. Moreover, the derived total NMR apparent porosity and the gamma-gamma density log apparent porosity can be combined to estimate gas hydrate saturation in hydrate-bearing sediments. To avoid potential loss of information, in our new approach we analyze the entire T2 distribution curves as quasi-continuous signals to characterize the rock formation. The approach is applied to NMR data measured in gas hydrate research well Mallik 5L-38. We use self-organizing maps, a neural network clustering technique, to subdivide the data set of NMR T2 distribution curves into classes with a similar and distinctive signal shape. The method includes (1) preparation of data vectors, (2) unsupervised learning, (3) cluster definition, and (4) classification and depth mapping of all NMR signals. Each signal class thus represents a specific pore size distribution which can be interpreted in terms of distinct lithologies and reservoir types. A key step in the interpretation strategy is to reconcile the NMR classes with other log data not considered in the clustering analysis, such as gamma ray, photo-electric factor, hydrate saturation, and other logs. Our results defined six main lithologies within the target zone. Gas hydrate layers were recognized by their low signal

  5. Toward cardiac electrophysiological mapping based on micro-Tesla NMR: a novel modality for localizing the cardiac reentry

    Kiwoong Kim

    2012-01-01

    Matching the proton magnetic resonance frequency to the frequency of a periodic electrophysiological excitation of myocardium enables direct localization of the cardiac reentry by magnetic resonance imaging techniques. The feasibility of this new idea has been demonstrated by conducting a numerical simulation based on a realistic heart model and experimental parameters in SQUID-based micro-Tesla NMR.

  6. Toward cardiac electrophysiological mapping based on micro-Tesla NMR: a novel modality for localizing the cardiac reentry

    Kim, Kiwoong

    2012-06-01

    Matching the proton magnetic resonance frequency to the frequency of a periodic electrophysiological excitation of myocardium enables direct localization of the cardiac reentry by magnetic resonance imaging techniques. The feasibility of this new idea has been demonstrated by conducting a numerical simulation based on a realistic heart model and experimental parameters in SQUID-based micro-Tesla NMR.

  7. Toward cardiac electrophysiological mapping based on micro-Tesla NMR: a novel modality for localizing the cardiac reentry

    Kiwoong Kim

    2012-06-01

    Full Text Available Matching the proton magnetic resonance frequency to the frequency of a periodic electrophysiological excitation of myocardium enables direct localization of the cardiac reentry by magnetic resonance imaging techniques. The feasibility of this new idea has been demonstrated by conducting a numerical simulation based on a realistic heart model and experimental parameters in SQUID-based micro-Tesla NMR.

  8. STUDY ON THE SEQUENCE STRUCTURE OF SBR BY 13C- NMR METHOD Ⅰ. ASSIGNMENT FOR UNSATURATED CARBONS SPECTRA

    JIAO Shuke; CHEN Xiaonong; HU Liping; YAN Baozhen

    1990-01-01

    The sequence structures of emulsion- processed SBR and solution- processed ( by lithium catalyst )SBR were investigated by 13C- NMR spectroscopy. Seventeen peaks within unsaturated carbon region were recorded under the adopted experimental conditions. Assignments for these peaks were made by empirical- parameter- evaluation method.

  9. STUDY ON THE SEQUENCE STRUCTURE OF SBR BY 13C- NMR METHOD Ⅱ . PEAK ASSIGNMENT FOR ALIPHATIC CARBONS SPECTRA

    JIAO Shuke; CHEN Xiaonong; HU Liping; YAN Baozhen

    1990-01-01

    The study on 13C-NMR spectra of aliphatic carbon region of emulsion-processed and solution-processed ( by lithium catalyst ) SBR was carried out. The assignments for more than thirty odd peaks observed experimentally were made by using " corresponding analysis " method, combined with the empirical parameters reported in literature. The peak intensities were calculated based on Bernoullian statistic assumption.

  10. NMR with excitation modulated by Frank sequences.

    Blümich, Bernhard; Gong, Qingxia; Byrne, Eimear; Greferath, Marcus

    2009-07-01

    Miniaturized NMR is of growing importance in bio-, chemical, and -material sciences. Other than the magnet, bulky components are the radio-frequency power amplifier and the power supply or battery pack. We show that constant flip-angle excitation with phase modulation following a particular type of polyphase perfect sequences results in low peak excitation power at high response peak power. It has ideal power distribution in both the time domain and the frequency domain. A savings in peak excitation power of six orders of magnitude has been realized compared to conventionally pulsed excitation. Among others, the excitation promises to be of use for button-cell operated miniature NMR devices as well as for complying with specific-absorption-rate regulations in high-field medical imaging. PMID:19386525

  11. Nuclear spin noise in NMR revisited

    Ferrand, Guillaume; Huber, Gaspard; Luong, Michel; Desvaux, Hervé

    2015-09-01

    The theoretical shapes of nuclear spin-noise spectra in NMR are derived by considering a receiver circuit with finite preamplifier input impedance and a transmission line between the preamplifier and the probe. Using this model, it becomes possible to reproduce all observed experimental features: variation of the NMR resonance linewidth as a function of the transmission line phase, nuclear spin-noise signals appearing as a "bump" or as a "dip" superimposed on the average electronic noise level even for a spin system and probe at the same temperature, pure in-phase Lorentzian spin-noise signals exhibiting non-vanishing frequency shifts. Extensive comparisons to experimental measurements validate the model predictions, and define the conditions for obtaining pure in-phase Lorentzian-shape nuclear spin noise with a vanishing frequency shift, in other words, the conditions for simultaneously obtaining the spin-noise and frequency-shift tuning optima.

  12. Nuclear spin noise in NMR revisited

    Ferrand, Guillaume; Luong, Michel; Desvaux, Hervé

    2015-01-01

    The theoretical shapes of nuclear spin-noise spectra in NMR are derived by considering a receiver circuit with finite, preamplifier input impedance and a transmission line between the preamplifier and the probe. Using this model, it becomes possible to reproduce all observed experimental features: variation of the NMR resonance linewidth as a function of the transmission line phase, nuclear spin-noise signals appearing as a "bump" or as a "dip" superimposed on the average electronic noise level even for a spin system and probe at the same temperature, pure in-phase Lorentzian spin-noise signals exhibiting non-vanishing frequency shifts. Extensive comparison to experimental measurements validate the model predictions, and define the conditions for obtaining pure in-phase Lorentzian-shape nuclear spin noise with a vanishing frequency shift, in other words, the conditions for simultaneously obtaining the Spin-Noise and Frequency-Shift Tuning Optima.

  13. TROSY NMR with partially deuterated proteins.

    Eletsky, A; Kienhöfer, A; Pervushin, K

    2001-06-01

    TROSY-type optimization of liquid-state NMR experiments is based on the preservation of unique coherence transfer pathways with distinct transverse relaxation properties. The broadband decoupling of the 1H spins interchanges the TROSY and anti-TROSY magnetization transfer pathways and thus is not used in TROSY-type triple resonance experiments or is replaced with narrowband selective decoupling. To achieve the full advantage of TROSY, the uniform deuteration of proteins is usually required. Here we propose a new and general method for 1H broadband decoupling in TROSY NMR, which does not compromise the relaxation optimization in the 15N-1H moieties, but uniformly and efficiently refocuses the 1JCH scalar coupling evolution in the 13C-1H moieties. Combined with the conventional 2H decoupling, this method enables obtaining high sensitivity TROSY-type triple resonance spectra with partially deuterated or fully protonated 13C,15N labeled proteins. PMID:11495249

  14. NMR Quantum Calculations of the Jones Polynomial

    Marx, Raimund; Kauffman, Louis; Lomonaco, Samuel; Spörl, Andreas; Pomplun, Nikolas; Myers, John; Glaser, Steffen J

    2009-01-01

    The repertoire of problems theoretically solvable by a quantum computer recently expanded to include the approximate evaluation of knot invariants, specifically the Jones polynomial. The experimental implementation of this evaluation, however, involves many known experimental challenges. Here we present experimental results for a small-scale approximate evaluation of the Jones Polynomial by nuclear-magnetic resonance (NMR), in addition we show how to escape from the limitations of NMR approaches that employ pseudo pure states. Specifically, we use two spin 1/2 nuclei of natural abundance chloroform and apply a sequence of unitary transforms representing the Trefoil Knot, the Figure Eight Knot and the Borromean Rings. After measuring the state of the molecule in each case, we are able to estimate the value of the Jones Polynomial for each of the knots.

  15. NMR-based diffusion lattice imaging.

    Laun, Frederik Bernd; Müller, Lars; Kuder, Tristan Anselm

    2016-03-01

    Nuclear magnetic resonance (NMR) diffusion experiments are widely employed as they yield information about structures hindering the diffusion process, e.g., about cell membranes. While it has been shown in recent articles that these experiments can be used to determine the shape of closed pores averaged over a volume of interest, it is still an open question how much information can be gained in open well-connected systems. In this theoretical work, it is shown that the full structure information of connected periodic systems is accessible. To this end, the so-called "SEquential Rephasing by Pulsed field-gradient Encoding N Time intervals" (SERPENT) sequence is used, which employs several diffusion encoding gradient pulses with different amplitudes. Two two-dimensional solid matrices that are surrounded by an NMR-visible medium are considered: a hexagonal lattice of cylinders and a rectangular lattice of isosceles triangles. PMID:27078384

  16. An NMR study on shale wettability

    Odusina, Elijah; Sondergeld, Carl; Rai, Chandra [University of Oklahoma (United States)

    2011-07-01

    In recent years, the importance of shales as unconventional gas resources has grown significantly. It is therefore important to reach a better understanding of their petrophysical properties. One of the important rock properties that is directly linked to successful hydrocarbon recovery is wettability. This paper presents a study on shale wettability using nuclear magnetic resonance (NMR) to monitor sequential imbibition of brine and oil. Due to the presence of mineralogical variations, low permeability and viscosity, and complex pore structure, the interpretation of wettability using conventional approaches becomes complex. Samples that included 21 core plugs from the Eagle Ford shale, 12 from the Barnett, 11 from the Floyd, and 10 from the Woodford shale were analyzed. The NMR study confirmed the water-wet behavior of Berea sandstone. From the study, it was seen that the Woodford shale showed more affinity for dodecane than did the other shales.

  17. NMR-Based Diffusion Lattice Imaging

    Laun, Frederik Bernd

    2013-01-01

    Nuclear magnetic resonance (NMR) diffusion experiments are widely employed as they yield information about structures hindering the diffusion process, e.g. about cell membranes. While it has been shown in recent articles, that these experiments can be used to determine the exact shape of closed pores averaged over a volume of interest, it is still an open question how much information can be gained in open systems. In this theoretical work, we show that the full structure information of periodic open systems is accessible. To this end, the so-called 'SEquential Rephasing by Pulsed field-gradient Encoding N Time-intervals' (SERPENT) sequence is used, which employs several diffusion weighting gradient pulses with different amplitudes. The structural information is obtained by an iterative technique relying on a Gaussian envelope model of the diffusion propagator. Two solid matrices that are surrounded by an NMR-visible medium are considered: a hexagonal lattice of cylinders and a cubic lattice of triangles.

  18. NMR spectral analysis using prior knowledge

    Kasai, Takuma; Nagata, Kenji; Okada, Masato; Kigawa, Takanori

    2016-03-01

    Signal assignment is a fundamental step for analyses of protein structure and dynamics with nuclear magnetic resonance (NMR). Main-chain signal assignment is achieved with a sequential assignment method and/or an amino-acid selective stable isotope labeling (AASIL) method. Combinatorial selective labeling (CSL) methods, as well as our labeling strategy, stable isotope encoding (SiCode), were developed to reduce the required number of labeled samples, since one of the drawbacks of AASIL is that many samples are needed. Signal overlapping in NMR spectra interferes with amino-acid determination by CSL and SiCode. Since spectral deconvolution by peak fitting with a gradient method cannot resolve closely overlapped signals, we developed a new method to perform both peak fitting and amino acid determination simultaneously, with a replica exchange Monte Carlo method, incorporating prior knowledge of stable-isotope labeling ratios and the amino-acid sequence of the protein.

  19. NMR-based diffusion lattice imaging

    Laun, Frederik Bernd; Müller, Lars; Kuder, Tristan Anselm

    2016-03-01

    Nuclear magnetic resonance (NMR) diffusion experiments are widely employed as they yield information about structures hindering the diffusion process, e.g., about cell membranes. While it has been shown in recent articles that these experiments can be used to determine the shape of closed pores averaged over a volume of interest, it is still an open question how much information can be gained in open well-connected systems. In this theoretical work, it is shown that the full structure information of connected periodic systems is accessible. To this end, the so-called "SEquential Rephasing by Pulsed field-gradient Encoding N Time intervals" (SERPENT) sequence is used, which employs several diffusion encoding gradient pulses with different amplitudes. Two two-dimensional solid matrices that are surrounded by an NMR-visible medium are considered: a hexagonal lattice of cylinders and a rectangular lattice of isosceles triangles.

  20. 1H NMR in a-Si

    Carlos, W. E.; Taylor, P. C.

    1982-10-01

    Results of pulsed NMR studies of hydrogen in a-Si: H prepared at several laboratories by glow discharge of silane are presented. The origins of the two 1H NMR lines seen in almost all samples of a-Si: H are discussed. Solid-echo measurements are presented which indicate that these two components are due to spatially isolated groups of protons. We attribute the narrow line to protons slightly clustered in the bulk of the material and the broad line to protons distributed on internal surfaces. The spin-lattice relaxation time shows a minimum at T~30 K which is interpreted as due to relaxation via spin diffusion to a small number of H2 molecules acting as relaxation centers. Annealing results suggest that all the hydrogen molecules are trapped in very similar sites.

  1. NMR studies of nucleic acid dynamics

    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.

  2. Nuclear spin noise in NMR revisited

    Ferrand, Guillaume; Luong, Michel [Laboratoire d’Ingénierie des Systèmes Accélérateurs et des Hyperfréquences, SACM, CEA, Université Paris-Saclay, CEA/Saclay, F-91191 Gif-sur-Yvette (France); Huber, Gaspard; Desvaux, Hervé, E-mail: herve.desvaux@cea.fr [Laboratoire Structure et Dynamique par Résonance Magnétique, NIMBE, CEA, CNRS, Université Paris-Saclay, CEA/Saclay, F-91191 Gif-sur-Yvette (France)

    2015-09-07

    The theoretical shapes of nuclear spin-noise spectra in NMR are derived by considering a receiver circuit with finite preamplifier input impedance and a transmission line between the preamplifier and the probe. Using this model, it becomes possible to reproduce all observed experimental features: variation of the NMR resonance linewidth as a function of the transmission line phase, nuclear spin-noise signals appearing as a “bump” or as a “dip” superimposed on the average electronic noise level even for a spin system and probe at the same temperature, pure in-phase Lorentzian spin-noise signals exhibiting non-vanishing frequency shifts. Extensive comparisons to experimental measurements validate the model predictions, and define the conditions for obtaining pure in-phase Lorentzian-shape nuclear spin noise with a vanishing frequency shift, in other words, the conditions for simultaneously obtaining the spin-noise and frequency-shift tuning optima.

  3. Nuclear spin noise in NMR revisited

    The theoretical shapes of nuclear spin-noise spectra in NMR are derived by considering a receiver circuit with finite preamplifier input impedance and a transmission line between the preamplifier and the probe. Using this model, it becomes possible to reproduce all observed experimental features: variation of the NMR resonance linewidth as a function of the transmission line phase, nuclear spin-noise signals appearing as a “bump” or as a “dip” superimposed on the average electronic noise level even for a spin system and probe at the same temperature, pure in-phase Lorentzian spin-noise signals exhibiting non-vanishing frequency shifts. Extensive comparisons to experimental measurements validate the model predictions, and define the conditions for obtaining pure in-phase Lorentzian-shape nuclear spin noise with a vanishing frequency shift, in other words, the conditions for simultaneously obtaining the spin-noise and frequency-shift tuning optima

  4. Exploring the limits to spatially resolved NMR

    Gaedke, Achim; Nestle, Nikolaus [TU Darmstadt, Institute of Condensed Matter Physics (Germany)

    2010-07-01

    Recent advances in MRI have demonstrated resolutions down to 1 {mu}m. Magnetic resonance force microscopy has the potential to reach sensitivity for single nuclear spins. Given these numbers, in vivo imaging of single cells or even biomacromolecules may seem possible. However, for in vivo applications, there are fundamental differences in the contrast mechanisms compared to MRI at macroscopic scales as the length scale of of molecular self-diffusion exceeds that of the spatial resolution on the NMR time scale. Those effects - which are fundamentally different from the echo attenuation in field gradient NMR - even may lead to general limitations on the spatial resolution achievable in aqueous systems with high water content. In our contribution, we explore those effects on a model system in a high-resolution stray-field imaging setup. In addition to experimental results, simulations based on the Bloch-Torrey equation are presented.

  5. Molecular mobility in Medicago truncatula seed during early stage of germination: Neutron scattering and NMR investigations

    Highlights: • Neutron scattering and NMR approaches were used to characterize seed germination. • A parallel between macromolecular motions and water dynamics was established. • Freezing/thawing cycle revealed a hysteresis connected to the seed hydration level. - Abstract: First hours of Medicago truncatula (MT) seeds germination were investigated using elastic incoherent neutron scattering (EINS) and nuclear magnetic resonance (NMR), to follow respectively how macromolecular motions and water mobility evolve when water permeates into the seed. From EINS results, it was shown that there is an increase in macromolecular mobility with the water uptake. Changes in NMR relaxation parameters reflected microstructural changes associated with the recovery of the metabolic processes. The EINS investigation of the effect of temperature on macromolecular motions showed that there is a relationship between the amount of water in the seeds and the effect of freezing–thawing cycle. The NMR relaxometry results obtained at 253 K allowed establishing possible link between the freezing of water molecules tightly bound to macromolecules and their drastic motion restriction around 250 K, as observed with EINS at the highest water content

  6. Real-time reaction monitoring by ultrafast 2D NMR on a benchtop spectrometer.

    Gouilleux, Boris; Charrier, Benoît; Danieli, Ernesto; Dumez, Jean-Nicolas; Akoka, Serge; Felpin, François-Xavier; Rodriguez-Zubiri, Mireia; Giraudeau, Patrick

    2015-12-01

    Reaction monitoring is widely used to follow chemical processes in a broad range of application fields. Recently, the development of robust benchtop NMR spectrometers has brought NMR under the fume hood, making it possible to monitor chemical reactions in a safe and accessible environment. However, these low-field NMR approaches suffer from limited resolution leading to strong peak overlaps, which can limit their application range. Here, we propose an approach capable of recording ultrafast 2D NMR spectra on a compact spectrometer and of following in real time reactions in the synthetic chemistry laboratory. This approach--whose potential is shown here on a Heck-Matsuda reaction--is highly versatile; the duration of the measurement can be optimized to follow reactions whose time scale ranges from between a few tens of seconds to a few hours. It makes it possible to monitor complex reactions in non-deuterated solvents, and to confirm in real time the molecular structure of the compounds involved in the reaction while giving access to relevant kinetic parameters. PMID:26501887

  7. Non-destructive characterization of materials by single-sided NMR

    Goga, Nicolae-Octavian

    2007-08-20

    The experiments conducted in this work demonstrate the efficiency and sensitivity of single-sided NMR for investigating macromolecular materials on large time and length scales. Elastomers can readily be characterized by unilateral NMR of protons in terms of a variety of parameters, which correlate with the overall molecular mobility. In this way information about the cross-link density, state of cure and strain, the effects of aging and product heterogeneity can obtained. For these purposes, the NMR-MOUSE was used to optimize product development and to monitor product and production quality on-line. The sensor is also suitable for nondestructive probing of the mechanical deformation in cross-linked elastomers. A special magnet design that fits a stress-strain device has been used for complementary investigation of a series of different rubber stripes during mechanical testing. The profile NMR-MOUSE was found to be a unique tool for the characterization of changes induced by the UV irradiation in natural rubber. The aging profiles were interpreted for the first time based on a novel model in which the radiation absorption coefficient depends on the depth in the sample. (orig.)

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

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

    2011-06-01

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

  9. NMR imaging and spectroscopy of the mammalian central nervous system after heavy ion radiation

    Richards, T.

