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Sample records for 1h nmr x-ray

  1. (1)H, (13)C NMR and X-ray crystallographic studies of highly polyhalogenated derivatives of costunolide lactone.

    PubMed

    Corona, D; Díaz, E; Nava, J L; Guzmán, A; Barrios, H; Fuentes, A; Hernandez-Plata, S A; Allard, J; Jankowski, C K

    2005-11-01

    The costunolide lactone, a sesquiterpene compound isolated from Zaluzania triiloba species, reacted with several dihalocarbene sources produced by trihaloform-NaOH under successive phase transfer reactions yielding mono-, bis- and tris-dihalocyclopropane adducts. The structures, as well as the configurational assignments of the different derivatives, were established by (1)H and (13)C NMR spectroscopy and assisted by X-ray crystallographic and molecular modelling studies. The specific shielding of protons in the neighbourhood of different halogens on the cyclopropane moieties was correlated to the pseudocontact interactions.

  2. New lanthanide complexes for sensitized visible and near-IR light emission: synthesis, 1H NMR, and X-ray structural investigation and photophysical properties.

    PubMed

    Quici, Silvio; Marzanni, Giovanni; Forni, Alessandra; Accorsi, Gianluca; Barigelletti, Francesco

    2004-02-23

    We describe the syntheses, the 1H NMR studies in CD3OD and D2O as solvent, the X-ray characterization, and the luminescence properties in D2O solution of the two complexes Eu.1 and Er.1, where 1 is a dipartite ligand that includes (i) a 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) unit serving as hosting site for the metal center; and (ii) a phenanthroline unit which plays the role of light antenna for the sensitization process of the metal centered luminescence. In a previous report (Inorg. Chem. 2002, 41, 2777), we have shown that for Eu.1 there are no water molecules within the first coordination sphere. X-ray and 1H NMR results reported here are consistent with full saturation of the nine coordination sites within the Eu.1 and Er.1 complexes. In addition, these studies provide important details regarding the conformations, square antiprism (SAP) and twisted square antiprism (TSAP), adopted in solution by these complexes. The luminescence results are consistent with both an effective intersystem crossing (ISC) at the light absorbing phenanthroline unit (lambda(exc) = 278 nm) and an effective energy transfer (en) process from the phenanthroline donor to the cation acceptor (with unit or close to unit efficiency for both steps). In D2O solvent, the overall sensitization efficiency, phi(se), is 0.3 and 5 x 10(-6), for Eu.1 (main luminescence peaks at 585, 612, 699 nm) and Er.1 (luminescence peak at 1530 nm), respectively. The photophysical properties of both complexes are discussed with reference to their structural features as elucidated by the obtained 1H NMR and X-ray results.

  3. Contrasting coordination behavior of Group 12 perchlorate salts with an acyclic N3O2 donor ligand by X-ray crystallography and (1)H NMR.

    PubMed

    Tice, Daniel B; Pike, Robert D; Bebout, Deborah C

    2016-08-09

    An unbranched N3O2 ligand 2,6-bis[((2-pyridinylmethyl)oxy)methyl]pyridine (L1) was used to prepare new mononuclear heteroleptic Group 12 perchlorate complexes characterized by IR, (1)H NMR and X-ray crystallography. Racemic complexes with pentadentate L1 and one to four oxygens from either water or perchlorate bound to a metal ion were structurally characterized. Octahedral [Zn(L1)(OH2)](ClO4)2 (1) and pentagonal bipyramidal [Cd(L1)(OH2)(OClO3)]ClO4 (2) structures were found with lighter congeners. The polymorphic forms of [Hg(L1)(ClO4)2] characterized (3 in P1[combining macron] and 4 in P21/c) had a mix of monodentate, anisobidentate and bidentate perchlorates, providing the first examples of a tricapped trigonal prismatic Hg(ii) coordination geometry, as well as additional examples of a rare square antiprismatic Hg(ii) coordination geometry. Solution state (1)H NMR characterization of the Group 12 complexes in CD3CN indicated intramolecular reorganization remained rapid under conditions where intermolecular M-L1 exchange was slow on the chemical shift time scale for Zn(ii) and on the J(M(1)H) time scale for Cd(ii) and Hg(ii). Solution studies with more than one equivalent of ligand also suggested that a complex with a 1 : 2 ratio of M : L1 contributed significantly to solution equilibria with Hg(ii) but not the other metal ions. The behavior of related linear pentadentate ligands with Group 12 perchlorate salts is discussed.

  4. X-ray and 1H-NMR spectroscopic studies of the structures and conformations of the new nootropic agents RU-35929, RU-47010 and RU-35965

    NASA Astrophysics Data System (ADS)

    Amato, Maria E.; Bandoli, Giuliano; Casellato, Umberto; Pappalardo, Giuseppe C.; Toja, Emilio

    1990-10-01

    The crystal and molecular structures of the nootropics (±)1-benzenesulphonyl-2-oxo-5-ethoxypyrrolidine ( 1), (±)1-(3-pyridinylsulphonyl)-2-oxo-5-ethoxypyrrolidine ( 2) and (±)1-benzenesulphonyl-2-oxo-5-isopropyloxypyrrolidine ( 3) have been determined by X-ray analysis. The solution conformation of 1, 2 and 3 has been investigated by 1H NMR spectroscopy. In the solid state, the main feature consists of the similar structural parameters and conformations, with the exception of the conformation adopted by the 5-ethoxy moiety which changes on passing from 1 to 2. The solid state overall enveloped conformation of the 2-pyrrolidinone ring for the three nootropics is found to be retained in solution on the basis of NMR evidence. Comparison between calculated and experimental coupling constant values shows that one of the two possible puckered opposite conformational isomers (half-chair shapes) occurs in solution. The relative pharmacological potencies of 1, 2 and 3 cannot therefore be interpreted in terms of the different conformation features presently detectable by available experimental methods.

  5. Solid state and solution properties of lanthanide(III) complexes of a tetraiminodiphenolate macrocyclic ligand. X-ray structure, 1H NMR and luminescence spectral studies

    NASA Astrophysics Data System (ADS)

    Bag, Pradip; Dutta, Supriya; Flörke, Ulrich; Nag, Kamalaksha

    2008-11-01

    The lanthanide(III) complexes of composition [Ln(LH 2)(H 2O) 3Cl]Cl 2 (Ln = La-Lu and Y, 1- 15) derived from the tetraiminodiphenolate macrocyclic ligand L 2- have been prepared and characterized. In these compounds, the two uncoordinated imine nitrogens of the macrocycle are protonated and hydrogen-bonded with the metal-bound phenolate oxygens and thereby provide a zwitterionic structure to the ligand. The X-ray crystal structure of the compounds of La and Nd have been determined and they are found to be isostructural. The coordination polyhedra for the eight-coordinated metal centre in the complex cation [Ln(N 2O 2)(O 3Cl)] 2+ can be described as distorted square antiprism. Intermolecular hydrogen-bondings involving the three coordinated water molecules and the two uncoordinated chloride ions give rise to the 2-D network in which the chlorides are triply hydrogen-bridged and the water molecules are doubly hydrogen-bridged. Moreover, the aromatic rings in this network are involved in π-π interaction in two different ways. 1H NMR spectra of the complexes in (CD 3) 2SO have been studied. The spectral assignments for the paramagnetic complexes of Ce-Eu have been made from { 1H- 1H} COSY spectra and longitudinal relaxation time ( T1) measurements. It is inferred that the complex species [Ln(LH 2){(CD 3) 2SO} 4] 3+ that exist in solution are isostructural for the compounds of La-Eu. The contact and pseudo-contact contribution to the isotropic paramagnetic shifts in the complexes of Ce-Eu have been estimated. The luminescence spectra of the complexes of La, Sm, Eu and Tb have been studied in methanol-ethanol (1:4) glassy matrix and in the solid state at 77 K, and the quantum yields have been estimated.

  6. Investigation of group 12 metal complexes with a tridentate SNS ligand by X-ray crystallography and 1H NMR spectroscopy.

    PubMed

    Lai, Wei; Berry, Steven M; Bebout, Deborah C; Butcher, Raymond J

    2006-01-23

    Two series of zinc triad complexes containing the ligand 2,6-bis(methylthiomethyl)pyridine (L1) were synthesized and characterized by X-ray crystallography and solution-state 1H NMR spectroscopy. The distorted meridional octahedral M(L1)2(ClO4)2 series includes the first structurally characterized Zn(II) and Cd(II) complexes with N2(SR2)4 coordination spheres. Coordination of HgCl2 and ZnCl2 with 1 equiv of ligand afforded mononuclear, five-coordinate species Hg(L1)Cl2 and Zn(L1)Cl2, respectively, with distorted square-pyramidal and trigonal-bipyramidal geometries. With CdCl2, the dimeric [Cd(L1)Cl(mu-Cl)]2 complex was obtained. The distorted octahedral coordination geometry of each Cd(II) center in this complex is formed by one tridentate ligand, two bridging chloride ions, and one terminal chloride ion. NMR spectra indicate that the intermolecular ligand-exchange rate of [M(L1)2](2+) decreased in the order Cd(II) > Zn(II) > Hg(II). Slow intermolecular ligand-exchange conditions on the chemical-shift time scale were found for 1:2 metal-to-ligand complexes of L(1) with Hg(II) and Zn(II) but not Cd(II). Slow intermolecular ligand-exchange conditions in acetonitrile-d(3) solutions permitting detection of (3-5)J(199Hg1H) were found for 1:1 and 1:2 Hg(ClO4)2/L1 complexes, but not for the related Cd(ClO4)2) complexes. The magnitudes of J(199Hg1H) for equivalent protons were smaller in [Hg(L1)2](2+) than in [Hg(L1)(NCCH3)x](2+). The relative intermolecular ligand-exchange rates of the zinc triad complexes investigated here suggest that the toxicity of Hg(II) is accentuated by the relative difficulty of displacing it from the coordination sites encountered.

  7. Investigation of relative metabolic changes in the organs and plasma of rats exposed to X-ray radiation using HR-MAS (1)H NMR and solution (1)H NMR.

    PubMed

    Jang, Won Gyo; Park, Ju Yeon; Lee, Jueun; Bang, Eunjung; Kim, So Ra; Lee, Eun Kyeong; Yun, Hyun Jin; Kang, Chang-Mo; Hwang, Geum-Sook

    2016-04-01

    Excess exposure to ionizing radiation generates reactive oxygen species and increases the cellular inflammatory response by modifying various metabolic pathways. However, an investigation of metabolic perturbations and organ-specific responses based on the amount of radiation during the acute phase has not been conducted. In this study, high-resolution magic-angle-spinning (HR-MAS) NMR and solution NMR-based metabolic profiling were used to investigate dose-dependent metabolic changes in multiple organs and tissues--including the jejunum, spleen, liver, and plasma--of rats exposed to X-ray radiation. The organs, tissues, and blood samples were obtained 24, 48, and 72 h after exposure to low-dose (2 Gy) and high-dose (6 Gy) X-ray radiation and subjected to metabolite profiling and multivariate analyses. The results showed the time course of the metabolic responses, and many significant changes were detected in the high-dose compared with the low-dose group. Metabolites with antioxidant properties showed acute responses in the jejunum and spleen after radiation exposure. The levels of metabolites related to lipid and protein metabolism were decreased in the jejunum. In addition, amino acid levels increased consistently at all post-irradiation time points as a consequence of activated protein breakdown. Consistent with these changes, plasma levels of tricarboxylic acid cycle intermediate metabolites decreased. The liver did not appear to undergo remarkable metabolic changes after radiation exposure. These results may provide insight into the major metabolic perturbations and mechanisms of the biological systems in response to pathophysiological damage caused by X-ray radiation.

  8. Structural study of (±) ethyl 3-acyloxy-1-azabicyclo[2.2.2]octane-3-carboxylates by 1H, 13C NMR spectroscopy, X-ray crystallography and DFT calculations

    NASA Astrophysics Data System (ADS)

    Arias-Pérez, M. S.; Cosme, A.; Gálvez, E.; Morreale, A.; Sanz-Aparicio, J.; Fonseca, I.

    2006-05-01

    1H, 13C NMR spectroscopy and DFT/B3LYP calculations were applied to investigate the conformational preferences of the ethoxycarbonyl and acyloxy groups of some α-acyloxyesters derived from (±) ethyl 3-hydroxy-1-azabicyclo[2.2.2]octane-3-carboxylate. The crystal structure of (±) ethyl 3-diphenylacetoxy-1-azabicyclo[2.2.2]octane-3-carboxylate was determined by X-ray diffraction. To correlate between calculated conformations and the structure in solution, NMR chemical shifts calculations were also performed using the GIAO approach. It has been found that the lowest energetic conformer computed gives the greatest correspondance with experimental solution and solid state data.

  9. Solid-state structure and solution conformation of the nootropic agent N[2-( N,N-Diisopropylamino)ethyl]-2-oxo-1-pyrrolidinacetamide sulphate. X-ray and homonuclear two-dimensional 1H NMR studies

    NASA Astrophysics Data System (ADS)

    Bandoli, Giuliano; Nicolini, Marino; Pappalardo, Giuseppe C.; Grassi, Antonio; Perly, Bruno

    1987-04-01

    The crystal and molecular structure of the nootropic agent N-[2-( N,N-diisopropyl-amino)ethyl]-2-oxo-1-pyrrolidinacetamide sulphate was determined by X-ray analysis. The conformational properties in the solution state were deduced from the 1H-NMR spectrum run in 2H 2O at 500 MHz. Spectral assignments were made with the aid of the COSY 45 shift correlation experiment. Crystals were triclinic with unit cell dimensions a = 13.410(10), b = 11.382(8), c = 6.697(4) », α = 83.80(3), β = 88.61(3)and γ = 72.25(6)° ; space group Poverline1. The structure was determined from 1047 three-dimensional counter data and refined to a value of 7.5% for the conventional discrepancy factor R. One molecule of the solvent acetonitrile is incorporated per two of the (C 14H 28N 3O 2) +-(HSO 4) -. The five-membered heterocyclic ring is in an envelope ( Cs) conformation and the "flap" atom deviates by 0.31 » from the plane of the other four. This plane forms a dihedral angle of 71.4° with the amide group, with the CO fragment directed toward the ring. All bond angles and distances are in good agreement with expected standard values. A strong OH⋯O intermolecular bond (2.61 ») links the cation of the hydrogen-sulphate anion, while the loosely held MeCN molecule is trapped in the polar pockets. The molecular conformation in the solid was compared with results from 1H NMR spectral analysis which showed that in solution wide torsional oscillations can occur about the bonds of the chain bonded to the N(1) atom.

  10. Lanthanide(III) complexes with a tetrapyridine pendant-armed macrocyclic ligand: 1H NMR structural determination in solution, X-ray diffraction, and density-functional theory calculations.

    PubMed

    Del C Fernandez-Fernandez, M; Bastida, R; Macías, A; Pérez-Lourido, P; Platas-Iglesias, C; Valencia, L

    2006-05-29

    Complexes between the tetrapyridyl pendant-armed macrocyclic ligand (L) and the trivalent lanthanide ions have been synthesized, and structural studies have been made both in the solid state and in aqueous solution. The crystal structures of the La, Ce, Pr, Gd, Tb, Er, and Tm complexes have been determined by single-crystal X-ray crystallography. In the solid state, all the cation complexes show a 10-coordinated geometry close to a distorted bicapped antiprism, with the pyridine pendants situated alternatively above and below the main plane of the macrocycle. The conformations of the two five-membered chelate rings present in the complexes change along the lanthanide series. The La(III) and Ce(III) complexes show a lambdadelta (or deltalambda) conformation, while the complexes of the heavier lanthanide ions present lambdalambda (or deltadelta) conformation. The cationic [Ln(L)]3+ complexes (Ln = La, Pr, Eu, Tb, and Tm) were also characterized by theoretical calculations at the density-functional theory (DFT) B3LYP level. The theoretical calculations predict a stabilization of the lambdalambda (or deltadelta) conformation on decreasing the ionic radius of the Ln(III) ion, in agreement with the experimental evidence. The solution structures show a good agreement with the calculated ones, as demonstrated by paramagnetic NMR measurements (lanthanide induced shifts and relaxation rate enhancements). The 1H NMR spectra indicate an effective D2 symmetry of the complexes in D2O solution. The 1H lanthanide induced shifts (LIS) observed for the Ce(III), Tm(III), and Yb(III) complexes can be fit to a theoretical model assuming that dipolar contributions are dominant for all protons. The resulting calculated values are consistent with highly rhombic magnetic susceptibility tensors with the magnetic axes being coincident with the symmetry axes of the molecule. In contrast with the solid-state structure, the analysis of the LIS data indicates that the Ce(III) complexes present a

  11. Molecular structures and conformations of 1-benzenesulphonyl-2-oxo-5-alkoxypyrrolidines with anti-amnesic activity. X-ray, 1H-NMR and quantum mechanical (PM3) studies

    NASA Astrophysics Data System (ADS)

    Amato, Maria E.; Bandoli, Giuliano; Dolmella, Alessandro; Grassi, Antonio; Pappalardo, Giuseppe C.; Toja, Emilio

    1991-04-01

    The crystal and molecular structures of the nootropic agents RU-47001 ((±) 1-(4-nitrobenzenesulphonyl)-2-oxo-5-ethoxypyrrolidine) and RU-47064 ((±) 1-(4-nitrobenzenesulphonyl)-2-oxo-5-isopropyloxypyrrolidine) have been determined by X-ray analysis and their solution conformation has been investigated using 1H NMR spectroscopy. The conformations of these molecules together with those of their analogues RU-35929 ((±) 1-benzenesulphonyl-2-oxo-5-ethoxypyrrolidine), RU-47010 ((±) 1-(3-pyridinylsulphonyl)-2-oxo-5-ethoxypyrrolidine) and RU-35965 ((±) 1-benzenesulphonyl-2-oxo-5-isopropyloxypyrrolidine) have been deduced from semi-quantitative PM3 type theoretical calculations. The main feature of all compounds consists of a common envelope conformation with C (4) at the flap of the pyrrolidinone ring in the solid, that in solution changes into the analogous, but opposite, possible puckered conformational isomer. The 5-alkoxy groups were found rather flexible in solution. Theoretical preferred conformations about NS and SC bonds were in acceptable agreement with those of the solid state. The calculated torsional energetics suggested that 1- 5 do not undergo conformational interconversion.

  12. Combined experimental and theoretical studies on the X-ray crystal structure, FT-IR, 1H NMR, 13C NMR, UV-Vis spectra, NLO behavior and antimicrobial activity of 2-hydroxyacetophenone benzoylhydrazone.

    PubMed

    Sheikhshoaie, Iran; Ebrahimipour, S Yousef; Sheikhshoaie, Mahdeyeh; Rudbari, Hadi Amiri; Khaleghi, Moj; Bruno, Giuseppe

    2014-04-24

    A Schiff base ligand, 2-hydroxyacetophenone benzoylhydrazone (HL) was synthesized and fully characterized with FT-IR, elemental analyses, UV-Vis, (1)H NMR and (13)C NMR spectra. DFT calculations using B3LYP/6-31+G(d,p) and PW91/DZP are performed to optimize the molecular geometry. Optimized structures are used to calculate FT-IR, UV-Vis, (1)H NMR and (13)C NMR spectra of the compound. Also the energies of the frontier molecular orbitals (FMOs) have been determined. The results obtained from the optimization and spectral analyses are in good agreement with the experimental data. To investigate non-linear optical properties, the electric dipole moment (μ), polarizability (α) and molecular first hyperpolarizability (β) were computed. The linear polarizabilities and first hyperpolarizabilities of the studied molecule indicate that the compound can be a good candidate of nonlinear optical materials. In addition, the minimal inhibitory concentration (MIC) of this compound against Staphylococcus aureus, and Candida albicans was determined.

  13. Synthesis, NMR, FT-IR, X-ray structural characterization, DFT analysis and isomerism aspects of 5-(2,6-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione

    NASA Astrophysics Data System (ADS)

    Barakat, Assem; Al-Najjar, Hany J.; Al-Majid, Abdullah Mohammed; Soliman, Saied M.; Mabkhot, Yahia Nasser; Shaik, Mohammed Rafi; Ghabbour, Hazem A.; Fun, Hoong-Kun

    2015-08-01

    The synthesis and spectral characterization of the 5-(2,6-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione;3 was reported. The solid state molecular structure of 3 was studied using X-ray crystallography. The relative stabilities of the seven possible isomers of 3 were calculated by DFT/B3LYP method using 6-311G(d,p) basis set. The calculated total energies and thermodynamic parameters were used to predict the relative stabilities of these isomers. The effect of solvent polarity on the relative stability of these isomers was studied at the same level of theory using PCM. It was found that the keto form, (T0), is the most stable isomer both in the gaseous state and solution. In solution, the calculated total energies of all isomers are decreased indicating that all isomers are stabilized by the solvent effect. The vibrational spectra of the most stable isomer, 3(T0) are calculated using the same level of theory and the results are compared with the experimentally measured FTIR spectra. Good correlation was obtained between the experimental and calculated vibrational frequencies (R2 = 0.9992). The electronic spectra of 3(T0) in gas phase as well as in solutions were calculated using the TD-DFT method. All the predicted electronic transitions showed very little spectral shifts and increase in the intensity of absorption due to solvent effect. Also the 1H- and 13C-NMR chemical shifts of the stable isomer were calculated and the results were correlated with the experimental data. Good correlations between the experimental and calculated chemical shifts were obtained.

  14. Synthesis, NMR, FT-IR, X-ray structural characterization, DFT analysis and isomerism aspects of 5-(2,6-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione.

    PubMed

    Barakat, Assem; Al-Najjar, Hany J; Al-Majid, Abdullah Mohammed; Soliman, Saied M; Mabkhot, Yahia Nasser; Shaik, Mohammed Rafi; Ghabbour, Hazem A; Fun, Hoong-Kun

    2015-08-05

    The synthesis and spectral characterization of the 5-(2,6-dichlorobenzylidene)pyrimidine-2,4,6(1H,3H,5H)-trione;3 was reported. The solid state molecular structure of 3 was studied using X-ray crystallography. The relative stabilities of the seven possible isomers of 3 were calculated by DFT/B3LYP method using 6-311 G(d,p) basis set. The calculated total energies and thermodynamic parameters were used to predict the relative stabilities of these isomers. The effect of solvent polarity on the relative stability of these isomers was studied at the same level of theory using PCM. It was found that the keto form, (T0), is the most stable isomer both in the gaseous state and solution. In solution, the calculated total energies of all isomers are decreased indicating that all isomers are stabilized by the solvent effect. The vibrational spectra of the most stable isomer, 3(T0) are calculated using the same level of theory and the results are compared with the experimentally measured FTIR spectra. Good correlation was obtained between the experimental and calculated vibrational frequencies (R(2)=0.9992). The electronic spectra of 3(T0) in gas phase as well as in solutions were calculated using the TD-DFT method. All the predicted electronic transitions showed very little spectral shifts and increase in the intensity of absorption due to solvent effect. Also the (1)H- and (13)C-NMR chemical shifts of the stable isomer were calculated and the results were correlated with the experimental data. Good correlations between the experimental and calculated chemical shifts were obtained.

  15. Lead hydro sodalite [Pb2(OH)(H2O)3]2[Al3Si3O12]2: synthesis and structure determination by combining X-ray rietveld refinement, 1H MAS NMR FTIR and XANES spectroscopy.

    PubMed

    Eiden-Assmann, S; Schneider, A M; Behrens, P; Wiebcke, M; Engelhardt, G; Felsche, J

    2000-01-01

    Ion exchange of the sodium hydro sodalites [Na3(H2O)4]2-[Al3Si3O12]2 [Na4(H3O2)]2[Al3Si3O12]2 and [Na4(OH)]2[Al3Si3O12]2 with aqueous Pb(NO3)2 solutions yielded, whichever reactant sodalite phase was used, the same lead hydro sodalite, [Pb2(OH)-(H2O)3]2[Al3Si3O12]2. Thus, in the case of the non-basic reactant [Na3(H2O)4]2-[Al3Si3O12]2 an overexchange occurs with respect to the number of nonframework cationic charges. Rietveld structure refinement of the lead hydro sodalite based on powder X-ray diffraction data (cubic, a = 9.070 A, room temperature, space group P43n) revealed that the two lead cations within each polyhedral sodalite cage form an orientationally disordered dinuclear [Pb2(micro-OH)(micro-H2O)(H2O)2]3+ complex. Due to additional lead framework oxygen bonds the coordination environment of each metal cation (CN 3+3) is approximately spherical, and clearly the lead 6s electron lone pair is stereochemically inactive. This is also suggested by the absence of a small peak at 13.025 keV, attributed in other Pb2+-O compounds to an electronic 2p-6s transition, in the PbL3 edge XANES spectrum. 1H MAS NMR and FTIR spectra show that the hydrogen atoms of the aqua hydroxo complex (which could not be determined in the Rietveld analysis) are involved in hydrogen bonds of various strengths.

  16. X-ray CT and NMR imaging of rocks

    SciTech Connect

    Vinegar, H.J.

    1986-03-01

    In little more than a decade, X-ray computerized tomography (CT) and nuclear magnetic resonance (NMR) imaging have become the premier modalities of medical radiology. Both of these imaging techniques also promise to be useful tools in petrophysics and reservoir engineering, because CT and NMR can nondestructively image a host of physical and chemical properties of porous rocks and multiple fluid phases contained within their pores. The images are taken within seconds to minutes, at reservoir temperatures and pressures, with spatial resolution on the millimeter and submillimeter level. The physical properties imaged by the two techniques are complementary. CT images bulk density and effective atomic number. NMR images the nuclide concentration, M/sub 0/, of a variety of nuclei (/sup 1/H, /sup 19/F, /sup 23/Na, /sup 31/P, etc.), their longitudinal and transverse relaxation-time curves (t/sub 1/ and t/sub 2/), and their chemical shift spectra. In rocks, CT images both rock matrix and pore fluids, while NMR images only mobile fluids and the interactions of these mobile fluids with the confining surfaces of the pores.