    1984-09-01

    NMR imaging, NMR spectroscopic, and histopathologic techniques were used to study the proton relaxation time and related biochemical changes in the central nervous system after helium beam in vivo irradiation of the rodent brain. The spectroscopic observations reported in this dissertation were made possible by development of methods for measuring the NMR parameters of the rodent brain in vivo and in vitro. The methods include (1) depth selective spectroscopy using an optimization of rf pulse energy based on a priori knowledge of N-acetyl aspartate and lipid spectra of the normal brain, (2) phase-encoded proton spectroscopy of the living rodent using a surface coil, and (3) dual aqueous and organic tissue extraction technique for spectroscopy. Radiation induced increases were observed in lipid and p-choline peaks of the proton spectrum, in vivo. Proton NMR spectroscopy measurements on brain extracts (aqueous and organic solvents) were made to observe chemical changes that could not be seen in vivo. Radiation-induced changes were observed in lactate, GABA, glutamate, and p-choline peak areas of the aqueous fraction spectra. In the organic fraction, decreases were observed in peak area ratios of the terminal-methyl peaks, the N-methyl groups of choline, and at a peak at 2.84 ppM (phosphatidyl ethanolamine and phosphatidyl serine resonances) relative to TMS. With histology and Evans blue injections, blood-brain barrier alternations were seen as early as 4 days after irradiation. 83 references, 53 figures.

  10. Non-destructive characterization of materials by single-sided NMR

    The experiments conducted in this work demonstrate the efficiency and sensitivity of single-sided NMR for investigating macromolecular materials on large time and length scales. Elastomers can readily be characterized by unilateral NMR of protons in terms of a variety of parameters, which correlate with the overall molecular mobility. In this way information about the cross-link density, state of cure and strain, the effects of aging and product heterogeneity can obtained. For these purposes, the NMR-MOUSE was used to optimize product development and to monitor product and production quality on-line. The sensor is also suitable for nondestructive probing of the mechanical deformation in cross-linked elastomers. A special magnet design that fits a stress-strain device has been used for complementary investigation of a series of different rubber stripes during mechanical testing. The profile NMR-MOUSE was found to be a unique tool for the characterization of changes induced by the UV irradiation in natural rubber. The aging profiles were interpreted for the first time based on a novel model in which the radiation absorption coefficient depends on the depth in the sample. (orig.)

  11. Molecular mobility in Medicago truncatula seed during early stage of germination: Neutron scattering and NMR investigations

    Falourd, Xavier [UR1268 Biopolymères Interactions Assemblages, INRA, F-44316 Nantes (France); Natali, Francesca [CNR-IOM-OGG, c/o Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9 (France); Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9 (France); Peters, Judith [Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9 (France); Université Joseph Fourier UFR PhITEM, BP 53, 38041 Grenoble Cedex 9 (France); Institut de Biologie Structurale, 41 rue Jules Horowitz, 38027 Grenoble Cedex 1 (France); Foucat, Loïc, E-mail: Loic.Foucat@nantes.inra.fr [UR1268 Biopolymères Interactions Assemblages, INRA, F-44316 Nantes (France)

    2014-01-15

    Highlights: • Neutron scattering and NMR approaches were used to characterize seed germination. • A parallel between macromolecular motions and water dynamics was established. • Freezing/thawing cycle revealed a hysteresis connected to the seed hydration level. - Abstract: First hours of Medicago truncatula (MT) seeds germination were investigated using elastic incoherent neutron scattering (EINS) and nuclear magnetic resonance (NMR), to follow respectively how macromolecular motions and water mobility evolve when water permeates into the seed. From EINS results, it was shown that there is an increase in macromolecular mobility with the water uptake. Changes in NMR relaxation parameters reflected microstructural changes associated with the recovery of the metabolic processes. The EINS investigation of the effect of temperature on macromolecular motions showed that there is a relationship between the amount of water in the seeds and the effect of freezing–thawing cycle. The NMR relaxometry results obtained at 253 K allowed establishing possible link between the freezing of water molecules tightly bound to macromolecules and their drastic motion restriction around 250 K, as observed with EINS at the highest water content.

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

    Tan, Maojin; Wang, Peng; Mao, Keyu

    2014-04-01

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

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

    Bevilaqua, Rochele C. A.; Miranda, Caetano R. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Rigo, Vagner A. [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Universidade Tecnológica Federal do Paraná, UTFPR, Cornélio Procópio, PR (Brazil); Veríssimo-Alves, Marcos [Centro de Ciências Naturais e Humanas, Universidade Federal do ABC, UFABC, Santo André, SP (Brazil); Departamento de Física, ICEx, Universidade Federal Fluminense, UFF, Volta Redonda, RJ (Brazil)

    2014-11-28

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

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

    The electronic and coordination environment of minerals surfaces, as calcite, are very difficult to characterize experimentally. This is mainly due to the fact that there are relatively few spectroscopic techniques able to detect Ca2+. Since calcite is a major constituent of sedimentary rocks in oil reservoir, a more detailed characterization of the interaction between hydrocarbon molecules and mineral surfaces is highly desirable. Here we perform a first principles study on the adsorption of hydrocarbon molecules on calcite surface (CaCO3 (101¯4)). The simulations were based on Density Functional Theory with Solid State Nuclear Magnetic Resonance (SS-NMR) calculations. The Gauge-Including Projector Augmented Wave method was used to compute mainly SS-NMR parameters for 43Ca, 13C, and 17O in calcite surface. It was possible to assign the peaks in the theoretical NMR spectra for all structures studied. Besides showing different chemical shifts for atoms located on different environments (bulk and surface) for calcite, the results also display changes on the chemical shift, mainly for Ca sites, when the hydrocarbon molecules are present. Even though the interaction of the benzene molecule with the calcite surface is weak, there is a clearly distinguishable displacement of the signal of the Ca sites over which the hydrocarbon molecule is located. A similar effect is also observed for hexane adsorption. Through NMR spectroscopy, we show that aromatic and alkane hydrocarbon molecules adsorbed on carbonate surfaces can be differentiated

  15. Refinement of the protein backbone angle {psi} in NMR structure calculations

    Sprangers, R.; Bottomley, M.J.; Linge, J.P.; Schultz, J.; Nilges, M.; Sattler, M. [European Molecular Biology Laboratory (Germany)

    2000-01-15

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

  16. NMR imaging and spectroscopy of the mammalian central nervous system after heavy ion radiation

    NMR imaging, NMR spectroscopic, and histopathologic techniques were used to study the proton relaxation time and related biochemical changes in the central nervous system after helium beam in vivo irradiation of the rodent brain. The spectroscopic observations reported in this dissertation were made possible by development of methods for measuring the NMR parameters of the rodent brain in vivo and in vitro. The methods include (1) depth selective spectroscopy using an optimization of rf pulse energy based on a priori knowledge of N-acetyl aspartate and lipid spectra of the normal brain, (2) phase-encoded proton spectroscopy of the living rodent using a surface coil, and (3) dual aqueous and organic tissue extraction technique for spectroscopy. Radiation induced increases were observed in lipid and p-choline peaks of the proton spectrum, in vivo. Proton NMR spectroscopy measurements on brain extracts (aqueous and organic solvents) were made to observe chemical changes that could not be seen in vivo. Radiation-induced changes were observed in lactate, GABA, glutamate, and p-choline peak areas of the aqueous fraction spectra. In the organic fraction, decreases were observed in peak area ratios of the terminal-methyl peaks, the N-methyl groups of choline, and at a peak at 2.84 ppM (phosphatidyl ethanolamine and phosphatidyl serine resonances) relative to TMS. With histology and Evans blue injections, blood-brain barrier alternations were seen as early as 4 days after irradiation. 83 references, 53 figures

  17. An efficient spectra processing method for metabolite identification from 1H-NMR metabolomics data.

    Jacob, Daniel; Deborde, Catherine; Moing, Annick

    2013-06-01

    The spectra processing step is crucial in metabolomics approaches, especially for proton NMR metabolomics profiling. During this step, noise reduction, baseline correction, peak alignment and reduction of the 1D (1)H-NMR spectral data are required in order to allow biological information to be highlighted through further statistical analyses. Above all, data reduction (binning or bucketing) strongly impacts subsequent statistical data analysis and potential biomarker discovery. Here, we propose an efficient spectra processing method which also provides helpful support for compound identification using a new data reduction algorithm that produces relevant variables, called buckets. These buckets are the result of the extraction of all relevant peaks contained in the complex mixture spectra, rid of any non-significant signal. Taking advantage of the concentration variability of each compound in a series of samples and based on significant correlations that link these buckets together into clusters, the method further proposes automatic assignment of metabolites by matching these clusters with the spectra of reference compounds from the Human Metabolome Database or a home-made database. This new method is applied to a set of simulated (1)H-NMR spectra to determine the effect of some processing parameters and, as a proof of concept, to a tomato (1)H-NMR dataset to test its ability to recover the fruit extract compositions. The implementation code for both clustering and matching steps is available upon request to the corresponding author. PMID:23525538

  18. From NMR chemical shifts to amino acid types: Investigation of the predictive power carried by nuclei

    An approach to automatic prediction of the amino acid type from NMR chemical shift values of its nuclei is presented here, in the frame of a model to calculate the probability of an amino acid type given the set of chemical shifts. The method relies on systematic use of all chemical shift values contained in the BioMagResBank (BMRB). Two programs were designed, one (BMRB stats) for extracting statistical chemical shift parameters from the BMRB and another one (RESCUE2) for computing the probabilities of each amino acid type, given a set of chemical shifts. The Bayesian prediction scheme presented here is compared to other methods already proposed: PROTYP (Grzesiek and Bax, J. Biomol. NMR, 3, 185-204, 1993) RESCUE (Pons and Delsuc, J. Biomol. NMR, 15, 15-26, 1999) and PLATON (Labudde et al., J. Biomol. NMR, 25, 41-53, 2003) and is found to be more sensitive and more specific. Using this scheme, we tested various sets of nuclei. The two nuclei carrying the most information are Cβ and Hβ, in agreement with observations made in Grzesiek and Bax, 1993. Based on four nuclei: Hβ, Cβ, Cα and C', it is possible to increase correct predictions to a rate of more than 75%. Taking into account the correlations between the nuclei chemical shifts has only a slight impact on the percentage of correct predictions: indeed, the largest correlation coefficients display similar features on all amino acids

  19. 3D Reconstruction of NMR Images

    Peter Izak

    2007-01-01

    Full Text Available This paper introduces experiment of 3D reconstruction NMR images scanned from magnetic resonance device. There are described methods which can be used for 3D reconstruction magnetic resonance images in biomedical application. The main idea is based on marching cubes algorithm. For this task was chosen sophistication method by program Vision Assistant, which is a part of program LabVIEW.

  20. Probing Organometallic Reactions With 19F NMR

    Hawrelak, Eric James

    2002-01-01

    This dissertation explores fundamental aspects of the reaction of group 4 metallocenes with methylaluminoxane (MAO) that lead to active Ziegler-Natta olefin polymerization catalysts. A novel experimental approach is described, in which a unique spectroscopic probe (a fluorinated substituent) is attached to the metallocene ancillary ligands and the metallocene/MAO mixtures are analyzed using 19F NMR spectroscopy. Group 4 metallocene dimethides bearing pentafluorophenyl (C6F5) substituents ...

  1. NMR investigations of G-quadruplex structures

    Bessi, Irene

    2016-01-01

    This thesis deals with the NMR characterization of the structure and the folding dynamics of DNA G quadruplexes as potential therapeutic target in cancer therapy and building block for DNA based nanotechnology. The first part of this thesis (Chapters 1-5) introduces the reader to the world of G quadruplexes. The main features of the classic Watson Crick double helix and alternative non B DNA structures are illustrated in Chapter 1. Many different base pairing schemes are possible, besid...

  2. NMR of 1,2-dioxiquinolines

    Several derivates of quinoline are known for presenting pharmacological activity as antibiotics and anti-parasites, from which an important group are the antibiotics for the treatment of malaria and infections of the urinary tract. This work presents the structures and the NMR spectra of three new derivates of quinoline. These compounds are being tested as possible antibiotics for the treatment of urinary infections caused by Escherichia coli which are extremely resistant to other types of antibiotics

  3. NMR Studies on Organic and Biological Solids

    Yang, Chen

    2015-01-01

    Solid-state NMR (SSNMR) studies on biomolecules and organic molecular crystals are presented here. The biological part of the work is focused on improving resolution and sensitivity of SSNMR techniques for larger protein systems, while the studies on organic molecular crystals extend the application of SSNMR to determining the crystal structure of a photoreaction intermediate. First, a long-observation-window band-selective homonuclear decoupling scheme is introduced. The homonuclear decoupli...

  4. Structure of high-resolution NMR spectra

    Corio, PL

    2012-01-01

    Structure of High-Resolution NMR Spectra provides the principles, theories, and mathematical and physical concepts of high-resolution nuclear magnetic resonance spectra.The book presents the elementary theory of magnetic resonance; the quantum mechanical theory of angular momentum; the general theory of steady state spectra; and multiple quantum transitions, double resonance and spin echo experiments.Physicists, chemists, and researchers will find the book a valuable reference text.

  5. Funktionelle NMR-Mikroskopie an Pflanzenwurzeln

    Kaufmann, Ilja

    2009-01-01

    Als nicht-invasive Methode bietet die magnetische Kernspinresonanztomographie durch ihre Vielzahl an messbaren Größen wie Wassergehalt und Flussgeschwindigkeiten gute Voraussetzungen, um funktionelle Abläufe in Pflanzen und insbesondere Pflanzenwurzeln zu untersuchen. Für funktionelle NMR-Mikroskopie notwendige Hardware und Methoden wurden in dieser Arbeit entwickelt und angewendet. Aufgrund der starken Suszeptibilitätsunterschiede in den Proben und der notwendigen Zeitauflösung für funktione...

  6. Randomization improves sparse sampling in multidimensional NMR

    Hoch, Jeffrey C.; Maciejewski, Mark W.; Filipovic, Blagoje

    2008-01-01

    While a number of strategies have been developed to reduce data collection requirements for multidimensional NMR based on non-Fourier methods of spectrum analysis, there is an increasing awareness that the principal differences in the performance of these methods is attributable to the sampling strategies employed, and not the method of spectrum analysis per se. The ability of maximum entropy reconstruction to utilize essentially arbitrary sampling schemes makes it an useful platform for comp...

  7. NMR methodologies for studying mitochondrial bioenergetics.

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

    2012-01-01

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

  8. Principles of high resolution NMR in solids

    Mehring, Michael

    1983-01-01

    The field of Nuclear Magnetic Resonance (NMR) has developed at a fascinating pace during the last decade. It always has been an extremely valuable tool to the organic chemist by supplying molecular "finger print" spectra at the atomic level. Unfortunately the high resolution achievable in liquid solutions could not be obtained in solids and physicists and physical chemists had to live with unresolved lines open to a wealth of curve fitting procedures and a vast amount of speculations. High resolution NMR in solids seemed to be a paradoxon. Broad structure­ less lines are usually encountered when dealing with NMR in solids. Only with the recent advent of mUltiple pulse, magic angle, cross-polarization, two-dimen­ sional and multiple-quantum spectroscopy and other techniques during the last decade it became possible to resolve finer details of nuclear spin interactions in solids. I have felt that graduate students, researchers and others beginning to get involved with these techniques needed a book which trea...

  9. Cutoff-Free Traveling Wave NMR

    Tang, Joel A; Sodickson, Daniel K; Jerschow, Alexej

    2011-01-01

    Recently, the concept of traveling-wave NMR/MRI was introduced by Brunner et al. (Nature 457, 994-992 (2009)), who demonstrated MR images acquired using radio frequency (RF) waves propagating down the bore of an MR scanner. One of the significant limitations of this approach is that each bore has a specific cutoff frequency, which can be higher than most Larmor frequencies of at the magnetic field strengths commonly in use for MR imaging and spectroscopy today. We overcome this limitation by using a central conductor in the waveguide and thereby converting it to a transmission line (TL), which has no cutoff frequency. Broadband propagation of waves through the sample thus becomes possible. NMR spectra and images with such an arrangement are presented and genuine traveling wave behavior is demonstrated. In addition to facilitating NMR spectroscopy and imaging in smaller bores via traveling waves, this approach also allows one to perform multinuclear traveling wave experiments (an example of which is shown), an...

  10. Multispectral dual isotope and NMR image analysis

    Dual isotope scintigraphy and nuclear magnetic resonance imaging produce image data that is intrinsically multispectral. That is multiple images of the same anatomic region are generated with different gray scale distribution and morphologic content that is largely redundant. Image processing technology, originally developed by NASA for satellite imaging, is available for multispectral analysis. These methods have been applied to provide tissue characterization. Tissue specific information encoded in the grapy scale data from dual isotope and NMR studies may be extracted using multispectral pattern recognition methods. The authors used table lookup minimum distance, maximum likelihood and cluster analysis techniques with data sets from Ga-67 / Tc-99m, 1-131 labeled antibodies / Tc-99m, Tc-99m perfusion / Xe-133 ventilation, and NMR studies. The results show; tissue characteristic signatures exist in dual isotope and NMR imaging, and these spectral signatures are identifiable using multispectral image analysis and provide tissue classification maps with scatter diagrams that facilitate interpretation and assist in elucidating subtle changes

  11. Discrete analysis of stochastic NMR.II

    Wong, S. T. S.; Rods, M. S.; Newmark, R. D.; Budinger, T. F.

    Stochastic NMR is an efficient technique for high-field in vivo imaging and spectroscopic studies where the peak RF power required may be prohibitively high for conventional pulsed NMR techniques. A stochastic NMR experiment excites the spin system with a sequence of RF pulses where the flip angles or the phases of the pulses are samples of a discrete stochastic process. In a previous paper the stochastic experiment was analyzed and analytic expressions for the input-output cross-correlations, average signal power, and signal spectral density were obtained for a general stochastic RF excitation. In this paper specific cases of excitation with random phase, fixed flip angle, and excitation with two random components in quadrature are analyzed. The input-output cross-correlation for these two types of excitations is shown to be Lorentzian. Line broadening is the only spectral distortion as the RF excitation power is increased. The systematic noise power is inversely proportional to the number of data points N used in the spectral reconstruction. The use of a complete maximum length sequence (MLS) may improve the signal-to-systematic-noise ratio by 20 dB relative to random binary excitation, but peculiar features in the higher-order autocorrelations of MLS cause noise-like distortion in the reconstructed spectra when the excitation power is high. The amount of noise-like distortion depends on the choice of the MLS generator.

  12. Guiding automated NMR structure determination using a global optimization metric, the NMR DP score

    Huang, Yuanpeng Janet, E-mail: yphuang@cabm.rutgers.edu; Mao, Binchen; Xu, Fei; Montelione, Gaetano T., E-mail: gtm@rutgers.edu [Rutgers, The State University of New Jersey, Department of Molecular Biology and Biochemistry, Center for Advanced Biotechnology and Medicine, and Northeast Structural Genomics Consortium (United States)

    2015-08-15

    ASDP is an automated NMR NOE assignment program. It uses a distinct bottom-up topology-constrained network anchoring approach for NOE interpretation, with 2D, 3D and/or 4D NOESY peak lists and resonance assignments as input, and generates unambiguous NOE constraints for iterative structure calculations. ASDP is designed to function interactively with various structure determination programs that use distance restraints to generate molecular models. In the CASD–NMR project, ASDP was tested and further developed using blinded NMR data, including resonance assignments, either raw or manually-curated (refined) NOESY peak list data, and in some cases {sup 15}N–{sup 1}H residual dipolar coupling data. In these blinded tests, in which the reference structure was not available until after structures were generated, the fully-automated ASDP program performed very well on all targets using both the raw and refined NOESY peak list data. Improvements of ASDP relative to its predecessor program for automated NOESY peak assignments, AutoStructure, were driven by challenges provided by these CASD–NMR data. These algorithmic improvements include (1) using a global metric of structural accuracy, the discriminating power score, for guiding model selection during the iterative NOE interpretation process, and (2) identifying incorrect NOESY cross peak assignments caused by errors in the NMR resonance assignment list. These improvements provide a more robust automated NOESY analysis program, ASDP, with the unique capability of being utilized with alternative structure generation and refinement programs including CYANA, CNS, and/or Rosetta.