  17. Synthesis, X-ray crystallography, spectroscopic (FT-IR, 1H &13C NMR and UV), computational (DFT/B3LYP) and enzymes inhibitory studies of 7-hydroximinocholest-5-en-3-ol acetate

    NASA Astrophysics Data System (ADS)

    Ahmad, Faheem; Parveen, Mehtab; Alam, Mahboob; Azaz, Shaista; Malla, Ali Mohammed; Alam, Mohammad Jane; Lee, Dong-Ung; Ahmad, Shabbir

    2016-07-01

    The present study reports the synthesis of 7-Hydroximinocholest-5-en-3-ol acetate (syn. 3β-acetoxycholest-5-en-7-one oxime; in general, steroidal oxime). The identity of steroidal molecule was confirmed by NMR, FT-IR, MS, CHN microanalysis and X-ray crystallography. DFT calculations on the titled molecule have been performed. The molecular structure and spectra interpreted by Gaussian hybrid computational analysis theory (B3LYP) are found to be in good correlation with the experimental data obtained from the various spectrophotometric techniques. The vibrational bands appearing in the FTIR are assigned with great accuracy using harmonic frequencies along with intensities and animated modes. Molecular properties like HOMO-LUMO analysis, chemical reactivity descriptors, MEP mapping, dipole moment and natural atomic charges have been presented at the same level of theory. Moreover, the Hirshfeld analysis was carried out to ascertain the secondary interactions and associated 2D fingerprint plots. The percentages of various interactions are pictorialized by fingerprint plots of Hirshfeld surface. Steroidal oxime exhibited promising inhibitory activity against acetylcholinesterase (AChE) as compared to the reference drug, tacrine. Molecular docking was performed to introduce steroidal molecules into the X-ray crystal structures of acetylcholinesterase at the active site to find out the probable binding mode. The results of molecular docking admitted that steroidal oxime may exhibit enzyme inhibitor activity.

  18. Vibrational spectroscopic studies, NMR, HOMO-LUMO, NLO and NBO analysis of 1-(2-nitrobenzoyl)-3,5-diphenyl-4,5-dihydro-1H-pyrazole with use X-ray diffractions and DFT calculations

    NASA Astrophysics Data System (ADS)

    Demir, Sibel; Tinmaz, Feyza; Dege, Necmi; Ilhan, Ilhan Ozer

    2016-03-01

    The crystal and molecular structure of the title compound, 1-(2-nitrobenzoyl)-3,5-diphenyl-4,5-dihydro-1H-pyrazole, was reported and confirmed by single crystal X-ray diffraction and spectroscopic data. The structure, geometry optimization, vibrational frequencies and nuclear magnetic resonance were also investigated. Stability of the molecule arising from hyperconjugative interactions and charge delocalisation was analysed using natural bond orbital analysis. The results show that charge in electron density (ED) in the σ∗ and π∗ antibonding orbitals and second-order delocalisation energies E(2) confirms the occurrence of intramolecular charge transfer within the molecule. Satisfactory theoretical aspects were made for the stable conformer of the molecule using density functional theory DFT-B3LYP methods with the 6-311G++(d,p) basis set.

  19. NMR assignments and X-ray diffraction spectra for two unusual kaurene diterpenes from Erythroxylum barbatum.

    PubMed

    dos Santos, Claudio Costa; Sousa Lima, Mary Anne; Braz-Filho, Raimundo; de Simone, Carlos Alberto; Silveira, Edilberto Rocha

    2005-12-01

    The structural characterization of two new, unusual kaurene diterpenes isolated from roots of Erythroxylum barbatum is described. 1D NMR and several 2D shift-correlated NMR pulse sequences (1H,1H-COSY, HMQC, HMBC and NOESY) were used for structure elucidation and the unambiguous 1H and 13C chemical shifts assignments. Single crystal X-ray diffraction analysis was also used to confirm the final relative configuration of the compounds possessing the C-20 methyl and the CH2-15 methylene groups in cis-orientation.

  20. A community resource of experimental data for NMR / X-ray crystal structure pairs.

    PubMed

    Everett, John K; Tejero, Roberto; Murthy, Sarath B K; Acton, Thomas B; Aramini, James M; Baran, Michael C; Benach, Jordi; Cort, John R; Eletsky, Alexander; Forouhar, Farhad; Guan, Rongjin; Kuzin, Alexandre P; Lee, Hsiau-Wei; Liu, Gaohua; Mani, Rajeswari; Mao, Binchen; Mills, Jeffrey L; Montelione, Alexander F; Pederson, Kari; Powers, Robert; Ramelot, Theresa; Rossi, Paolo; Seetharaman, Jayaraman; Snyder, David; Swapna, G V T; Vorobiev, Sergey M; Wu, Yibing; Xiao, Rong; Yang, Yunhuang; Arrowsmith, Cheryl H; Hunt, John F; Kennedy, Michael A; Prestegard, James H; Szyperski, Thomas; Tong, Liang; Montelione, Gaetano T

    2016-01-01

    We have developed an online NMR / X-ray Structure Pair Data Repository. The NIGMS Protein Structure Initiative (PSI) has provided many valuable reagents, 3D structures, and technologies for structural biology. The Northeast Structural Genomics Consortium was one of several PSI centers. NESG used both X-ray crystallography and NMR spectroscopy for protein structure determination. A key goal of the PSI was to provide experimental structures for at least one representative of each of hundreds of targeted protein domain families. In some cases, structures for identical (or nearly identical) constructs were determined by both NMR and X-ray crystallography. NMR spectroscopy and X-ray diffraction data for 41 of these "NMR / X-ray" structure pairs determined using conventional triple-resonance NMR methods with extensive sidechain resonance assignments have been organized in an online NMR / X-ray Structure Pair Data Repository. In addition, several NMR data sets for perdeuterated, methyl-protonated protein samples are included in this repository. As an example of the utility of this repository, these data were used to revisit questions about the precision and accuracy of protein NMR structures first outlined by Levy and coworkers several years ago (Andrec et al., Proteins 2007;69:449-465). These results demonstrate that the agreement between NMR and X-ray crystal structures is improved using modern methods of protein NMR spectroscopy. The NMR / X-ray Structure Pair Data Repository will provide a valuable resource for new computational NMR methods development.

  1. Barbiturate bearing aroylhydrazine derivatives: Synthesis, NMR investigations, single crystal X-ray studies and biological activity

    NASA Astrophysics Data System (ADS)

    Giziroglu, Emrah; Sarikurkcu, Cengiz; Aygün, Muhittin; Basbulbul, Gamze; Soyleyici, H. Can; Firinci, Erkan; Kirkan, Bulent; Alkis, Ayse; Saylica, Tayfur; Biyik, Halil

    2016-03-01

    A series of barbituric acid aroylhydrazine derivatives have been prepared from their corresponding 1,3-dimethyl-5-acetyl barbituric acid and aroylhydrazines. All compounds have been fully characterized by using FT-IR, multinuclear NMR (1H, 13C) and Mass (MS) spectrometry. We also describe the X-ray crystal structure of 3a, which crystallizes in the monoclinic P21/n space group. The crystal structure is stabilized with infinite linear chains of dimeric units. Furthermore, all compounds were investigated for their tyrosinase inhibition, antioxidative and antimicrobial activies. The results from biological activity assays have shown that all of compounds have excellent antioxidant, significant tyrosinase inhibition and moderate antimicrobial activity.

  2. Conformation of the nootropic agents 1-(4-methoxybenzoyl)-5-oxo-2-pyrrolidinepropanoic acid (CI-933) and 4-hydroxymethyl-1-benzyl-pyrrolidin-2-one (WEB-1868): X-ray crystal structures, theoretical MO calculations (AM-1) and 600 MHZ 1H NMR spectra

    NASA Astrophysics Data System (ADS)

    Amato, Maria E.; Bandoli, Giuliano; Djedaïni, Florence; Dolmella, Alessandro; Grassi, Antonio; Pappalardo, Giuseppe C.

    1990-05-01

    The crystal and molecular structures of the cognition activators 1-(4-methoxybenzoyl)-5-oxo-2-pyrrolidinepropanoic acid (CI-933) ( 1) and 4-hydroxymethyl-1-benzyl-pyrrolidin-2-one (WEB-1868) ( 2) have been determined by X-ray analysis. The conformations of the isolated molecules 1 and 2 have been deduced from AM1-type theoretical calculations. Whilst in 1 there are no hydrogen bonds, in 2 stabilization of the crystal occurs through effective inter- and intramolecular ? bonds. The five-membered ring in both 1 and 2 adopts an envelope conformation in the solid with C(3) at the flap displaced from the C(1), C(2), C(4), N(5) mean plane. Bond distances and angles are normal and comparable with previously known similar structures. In the crystal, the torsion angles C(1)-N(5)-C(6)-C(7) and N(5)-C(6)-C(7)-C(8) in 1 are 43.1° and 44.8°, respectively; the same torsion angles in 2 are -101° and 42°, respectively. Results of theoretical calculations correlate well with the conformation of 1 in the solid, whilst in the case of 2 these indicate that the conformation in the crystal should not be retained by the isolated molecule. The complete analysis of the very high field (600 MHz) 1H NMR spectra of both compounds in CDCl 3, gives results well in line with the above established conformational features.

  3. X-ray supramolecular structure, NMR spectroscopy and synthesis of 3-methyl-1-phenyl-1H-chromeno[4,3-c]pyrazol-4-ones formed by the unexpected cyclization of 3-[1-(phenyl-hydrazono)ethyl]-chromen-2-ones.

    PubMed

    Padilla-Martinez, Itzia I; Flores-Larios, Irma Y; García-Baez, Efren V; Gonzalez, Jorge; Cruz, Alejandro; Martínez-Martinez, Francisco J

    2011-01-21

    The molecular structures of nine 3-methyl-1-phenyl-1H-chromeno[4,3-c]pyrazol-4-one isomers, obtained by the oxidative cyclization of the corresponding 1-phenylhydrazono chromen-2-ones with copper acetate as catalyst, are reported. The molecular and supramolecular structures of the 8-chloro, 8-bromo- and 8-nitro isomers 2b-d, were established by X-ray diffraction. The halogenated isomers 2b and 2c are isomorphs, they crystallize as a triclinic system, space group P-1 with two molecules in the asymmetric unit. Compound 2d crystallizes as a monoclinic system, space group P2₁/m with two molecules in the unit cell. The 1-phenyl ring [Cg(4)] is almost perpendicularly positioned to the chromene-pyrazole ring system. This conformation is in agreement with the anisotropic NMR shielding effect exerted by the phenyl ring over H-9 in solution. The supramolecular architecture is almost controlled by C-H···A (A = O, p) and face to face p-stacking interactions. The observed p-stacking trend between chromene and pyrazole rings is given by the overlapping between the best donor and acceptor rings in each compound.

  4. Characterization of heroin samples by 1H NMR and 2D DOSY 1H NMR.

    PubMed

    Balayssac, Stéphane; Retailleau, Emmanuel; Bertrand, Geneviève; Escot, Marie-Pierre; Martino, Robert; Malet-Martino, Myriam; Gilard, Véronique

    2014-01-01

    Twenty-four samples of heroin from different illicit drug seizures were analyzed using proton Nuclear Magnetic Resonance ((1)H NMR) and two-dimensional diffusion-ordered spectroscopy (2D DOSY) (1)H NMR. A careful assignment and quantification of (1)H signals enabled a comprehensive characterization of the substances present in the samples investigated: heroin, its main related impurities (6-acetylmorphine, acetylcodeine, morphine, noscapine and papaverine) and cutting agents (caffeine and acetaminophen in nearly all samples as well as lactose, lidocaine, mannitol, piracetam in one sample only), and hence to establish their spectral signatures. The good agreement between the amounts of heroin, noscapine, caffeine and acetaminophen determined by (1)H NMR and gas chromatography, the reference method in forensic laboratories, demonstrates the validity of the (1)H NMR technique. In this paper, 2D DOSY (1)H NMR offers a new approach for a whole characterization of the various components of these complex mixtures.

  5. Chalcogen analogues of nicotine lactam studied by NMR, FTIR, DFT and X-ray methods

    NASA Astrophysics Data System (ADS)

    Jasiewicz, Beata; Malczewska-Jaskóła, Karolina; Kowalczyk, Iwona; Warżajtis, Beata; Rychlewska, Urszula

    2014-07-01

    The selenoanalogue of nicotine has been synthesized and characterized by spectroscopic and X-ray diffraction methods. The crystals of selenonicotine are isomorphic with the thionicotine homologue and consist of molecules engaged in columnar π⋯π stacking interactions between antiparallely arranged pyridine moieties. These interactions, absent in other crystals containing nicotine fragments, seem to be induced by the presence of a lactam group. The molecular structures in the vacuum of the oxo-, thio- and selenonicotine homologues have been calculated by the DFT method and compared with the available X-ray data. The delocalized structure of thionicotine is stabilized by intramolecular Csbnd H⋯S hydrogen bond, which becomes weaker in the partial zwitterionic resonance structure of selenonicotine in favor of multiple Csbnd H⋯Se intermolecular hydrogen-bonds. The calculated data allow a complete assignment of vibration modes in the solid state FTIR spectra. The 1H and 13C NMR chemical shifts were calculated by the GIAO method with B3LYP/6-311G(3df) level. A comparison between experimental and calculated theoretical results indicates that the density functional B3LYP method provided satisfactory results for predicting FTIR, 1H, 13C NMR spectra properties.

  6. Complete (1) H NMR assignment of cedranolides.

    PubMed

    Perez-Hernandez, Nury; Gordillo-Roman, Barbara; Arrieta-Baez, Daniel; Cerda-Garcia-Rojas, Carlos M; Joseph-Nathan, Pedro

    2017-03-01

    Complete and unambiguous (1) H NMR chemical shift assignment of α-cedrene (2) and cedrol (9), as well as for α-pipitzol (1), isocedrol (10), and the six related compounds 3-8 has been established by iterative full spin analysis using the PERCH NMR software (PERCH Solutions Ltd., Kuopio, Finland). The total sets of coupling constants are described and correlated with the conformational equilibria of the five-membered ring of 1-10, which were calculated using the complete basis set method. Copyright © 2015 John Wiley & Sons, Ltd.

  7. Non-invasive predictors of human cortical bone mechanical properties: T(2)-discriminated H NMR compared with high resolution X-ray.

    PubMed

    Horch, R Adam; Gochberg, Daniel F; Nyman, Jeffry S; Does, Mark D

    2011-01-21

    Recent advancements in magnetic resonance imaging (MRI) have enabled clinical imaging of human cortical bone, providing a potentially powerful new means for assessing bone health with molecular-scale sensitivities unavailable to conventional X-ray-based diagnostics. To this end, (1)H nuclear magnetic resonance (NMR) and high-resolution X-ray signals from human cortical bone samples were correlated with mechanical properties of bone. Results showed that (1)H NMR signals were better predictors of yield stress, peak stress, and pre-yield toughness than were the X-ray derived signals. These (1)H NMR signals can, in principle, be extracted from clinical MRI, thus offering the potential for improved clinical assessment of fracture risk.

  8. First X-ray structural characterization of isatin Schiff base derivative. NMR and theoretical conformational studies

    NASA Astrophysics Data System (ADS)

    Davidovich, Pavel; Novikova, Daria; Tribulovich, Vyacheslav; Smirnov, Sergey; Gurzhiy, Vlad; Melino, Gerry; Garabadzhiu, Alexander

    2014-10-01

    Isatin (1H-indole-2,3-dione) is an endogenous natural compound under intense development in medicinal chemistry. Here, we characterize isatin Schiff base derivative by X-ray crystallography. We describe a derivative that crystallizes E-isomer form in the triclinic space group P 1bar;a = 5.9580 (4) Å, b = 8.4184 (7) Å, c = 14.1801 (14) Å, α = 73.962 (8)°, β = 83.184 (7)°, γ = 81.143 (6)°. NMR data show that E-conformer interconverts to the Z-conformer when dissolved, this equilibrium weakly depends on the solvent type. The Z-isomer geometry and the energetics of ΔEE-Z interconversion barriers were determined by quantum chemical calculations. The isomers are further characterized by means of FT-IR and UV-Vis spectroscopy.

  9. Synthesis, spectroscopic characterization, X-ray structure and DFT studies on 2,6-bis(1-benzyl-1H-benzo[d]imidazol-2-yl)pyridine

    NASA Astrophysics Data System (ADS)

    İnkaya, Ersin; Günnaz, Salih; Özdemir, Namık; Dayan, Osman; Dinçer, Muharrem; Çetinkaya, Bekir

    2013-02-01

    The title molecule, 2,6-bis(1-benzyl-1H-benzo[d]imidazol-2-yl)pyridine (C33H25N5), was synthesized and characterized by elemental analysis, FT-IR spectroscopy, one- and two-dimensional NMR spectroscopies, and single-crystal X-ray diffraction. In addition, the molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the title compound in the ground state have been calculated using the density functional theory at the B3LYP/6-311G(d,p) level, and compared with the experimental data. The complete assignments of all vibrational modes were performed by potential energy distributions using VEDA 4 program. The geometrical parameters of the optimized structure are in good agreement with the X-ray crystallographic data, and the theoretical vibrational frequencies and GIAO 1H and 13C NMR chemical shifts show good agreement with experimental values. Besides, molecular electrostatic potential (MEP) distribution, frontier molecular orbitals (FMO) and non-linear optical properties of the title compound were investigated by theoretical calculations at the B3LYP/6-311G(d,p) level. The linear polarizabilities and first hyper polarizabilities of the molecule indicate that the compound is a good candidate of nonlinear optical materials. The thermodynamic properties of the compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures.

  10. Synthesis, spectroscopic characterization, X-ray structure and DFT studies on 2,6-bis(1-benzyl-1H-benzo[d]imidazol-2-yl)pyridine.

    PubMed

    İnkaya, Ersin; Günnaz, Salih; Özdemir, Namık; Dayan, Osman; Dinçer, Muharrem; Çetinkaya, Bekir

    2013-02-15

    The title molecule, 2,6-bis(1-benzyl-1H-benzo[d]imidazol-2-yl)pyridine (C(33)H(25)N(5)), was synthesized and characterized by elemental analysis, FT-IR spectroscopy, one- and two-dimensional NMR spectroscopies, and single-crystal X-ray diffraction. In addition, the molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) (1)H and (13)C NMR chemical shift values of the title compound in the ground state have been calculated using the density functional theory at the B3LYP/6-311G(d,p) level, and compared with the experimental data. The complete assignments of all vibrational modes were performed by potential energy distributions using VEDA 4 program. The geometrical parameters of the optimized structure are in good agreement with the X-ray crystallographic data, and the theoretical vibrational frequencies and GIAO (1)H and (13)C NMR chemical shifts show good agreement with experimental values. Besides, molecular electrostatic potential (MEP) distribution, frontier molecular orbitals (FMO) and non-linear optical properties of the title compound were investigated by theoretical calculations at the B3LYP/6-311G(d,p) level. The linear polarizabilities and first hyper polarizabilities of the molecule indicate that the compound is a good candidate of nonlinear optical materials. The thermodynamic properties of the compound at different temperatures were calculated, revealing the correlations between standard heat capacity, standard entropy, standard enthalpy changes and temperatures.

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

    NASA Astrophysics Data System (ADS)

    Gupta, Richa; Chaudhary, R. P.

    2013-10-01

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

  12. 1,3-Alternate calix[4]arene nitronyl nitroxide tetraradical and diradical: synthesis, X-ray crystallography, paramagnetic NMR spectroscopy, EPR spectroscopy, and magnetic studies

    SciTech Connect

    Rajca, Andrzej; Pink, Maren; Mukherjee, Sumit; Rajca, Suchada; Das, Kausik

    2008-04-02

    Calix[4]arenes constrained to 1,3-alternate conformation and functionalized at the upper rim with four and two nitronyl nitroxides have been synthesized, and characterized by X-ray crystallography, magnetic resonance (EPR and {sup 1}H NMR) spectroscopy, and magnetic studies. Such calix[4]arene tetraradicals and diradicals provide scaffolds for through-bond and through-space intramolecular exchange couplings.

  13. "Solvent Effects" in 1H NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Cavaleiro, Jose A. S.

    1987-01-01

    Describes a simple undergraduate experiment in chemistry dealing with the "solvent effects" in nuclear magnetic resonance (NMR) spectroscopy. Stresses the importance of having students learn NMR spectroscopy as a tool in analytical chemistry. (TW)

  14. Structural studies of PCU-hydrazones: NMR spectroscopy, X-ray diffractions, and DFT calculations

    NASA Astrophysics Data System (ADS)

    Veljković, Jelena; Šekutor, Marina; Molčanov, Krešimir; Lo, Rabindranath; Ganguly, Bishwajit; Mlinarić-Majerski, Kata

    2011-06-01

    In this article we present a detailed structural investigation for the configurational isomers of PCU-hydrazones. The structural characterization of these hydrazones was performed using NMR spectroscopy, X-ray diffraction analysis and theoretical calculations. The single crystal X-ray structures of PCU-hydrazones 6B and 6C have been solved and used to conclusively confirm the characterization obtained via NMR spectra of a particular isomer. Nuclear magnetic shielding values calculated for 6A-C using DFT calculations were correlated with the experimentally determined chemical shifts. The computed results were found to be in good agreement with the observed 13C NMR values. The computed NMR results helped to ascertain the isomers of PCU-hydrazones 4A-C.

  15. Silver metallation of hen egg white lysozyme: X-ray crystal structure and NMR studies.

    PubMed

    Panzner, Matthew J; Bilinovich, Stephanie M; Youngs, Wiley J; Leeper, Thomas C

    2011-12-14

    The X-ray crystal structure, NMR binding studies, and enzyme activity of silver(I) metallated hen egg white lysozyme are presented. Primary bonding of silver is observed through His15 with secondary bonding interactions coming from nearby Arg14 and Asp87. A covalently bound nitrate completes a four coordinate binding pocket.

  16. Structure of dimethylphenyl betaine hydrochloride studied by X-ray diffraction, DFT calculation, NMR and FTIR spectra

    NASA Astrophysics Data System (ADS)

    Szafran, M.; Katrusiak, A.; Dega-Szafran, Z.; Kowalczyk, I.

    2013-01-01

    The structure of dimethylphenyl betaine hydrochloride (1) has been studied by X-ray diffraction, DFT calculations, NMR and FTIR spectra. The crystals are monoclinic, space group P21/c. In the crystal, the Cl- anion is connected with protonated betaine through the O-H⋯Cl- hydrogen bond of 2.943(2) Å. The structures in the gas phase (2) and water solution (3) have been optimized by the B3LYP/6-311++G(d,p) approach and the geometrical results have been compared with the X-ray data of 1. The FTIR spectrum of the solid compound is consistent with the X-ray results. The probable assignments of the anharmonic experimental vibrational frequencies of the investigated chloride (1) based on the calculated harmonic frequencies in water solution (3) are proposed. The correlations between the experimental 1H and 13C NMR chemical shifts (δexp) of 1 in D2O and the magnetic isotropic shielding constants (σcalc) calculated by the GIAO/B3LYP/6-311G++(d,p) approach, using the screening solvation model (COSMO), δexp = a + b σcalc, for optimized molecule 3 in water solution are linear and correctly reproduce the experimental chemical shifts.

  17. Quantum-chemical, NMR and X-ray diffraction studies on (+/-)-1-[3,4-(methylenedioxy)phenyl]-2-methylaminopropane.

    PubMed

    Zapata-Torres, Gerald; Cassels, Bruce K; Parra-Mouchet, Julia; Mascarenhas, Yvonne P; Ellena, Javier; De Araujo, A S

    2008-06-01

    Time-averaged conformations of (+/-)-1-[3,4-(methylenedioxy)phenyl]-2-methylaminopropane hydrochloride (MDMA, "ecstasy") in D(2)O, and of its free base and trifluoroacetate in CDCl(3), were deduced from their (1)H NMR spectra and used to calculate their conformer distribution. Their rotational potential energy surface (PES) was calculated at the RHF/6-31G(d,p), B3LYP/6-31G(d,p), B3LYP/cc-pVDZ and AM1 levels. Solvent effects were evaluated using the polarizable continuum model. The NMR and theoretical studies showed that, in the free base, the N-methyl group and the ring are preferentially trans. This preference is stronger in the salts and corresponds to the X-ray structure of the hydrochloride. However, the energy barriers separating these forms are very low. The X-ray diffraction crystal structures of the anhydrous salt and its monohydrate differed mainly in the trans or cis relationship of the N-methyl group to the alpha-methyl, although these two forms interconvert freely in solution.

  18. X-ray crystallography characterization, vibrational spectroscopy, NMR spectra and quantum chemical DFT/HF study of N, N'-di(2-methoxyphenyl)formamidine

    NASA Astrophysics Data System (ADS)

    Rofouei, M. K.; Sohrabi, N.; Shamsipur, M.; Fereyduni, E.; Ayyappan, S.; Sundaraganesan, N.

    2010-07-01

    The title compound, N, N'-di(2-methoxyphenyl)formamidine (DMPF) was synthesized and characterized byFT-IR, FT-Raman, 1H NMR, 13C NMR spectroscopy and X-ray single crystal diffraction. The results show that the compound crystallizes in anorthorhombic system, with space group of Pbca and eight molecules in the unit cell. The unit cell parameters are: a = 11.1118 (7) Å, b = 14.9878 (9) Å and c = 16.2851 (10) Å. The molecular geometry, the normal mode frequencies and corresponding vibrational assignments of DMPF at the ground state were performed by HF and B3LYP methods with 6-311+G(d,p) basis set. It was observed that the bond lengths and angles in the molecule, obtained by X-ray at the level of theory, were in good agreement with those of the experiment. A detailed interpretation of the infrared and Raman spectra of DMPF was reported. The 13C NMR and 1H NMR of DMPF have been calculated usingHF and B3LYP methods with 6-311+G(d,p) basis set. Comparison between experimental and theoretical results showed that B3LYP/6-311+G(d,p) method is able to provide more satisfactory results for predicting IR, Raman, 1H NMR and 13C NMR properties.

  19. Teaching 1H NMR Spectrometry Using Computer Modeling.

    ERIC Educational Resources Information Center

    Habata, Yoichi; Akabori, Sadatoshi

    2001-01-01

    Molecular modeling by computer is used to display stereochemistry, molecular orbitals, structure of transition states, and progress of reactions. Describes new ideas for teaching 1H NMR spectroscopy using computer modeling. (Contains 12 references.) (ASK)

  20. Syntheses, structures, and 1H, 13C{1H} and 119Sn{1H} NMR chemical shifts of a family of trimethyltin alkoxide, amide, halide and cyclopentadienyl compounds

    DOE PAGES

    Lichtscheidl, Alejandro G.; Janicke, Michael T.; Scott, Brian L.; ...

    2015-08-21

    The synthesis and full characterization, including Nuclear Magnetic Resonance (NMR) data (1H, 13C{1H} and 119Sn{1H}), for a series of Me3SnX (X = O-2,6-tBu2C6H3 (1), (Me3Sn)N(2,6-iPr2C6H3) (3), NH-2,4,6-tBu3C6H2 (4), N(SiMe3)2 (5), NEt2, C5Me5 (6), Cl, Br, I, and SnMe3) compounds in benzene-d6, toluene-d8, dichloromethane-d2, chloroform-d1, acetonitrile-d3, and tetrahydrofuran-d8 are reported. The X-ray crystal structures of Me3Sn(O-2,6-tBu2C6H3) (1), Me3Sn(O-2,6-iPr2C6H3) (2), and (Me3Sn)(NH-2,4,6-tBu3C6H2) (4) are also presented. As a result, these compiled data complement existing literature data and ease the characterization of these compounds by routine NMR experiments.

  1. Structure in solid state of 3,3‧-diindolylmethane derivatives, potent cytotoxic agents against human tumor cells, followed X-ray diffraction and 13C CP/MAS NMR analyses

    NASA Astrophysics Data System (ADS)

    Maciejewska, Dorota; Wolska, Irena; Niemyjska, Maria; Żero, Paweł

    2005-10-01

    The 5,5'-disubstituted-3,3'-diindolylmethanes 1, 2 have been prepared and their structure was analyzed by X-ray and NMR techniques. The X-ray diffraction studies revealed interesting C-H⋯ π intermolecular interactions which may play role in characterization of their biological features. In 1H and 13C NMR spectra in solution and in 13C CPMAS NMR spectra in solid state only a single pattern of signals was observed. Both compounds reduce the growth of MCF7 (breast), NCI-H460 (lung), and SF-268 (NCS) cells dramatically.

  2. NMR and X-ray investigations of model tris- and bis-pyridinium fluoroborates

    NASA Astrophysics Data System (ADS)

    Schilf, Wojciech; Kołodziej, Beata; Grech, Eugeniusz; Dobrzycki, Łukasz; Woźniak, Krzysztof

    2004-11-01

    Spectroscopic and structural properties of two distinctly different products of the reaction of 2,4,6-trimethylpyrylium ion (and 2,4,6-triphenylpyrylium), with triple primary amine-tris(2-aminoethyl)amine (tren)—have been isolated and identified. In the case of the first moiety, one of the products is a symmetric tris-pyridinium salt, whereas the second one has only two groups reacting towards the pyridinium salt and the third group giving 3,5-xylidine derivative. For the second ion (2,4,6-triphenylpyrylium salt), we obtained only one symmetric product—trispyridinium salt. All structures have been confirmed by NMR data in solution and the structure of the asymmetric pyrydinium salt in the solid state by single crystal X-ray analysis. The structure of symmetric salt has been confirmed by 13C and 15N CPMAS NMR spectra.

  3. The crystallization of hectorite clays as monitored by small angle X-ray scattering and NMR

    SciTech Connect

    Carrado, K. A.; Xu, L.; Seifert, S.; Gregory, D.; Song, K.; Botto, R. E.

    1999-12-13

    The authors have probed the 48-hr crystallization of a magnesium silicate clay called hectorite. Small angle X-ray scattering (SAXS) at the Advanced Photon Source using aliquots ex situ has revealed that data is consistent with ex situ XRD, TGA, AFM, and IR data in that all these techniques see clay crystallite beginning to form in the first few hours of reaction. Tetraethylammonium (TEA) ions are used to aid crystallization and become incorporated as the exchange cations within the interlayers. {sup 13}C NMR shows that 80% of the final TEA loading is accomplished in the first 10 hrs. {sup 29}Si NMR displays a visible clay silicate peak after just 1 hr. In addition, the first in situ study of clay crystallization of any kind was performed by in situ SAXS. Results are consistent with the ex situ data as well as showing the sensitivity of SAXS to sol gel reactions occurring on the order of minutes.

  4. 2-Acylamino- and 2,4-bis(acylamino)pyrimidines as supramolecular synthons analyzed by multiple noncovalent interactions. DFT, X-ray diffraction, and NMR spectral studies.

    PubMed

    Ośmiałowski, Borys; Kolehmainen, Erkki; Ikonen, Satu; Valkonen, Arto; Kwiatkowski, Adam; Grela, Izabela; Haapaniemi, Esa

    2012-11-02

    Intermolecular interactions of ten 2-acylamino and 2,4-bis(acylamino)pyrimidines (7 of which are previously unknown) have been investigated by X-ray structural, quantum chemical (DFT), and NMR spectral methods. Especially the concentration dependencies of the (1)H NMR chemical shifts and titrations with other molecules capable of multiple hydrogen bonding provided useful information regarding their association via triple or quadruple hydrogen bonding, which is controlled by the conformational preferences of 2-acylamino- and 2,4-bis(acylamino)pyrimidines. On comparison of the properties of 2-acylamino- and 2,4-bis(acylamino)pyrimidines with the corresponding pyridines, an additional nitrogen in the heterocyclic ring is the crucial factor in explaining the stability of various conformers and dimers of pyrimidines. Computational modeling of their dimerization (self-association) and heteroassociation supports the experimental findings. The substituent effects in 2-acylamino- and 2,4-bis(acylamino)pyrimidines are discussed via inter- and intramolecular terms. The subtle balance between several structural factors and their influence on the aggregation of studied pyrimidines was confirmed also by variable-temperature NMR and NOE experiments. X-ray structures of 2-methyl- and 2-adamantyl-CONH-pyrimidines revealed very different intermolecular interactions, showing the importance of the substituent size on the self-assembly process. As a whole NMR spectral, X-ray structural, and computational data of 2-acylamino- and 2,4-bis(acylamino)pyrimidines can be interpreted in terms of multiple intra-/intermolecular interactions.

  5. The influence of sulfur configuration in (1) H NMR chemical shifts of diasteromeric five-membered cyclic sulfites.

    PubMed

    Obregón-Mendoza, Marco A; Sánchez-Castellanos, Mariano; Cuevas, Gabriel; Gnecco, Dino; Cassani, Julia; Poveda-Jaramillo, Juan C; Reynolds, William F; Enríquez, Raúl G

    2017-03-01

    The effect of the stereochemistry of the sulfur atom on (1) H chemical shifts of the diasteromeric pair of cyclic sulfites of 4-[methoxy(4-nitrophenyl)methyl]-5-phenyl-1,3,2-dioxathiolan-2-oxide was investigated. The complete (1) H and (13) C NMR spectral assignment was achieved by the use of one-dimensional and two-dimensional NMR techniques in combination with X-ray data. A correlation of experimental data with theoretical calculations of chemical shift tensors using density functional theory and topological theory of atoms in molecules was made. Copyright © 2016 John Wiley & Sons, Ltd.

  6. Structure of 6-hydroxy-1-methylquinolinium chloride hydrate studied by X-ray, DFT calculations, FTIR and NMR spectroscopes

    NASA Astrophysics Data System (ADS)

    Barczyński, P.; Komasa, A.; Ratajczak-Sitarz, M.; Katrusiak, A.; Koput, J.; Dega-Szafran, Z.; Szafran, M.

    2010-12-01

    The crystal structure of 6-hydroxy-1-methylquinolinium chloride hydrate ( 1), 6QBWHCl, is monoclinic, space group P2 1/ n and Z = 4. 1-Methyl-6-oxyquinolinium betaine, 6QB, is protonated and its OH group participates in a moderate hydrogen bond with water molecule (O(1)-H⋯O(W1) = 2.636(2) Å). The water molecule is further connected by a hydrogen bond to chloride ion (O(W1)-H(W2)⋯Cl(1) = 3.090(3) Å). Structures of five complexes ( 2- 6) have been optimized by the B3LYP/6-311G(d, p) level of theory and the results have been compared with the X-ray data of 1. Linear correlations between the experimental 1H and 13C NMR chemical shifts ( δexp) of complexes 2- 5 and the magnetic isotropic shielding constants ( σcal) calculated by the GIAO/B3LYP/6-311G(d, p) approach, using the screening solvation model (COSMO), δexp = a + bσcal, are reported. The probable assignments of the anharmonic experimental solid state vibrational frequencies of anhydrous complex, 6QBHCl, based on the calculated B3LYP/6-311G(d, p) harmonic frequencies have been proposed.

  7. Domain motion in cytochrome P450 reductase: conformational equilibria revealed by NMR and small-angle x-ray scattering.

    PubMed

    Ellis, Jacqueline; Gutierrez, Aldo; Barsukov, Igor L; Huang, Wei-Cheng; Grossmann, J Günter; Roberts, Gordon C K

    2009-12-25

    NADPH-cytochrome P450 reductase (CPR), a diflavin reductase, plays a key role in the mammalian P450 mono-oxygenase system. In its crystal structure, the two flavins are close together, positioned for interflavin electron transfer but not for electron transfer to cytochrome P450. A number of lines of evidence suggest that domain motion is important in the action of the enzyme. We report NMR and small-angle x-ray scattering experiments addressing directly the question of domain organization in human CPR. Comparison of the (1)H-(15)N heteronuclear single quantum correlation spectrum of CPR with that of the isolated FMN domain permitted identification of residues in the FMN domain whose environment differs in the two situations. These include several residues that are solvent-exposed in the CPR crystal structure, indicating the existence of a second conformation in which the FMN domain is involved in a different interdomain interface. Small-angle x-ray scattering experiments showed that oxidized and NADPH-reduced CPRs have different overall shapes. The scattering curve of the reduced enzyme can be adequately explained by the crystal structure, whereas analysis of the data for the oxidized enzyme indicates that it exists as a mixture of approximately equal amounts of two conformations, one consistent with the crystal structure and one a more extended structure consistent with that inferred from the NMR data. The correlation between the effects of adenosine 2',5'-bisphosphate and NADPH on the scattering curve and their effects on the rate of interflavin electron transfer suggests that this conformational equilibrium is physiologically relevant.

  8. Temperature imaging by 1H NMR and suppression of convection in NMR probes

    PubMed

    Hedin; Furo

    1998-03-01

    A simple arrangement for suppressing convection in NMR probes is tested experimentally. Diffusion experiments are used to determine the onset of convection and 1H temperature imaging helps to rationalize the somewhat surprising results. A convenient new 1H NMR thermometer, CH2Br2 dissolved in a nematic thermotropic liquid crystal, is presented. Copyright 1998 Academic Press.

  9. Applications of 1H-NMR to Biodiesel Research

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Biodiesel is an alternative diesel fuel derived from vegetable oils, animal fats, or used cooking oils. It is produced by reacting these materials with an alcohol in the presence of a catalyst to give the corresponding mono-alkyl esters. 1H-NMR is a routine analytical method that has been used for...

  10. Protein NMR structures refined with Rosetta have higher accuracy relative to corresponding X-ray crystal structures.

    PubMed

    Mao, Binchen; Tejero, Roberto; Baker, David; Montelione, Gaetano T

    2014-02-05

    We have found that refinement of protein NMR structures using Rosetta with experimental NMR restraints yields more accurate protein NMR structures than those that have been deposited in the PDB using standard refinement protocols. Using 40 pairs of NMR and X-ray crystal structures determined by the Northeast Structural Genomics Consortium, for proteins ranging in size from 5-22 kDa, restrained Rosetta refined structures fit better to the raw experimental data, are in better agreement with their X-ray counterparts, and have better phasing power compared to conventionally determined NMR structures. For 37 proteins for which NMR ensembles were available and which had similar structures in solution and in the crystal, all of the restrained Rosetta refined NMR structures were sufficiently accurate to be used for solving the corresponding X-ray crystal structures by molecular replacement. The protocol for restrained refinement of protein NMR structures was also compared with restrained CS-Rosetta calculations. For proteins smaller than 10 kDa, restrained CS-Rosetta, starting from extended conformations, provides slightly more accurate structures, while for proteins in the size range of 10-25 kDa the less CPU intensive restrained Rosetta refinement protocols provided equally or more accurate structures. The restrained Rosetta protocols described here can improve the accuracy of protein NMR structures and should find broad and general for studies of protein structure and function.

  11. Investigation of the role of stereoelectronic effects in the conformation of piperidones by NMR spectroscopy and X-ray diffraction

    PubMed Central

    Garcias-Morales, Cesar; Ortegón-Reyna, David

    2015-01-01

    Summary This paper reports the synthesis of a series of piperidones 1–8 by the Mannich reaction and analysis of their structures and conformations in solution by NMR and mass spectrometry. The six-membered rings in 2,4,6,8-tetraphenyl-3,7-diazabicyclo[3.3.1]nonan-9-ones, compounds 1 and 2, adopt a chair–boat conformation, while those in 2,4-diphenyl-3-azabicyclo[3.3.1]nonan-9-ones, compounds 3–8, adopt a chair–chair conformation because of stereoelectronic effects. These stereoelectronic effects were analyzed by the 1 J C–H coupling constants, which were measured in the 13C satellites of the 1H NMR spectra obtained with the hetero-dqf pulse sequence. In the solid state, these stereoelectronic effects were investigated by measurement of X-ray diffraction data, the molecular geometry (torsional bond angles and bond distances), and inter- and intramolecular interactions, and by natural bond orbital analysis, which was performed using density functional theory at the ωB97XD/6311++G(d,p) level. We found that one of the main factors influencing the conformational stability of 3–8 is the interaction between the lone-pair electrons of nitrogen and the antibonding sigma orbital of C(7)–Heq (nN→σ*C–H(7)eq), a type of hyperconjugative interaction. PMID:26664617

  12. Packing interactions in hydrated and anhydrous forms of the antibiotic Ciprofloxacin: a solid-state NMR, X-ray diffraction, and computer simulation study.

    PubMed

    Mafra, Luís; Santos, Sérgio M; Siegel, Renée; Alves, Inês; Paz, Filipe A Almeida; Dudenko, Dmytro; Spiess, Hans W

    2012-01-11

    We present an experimental NMR, X-ray diffraction (XRD), and computational study of the supramolecular assemblies of two crystalline forms of Ciprofloxacin: one anhydrate and one hydrate forming water wormholes. The resonance assignment of up to 51 and 54 distinct (13)C and (1)H resonances for the hydrate is reported. The effect of crystal packing, identified by XRD, on the (1)H and (13)C chemical shifts including weak interionic H-bonds, is quantified; (1)H chemical shift changes up to ∼-3.5 ppm for CH···π contacts and ∼+2 ppm (CH···O((-))); ∼+4.7 ppm (((+))NH···O((-))) for H-bonds. Water intake induces chemical shift changes up to 2 and 5 ppm for (1)H and (13)C nuclei, respectively. Such chemical shifts are found to be sensitive detectors of hydration/dehydration in highly insoluble hydrates.

  13. Quantitative produced water analysis using mobile 1H NMR

    NASA Astrophysics Data System (ADS)

    Wagner, Lisabeth; Kalli, Chris; Fridjonsson, Einar O.; May, Eric F.; Stanwix, Paul L.; Graham, Brendan F.; Carroll, Matthew R. J.; Johns, Michael L.

    2016-10-01

    Measurement of oil contamination of produced water is required in the oil and gas industry to the (ppm) level prior to discharge in order to meet typical environmental legislative requirements. Here we present the use of compact, mobile 1H nuclear magnetic resonance (NMR) spectroscopy, in combination with solid phase extraction (SPE), to meet this metrology need. The NMR hardware employed featured a sufficiently homogeneous magnetic field, such that chemical shift differences could be used to unambiguously differentiate, and hence quantitatively detect, the required oil and solvent NMR signals. A solvent system consisting of 1% v/v chloroform in tetrachloroethylene was deployed, this provided a comparable 1H NMR signal intensity for the oil and the solvent (chloroform) and hence an internal reference 1H signal from the chloroform resulting in the measurement being effectively self-calibrating. The measurement process was applied to water contaminated with hexane or crude oil over the range 1-30 ppm. The results were validated against known solubility limits as well as infrared analysis and gas chromatography.

  14. Organobase catalyzed 1,4-conjugate addition of 4-hydroxycoumarin on chalcones: Synthesis, NMR and single-crystal X-ray diffraction studies of novel warfarin analogues

    NASA Astrophysics Data System (ADS)

    Talhi, Oualid; Fernandes, José A.; Pinto, Diana C. G. A.; Almeida Paz, Filipe A.; Silva, Artur M. S.

    2015-08-01

    The synthesis of a new series of warfarin analogues by convenient organobase catalyzed 1,4-conjugate addition of 4-hydroxycoumarin to chalcone derivatives is described. 1H NMR spectroscopy evidenced the presence of a predominant acyclic open-form together with the cyclic hemiketal tautomers of the resulting Michael adducts. The acyclic open-form has been unequivocally proved by single-crystal X-ray diffraction analysis. The use of the B ring ortho-hydroxychalcone synthons in this reaction has led to a diastereoselective synthesis of warfarin bicyclo[3.3.1]nonane ketal derivatives.

  15. Supramolecular organization of perfluorinated 1H-indazoles in the solid state using X-ray crystallography, SSNMR and sensitive (VCD) and non sensitive (MIR, FIR and Raman) to chirality vibrational spectroscopies.

    PubMed

    Quesada-Moreno, María M; Avilés-Moreno, Juan Ramón; López-González, Juan Jesús; Jacob, Kane; Vendier, Laure; Etienne, Michel; Alkorta, Ibon; Elguero, José; Claramunt, Rosa M

    2017-01-04

    1H-Indazole derivatives exhibit a remarkable property since some of them form chiral supramolecular structures starting from achiral monomers. The present work deals with the study of three perfluorinated 1H-indazoles that resolve spontaneously as conglomerates. These conglomerates can contain either a pure enantiomer (one helix) or a mixture of both enantiomers (both helices) with an enantiomeric excess (e.e.) of one of them. The difficulty of the structural analysis of these types of compounds is thus clear. We outline a complete strategy to determine the structures and configurations (M or P helices) of the enantiomers (helices) forming the conglomerates of these perfluorinated 1H-indazoles based on X-ray crystallography, solid state NMR spectroscopy and different solid state vibrational spectroscopies that are either sensitive (VCD) or not (FarIR, IR and Raman) to chirality, together with quantum chemical calculations (DFT).

  16. Electron paramagnetic resonance, scanning electron microscopy with energy dispersion X-ray spectrometry, X-ray powder diffraction, and NMR characterization of iron-rich fired clays.

    PubMed

    Presciutti, Federica; Capitani, Donatella; Sgamellotti, Antonio; Brunetti, Brunetto Giovanni; Costantino, Ferdinando; Viel, Stéphane; Segre, Annalaura

    2005-12-01

    The aim of this study is to clarify the structure of an iron-rich clay and the structural changes involved in the firing process as a preliminary step to get information on ancient ceramic technology. To this purpose, illite-rich clay samples fired at different temperatures were characterized using a multitechnique approach, i.e., by electron paramagnetic resonance, scanning electron microscopy with electron dispersion X-ray spectrometry, X-ray powder diffraction, magic angle spinning and multiple quantum magic angle spinning NMR. During firing, four main reaction processes occur: dehydration, dehydroxylation, structural breakdown, and recrystallization. When the results are combined from all characterization methods, the following conclusions could be obtained. Interlayer H2O is located close to aluminum in octahedral sites and is driven off at temperatures lower than 600 degrees C. Between 600 and 700 degrees C dehydroxylation occurs whereas, between 800 and 900 degrees C, the aluminum in octahedral sites disappears, due to the breakdown of the illite structure, and all iron present is oxidized to Fe3+. In samples fired at 1000 and 1100 degrees C iron clustering was observed as well as large single crystals of iron with the occurrence of ferro- or ferrimagnetic effects. Below 900 degrees C the aluminum in octahedral sites presents a continuous distribution of chemical shift, suggesting the presence of slightly distorted sites. Finally, over the whole temperature range, the presence of at least two tetrahedral aluminum sites was revealed, characterized by different values of the quadrupolar coupling constant.

  17. The Stoichiometry of Synthetic Alunite as a Function of Hydrothermal Aging Investigated by Solid-State NMR Spectroscopy, Powder X-ray Diffraction and Infrared Spectroscopy

    SciTech Connect

    Grube, Elisabeth; Nielsen, Ulla Gro

    2015-05-01

    The stoichiometry of a series of synthetic alunite [nominally KAl3(SO4)2(OH)6] samples prepared by hydrothermal methods as a function of reaction time (1–31 days) has been investigated by powder X-ray diffraction, Fourier transform infrared spectroscopy as well as solid-state 1H and 27Al magic 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.

  18. 23Na and 1H NMR Microimaging of Intact Plants

    NASA Astrophysics Data System (ADS)

    Olt, Silvia; Krötz, Eva; Komor, Ewald; Rokitta, Markus; Haase, Axel

    2000-06-01

    23Na NMR microimaging is described to map, for the first time, the sodium distribution in living plants. As an example, the response of 6-day-old seedlings of Ricinus communis to exposure to sodium chloride concentrations from 5 to 300 mM was observed in vivo using 23Na as well as 1H NMR microimaging. Experiments were performed at 11.75 T with a double resonant 23Na-1H probehead. The probehead was homebuilt and equipped with a climate chamber. T1 and T2 of 23Na were measured in the cross section of the hypocotyl. Within 85 min 23Na images with an in-plane resolution of 156 × 156 μm were acquired. With this spatial information, the different types of tissue in the hypocotyl can be discerned. The measurement time appears to be short compared to the time scale of sodium uptake and accumulation in the plant so that the kinetics of salt stress can be followed. In conclusion, 23Na NMR microimaging promises great potential for physiological studies of the consequences of salt stress on the macroscopic level and thus may become a unique tool for characterizing plants with respect to salt tolerance and salt sensitivity.

  19. 23Na and (1)H NMR microimaging of intact plants.

    PubMed

    Olt, S; Krötz, E; Komor, E; Rokitta, M; Haase, A

    2000-06-01

    (23)Na NMR microimaging is described to map, for the first time, the sodium distribution in living plants. As an example, the response of 6-day-old seedlings of Ricinus communis to exposure to sodium chloride concentrations from 5 to 300 mM was observed in vivo using (23)Na as well as (1)H NMR microimaging. Experiments were performed at 11.75 T with a double resonant (23)Na-(1)H probehead. The probehead was homebuilt and equipped with a climate chamber. T(1) and T(2) of (23)Na were measured in the cross section of the hypocotyl. Within 85 min (23)Na images with an in-plane resolution of 156 x 156 micrometer were acquired. With this spatial information, the different types of tissue in the hypocotyl can be discerned. The measurement time appears to be short compared to the time scale of sodium uptake and accumulation in the plant so that the kinetics of salt stress can be followed. In conclusion, (23)Na NMR microimaging promises great potential for physiological studies of the consequences of salt stress on the macroscopic level and thus may become a unique tool for characterizing plants with respect to salt tolerance and salt sensitivity.

  20. Synthesis, spectroscopic characterization, X-ray structure and DFT studies on 4-(2-hydroxyphenyl)-4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridin-5-ium chloride hydrate.

    PubMed

    Türkyılmaz, Murat; Özdemir, Namık; Baran, Yakup

    2011-11-01

    The title molecular salt, 4-(2-hydroxyphenyl)-4,5,6,7-tetrahydro-1H-imidazo[4,5-c]pyridin-5-ium chloride hydrate (C(12)H(14)N(3)O(+)·Cl-·H(2)O), was synthesized and characterized by IR-NMR spectroscopy and single-crystal X-ray diffraction. In addition to the molecular geometry from X-ray experiment, the molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) (1)H and (13)C NMR chemical shift values of the title compound in the ground state have been calculated using the density functional theory (DFT/B3LYP) method with the 6-31++G(d,p) and 6-311++G(d,p) basis sets, and compared with the experimental data. Besides, molecular electrostatic potential (MEP) distribution and non-linear optical properties of the title compound were investigated by theoretical calculations at the B3LYP/6-311++G(d,p) level.

  1. Characterization of the complex formation of 1,6-anhydro-β-maltose and potassium ions using NMR spectroscopy and single-crystal X-ray crystallography.

    PubMed

    Fujimoto, Takashi; Kato, Takayuki; Usui, Yosuke; Kamo, Osamu; Furihata, Kazuo; Tsubono, Koji; Kato, Toshiyo; Machinami, Tomoya; Tashiro, Mitsuru

    2011-09-27

    The formation of a complex between 1,6-anhydro-β-maltose and potassium ions was characterized using (1)H, (13)C and (39)K NMR spectroscopy and single-crystal X-ray crystallography. In the NMR study, the spin-lattice relaxation times (T(1)) of C1, C3, C5, C6, and C5' significantly decreased in the presence of potassium ions, and (39)K-T(1) also decreased in the presence of 1,6-anhydro-β-maltose, indicating complex formation. In a crystal, both 8- and 9-coordination structures, corresponding to the distorted capped pentagonal bipyramidal structure and the capped hexagonal bipyramidal structure, respectively, were identified. A potassium ion was positioned in the center of each bipyramidal structure.