  13. Guiding automated NMR structure determination using a global optimization metric, the NMR DP score

    ASDP is an automated NMR NOE assignment program. It uses a distinct bottom-up topology-constrained network anchoring approach for NOE interpretation, with 2D, 3D and/or 4D NOESY peak lists and resonance assignments as input, and generates unambiguous NOE constraints for iterative structure calculations. ASDP is designed to function interactively with various structure determination programs that use distance restraints to generate molecular models. In the CASD–NMR project, ASDP was tested and further developed using blinded NMR data, including resonance assignments, either raw or manually-curated (refined) NOESY peak list data, and in some cases 15N–1H residual dipolar coupling data. In these blinded tests, in which the reference structure was not available until after structures were generated, the fully-automated ASDP program performed very well on all targets using both the raw and refined NOESY peak list data. Improvements of ASDP relative to its predecessor program for automated NOESY peak assignments, AutoStructure, were driven by challenges provided by these CASD–NMR data. These algorithmic improvements include (1) using a global metric of structural accuracy, the discriminating power score, for guiding model selection during the iterative NOE interpretation process, and (2) identifying incorrect NOESY cross peak assignments caused by errors in the NMR resonance assignment list. These improvements provide a more robust automated NOESY analysis program, ASDP, with the unique capability of being utilized with alternative structure generation and refinement programs including CYANA, CNS, and/or Rosetta

  14. Portable NMR systems for non destructive testing

    Nuclear Magnetic Resonance (NMR) is one of the more recent sensing technologies and has become very popular for its ability to non-invasively probe down to the molecular level the properties of many materials and living organisms. Its greatest impact has been in the areas of chemistry and medical radiology, but now it is being applied to biochemistry, structural biology, and materials science research. In the past ten years, NMR has made significant contributions to horticulture, biotechnology, chemical engineering, petroleum science and food technology and now stands on the threshold of making an impact on environmental monitoring, building technology, and security technology. Traditionally NMR/MRI is performed using laboratory or clinic based superconducting magnets, but now it is moving out into industry in the form of portable permanent magnet based systems. NMR development is being driven by advancements in electronics, computing and magnet technology and so continues to advance in capability and application. In the building industry, it is often necessary to determine the moisture content of concrete so that it can be optimally cured for strength or to know when floor coverings can be applied. Presently the only way to accurately gauge the true moisture content is to use destructive techniques. This is the method that Parrot used to generate the graph shown in figure 1. Typically the industry yardstick of a 'month per inch' is used for estimating the time required before the concrete surface can be covered, but from this data it is clear that even after a year there can still remain a significant amount of moisture. Concrete is inherently porous and so is greatly affected by the environment and the laying process methods. This makes it very difficult to make predictions based on calibrated standards. What is required is a portable instrument that can be taken to a site to non-destructively obtain the moisture content. NMR technology is now being developed for

  15. Calculations of NMR properties for sI and sII clathrate hydrates of carbon dioxide

    Graphical abstract: - Highlights: • We studied the influence of a type of clathrate hydrate cage on NMR parameters of the encaged CO2. • The interaction-induced shifts of σ(17O) of CO2 form a decreasing trend from 512 through 51262 and 51264 to monomeric one. • We observed a correlation of the 1hJOH transmitted through H-bonds H⋯O with the strength of H-bonds. - Abstract: Nuclear shielding and spin–spin coupling constants (intra- and intermolecular) have been calculated for cages forming sI and sII clathrate hydrates of carbon dioxide (for all atoms of host and guest molecules). Structures of 512, 51262 and 51264 cages have been constructed using neutronographic data and DFT/B3LYP calculations conducted with HuzIII-su3 basis set for NMR parameters determination. Based on those results it is possible to discriminate between CO2 molecules residing in each type of the cage. The analysis of NMR parameters calculated for water molecules is focused on their dependence on geometry of the molecular environment. It is possible to connect changes in NMR parameters with types of H-bond patterns present in cages of hydrates and the strength of H-bonds formed. Moreover, our results show that topologically differentiable water molecules forming cages are characterized by distinct NMR parameters, for example 17O shielding constants for water molecules of different topologies differ by 1.6 and 2.1 ppm for cages 51262 and 51264, respectively. This observation could be confirmed experimentally

  16. Magic-angle-spinning NMR (MAS-NMR) spectroscopy and the structure of zeolites

    After outlining the chemical features and properties which make zeolites such an important group of catalysts and sorbents, the article explains how high-resolution solid-state NMR with magic-angle spinning reveals numerous new insights into their structure. 29Si-MAS-NMR readily and quantitatively identifies five distinct Si(OAl)sub(n)(OSi)sub(4-n) structural groups in zeolitic frameworks (n=0,1,...4), corresponding to the first tetrahedral coordination shell of a silicon atom. Many catalytic and other chemical properties of zeolites are governed by the short-range Si, Al order, the nature of which is greatly clarified by 29Si-MAS-NMR. (orig./EF)

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

    Hajari, Adam James

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

  18. Lipid Dynamics Studied by Calculation of 31P Solid-State NMR Spectra Using Ensembles from Molecular Dynamics Simulations

    Hansen, Sara Krogh; Vestergaard, Mikkel; Thøgersen, Lea; Schiøtt, Birgit; Nielsen, Niels Christian; Vosegaard, Thomas

    2014-01-01

    We present a method to calculate 31P solid-state NMR spectra based on the dynamic input from extended molecular dynamics (MD) simulations. The dynamic information confered by MD simulations is much more comprehensive than the information provided by traditional NMR dynamics models based on, for...... example, order parameters. Therefore, valuable insight into the dynamics of biomolecules may be achieved by the present method. We have applied this method to study the dynamics of lipid bilayers containing the antimicrobial peptide alamethicin, and we show that the calculated 31P spectra obtained with...

  19. The (1) H NMR spectrum of pyrazole in a nematic phase.

    Provasi, Patricio; Jimeno, María Luisa; Alkorta, Ibon; Reviriego, Felipe; Elguero, José; Jokisaari, Jukka

    2016-08-01

    The experimental (1) H nuclear magnetic resonance (NMR) spectrum of 1H-pyrazole was recorded in thermotropic nematic liquid crystal N-(p-ethoxybenzylidene)-p-butylaniline (EBBA) within the temperature range of 299-308 K. Two of three observable dipolar DHH -couplings appeared to be equal at each temperature because of fast prototropic tautomerism. Analysis of the Saupe orientational order parameters using fixed geometry determined by computations and experimental dipolar couplings results in a situation in which the molecular orientation relative to the magnetic field (and the liquid crystal director) can be described exceptionally by a single parameter. Copyright © 2016 John Wiley & Sons, Ltd. PMID:26947581

  20. Fast automated protein NMR data collection and assignment by ADAPT-NMR on Bruker spectrometers

    Lee, Woonghee; Hu, Kaifeng; Tonelli, Marco; Bahrami, Arash; Neuhardt, Elizabeth; Glass, Karen C.; Markley, John L.

    2013-11-01

    ADAPT-NMR (Assignment-directed Data collection Algorithm utilizing a Probabilistic Toolkit in NMR) supports automated NMR data collection and backbone and side chain assignment for [U-13C, U-15N]-labeled proteins. Given the sequence of the protein and data for the orthogonal 2D 1H-15N and 1H-13C planes, the algorithm automatically directs the collection of tilted plane data from a variety of triple-resonance experiments so as to follow an efficient pathway toward the probabilistic assignment of 1H, 13C, and 15N signals to specific atoms in the covalent structure of the protein. Data collection and assignment calculations continue until the addition of new data no longer improves the assignment score. ADAPT-NMR was first implemented on Varian (Agilent) spectrometers [A. Bahrami, M. Tonelli, S.C. Sahu, K.K. Singarapu, H.R. Eghbalnia, J.L. Markley, PLoS One 7 (2012) e33173]. Because of broader interest in the approach, we present here a version of ADAPT-NMR for Bruker spectrometers. We have developed two AU console programs (ADAPT_ORTHO_run and ADAPT_NMR_run) that run under TOPSPIN Versions 3.0 and higher. To illustrate the performance of the algorithm on a Bruker spectrometer, we tested one protein, chlorella ubiquitin (76 amino acid residues), that had been used with the Varian version: the Bruker and Varian versions achieved the same level of assignment completeness (98% in 20 h). As a more rigorous evaluation of the Bruker version, we tested a larger protein, BRPF1 bromodomain (114 amino acid residues), which yielded an automated assignment completeness of 86% in 55 h. Both experiments were carried out on a 500 MHz Bruker AVANCE III spectrometer equipped with a z-gradient 5 mm TCI probe. ADAPT-NMR is available at http://pine.nmrfam.wisc.edu/ADAPT-NMR in the form of pulse programs, the two AU programs, and instructions for installation and use.

  1. Action of the multifunctional peptide BP100 on native biomembranes examined by solid-state NMR

    Misiewicz, Julia [Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (Germany); Afonin, Sergii; Grage, Stephan L.; Berg, Jonas van den; Strandberg, Erik; Wadhwani, Parvesh [Karlsruhe Institute of Technology (KIT), Institute of Biological Interfaces (IBG-2) (Germany); Ulrich, Anne S., E-mail: anne.ulrich@kit.edu [Karlsruhe Institute of Technology (KIT), Institute of Organic Chemistry (Germany)

    2015-04-15

    Membrane composition is a key factor that regulates the destructive activity of antimicrobial peptides and the non-leaky permeation of cell penetrating peptides in vivo. Hence, the choice of model membrane is a crucial aspect in NMR studies and should reflect the biological situation as closely as possible. Here, we explore the structure and dynamics of the short multifunctional peptide BP100 using a multinuclear solid-state NMR approach. The membrane alignment and mobility of this 11 amino acid peptide was studied in various synthetic lipid bilayers with different net charge, fluidity, and thickness, as well as in native biomembranes harvested from prokaryotic and eukaryotic cells. {sup 19}F-NMR provided the high sensitivity and lack of natural abundance background that are necessary to observe a labelled peptide even in protoplast membranes from Micrococcus luteus and in erythrocyte ghosts. Six selectively {sup 19}F-labeled BP100 analogues gave remarkably similar spectra in all of the macroscopically oriented membrane systems, which were studied under quasi-native conditions of ambient temperature and full hydration. This similarity suggests that BP100 has the same surface-bound helical structure and high mobility in the different biomembranes and model membranes alike, independent of charge, thickness or cholesterol content of the system. {sup 31}P-NMR spectra of the phospholipid components did not indicate any bilayer perturbation, so the formation of toroidal wormholes or micellarization can be excluded as a mechanism of its antimicrobial or cell penetrating action. However, {sup 2}H-NMR analysis of the acyl chain order parameter profiles showed that BP100 leads to considerable membrane thinning and thereby local destabilization.

  2. 31P NMR spectroscopy measurements of hum ovarian carcinoma xenografts

    /sup 31/P NMR spectroscopy was used to study lipid and energy metabolism as well as tumour pH in three human ovarian carcinoma xenograft lines with widely differing growth rate, necrotic fraction and differentiation status. Two of the liines showed decreasing PCr (phosphocreatine) and NTPbhta (nucleoside triphosphates bhta) resonances and an increasing P/sub i/ (inorganic phosphate) resonance with increasing tumour volume in the volume range 100-4000 mm/sup 3/. This decrease in bioenergetic status was accompanied by a decrease in tumour pH from about 7.15 to about 6.95. The volume-dependence of these spectral parametes probably reflected increased nutritional deprivation and development of hypoxia and necrosis during tumour growth. The third xenograft line did not show changes in the intensity of any of the resonances during tumour growth. The spectral parameters differed significantly among the xenograft lines at given tumour volumes, but no correlations with volume-doubling time, necrotic fraction of differentiation status were found

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

    Wright, P.E. [Scripps Research Institute, La Jolla, CA (United States)

    1994-12-01

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

  4. In-cell NMR in Xenopus laevis oocytes.

    Thongwichian, Rossukon; Selenko, Philipp

    2012-01-01

    For the purpose of studying IDPs inside cells of higher organisms, several eukaryotic in-cell NMR systems have been developed over the past years. In this chapter we will focus on high-resolution in-cell NMR applications in Xenopus laevis oocytes, the first eukaryotic cellular model system to be established. In contrast to prokaryotic in-cell NMR samples, eukaryotic in-cell NMR specimens are prepared by cytoplasmic delivery of an exogenously produced, isotope-labeled protein into the non-isotope-labeled environment of the respective "host" cell. In-cell NMR applications in Xenopus oocytes rely on intracellular sample deposition by direct microinjection into the oocyte cytoplasm. Here, we describe the preparation of oocyte in-cell NMR samples for IDP studies in this cellular model environment. PMID:22760310

  5. 13C-NMR assignment, structure, and dynamics of deoxyoligonucleotides

    The unique spectral properties of 13C-NMR for studying nucleic acids and some of the important features of 13C-NMR in oligonucleotide studies are demostrated. The main difficulty in studying oligonucleotides by 13C-NMR and recent improvements in NMR instrumentation and advances in oligonucleotide synthesis are presented. The high resolution 13C-NMR spectra, T1 relaxation times and NOEs were measured for duplex of the self-complementary oligo-DNAs: d(CG)3 and d(GGTATACC) are studied. The target of this study is to developed a systematic 13C-NMR spectral assignment and to investigate the structure and dynamics of these two sequences by this techniques. (M.J.C.)

  6. The Expanding Role of NMR in Drug Discovery and Development

    2002-01-01

    @@ The role of NMR in the pharmaceutical industry has changed dramatically over the last decade. Once thought of as an analytical technique used primarily to support synthetic chemistry, NMR now has an important role in the investigation of biochemical changes involved in clinical diseases and drug toxicity. It is also used extensively to elucidate the structures of drug metabolites. Data obtained using LC NMR MS and 19F NMR will be used to illustrate the utility of hyphenated methods in identifying xenobiotic metabolites as part of a drug development program. The application of NMR to the study of potential drug toxicity will also be described using the cationic, amphiphilic drugs chloroquine and amiodarone. These drugs are known to induce phospholipidosis characterized by lysosomal lamellar bodies and drug accumulation. Using a metabonomic approach, NMR spectroscopy of urine allowed the identification of a combination of urinary biomarkers of phospholipidosis.

  7. Computer-intensive simulation of solid-state NMR experiments using SIMPSON

    Tošner, Zdeněk; Andersen, Rasmus; Stevensson, Baltzar; Edén, Mattias; Nielsen, Niels Chr.; Vosegaard, Thomas

    2014-09-01

    Conducting large-scale solid-state NMR simulations requires fast computer software potentially in combination with efficient computational resources to complete within a reasonable time frame. Such simulations may involve large spin systems, multiple-parameter fitting of experimental spectra, or multiple-pulse experiment design using parameter scan, non-linear optimization, or optimal control procedures. To efficiently accommodate such simulations, we here present an improved version of the widely distributed open-source SIMPSON NMR simulation software package adapted to contemporary high performance hardware setups. The software is optimized for fast performance on standard stand-alone computers, multi-core processors, and large clusters of identical nodes. We describe the novel features for fast computation including internal matrix manipulations, propagator setups and acquisition strategies. For efficient calculation of powder averages, we implemented interpolation method of Alderman, Solum, and Grant, as well as recently introduced fast Wigner transform interpolation technique. The potential of the optimal control toolbox is greatly enhanced by higher precision gradients in combination with the efficient optimization algorithm known as limited memory Broyden-Fletcher-Goldfarb-Shanno. In addition, advanced parallelization can be used in all types of calculations, providing significant time reductions. SIMPSON is thus reflecting current knowledge in the field of numerical simulations of solid-state NMR experiments. The efficiency and novel features are demonstrated on the representative simulations.

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

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

    2011-12-01

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

  9. Perspectives of Deuteron Field-Cycling NMR Relaxometry for Probing Molecular Dynamics in Soft Matter.

    Flämig, M; Becher, M; Hofmann, M; Körber, T; Kresse, B; Privalov, A F; Willner, L; Kruk, D; Fujara, F; Rössler, E A

    2016-08-11

    Due to the single-particle character of the quadrupolar interaction in molecular systems, (2)H NMR poses a unique method for probing reorientational dynamics. Spin-lattice relaxation gives access to the spectral density, and its frequency dependency can be monitored by field-cycling (FC) techniques. However, most FC NMR studies employ (1)H; the use of (2)H is still rare. We report on the application of (2)H FC NMR for investigating the dynamics in molecular liquids and polymers. Commercial as well as home-built relaxometers are employed accessing a frequency range from 30 Hz to 6 MHz. Due to low gyromagnetic ratio, high coupling constants, and finite FC switching times, current (2)H FC NMR does not reach the dispersion region in liquids (toluene and glycerol), yet good agreement with the results from conventional high-field (HF) relaxation studies is demonstrated. The pronounced difference at low frequencies between (2)H and (1)H FC NMR data shows the relevance of intermolecular relaxation in the case of (1)H NMR. In the case of the polymers polybutadiene and poly(ethylene-alt-propylene), very similar relaxation dispersion is observed and attributed to Rouse and entanglement dynamics. Combination with HF (2)H relaxation data via applying frequency-temperature superposition allows the reconstruction of the full spectral density reflecting both polymer as well as glassy dynamics. Transformation into the time domain yields the reorientational correlation function C2(t) extending over nine decades in time with a long-time power law, C2(t) ∝ t(-0.45±0.05), which does not conform to the prediction of the tube-reptation model, for which ∝ t(-0.25) is expected. Entanglement sets in below C2(t = τe) ≅ S(2) = 0.001, where τe is the entanglement time and S the corresponding order parameter. Finally, we discuss the future prospects of the (2)H FC NMR technique. PMID:27420118

  10. NMR Studies on the Internal Structure of High-T{sub c} Superconductors and Other Anorganic Compounds

    Kumagai, K., E-mail: kumagai@phys.sci.hokudai.ac.jp; Kakuyanagi, K.; Saitoh, M. [Hokkaido University, Division of Physics, Graduate School of Science (Japan); Matsuda, Y. [University of Tokyo, Institute for Solid State Physics (Japan); Hasegawa, M. [Tohoku University, Institute of Material Research (Japan); Takashima, S.; Nohara, M.; Takagi, H. [University of Tokyo, Department of Advanced Materials Science (Japan)

    2004-12-15

    Spatially-resolved NMR is used to probe internal structures in highly correlated superconductors of optimally-doped Tl{sub 2}Ba{sub 2}CuO{sub 6+{delta}} (T{sub c} 85 K) and a heavy fermion superconductor CeCoIn{sub 5} (T{sub c} = 2.3 K). The characteristic change of the properties of {sup 205}Tl-NMR in the vortex state provides a clear evidence of the antiferromagnetic order in the vortex cores below 20 K in Tl{sub 2}Ba{sub 2}CuO{sub 6+{delta}}. We also obtain anomalous {sup 115}In-NMR spectra of CeCoIn{sub 5}, which provides a microscopic evidence for the occurrence of a spatially-modulated superconducting order parameter expected in a Fulde-Ferrel-Larkin-Ovchinnkov (FFLO) state.

  11. Synthesis and biological characterization of new amino-phosphonates for mitochondrial pH determination by 31P NMR spectroscopy

    A series of mitochondria targeted α-amino-phosphonates combining a diethoxy-phosphoryl group and an alkyl chain-connected triphenylphosphonium bromide tail were designed and synthesized, and their pH-sensitive 31P NMR properties and biological activities in vitro and in vivo were evaluated. The results showed a number of these mitoaminophosphonates exhibiting pKa values fitting the mitochondrial pH range, short relaxation, and chemical shift parameters compatible with sensitive 31P NMR detection, and low cytotoxicity on green algae and murine fibroblasts cell cultures. Of these, two selected compounds demonstrated to distribute at NMR detectable levels within the cytosolic and mitochondrial sites following their perfusion to isolated rat livers, with no detrimental effects on cell energetics and aerobic respiration. This study provided a new molecular scaffold for further development of in situ spectroscopic real-time monitoring of mitochondrion/cytosol pH gradients. (authors)

  12. The NMR and X-ray study of L-arginine derived Schiff bases and its cadmium complexes

    Kołodziej, B.; Grech, E.; Schilf, W.; Kamieński, B.; Pazio, A.; Woźniak, K.