  2. The 1H NMR Profile of Healthy Dog Cerebrospinal Fluid

    PubMed Central

    Musteata, Mihai; Nicolescu, Alina; Solcan, Gheorghe; Deleanu, Calin

    2013-01-01

    The availability of data for reference values in cerebrospinal fluid for healthy humans is limited due to obvious practical and ethical issues. The variability of reported values for metabolites in human cerebrospinal fluid is quite large. Dogs present great similarities with humans, including in cases of central nervous system pathologies. The paper presents the first study on healthy dog cerebrospinal fluid metabolomic profile using 1H NMR spectroscopy. A number of 13 metabolites have been identified and quantified from cerebrospinal fluid collected from a group of 10 mix breed healthy dogs. The biological variability as resulting from the relative standard deviation of the physiological concentrations of the identified metabolites had a mean of 18.20% (range between 9.3% and 44.8%). The reported concentrations for metabolites may be used as normal reference values. The homogeneity of the obtained results and the low biologic variability show that the 1H NMR analysis of the dog’s cerebrospinal fluid is reliable in designing and interpreting clinical and therapeutic trials in dogs with central nervous system pathologies. PMID:24376499

  3. Metabolomic insight into soy sauce through (1)H NMR spectroscopy.

    PubMed

    Ko, Bong-Kuk; Ahn, Hyuk-Jin; van den Berg, Frans; Lee, Cherl-Ho; Hong, Young-Shick

    2009-08-12

    Soy sauce, a well-known seasoning in Asia and throughout the world, consists of many metabolites that are produced during fermentation or aging and that have various health benefits. However, their comprehensive assessment has been limited due to targeted or instrumentally specific analysis. This paper presents for the first time a metabolic characterization of soy sauce, especially that aged up to 12 years, to obtain a global understanding of the metabolic variations through (1)H NMR spectroscopy coupled with multivariate pattern recognition techniques. Elevated amino acids and organic acids and the consumption of carbohydrate were associated with continuous involvement of microflora in aging for 12 years. In particular, continuous increases in the levels of betaine were found during aging for up to 12 years, demonstrating that microbial- or enzyme-related metabolites were also coupled with osmotolerant or halophilic bacteria present during aging. This work provides global insights into soy sauce through a (1)H NMR-based metabolomic approach that enhances the current understanding of the holistic metabolome and allows assessment of soy sauce quality.

  4. (1)H NMR spectra dataset and solid-state NMR data of cowpea (Vigna unguiculata).

    PubMed

    Alves Filho, Elenilson G; Silva, Lorena M A; Teofilo, Elizita M; Larsen, Flemming H; de Brito, Edy S

    2017-04-01

    In this article the NMR data from chemical shifts, coupling constants, and structures of all the characterized compounds were provided, beyond a complementary PCA evaluation for the corresponding manuscript (E.G. Alves Filho, L.M.A. Silva, E.M. Teofilo, F.H. Larsen, E.S. de Brito, 2017) [3]. In addition, a complementary assessment from solid-state NMR data was provided. For further chemometric analysis, numerical matrices from the raw (1)H NMR data were made available in Microsoft Excel workbook format (.xls).

  5. Molecular dynamics studies on the NMR and X-ray structures of rabbit prion proteins.

    PubMed

    Zhang, Jiapu; Zhang, Yuanli

    2014-02-07

    Prion diseases, traditionally referred to as transmissible spongiform encephalopathies (TSEs), are invariably fatal and highly infectious neurodegenerative diseases that affect a wide variety of mammalian species, manifesting as scrapie in sheep and goats, bovine spongiform encephalopathy (BSE or mad-cow disease) in cattle, chronic wasting disease in deer and elk, and Creutzfeldt-Jakob diseases, Gerstmann-Sträussler-Scheinker syndrome, fatal familial insomnia, and kulu in humans, etc. These neurodegenerative diseases are caused by the conversion from a soluble normal cellular prion protein (PrP(C)) into insoluble abnormally folded infectious prions (PrP(Sc)), and the conversion of PrP(C) to PrP(Sc) is believed to involve conformational change from a predominantly α-helical protein to one rich in β-sheet structure. Such a conformational change may be amenable to study by molecular dynamics (MD) techniques. For rabbits, classical studies show that they have a low susceptibility to be infected by PrP(Sc), but recently it was reported that rabbit prions can be generated through saPMCA (serial automated Protein Misfolding Cyclic Amplification) in vitro and the rabbit prion is infectious and transmissible. In this paper, we first do a detailed survey on the research advances of rabbit prion protein (RaPrP) and then we perform MD simulations on the NMR and X-ray molecular structures of rabbit prion protein wild-type and mutants. The survey shows to us that rabbits were not challenged directly in vivo with other known prion strains and the saPMCA result did not pass the test of the known BSE strain of cattle. Thus, we might still look rabbits as a prion resistant species. MD results indicate that the three α-helices of the wild-type are stable under the neutral pH environment (but under low pH environment the three α-helices have been unfolded into β-sheets), and the three α-helices of the mutants (I214V and S173N) are unfolded into rich β-sheet structures under

  6. Preparation of Pt-Tl clusters showing new geometries. X-ray, NMR and luminescence studies.

    PubMed

    Belío, Úrsula; Fuertes, Sara; Martín, Antonio

    2014-07-28

    Square planar complexes [Pt(CNC)L] (CNC = C,N,C-2,6-NC5H3(C6H4-2)2; L = tht (tetrahydrothiophene, SC4H8, 1), L = CN(t)Bu (2)) react with TlPF6 in different Pt/Tl molar ratios (3/1 in the case of 1 and 1/1 in the case of 2) yielding the complexes [{Pt(CNC)(tht)}3Tl](PF6) (3) and [Pt(CNC)(CN(t)Bu)Tl](PF6) (4), respectively. The structures of 3 and 4 (X-ray) show the presence of Pt→Tl dative bonds unsupported by any bridging ligands. In complex 3, the only Tl centre is simultaneously bonded to three Pt atoms forming a perfect equilateral triangle with Pt-Tl distances of 2.9088(5) Å, remarkably short. Complex 4 is formed by three "Pt(CNC)(CN(t)Bu)Tl" units, disposed in a triangular fashion, linked together through η(6)-Tl-arene interactions, and showing Pt-Tl bonds with distances of ca. 3.04 Å. The study of these crystal structures would seem to indicate that the difference between the Pt/Tl ratios found in the complexes 3 and 4 is due to the steric requirements of the L ligand bonded to Pt. NMR studies both in solution and in the solid state show that the Pt-Tl bond persists in solutions of 3 and 4. The UV-vis spectra of 3 and 4 in solution display the same profiles as those of 1 and 2, which may suggest a partial dissociation of the Pt-Tl bond in solution. However, by DFT calculations it was proved that in this case the formation of the Pt-Tl dative bond does not produce the expected blue-shift in the UV-vis absorptions. The emissive behaviour of 1-4 in the solid state and in frozen solutions is also studied and included in this work.

  7. Arrangement and mobility of water in vermiculite hydrates followed by 1H NMR spectroscopy.

    PubMed

    Sanz, J; Herrero, C P; Serratosa, J M

    2006-04-20

    The arrangement of water molecules in one- and two-layer hydrates of high-charged vermiculites, saturated with alkaline (Li(+), Na(+)) and alkali-earth (Mg(2+), Ca(2+), Ba(2+)) cations, has been analyzed with (1)H NMR spectroscopy. Two different orientations for water molecules have been found, depending on the hydration state and the sites occupied by interlayer cations. As the amount of water increases, hydrogen bond interactions between water molecules increase at expenses of water-silicate interactions. This interaction favors water mobility in vermiculites. A comparison of the temperature dependence of relaxation times T(1) and T(2) for one and two-layer hydrates of Na-vermiculite shows that the rotations of water molecules around C(2)-axes and that of cation hydration shells around the c-axis is favored in the two-layer hydrate. In both hydrates, the anisotropic diffusion of water takes place at room temperature, preserving the orientation of water molecules relative to the silicate layers. Information obtained by NMR spectroscopy is compatible with that deduced by infrared spectroscopy and with structural studies carried out with X-ray and neutron diffraction techniques on single-crystals of vermiculite.

  8. N-(4-Nitrobenzoyl)-N'-(1,5-dimethyl-3-oxo-2-phenyl-1H-3(2H)-pyrazolyl)-thiourea hydrate: Synthesis, spectroscopic characterization, X-ray structure and DFT studies

    NASA Astrophysics Data System (ADS)

    Arslan, N. Burcu; Kazak, Canan; Aydın, Fatma

    2012-04-01

    The title molecule (C19H17N5O4S·H2O) was synthesized and characterized by IR-NMR spectroscopy, MS and single-crystal X-ray diffraction. The molecular geometry, vibrational frequencies and gauge-independent atomic orbital (GIAO) 1H and 13C NMR chemical shift values of the compound in the ground state have been calculated by using the density functional theory (DFT) method with 6-31G(d) basis set, and compared with the experimental data. All the assignments of the theoretical frequencies were performed by potential energy distributions using VEDA 4 program. The calculated results show that the optimized geometries can well reproduce the crystal structural parameters, and the theoretical vibrational frequencies and 1H and 13C NMR chemical shift values show good agreement with experimental data. To determine conformational flexibility, the molecular energy profile of the title compound was obtained with respect to the selected torsion angle, which was varied from -180° to +180° in steps of 10°. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis and thermodynamic properties of the compound were investigated by theoretical calculations.

  9. Molecular structure of quinuclidine betaine hydrate studied by X-ray diffraction, DFT, FTIR, Raman, NMR methods

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.

    2009-03-01

    A new quinuclidine betaine (1-carboxymethyl-quinuclidinium inner salt), QNB, has been synthesized and characterized by X-ray diffraction, FTIR, NMR, and Raman spectra, and DFT calculations. QNB crystallized as monohydrate in monoclinic space group P2 1/n. Two water molecules link two QNB molecules into a cyclic system by two O-H···O hydrogen bonds of 2.731(1) and 2.760(1) Å. The optimized structure of (QNB·H 2O) 2 by the B3LYP/6-31G(d,p) method is more bent than in the crystal. The FTIR spectrum of the solid compound is consistent with the X-ray structure.

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

    NASA Astrophysics Data System (ADS)

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

    2014-04-01

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

  11. 1H NMR Metabolomics Analysis of Glioblastoma Subtypes

    PubMed Central

    Cuperlovic-Culf, Miroslava; Ferguson, Dean; Culf, Adrian; Morin, Pier; Touaibia, Mohamed

    2012-01-01

    Glioblastoma multiforme (GBM) is the most common form of malignant glioma, characterized by unpredictable clinical behaviors that suggest distinct molecular subtypes. With the tumor metabolic phenotype being one of the hallmarks of cancer, we have set upon to investigate whether GBMs show differences in their metabolic profiles. 1H NMR analysis was performed on metabolite extracts from a selection of nine glioblastoma cell lines. Analysis was performed directly on spectral data and on relative concentrations of metabolites obtained from spectra using a multivariate regression method developed in this work. Both qualitative and quantitative sample clustering have shown that cell lines can be divided into four groups for which the most significantly different metabolites have been determined. Analysis shows that some of the major cancer metabolic markers (such as choline, lactate, and glutamine) have significantly dissimilar concentrations in different GBM groups. The obtained lists of metabolic markers for subgroups were correlated with gene expression data for the same cell lines. Metabolic analysis generally agrees with gene expression measurements, and in several cases, we have shown in detail how the metabolic results can be correlated with the analysis of gene expression. Combined gene expression and metabolomics analysis have shown differential expression of transporters of metabolic markers in these cells as well as some of the major metabolic pathways leading to accumulation of metabolites. Obtained lists of marker metabolites can be leveraged for subtype determination in glioblastomas. PMID:22528487

  12. Protein secondary structure of Green Lynx spider dragline silk investigated by solid-state NMR and X-ray diffraction

    PubMed Central

    Xu, Dian; Shi, Xiangyan; Thompson, Forrest; Weber, Warner S.; Mou, Qiushi; Yarger, Jeffery L

    2016-01-01

    In this study, the secondary structure of the major ampullate silk from Peucetia viridans (Green Lynx) spiders is characterized by X-ray diffraction and solid-state NMR spectroscopy. From X-ray diffraction measurement, β-sheet nanocrystallites were observed and found to be highly oriented along the fiber axis, with an orientational order, fc ≈ 0.98. The size of the nanocrystallites was determined to be on average 2.5 nm × 3.3 nm × 3.8 nm. Besides a prominent nanocrystalline region, a partially oriented amorphous region was also observed with an fa ≈ 0.89. Two-dimensional 13C–13C through-space and through-bond solid-state NMR experiments were employed to elucidate structure details of P. viridans silk proteins. It reveals that β-sheet nanocrystallites constitutes 40.0 ± 1.2% of the protein and are dominated by alanine-rich repetitive motifs. Furthermore, based upon the NMR data, 18 ± 1% of alanine, 60 ± 2% glycine and 54 ± 2% serine are incorporated into helical conformations. PMID:26226457

  13. Insights into RNA structure and dynamics from recent NMR and X-ray studies of the Neurospora Varkud satellite ribozyme.

    PubMed

    Dagenais, Pierre; Girard, Nicolas; Bonneau, Eric; Legault, Pascale

    2017-04-06

    Despite the large number of noncoding RNAs and their importance in several biological processes, our understanding of RNA structure and dynamics at atomic resolution is still very limited. Like many other RNAs, the Neurospora Varkud satellite (VS) ribozyme performs its functions through dynamic exchange of multiple conformational states. More specifically, the VS ribozyme recognizes and cleaves its stem-loop substrate via a mechanism that involves several structural transitions within its stem-loop substrate. The recent publications of high-resolution structures of the VS ribozyme, obtained by NMR spectroscopy and X-ray crystallography, offer an opportunity to integrate the data and closely examine the structural and dynamic properties of this model RNA system. Notably, these investigations provide a valuable example of the divide-and-conquer strategy for structural and dynamic characterization of a large RNA, based on NMR structures of several individual subdomains. The success of this divide-and-conquer approach reflects the modularity of RNA architecture and the great care taken in identifying the independently-folding modules. Together with previous biochemical and biophysical characterizations, the recent NMR and X-ray studies provide a coherent picture into how the VS ribozyme recognizes its stem-loop substrate. Such in-depth characterization of this RNA enzyme will serve as a model for future structural and engineering studies of dynamic RNAs and may be particularly useful in planning divide-and-conquer investigations. For further resources related to this article, please visit the WIREs website.

  14. Synthesis, X-ray diffraction structures, spectroscopic properties, and in vitro antitumor activity of isomeric (1H-1,2,4-triazole)Ru(III) complexes.

    PubMed

    Arion, Vladimir B; Reisner, Erwin; Fremuth, Madeleine; Jakupec, Michael A; Keppler, Bernhard K; Kukushkin, Vadim Yu; Pombeiro, Armando J L

    2003-09-22

    Three ruthenium(III) complexes containing 1H-1,2,4-triazole (Htrz), viz., (H(2)trz)[cis-RuCl(4)(Htrz)(2)], 1, (H(2)trz)[trans-RuCl(4)(Htrz)(2)], 2, and (Ph(3)PCH(2)Ph)[trans-RuCl(4)(Htrz)(2)], 3, have been synthesized by reaction between RuCl(3) and excess of the triazole in 2.38 M HCl (1 and 2), while 3 was obtained by metathesis of 2 and [Ph(3)PCH(2)Ph]Cl in water. The products were characterized by IR, UV-vis, electrospray mass spectrometry, cyclic voltammetry, and X-ray crystallography (1 and 3). X-ray diffraction study revealed cis and trans arrangements of the triazole ligands in 1 and 3, correspondingly, and unprecedented monodentate coordination of the triazole through N2 and stabilization of its 4H tautomeric form, which is the disfavored one for the free triazole. The cytotoxicity of 1 and 2 has been assayed in three human carcinoma cell lines SW480, HT29 (colon carcinoma), and SK-BR-3 (mammary carcinoma). Both compounds exhibit antiproliferative activity in vitro. Time-dependent response of all three lines to 1 and 2 and a structure-activity relationship, i.e., higher activity of the trans-isomer 2 than that of cis-species 1, have been observed.

  15. Continuous Flow 1H and 13C NMR Spectroscopy in Microfluidic Stripline NMR Chips

    PubMed Central

    2017-01-01

    Microfluidic stripline NMR technology not only allows for NMR experiments to be performed on small sample volumes in the submicroliter range, but also experiments can easily be performed in continuous flow because of the stripline’s favorable geometry. In this study we demonstrate the possibility of dual-channel operation of a microfluidic stripline NMR setup showing one- and two-dimensional 1H, 13C and heteronuclear NMR experiments under continuous flow. We performed experiments on ethyl crotonate and menthol, using three different types of NMR chips aiming for straightforward microfluidic connectivity. The detection volumes are approximately 150 and 250 nL, while flow rates ranging from 0.5 μL/min to 15 μL/min have been employed. We show that in continuous flow the pulse delay is determined by the replenishment time of the detector volume, if the sample trajectory in the magnet toward NMR detector is long enough to polarize the spin systems. This can considerably speed up quantitative measurement of samples needing signal averaging. So it can be beneficial to perform continuous flow measurements in this setup for analysis of, e.g., reactive, unstable, or mass-limited compounds. PMID:28194934

  16. Continuous Flow (1)H and (13)C NMR Spectroscopy in Microfluidic Stripline NMR Chips.

    PubMed

    Oosthoek-de Vries, Anna Jo; Bart, Jacob; Tiggelaar, Roald M; Janssen, Johannes W G; van Bentum, P Jan M; Gardeniers, Han J G E; Kentgens, Arno P M

    2017-02-21

    Microfluidic stripline NMR technology not only allows for NMR experiments to be performed on small sample volumes in the submicroliter range, but also experiments can easily be performed in continuous flow because of the stripline's favorable geometry. In this study we demonstrate the possibility of dual-channel operation of a microfluidic stripline NMR setup showing one- and two-dimensional (1)H, (13)C and heteronuclear NMR experiments under continuous flow. We performed experiments on ethyl crotonate and menthol, using three different types of NMR chips aiming for straightforward microfluidic connectivity. The detection volumes are approximately 150 and 250 nL, while flow rates ranging from 0.5 μL/min to 15 μL/min have been employed. We show that in continuous flow the pulse delay is determined by the replenishment time of the detector volume, if the sample trajectory in the magnet toward NMR detector is long enough to polarize the spin systems. This can considerably speed up quantitative measurement of samples needing signal averaging. So it can be beneficial to perform continuous flow measurements in this setup for analysis of, e.g., reactive, unstable, or mass-limited compounds.

  17. Structural investigations of PuIII phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

    NASA Astrophysics Data System (ADS)

    Popa, Karin; Raison, Philippe E.; Martel, Laura; Martin, Philippe M.; Prieur, Damien; Solari, Pier L.; Bouëxière, Daniel; Konings, Rudy J. M.; Somers, Joseph

    2015-10-01

    PuPO4 was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β- decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state 31P NMR agrees with the XANES results and the presence of a solid-solution.

  18. Molecular structure of 4-hidroxy-3-(3-methyl-2-butenyl) acetophenone, a plant antifungal, by X-ray diffraction, DFT calculation, and NMR and FTIR spectroscopy

    NASA Astrophysics Data System (ADS)

    Piro, Oscar Enrique; Echeverría, Gustavo Alberto; Lizarraga, Emilio; Romano, Elida; Catalán, César Atilio Nazareno; Brandán, Silvia Antonia

    2013-01-01

    The molecular structure of two mixed and closely related conformers of the title compound, C13H16O2, found in the solid with unequal occupancies has been determined by X-ray diffraction methods. The substance crystallizes in the monoclinic Pca21 space group with a = 17.279(2), b = 5.1716(7), c = 12.549(2) Å, and Z = 4 molecules per unit cell. The structure was solved from 1314 reflections with I > 2σ(I) and refined to an agreement R1-factor of 0.049. The minor conformer (34.7%) is nearly mirror-related to and extensively overlapped with the major one. The skeleton of the 4-hydroxyacetophenone molecular fragment and the prenyl group, sbnd (CH2)sbnd (CH)dbnd C(CH3)2, pendant arm attached to it are both planar and perpendicular to each other. A strong intermolecular Osbnd H⋯O bond links neighboring molecules in the lattice to produce a polymeric structure. The conformational structures of the compound in the gas phase have been calculated by the DFT method and the geometrical results have been compared with the X-ray data. These data allow a complete assignment of vibration modes in the solid state FTIR and Raman spectra. The calculated 1H and 13C chemicals shifts are in good agreement with the corresponding experimental NMR spectra of the compound in solution.

  19. Conformation analysis of aspartame-based sweeteners by NMR spectroscopy, molecular dynamics simulations, and X-ray diffraction studies.

    PubMed

    De Capua, Antonia; Goodman, Murray; Amino, Yusuke; Saviano, Michele; Benedetti, Ettore

    2006-02-01

    We report here the synthesis and the conformation analysis by 1H NMR spectroscopy and computer simulations of six potent sweet molecules, N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-S-tert-butyl-L-cysteine 1-methylester (1; 70 000 times more potent than sucrose), N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-beta-cyclohexyl-L-alanine 1-methylester (2; 50 000 times more potent than sucrose), N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-4-cyan-L-phenylalanine 1-methylester (3; 2 000 times more potent than sucrose), N-[3,3-dimethylbutyl]-alpha-L-aspartyl-(1R,2S,4S)-1-methyl-2-hydroxy-4-phenylhexylamide (4; 5500 times more potent than sucrose), N-[3-(3-hydroxy-4-methoxyphenyl)propyl]-alpha-L-aspartyl-(1R,2S,4S)-1-methyl-2-hydroxy-4-phenylhexylamide (5; 15 000 times more potent than sucrose), and N-[3-(3-hydroxy-4-methoxyphenyl)-3-methylbutyl]-alpha-L-aspartyl-(1R,2S,4S)-1-methyl-2-hydroxy-4-phenylhexylamide (6; 15 000 times more potent than sucrose). The "L-shaped" structure, which we believe to be responsible for sweet taste, is accessible to all six molecules in solution. This structure is characterized by a zwitterionic ring formed by the AH- and B-containing moieties located along the +y axis and by the hydrophobic group X pointing into the +x axis. Extended conformations with the AH- and B-containing moieties along the +y axis and the hydrophobic group X pointing into the -y axis were observed for all six sweeteners. For compound 5, the crystal-state conformation was also determined by an X-ray diffraction study. The result indicates that compound 5 adopts an L-shaped structure even in the crystalline state. The extraordinary potency of the N-arylalkylated or N-alkylated compounds 1-6, as compared with that of the unsubstituted aspartame-based sweet taste ligands, can be explained by the effect of a second hydrophobic binding domain in addition to interactions arising from the L-shaped structure. In our

  20. Structural investigations of Pu{sup III} phosphate by X-ray diffraction, MAS-NMR and XANES spectroscopy

    SciTech Connect

    Popa, Karin; Raison, Philippe E.; Martel, Laura; Martin, Philippe M.; Solari, Pier L.; Bouëxière, Daniel; Konings, Rudy J.M.; Somers, Joseph

    2015-10-15

    PuPO{sub 4} was prepared by a solid state reaction method and its crystal structure at room temperature was solved by powder X-ray diffraction combined with Rietveld refinement. High resolution XANES measurements confirm the +III valence state of plutonium, in agreement with valence bond derivation. The presence of the americium (as β{sup −} decay product of plutonium) in the +III oxidation state was determined based on XANES spectroscopy. High resolution solid state {sup 31}P NMR agrees with the XANES results and the presence of a solid-solution. - Graphical abstract: A full structural analysis of PuPO{sub 4} based on Rietveld analysis of room temperature X-ray diffraction data, XANES and MAS NMR measurements was performed. - Highlights: • The crystal structure of PuPO{sub 4} monazite is solved. • In PuPO{sub 4} plutonium is strictly trivalent. • The presence of a minute amount of Am{sup III} is highlighted. • We propose PuPO{sub 4} as a potential reference material for spectroscopic and microscopic studies.

  1. Synthesis, X-ray crystal structure and optical properties of novel 5-(3-aryl-1 H-pyrazol-5-yl)-2-(6-methoxy-3-methylbenzofuran-2-yl)-1,3,4-oxadiazole

    NASA Astrophysics Data System (ADS)

    Jiang, Zhen-Ju; Liu, Jin-Ting; Lv, Hong-Shui; Zhao, Bao-Xiang

    2012-02-01

    A series of novel 5-(3-aryl-1 H-pyrazol-5-yl)-2-(6-methoxy-3-methylbenzofuran-2-yl)-1,3,4-oxadiazole derivatives has been synthesized from 6-methoxy-3-methylbenzofuran-2-carboxylic acid and ethyl 3-aryl-1 H-pyrazole-5-carboxylate. The structures of compounds obtained were determined by IR, 1H NMR and HRMS spectra. Typically, the spatial structure of compound 7e was determined by using X-ray diffraction analysis. UV-vis absorption and fluorescence spectral characteristics of the compounds in dichloromethane and acetonitrile were investigated. The results showed that the absorption maxima of the compounds vary from 321 to 339 nm depending on the substituents in N-1 position of pyrazole moiety and para position of benzene moiety. The maximum emission spectra of compounds in two different solvents were mainly dependent on groups in N-1 position of pyrazole moiety. The intensity of absorption and fluorescence was also correlated with substituents on the aryl ring bonded to pyrazole moiety. In addition, the absorption and emission spectra of these compounds change with increasing solvent polarity.

  2. Simultaneous use of solution NMR and X-ray data in REFMAC5 for joint refinement/detection of structural differences

    SciTech Connect

    Rinaldelli, Mauro; Ravera, Enrico; Calderone, Vito; Parigi, Giacomo; Murshudov, Garib N.; Luchinat, Claudio

    2014-04-01

    Paramagnetic NMR data (pseudocontact shifts and self-orientation residual dipolar couplings) and diamagnetic residual dipolar couplings can now be used in the program REFMAC5 from CCP4 as structural restraints together with X-ray crystallographic data. These NMR restraints can reveal differences between solid state and solution conformations of molecules or, in their absence, can be used together with X-ray crystallographic data for structural refinement. The program REFMAC5 from CCP4 was modified to allow the simultaneous use of X-ray crystallographic data and paramagnetic NMR data (pseudocontact shifts and self-orientation residual dipolar couplings) and/or diamagnetic residual dipolar couplings. Incorporation of these long-range NMR restraints in REFMAC5 can reveal differences between solid-state and solution conformations of molecules or, in their absence, can be used together with X-ray crystallographic data for structural refinement. Since NMR and X-ray data are complementary, when a single structure is consistent with both sets of data and still maintains reasonably ‘ideal’ geometries, the reliability of the derived atomic model is expected to increase. The program was tested on five different proteins: the catalytic domain of matrix metalloproteinase 1, GB3, ubiquitin, free calmodulin and calmodulin complexed with a peptide. In some cases the joint refinement produced a single model consistent with both sets of observations, while in other cases it indicated, outside the experimental uncertainty, the presence of different protein conformations in solution and in the solid state.

  3. Complete assignment of NMR data of 22 phenyl-1H-pyrazoles' derivatives.

    PubMed

    de Oliveira, Aline Lima; Alves de Oliveira, Carlos Henrique; Mairink, Laura Maia; Pazini, Francine; Menegatti, Ricardo; Lião, Luciano Morais

    2011-08-01

    Complete assignment of (1)H and (13)C NMR chemical shifts and J((1)H/(1)H and (1)H/(19)F) coupling constants for 22 1-phenyl-1H-pyrazoles' derivates were performed using the concerted application of (1)H 1D and (1)H, (13)C 2D gs-HSQC and gs-HMBC experiments. All 1-phenyl-1H-pyrazoles' derivatives were synthesized as described by Finar and co-workers. The formylated 1-phenyl-1H-pyrazoles' derivatives were performed under Duff's conditions.

  4. X-ray, NMR, and Mutational Studies of the Catalytic Cycle of the GDP-Mannose Mannosyl Hydrolase Reaction

    SciTech Connect

    Gabelli,S.; Azurmendi, H.; Bianchet, M.; Amzel, L.; Mildva, A.

    2006-01-01

    GDP-mannose hydrolase catalyzes the hydrolysis with inversion of GDP-{alpha}-D-hexose to GDP and {beta}-D-hexose by nucleophilic substitution by water at C1 of the sugar. Two new crystal structures (free enzyme and enzyme-substrate complex), NMR, and site-directed mutagenesis data, combined with the structure of the enzyme-product complex reported earlier, suggest a four-stage catalytic cycle. An important loop (L6, residues 119-125) contains a ligand to the essential Mg{sup 2+} (Gln-123), the catalytic base (His-124), and three anionic residues. This loop is not ordered in the X-ray structure of the free enzyme due to dynamic disorder, as indicated by the two-dimensional 1H-15N HMQC spectrum, which shows selective exchange broadening of the imidazole nitrogen resonances of His-124 (k{sub ex} = 6.6 x 10{sup 4} s{sup -1}). The structure of the enzyme-Mg{sup 2+}-GDP-mannose substrate complex of the less active Y103F mutant shows loop L6 in an open conformation, while the structure of the enzyme-Mg{sup 2+}-GDP product complex showed loop L6 in a closed, 'active' conformation. 1H-15N HMQC spectra show the imidazole N of His-124 to be unprotonated, appropriate for general base catalysis. Substituting Mg{sup 2+} with the more electrophilic metal ions Mn{sup 2+} or Co{sup 2+} decreases the pK{sub a} in the pH versus k{sub cat} rate profiles, showing that deprotonation of a metal-bound water is partially rate-limiting. The H124Q mutation, which decreases k{sub cat} 103.4-fold and largely abolishes its pH dependence, is rescued by the Y103F mutation, which increases k{sub cat} 23-fold and restores its pH dependence. The structural basis of the rescue is the fact that the Y103F mutation shifts the conformational equilibrium to the open form moving loop L6 out of the active site, thus permitting direct access of the specific base hydroxide from the solvent. In the proposed dissociative transition state, which occurs in the closed, active conformation of the enzyme, the

  5. Rapid global structure determination of large RNA and RNA complexes using NMR and small-angle X-ray scattering

    PubMed Central

    Wang, Yun-Xing; Zuo, Xiaobing; Wang, Jinbu; Yu, Ping; Butcher, Samuel E.

    2013-01-01

    Among the greatest advances in biology today are the discoveries of various roles played by RNA in biological processes. However, despite significant advances in RNA structure determination using X-ray crystallography [1] and solution NMR [2–4], the number of bona fide RNA structures is very limited, in comparison with the growing number of known functional RNAs. This is because of great difficulty in growing crystals or/and obtaining phase information, and severe size constraints on structure determination by solution NMR spectroscopy. Clearly, there is an acute need for new methodologies for RNA structure determination. The prevailing approach for structure determination of RNA in solution is a “bottom-up” approach that was basically transplanted from the approach used for determining protein structures, despite vast differences in both structural features and chemical compositions between these two types of biomacromolecules. In this chapter, we describe a new method, which has been reported recently, for rapid global structure determination of RNAs using solution-based NMR spectroscopy and small-angle X-ray scattering. The method treats duplexes as major building blocks of RNA structures. By determining the global orientations of the duplexes and the overall shape, the global structure of an RNA can be constructed and further regularized using Xplor-NIH. The utility of the method was demonstrated in global structure determination of two RNAs, a 71-nt and 102-nt RNAs with an estimated backbone RMSD ~3.0 Å. The global structure opens door to high-resolution structure determination in solution. PMID:20554045

  6. Water Structure and Dynamics in Smectites: X-ray Diffraction and 2 H NMR Spectroscopy of Mg–, Ca–, Sr–, Na–, Cs–, and Pb–Hectorite

    SciTech Connect

    Reddy, U. Venkateswara; Bowers, Geoffrey M.; Loganathan, Narasimhan; Bowden, Mark; Yazaydin, A. Ozgur; Kirkpatrick, R. James

    2016-04-06

    Variable-temperature X-ray diffraction and 2H NMR spectroscopy of the smectite mineral, hectorite, containing interlayer Na+, K+, Cs+, Mg2+, Ca2+, Sr2+, and Pb2+ equilibrated at 43% relative humidity (RH) and mixed with 2H2O to form a paste provide a comprehensive picture of the structural environments and dynamics of interlayer 2H2O and the relationships of these properties to interlayer hydration state, the hydration energy and polarizability of the cation, temperature, and the formation of ice-1h in the interparticle pores. The variation in basal spacing shown by the XRD data correlates well with the 2H NMR behavior, and the XRD data show for the first time in hectorites that crystallization of interparticle ice-1h causes a decrease in the interlayer spacing, likely due to removal of interlayer 2H2O. The variation of the 2H NMR behavior of all the samples with decreasing temperature reflects decreasing frequencies of motion for the rotation of the 2H2O molecules around their dipoles, reorientation of the 2H2O molecules, and exchange of the 2H2O molecules between interlayer sites coordinated to and not coordinated to the cations.

  7. Novel phthalocyaninatobis(alkylcarboxylato)silicon(IV) compounds: NMR data and X-ray structures to study the spacing provided by long hydrocarbon tails that enhance their solubility.

    PubMed

    Sosa-Sánchez, Jose L; Sosa-Sánchez, Arturo; Farfán, Norberto; Zamudio-Rivera, Luis S; López-Mendoza, Gerson; Pérez Flores, Javier; Beltrán, Hiram I

    2005-07-04

    The reaction between trans-PcSiCl2 (1) and the potassium salts of six fatty acids (2 a-2 f) led to the trans-PcSi[OOC(CH2)nCH3]2 compounds (3 a-3 f), which were characterised by elemental analysis, IR, UV/Vis and 1H, 13C, and 29Si NMR spectroscopy. From a detailed study of the NMR spectra, the strong anisotropic currents of the Pc macrocycle were found to have an effect on up to the sixth methylenic group. As expected, the length of the hydrocarbon tail does not affect the chemical shift of the 29Si nucleus of any of the compounds, appearing at around -222.6. The structures of PcSi[OOC(CH2)nCH3]2, where n = 7, 10, 12, 13 and 20, were determined by X-ray crystallography. All the compounds were found to be triclinic with a P1 space group. In all cases the observed crystallographic pseudosymmetry is Ci and the asymmetric unit consists of half a molecule. The silicon atom is at the centre of a distorted octahedron and hence its coordination number is six. The carboxylate fragments are in a trans configuration with respect to the Pc macrocycle. The supramolecular structures are discussed in detail herein. The correlation between the 1H NMR chemical shifts and the position of the corresponding carbon atoms in the hydrocarbon tail reveals that the dicarboxylate substituents exhibit a spacer-like behaviour that enhances the solubility. A detailed study of the tail variable allowed us to evaluate the loss of radial shielding along the Pc2- ligand.

  8. Derivatives of pyrazinecarboxylic acid: 1H, 13C and 15N NMR spectroscopic investigations.

    PubMed

    Holzer, Wolfgang; Eller, Gernot A; Datterl, Barbara; Habicht, Daniela

    2009-07-01

    NMR spectroscopic studies are undertaken with derivatives of 2-pyrazinecarboxylic acid. Complete and unambiguous assignment of chemical shifts ((1)H, (13)C, (15)N) and coupling constants ((1)H,(1)H; (13)C,(1)H; (15)N,(1)H) is achieved by combined application of various 1D and 2D NMR spectroscopic techniques. Unequivocal mapping of (13)C,(1)H spin coupling constants is accomplished by 2D (delta,J) long-range INEPT spectra with selective excitation. Phenomena such as the tautomerism of 3-hydroxy-2-pyrazinecarboxylic acid are discussed.

  9. Reliability of ^1^H NMR analysis for assessment of lipid oxidation at frying temperatures

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The reliability of a method using ^1^H NMR analysis for assessment of oil oxidation at a frying temperature was examined. During heating and frying at 180 °C, changes of soybean oil signals in the ^1^H NMR spectrum including olefinic (5.16-5.30 ppm), bisallylic (2.70-2.88 ppm), and allylic (1.94-2.1...

  10. Hydrogen bonding and molecular association in 2-(quinuclidinium)-butyric acid bromide hydrate studied by X-ray diffraction, DFT calculations, FTIR and NMR spectroscopy, and potentiometric titration

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.; Barczyński, P.

    2010-06-01

    The structure of 2-(quinuclidinium)-butyric acid bromide hydrate (QNBu·H 2O·HBr, 3) has been determined by X-ray diffraction, DFT calculations and characterized by FTIR and NMR spectroscopy. Crystals of 3 are monoclinic, space group P2 1. The water molecule interacts with the carboxylic group of 2-(quinuclidinium)-butyric acid and with the bromide anion by the COOH⋯OH 2 and HOH⋯Br hydrogen bonds of 2.575(3) and 3.293(2) Å, respectively. The structures of monomer ( 4) and dimeric cation ( 5) of the title complex have been optimized by the B3LYP/6-31G(d,p) approach, yielding conformations consistent with this in the crystal. The solid-state FTIR spectra of 3 and its deuterated analogue have been measured and compared with the theoretical spectrum of 4. The assignments of the observed and predicted bands have been proposed. The molecule of 3 has a chiral center at the C(9) atom, which is responsible for the non-magnetically equivalence of the α-ring and C(11)H 2 methylene protons in 1H NMR spectrum. The values of p Ka of quinuclidinium-acetate (quinuclidine betaine), 2-(quinuclidinium)-propionate and 2-(quinuclidinium)-butyrate have been determined by the potentiometric titration of their hydrohalides.

  11. Molecular structure of actein: 13C CPMAS NMR, IR, X-ray diffraction studies and theoretical DFT-GIAO calculations

    NASA Astrophysics Data System (ADS)

    Jamróz, Marta K.; Bąk, Joanna; Gliński, Jan A.; Koczorowska, Agnieszka; Wawer, Iwona

    2009-09-01

    Actein is a prominent triterpene glycoside occurring in Actaea racemosa. The triterpene glycosides are believed to be responsible for the estrogenic activity of an extract prepared from this herb. We determined in the crystal structure of actein by X-ray crystallography to be monoclinic P2(1) chiral space group. Refining the disorder, we determined 70% and 30% of contributions of ( S)- and ( R)-actein, respectively. The IR and Raman spectra suggest that actein forms at least four different types of hydrogen bonds. The 13C NMR spectra of actein were recorded both in solution and solid state. The 13C CPMAS spectrum of actein displays multiplet signals, in agreement with the crystallographic data. The NMR shielding constants were calculated for actein using GIAO approach and a variety of basis sets: 6-31G**, 6-311G**, 6-31+G**, cc-pVDZ, cc-pVDZ-su1 and 6-31G**-su1, as well as IGLO approach combined with the IGLO II basis set. The best results (RMSD of 1.6 ppm and maximum error of 3.4 ppm) were obtained with the 6-31G**-su1 basis set. The calculations of the shielding constants are helpful in the interpretation of the 13C CPMAS NMR spectra of actein and actein's analogues.

  12. IR, 1H NMR, mass, XRD and TGA/DTA investigations on the ciprofloxacin/iodine charge-transfer complex

    NASA Astrophysics Data System (ADS)

    Refat, Moamen S.; El-Hawary, W. F.; Moussa, Mohamed A. A.

    2011-05-01

    The charge-transfer complex (CTC) of ciprofloxacin drug (CIP) as a donor with iodine (I 2) as a sigma acceptor has been studied spectrophotometrically in CHCl 3. At maximum absorption bands, the stoichiometry of CIP:iodine system was found to be 1:1 ratio according to molar ratio method. The essential spectroscopic data like formation constant ( KCT), molar extinction coefficient ( ɛCT), standard free energy (Δ G°), oscillator strength ( f), transition dipole moment ( μ), resonance energy ( RN) and ionization potential ( ID) were estimated. The spectroscopic techniques such as IR, 1H NMR, mass and UV-vis spectra and elemental analyses (CHN) as well as TG-DTG and DTA investigations were used to characterize the chelating behavior of CIP/iodine charge-transfer complex. The iodine CT interaction was associated with a presence of intermolecular hydrogen bond. The X-ray investigation was carried out to investigate the iodine doping in the synthetic CT complex.

  13. Analysis of Cytochrome P450 CYP119 Ligand-dependent Conformational Dynamics by Two-dimensional NMR and X-ray Crystallography

    SciTech Connect

    Basudhar, Debashree; Madrona, Yarrow; Kandel, Sylvie; Lampe, Jed N.; Nishida, Clinton R.; de Montellano, Paul R. Ortiz

    2015-02-10

    Defining the conformational states of cytochrome P450 active sites is critical for the design of agents that minimize drug-drug interactions, the development of isoform-specific P450 inhibitors, and the engineering of novel oxidative catalysts. In this paper, we used two-dimensional 1H,15N HSQC chemical shift perturbation mapping of 15N-labeled Phe residues and x-ray crystallography to examine the ligand-dependent conformational dynamics of CYP119. Active site Phe residues were most affected by the binding of azole inhibitors and fatty acid substrates, in agreement with active site localization of the conformational changes. This was supported by crystallography, which revealed movement of the F-G loop with various azoles. Nevertheless, the NMR chemical shift perturbations caused by azoles and substrates were distinguishable. The absence of significant chemical shift perturbations with several azoles revealed binding of ligands to an open conformation similar to that of the ligand-free state. In contrast, 4-phenylimidazole caused pronounced NMR changes involving Phe-87, Phe-144, and Phe-153 that support the closed conformation found in the crystal structure. The same closed conformation is observed by NMR and crystallography with a para-fluoro substituent on the 4-phenylimidazole, but a para-chloro or bromo substituent engendered a second closed conformation. An open conformation is thus favored in solution with many azole ligands, but para-substituted phenylimidazoles give rise to two closed conformations that depend on the size of the para-substituent. Finally, the results suggest that ligands selectively stabilize discrete cytochrome P450 conformational states.

  14. Analysis of Cytochrome P450 CYP119 Ligand-dependent Conformational Dynamics by Two-dimensional NMR and X-ray Crystallography

    DOE PAGES

    Basudhar, Debashree; Madrona, Yarrow; Kandel, Sylvie; ...

    2015-02-10

    Defining the conformational states of cytochrome P450 active sites is critical for the design of agents that minimize drug-drug interactions, the development of isoform-specific P450 inhibitors, and the engineering of novel oxidative catalysts. In this paper, we used two-dimensional 1H,15N HSQC chemical shift perturbation mapping of 15N-labeled Phe residues and x-ray crystallography to examine the ligand-dependent conformational dynamics of CYP119. Active site Phe residues were most affected by the binding of azole inhibitors and fatty acid substrates, in agreement with active site localization of the conformational changes. This was supported by crystallography, which revealed movement of the F-G loop withmore » various azoles. Nevertheless, the NMR chemical shift perturbations caused by azoles and substrates were distinguishable. The absence of significant chemical shift perturbations with several azoles revealed binding of ligands to an open conformation similar to that of the ligand-free state. In contrast, 4-phenylimidazole caused pronounced NMR changes involving Phe-87, Phe-144, and Phe-153 that support the closed conformation found in the crystal structure. The same closed conformation is observed by NMR and crystallography with a para-fluoro substituent on the 4-phenylimidazole, but a para-chloro or bromo substituent engendered a second closed conformation. An open conformation is thus favored in solution with many azole ligands, but para-substituted phenylimidazoles give rise to two closed conformations that depend on the size of the para-substituent. Finally, the results suggest that ligands selectively stabilize discrete cytochrome P450 conformational states.« less

  15. Analysis of Cytochrome P450 CYP119 Ligand-dependent Conformational Dynamics by Two-dimensional NMR and X-ray Crystallography*

    PubMed Central

    Basudhar, Debashree; Madrona, Yarrow; Kandel, Sylvie; Lampe, Jed N.; Nishida, Clinton R.; de Montellano, Paul R. Ortiz

    2015-01-01

    Defining the conformational states of cytochrome P450 active sites is critical for the design of agents that minimize drug-drug interactions, the development of isoform-specific P450 inhibitors, and the engineering of novel oxidative catalysts. We used two-dimensional 1H,15N HSQC chemical shift perturbation mapping of 15N-labeled Phe residues and x-ray crystallography to examine the ligand-dependent conformational dynamics of CYP119. Active site Phe residues were most affected by the binding of azole inhibitors and fatty acid substrates, in agreement with active site localization of the conformational changes. This was supported by crystallography, which revealed movement of the F-G loop with various azoles. Nevertheless, the NMR chemical shift perturbations caused by azoles and substrates were distinguishable. The absence of significant chemical shift perturbations with several azoles revealed binding of ligands to an open conformation similar to that of the ligand-free state. In contrast, 4-phenylimidazole caused pronounced NMR changes involving Phe-87, Phe-144, and Phe-153 that support the closed conformation found in the crystal structure. The same closed conformation is observed by NMR and crystallography with a para-fluoro substituent on the 4-phenylimidazole, but a para-chloro or bromo substituent engendered a second closed conformation. An open conformation is thus favored in solution with many azole ligands, but para-substituted phenylimidazoles give rise to two closed conformations that depend on the size of the para-substituent. The results suggest that ligands selectively stabilize discrete cytochrome P450 conformational states. PMID:25670859

  16. A new salen base 5-(phenylazo)-N-(2-amino pyridine) salicyliden Schiff base ligand: synthesis, experimental and density functional studies on its crystal structure, FTIR, 1H NMR and 13C NMR spectra.

    PubMed

    Sheikhshoaie, Iran; Saheb, Vahid

    2010-12-01

    A novel Schiff base ligand 5-(phenylazo)-N-(2-amino pyridine) salicyliden is prepared through the condensation of 5-(phenylazo) salicylaldehyde and 2-amino pyridine in methanol at room temperature. The orange crystalline precipitate is used for X-ray crystallography and measuring Fourier transform (FTIR), 1H NMR and 13C NMR spectra. Density functional theory (DFT) calculations at the B3LYP, MPWB1K and B3PW91 levels of theory is used to optimize the geometry and calculate the FTIR, 1H NMR and 13C NMR spectra of the compound. The vibrational frequencies determined experimentally are compared with those obtained theoretically and a vibrational assignment and analysis of the fundamental modes of the compound is performed. We found that the MPWB1K method predicts low vibrational frequencies better than the commonly used B3LYP method. Although the B3PW91 method overestimates the 1H NMR chemical shifts, the values computed at the B3LYP level of theory are in accordance with experimental 1H NMR spectrum. However, both B3LYP and B3PW91 methods tend to overestimate 13C NMR chemical shifts. In addition, a few quantum descriptors of the molecule are calculated and conformational analysis is performed and the result was compared with crystallographic data.

  17. 1H NMR investigation of thermally triggered insulin release from poly(N-isopropylacrylamide) microgels.

    PubMed

    Nolan, Christine M; Gelbaum, Leslie T; Lyon, L Andrew

    2006-10-01

    We describe investigations of insulin release from thermoresponsive microgels using variable temperature (1)H NMR. Microgel particles composed of poly(N-isopropylacrylamide) were loaded with the peptide via a swelling technique, and this method was compared to simple equilibrium partitioning. Variable temperature (1)H NMR studies suggest that the swelling loading method results in enhanced entrapment of the peptide versus equilibrium partitioning. A centrifugation-loading assay supports this finding. Pseudo-temperature jump (1)H NMR measurements suggest that the insulin release rate is partially decoupled from microgel collapse. These types of direct release investigations could prove to be useful methods in the future design of controlled macromolecule drug delivery devices.

  18. Direct Comparison of 19F qNMR and 1H qNMR by Characterizing Atorvastatin Calcium Content

    PubMed Central

    Liu, Yang; Liu, Zhaoxia; Yang, Huaxin

    2016-01-01

    Quantitative nuclear magnetic resonance (qNMR) is a powerful tool in measuring drug content because of its high speed, sensitivity, and precision. Most of the reports were based on proton qNMR (1H qNMR) and only a few fluorine qNMR (19F qNMR) were reported. No research has been conducted to directly compare the advantage and disadvantage between these two methods. In the present study, both 19F and 1H qNMR were performed to characterize the content of atorvastatin calcium with the same internal standard. Linearity, precision, and results from two methods were compared. Results showed that 19F qNMR has similar precision and sensitivity to 1H qNMR. Both methods generate similar results compared to mass balance method. Major advantage from 19F qNMR is that the analyte signal is with less or no interference from impurities. 19F qNMR is an excellent approach to quantify fluorine-containing analytes. PMID:27688925

  19. Characterization of various magnesium oxides by XRD and {sup 1}H MAS NMR spectroscopy

    SciTech Connect

    Aramendia, M.A.; Benitez, J.A.; Borau, V.; Jimenez, C.; Marinas, J.M.; Ruiz, J.R.; Urbano, F.

    1999-04-01

    A magnesium oxide obtained by thermal decomposition of commercially available magnesium hydroxide was refluxed in water and acetone in order to improve its chemical and textural properties with the purpose of using it as a support for metals in heterogeneous catalysts. X-ray diffraction, CO{sub 2} chemisorption, and {sup 1}H magic-angle spinning nuclear magnetic resonance were used to identify crystal phases, the number of basic sites, and the nature of OH groups in the oxide, respectively.

  20. Synthesis, NMR analysis and X-ray crystal structure of 3-(2-naphthoyl)-6,12-diphenyl-3,9-diazatetraasterane

    NASA Astrophysics Data System (ADS)

    Tan, Hong-bo; Song, Xiu-qing; Yan, Hong; Xin, Hong-xing

    2017-02-01

    Novel 3-(2-naphthoyl)-6,12-diphenyl-3,9-diazatetraasterane (3, Tetraethyl 3-(2-naphthoyl)-6,12-diphenyl-3,9-diazapentacyclo [6.4.0.02,7.04,11.05,10]dodecane-1,5,7,11-tetracarboxylate) was prepared by naphthoylation of 3,9-diazatetraasterane (2). The target compound was isolated and unambiguously confirmed by NMR spectra, high-resolution mass spectrometry, and single-crystal X-ray diffraction analysis. In order to discuss the spatial effects on the NMR of 3 by the naphthoyl group, spectra analysis (1D-NMR and 2D-NMR) of 2 and 3 was conducted in details by the shifts and assignments of signals. Single-crystal X-ray diffraction assists to explain the molecular asymmetry of 3 and elucidates the effects of naphthoyl group on the geometry of the central cage of 3,9-diazatetraasterane.

  1. Protein-Observed Fluorine NMR Is a Complementary Ligand Discovery Method to (1)H CPMG Ligand-Observed NMR.

    PubMed

    Urick, Andrew K; Calle, Luis Pablo; Espinosa, Juan F; Hu, Haitao; Pomerantz, William C K

    2016-11-18

    To evaluate its potential as a ligand discovery tool, we compare a newly developed 1D protein-observed fluorine NMR (PrOF NMR) screening method with the well-characterized ligand-observed (1)H CPMG NMR screen. We selected the first bromodomain of Brd4 as a model system to benchmark PrOF NMR because of the high ligandability of Brd4 and the need for small molecule inhibitors of related epigenetic regulatory proteins. We compare the two methods' hit sensitivity, triaging ability, experiment speed, material consumption, and the potential for false positives and negatives. To this end, we screened 930 fragment molecules against Brd4 in mixtures of five and followed up these studies with mixture deconvolution and affinity characterization of the top hits. In selected examples, we also compare the environmental responsiveness of the (19)F chemical shift to (1)H in 1D-protein observed (1)H NMR experiments. To address concerns of perturbations from fluorine incorporation, ligand binding trends and affinities were verified via thermal shift assays and isothermal titration calorimetry. We conclude that for the protein understudy here, PrOF NMR and (1)H CPMG have similar sensitivity, with both being effective tools for ligand discovery. In cases where an unlabeled protein can be used, 1D protein-observed (1)H NMR may also be effective; however, the (19)F chemical shift remains significantly more responsive.

  2. Experimental (XRD, IR and NMR) and theoretical investigations on 1-(2-nitrobenzoyl)3,5-bis(4-methoxyphenyl)-4,5-dihydro-1H-pyrazole

    NASA Astrophysics Data System (ADS)

    Evecen, Meryem; Tanak, Hasan; Tinmaz, Feyza; Dege, Necmi; Özer İlhan, İlhan

    2016-12-01

    The pyrazole compound 1-(2-nitrobenzoyl)3,5-bis(4-methoxyphenyl)-4,5-dihydro-1H-pyrazole (I) has been synthesized and characterized by IR, NMR and X-ray diffraction methods. The compound crystallizes in the monoclinic space group C2/c with a = 36.126(5) Ǻ, b = 8.1963(7) Ǻ, c = 14.3983(18) Ǻ, β = 100.825(10)° and Z = 8. The molecular geometry, vibrational frequencies and Gauge-Independent Atomic Orbital (GIAO) 1H and 13C NMR chemical shift values of 1-(2-nitrobenzoyl)3,5-bis(4-methoxyphenyl)-4,5-dihydro-1H-pyrazole in the ground state have been calculated using the density functional method (B3LYP) with the 6-311++G(d,p) basis set. The optimized parameters are in agreement with X-ray data. The calculated vibrational frequencies and chemical shift values were compared with experimental IR and NMR values. In addition, frontier molecular orbitals, molecular electrostatic potential and NBO analysis of (I) were investigated by DFT calculations.

  3. Synthesis of 24-phenyl-24-oxo steroids derived from bile acids by palladium-catalyzed cross coupling with phenylboronic acid. NMR characterization and X-ray structures.