    2014-04-01

    The structure study of five Schiff bases derived from L-arginine (L-Arg) and 2-hydroxy carbonyl compounds were performed in both solution and solid state using NMR and X-ray methods. Both analytical methods applied to the solid state sample of two Schiff bases showed a significant difference in molecular structures of unsubstituted and 7-CH3 substituted compounds. This effect was explained as a steric interaction of methyl group. Additionally the structure of two Cd2+ complexes with some Schiff bases were determined by NMR methods in DMSO solution and in the solid state. On the base of heteronuclear NMR measurement (13C, 15N and 113Cd) it was possible to define the complexation site on nitrogen atom. The large set of spectral parameters: chemical shifts, homo- and heteronuclear coupling constants, were used in structure study.

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

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

    1988-01-01

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

  14. Classical model for bulk-ensemble NMR quantum computation

    Schack, R.; Caves, C. M.

    1999-01-01

    We present a classical model for bulk-ensemble NMR quantum computation: the quantum state of the NMR sample is described by a probability distribution over the orientations of classical tops, and quantum gates are described by classical transition probabilities. All NMR quantum computing experiments performed so far with three quantum bits can be accounted for in this classical model. After a few entangling gates, the classical model suffers an exponential decrease of the measured signal, whe...

  15. Studies on irradiation stability of polystyrene by NMR

    ZHAO Xin; SUN Wan-Fu; XIE Cheng-Xi

    2004-01-01

    The irradiation stability of polystyrene (PS) was studied by 13C and 1H NMR spectra, Nuclear Overhauser Relaxation (NOE) and 13C NMR spin-lattice relaxation time (T1). The results indicate that 13C and 1H NMR chemical shifts, NOE and T1 were almost invariant with the increase of irradiation dose. This shows that polystyrene is particularly stable within 2.5 kGy doses and the mechanism of its stability is discussed.

  16. Nuclear Magnetic Resonance Logging While Drilling (NMR-LWD)

    Blanz, Martin; Kruspe, Thomas; Thern, Holger Frank; Kurz, Gerhard Alfons

    2015-01-01

    NMR T2 distribution measurement is our chosen everyday method for NMR logging while drilling oil and gas wells. This method yields straightforward preparation and execution of the job as well as a normally easy interpretation of the measured data. For instance, gas and light oil discrimination against water is feasible by direct observation of the T2 distribution. A condition for this measurement method is a NMR logging tool that hardly moves while drilling and in addition uses a small static...

  17. Solid-state NMR studies of globular and membrane proteins

    Luca, Sorin

    2003-01-01

    Spektroskopie erlaubt die Eigenschaften und Struktur der Materie durch Einsatz elektromagnetischer Strahlung auf molekularer Ebene zu untersuchen. Die Kernspinresonanz (NMR) ist ein spezielles Gebiet der Spektroskopie, die die magnetischen Eigenschaften der Atomkerne auswertet. Ein kurzer Überblick über die historischen Weiterentwicklungen im Bereich der NMR ergibt sich aus einer Betrachtung der Nobelpreise, die bisher im Zusammenhang der NMR vergeben wurden: 1952 empfingen Felix Bloch und Ed...

  18. NMR Studies of Quantum Rotors Confined in Zeolite

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

    2010-02-01

    We report the results of NMR studies of methane trapped in zeolite at low temperatures. Samples were prepared to contain 1.0±0.2 molecules per α-sodalite cage of zeolite-13X. The NMR spin-spin and spin-lattice relaxation times were measured for 4NMR spin-spin relaxation is seen at this “melting” transition.

  19. Hochfeld 1H-NMR-Mikroskopie zur biophysikalischen Grundlagenforschung

    Haddad, Daniel

    2005-01-01

    Dank der mit modernen NMR-Spektrometern (Kernspintomographen) routinemäßig realisierbaren isotropen räumlichen Auflösungen von wenigen Mikrometern, ergeben sich für die 1H NMR-Mikroskopie zahlreiche neue Anwendungsgebiete. Allerdings sind die Möglichkeiten und Grenzen der NMR-Mikroskopie bezüglich ihrer praktischen Anwendbarkeit bisher nur wenig untersucht worden. Die vorliegende Arbeit ist im Bereich der biophysikalischen Grundlagenforschung angesiedelt und soll die praktische Anwendbarkeit ...

  20. Stroke, evolution of NMR imaging characteristics

    This study evaluates the NMR imaging characteristics of stroke and temporal evolution of these features. Patients with acute stroke clinically had NMR imaging (prototype 0.15T resistive imager, Technicare, Inc.) acutely (n=37), at approximately 2 weeks (n=31) and 3 months (n=10). Patients with old (> 1 yr.) stroke were also imaged (n=7). Partial saturation sequences were used employing echo time (T/sub E/) of 30, 60 and 120 msec, as well as inversion recovery (TR) sequences. Partial saturation images displayed a homogeneous increase in signal at lesion sites in both bland and hemorrhagic infarcts, reflection prolongation of spin-spin relaxation (T/sub 2/) due to increased tissue water content, blood and edema being indistinguishable. IR images recovered low signal from bland infarcts due to prolongation of spinlattice relaxation (T/sub 1/) by tissue edema, hemorrhagic lesions and short (T/sub 1/) centrally (blood) with moderate or increased IR signal, and low signal peripherally (edema). On follow-up IR imaging, hematomas developed low signal centres, possibly reflection cavitation, with short T/sub 2/ rims, possibly indicating the presence of iron-laden macrophages. In 2 patients with hemorrhagic infarcts an area of increased signal (prolonged T/sub 2/) was seen on initial partial saturation images in the homologous portion of the other hemisphere (normal by CT). This may reflect a local alteration of blood volume or velocity. In 5 patients with old infarcts, a rim of prolonged T/sub 2/ was seen at the periphery of old lesions, possibly reflecting a local chronic increase in extravascular or intravascular water, slowing of blood velocity, or a zone of neuronal dropout. Detailed pathophysiologic correlation is required to understand the basis of these NMR findings

  1. Stroke, evolution of NMR imaging characteristics

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

    1984-01-01

    This study evaluates the NMR imaging characteristics of stroke and temporal evolution of these features. Patients with acute stroke clinically had NMR imaging (prototype 0.15T resistive imager, Technicare, Inc.) acutely (n=37), at approximately 2 weeks (n=31) and 3 months (n=10). Patients with old (> 1 yr.) stroke were also imaged (n=7). Partial saturation sequences were used employing echo time (T/sub E/) of 30, 60 and 120 msec, as well as inversion recovery (TR) sequences. Partial saturation images displayed a homogeneous increase in signal at lesion sites in both bland and hemorrhagic infarcts, reflection prolongation of spin-spin relaxation (T/sub 2/) due to increased tissue water content, blood and edema being indistinguishable. IR images recovered low signal from bland infarcts due to prolongation of spinlattice relaxation (T/sub 1/) by tissue edema, hemorrhagic lesions and short (T/sub 1/) centrally (blood) with moderate or increased IR signal, and low signal peripherally (edema). On follow-up IR imaging, hematomas developed low signal centres, possibly reflection cavitation, with short T/sub 2/ rims, possibly indicating the presence of iron-laden macrophages. In 2 patients with hemorrhagic infarcts an area of increased signal (prolonged T/sub 2/) was seen on initial partial saturation images in the homologous portion of the other hemisphere (normal by CT). This may reflect a local alteration of blood volume or velocity. In 5 patients with old infarcts, a rim of prolonged T/sub 2/ was seen at the periphery of old lesions, possibly reflecting a local chronic increase in extravascular or intravascular water, slowing of blood velocity, or a zone of neuronal dropout. Detailed pathophysiologic correlation is required to understand the basis of these NMR findings.

  2. Monitoring organic reactions by UF-NMR spectroscopy.

    Herrera, Antonio; Fernández-Valle, Encarnación; Martínez-Álvarez, Roberto; Molero-Vílchez, Dolores; Pardo-Botero, Zulay D; Sáez-Barajas, Elena

    2015-11-01

    Standard 2D NMR experiments suffer from the many t1 increments needed for spectra with sufficient digital resolution in the indirect dimension. Despite the different methodological approaches to overcome this problem, these increments have prevented studies of fast reactions. The development of ultrafast NMR (UF-NMR) has decisively speeded up the time scale of standard NMR to allow the study of organic reactions as they happen in real time to reveal mechanistic details. This mini-review summarizes the results achieved in monitoring organic reactions through this exciting technique. PMID:25998506

  3. Rotational Doppler Effect and Barnett Field in Spinning NMR

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

    2015-04-01

    We report the observation of the rotational Doppler effect using nuclear magnetic resonance (NMR). We have developed a coil-spinning technique that enables measurements by rotating a detector and fixing a sample. We found that the rotational Doppler effect gives rise to NMR frequency shifts equal to the rotation frequency. We formulate the rotational Doppler effect and the Barnett field using a vector model for the nuclear magnetic moment. This formulation reveals that, with just the sample rotating, both effects cancel each other, thereby explaining the absence of an NMR frequency shift in conventional sample-spinning NMR measurements.

  4. Structural study of pyrones by NMR

    Extracts of two species of Aniba, designed Aniba-SA (light petroleum extract) and Aniba-SB (benzene extract), afforded by chromatographic fraccionation some compounds. The isolated compounds were identified using spectrometric data and C13-NMR coupled and decompled spectra of pyrones were registered. Measurement of the heteronuclear residual coupling by irradiation proton frequency off-resonance was used for distinguish C-5, C-7 and C-8 carbons of the pyrones SB-1, SB-3, SB-4 and SB-5. (M.J.C.)

  5. Measurement of vorticity diffusion by NMR microscopy.

    Brown, Jennifer R; Callaghan, Paul T

    2010-05-01

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

  6. Wideband transmitter for pulse NMR spectrometer

    A wideband pulse transmitter for NMR excitation in fields of up to 2.4 T (except for 1H, 1F, 203Tl, and 205Tl nuclei) is described. The transmitter provides a pulse power of 400-600 W into a 50-Omega load at frequencies of 2-40 MHz. The transmitter is equipped with a pulse programmer, which allows independent setting, in each of 16 program steps, of pulse durations or pauses of from 10-7 to 103 sec, output powers of from 0 to -63 dB, and a phase of radio-frequency filling of 0 or 1800

  7. Solid state NMR study calcium phosphate ceramics

    High-resolution 31P and 1H NMR spectra at 40 and 121 MHz 31P and 300 MHz 1H of synthetic and biological samples of calcium phosphates have been obtained by magic angle spinning (MAS) at spinning speeds up to 6.5 kHz, and high power proton decoupling. The samples include crystalline hydroxyapatite, a deficient hydroxyapatite characterized by a Ca/P atomic ratio of 1.5, a poorly crystallized hydroxyapatite, monetite, brushite, octacalcium phosphate, β-tricalcium phosphate and rabbit femoral bone. The interactions between nuclei in unlike structures and the mobility of acid protons are discussed. (author). 11 refs.; 2 figs.; 1 tab

  8. In Vivo Measurements of NMR Relaxation Times

    Kroeker, Randall M.; Mcveigh, Elliot R.; Hardy, Peter; Bronskill, Michael J.; Henkelman, R. Mark

    1985-01-01

    A series of solenoidal NMR probes were built to measure T1 and T2 relaxation times in vivo in the mouse, over the frequency range of 5 to 60 MHz, using inversion-recovery and spin-echo pulse sequences. KHT tumors growing in the legs of C3H mice were studied and compared with normal mouse legs. The tumor relaxation times were studied at 10 MHz during the course of tumor growth and as a function of frequency when the tumor had a mass of approximately 0.9 g. Mouse legs with tumors have higher T1...

  9. Analysis of multiple pulse NMR in solids

    Rhim, W.-K.; Elleman, D. D.; Vaughan, R. W.

    1973-01-01

    The general problems associated with the removal of the effects of dipolar broadening from solid-state NMR spectra are analyzed. The effects of finite pulse width and H sub 1 inhomogeneity are shown to have limited the resolution of previous pulse cycles, and a new eight-pulse cycle designed to minimize these problems is discussed. Spectra for F-19 in CaF2 taken with this cycle are presented which show residual linewidth near 10 Hz. The feasibility of measuring proton chemical shift tensors is discussed.

  10. A 45Sc-NMR and DFT calculation study of crystalline scandium compounds

    Bräuniger, Thomas; Hofmann, Andreas J.; Moudrakovski, Igor L.; Hoch, Constantin; Schnick, Wolfgang

    2016-01-01

    A series of scandium compounds, namely ScPO4, ScOF, Li3Sc(BO3)2, and CaSc2O4, were prepared according to procedures described in the literature, and then characterised by powder X-ray diffraction and solid-state 45Sc-NMR spectroscopy. By computer fitting, the quadrupolar interaction parameters χ and η, as well as the isotropic chemical shifts δiso were extracted from the NMR spectra. For comparison and site assignment of 45Sc, density functional theory (DFT) calculations of the EFG tensor were carried out with the CASTEP code. For the compounds with a well-defined formal coordination number (CN), a convincing linear correlation between CN and isotropic chemical shift could be established.

  11. NMR doesn't lie or how solid-state NMR spectroscopy contributed to a better understanding of the nature and function of soil organic matter (Philippe Duchaufour Medal Lecture)

    Knicker, Heike

    2016-04-01

    "Nuclear magnetic resonance (NMR) does not lie". More than anything else, this statement of a former colleague and friend has shaped my relation to solid-state NMR spectroscopy. Indeed, if this technique leads to results which contradict the expectations, it is because i) some parts of the instrument are broken, ii) maladjustment of the acquisition parameters or iii) wrong preparation or confusion of samples. However, it may be even simpler, namely that the expectations were wrong. Of course, for researchers, the latter is the most interesting possibility since it forces to reassess accepted views and to search for new explanations. As my major analytical tool, NMR spectroscopy has confronted me with this challenge often enough to turn this issue into the main subject of my talk and to share with the audience how it formed my understanding of function and nature of soil organic matter (SOM). Already shortly after its introduction into soil science in the 1980's, the data obtained with solid-state 13C NMR spectroscopy opened the stage for ongoing discussions, since they showed that in humified SOM aromatic carbon is considerably less important than previously thought. This finding had major implications regarding the understanding of the origin of SOM and the mechanisms by which it is formed. Certainly, the discrepancy between the new results and previous paradigms contributed to mistrust in the reliability of solid-state NMR techniques. The respective discussion has survived up to our days, although already in the 1980's and 1990's fundamental studies could demonstrate that quantitative solid-state NMR data can be obtained if i) correct acquisition parameters are chosen, ii) the impact of paramagnetic compounds is reduced and iii) the presence of soot in soils can be excluded. On the other hand, this mistrust led to a detailed analysis of the impact of paramagnetics on the NMR behavior of C groups which then improved our understanding of the role of carbohydrates

  12. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoaceticum metabolic profiles

    Xue, Junfeng; Isern, Nancy G.; Ewing, R James; Liyu, Andrey V.; Sears, Jesse A.; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R.; Ahring, Birgitte K.; Majors, Paul D.

    2014-06-20

    An in-situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch-growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution, high sensitivity NMR (HR-NMR) spectroscopy. In-situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at an NMR frequency of 500 MHz, and aliquots of the bioreactor contents were taken for 600 MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in-situ NMR bioreactor facilitated monitoring of the fermentation process in real time, enabling identification of intermediate and end-point metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with the HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts.

  13. The stoichiometry of synthetic alunite as a function of hydrothermal aging investigated by solid-state NMR spectroscopy, powder X-ray diffraction and infrared spectroscopy

    Grube, Elisabeth; Nielsen, Ulla Gro

    2015-01-01

    angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. The 1H MAS NMR spectra recorded at high magnetic field (21.1 T, 900 MHz) allowed for a clear separation of the different proton environments and for quantitative determination of the aluminum vacancy concentration as a function of time....... The concentration of structural defects determined from, i.e., aluminum vacancies was reduced from 4 to 1 %, as the reaction time was extended from one to 31 days based on 1H MAS NMR. This was further supported by an increase of the unit cell parameter c, which is indicative of the relative...... concentration of potassium defects present, from 17.261(1) to 17.324(5) Å. Solid-state 27Al MAS NMR revealed a decrease in the defect concentration as a function of time and showed the presence of 7-10 % impurities in the samples....

  14. (11)B MAS NMR and First-Principles Study of the [OBO3] Pyramids in Borates.

    Zhou, Bing; Sun, Wei; Zhao, Biao-Chun; Mi, Jin-Xiao; Laskowski, Robert; Terskikh, Victor; Zhang, Xi; Yang, Lingyun; Botis, Sanda M; Sherriff, Barbara L; Pan, Yuanming

    2016-03-01

    Borates are built from the [Bϕ3] planar triangles and the [Bϕ4] tetrahedral groups, where ϕ denotes O or OH. However, the [Bϕ4] groups in some borates are highly distorted to include three normal B-O bonds and one anomalously long B-O bond and, therefore, are best described as the [OBO3] pyramids. Four synthetic borates of the boracite-type structures (Mg3B7O13Br, Cu3B7O13Br, Zn3B7O13Cl, and Mg3B7O13Cl) containing a range of [OBO3] pyramids were investigated by multifield (7.05, 14.1, and 21.1 T) (11)B magic-angle spinning nuclear magnetic resonance (MAS NMR), triple quantum (3Q) MAS NMR experiments, as well as density functional theory calculations. The high-resolution (11)B MAS NMR spectra supported by theoretical predictions show that the [OBO3] pyramids are characterized by isotropic chemical shifts δiso((11)B) from 1.4(1) to 4.9(1) ppm and nuclear quadrupole parameters CQ((11)B) up to 1.3(1) MHz, both significantly different from those of the [BO4] and [BO3] groups in borates. These δiso((11)B) and CQ((11)B) values indicate that the [OBO3] pyramids represent an intermediate state between the [BO4] tetrahedra and [BO3] triangles and demonstrate that the (11)B NMR parameters of four-coordinate boron oxyanions are sensitive to local structural environments. The orientation of the calculated unique electronic field gradient tensor element Vzz of the [OBO3] pyramids is aligned approximately along the direction of the anomalously long B-O bond, corresponding to B-2pz with the lowest electron density. PMID:26914372

  15. The Sensitivity of Dielectric and NMR Measurements to Sorption at the Solid/Water Interface

    Knight, R. J.

    2011-12-01

    Measurements of the real part of the relative dielectric permittivity (dielectric constant) and the NMR relaxation time constants (T1 and T2) of water-saturated geological materials, contain information about molecular-scale processes and are used to estimate pore-scale properties. While the measurements probe different aspects of the response of a porous medium, it is well-established that the measured dielectric and NMR parameters are sensitive to the size and state of the solid/water interface. Laboratory and theoretical studies have shown the dielectric constant and NMR relaxation rates (1/T1 and 1/T2) of water-saturated geological materials to be proportional to the surface-area-to-volume ratio of the pore space. It is important to emphasize that the surface area, related to the magnitude of these measured parameters, is the water-wet surface area of a material. The fact that the sorption of chemical species (other than water) at the solid/water interface reduces the size of the water-wet surface area, raises the following question: Can dielectric and NMR measurements provide a sensitive, reliable tool for monitoring the sorption and desorption of contaminants in geological materials? Laboratory studies have explored the way in which changes in the wettability of a material affect the dielectric constant. In studies where the geological material was altered so as to be fully hydrophobic or oil-wet, a significant decrease was seen in the dielectric constant. Eliminating the solid/water interface appears to eliminate the contributions of surface processes to the dielectric response. In another study, as oil sorbed to the surfaces of water-saturated samples of sand and clay, a gradual decrease in dielectric constant was seen due to the decrease in water-wet surface area with increasing sorption. While this behavior is consistent with developed theoretical models, accurately predicting the magnitude of the effect remains a topic of research. Unlike the dielectric

  16. NMR study of high-TC superconductors

    Recent NMR study of high-TC superconductors carried out by Osaka group is reviewed. NQR frequency νQ, Knight shift K, T1 of 63Cu and 17O were measured over a wide hole doping range from light- to heavy-doped systems, LSCO, YBCO, HBCCO, BSCCO, TBCCO and TBCO, together with impurity and pressure effect. By analysing νQ, K and T1, the local hole numbers of Cu and O at the CuO2 plane, n(Cu) and n(O) the relative magnitude of the uniform susceptibility, χ0 and the low-frequency component of the antiferromagnetic spin fluctuations (AFSF), χQ/Γ (χQ is the staggered susceptibility and Γ is the characteristic energy of the spin fluctuation at q=0) are obtained. The relation between n(Cu), n(O) and χQ, χQ/Γ, TC, etc. were discussed. There are optimum values of n(Cu)/2n(O) and n(Cu)+2n(O) to give maximum TC. The NMR results in the superconducting state are well-explained by d-wave pairing model. The result is consistent with the AFSF mediated superconducting model. (orig.)

  17. Nuclear magnetic resonance (NMR)-based metabolomics.

    Keun, Hector C; Athersuch, Toby J

    2011-01-01

    Biofluids are by far the most commonly studied sample type in metabolic profiling studies, encompassing blood, urine, cerebrospinal fluid, cell culture media and many others. A number of these fluids can be obtained at a high sampling frequency with minimal invasion, permitting detailed characterisation of dynamic metabolic events. One of the attractive properties of solution-state metabolomics is the ability to generate profiles from these fluids following simple preparation, allowing the analyst to gain a naturalistic, largely unbiased view of their composition that is highly representative of the in vivo situation. Solution-state samples can also be generated from the extraction of tissue or cellular samples that can be tailored to target metabolites with particular properties. Nuclear magnetic resonance (NMR) provides an excellent technique for profiling these fluids and is especially adept at characterising complex solutions. Profiling biofluid samples by NMR requires appropriate preparation and experimental conditions to overcome the demands of varied sample matrices, including those with high protein, lipid or saline content, as well as the presence of water in aqueous samples. PMID:21207299

  18. In vivo NMR spectroscopy of ripening avocado

    Ripening of avocado fruit is associated with a dramatic increase in respiration. Previous studies have indicated that the increase in respiration is brought about by activation of the glycolytic reaction catalyzing the conversion of fructose-6-phosphate to fructose 1,6-bisphosphate. The authors reinvestigated the proposed role of glycolytic regulation in the respiratory increase using in vivo 31P nuclear magnetic resonance (NMR) spectroscopy using an external surface coil and analysis of phosphofructokinase (PFK), phosphofructophosphotransferase (PFP), and fructose 2,6-bisphosphate (fru 2,6-P2) levels in ripening avocado fruit. In vivo 31P NMR spectroscopy revealed large increases in ATP levels accompanying the increase in respiration. Both glycolytic enzymes, PFK and PFP, were present in avocado fruit, with the latter activity being highly stimulated by fru 2,6-P2. Fructose 2,6-bisphosphate levels increased approximately 90% at the onset of ripening, indicating that the respiratory increase in ripening avocado may be regulated by the activation of PFP brought about by an increase in fru 2,6-P2

  19. Ligand exchange and complex formation kinetics studied by NMR exemplified on fac-[(CO)3M(H2O)]+ (M = Mn, Tc, Re)

    Helm, Lothar

    2008-01-01

    In this review ligand exchange and complex formation reactions on fac-[(CO)3M(H2O)3]+ (M = Mn, Tc, Re) and on fac-[(CO)2(NO)Re(H2O)3]2+ are presented. A variety of experimental NMR techniques are described and it is shown that sometimes combinations of techniques applied at variable temperature or variable pressure allowed to measure exchange rate constants and their activation parameters as well as thermodynamic parameters. Furthermore, the use of uncommon nuclei for NMR like 17O or 99Tc ext...

  20. Solid state NMR and DFT study of polymer electrolytes

    Spěváček, Jiří; Brus, Jiří; Dybal, Jiří; Kang, Y. S.

    Linz : Institut für Organische Chemie, Johannes Kepler Universität, 2004 - (Müller, N.). s. 28 [Central European NMR Symposium /6./. 27.09.2004, Linz] R&D Projects: GA AV ČR IAA4050209 Keywords : solid polymer electrolytes * solid state NMR * quantum-chemical DFT calculation Subject RIV: CD - Macromolecular Chemistry

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

    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.

  2. Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy

    Ardenkjær-Larsen, Jan Henrik; Boebinger, Gregory S.; Comment, Arnaud;

    2015-01-01

    of the primary approaches that were considered. Topics discussed included the future of ultrahigh‐field NMR systems, emerging NMR detection technologies, new approaches to nuclear hyperpolarization, and progress in sample preparation. All of these are orthogonal efforts, whose gains could multiply...... optical measurements. These challenges, and the ways by which scientists and engineers are striving to solve them, are also addressed....

  3. NMR study of phase separation in solutions of linear polymers

    Kouřilová, H.; Šťastná, J.; Hanyková, L.; Spěváček, Jiří

    Poznań : Adam Mickiewicz University, 2010 - (Jurga, S.). s. 27 [AMPERE NMR School. 17.06.2010-26.06.2010, Poznań - Wierzba] R&D Projects: GA ČR GA202/09/1281 Institutional research plan: CEZ:AV0Z40500505 Keywords : phase separation * polymer solution * NMR Subject RIV: CD - Macromolecular Chemistry

  4. NMR crystallography of active pharmaceuticals ingredients for industrial applications

    Urbanová, Martina; Brus, Jiří; Kobera, Libor

    Herceg Novi : Materials Research Society, 2008. s. 165. [Annual Conference YUCOMAT 2008 /10./. 08.09.2008-12.09.2008, Herceg Novi] R&D Projects: GA MŠk 2B08021 Institutional research plan: CEZ:AV0Z40500505 Keywords : MAS NMR * atorvastatin * NMR crystallography Subject RIV: CF - Physical ; Theoretical Chemistry

  5. What can be expected from NMR in reversed micelles?

    A review is given of NMR studies on reversed micellar systems since 1970. General principles are emphasized through examples which have led to relevant physico-chemical results in the area. NMR techniques or theories are not detailed in order to focus primarily on the information obtained on the micelles. (author). 50 refs.; 9 figs

  6. Development of portable NMR polarimeter system for polarized HD target

    Ohta, T; Didelez, J -P; Fujiwara, M; Fukuda, K; Kohri, H; Kunimatsu, T; Morisaki, C; Ono, S; Rouille, G; Tanaka, M; Ueda, K; Uraki, M; Utsuro, M; Wang, S Y; Yosoi, M

    2011-01-01

    A portable NMR polarimeter system has been developed to measure the polarization of a polarized Hydrogen-Deuteride (HD) target for hadron photoproduction experiments at SPring-8. The polarized HD target is produced at the Research Center for Nuclear Physics (RCNP), Osaka university and is transported to SPring-8. The HD polarization should be monitored at both places. We have constructed the portable NMR polarimeter system by replacing the devices in the conventional system with the software system with PCI eXtensions for Instrumentation (PXI). The weight of the NMR system is downsized from 80 kg to 7 kg, and the cost is reduced to 25%. We check the performance of the portable NMR polarimeter system. The signal-to-noise (S/N) ratio of the NMR signal for the portable system is about 50% of that for the conventional NMR system. This performance of the portable NMR system is proved to be compatible with the conventional NMR system for the polarization measurement.

  7. What can Lattice QCD theorists learn from NMR spectroscopists?

    Euclidean-time hadron correlation functions computed in Lattice QCD (LQCD) are modeled by a sum of decaying exponentials, reminiscent of the exponentially damped sinusoid models of free induction decay (FID) in Nuclear Magnetic Resonance (NMR) spectroscopy. We present our initial progress in studying how data modeling techniques commonly used in NMR perform when applied to LQCD data

  8. The Characterization of Comblike Polymer Electrolyte by Means of NMR

    2000-01-01

    The comblike polymers based on poly (styrene-co-maleic anhydride) backbone with poly (ethylene glycol) methyl ether as side chains were synthesized and characterized by 1H NMR, with the result compared with that of IR.It is found that it is both feasible and simple to synthesize this kind of compounds with the help of 1H NMR.

  9. Heteronuclear Multidimensional Protein NMR in a Teaching Laboratory

    Wright, Nathan T.

    2016-01-01

    Heteronuclear multidimensional NMR techniques are commonly used to study protein structure, function, and dynamics, yet they are rarely taught at the undergraduate level. Here, we describe a senior undergraduate laboratory where students collect, process, and analyze heteronuclear multidimensional NMR experiments using an unstudied Ig domain (Ig2…

  10. Current progress and future prospects in NMR imaging

    Future prospects in NMR imaging will depend not only on the extent to which images of diagnostic quality can be obtained in reasonable short times, but, more importantly, on whether the whole range of NMR measurements and techniques can be applied to achieve a useful degree of tissue characterization and the measurement of blood flow in vivo. (orig./VJ)

  11. What can Lattice QCD theorists learn from NMR spectroscopists?

    George Fleming

    2003-06-01

    Euclidean-time hadron correlation functions computed in Lattice QCD (LQCD) are modeled by a sum of decaying exponentials, reminiscent of the exponentially damped sinusoid models of free induction decay (FID) in Nuclear Magnetic Resonance (NMR) spectroscopy. We present our initial progress in studying how data modeling techniques commonly used in NMR perform when applied to LQCD data.

  12. New generation NMR bioreactor coupled with high-resolution NMR spectroscopy leads to novel discoveries in Moorella thermoacetica metabolic profiles.

    Xue, Junfeng; Isern, Nancy G; Ewing, R James; Liyu, Andrei V; Sears, Jesse A; Knapp, Harlan; Iversen, Jens; Sisk, Daniel R; Ahring, Birgitte K; Majors, Paul D

    2014-10-01

    An in situ nuclear magnetic resonance (NMR) bioreactor was developed and employed to monitor microbial metabolism under batch growth conditions in real time. We selected Moorella thermoacetica ATCC 49707 as a test case. M. thermoacetica (formerly Clostridium thermoaceticum) is a strictly anaerobic, thermophilic, acetogenic, gram-positive bacterium with potential for industrial production of chemicals. The metabolic profiles of M. thermoacetica were characterized during growth in batch mode on xylose (a component of lignocellulosic biomass) using the new generation NMR bioreactor in combination with high-resolution NMR (HR-NMR) spectroscopy. In situ NMR measurements were performed using water-suppressed H-1 NMR spectroscopy at 500 MHz, and aliquots of the bioreactor contents were taken for 600-MHz HR-NMR spectroscopy at specific intervals to confirm metabolite identifications and expand metabolite coverage. M. thermoacetica demonstrated the metabolic potential to produce formate, ethanol, and methanol from xylose, in addition to its known capability of producing acetic acid. Real-time monitoring of bioreactor conditions showed a temporary pH decrease, with a concomitant increase in formic acid during exponential growth. Fermentation experiments performed outside of the magnet showed that the strong magnetic field employed for NMR detection did not significantly affect cell metabolism. Use of the in situ NMR bioreactor facilitated monitoring of the fermentation process, enabling identification of intermediate and endpoint metabolites and their correlation with pH and biomass produced during culture growth. Real-time monitoring of culture metabolism using the NMR bioreactor in combination with HR-NMR spectroscopy will allow optimization of the metabolism of microorganisms producing valuable bioproducts. PMID:24946863

  13. Dynamics of solutions and fluid mixtures by NMR

    After a short introduction to NMR spectroscopy, with a special emphasis on dynamical aspects, an overview on two fundamental aspects of molecular dynamics, NMR relaxation and its relationship with molecular reorientation, and magnetization transfer phenomena induced by molecular rate processes (dynamic NMR) is presented, followed by specific mechanisms of relaxation encountered in paramagnetic systems or with quadrupolar nuclei. Application fields are then reviewed: solvent exchange on metal ions with a variable pressure NMR approach, applications of field gradients in NMR, aggregation phenomena and micro-heterogeneity in surfactant solutions, polymers and biopolymers in the liquid state, liquid-like molecules in rigid matrices and in soft matter (swollen polymers and gels, fluids in and on inorganic materials, food)

  14. $\\beta$-NMR of copper isotopes in ionic liquids

    We propose to test the feasibility of spin-polarization and $\\beta$-NMR studies on several short-lived copper isotopes, $^{58}$ Cu, $^{74}$Cu and $^{75}$Cu in crystals and liquids. The motivation is given by biological studies of Cu with $\\beta$-NMR in liquid samples, since Cu is present in a large number of enzymes involved in electron transfer and activation of oxygen. The technique is based on spin-polarization via optical pumping in the new VITO beamline. We will use the existing lasers, NMR magnet and NMR chambers and we will prepare a new optical pumping system. The studies will be devoted to tests of achieved $\\beta$-asymmetry in solid hosts, the behaviour of asymmetry when increasing vacuum, and finally NMR scans in ionic liquids. The achieved spin polarization will be also relevant for the plans to measure with high precision the magnetic moments of neutron-rich Cu isotopes.

  15. A nomenclature and data model to describe NMR experiments

    Despite ongoing efforts in organising NMR information, there is no consistent and well-described generic standard for naming NMR experiments. The main reason for the absence of a universal naming system is that the information content of the coherence pathways is difficult to describe in full detail. We propose a system that describes the common and generic elements of the coherence pathways produced by pulse sequences. The system itself is formalised by an 'NMR experiment protocol' model, which is described in the Universal Modelling Language (UML) as part of the CCPN data model. Furthermore, normalized experiment names can be derived from this proposed model. We hope this article will stimulate discussion to organise the wealth of NMR experiments, and that by bringing this discussion into the public domain we can improve and expand our proposed system to include as much information and as many NMR experiments as possible

  16. Dynamics of antibody domains studied by solution NMR.

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

    2009-01-01

    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

  17. NMR screening for rapid protein characterization in structural proteomics.

    Hill, Justine M

    2008-01-01

    In the age of structural proteomics when protein structures are targeted on a genome-wide scale, the identification of proteins that are amenable to analysis using x-ray crystallography or NMR spectroscopy is the key to high throughput structure determination. NMR screening is a beneficial part of a structural proteomics pipeline because of its ability to provide detailed biophysical information about the protein targets under investigation at an early stage of the structure determination process. This chapter describes efficient methods for the production of uniformly (15)N-labeled proteins for NMR screening using both conventional IPTG induction and autoinduction approaches in E. coli. Details of sample preparation for NMR and the acquisition of 1D (1)H NMR and 2D (1)H-(15)N HSQC spectra to assess the structural characteristics and suitability of proteins for further structural studies are also provided. PMID:18542882

  18. Dispersions of pyrogenic alumina in pentylcyanobiphenyl studied by deuteron NMR

    Yim, C. T.

    2009-09-01

    Dispersions of hydrophilic (Aeroxide Alu C) and hydrophobic (Aeroxide Alu C 805) pyrogenic alumina (Al2O3) in liquid crystal 4' -n-pentyl-4-cyanobiphenyl (5CB) were investigated with deuteron nuclear magnetic resonance. The disorder effects of Al2O3 particles on the orientational order of liquid-crystal media and on the field-induced director configuration were studied as a function of alumina density in samples prepared by zero-field cooling and in-field cooling procedures. The order parameters and their variation with alumina density suggest a stronger disordering effect from the nonpolar surface of Alu C 805 particles. For dispersions of hydrophobic Alu C 805 experiments involving in-field cooling from the isotropic phase indicate that the director of “disordered” domains can be aligned, though not perfectly, by the field-aided annealing process. But the same in-field cooling procedure has shown rather limited alignment effects for hydrophilic Alu C/5CB samples. The more robust network of hydrophilic gel possibly coupled with weak liquid-crystal-network interactions could be responsible for the observed behavior. Spectra recorded during in-field cooling and within the isotropic-nematic coexistence region reveal the augmentation of the disorder strength during the transition and illustrate the effect of field-aided annealing. The stability of the aligned states as revealed by deuteron NMR is described. The results are discussed in comparison with previous studies of aerosil dispersions in alkylcyanobiphenyl.

  19. Non-uniform sampling of NMR relaxation data

    The use of non-uniform sampling of NMR spectra may give significant reductions in the data acquisition time. For quantitative experiments such as the measurement of spin relaxation rates, non-uniform sampling is however not widely used as inaccuracies in peak intensities may lead to errors in the extracted dynamic parameters. By systematic reducing the coverage of the Nyquist grid of 15N Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion datasets for four different proteins and performing a full data analysis of the resulting non-uniform sampled datasets, we have compared the performance of the multi-dimensional decomposition and iterative re-weighted least-squares algorithms in reconstructing spectra with accurate peak intensities. As long as a single fully sampled spectrum is included in a series of otherwise non-uniform sampled two-dimensional spectra, multi-dimensional decomposition reconstructs the non-uniform sampled spectra with high accuracy. For two of the four analyzed datasets, a coverage of only 20 % results in essentially the same results as the fully sampled data. As exemplified by other data, such a low coverage is in general not enough to produce reliable results. We find that a coverage level not compromising the final results can be estimated by recording a single full two-dimensional spectrum and reducing the spectrum quality in silico

  20. In situ deuteron NMR investigations of sheared liquid crystalline polymers.

    Siebert, Hartmut; Becker, Patrick; Quijada-Garrido, Isabel; Grabowski, David A; Schmidt, Claudia

    2002-01-01

    The flow behavior of nematic liquid crystalline polysiloxanes of the side-chain type is studied by in situ 2H NMR spectroscopy on samples under shear in a cone-and-plate cell. The director orientation as a function of applied shear rate is determined from the quadrupole splitting of the spectra. The data analysis yields the two Leslie viscosity coefficients alpha2 and alpha3 and the flow-alignment parameter lambda = -(alpha3 + alpha2)/(alpha3 - alpha2). The values of lambda were determined for several homopolymers with only one type of side chain and random copolymers containing two different side chains. The results show that the flow behavior is related to the phase structure of the polymers, which varies with their composition. Only polymers with large amounts of smectic clusters in the nematic state show the tumbling instability (absolute value(lambda) polymers are flow aligning (absolute value(lambda) > or = 1). For some polymers, a transition from tumbling at low temperature to flow aligning at high temperatures was observed. PMID:12469817

  1. Non-uniform sampling of NMR relaxation data

    Linnet, Troels E.; Teilum, Kaare, E-mail: kaare.teilum@bio.ku.dk [University of Copenhagen, SBiNLab and the Linderstrøm-Lang Centre for Protein Science, Department of Biology (Denmark)

    2016-02-15

    The use of non-uniform sampling of NMR spectra may give significant reductions in the data acquisition time. For quantitative experiments such as the measurement of spin relaxation rates, non-uniform sampling is however not widely used as inaccuracies in peak intensities may lead to errors in the extracted dynamic parameters. By systematic reducing the coverage of the Nyquist grid of {sup 15}N Carr-Purcell-Meiboom-Gill (CPMG) relaxation dispersion datasets for four different proteins and performing a full data analysis of the resulting non-uniform sampled datasets, we have compared the performance of the multi-dimensional decomposition and iterative re-weighted least-squares algorithms in reconstructing spectra with accurate peak intensities. As long as a single fully sampled spectrum is included in a series of otherwise non-uniform sampled two-dimensional spectra, multi-dimensional decomposition reconstructs the non-uniform sampled spectra with high accuracy. For two of the four analyzed datasets, a coverage of only 20 % results in essentially the same results as the fully sampled data. As exemplified by other data, such a low coverage is in general not enough to produce reliable results. We find that a coverage level not compromising the final results can be estimated by recording a single full two-dimensional spectrum and reducing the spectrum quality in silico.

  2. Variations of NMR signals by hyperpolarization and ultrasound; Variation von NMR-Signalen durch Hyperpolarisation und Ultraschall

    Engelbertz, A.

    2006-07-01

    In this thesis it is described how p-NMR can be applied to metals with verlo low hydrogen concentrations and how a combination of ultrasound and NMR can lead to an improvement of the measureing method. As examples measurements on H{sub 2}O and ethanol are described. (HSI)

  3. A solid state pulsed NMR spectrometer

    A 10 MHz pulsed NMR spectrometer, built using mostly solid state devices, is described. The pulse programmer provides 2-pulse, 3-pulse, saturation burst and Carr-Purcell sequences both in repetitive and manual modes of operation. The transmitter has a maximum power output of approximately 2 kW with a 75Ω output impedance termination. The total gain of the receiver system is around 120 dB with a minimum band width of 2 MHz. The recovery time of the receiver is approximately 7μsec. A two-channel boxcar integrator capable of working in the single channel, differential and double boxcar modes provides signal to noise ratio improvement. The sensitivity and the linearity of the boxcar integrator are approximately 2 mV and approximately 0.1% respectively. (auth.)