    PubMed

    Mayorquín-Torres, Martha C; Romero-Ávila, Margarita; Flores-Álamo, Marcos; Iglesias-Arteaga, Martin A

    2013-11-01

    Palladium-catalyzed cross coupling of phenyboronic acid with acetylated bile acids in which the carboxyl functions have been activated by formation of a mixed anhydride with pivalic anhydride afforded moderate to good yield of 24-phenyl-24-oxo-steroids. Unambiguous assignments of the NMR signals were made with the aid of combined 1D and 2D NMR techniques. X-ray diffraction studies confirmed the obtained structures.

  4. A combined solid-state NMR and synchrotron x-ray diffraction powder study on the structure of the antioxidant(+)-catechin 4.5 hydrate.

    SciTech Connect

    Harper, J. K.; Doebbler, J. A.; Jaccques, E.; Grant, D. M.; Von Dreele, R. B.; Univ. of Utah

    2010-03-10

    Analyses combining X-ray powder diffraction (XRD) and solid-state NMR (SSNMR) data can now provide crystal structures in challenging powders that are inaccessible by traditional methods. The flavonoid catechin is an ideal candidate for these methods, as it has eluded crystallographic characterization despite extensive study. Catechin was first described nearly two centuries ago, and its powders exhibit numerous levels of hydration. Here, synchrotron XRD data provide all heavy-atom positions in (+)-catechin 4.5-hydrate and establish the space group as C2. SSNMR data ({sup 13}C tensor and {sup 1}H/{sup 13}C correlation) complete the conformation by providing catechin's five OH hydrogen orientations. Since 1903, this phase has been erroneously identified as a 4.0 hydrate, but XRD and density data establish that this discrepancy is due to the facile loss of the water molecule located at a Wyckoff special position in the unit cell. A final improvement to heavy-atom positions is provided by a geometry optimization of bond lengths and valence angles with XRD torsion angles held constant. The structural enhancement in this final structure is confirmed by the significantly improved fit of computed {sup 13}C tensors to experimental data.

  5. Alternative determination of blood alcohol concentration by (1)H NMR spectroscopy.

    PubMed

    Zailer, Elina; Diehl, Bernd W K

    2016-02-05

    A rapid, accurate and specific proton nuclear magnetic resonance ((1)H NMR) spectroscopic method is developed to determine ethanol in blood, known as the blood alcohol concentration (BAC). The limits of detection and quantification are 0.02g/L and 0.07g/L, respectively. The (1)H NMR spectra show linearity for whole blood and serum samples of a concentration range of 0.00-3.00g/L (R(2)>0.9995). The (1)H NMR method is applied and validated for whole blood as the sample media. Real driving under influence case samples are analyzed with the reference enzyme-based alcohol dehydrogenase and headspace gas chromatography techniques by the Forensic Medicine in Bonn. The reference results are compared with the (1)H NMR spectroscopic results. The validation and comparison indicate that (1)H NMR is suitable for the quantification of BAC in whole blood. This technique has the advantages of automated analysis with good measurement precision and fast sample throughput. A drop of blood (V=20μL) is adequate for an analysis leading to a possible simplification of the sample collection. Due to the non-destructive method, follow-up examinations by (1)H NMR spectroscopy or DNA determinations by different techniques (PCR, in situ hybridization) are possible in resolving legal disputes.

  6. Complete Assignment of (1)H-NMR Resonances of the King Cobra Neurotoxin CM-11.

    PubMed

    Pang, Yu-Xi; Liu, Wei-Dong; Liu, Ai-Zhuo; Pei, Feng-Kui

    1997-01-01

    The king cobra (Ophiophagus Hannah) neurotoxin CM-Il is long-chain peptide with 72 amino acid residues. Its complete assignment of (1)H-NMR resonances was obtained using various 2D-NMR technologies, including DQF-COSY, clean-TOCSY and NOESY.

  7. 1H and 13C NMR assignments for two new angular furanocoumarin glycosides from Peucedanum praeruptorum.

    PubMed

    Chang, Haitao; Okada, Yoshihito; Okuyama, Toru; Tu, Pengfei

    2007-07-01

    Two novel angular-type furanocoumarin glycosides, peucedanoside A (1) and peucedanoside B (2), along with a known compound apterin (3), were isolated from the roots of Peucedanum praeruptorum Dunn. Their chemical structures were determined by MS, NMR spectroscopy and chemical analysis. Complete assignments of the 1H and 13C NMR spectroscopic data were achieved by 1D and 2D NMR experiments including DEPT, HSQC, HMBC and ROESY.

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

    PubMed

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

    2005-01-01

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

  9. 1H-NMR and 13C-NMR lipid profiles of human renal tissues.

    PubMed

    Tugnoli, V; Bottura, G; Fini, G; Reggiani, A; Tinti, A; Trinchero, A; Tosi, M R

    2003-01-01

    Lipids from human renal tissues are studied by means of (1)H- and (13)C-NMR spectroscopy. The total lipid fractions obtained from healthy kidneys, malignant renal cell carcinomas, and benign oncocytomas are characterized and analyzed to elucidate the main differences between the functional and neoplastic tissues. In all cases the lipid components are well identified. The healthy kidney is characterized by high amounts of triglycerides and the presence of cholesterol in its free form. On the contrary, renal cell carcinomas contain high amounts of cholesterol that are almost completely esterified as oleate, suggesting an intracellular localization of the cholesteryl esters synthesis. Cholesteryl esters are considered markers of renal cell carcinomas, thus supporting recent theories that these compounds play a leading role in cell proliferation. Oncocytomas are particularly rich in phosphatidylcholine and, analogous to the healthy kidney, are completely lacking in cholesteryl esters. Healthy kidneys and oncocytomas appear to have other similarities if compared with renal cell carcinomas: a very high fatty acyl/cholesterol ratio, the presence of dolichols, and a higher grade of unsaturation. The (13)C data suggest a new method for the direct evaluation of the saturated/unsaturated fatty acyl ratio.

  10. Characterizing the secondary protein structure of black widow dragline silk using solid-state NMR and X-ray diffraction.

    PubMed

    Jenkins, Janelle E; Sampath, Sujatha; Butler, Emily; Kim, Jihyun; Henning, Robert W; Holland, Gregory P; Yarger, Jeffery L

    2013-10-14

    This study provides a detailed secondary structural characterization of major ampullate dragline silk from Latrodectus hesperus (black widow) spiders. X-ray diffraction results show that the structure of black widow major ampullate silk fibers is comprised of stacked β-sheet nanocrystallites oriented parallel to the fiber axis and an amorphous region with oriented (anisotropic) and isotropic components. The combination of two-dimensional (2D) (13)C-(13)C through-space and through-bond solid-state NMR experiments provide chemical shifts that are used to determine detailed information about the amino acid motif secondary structure in black widow spider dragline silk. Individual amino acids are incorporated into different repetitive motifs that make up the majority of this protein-based biopolymer. From the solid-state NMR measurements, we assign distinct secondary conformations to each repetitive amino acid motif and, hence, to the amino acids that make up the motifs. Specifically, alanine is incorporated in β-sheet (poly(Alan) and poly(Gly-Ala)), 3(1)-helix (poly(Gly-Gly-Xaa), and α-helix (poly(Gln-Gln-Ala-Tyr)) components. Glycine is determined to be in β-sheet (poly(Gly-Ala)) and 3(1)-helical (poly(Gly-Gly-X(aa))) regions, while serine is present in β-sheet (poly(Gly-Ala-Ser)), 3(1)-helix (poly(Gly-Gly-Ser)), and β-turn (poly(Gly-Pro-Ser)) structures. These various motif-specific secondary structural elements are quantitatively correlated to the primary amino acid sequence of major ampullate spidroin 1 and 2 (MaSp1 and MaSp2) and are shown to form a self-consistent model for black widow dragline silk.

  11. Retro-Curcuminoids as Mimics of Dehydrozingerone and Curcumin: Synthesis, NMR, X-ray, and Cytotoxic Activity.

    PubMed

    Obregón-Mendoza, Marco A; Estévez-Carmona, María Mirian; Hernández-Ortega, Simón; Soriano-García, Manuel; Ramírez-Apan, María Teresa; Orea, Laura; Pilotzi, Hugo; Gnecco, Dino; Cassani, Julia; Enríquez, Raúl G

    2016-12-29

    Curcumin and its derivatives have been extensively studied for their remarkable medicinal properties, and their chemical synthesis has been an important step in the optimization of well-controlled laboratory production. A family of new compounds that mimic the structure of curcumin and curcuminoids, here named retro-curcuminoids (7-14), was synthesized and characterized using 1D ¹H- and (13)C-NMR, IR, and mass spectrometry; the X-ray structure of 7, 8, 9, 10, 12, 13, and 14 are reported here for the first time. The main structural feature of these compounds is the reverse linkage of the two aromatic moieties, where the acid chloride moiety is linked to the phenolic group while preserving α, β-unsaturated ketone functionality. The cytotoxic screening of 7, 8, 9, and 10 at 50 and 10 µg/mL was carried out with human cancer cell lines K562, MCF-7, and SKLU-1. Lipid peroxidation on rat brain was also tested for compounds 7 and 10. Compounds 7, 8, and 10 showed relevant cytotoxic activity against these cancer cell lines, and 10 showed a protective effect against lipid peroxidation. The molecular resemblance to curcuminoids and analogs with ortho substituents suggests a potential source of useful bioactive compounds.

  12. Quantitative Characterization of Configurational Space Sampled by HIV-1 Nucleocapsid Using Solution NMR, X-ray Scattering and Protein Engineering.

    PubMed

    Deshmukh, Lalit; Schwieters, Charles D; Grishaev, Alexander; Clore, G Marius

    2016-06-03

    Nucleic-acid-related events in the HIV-1 replication cycle are mediated by nucleocapsid, a small protein comprising two zinc knuckles connected by a short flexible linker and flanked by disordered termini. Combining experimental NMR residual dipolar couplings, solution X-ray scattering and protein engineering with ensemble simulated annealing, we obtain a quantitative description of the configurational space sampled by the two zinc knuckles, the linker and disordered termini in the absence of nucleic acids. We first compute the conformational ensemble (with an optimal size of three members) of an engineered nucleocapsid construct lacking the N- and C-termini that satisfies the experimental restraints, and then validate this ensemble, as well as characterize the disordered termini, using the experimental data from the full-length nucleocapsid construct. The experimental and computational strategy is generally applicable to multidomain proteins. Differential flexibility within the linker results in asymmetric motion of the zinc knuckles which may explain their functionally distinct roles despite high sequence identity. One of the configurations (populated at a level of ≈40 %) closely resembles that observed in various ligand-bound forms, providing evidence for conformational selection and a mechanistic link between protein dynamics and function.

  13. Comparison of the structure of human recombinant short form stromelysin by multidimensional heteronuclear NMR and X-ray crystallography.

    PubMed

    Gooley, P R; O'Connell, J F; Marcy, A I; Cuca, G C; Axel, M G; Caldwell, C G; Hagmann, W K; Becker, J W

    1996-01-01

    Stromelysin-1 is a matrix metalloprotease that has been implicated in a number of degenerative diseases. Here we present the refined NMR solution structure of the catalytic domain of stromelysin-1 complexed with a small inhibitor and compare it to the X-ray crystal structure of the same complex. The structures are similar in global fold and show an unusual bottomless S1' subsite. There are differences, however, in the least well defined regions, Phe83-Ile89, His224-Phe232 and Pro249- Pro250, reflecting the lack of NOE data and large B-factors. The region His224-Phe232 contains residues of the S1' subsite and, consequently, small differences are observed in this subsite. Hydrogen-bond data show that, in contrast to the crystal structure, the solution structure lacks a hydrogen bond between the amide of Tyr223 and the carbonyl of the P3' residue. Analysis of bound water shows two tightly bound water molecules both in the solution and the crystal structure; neither of these waters are in the inhibitor binding site.

  14. Conformational distribution of baclofen analogues by 1H and 13C NMR analysis and ab initio HF MO STO-3G or STO-3G* calculations

    NASA Astrophysics Data System (ADS)

    Vaccher, Claude; Berthelot, Pascal; Debaert, Michel; Vermeersch, Gaston; Guyon, René; Pirard, Bernard; Vercauteren, Daniel P.; Dory, Magdalena; Evrard, Guy; Durant, François

    1993-12-01

    The conformations of 3-(substituted furan-2-yl) and 3-(substituted thien-2-yl)-γ-aminobutyric acid 1-9 in solution (D 2O) are estimated from high-resolution (300 MHz) 1H NMR coupling data. Conformations and populations of conformers are calculated by means of a modified Karplus-like relationship for the vicinal coupling constants. The results are compared with X-ray crystallographic investigations (torsion angles) and ab initio HF MO ST-3G or STO-3G* calculations. 1H NMR spectral analysis shows how 1-9 in solution retain the preferred g- conformation around the C3C4 bond, as found in the solid state, while a partial rotation is set up around the C2C3 bond: the conformations about C2C3 are all highly populated in solution. The 13C spin-lattice relaxation times are also discussed.

  15. Quantitative Determination of Carthamin in Carthamus Red by 1H-NMR Spectroscopy.

    PubMed

    Yoshida, Takamitsu; Terasaka, Kazuyoshi; Kato, Setsuko; Bai, Fan; Sugimoto, Naoki; Akiyama, Hiroshi; Yamazaki, Takeshi; Mizukami, Hajime

    2013-01-01

    Carthamus Red is a food colorant prepared from the petals of Carthamus tinctorius (Asteraceae) whose major pigment is carthamin. Since an authentic carthamin standard is difficult to obtain commercially for the preparation of calibration curves in HPLC assays, we applied (1)H-NMR spectroscopy to the quantitative determination of carthamin in commercial preparations of Carthamus Red. Carthamus Red was repeatedly extracted in methanol and the extract was dissolved in pyridine-d(5) containing hexamethyldisilane (HMD) prior to (1)H-NMR spectroscopic analysis. The carthamin contents were calculated from the ratios of singlet signal intensities at approximately σ: 9.3 derived from H-16 of carthamin to those of the HMD signal at σ: 0. The integral ratios exhibited good repeatability among NMR spectroscopic analyses. Both the intra-day and inter-day assay variations had coefficients of variation of <5%. Based on the coefficient of absorption, the carthamin contents of commercial preparations determined by (1)H-NMR spectroscopy correlated well with those determined by colorimetry, although the latter were always approximately 1.3-fold higher than the former, irrespective of the Carthamus Red preparations. In conclusion, the quantitative (1)H-NMR spectroscopy used in the present study is simple and rapid, requiring no carthamin standard for calibration. After HMD concentration has been corrected using certified reference materials, the carthamin contents determined by (1)H-NMR spectroscopy are System of Units (SI)-traceable.

  16. Synthesis, crystal structure analysis, spectral IR, NMR UV-Vis investigations, NBO and NLO of 2-benzoyl-N-(4-chlorophenyl)-3-oxo-3-phenylpropanamide with use of X-ray diffractions studies along with DFT calculations

    NASA Astrophysics Data System (ADS)

    Demir, Sibel; Sarioğlu, Ahmet Oral; Güler, Semih; Dege, Necmi; Sönmez, Mehmet

    2016-08-01

    The title compound, 2-benzoyl-N-(4-chlorophenyl)-3-oxo-3-phenylpropanamide compound (C22H16NO3Cl) has been synthesized and characterized by X-ray diffraction, IR, 1H and 13C NMR and UV-Vis spectra. Optimized geometrical structure, harmonic vibrational frequencies and chemical shifts were computed using hybrid-DFT (B3LYP and B3PW91) methods and 6-311G(d,p) as the basis set. The results of the optimized molecular structure are presented and compared with the experimental X-ray diffraction. The calculated optimized geometries, vibrational frequencies and 1H NMR chemical shift values are in strong agreement with experimentally measured values. UV-Vis spectrum of the title compound, was also recorded and the electronic properties, such as calculated energies, excitation energies, oscillator strengths, dipole moments and frontier orbital energies and band gap energies were computed with TDDFT-B3LYP methodolgy and using 6-311G(d,p) as the basis set. Furthermore, frontier molecular orbitals (FMO), molecular electrostatic potential (MEP), natural bond orbital (NBO) and non linear optical (NLO) properties were performed by using B3LYP/6-311G(d,p) level for the title compound.

  17. Difference in the structures of alanine tri- and tetra-peptides with antiparallel β-sheet assessed by X-ray diffraction, solid-state NMR and chemical shift calculations by GIPAW.

    PubMed

    Asakura, Tetsuo; Yazawa, Koji; Horiguchi, Kumiko; Suzuki, Furitsu; Nishiyama, Yusuke; Nishimura, Katsuyuki; Kaji, Hironori

    2014-01-01

    Alanine oligomers provide a key structure for silk fibers from spider and wild silkworms.We report on structural analysis of L-alanyl-L-alanyl-L-alanyl-L-alanine (Ala)4 with anti-parallel (AP) β-structures using X-ray and solid-state NMR. All of the Ala residues in the (Ala)4 are in equivalent positions, whereas for alanine trimer (Ala)3 there are two alternative locations in a unit cell as reported previously (Fawcett and Camerman, Acta Cryst., 1975, 31, 658-665). (Ala)4 with AP β-structure is more stable than AP-(Ala)3 due to formation of the stronger hydrogen bonds. The intermolecular structure of (Ala)4 is also different from polyalanine fiber structure, indicating that the interchain arrangement of AP β-structure changes with increasing alanine sequencelength. Furthermore the precise (1)H positions, which are usually inaccesible by X-ray diffraction method, are determined by high resolution (1)H solid state NMR combined with the chemical shift calculations by the gauge-including projector augmented wave method.

  18. Cd(II) and Zn(II) complexes of two new hexadentate Schiff base ligands derived from different aldehydes and ethanol amine; X-ray crystal structure, IR and NMR spectroscopy studies

    NASA Astrophysics Data System (ADS)

    Golbedaghi, Reza; Rezaeivala, Majid; Albeheshti, Leila

    2014-11-01

    Four new [Cd(H2L1)(NO3)]ClO4 (1), [Zn(H2L1)](ClO4)2 (2), [Cd(H2L2)(NO3)]ClO4 (3), and [Zn(H2L2)](ClO4)2 (4), complexes were prepared by the reaction of two new Schiff base ligands and Cd(II) and Zn(II) metal ions in equimolar ratios. The ligands H2L1 and H2L2 were synthesized by reaction of 2-[2-(2-formyl phenoxy)ethoxy]benzaldehyde and/or 2-[2-(3-formyl phenoxy)propoxy]benzaldehyde and ethanol amine and characterized by IR, 1H and 13C NMR spectroscopy. All complexes were characterized by IR, 1H and 13C NMR, COSY, and elemental analysis. Also, the complex 1 was characterized by X-ray in addition to the above methods. The X-ray crystal structure of compound 1 showed that all nitrogen and oxygen atoms of ligand (N2O4) and a molecule of nitrate with two donor oxygen atom have been coordinated to the metal ion and the Cd(II) ion is in an eight-coordinate environment that is best described as a distorted dodecahedron geometry.

  19. Synthesis, characterization and spectroscopy studying of some metal complexes of a new Schiff base ligand; X-ray crystal structure, NMR and IR investigation of a new dodecahedron Cd(II) complex

    NASA Astrophysics Data System (ADS)

    Golbedaghi, Reza; Rezaeivala, Majid; Khalili, Maryam; Notash, Behrouz; Karimi, Javad

    2016-12-01

    Some new [Cd(H2L1)(NO3)]ClO4 (1), [Mn(H2L1)](ClO4)2 (2), [Ni(H2L1)](ClO4)2 (3) and [Cu(H2L1)](ClO4)2 (4) complexes were prepared by the reaction of a Schiff base ligand and M (II) metal ions in equimolar ratios (M = Cd, Mn, Ni and Cu). The ligand H2L1 was synthesized by reaction of 2-[2-(3-formyl phenoxy)propoxy]benzaldehyde and ethanol amine and characterized by IR, 1H,13C NMR spectroscopy and elemental analysis. The synthesized complexes were characterized with IR and elemental analysis in all cases and 1H, 13C NMR, and X-ray in the case of Cd(II) complex. The X-ray crystal structure of compound 1 showed that all nitrogen and oxygen atoms of Schiff base ligand (N2O4) and a molecule of nitrate with two donor oxygen atom have been coordinated to the metal ion and the Cd(II) ion is in an eight-coordinate environment that is best described as a distorted dodecahedron geometry.

  20. N,N‧-Dimethylpiperazine mono-betaine complex with two molecules of 3-iodobenzoic acid and water studied by X-ray diffraction, DFT, FTIR and NMR methods

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Katrusiak, A.; Szafran, M.

    2008-03-01

    N, N'-Dimethylpiperazine mono-betaine ( N-carboxymethyl- N, N'-dimethylpiperazinium inner salt, MBPZ) forms a crystalline complex with two molecules of 3-iodobenzoic acid (3IBA). The complex crystallizes as a monohydrate, MBPZ(3IBA) 2H 2O. The complex has been characterized by X-ray diffraction and FTIR, Raman, 1H and 13C NMR spectroscopies. The crystals are monoclinic, space group P2 1/ c, with a = 6.7810(17), b = 38.391(4), c = 10.0542(16) Å, β = 90.024(18)°. The piperazinium ring has a chair conformation with the N +CH 2COO - substituent in the axial and both methyl groups in the equatorial positions. The 3IBA molecules interact with the carboxylate group of N +CH 2COO - and N' atom through the O-H···O and O-H···N hydrogen bonds of the lengths 2.550 and 2.695 Å. The water molecules link MBPZ(3IBA) 2 complexes by the O-H···OOCCH 2N + hydrogen bonds of 2.850 and 2.793 Å into infinite chains. The MBPZ(3XBA) 2H 2O (X = I, Br, Cl), MBPZ(3IBA) 2 complexes and MBPZ have been analyzed by the B3LYP/MidiX level of theory. The conformers with the axial CH 2COO - substituent have lower energies than these with the equatorial CH 2COO - one. The bands at 3433, 2790, 2450, 1915 cm -1 assigned to the ν(OH) vibration of the various hydrogen bonds, and two bands attributed to the ν(C dbnd O) (1680 cm -1) and ν as(COO) (1660 cm -1) vibrations in the FTIR spectrum confirm the structure of the title complex. The 1H- 13C HMBC spectrum has been analyzed in order to assign the carbon-13 chemical shifts.

  1. Intermolecular Interactions between Eosin Y and Caffeine Using 1H-NMR Spectroscopy

    PubMed Central

    Okuom, Macduff O.; Wilson, Mark V.; Jackson, Abby; Holmes, Andrea E.

    2014-01-01

    DETECHIP has been used in testing analytes including caffeine, cocaine, and tetrahydrocannabinol (THC) from marijuana, as well as date rape and club drugs such as flunitrazepam, gamma-hydroxybutyric acid (GHB), and methamphetamine. This study investigates the intermolecular interaction between DETECHIP sensor eosin Y (DC1) and the analyte (caffeine) that is responsible for the fluorescence and color changes observed in the actual array. Using 1H-NMR, 1H-COSY, and 1H-DOSY NMR methods, a proton exchange from C-8 of caffeine to eosin Y is proposed. PMID:25018772

  2. Conformational evaluation and detailed 1H and 13C NMR assignments of eremophilanolides.

    PubMed

    Burgueño-Tapia, Eleuterio; Hernández, Luis R; Reséndiz-Villalobos, Adriana Y; Joseph-Nathan, Pedro

    2004-10-01

    Extensive application of 1D and 2D NMR methodology, combined with molecular modeling, allowed the complete 1H and 13C NMR assignments of eremophilanolides from Senecio toluccanus. Comparison of the experimental 1H, 1H coupling constant values with those generated employing a generalized Karplus-type relationship, using dihedral angles extracted from MMX and DFT calculations, revealed that the epoxidized eremophilanolides 1 and 2 show conformational rigidity at room temperature, whereas molecules 3-6, containing an isolated double bond, are conformationally mobile.

  3. Digital NMR Profiles as Building Blocks: Assembling 1H Fingerprints of Steviol Glycosides

    PubMed Central

    Napolitano, José G.; Simmler, Charlotte; McAlpine, James B.; Lankin, David C.; Chen, Shao-Nong; Pauli, Guido F.

    2015-01-01

    This report describes a fragment-based approach to the examination of congeneric organic compounds by NMR spectroscopy. The method combines the classic interpretation of 1D- and 2D-NMR data sets with contemporary computer-assisted NMR analysis. Characteristic NMR profiles of key structural motifs were generated by 1H iterative full spin analysis and then joined together as building blocks to recreate the 1H NMR spectra of increasingly complex molecules. To illustrate the methodology described, a comprehensive analysis of steviol (1), seven steviol glycosides (2–8) and two structurally related isosteviol compounds (9, 10) was carried out. The study also assessed the potential impact of this method on relevant aspects of natural product research including structural verification, chemical dereplication, and mixture analysis. PMID:25714117

  4. Synthesis, X-ray, NMR, FT-IR, UV/vis, DFT and TD-DFT studies of N-(4-chlorobutanoyl)-N'-(2-, 3- and 4-methylphenyl)thiourea derivatives.

    PubMed

    Abosadiya, Hamza M; Anouar, El Hassane; Hasbullah, Siti Aishah; Yamin, Bohari M

    2015-06-05

    A new isomers of thiourea derivatives, namely N-(4-chlorobutanoyl)-N'-(2-methylphenyl)-thiourea (1a), N-(4-chlorobutanoyl)-N'-(3-methylphenyl)thiourea (1b) and N-(4-chlorobutanoyl)-N'-(4-methylphenyl)thiourea (1c) have been synthesized by refluxing mixture of equimolar amounts of 4-chlorobutanoylisothiocyanate with 2, 3 or 4-toluidine, respectively. The three isomers were characterized by spectroscopic (UV/vis, FT-IR and NMR) and X-ray crystallography techniques. To investigate the isomerization effect on spectroscopic data, DFT and TD-DFT calculations have been carried out using five hybrid functionals (B3LYP, B3P86, CAM-B3LYP, M06-2X and PBE0) to predict UV/vis absorption bands (n→π∗ and π→π∗), (1)H and (13)C NMR chemical shifts, FT-IR vibration modes and X-ray parameters (bonds, bond angles and torsion angles) for 1a, 1b and 1c isomers. The results showed that the isomerization effect is significant on λ(MAX) absorption bands, while for IR and NMR the effect is negligible. In accordance with previous studies, B3LYP, B3P86 and PBE0 gave the most reliable to predict the excitation energies of thiourea derivatives.