  4. NMR investigations of YMn2Hx hydrides

    The YMn2Hx hydrides with x = 1, 2, 3 were investigated by 55Mn NMR spin echo measurements at atmospheric and high pressure. Resonance lines at frequencies up to 440 MHz were observed for the hydrides, corresponding to a huge increase of the hyperfine fields at those Mn with hydrogen neighbours. At high pressure the initial decrease of the magnitude of the Mn hyperfine field of YMn2H1 at 4.2 K was found to be 4% per kbar which is an order of magnitude bigger than observed in the other magnetically ordered materials. The effects are interpreted in terms of changes of the orbital contribution and valence electron contribution to the hyperfine field caused by hydrogenation and the influence of the external pressure. (orig.)

  5. Long Lived NMR Signal in Bone

    Zhang, Boyang; Khitrin, Anatoly; Jerschow, Alexej

    2012-01-01

    Solids and rigid tissues such as bone, ligaments, and tendons, typically appear dark in magnetic resonance imaging (MRI), which is due to the extremely short-lived proton nuclear magnetic resonance (NMR) signals. This short lifetime is due to strong dipolar interactions between immobilized proton spins, which render it challenging to detect these signals with sufficient resolution and sensitivity. Here we show the possibility of exciting long-lived signals in cortical bone tissue with a signature consistent with that of bound water signals. Contrary to long-standing belief, it is further shown that dipolar coupling networks are an integral requirement for the excitation of these long-lived signals. The use of these signals could enhance the ability to visualize rigid tissues and solid samples with high sensitivity, resolution, and specificity via MRI.

  6. Experimental implementation of a NMR entanglement witness

    Filgueiras, J G; Auccaise, R E; Vianna, R O; Sarthour, R S; Oliveira, I S

    2012-01-01

    Entanglement witnesses (EW) allow the detection of entanglement in a quantum system, from the measurement of some few observables. They do not require the complete determination of the quantum state, which is regarded as a main advantage. On this paper it is experimentally analyzed an entanglement witness recently proposed in the context of Nuclear Magnetic Resonance (NMR) experiments to test it in some Bell-diagonal states. We also propose some optimal entanglement witness for Bell-diagonal states. The efficiency of the two types of EW's are compared to a measure of entanglement with tomographic cost, the generalized robustness of entanglement. It is used a GRAPE algorithm to produce an entangled state which is out of the detection region of the EW for Bell-diagonal states. Upon relaxation, the results show that there is a region in which both EW fails, whereas the generalized robustness still shows entanglement, but with the entanglement witness proposed here with a better performance.

  7. NMR spectroscopy assists synthetic fuels research

    There is little doubt that sources of liquid transport fuels, other than petroleum, will need to be developed for the future. While coal, oil shale and natural gas are potentially appropriate hydrocarbon resources, they all require chemical processing before a substitute crude oil (or synfuel) can be produced. There are many different possible pathways by which alternative crudes can be produced and subsequently upgraded to transport fuel quality. To develop and evaluate processing strategies it is necessary to gain some understanding of the nature of feedstocks, catalysts, process intermediates and potential final products. Nuclear Magnetic Resonance (NMR) spectroscopy has proven a useful and versatile technique for this purpose. Some contributions from this technique to coal and gas conversion research are illustrated and discussed

  8. Two-Dimensional NMR Lineshape Analysis.

    Waudby, Christopher A; Ramos, Andres; Cabrita, Lisa D; Christodoulou, John

    2016-01-01

    NMR titration experiments are a rich source of structural, mechanistic, thermodynamic and kinetic information on biomolecular interactions, which can be extracted through the quantitative analysis of resonance lineshapes. However, applications of such analyses are frequently limited by peak overlap inherent to complex biomolecular systems. Moreover, systematic errors may arise due to the analysis of two-dimensional data using theoretical frameworks developed for one-dimensional experiments. Here we introduce a more accurate and convenient method for the analysis of such data, based on the direct quantum mechanical simulation and fitting of entire two-dimensional experiments, which we implement in a new software tool, TITAN (TITration ANalysis). We expect the approach, which we demonstrate for a variety of protein-protein and protein-ligand interactions, to be particularly useful in providing information on multi-step or multi-component interactions. PMID:27109776

  9. Spatially resolved spectroscopy using tapered stripline NMR

    Tijssen, Koen C. H.; Bart, Jacob; Tiggelaar, Roald M.; Janssen, J. W. G. (Hans); Kentgens, Arno P. M.; van Bentum, P. Jan M.

    2016-02-01

    Magnetic field B0 gradients are essential in modern Nuclear Magnetic Resonance spectroscopy and imaging. Although RF/B1 gradients can be used to fulfill a similar role, this is not used in common practice because of practical limitations in the design of B1 gradient coils. Here we present a new method to create B1 gradients using stripline RF coils. The conductor-width of a stripline NMR chip and the strength of its radiofrequency field are correlated, so a stripline chip can be tapered to produce any arbitrary shaped B1 field gradient. Here we show the characterization of this tapered stripline configuration and demonstrate three applications: magnetic resonance imaging on samples with nL-μL volumes, reaction monitoring of fast chemical reactions (10-2-101 s) and the compensation of B0 field gradients to obtain high-resolution spectra in inhomogeneous magnetic fields.

  10. Ultrafast double-quantum NMR spectroscopy with optimized sensitivity for the analysis of mixtures.

    Rouger, Laetitia; Gouilleux, Boris; Pourchet-Gellez, Mariane; Dumez, Jean-Nicolas; Giraudeau, Patrick

    2016-02-15

    Ultrafast (UF) 2D NMR enables the acquisition of 2D spectra within a single-scan. This methodology has become a powerful analytical tool, used in a large array of applications. However, UF NMR spectroscopy still suffers from the need to compromise between sensitivity, spectral width and resolution. With the commonly used UF-COSY pulse sequence, resolution issues are compounded by the presence of strong auto-correlation signals, particularly in the case of samples with high dynamic ranges. The recently proposed concept of UF Double Quantum Spectroscopy (DQS) allows a better peak separation as it provides a lower spectral peak density. This paper presents the detailed investigation of this new NMR tool in an analytical chemistry context. Theoretical calculations and numerical simulations are used to characterize the modulation of peak intensities as a function of pulse-sequence parameters, and thus enable a significant enhancement of the sensitivity. The analytical comparison of UF-COSY and UF-DQS shows similar performances, however the ultrafast implementation of the DQS approach is found to have some sensitivity advantages over its conventional counterpart. The analytical performance of the pulse sequence is illustrated by the quantification of taurine in complex mixtures (homemade and commercial energy drinks). The results demonstrate the high potential of this experiment, which forms a valuable alternative to UF-COSY spectra when the latter are characterized by strong overlaps and high dynamic ranges. PMID:26865359

  11. An efficient procedure for studying pectin structure which combines limited depolymerization and 13C NMR

    A protocol for partial thermally-induced depolymerization of differently methoxylated pectin samples is described. The resulting macromolecules have been fully characterized with various complementary techniques, such as size exclusion chromatography (SEC), potentiometry, viscometry and 13C NMR. Optimum conditions afford samples at 50-80% yield with weight-average molecular weights in the 4 to 20 kDa range. The major fraction of these polysaccharides adopts the random-coil conformation and such samples are suitable for 13C NMR structural studies at room temperature. The methoxyl distributions of two apple pectin samples with a degree of esterification (DE) between 54 and 74% and a citrus pectin (DE, 72%) were shown to be random in nature, whereas that of a lightly methoxylated apple pectin (DE 39%) was partially blockwise. The carbon relaxation parameters of the depolymerized pectins attain asymptotic values for MW > 4 kDa. The MW values estimated from intrinsic viscosity data with the Mark-Houwink relationship reported for native pectins are in good agreement with those obtained by either end-group analysis (NMR) or SEC. Thus, all the physicochemical data indicate that the secondary structure of the isolated chains of depolymerized pectin is closely related to that of the parent polymers. Finally, pectinmethylesterase activity towards the depolymerized pectins was similar to that of the untreated samples. (orig.)

  12. Complete NMR spectral assignment in gibbsite by first-principle calculations

    The structure of the mineral gibbsite is often considered as a representative of many alumino-silicate clay minerals, and therefore we use it in the present study as a model compound to establish the suitability of the computational method. Here we apply a gradient-corrected DFT method with a plane-wave basis set to assign the crystallographically distinct Al sites in gibbsite and to relate them to the hydroxide network. The experimental observation is based on high-resolution solid-state 27Al NMR and 1H CRAMPS (combined rotation and multipulse spectroscopy) data. On the basis of DFT calculations, the 1H CRAMPS signals have been attributed to six symmetry independent hydrogen atoms and ascribed to two distinct types associated with intralayer and interlayer hydrogen bonds. The 27Al NMR spectrum shows signals for octahedral aluminium only, however with two distinguished signals. The correlation between experimental and theoretical NMR parameters demonstrates that the character of the hydrogen bonds formed by the hydroxide ions is responsible for the structural differentiation of Al sites. That is, the Al-I site (CQ=4.2 MHz) is surrounded by the OH-groups participating in 4 intralayer and 2 interlayer hydrogen bonds, while the Al-II site (CQ=2.4 MHz) is coordinated by the hydroxides, 2 of which point towards the intralayer cavities and 4 OH-bonds are aligned towards the interlayer gallery.

  13. Characterization of the insertase BamA in three different membrane mimetics by solution NMR spectroscopy

    The insertase BamA is the central protein of the Bam complex responsible for outer membrane protein biogenesis in Gram-negative bacteria. BamA features a 16-stranded transmembrane β-barrel and five periplasmic POTRA domains, with a total molecular weight of 88 kDa. Whereas the structure of BamA has recently been determined by X-ray crystallography, its functional mechanism is not well understood. This mechanism comprises the insertion of substrates from a dynamic, chaperone-bound state into the bacterial outer membrane, and NMR spectroscopy is thus a method of choice for its elucidation. Here, we report solution NMR studies of different BamA constructs in three different membrane mimetic systems: LDAO micelles, DMPC:DiC7PC bicelles and MSP1D1:DMPC nanodiscs. The impact of biochemical parameters on the spectral quality was investigated, including the total protein concentration and the detergent:protein ratio. The barrel of BamA is folded in micelles, bicelles and nanodiscs, but the N-terminal POTRA5 domain is flexibly unfolded in the absence of POTRA4. Measurements of backbone dynamics show that the variable insertion region of BamA, located in the extracellular lid loop L6, features high local flexibility. Our work establishes biochemical preparation schemes for BamA, which will serve as a platform for structural and functional studies of BamA and its role within the Bam complex by solution NMR spectroscopy

  14. Communication: Molecular dynamics and 1H NMR of n-hexane in liquid crystals

    The NMR spectrum of n-hexane orientationally ordered in the nematic liquid crystal ZLI-1132 is analysed using covariance matrix adaptation evolution strategy (CMA-ES). The spectrum contains over 150 000 transitions, with many sharp features appearing above a broad, underlying background signal that results from the plethora of overlapping transitions from the n-hexane as well as from the liquid crystal. The CMA-ES requires initial search ranges for NMR spectral parameters, notably the direct dipolar couplings. Several sets of such ranges were utilized, including three from MD simulations and others from the modified chord model that is specifically designed to predict hydrocarbon-chain dipolar couplings. In the end, only inaccurate dipolar couplings from an earlier study utilizing proton-proton double quantum 2D-NMR techniques on partially deuterated n-hexane provided the necessary estimates. The precise set of dipolar couplings obtained can now be used to investigate conformational averaging of n-hexane in a nematic environment

  15. An efficient procedure for studying pectin structure which combines limited depolymerization and {sup 13}C NMR

    Catoire, L.; Herve du Penhoat, C. [Dept. de Chimie, Ecole Normale Superieure, Paris (France); Goldberg, R.; Pierron, M. [Laboratoire d`enzymologie en Milieu Structure, Institut Jacques Monod, Paris (France); Morvan, C. [Faculte des Sciences, Universite de Rouen, Mont-Saint-Aignan (France)

    1998-04-01

    A protocol for partial thermally-induced depolymerization of differently methoxylated pectin samples is described. The resulting macromolecules have been fully characterized with various complementary techniques, such as size exclusion chromatography (SEC), potentiometry, viscometry and {sup 13}C NMR. Optimum conditions afford samples at 50-80% yield with weight-average molecular weights in the 4 to 20 kDa range. The major fraction of these polysaccharides adopts the random-coil conformation and such samples are suitable for {sup 13}C NMR structural studies at room temperature. The methoxyl distributions of two apple pectin samples with a degree of esterification (DE) between 54 and 74% and a citrus pectin (DE, 72%) were shown to be random in nature, whereas that of a lightly methoxylated apple pectin (DE 39%) was partially blockwise. The carbon relaxation parameters of the depolymerized pectins attain asymptotic values for M{sub W} > 4 kDa. The M{sub W} values estimated from intrinsic viscosity data with the Mark-Houwink relationship reported for native pectins are in good agreement with those obtained by either end-group analysis (NMR) or SEC. Thus, all the physicochemical data indicate that the secondary structure of the isolated chains of depolymerized pectin is closely related to that of the parent polymers. Finally, pectinmethylesterase activity towards the depolymerized pectins was similar to that of the untreated samples. (orig.) With 6 figs., 4 tabs., 27 refs.

  16. Characterization of the insertase BamA in three different membrane mimetics by solution NMR spectroscopy

    Morgado, Leonor; Zeth, Kornelius; Burmann, Björn M.; Maier, Timm; Hiller, Sebastian, E-mail: sebastian.hiller@unibas.ch [University of Basel, Biozentrum (Switzerland)

    2015-04-15

    The insertase BamA is the central protein of the Bam complex responsible for outer membrane protein biogenesis in Gram-negative bacteria. BamA features a 16-stranded transmembrane β-barrel and five periplasmic POTRA domains, with a total molecular weight of 88 kDa. Whereas the structure of BamA has recently been determined by X-ray crystallography, its functional mechanism is not well understood. This mechanism comprises the insertion of substrates from a dynamic, chaperone-bound state into the bacterial outer membrane, and NMR spectroscopy is thus a method of choice for its elucidation. Here, we report solution NMR studies of different BamA constructs in three different membrane mimetic systems: LDAO micelles, DMPC:DiC{sub 7}PC bicelles and MSP1D1:DMPC nanodiscs. The impact of biochemical parameters on the spectral quality was investigated, including the total protein concentration and the detergent:protein ratio. The barrel of BamA is folded in micelles, bicelles and nanodiscs, but the N-terminal POTRA5 domain is flexibly unfolded in the absence of POTRA4. Measurements of backbone dynamics show that the variable insertion region of BamA, located in the extracellular lid loop L6, features high local flexibility. Our work establishes biochemical preparation schemes for BamA, which will serve as a platform for structural and functional studies of BamA and its role within the Bam complex by solution NMR spectroscopy.

  17. Communication: Molecular dynamics and {sup 1}H NMR of n-hexane in liquid crystals

    Weber, Adrian C. J., E-mail: WeberA@BrandonU.CA [Chemistry Department, Brandon University, 270-18th Street, Brandon, Manitoba R7A 6A9 (Canada); Burnell, E. Elliott, E-mail: elliott.burnell@ubc.ca [Chemistry Department, University of British Columbia, 2036 Main Mall, Vancouver, British Columbia V6T 1Z1 (Canada); Meerts, W. Leo, E-mail: leo.meerts@science.ru.nl [Radboud University, Institute for Molecules and Materials, Heyendaalseweg 135, NL-6525 AJ Nijmegen (Netherlands); Atomic, Molecular and Laser Physics, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands); Lange, Cornelis A. de, E-mail: c.a.de.lange@vu.nl [Atomic, Molecular and Laser Physics, Vrije Universiteit, De Boelelaan 1081, 1081 HV Amsterdam (Netherlands); Dong, Ronald Y., E-mail: rondong@phas.ubc.ca [Department of Physics and Astronomy, University of British Columbia, 6224 Agricultural Road, Vancouver, British Columbia V6T 1Z1 (Canada); Muccioli, Luca, E-mail: Luca.Muccioli@unibo.it; Pizzirusso, Antonio, E-mail: Antonio.Pizzirusso80@gmail.com; Zannoni, Claudio, E-mail: Claudio.Zannoni@unibo.it [Dipartimento di Chimica Industriale “Toso Montanari,” Università di Bologna and INSTM, viale Risorgimento 4, 40136 Bologna (Italy)

    2015-07-07

    The NMR spectrum of n-hexane orientationally ordered in the nematic liquid crystal ZLI-1132 is analysed using covariance matrix adaptation evolution strategy (CMA-ES). The spectrum contains over 150 000 transitions, with many sharp features appearing above a broad, underlying background signal that results from the plethora of overlapping transitions from the n-hexane as well as from the liquid crystal. The CMA-ES requires initial search ranges for NMR spectral parameters, notably the direct dipolar couplings. Several sets of such ranges were utilized, including three from MD simulations and others from the modified chord model that is specifically designed to predict hydrocarbon-chain dipolar couplings. In the end, only inaccurate dipolar couplings from an earlier study utilizing proton-proton double quantum 2D-NMR techniques on partially deuterated n-hexane provided the necessary estimates. The precise set of dipolar couplings obtained can now be used to investigate conformational averaging of n-hexane in a nematic environment.

  18. (13)C NMR Studies, Molecular Order, and Mesophase Properties of Thiophene Mesogens.

    Veeraprakash, B; Lobo, Nitin P; Narasimhaswamy, T

    2015-12-01

    Three-ring mesogens with a core comprising thiophene linked to one phenyl ring directly and to the other via flexible ester are synthesized with terminal alkoxy chains to probe the mesophase properties and find the molecular order. The phenyl thiophene link in the core offers a comparison of the mesophase features with the molecular shape of the mesogen. The synthesized mesogens display enantiotropic polymesomorphism and accordingly nematic, smectic A, smectic C and smectic B mesophases are perceived depending upon the terminal chain length. For some of the homologues, monotropic higher order smectic phases such as smectic F and crystal E are also witnessed. The existence of polymesomorphism are originally observed by HOPM and DSC and further confirmed by powder X-ray diffraction studies. For the C8 homologue, high resolution solid state (13)C NMR spectroscopy is employed to find the molecular structure in the liquid crystalline phase and using the 2D SLF technique, the (13)C-(1)H dipolar couplings are extracted to calculate the order parameter. By comparing the ratio of local order of thiophene as well as phenyl rings, we establish the bent-core shape of the mesogen. Importantly, for assigning the carbon chemical shifts of the core unit of aligned C8 mesogen, the (13)C NMR measured in mesophase of the synthetic intermediate is employed. Thus, the proposed approach addresses the key step in the spectral assignment of target mesogens with the use of (13)C NMR data of mesomorphic intermediate. PMID:26551439

  19. Experimental and NMR theoretical methodology applied to geometric analysis of the bioactive clerodane trans-dehydrocrotonin

    Soares, Breno Almeida; Firme, Caio Lima, E-mail: firme.caio@gmail.com, E-mail: caiofirme@quimica.ufrn.br [Universidade Federal do Rio Grande do Norte (UFRN), Natal, RN (Brazil). Instituto de Quimica; Maciel, Maria Aparecida Medeiros [Universidade Potiguar, Natal, RN (Brazil). Programa de Pos-graduacao em Biotecnologia; Kaiser, Carlos R. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Instituto de Quimica; Schilling, Eduardo; Bortoluzzi, Adailton J. [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Departamento de Quimica

    2014-04-15

    trans-Dehydrocrotonin (t-DCTN) a bioactive 19-nor-diterpenoid clerodane type isolated from Croton cajucara Benth, is one of the most investigated clerodane in the current literature. In this work, a new approach joining X-ray diffraction data, nuclear magnetic resonance (NMR) data and theoretical calculations was applied to the thorough characterization of t-DCTN. For that, the geometry of t-DCTN was reevaluated by X-ray diffraction as well as {sup 1}H and {sup 13}C NMR data, whose geometrical parameters where compared to those obtained from B3LYP/6-311G++(d,p) level of theory. From the evaluation of both calculated and experimental values of {sup 1}H and {sup 13}C NMR chemical shifts and spin-spin coupling constants, it was found very good correlations between theoretical and experimental magnetic properties of t-DCTN. Additionally, the delocalization indexes between hydrogen atoms correlated accurately with theoretical and experimental spin-spin coupling constants. An additional topological analysis from quantum theory of atoms in molecules (QTAIM) showed intramolecular interactions for t-DCTN. (author)

  20. NMR study of hyper-polarized 129Xe and applications to liquid-phase NMR experiments

    In liquid samples where both nuclear polarization and spin density are strong, the magnetization dynamics, which can be analysed by NMR (nuclear magnetic resonance) methods, is deeply influenced by the internal couplings induced by local dipolar fields. The present thesis describes some of the many consequences associated to the presence in the sample of concentrated xenon hyper-polarized by an optical pumping process. First, we deal with the induced modifications in frequency and line width of the proton and xenon spectra, then we present the results of SPIDER, a coherent polarization transfer experiment designed to enhance the polarization of protons, in order to increase their NMR signal level. A third part is dedicated to the description of the apparition of repeated chaotic maser emissions by un unstable xenon magnetization coupled to the detection coil tuned at the xenon Larmor frequency (here 138 MHz). In the last part, we present a new method allowing a better tuning of any NMR detection probe and resulting in sensible gains in terms of sensitivity and signal shaping. Finally, we conclude with a partial questioning of the classical relaxation theory in the specific field of highly polarized and concentrated spin systems in a liquid phase. (author)

  1. Temperature Dependence of NMR Parameters Calculated from Path Integral Molecular Dynamics Simulations

    Dračínský, Martin; Bouř, Petr; Hodgkinson, P.

    2016-01-01

    Roč. 12, č. 3 (2016), s. 968-973. ISSN 1549-9618 R&D Projects: GA ČR GA15-11223S; GA ČR GA15-09072S Institutional support: RVO:61388963 Keywords : short hydrogen bonds * density functional theory * spin coupling constants Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 5.498, year: 2014

  2. Theoretical modeling of the metal ion effects on NMR parameters in nucleic acid backbone

    Benda, Ladislav; Schneider, Bohdan; Sychrovský, Vladimír

    Florence: -, 2010. s. 420-420. [WWMR2010. Joint EUROMAR 2010 and ISMAR Conference /17./. 04.07.2010-09.07.2010, Florence] R&D Projects: GA ČR GAP205/10/0228 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50520701 Keywords : nucleic acid phosphate * nucleic acids solvation * magnesium ion Subject RIV: CF - Physical ; Theoretical Chemistry

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

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

    2013-01-01

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

  4. NMR-based metabolomics in human disease diagnosis: Applications, limitations, and recommendations

    Emwas, Abdul-Hamid M.

    2013-04-03

    Metabolomics is a dynamic and emerging research field, similar to proteomics, transcriptomics and genomics in affording global understanding of biological systems. It is particularly useful in functional genomic studies in which metabolism is thought to be perturbed. Metabolomics provides a snapshot of the metabolic dynamics that reflect the response of living systems to both pathophysiological stimuli and/or genetic modification. Because this approach makes possible the examination of interactions between an organism and its diet or environment, it is particularly useful for identifying biomarkers of disease processes that involve the environment. For example, the interaction of a high fat diet with cardiovascular disease can be studied via such a metabolomics approach by modeling the interaction between genes and diet. The high reproducibility of NMR-based techniques gives this method a number of advantages over other analytical techniques in large-scale and long-term metabolomic studies, such as epidemiological studies. This approach has been used to study a wide range of diseases, through the examination of biofluids, including blood plasma/serum, urine, blister fluid, saliva and semen, as well as tissue extracts and intact tissue biopsies. However, complicating the use of NMR spectroscopy in biomarker discovery is the fact that numerous variables can effect metabolic composition including, fasting, stress, drug administration, diet, gender, age, physical activity, life style and the subject\\'s health condition. To minimize the influence of these variations in the datasets, all experimental conditions including sample collection, storage, preparation as well as NMR spectroscopic parameters and data analysis should be optimized carefully and conducted in an identical manner as described by the local standard operating protocol. This review highlights the potential applications of NMR-based metabolomics studies and gives some recommendations to improve sample

  5. GUARDD: user-friendly MATLAB software for rigorous analysis of CPMG RD NMR data

    Molecular dynamics are essential for life, and nuclear magnetic resonance (NMR) spectroscopy has been used extensively to characterize these phenomena since the 1950s. For the past 15 years, the Carr-Purcell Meiboom-Gill relaxation dispersion (CPMG RD) NMR experiment has afforded advanced NMR labs access to kinetic, thermodynamic, and structural details of protein and RNA dynamics in the crucial μs-ms time window. However, analysis of RD data is challenging because datasets are often large and require many non-linear fitting parameters, thereby confounding assessment of accuracy. Moreover, novice CPMG experimentalists face an additional barrier because current software options lack an intuitive user interface and extensive documentation. Hence, we present the open-source software package GUARDD (Graphical User-friendly Analysis of Relaxation Dispersion Data), which is designed to organize, automate, and enhance the analytical procedures which operate on CPMG RD data (http://code.google.com/p/guardd/http://code.google.com/p/guardd/). This MATLAB-based program includes a graphical user interface, permits global fitting to multi-field, multi-temperature, multi-coherence data, and implements χ2-mapping procedures, via grid-search and Monte Carlo methods, to enhance and assess fitting accuracy. The presentation features allow users to seamlessly traverse the large amount of results, and the RD Simulator feature can help design future experiments as well as serve as a teaching tool for those unfamiliar with RD phenomena. Based on these innovative features, we expect that GUARDD will fill a well-defined gap in service of the RD NMR community.

  6. GUARDD: user-friendly MATLAB software for rigorous analysis of CPMG RD NMR data

    Kleckner, Ian R., E-mail: ian.kleckner@gmail.com [Biophysics Program, Ohio State University (United States); Foster, Mark P., E-mail: Foster.281@osu.edu [Ohio State University, Biochemistry Department (United States)

    2012-01-15

    Molecular dynamics are essential for life, and nuclear magnetic resonance (NMR) spectroscopy has been used extensively to characterize these phenomena since the 1950s. For the past 15 years, the Carr-Purcell Meiboom-Gill relaxation dispersion (CPMG RD) NMR experiment has afforded advanced NMR labs access to kinetic, thermodynamic, and structural details of protein and RNA dynamics in the crucial {mu}s-ms time window. However, analysis of RD data is challenging because datasets are often large and require many non-linear fitting parameters, thereby confounding assessment of accuracy. Moreover, novice CPMG experimentalists face an additional barrier because current software options lack an intuitive user interface and extensive documentation. Hence, we present the open-source software package GUARDD (Graphical User-friendly Analysis of Relaxation Dispersion Data), which is designed to organize, automate, and enhance the analytical procedures which operate on CPMG RD data (http://code.google.com/p/guardd/http://code.google.com/p/guardd/). This MATLAB-based program includes a graphical user interface, permits global fitting to multi-field, multi-temperature, multi-coherence data, and implements {chi}{sup 2}-mapping procedures, via grid-search and Monte Carlo methods, to enhance and assess fitting accuracy. The presentation features allow users to seamlessly traverse the large amount of results, and the RD Simulator feature can help design future experiments as well as serve as a teaching tool for those unfamiliar with RD phenomena. Based on these innovative features, we expect that GUARDD will fill a well-defined gap in service of the RD NMR community.

  7. Structural investigation of molten fluorides of nuclear interest by NMR and XAFS spectroscopies

    In the frame of the renewal of the different nuclear plans, the molten salt reactor is one of the six concepts of reactors of 4. generation. This reactor has the particularity to use a liquid fuel based on LiF-ThF4 mixtures. In order to develop and to optimize this concept, it is important to characterize the structure of the melt and to describe its physical and chemical properties. Our work has been based on the study of the system MF-ZrF4 (M = Li, Na, K) selected as a model of ThF4 based systems. We have combined two spectroscopic techniques, the Nuclear Magnetic Resonance and the X-ray Absorption at high temperature, with molecular dynamics calculations. We particularly focused on the local environments of the fluorine and the zirconium. In order to interpret the NMR data obtain in the molten state, we performed a preliminary study on zirconium halides and rare earth and alkali fluoro zirconates using the 91Zr solid-state NMR at very high magnetic fields. New correlations between structural parameters and NMR data have been established. At high temperature, in MF-ZrF4 melts we have shown the coexistence of three different kind of Zr-based complexes with different proportions depending on the amount of ZrF4 and on the nature of the alkali. Depending on the ZrF4 content, three kinds of fluorine have been characterized: form free fluorines at low amount of zirconium fluorides, fluorines involved in Zr-based complexes and bridging fluorines at higher ZrF4 content. This original and innovative approach of molten fluorides mixtures, combining NMR and EXAFS at high temperature with molecular dynamics calculations, is very efficient to describe their speciation and thus their fluoro-acidity. (author)

  8. Quantum Mechanical Nature in Liquid NMR Quantum Computing

    LONGGui-Lu; YANHai-Yang; 等

    2002-01-01

    The quantum nature of bulk ensemble NMR quantum computing-the center of recent heated debate,is addressed.Concepts of the mixed state and entanglement are examined,and the data in a two-qubit liquid NMR quantum computation are analyzed.the main points in this paper are;i) Density matrix describes the "state" of an average particle in an ensemble.It does not describe the state of an individual particle in an ensemble;ii) Entanglement is a property of the wave function of a microscopic particle(such as a molecule in a liquid NMR sample),and separability of the density matrix canot be used to measure the entanglement of mixed ensemble;iii) The state evolution in bulkensemble NMR quantum computation is quantum-mechanical;iv) The coefficient before the effective pure state density matrix,ε,is a measure of the simultaneity of the molecules in an ensemble,It reflets the intensity of the NMR signal and has no significance in quantifying the entanglement in the bulk ensemble NMR system.The decomposition of the density matrix into product states is only an indication that the ensemble can be prepared by an ensemble with the particles unentangeld.We conclude that effective-pure-state NMR quantum computation is genuine,not just classical simulations.

  9. High-resolution NMR spectroscopy under the fume hood.

    Küster, Simon K; Danieli, Ernesto; Blümich, Bernhard; Casanova, Federico

    2011-08-01

    This work reports the possibility to acquire high-resolution (1)H NMR spectra with a fist-sized NMR magnet directly installed under the fume hood. The small NMR sensor based on permanent magnets was used to monitor the trimerization of propionaldehyde catalyzed by indium trichloride in real time by continuously circulating the reaction mixture through the magnet bore in a closed loop with the help of a peristaltic pump. Thanks to the chemical selectivity of NMR spectroscopy the progress of the reaction can be monitored on-line by determining the concentrations of both reactant and product from the area under their respective lines in the NMR spectra as a function of time. This in situ measurement demonstrates that NMR probes can be used in chemistry laboratories, e.g. for reaction optimization, or installed at specific points of interest along industrial process lines. Therefore, it will open the door for the implementation of feedback control based on spectroscopic NMR data. PMID:21698335

  10. Can NMR solve some significant challenges in metabolomics?

    Nagana Gowda, G. A.; Raftery, Daniel

    2015-11-01

    The field of metabolomics continues to witness rapid growth driven by fundamental studies, methods development, and applications in a number of disciplines that include biomedical science, plant and nutrition sciences, drug development, energy and environmental sciences, toxicology, etc. NMR spectroscopy is one of the two most widely used analytical platforms in the metabolomics field, along with mass spectrometry (MS). NMR's excellent reproducibility and quantitative accuracy, its ability to identify structures of unknown metabolites, its capacity to generate metabolite profiles using intact bio-specimens with no need for separation, and its capabilities for tracing metabolic pathways using isotope labeled substrates offer unique strengths for metabolomics applications. However, NMR's limited sensitivity and resolution continue to pose a major challenge and have restricted both the number and the quantitative accuracy of metabolites analyzed by NMR. Further, the analysis of highly complex biological samples has increased the demand for new methods with improved detection, better unknown identification, and more accurate quantitation of larger numbers of metabolites. Recent efforts have contributed significant improvements in these areas, and have thereby enhanced the pool of routinely quantifiable metabolites. Additionally, efforts focused on combining NMR and MS promise opportunities to exploit the combined strength of the two analytical platforms for direct comparison of the metabolite data, unknown identification and reliable biomarker discovery that continue to challenge the metabolomics field. This article presents our perspectives on the emerging trends in NMR-based metabolomics and NMR's continuing role in the field with an emphasis on recent and ongoing research from our laboratory.

  11. 1H NMR investigation of self-association of vanillin in aqueous solution

    A self-association of vanillin have been studied by 1H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration. The experimental results have been analysed using indefinite non-cooperative and cooperative models of molecular self-association, enabling the determination of equilibrium constants, parameters of cooperativity and the limiting values of vanillin proton chemical shifts in the complex. It was found that the dimer formation creates energetically favourable conditions for subsequent molecular association.

  12. Carbon-13 solid state NMR studies in the aromatization of residual coals from hydropyrolised cellulose

    Pure cellulose was pyrolyzed is a fixed-bed reactor under hydrogen pressure (hydropyrolysis). Residual chars were collected and analysed by solid state nmr 13 C (CP-MAS) and elemental. Hydrophyrolysis parameters such as final temperature in the range of 300 to 520 deg C and hydrogen pressure from 5 to 100 atm gave different char samples. CP-MAS spectra were obtained in a BRUKER MSL-100 spectrometer. The results showed that the aromatic and aliphatic fractions had strong dependence with temperature and no influence with pressure. Elemental analysis indicated the carbon content increased more with temperature than the pressure increasing. (author)

  13. Co(II) complexes of amino acids and peptides in aqueous solution studied by 170 NMR

    Structural, dynamic and kinetic 170 NMR investigations of the complexation of metal ions with amino acids and peptides were performed in Glicine, proling cyclo(Ala '1'70-Ala), cyclo-(Gly170-Pro) and cyclo(Pro170-Gly). The 170 carboxyl and carbonylsignals of paramagnetic complexes with amino acids were observed and allowed for the determinatio, in several cases, of the stoichiometry of the ocmplexes formed and the kinetic and thermodynamic parameters characterizing ligand exchange. It was found that the paramagnetic ions bind to the oxygen of the peptide carboxyl group. (H.W.). 25 refs.; 10 figs.; 3 tabs

  14. Qualitätskriterien für Proteinstrukturen aus NMR-Daten

    Rieping, Wolfgang

    2005-01-01

    Seit den Anfängen von makromolekularer Strukturbestimmung durch hochaufgelöste Kernspinresonanz-Spektroskopie ist die Frage nach der Qualität der erzeugten Strukturen wiederholt gestellt worden: Experimentelle Daten sind verrauscht und unvollständig, NMR-Parameter hängen von einer Vielzahl physikalischer Effekte ab, die nicht oder nur näherungsweise beschrieben werden können. Die vorliegende Arbeit befaßt sich mit der Fragestellung, wie sich experimentelle Ungenauigkeiten und Näherungen in...

  15. {sup 1}H NMR investigation of self-association of vanillin in aqueous solution

    Bogdan, Mircea; Floare, Calin G; PIrnau, Adrian, E-mail: mircea.bogdan@itim-cj.r [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania)

    2009-08-01

    A self-association of vanillin have been studied by {sup 1}H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration. The experimental results have been analysed using indefinite non-cooperative and cooperative models of molecular self-association, enabling the determination of equilibrium constants, parameters of cooperativity and the limiting values of vanillin proton chemical shifts in the complex. It was found that the dimer formation creates energetically favourable conditions for subsequent molecular association.

  16. 1H NMR investigation of self-association of vanillin in aqueous solution

    Bogdan, Mircea; Floare, Calin G.; Pîrnau, Adrian

    2009-08-01

    A self-association of vanillin have been studied by 1H NMR spectroscopy using the analysis of proton chemical shifts changes in aqueous solution as a function of concentration. The experimental results have been analysed using indefinite non-cooperative and cooperative models of molecular self-association, enabling the determination of equilibrium constants, parameters of cooperativity and the limiting values of vanillin proton chemical shifts in the complex. It was found that the dimer formation creates energetically favourable conditions for subsequent molecular association.

  17. 19F NMR study of LiTbF4 single crystals

    The angular dependences of 19F NMR spectra have been measured in the external magnetic field of 0.5 T oriented in the basis plane of LiTbF4 at the room temperature. We have obtained the constants of transferred hyperfine interaction and the corrected set of crystal field parameters for the Tb3+ ions in LiTbF4. The results of simulations of the magnetization in high pulsed magnetic fields with taking into account magnetoelastic interactions agree satisfactorily with experimental data presented in the literature.

  18. Crystal structure based design of signal enhancement schemes for solid-state NMR of insensitive half-integer quadrupolar nuclei.

    O'Dell, Luke A; Ratcliffe, Christopher I

    2011-02-10

    A combination of density functional and optimal control theory has been used to generate amplitude- and phase-modulated excitation pulses tailored specifically for the (33)S nuclei in taurine, based on one of several reported crystal structures. The pulses resulted in significant signal enhancement (stemming from population transfer from the satellite transitions) without the need for any experimental optimization. This allowed an accurate determination of the (33)S NMR interaction parameters at natural abundance and at a moderate magnetic field strength (11.7 T). The (33)S NMR parameters, along with those measured from (14)N using frequency-swept pulses, were then used to assess the accuracy of various proposed crystal structures. PMID:21174418

  19. Understanding NMR relaxometry of partially water-saturated rocks

    O. Mohnke

    2014-11-01

    Full Text Available Nuclear Magnetic Resonance (NMR relaxometry measurements are commonly used to characterize the storage and transport properties of water-saturated rocks. These assessments are based on the proportionality of NMR signal amplitude and relaxation time to porosity (water content and pore size, respectively. The relationship between pore size and NMR relaxation time depends on pore shape, which is usually assumed to be spherical or cylindrical. However, the NMR response at partial water saturation for natural sediments and rocks differs strongly from the response calculated for spherical or cylindrical pores, because these pore shapes cannot account for water menisci remaining in the corners of de-saturated angular pores. Therefore, we consider a bundle of pores with triangular cross-sections. We introduce analytical solutions of the NMR equations at partial saturation of these pores, which account for water menisci of de-saturated pores. After developing equations that describe the water distribution inside the pores, we calculate the NMR response at partial saturation for imbibition and drainage based on the deduced water distributions. For this pore model, NMR amplitude and NMR relaxation time at partial water saturation strongly depend on pore shape even so the NMR relaxation time at full saturation only depends on the surface to volume ratio of the pore. The pore-shape-dependence at partial saturation arises from the pore shape and capillary pressure dependent water distribution in pores with triangular cross-sections. Moreover, we show the qualitative agreement of the saturation dependent relaxation time distributions of our model with those observed for rocks and soils.