  5. New Insights into Chain Order Dynamics and Structural Development in Sulfur-Vulcanized Natural Rubber Latex using Multiple Quantum NMR and Synchrotron X-Ray Diffraction

    NASA Astrophysics Data System (ADS)

    Che, Justin; Toki, Shigeyuki; Valentin, Juan; Brasero, Justo; Rong, Lixia; Hsiao, Benjamin S.

    2012-02-01

    Network structure, chain dynamics, and structural development in sulfur-vulcanized natural rubber latex were studied by Multiple-Quantum (MQ) NMR and synchrotron x-ray scattering. Three important processes that can influence rubber network structure and its overall mechanical properties were the main focus and analyzed by both of these techniques: pre-vulcanization, drying, and post-vulcanization. MQ NMR experiments can provide quantitative information regarding networks at very small length scales, including network defects, number of cross-links, and spatial distribution of cross-links. Structural development in natural rubber was studied under uniaxial deformation by in-situ synchrotron x-ray diffraction, which can provide information on network structures at much larger length scales. Molecular orientation and strain-induced crystallization was analyzed by both stress-strain relations and wide-angle x-ray diffraction (WAXD). The morphology of the latex rubber particle during deformation was analyzed by small-angle x-ray scattering (SAXS). The combination of these techniques can provide a considerable amount of information regarding rubber network structure.

  6. Structure of an inclusive compound of bis(piperidinium-4-carboxylate)hydrogen semi-tartrate with water and methanol studied by X-ray diffraction, NMR, FTIR and DFT methods

    NASA Astrophysics Data System (ADS)

    Dega-Szafran, Z.; Fojud, Z.; Katrusiak, A.; Szafran, M.

    2009-06-01

    The complex consisting of two piperidine-4-carboxylic acid, L-tartaric acid, water and methanol molecules has been synthesized and characterized by X-ray diffraction, 1H, 13C NMR, 13C CP MAS NMR, FTIR spectra and DFT calculations. The title complex is composed of the following units: piperidinium-4-carboxylate (P4C), piperidinium-4-carboxylic acid (P4CH), semi-tartrate anion (TA), water and methanol; it crystallizes in orthorhombic space group P2 12 12 1. TA anions form infinite chains through the COOH···OOC hydrogen bond of 2.503(5) Å. The zwitterionic P4C molecules are linked by the N +H···OOC hydrogen bond of 2.780(5) Å into chains. The P4CH cation is a bridge between the TA and P4C chains. P4CH and P4C form a homoconjugated cation through the COOH···OOC hydrogen bonds of 2.559(5) Å. Water interacts with TA and P4CH, while methanol interacts only with water. In the optimized molecule of the (P4C) 2H·TA·H 2O·HOCH 3 complex, the components form a cyclic oligomer through four O-H···O and four N-H···O hydrogen bonds. The 1H and 13C NMR spectra elucidate the structure of the title complex in the aqueous solution. The 13C CP MAS NMR spectrum is consistent with the X-ray results. The FTIR spectrum confirms a very complex structure of the title compound.

  7. A new Schiff base compound N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone): synthesis, experimental and theoretical studies on its crystal structure, FTIR, UV-visible, 1H NMR and 13C NMR spectra.

    PubMed

    Saheb, Vahid; Sheikhshoaie, Iran

    2011-10-15

    The Schiff base compound, N,N'-(2,2-dimetylpropane)-bis(dihydroxylacetophenone) (NDHA) is synthesized through the condensation of 2-hydroxylacetophenone and 2,2-dimethyl 1,3-amino propane in methanol at ambient temperature. The yellow crystalline precipitate is used for X-ray single-crystal determination and measuring Fourier transform infrared (FTIR), UV-visible, (1)H NMR and (13)C NMR spectra. Electronic structure calculations at the B3LYP, PBEPBE and PW91PW91 levels of theory are performed to optimize the molecular geometry and to calculate the FTIR, (1)H NMR and (13)C NMR spectra of the compound. Time-dependent density functional theory (TDDFT) method is used to calculate the UV-visible spectrum of NDHA. Vibrational frequencies are determined experimentally and compared with those obtained theoretically. Vibrational assignments and analysis of the fundamental modes of the compound are also performed. All theoretical methods can well reproduce the structure of the compound. The (1)H NMR and (13)C NMR chemical shifts calculated by all DFT methods are consistent with the experimental data. However, the NMR shielding tensors computed at the B3LYP/6-31+G(d,p) level of theory are in better agreement with experimental (1)H NMR and (13)C NMR spectra. The electronic absorption spectrum calculated at the B3LYP/6-31+G(d,p) level by using TD-DFT method is in accordance with the observed UV-visible spectrum of NDHA. In addition, some quantum descriptors of the molecule are calculated and conformational analysis is performed and the results were compared with the crystallographic data.

  8. NMR and X-ray structural characterization and conformational aspects of fluorinated (5Z)-3-benzil-5-arylidenofuran-2(5H)-ones

    NASA Astrophysics Data System (ADS)

    Teixeira, R. R.; Barbosa, L. C. A.; Kabeshov, M. A.; Maltha, C. R. A.; Corrêa, R. S.; Doriguetto, A. C.

    2014-10-01

    Herein we describe structural insights of (5Z)-3-benzyl-5-(2-fluorobenzylidene)furan-2(5H)-one (6) and (5Z)-3-benzyl-5-(pentafluorobenzylidene)furan-2(5H)-one (7), γ-alkylidenebutenolides analogues of the natural products nostoclides. Their structures were investigated by NMR spectroscopy and X-ray crystallography. The stereochemistry of the exocyclic double bond of these fluorinated compounds was determined to be Z by NMR analysis and confirmed by X-ray data. Compounds 6 and 7 crystallized in the monoclinic crystal system P21/c group. A comparison between structural features of (6) and (7) and nostoclide derivatives previously published by us is described.

  9. Synthesis, spectroscopic investigations (X-ray, NMR and TD-DFT), antimicrobial activity and molecular docking of 2,6-bis(hydroxy(phenyl)methyl)cyclohexanone.

    PubMed

    Barakat, Assem; Ghabbour, Hazem A; Al-Majid, Abdullah Mohammed; Soliman, Saied M; Ali, M; Mabkhot, Yahia Nasser; Shaik, Mohammed Rafi; Fun, Hoong-Kun

    2015-07-21

    The synthesis of 2,6-bis(hydroxy(phenyl)methyl)cyclohexanone 1 is described. The molecular structure of the title compound 1 was confirmed by NMR, FT-IR, MS, CHN microanalysis, and X-ray crystallography. The molecular structure was also investigated by a set of computational studies and found to be in good agreement with the experimental data obtained from the various spectrophotometric techniques. The antimicrobial activity and molecular docking of the synthesized compound was investigated.

  10. 1H NMR quantitative determination of photosynthetic pigments from green beans (Phaseolus vulgaris L.).

    PubMed

    Valverde, Juan; This, Hervé

    2008-01-23

    Using 1H nuclear magnetic resonance spectroscopy (1D and 2D), the two types of photosynthetic pigments (chlorophylls, their derivatives, and carotenoids) of "green beans" (immature pods of Phaseolus vulgaris L.) were analyzed. Compared to other analytical methods (light spectroscopy or chromatography), 1H NMR spectroscopy is a fast analytical way that provides more information on chlorophyll derivatives (allomers and epimers) than ultraviolet-visible spectroscopy. Moreover, it gives a large amount of data without prior chromatographic separation.

  11. I. The synthesis and characterization of annulated uranocenes. II. The variable temperature /sup 1/H NMR of uranocenes

    SciTech Connect

    Luke, W.D.

    1980-01-01

    A general synthetic route to alkyl annulated cyclooctatetraene dianions and the corresponding annulated uranocenes has been developed. Dideprotonation of bicyclooctatrienes, resulting from reaction of cyclooctatetraene dianion with l,n-dialkylbromides or methanesulfonates, affords alkyl annulated cyclooctatetraene dianions in moderate yields. Dicyclopenteno-, bisdimethylcyclopenteno- and dicyclohexenouranocene were prepared from the corresponding cyclooctatetraene dianions and UCl/sub 4/. The structures of dicyclobuteno- and dicyclopentenouranocene were elucidated by single crystal X-ray diffraction, and the effects of annulation on the uranocene skeleton are discussed. Attempted synthesis of benzocyclooctatetraene and a benzannulated uranocene is reported. The variable temperature /sup 1/H NMR spectrum of uranocene has been reinvestigated from -100 to 100/sup 0/C. The isotropic shift was found to be linear in T/sup -1/ with an extrapolated intercept of 0 at T/sup -1/ = 0. Variable temperature /sup 1/H NMR spectra, from -80 to 70/sup 0/C, of 17 substituted uranocenes are reported. The energy barrier to ring rotation in 1,1', 4,4'-tetra-t-butyl-uranocene was determined to be 8.24 +- 0.5 kcal/mole while the barrier in the corresponding 1,1', 3,3'-tetra-t-butylferrocene was determined to be 13.1 kcal/mole. Alkyl substitution is shown to have little effect on the electronic and magnetic properties of the uranocene skeleton, and thus alkyl substituted uranocenes are treated as having effective axial symmetry in analysis of the observed isotropic shifts. Using diannulated uranocenes as model systems an analysis of the contact and pseudocontact components of the observed isotropic shifts in uranocene and alkyl substituted uranocenes is presented.

  12. Conformational studies by 1H and 13C NMR of lisinopril

    NASA Astrophysics Data System (ADS)

    Sakamoto, Yohko; Ishi, Tomoko

    1993-10-01

    Lisinopril, N-N-[( s-1-carboxy-3-phenylpropyl]- L-lysyl- L-proline) (MK-521), is an inhibitor of angiotensin-converting enzyme and a new drug for the treatment of hypertension. 1H and 13C NMR studies have shown that the s-cis equilibrium about the amide bond is strongly dependent on the configuration of the chiral centres. Vicinal coupling constants of stereochemical significance were obtained in deuterated solvent using NMR techniques. Comparison with values calculated for lisinopril using potential energy calculations and NMR show that lisinopril exists in preferred optimum conformation in solution.

  13. Importance of Purity Evaluation and the Potential of Quantitative 1H NMR as a Purity Assay

    PubMed Central

    2015-01-01

    In any biomedical and chemical context, a truthful description of chemical constitution requires coverage of both structure and purity. This qualification affects all drug molecules, regardless of development stage (early discovery to approved drug) and source (natural product or synthetic). Purity assessment is particularly critical in discovery programs and whenever chemistry is linked with biological and/or therapeutic outcome. Compared with chromatography and elemental analysis, quantitative NMR (qNMR) uses nearly universal detection and provides a versatile and orthogonal means of purity evaluation. Absolute qNMR with flexible calibration captures analytes that frequently escape detection (water, sorbents). Widely accepted structural NMR workflows require minimal or no adjustments to become practical 1H qNMR (qHNMR) procedures with simultaneous qualitative and (absolute) quantitative capability. This study reviews underlying concepts, provides a framework for standard qHNMR purity assays, and shows how adequate accuracy and precision are achieved for the intended use of the material. PMID:25295852

  14. Probing degradation in complex engineering silicones by 1H multiple quantum NMR

    SciTech Connect

    Maxwell, R S; Chinn, S C; Giuliani, J; Herberg, J L

    2007-09-05

    Static {sup 1}H Multiple Quantum Nuclear Magnetic Resonance (MQ NMR) has recently been shown to provide detailed insight into the network structure of pristine silicon based polymer systems. The MQ NMR method characterizes the residual dipolar couplings of the silicon chains that depend on the average molecular weight between physical or chemical constraints. Recently, we have employed MQ NMR methods to characterize the changes in network structure in a series of complex silicone materials subject to numerous degradation mechanisms, including thermal, radiative, and desiccative. For thermal degradation, MQ NMR shows that a combination of crosslinking due to post-curing reactions as well as random chain scissioning reactions occurs. For radiative degradation, the primary mechanisms are via crosslinking both in the network and at the interface between the polymer and the inorganic filler. For samples stored in highly desiccating environments, MQ NMR shows that the average segmental dynamics are slowed due to increased interactions between the filler and the network polymer chains.

  15. Simultaneous 19F-1H medium resolution NMR spectroscopy for online reaction monitoring

    NASA Astrophysics Data System (ADS)

    Zientek, Nicolai; Laurain, Clément; Meyer, Klas; Kraume, Matthias; Guthausen, Gisela; Maiwald, Michael

    2014-12-01

    Medium resolution nuclear magnetic resonance (MR-NMR) spectroscopy is currently a fast developing field, which has an enormous potential to become an important analytical tool for reaction monitoring, in hyphenated techniques, and for systematic investigations of complex mixtures. The recent developments of innovative MR-NMR spectrometers are therefore remarkable due to their possible applications in quality control, education, and process monitoring. MR-NMR spectroscopy can beneficially be applied for fast, non-invasive, and volume integrating analyses under rough environmental conditions. Within this study, a simple 1/16″ fluorinated ethylene propylene (FEP) tube with an ID of 0.04″ (1.02 mm) was used as a flow cell in combination with a 5 mm glass Dewar tube inserted into a benchtop MR-NMR spectrometer with a 1H Larmor frequency of 43.32 MHz and 40.68 MHz for 19F. For the first time, quasi-simultaneous proton and fluorine NMR spectra were recorded with a series of alternating 19F and 1H single scan spectra along the reaction time coordinate of a homogeneously catalysed esterification model reaction containing fluorinated compounds. The results were compared to quantitative NMR spectra from a hyphenated 500 MHz online NMR instrument for validation. Automation of handling, pre-processing, and analysis of NMR data becomes increasingly important for process monitoring applications of online NMR spectroscopy and for its technical and practical acceptance. Thus, NMR spectra were automatically baseline corrected and phased using the minimum entropy method. Data analysis schemes were designed such that they are based on simple direct integration or first principle line fitting, with the aim that the analysis directly revealed molar concentrations from the spectra. Finally, the performance of 1/16″ FEP tube set-up with an ID of 1.02 mm was characterised regarding the limit of detection (LOQ (1H) = 0.335 mol L-1 and LOQ (19F) = 0.130 mol L-1 for trifluoroethanol in

  16. Sudan dyes in adulterated saffron (Crocus sativus L.): Identification and quantification by (1)H NMR.

    PubMed

    Petrakis, Eleftherios A; Cagliani, Laura R; Tarantilis, Petros A; Polissiou, Moschos G; Consonni, Roberto

    2017-02-15

    Saffron, the dried red stigmas of Crocus sativus L., is considered as one of the most expensive spices worldwide, and as such, it is prone to adulteration. This study introduces an NMR-based approach to identify and determine the adulteration of saffron with Sudan I-IV dyes. A complete (1)H and (13)C resonance assignment for Sudan I-IV, achieved by two-dimensional homonuclear and heteronuclear NMR experiments, is reported for the first time. Specific different proton signals for the identification of each Sudan dye in adulterated saffron can be utilised for quantitative (1)H NMR (qHNMR), a well-established method for quantitative analysis. The quantification of Sudan III, as a paradigm, was performed in varying levels (0.14-7.1g/kg) by considering the NMR signal occurring at 8.064ppm. The high linearity, accuracy and rapidity of investigation enable high resolution (1)H NMR spectroscopy to be used for evaluation of saffron adulteration with Sudan dyes.

  17. Hyphenation of capillary HPLC to microcoil (1)H NMR spectroscopy for the determination of tocopherol homologues.

    PubMed

    Krucker, Manfred; Lienau, Annette; Putzbach, Karsten; Grynbaum, Marc David; Schuler, Paul; Albert, Klaus

    2004-05-01

    Highly selective reversed phases (C(30) phases) are self-packed in 250 microm inner diameter fused-silica capillaries and employed for capillary HPLC separation of shape-constrained natural compounds (tocopherol homologues, vitamin E). Miniaturized hyphenated systems such as capillary HPLC-ESI-MS (positive ionization mode) and, with special emphasis, continuous-flow capillary HPLC- NMR are used for structural determination of the separated compounds. Despite the small amount of sample available (1.33 microg of each tocopherol), the authors have been able to monitor the capillary HPLC separation under continuous-flow (1)H NMR conditions, thus allowing an immediate peak identification. Further structural assignment was carried out in the stopped-flow NMR mode as shown, for example, by a 2D (1)H,(1)H COSY NMR spectrum of alpha-tocopherol. We demonstrate in this paper the considerable potential of hyphenated capillary separations coupled to MS and NMR for the investigation of restricted amounts of sample.

  18. Molecular Structures from [superscript 1]H NMR Spectra: Education Aided by Internet Programs

    ERIC Educational Resources Information Center

    Debska, Barbara; Guzowska-Swider, Barbara

    2007-01-01

    The article presents the way in which freeware Internet programs can be applied to teach [superscript 1]H NMR spectroscopy. The computer programs described in this article are part of the educational curriculum that explores spectroscopy and spectra interpretation. (Contains 6 figures.)

  19. Synthesis of stereospecifically deuterated desoxypodophyllotoxins and 1H-nmr assignment of desoxypodophyllotoxin

    NASA Technical Reports Server (NTRS)

    Pullockaran, A. J.; Kingston, D. G.; Lewis, N. G.

    1989-01-01

    [4 beta- 2H1]Desoxypodophyllotoxin [3], [4 alpha- 2H1]desoxypodophyllotoxin [4], and [4, 4- 2 H2]desoxypodophyllotoxin [9] were prepared from podophyllotoxin [1] via its chloride [5]. A complete assignment of the 1H-nmr spectrum of desoxypodophyllotoxin [2] was made on the basis of the spectra of the deuterated compounds [3] and [4].

  20. Stereospecific assignment of 1H resonances through chemical shift calculation and their use in structure determination by NMR

    NASA Astrophysics Data System (ADS)

    Harvey, Timothy S.; van Gunsteren, Wilfred F.; Ikura, Mitsuhiko

    1995-04-01

    Understanding of the factors which influence proton chemical shifts in nuclear magnetic resonance (NMR) spectra of proteins has advanced steadily as the number of proteins, for which assignments in conjunction with high resolution structures have been obtained, has increased. Progress has been made in both the calculation of chemical shifts from given coordinates, both empirically for 1H (Williamson & Asakura J. Magn. Reson. (1991) 94, 557) and using ab initio approaches for calculation of 13C (De Dios et al. Science (1993) 260, 1491). Concomitantly Wishart et al. (J. Mol. Biol. (1992) 222, 311), using statistical methods have clarified the relationship between Hα chemical shift and regular secondary structure in proteins to a high degree of accuracy. We recently demonstrated the significant amount of structural information present in the Hα chemical shift through the use of chemical shift restrained molecular dynamics simulations (Harvey & van Gunsteren Techniques in Protein Chemistry IV (1993) 615, Academic Press). Here we apply a similar methodology to the stereospecific assignment of methylene and methyl proton resonances in proteins. Stereospecific assignment of such 1H resonances dramatically increases the degree of precision of ensembles of structures derived from NMR data. However, this is often a cumbersome process, requiring detailed analysis of large amounts of data. Furthermore, experimental considerations such as poor signal-to-noise ratios, spectral overlap and spin diffusion combine to make this process somewhat unreliable. We present calculations of the chemical shifts for the known structures of bovine pancreatic trypsin inhibitor (Mw 6.5 kDa) and the α-amylase inhibitor tendamistat (Mw 8 kDa), for which stereospecific assignments and high resolution structures from both NMR and crystallographic studies are available. The methods described are also applied to the ensemble of structures obtained for protein S (Mw 19 kDa) for both structure

  1. Stereochemistry and solid-state structure of an intrinsically chiral meso-patterned porphyrin: case study by NMR and single-crystal X-ray diffraction analysis.

    PubMed

    Yang, Liguo; Zhou, Yang; Zhu, Mengliang; Zhao, Luyang; Wei, Liye; Bian, Yongzhong

    2013-10-04

    A C1-symmerical meso-substituted ABCD-type porphyrin, [5-phenyl-10-(2-hydroxynaphthyl)-15-(4-hydroxyphenyl)porphyrinato]zinc(II) (1), has been synthesized and characterized. The molecular structure of 1 has been determined by single-crystal X-ray diffraction analysis. The complex 1 crystallizes in a triclinic system with one pair of enantiomeric molecules per unit cell. Resolution of the racemic mixture has been achieved by chiral HPLC techniques. In particular, the absolute configurations of the enantiomers have been assigned from NMR spectroscopic analysis with L-Phe-OMe as the chiral solvating agent (CSA). The assignments have also been unambiguously confirmed by single-crystal X-ray diffraction analysis. The present results suggest that the CSA-NMR anisotropy strategy is applicable for the stereochemistry determination of chiral host-guest complexes with multiple intermolecular interactions. In addition, the multiple intermolecular interactions between the enantiomerically pure porphyrin S-1 and L-Phe-OMe are proved in the solid state by single-crystal X-ray diffraction analysis.

  2. An infrared and 1H MAS NMR investigation of strong hydrogen bonding in ussingite, Na2AlSi3O8(OH)

    NASA Astrophysics Data System (ADS)

    Johnson, E. A.; Rossman, G. R.

    The mineral ussingite, Na2AlSi3O8(OH), an ``interrupted'' tectosilicate, has strong hydrogen bonding between OH and the other nonbridging oxygen atom in the structure. Infrared spectra contain a strongly polarized, very broad OH-stretching band with an ill-defined maximum between 1500 and 1800 cm-1, and a possible OH librational bending mode at 1295 cm-1. The IR spectra confirm the orientation of the OH vector within the triclinic unit cell as determined from X-ray refinement (Rossi et al. 1974). There are three distinct bands in the 1H NMR spectrum of ussingite: a predominant band at 13.5 ppm (TMS) representing 90% of the structural hydrogen, a second band at 15.9 ppm corresponding to 8% of the protons, and a third band at 11.0 ppm accounting for the remaining 2% of structural hydrogen. From the correlation between hydrogen bond length and 1H NMR chemical shift (Sternberg and Brunner 1994), the predominant hydrogen bond length (H...O) was calculated to be 1.49 Å, in comparison to the hydrogen bond length determined from X-ray refinement (1.54 Å). The population of protons at 15.9 ppm is consistent with 5-8% Al-Si disorder. Although the ussingite crystal structure and composition are similar to those of low albite, the bonding environment of OH in low albite and other feldspars, as characterized through IR and 1H NMR, is fundamentally different from the strong hydrogen bonding found in ussingite.

  3. X-ray diffraction, DFT, spectroscopic study and insecticidal activity of (3-cyano-1-(2,6-dichloro-4-(trifluoromethyl)phenyl)-4-((trifluoromethyl)sulfinyl)-1 H-pyrazol-5- yl)(2-(triethylammonio)acetyl)amide inner salt

    NASA Astrophysics Data System (ADS)

    Jiang, D. X.; Zheng, X. H.; Xu, H. H.; Wong, N. B.

    2014-12-01

    In the title compound, C20H19Cl2F6N5O2S, an inner salt derivative of fipronil was synthesized and characterized by X-ray diffraction, 1H NMR, 13C NMR, IR, ESI-MS, EI-HRMS. The crystal is monoclinic, space group P21/ n, with a = 15.1655(7) Å, b = 15.0465(7) Å, c = 21.0713(9) Å, V = 4754.7(4) Å3 and Z = 8 (at 173(2) K), and its phenyl pyrazole ring together with bond C-N-O form a big π bond while bonds C-N-C and N-C-H form an inner salt molecular. Crystal stacking scheme indicates the crystal consists of two different molecules. The two molecules are nonplanar with the torsion angles between the pyrazole rings and benzene rings of -99.7(7)° and 88.1(7)°, respectively, and linked by intermolecular C-H⋯O, C-H⋯F hydrogen bonds. By DFT calculations, molecular electrostatic potential clearly shows that the formation of hydrogen bonding interaction, which F5⋯H'42 and F6⋯H'41 are intermolecular hydrogen bonds, and F7⋯H44 is an intramolecular hydrogen bond in the crystal structure, is between the positive and negative regions. In addition, molecular geometry optimized by DFT methods is in good agreement with the experimental values. In the optimized structure, the O-S, S-C, C-F and C-Cl bonds are slightly longer in comparison with those in the crystal. The intermolecular interaction energy for the dimmer was calculated to be 4.96 kcal mol-1. The results reveal that the two monomers are slightly combined with each other through two weak F⋯H hydrogen bonds. The compound and fipronil exhibited high insecticidal activity against the third instar larvae of Asian Corn Borer ( Ostrinia furnacalis (Guenée)) at 48 h after treatment with LC50 values of 4.17 μg/mL ( r 2 = 0.9974) and 5.36 μg/mL ( r 2 = 0.9970), respectively.

  4. Solution structure of Ln(III) complexes with macrocyclic ligands through theoretical evaluation of 1H NMR contact shifts.

    PubMed

    Rodríguez-Rodríguez, Aurora; Esteban-Gómez, David; de Blas, Andrés; Rodríguez-Blas, Teresa; Botta, Mauro; Tripier, Raphaël; Platas-Iglesias, Carlos

    2012-12-17

    calculations. Our results show that spin polarization effects dominate the (1)H A(iso) values. The X-ray crystal structures of [Ln(Me-DODPA)](PF(6))·2H(2)O (Ln = Eu or Lu) are also reported.

  5. (1) H and (13) C NMR data on natural and synthetic capsaicinoids.

    PubMed

    Gómez-Calvario, Víctor; Garduño-Ramírez, María Luisa; León-Rivera, Ismael; Rios, María Yolanda

    2016-04-01

    Capsaicinoids are the compounds responsible for the pungency of chili peppers. These substances have attracted the attention of many research groups in recent decades because of their antinociceptive, analgesic, anti-inflammatory, and anti-obesity properties, among others. There are nearly 160 capsaicinoids reported in the literature. Approximately 25 of them are natural products, while the rest are synthetic or semi-synthetic products. A large amount of NMR data for the capsaicinoids is dispersed throughout literature. Therefore, there is a need to organize all this NMR data in a systematic and orderly way. This review summarizes the (1) H and (13) C NMR data on 159 natural and synthetic capsaicinoids, with a brief discussion of some typical and relevant aspects of these NMR data. Copyright © 2015 John Wiley & Sons, Ltd.