  20. NMR study of oligonucleotides containing base pair mismatches and a human growth hormone peptide for the determination of solution structures

    Formation of unusual basepairs in DNA for random mutations in DNA was proposed in the sixties. These mismatches arise due to errors in replication, and from deamination of the 5-methylcytosine. The author's interest in studying mismatches and other oligonucleotides has been two fold. One is related to 31P chemical shifts and the backbone structure of oligonucleotides. He wanted to find out the significance of the dispersion of 31p chemical shifts in oligonucleotides. He wished to address whether this dispersion in 31P chemical shifts is related to global structural parameters of oligonucleotides like helix twist and whether he can prove the relationship between 31P chemical shifts and the backbone torsional angles epsilon and zeta. How does a mismatch affect 31P chemical shifts and the backbone torsional angle? The second interest is related to solving the three dimensional structure of these biopolymers by using NMR data (NOESY distances) and computer simulations. His major study of these mismatches has been in the assignments of the protons resonances and the phosphorus resonances by 2D NMR. He has also tried to answer the question about the relationships between 31P chemical shifts and global parameters for DNA such as the helix twist. He has made substantial progress in determination of J(H3'-P) coupling constants by 2D NMR and also in determining the relationship between the SIP chemical shifts and the backbone torsional angles by using the mismatch dodecamer sequences and the tetradecamer sequences. The 2D NMR data for the GG and GT mismatch have been used to determine three dimensional structures by using distance restrained molecular dynamics. The second project involved studying a 28 residue synthetic peptide by NMR

  1. Resolution-by-proxy: a simple measure for assessing and comparing the overall quality of NMR protein structures

    Berjanskii, Mark; Zhou Jianjun; Liang Yongjie; Lin Guohui; Wishart, David S., E-mail: david.wishart@ualberta.ca [University of Alberta, Department of Computing Science (Canada)

    2012-07-15

    In protein X-ray crystallography, resolution is often used as a good indicator of structural quality. Diffraction resolution of protein crystals correlates well with the number of X-ray observables that are used in structure generation and, therefore, with protein coordinate errors. In protein NMR, there is no parameter identical to X-ray resolution. Instead, resolution is often used as a synonym of NMR model quality. Resolution of NMR structures is often deduced from ensemble precision, torsion angle normality and number of distance restraints per residue. The lack of common techniques to assess the resolution of X-ray and NMR structures complicates the comparison of structures solved by these two methods. This problem is sometimes approached by calculating 'equivalent resolution' from structure quality metrics. However, existing protocols do not offer a comprehensive assessment of protein structure as they calculate equivalent resolution from a relatively small number (<5) of protein parameters. Here, we report a development of a protocol that calculates equivalent resolution from 25 measurable protein features. This new method offers better performance (correlation coefficient of 0.92, mean absolute error of 0.28 A) than existing predictors of equivalent resolution. Because the method uses coordinate data as a proxy for X-ray diffraction data, we call this measure 'Resolution-by-Proxy' or ResProx. We demonstrate that ResProx can be used to identify under-restrained, poorly refined or inaccurate NMR structures, and can discover structural defects that the other equivalent resolution methods cannot detect. The ResProx web server is available at http://www.resprox.cahttp://www.resprox.ca.

  2. Resolution-by-proxy: a simple measure for assessing and comparing the overall quality of NMR protein structures

    In protein X-ray crystallography, resolution is often used as a good indicator of structural quality. Diffraction resolution of protein crystals correlates well with the number of X-ray observables that are used in structure generation and, therefore, with protein coordinate errors. In protein NMR, there is no parameter identical to X-ray resolution. Instead, resolution is often used as a synonym of NMR model quality. Resolution of NMR structures is often deduced from ensemble precision, torsion angle normality and number of distance restraints per residue. The lack of common techniques to assess the resolution of X-ray and NMR structures complicates the comparison of structures solved by these two methods. This problem is sometimes approached by calculating “equivalent resolution” from structure quality metrics. However, existing protocols do not offer a comprehensive assessment of protein structure as they calculate equivalent resolution from a relatively small number (<5) of protein parameters. Here, we report a development of a protocol that calculates equivalent resolution from 25 measurable protein features. This new method offers better performance (correlation coefficient of 0.92, mean absolute error of 0.28 Å) than existing predictors of equivalent resolution. Because the method uses coordinate data as a proxy for X-ray diffraction data, we call this measure “Resolution-by-Proxy” or ResProx. We demonstrate that ResProx can be used to identify under-restrained, poorly refined or inaccurate NMR structures, and can discover structural defects that the other equivalent resolution methods cannot detect. The ResProx web server is available at http://www.resprox.cahttp://www.resprox.ca.

  3. Developments of RF Coil for P in vivo NMR Spectroscopy .

    S. Khushu

    1993-07-01

    Full Text Available RF receiver coils are very important parts of an NMR System. The design of these coils is very critical and has a dramatic effect on the SNR of the NMR signal and are generally developed in TRA/REC mode. This paper reports the developments of a 3.5 cm TRA/REC 26 MHz RF coil for P spectroscopy of small organs like thyroid. The coil is small in size, fits well in the neck for thyroid spectroscopy and is successfully working with the 1.5 tesla whole body Superconducting NMR System available at INMAS.

  4. Developments of RF Coil for P in vivo NMR Spectroscopy .

    S. Khushu; S.B. Mehta; Sushil Chandra; A Jena

    1993-01-01

    RF receiver coils are very important parts of an NMR System. The design of these coils is very critical and has a dramatic effect on the SNR of the NMR signal and are generally developed in TRA/REC mode. This paper reports the developments of a 3.5 cm TRA/REC 26 MHz RF coil for P spectroscopy of small organs like thyroid. The coil is small in size, fits well in the neck for thyroid spectroscopy and is successfully working with the 1.5 tesla whole body Superconducting NMR System availab...

  5. Superparamagnetic particles as possible contrast agents for NMR imaging

    The development of 'magneto-pharmaceuticals' plays an important role in the extension of nuclear magnetic resonance (NMR) for diagnostic medicine. Fundamental investigations leading to the new area of NMR contrast agents are considered. Superparamagnetic particles represent a new class of NMR contrast agents that usually referred to as T2 or T*2 contrast agents as opposed to T1 agents, such as paramagnetic chelates. Another novelty presented by superparamagnetic agents is their specific distribution. The synthesis and the transverse R2 and longitudinal R1 relaxivity measurements of some ferro-, ferri- and superparamagnetic particles suspensions are presented. (authors)

  6. Molecular dynamics computer simulations based on NMR data

    In the work described in this thesis atom-atom distance information obtained from two-dimensional cuclear magnetic resonance is combined with molecular dynamics simulaitons. The simulation is used to improve the accuracy of a structure model constructed on the basis of NMR data. During the MD refinement the crude NMR structure is simultaneously optimized with respect to the atomic interaction function and to the set of atom-atom distances or other NMR information. This means that insufficient experimental data is completed with theoretical knowledge and the combination will lead to more reliable structures than would be obtained from one technique alone. (author). 191 refs.; 17 figs.; 12 schemes; 22 tabs

  7. Room Temperature Chiral Discrimination in Paramagnetic NMR Spectroscopy

    Soncini, Alessandro; Calvello, Simone

    2016-04-01

    A recently proposed theory of chiral discrimination in NMR spectroscopy based on the detection of a molecular electric polarization P rotating in a plane perpendicular to the NMR magnetic field [A. D. Buckingham, J. Chem. Phys. 140, 011103 (2014)] is generalized here to paramagnetic systems. Our theory predicts new contributions to P , varying as the square of the inverse temperature. Ab initio calculations for ten Dy3 + complexes, at 293 K, show that, in strongly anisotropic paramagnetic molecules, P can be more than 1000 times larger than in diamagnetic molecules, making paramagnetic NMR chiral discrimination amenable to room temperature detection.

  8. Holographic reconstruction of NMR images in Fresnel transform technique

    The free induction signal in the NMR Fresnel transform imaging technique is expressed by a similar equation to that of the Fresnel diffraction equation in light. It is possible to record NMR signals on a photographic film as a hologram in the same manner as optical holography. Since the dynamic range of the signal in the Fresnel transform technique is small, image information can be recorded on a hologram at a high efficiency. Very clear images are reconstructed optically from the NMR hologram in many experiments. Image brightness are improved by using a compound hologram in which several same holograms are arranged periodically. (author)

  9. A simple low-cost single-crystal NMR setup

    Vinding, Mads S.; Kessler, Tommy O.; Vosegaard, Thomas

    2016-08-01

    A low-cost single-crystal NMR kit is presented along with a web-based post-processing software. The kit consists of a piezo-crystal motor and a goniometer for the crystal, both embedded in a standard wide-bore NMR probe with a 3D printed scaffold. The NMR pulse program controls the angle setting automatically, and the post-processing software incorporates a range of orientation-angle discrepancies present in the kit and other single-crystal setups. Results with a NaNO3 single-crystal show a high degree of reproducibility and excellent agreement with previous findings for the anisotropic quadrupolar interaction.

  10. Room temperature chiral discrimination in paramagnetic NMR spectroscopy

    Soncini, Alessandro

    2016-01-01

    A recently proposed theory of chiral discrimination in NMR spectroscopy based on the detection of a molecular electric polarization $\\mathbf{P}$ rotating in a plane perpendicular to the NMR magnetic field [A. D. Buckingham, J. Chem. Phys. $\\mathbf{140}$, 011103 (2014)], is here generalized to paramagnetic systems. Our theory predicts new contributions to $\\mathbf{P}$, varying as the square of the inverse temperature. Ab initio calculations for ten Dy$^{3+}$ complexes, at 293K, show that in strongly anisotropic paramagnetic molecules $\\mathbf{P}$ can be more than 1000 times larger than in diamagnetic molecules, making paramagnetic NMR chiral discrimination amenable to room temperature detection.

  11. Structural biology applications of solid state MAS DNP NMR

    Akbey, Ümit; Oschkinat, Hartmut

    2016-08-01

    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  12. 4.7 T superconducting magnets for NMR from Czechoslovak made single-wire NbTi superconductors

    A brief overview is presented of the history of superconducting magnets for NMR. The first ever magnet was designed as a system of 6th order solenoids with external compensation coils at the ends of the windings. Multi-frame magnets of the 8th order followed provided with both internal and external compensation coils. The calculated, implemented and measured parameters are compared of superconducting magnets. (M.D.). 1 tab., 5 refs

  13. NMR Methods, Applications and Trends for Groundwater Evaluation and Management

    Walsh, D. O.; Grunewald, E. D.

    2011-12-01

    Nuclear magnetic resonance (NMR) measurements have a tremendous potential for improving groundwater characterization, as they provide direct detection and measurement of groundwater and unique information about pore-scale properties. NMR measurements, commonly used in chemistry and medicine, are utilized in geophysical investigations through non-invasive surface NMR (SNMR) or downhole NMR logging measurements. Our recent and ongoing research has focused on improving the performance and interpretation of NMR field measurements for groundwater characterization. Engineering advancements have addressed several key technical challenges associated with SNMR measurements. Susceptibility of SNMR measurements to environmental noise has been dramatically reduced through the development of multi-channel acquisition hardware and noise-cancellation software. Multi-channel instrumentation (up to 12 channels) has also enabled more efficient 2D and 3D imaging. Previous limitations in measuring NMR signals from water in silt, clay and magnetic geology have been addressed by shortening the instrument dead-time from 40 ms to 4 ms, and increasing the power output. Improved pulse sequences have been developed to more accurately estimate NMR relaxation times and their distributions, which are sensitive to pore size distributions. Cumulatively, these advancements have vastly expanded the range of environments in which SNMR measurements can be obtained, enabling detection of groundwater in smaller pores, in magnetic geology, in the unsaturated zone, and nearby to infrastructure (presented here in case studies). NMR logging can provide high-resolution estimates of bound and mobile water content and pore size distributions. While NMR logging has been utilized in oil and gas applications for decades, its use in groundwater investigations has been limited by the large size and high cost of oilfield NMR logging tools and services. Recently, engineering efforts funded by the US Department of

  14. Study of multi-site chemical exchange in solution state by NMR: 1D experiments with multiply selective excitation

    Samanwita Pal

    2010-07-01

    Chemical exchange in solution state has been investigated traditionally by both 1D and 2D NMR, permitting the extraction of kinetic parameters (e.g. the spin-lattice relaxation time 1, the exchange rate constant and the activation parameters). This work demonstrates a simple 1D NMR approach employing multiply selective excitation to study multi-site exchange processes in solution, applying it to systems that exhibit three-site exchange. This approach involves simultaneous excitation of all - or a chosen subset of - the exchanging sites by using an appropriately modulated shaped radiofrequency pulse. The pulse sequence, as well as analysis is summarized. Significant features of the experiment, which relies on sign labelling of the exchanging sites, include considerably shorter experiment time compared to standard 2D exchange work, clear definition of the exchange time window and uniform pulse non-ideality effects for all the exchanging sites. Complete kinetic information is reported in the study of dynamic processes in superacid solutions of two weak bases, studied by 1H NMR. An analytical solution, leading to the determination of four rate parameters, is presented for proton exchange studies on these systems, which involve a mixture of two weak bases in arbitrary concentration ratio, and stoichiometric excess of the superacid.

  15. (13)C solid-state NMR analysis of the most common pharmaceutical excipients used in solid drug formulations Part II: CP kinetics and relaxation analysis.

    Pisklak, Dariusz Maciej; Zielińska-Pisklak, Monika; Szeleszczuk, Łukasz; Wawer, Iwona

    2016-04-15

    Excipients used in the solid drug formulations differ in their NMR relaxation and (13)C cross-polarization (CP) kinetics parameters. Therefore, experimental parameters like contact time of cross-polarization and repetition time have a major impact on the registered solid state NMR spectra and in consequence on the results of the NMR analysis. In this work the CP kinetics and relaxation of the most common pharmaceutical excipients: anhydrous α-lactose, α-lactose monohydrate, mannitol, sucrose, sorbitol, sodium starch glycolate type A and B, starch of different origin, microcrystalline cellulose, hypromellose, ethylcellulose, methylcellulose, hydroxyethylcellulose, sodium alginate, magnesium stearate, sodium laurilsulfate and Kollidon(®) were analyzed. The studied excipients differ significantly in their optimum repetition time (from 5s to 1200s) and T1ρ(I) parameters (from 2ms to 73ms). The practical use of those differences in the excipients composition analysis was demonstrated on the example of commercially available tablets containing indapamide as an API. The information presented in this article will help to choose the correct acquisition parameters and also will save the time and effort needed for their optimization in the NMR analysis of the solid drug formulations. PMID:26836362

  16. Dynamics of the time dependent Bloch NMR equations for complex rFB1(t) magnetic field

    This study examines the dynamical changes produced by a complex time-dependent rFB1(t) magnetic field in an initially unperturbed magnetic resonance system. The analysis uses the Green's function algorithm as a tool to solve the transverse component of the time-dependent Bloch NMR equations with complex rFB1(t) field. The time development of the system is studied in the Hersenberg picture in which the operators are subject to unitary transformation as the applied rFB1(t) field changes the state of the NMR system from its initial ground state into another coherent state. The detailed features of the rFB1(t) field essentially affect the evolution of the state during its application. The state of the system after the complete cessation of the radio-frequency field is determined exclusively by a Fourier component which is in resonance with the NMR system. The unitary operator allows us to determine all the physically relevant information about the system in terms of a NMR relaxation parameter. (author)

  17. Recommendations and Standardization of Biomarker Quantification Using NMR-based Metabolomics with Particular Focus on Urinary Analysis

    Emwas, Abdul-Hamid M.

    2016-01-08

    NMR-based metabolomics has shown considerable promise in disease diagnosis and biomarker discovery because it allows one to non-destructively identify and quantify large numbers of novel metabolite biomarkers in both biofluids and tissues. Indeed, precise metabolite quantification is a necessary prerequisite to move any chemical biomarker or biomarker panel from the lab into the clinic. Among the many biofluids (urine, serum, plasma, cerebrospinal fluid and saliva) commonly used for disease diagnosis and prognosis, urine has several advantages. It is abundant, sterile, easily obtained, needs little sample preparation and does not require any invasive medical procedures for collection. Furthermore, urine captures and concentrates many “unwanted” or “undesirable” compounds throughout the body, thereby providing a rich source of potentially useful disease biomarkers. However, the incredible variation in urine chemical concentrations due to effects such as gender, age, diet, life style, health conditions, and physical activity make the analysis of urine and the identification of useful urinary biomarkers by NMR quite challenging. In this review, we discuss a number of the most significant issues regarding NMR-based urinary metabolomics with a specific emphasis on metabolite quantification for disease biomarker applications. We also propose a number of data collection and instrumental recommendations regarding NMR pulse sequences, acceptable acquisition parameter ranges, relaxation effects on quantitation, proper handling of instrumental differences, as well as recommendations regarding sample preparation and biomarker assessment.

  18. Chemical Origins of Permanent Set in a Peroxide Cured Filled Silicone Elastomer - Tensile and 1H NMR Analysis

    Chinn, S; Deteresa, S; Shields, A; Sawvel, A; Balazs, B; Maxwell, R S

    2004-10-29

    The aging of a commercial filled siloxane polymeric composite in states of high stress and Co-60 {gamma}-radiation exposure has been studied. DC-745 is a commercially available silicone elastomer consisting of dimethyl, methyl-phenyl, and vinyl-methyl siloxane monomers crosslinked with a peroxide vinyl specific curing agent. It is filled with {approx}30 wt.% mixture of high and low surface area silicas. This filled material is shown to be subject to permanent set if exposed to radiation while under tensile stress. Tensile modulus measurements show that the material gets marginally softer with combined radiation exposure and tensile strain as compared to material exposed to radiation without tensile strain. In addition, the segmental dynamics as measured by both uniaxial NMR relaxometry and Multiple Quantum NMR methods indicate that the material is undergoes radiatively-induced crosslinking in the absence of tensile strain and a combination of crosslinking and strain dependent increase in dynamic order parameter for the network chains. The MQ-NMR also suggests a small change in the number of polymer chains associated with the silica filler surface. Comparison of the prediction of the relative change in crosslink density from the NMR data as well as solvent swelling data and from that predicted from the Tobolsky model suggest that degradation leads to a deviation from Gaussian chain statistics and the formation of increased numbers of elastically ineffective network chains.

  19. Identification and quantification of the main organic components of vinegars by high resolution 1H NMR spectroscopy

    A detailed analysis of the proton high-field NMR spectra of vinegars (in particular of Italian balsamic vinegars) is reported. A large number of organic substances belonging to different classes, such as carbohydrates, alcohols, organic acids, volatile compounds and amino acids, were assigned. The possibility of quantification of the substances identified in the whole vinegar sample, without extraction or pre-concentration steps, was also tested. The data validity was demonstrated in terms of precision, accuracy, repeatability and inter-day reproducibility. The effects of the most critical experimental parameters (sample concentration, water suppression and relaxation time) on the analysis response were also discussed. 1H NMR results were compared with those obtained by traditional techniques (GC-MS, titrations), and good correlations were obtained. The results showed that 1H NMR with water suppression allows a rapid, simultaneous determination of carbohydrates (glucose and fructose), organic acids (acetic, formic, lactic, malic, citric, succinic and tartaric acids), alcohols and polyols (ethanol, acetoin, 2,3-butanediol, hydroxymethylfurfural), and volatile substances (ethyl acetate) in vinegar samples. On the contrary, the amino acid determination without sample pre-concentration was critical. The 1H NMR method proposed was applied to different samples of vinegars, allowing, in particular, the discrimination of vinegars and balsamic vinegars

  20. Identification and quantification of the main organic components of vinegars by high resolution {sup 1}H NMR spectroscopy

    Caligiani, A. [Dipartimento di Chimica Organica e Industriale, Universita degli Studi di Parma, Via Usberti 17A, 43100-Parma (Italy)]. E-mail: augusta.caligiani@unipr.it; Acquotti, D. [Centro Interfacolta Misure, Universita degli Studi di Parma, Via Usberti 23A, 43100-Parma (Italy); Palla, G. [Dipartimento di Chimica Organica e Industriale, Universita degli Studi di Parma, Via Usberti 17A, 43100-Parma (Italy); Bocchi, V. [Dipartimento di Chimica Organica e Industriale, Universita degli Studi di Parma, Via Usberti 17A, 43100-Parma (Italy)

    2007-02-28

    A detailed analysis of the proton high-field NMR spectra of vinegars (in particular of Italian balsamic vinegars) is reported. A large number of organic substances belonging to different classes, such as carbohydrates, alcohols, organic acids, volatile compounds and amino acids, were assigned. The possibility of quantification of the substances identified in the whole vinegar sample, without extraction or pre-concentration steps, was also tested. The data validity was demonstrated in terms of precision, accuracy, repeatability and inter-day reproducibility. The effects of the most critical experimental parameters (sample concentration, water suppression and relaxation time) on the analysis response were also discussed. {sup 1}H NMR results were compared with those obtained by traditional techniques (GC-MS, titrations), and good correlations were obtained. The results showed that {sup 1}H NMR with water suppression allows a rapid, simultaneous determination of carbohydrates (glucose and fructose), organic acids (acetic, formic, lactic, malic, citric, succinic and tartaric acids), alcohols and polyols (ethanol, acetoin, 2,3-butanediol, hydroxymethylfurfural), and volatile substances (ethyl acetate) in vinegar samples. On the contrary, the amino acid determination without sample pre-concentration was critical. The {sup 1}H NMR method proposed was applied to different samples of vinegars, allowing, in particular, the discrimination of vinegars and balsamic vinegars.