  6. X-ray, FT-IR, NMR and PM5 structural studies and antibacterial activity of unexpectedly stable salinomycin-benzotriazole intermediate ester

    NASA Astrophysics Data System (ADS)

    Huczyński, Adam; Janczak, Jan; Antoszczak, Michał; Stefańska, Joanna; Brzezinski, Bogumil

    2012-08-01

    The unexpectedly stable benzotriazole ester of salinomycin (SAL-HOBt) - an intermediate product of the amidation reaction of salinomycin has been isolated and structurally characterised (using a single crystal) by X-ray, FT-IR, NMR and semiempirical methods. The results of the X-ray and spectroscopic studies demonstrated that this intermediate ester exist in the solid state and in solution exclusively as the stable O-acyl form. The molecular structure of SAL-HOBt is stabilised by relatively weak intramolecular hydrogen bonds. The PM5 calculation of possible structures of SAL-HOBt has shown that the O-acyl form is more energetically favourable than its N-oxide-N-acyl isomers. The antimicrobial tests show that SAL-HOBt is active against Gram-positive bacteria and clinical isolates methicillin-resistant Staphylococcus aureus (MIC = 1-2 μg/ml).

  7. Local environment and composition of magnesium gallium layered double hydroxides determined from solid-state {sup 1}H and {sup 71}Ga NMR spectroscopy

    SciTech Connect

    Petersen, Line Boisen; Lipton, Andrew S.; Zorin, Vadim; Nielsen, Ulla Gro

    2014-11-15

    Ordering of gallium(III) in a series of magnesium gallium (MgGa) layered double hydroxides (LDHs), [Mg{sub 1−x}Ga{sub x}(OH){sub 2}(NO{sub 3}){sub x}·yH{sub 2}O] was investigated using solid-state {sup 1}H and {sup 71}Ga NMR spectroscopy as well as powder X-ray diffraction. Three different proton environments from Mg{sub 3}-OH, Mg{sub 2}Ga-OH and intergallery water molecules were assigned and quantified using ({sup 1}H,{sup 71}Ga) HETCOR and {sup 1}H MAS NMR. A single {sup 71}Ga site originating from the unique Ga site in the MgGa LDH's was observed in {sup 71}Ga MAS and 3QMAS NMR spectra. Both {sup 1}H MAS NMR spectra recorded at 21.1 T (900 MHz) and elemental analysis show that the synthesized MgGa LDH's had a lower Mg:Ga ratio than that of the starting reactant solution. The origin of this is the formation of soluble [Ga(OH){sub 4}]{sup −} complexes formed during synthesis, and not due to formation of insoluble gallium (oxy)hydroxides. No sign of Ga-O-Ga connectivities or defects were detected for the MgGa LDH's. - Graphical abstract: Two types of hydroxides groups are observed in magnesium gallium layered double hydroxides revealing an ordering of Ga in the cation layer. - Highlights: • Ga is ordered in our magnesium gallium layered double hydroxides. • Ga depletion due to formation of soluble Ga complexes during synthesis. • No sign of Ga rich regions in magnesium gallium LDHs. • Solid state {sup 1}H and {sup 71}Ga give detailed insight into the structure.

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

    SciTech Connect

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

    2014-01-03

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

  9. Study of molecular dynamics and the solid state phase transition mechanism for unsymmetrical thiopyrophosphate using X-ray diffraction, DFT calculations and NMR spectroscopy.

    PubMed

    Potrzebowski, Marek J; Bujacz, Grzegorz D; Bujacz, Anna; Olejniczak, Sebastian; Napora, Paweł; Heliński, Jan; Ciesielski, Włodzimierz; Gajda, Jarosław

    2006-01-19

    Differential scanning calorimetry (DSC) and low-temperature X-ray diffraction studies showed that 2-thio-(5,5-dimethyl-1,3,2-dioxaphosphorinanyl)2'-oxo-dineopentyl-thiophosphate (compound 1) undergoes reversible phase transition at 203 K related to the change of symmetry of the crystallographic unit. Solid state NMR spectroscopy was used to establish the dynamic processes of aliphatic groups and the phosphorus skeleton. 13C and 31P variable temperature NMR studies as well as T1 and T1rho measurements of relaxation times revealed the different mode of molecular motion for each neopentyl residue directly bonded to phosphorus. It is concluded that molecular dynamics of aliphatic groups causes different van der Waals interactions in the crystal lattice and is the driving force of phase transition for compound 1. Finally, we showed that very sharp phase transition temperature makes compound 1 an excellent candidate as a low-temperature NMR thermometer in the solid phase.

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

    PubMed

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

    2014-10-01

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

  11. Identifying metabolites related to nitrogen mineralisation using 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    . T McDonald, Noeleen; Graham, Stewart; Watson, Catherine; Gordon, Alan; Lalor, Stan; Laughlin, Ronnie; Elliott, Chris; . P Wall, David

    2015-04-01

    Exploring new analysis techniques to enhance our knowledge of the various metabolites within our soil systems is imperative. Principally, this knowledge would allow us to link key metabolites with functional influences on critical nutrient processes, such as the nitrogen (N) mineralisation in soils. Currently there are few studies that utilize proton nuclear magnetic resonance spectroscopy (1H NMR) to characterize multiple metabolites within a soil sample. The aim of this research study was to examine the effectiveness of 1H NMR for isolating multiple metabolites that are related to the mineralizable N (MN) capacity across a range of 35 Irish grassland soils. Soils were measured for MN using the standard seven day anaerobic incubation (AI-7). Additionally, soils were also analysed for a range of physio-chemical properties [e.g. total N, total C, mineral N, texture and soil organic matter (SOM)]. Proton NMR analysis was carried on these soils by extracting with 40% methanol:water, lyophilizing and reconstituting in deuterium oxide and recording the NMR spectra on a 400MHz Bruker AVANCE III spectrometer. Once the NMR data were spectrally processed and analysed using multivariate statistical analysis, seven metabolites were identified as having significant relationships with MN (glucose, trimethylamine, glutamic acid, serine, aspartic acid, 4-aminohippuirc acid and citric acid). Following quantification, glucose was shown to explain the largest percentage variability in MN (72%). These outcomes suggest that sources of labile carbon are essential in regulating N mineralisation and the capacity of plant available N derived from SOM-N pools in these soils. Although, smaller in concentration, the amino acids; 4-aminohippuirc acid, glutamic acid and serine also significantly (P<0.05) explained 43%, 27% and 19% of the variability in MN, respectively. This novel study highlights the effectiveness of using 1H NMR as a practical approach to profile multiple metabolites in

  12. Photosensitized Peroxidation of Lipids: An Experiment Using 1H-NMR

    NASA Astrophysics Data System (ADS)

    Smith, Marion W.; Brown, Renee; Smullin, Steven; Eager, Jon

    1997-12-01

    The photoperoxidation of methyl linoleate, using 5,10,15,20-tetraphenyl porphyrin as photosensitizer, was monitored by 60 MHz 1H-NMR. Samples were irradiated for 10-24 hours in front of a 15 W fluorescent light, and NMR signals in the 5-6 ppm and 10-11 ppm region of the spectrum indicated peroxidation products were formed. The absorption of oxygen from the air was measured by attaching the sample tube to a gas burette. When vitamin E was added to the mixture the extent of peroxidation was reduced, showing the protective effect of the antioxidant. These experiments are appropriate for students of biochemistry

  13. (1) H and (13) C NMR characterization of new cycloartane triterpenes from Mangifera indica.

    PubMed

    Escobedo-Martínez, Carolina; Concepción Lozada, M; Hernández-Ortega, Simón; Villarreal, María Luisa; Gnecco, Dino; Enríquez, Raúl G; Reynolds, William

    2012-01-01

    From the stem bark of Mangifera indica, seven cycloartane-type secondary metabolites were isolated. Compound 1 has been isolated for the first time from M. indica, whereas compounds 2 (2a and 2b, as an epimeric mixture), 3, and 4 are new triterpenoid-type cycloartanes. Unambiguous (13) C and (1) H NMR assignments for these compounds and the known compounds mangiferonic acid (compound 5), isomangiferolic acid (compound 6), ambolic acid (compound 7), and friedelin (compound 8) are reported; the latter because full NMR data for these compounds are not available in the literature.

  14. Investigations of La Rioja terroir for wine production using 1H NMR metabolomics.

    PubMed

    López-Rituerto, Eva; Savorani, Francesco; Avenoza, Alberto; Busto, Jesús H; Peregrina, Jesús M; Engelsen, Søren Balling

    2012-04-04

    In this study, La Rioja wine terroir was investigated by the use of (1)H NMR metabolomics on must and wine samples. Rioja is a small wine region in central northern Spain which can geographically be divided into three subareas (Rioja Alta, Rioja Baja, and Rioja Alavesa). The winemaking process from must, through alcoholic and malolactic fermentation, was followed by NMR metabolomics and chemometrics of nine wineries in the Rioja subareas (terroirs). Application of interval extended canonical variate analysis (iECVA) showed discriminative power between wineries which are geographically very close. Isopentanol and isobutanol compounds were found to be key biomarkers for this differentiation.

  15. (1)H chemical shift differences of Prelog-Djerassi lactone derivatives: DFT and NMR conformational studies.

    PubMed

    Aímola, Túlio J; Lima, Dimas J P; Dias, Luiz C; Tormena, Cláudio F; Ferreira, Marco A B

    2015-02-21

    This work reports an experimental and theoretical study of the conformational preferences of several Prelog-Djerassi lactone derivatives, to elucidate the (1)H NMR chemical shift differences in the lactonic core that are associated with the relative stereochemistry of these derivatives. The boat-like conformation of explains the anomalous (1)H chemical shift between H-5a and H-5b, in which the two methyl groups (C-8 and C-9) face H-5b, leading to its higher shielding effect.

  16. Evaluation of saffron (Crocus sativus L.) adulteration with plant adulterants by (1)H NMR metabolite fingerprinting.

    PubMed

    Petrakis, Eleftherios A; Cagliani, Laura R; Polissiou, Moschos G; Consonni, Roberto

    2015-04-15

    In the present work, a preliminary study for the detection of adulterated saffron and the identification of the adulterant used by means of (1)H NMR and chemometrics is reported. Authentic Greek saffron and four typical plant-derived materials utilised as bulking agents in saffron, i.e., Crocus sativus stamens, safflower, turmeric, and gardenia were investigated. A two-step approach, relied on the application of both OPLS-DA and O2PLS-DA models to the (1)H NMR data, was adopted to perform authentication and prediction of authentic and adulterated saffron. Taking into account the deficiency of established methodologies to detect saffron adulteration with plant adulterants, the method developed resulted reliable in assessing the type of adulteration and could be viable for dealing with extensive saffron frauds at a minimum level of 20% (w/w).

  17. Total (1)H NMR assignment of 3β-acetoxypregna-5,16-dien-20-one.

    PubMed

    Becerra-Martinez, Elvia; Ramírez-Gualito, Karla E; Pérez-Hernández, Nury; Joseph-Nathan, Pedro

    2015-12-01

    This work describes the total and unambiguous assignment of the 750 MHz (1)H NMR spectrum of 3β-acetoxypregna-5,16-dien-20-one or 16-DPA (1), the well-known intermediate utilized in the synthesis of biological important commercial steroids. The task was accomplished by extracting the coupling constant values in the overlapped spectrum region by HSQC, and using these values in the (1)H iterative full spin analysis integrated in the PERCH NMR software. Comparison of the experimental vicinal coupling constants of 1 with the values calculated using Altona provides an excellent correlation. The same procedure, when applied to the published data of progesterone (2) and testosterone (3), afforded an acceptable correlation for 2 and a poor correlation for 3. In the last case, this suggested the reassignment of all four vicinal coupling constants for the methylene signals at the C-15 and C-16 positions, demonstrating the utility of this methodology.

  18. Inclusion complex of benzocaine and β-cyclodextrin: 1H NMR and isothermal titration calorimetry studies

    NASA Astrophysics Data System (ADS)

    Mic, Mihaela; Pırnǎu, Adrian; Bogdan, Mircea; Turcu, Ioan

    2013-11-01

    The supramolecular structure of the inclusion complex of β-cyclodextrin with benzocaine in aqueous solution has been investigated by 1H NMR spectroscopy and isothermal titration nanocalorimetry (ITC). Analysis of 1H NMR data by continuous variation method indicates that the benzocaine: β-cyclodextrin inclusion complex occurs and has a 1:1 stoichiometry. Rotating frame NOE spectroscopy (ROESY) was used to ascertain the solution geometry of the host-guest complex which indicates that the benzocaine molecule was included with the aromatic ring into the cyclodextrin cavity. Although the affinity of benzocaine for cyclodextrin is relatively high, the association constant cannot be measured using ITC due to the low solubility of benzocaine in water.

  19. 1H NMR profiling as an approach to differentiate conventionally and organically grown tomatoes.

    PubMed

    Hohmann, Monika; Christoph, Norbert; Wachter, Helmut; Holzgrabe, Ulrike

    2014-08-20

    This study describes the approach of (1)H NMR profiling for the authentication of organically produced tomatoes (Solanum lycopersicum). Overall, 361 tomato samples of two different cultivars and four different producers were regularly analyzed during a 7 month period. The results of principal component analysis showed a significant trend for the separation between organically and conventionally produced tomatoes (p < 0.001 using the t test). Linear discriminant analysis demonstrated good discrimination between the growing regimens, and external validation showed 100% correctly classified tomato samples. Further validation studies, however, also disclosed unexpected differences between individual producers, which interfere with the aim of predicting the cultivation method, yet the results indicate significant differences between (1)H NMR spectra of organically and conventionally grown tomatoes.

  20. (1)H-(13)C NMR-Based Profiling of Biotechnological Starch Utilization.

    PubMed

    Sundekilde, Ulrik K; Meier, Sebastian

    2016-10-04

    Starch is used in food- and nonfood applications as a renewable and degradable source of carbon and energy. Insight into the chemical detail of starch degradation remains challenging as the starch constituents amylose and amylopectin are homopolymers. We show that considerable molecular detail of starch fragmentation can be obtained from multivariate analysis of spectral features in optimized (1)H-(13)C NMR spectroscopy of starch fragments to identify relevant features that distinguish processes in starch utilization. As a case study, we compare the profiles of starch fragments in commercial beer samples. Spectroscopic profiles of homooligomeric starch fragments can be excellent indicators of process conditions. In addition, differences in the structure and composition of starch fragments have predictive value for downstream process output such as ethanol production from starch. Thus, high-resolution (1)H-(13)C NMR spectroscopic profiles of homooligomeric fragment mixtures in conjunction with chemometric methods provide a useful addition to the analytical chemistry toolbox of biotechnological starch utilization.

  1. The structure of polycaprolactone-clay nanocomposites investigated by 1H NMR relaxometry.

    PubMed

    Monteiro, Mariana S S B; Rodrigues, Claudia Lopes; Neto, Roberto P C; Tavares, Maria Inês Bruno

    2012-09-01

    Nanocomposites based on polycaprolactone (PCL), containing concentrations of 1, 3 and 5 wt% of sodium montmorillonite (NT-25) and organo-modified montmorillonite clay, with three different salts (Viscogel B7, Viscogel S4 and Viscogel B8), were prepared employing the solution intercalation method using chloroform. The PCL nanocomposites were characterized by relaxometry, through determination of the hydrogen spin-lattice relaxation times using low-field nuclear magnetic resonance (NMR). Conventional X-ray diffraction (XDR) was also used to measure the basal space of the nanoclay. The proton spin-lattice relaxation parameters showed that hybrid nanocomposites were formed, containing different parts of intercalated and exfoliated organoclay. The proton T1rhoH also indicated changes in the microstructure, organization and the molecular mobility of the hybrid materials. NMR relaxometry is a good way to evaluate nanomaterials because it provides complementary information, since it is measured in a different time scale. Furthermore, differential scanning calorimetry and thermogravimetric analysis were also used to investigate the crystallization and thermal behavior of the nanocomposites, respectively. All materials had low crystallization temperature (Tc) and the melting temperature (Tm) were very close to that of the PCL matrix, but the degree of crystallinity of the nanocomposites decreased. TGA analysis demonstrated that montmorillonite accelerates PCL's decomposition while unmodified montmorillonite has the opposite effect.

  2. Measurement of Ligand–Target Residence Times by 1H Relaxation Dispersion NMR Spectroscopy

    PubMed Central

    2016-01-01

    A ligand-observed 1H NMR relaxation experiment is introduced for measuring the binding kinetics of low-molecular-weight compounds to their biomolecular targets. We show that this approach, which does not require any isotope labeling, is applicable to ligand–target systems involving proteins and nucleic acids of variable molecular size. The experiment is particularly useful for the systematic investigation of low affinity molecules with residence times in the micro- to millisecond time regime. PMID:27933946

  3. Theoretical and experimental investigation of the 1H NMR spectrum of putrescine

    NASA Astrophysics Data System (ADS)

    Allouche, A. R.; Graveron-Demilly, D.; Fauvelle, F.; Aubert-Frécon, M.

    2008-12-01

    Chemical shifts δ and spin-spin coupling constants J have been calculated for the putrescine molecule, a polyamine present in prostate tissue, through a DFT/B3LYP/6-311++G(d,p)/PCM/(GIAO) approach, which has been shown to be accurate in previous work. From δ and J values, calculated for the first time for the isolated and the solvated putrescine, the 1H NMR spectra have been simulated. Comparisons between the calculated and the experimental NMR spectra at 400 MHz show a good agreement and allow to propose reliable values for the NMR spin Hamiltonian parameters of putrescine to be used as good starting values for further quantitation methods of metabolites in prostate tissue.

  4. Detection of Apoptosis and Necrosis in Normal Human Lung Cells Using 1H NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Shih, Chwen-Ming; Ko, Wun-Chang; Yang, Liang-Yo; Lin, Chien-Ju; Wu, Jui-Sheng; Lo, Tsui-Yun; Wang, Shwu-Huey; Chen, Chien-Tsu

    2005-05-01

    This study aimed to detect apoptosis and necrosis in MRC-5, a normal human lung cell line, by using noninvasive proton nuclear magnetic resonance (1H NMR). Live MRC-5 cells were processed first for 1H NMR spectroscopy; subsequently their types and the percentage of cell death were assessed on a flow cytometer. Cadmium (Cd) and mercury (Hg) induced apoptosis and necrosis in MRC-5 cells, respectively, as revealed by phosphatidylserine externalization on a flow cytometer. The spectral intensity ratio of methylene (CH2) resonance (at 1.3 ppm) to methyl (CH3) resonance (at 0.9 ppm) was directly proportional to the percentage of apoptosis and strongly and positively correlated with PI staining after Cd treatment (r2 = 0.9868, P < 0.01). In contrast, this ratio only increased slightly within 2-h Hg treatment, and longer Hg exposure failed to produce further increase. Following 2-h Hg exposure, the spectral intensity of choline resonance (at 3.2 ppm) was abolished, but this phenomenon was absent in Cd-induced apoptosis. These findings together demonstrate that 1H NMR is a novel tool with a quantitative potential to distinguish apoptosis from necrosis as early as the onset of cell death in normal human lung cells.

  5. (1)H NMR metabonomic analysis in renal cell carcinoma: a possible diagnostic tool.

    PubMed

    Zira, Athina N; Theocharis, Stamatios E; Mitropoulos, Dionisios; Migdalis, Vasilios; Mikros, Emmanuel

    2010-08-06

    (1)H NMR based metabonomic approach was applied in order to monitor the alterations of plasma metabolic profile in Renal Cell Carcinoma (RCC) patients and controls. (1)H NMR spectra of plasma samples from 32 RCC patients and 13 controls (patients exhibiting benign urologic disease) were recorded and analyzed using multivariate statistical techniques. Alterations in the levels of LDL/VLDL, NAC, lactate, and choline were observed between RCC patients and controls discriminating these groups in Principal Component Analysis (PCA) plots. Post OSC PLS-DA presented a satisfactory clustering between T1 with T3 RCC patients. Decrease in plasma lipid concentrations in RCC patients was verified using conventional clinical chemistry analysis. The results suggest that combination of (1)H NMR spectroscopy with PCA has potential in cancer diagnosis; however, a limitation of the method to monitor RCC is that major biomarkers revealed (lipoproteins and choline) in this metabolic profile are not unique to RCC but may be the result of the presence of any malignancy.

  6. Investigation of 1H NMR chemical shifts of organic dye with hydrogen bonds and ring currents.

    PubMed

    Park, Sung Soo; Won, Yong Sun; Lee, Woojin; Kim, Jae Hong

    2011-04-07

    The (1)H NMR chemical shifts were theoretically computed for the organic dyes 2-(2,6-dimethyl-4H-pyran-4-ylidene)-malononitrile (1), cyano-(2,6-dimethyl-4H-pyran-4-ylidene)-acetic acid methyl ester (2), 2-(2,6-bis(4-(dimethylamino)styryl)-4H-pyran-4-ylidene)-malononitrile (3), and methyl 2-(2,6-bis(4-(dimethylamino)styryl)-4H-pyran-4-ylidene)-2-cyanoacetate (4) at the GIAO/B3LYP/6-311++G(d,p)//B3LYP/6-311++G(d,p) level of theory. Moreover, the intramolecular rotational barriers of the molecules were calculated to evaluate the internal flexibility with respect to the torsional degrees of freedom, and the nuclear-independent chemical shifts (NICS) were employed to analyze the ring currents. The difference was explained in terms of intramolecular hydrogen bonds and ring currents of the molecules. The (1)H NMR spectra were reproduced by experiments for the comparison with computationally constructed data. Our results suggest a good guideline in interpreting (1)H NMR chemical shifts using computational methods and furthermore a reliable perspective for designing molecular structures.

  7. 1H-NMR METABONOMICS ANALYSIS OF SERA DIFFERENTIATES BETWEEN MAMMARY TUMOR-BEARING MICE AND HEALTHY CONTROLS

    EPA Science Inventory

    Global analysis of 1H-NMR spectra of serum is an appealing approach for the rapid detection of cancer. To evaluate the usefulness of this method in distinguishing between mammary tumor-bearing mice and healthy controls, we conducted 1H-NMR metabonomic analyses on serum samples ob...

  8. Translational diffusion in paramagnetic liquids by 1H NMR relaxometry: nitroxide radicals in solution.

    PubMed

    Kruk, D; Korpała, A; Kubica, A; Meier, R; Rössler, E A; Moscicki, J

    2013-01-14

    For nitroxide radicals in solution one can identify three frequency regimes in which (1)H spin-lattice relaxation rate of solvent molecules depend linearly on square root of the (1)H resonance frequency. Combining a recently developed theory of nuclear (proton) spin-lattice relaxation in solutions of nitroxide radicals [D. Kruk et al., J. Chem. Phys. 137, 044512 (2012)] with properties of the spectral density function associated with translational dynamics, relationships between the corresponding linear changes of the relaxation rate (for (14)N spin probes) and relative translational diffusion coefficient of the solvent and solute molecules have been derived (in analogy to (15)N spin probes [E. Belorizky et al., J. Phys. Chem. A 102, 3674 (1998)]). This method allows a simple and straightforward determination of diffusion coefficients in spin-labeled systems, by means of (1)H nuclear magnetic resonance (NMR) relaxometry. The approach has thoroughly been tested by applying to a large set of experimental data-(1)H spin-lattice relaxation dispersion results for solutions of different viscosity (decalin, glycerol, propylene glycol) of (14)N and (15)N spin probes. The experiments have been performed versus temperature (to cover a broad range of translational diffusion coefficients) using field cycling spectrometer which covers three decades in (1)H resonance frequency, 10 kHz-20 MHz. The limitations of NMR relaxometry caused by the time scale of the translational dynamics as well as electron spin relaxation have been discussed. It has been shown that for spin-labeled systems NMR relaxometry gives access to considerably faster diffusion processes than for diamagnetic systems.

  9. Translational diffusion in paramagnetic liquids by 1H NMR relaxometry: Nitroxide radicals in solution

    NASA Astrophysics Data System (ADS)

    Kruk, D.; Korpała, A.; Kubica, A.; Meier, R.; Rössler, E. A.; Moscicki, J.

    2013-01-01

    For nitroxide radicals in solution one can identify three frequency regimes in which 1H spin-lattice relaxation rate of solvent molecules depend linearly on square root of the 1H resonance frequency. Combining a recently developed theory of nuclear (proton) spin-lattice relaxation in solutions of nitroxide radicals [D. Kruk et al., J. Chem. Phys. 137, 044512 (2012)], 10.1063/1.4736854 with properties of the spectral density function associated with translational dynamics, relationships between the corresponding linear changes of the relaxation rate (for 14N spin probes) and relative translational diffusion coefficient of the solvent and solute molecules have been derived (in analogy to 15N spin probes [E. Belorizky et al., J. Phys. Chem. A 102, 3674 (1998)], 10.1021/jp980397h). This method allows a simple and straightforward determination of diffusion coefficients in spin-labeled systems, by means of 1H nuclear magnetic resonance (NMR) relaxometry. The approach has thoroughly been tested by applying to a large set of experimental data—1H spin-lattice relaxation dispersion results for solutions of different viscosity (decalin, glycerol, propylene glycol) of 14N and 15N spin probes. The experiments have been performed versus temperature (to cover a broad range of translational diffusion coefficients) using field cycling spectrometer which covers three decades in 1H resonance frequency, 10 kHz-20 MHz. The limitations of NMR relaxometry caused by the time scale of the translational dynamics as well as electron spin relaxation have been discussed. It has been shown that for spin-labeled systems NMR relaxometry gives access to considerably faster diffusion processes than for diamagnetic systems.

  10. (13)C and (19)F solid-state NMR and X-ray crystallographic study of halogen-bonded frameworks featuring nitrogen-containing heterocycles.

    PubMed

    Szell, Patrick M J; Gabriel, Shaina A; Gill, Russell D D; Wan, Shirley Y H; Gabidullin, Bulat; Bryce, David L

    2017-03-01

    Halogen bonding is a noncovalent interaction between the electrophilic region of a halogen (σ-hole) and an electron donor. We report a crystallographic and structural analysis of halogen-bonded compounds by applying a combined X-ray diffraction (XRD) and solid-state nuclear magnetic resonance (SSNMR) approach. Single-crystal XRD was first used to characterize the halogen-bonded cocrystals formed between two fluorinated halogen-bond donors (1,4-diiodotetrafluorobenzene and 1,3,5-trifluoro-2,4,6-triiodobenzene) and several nitrogen-containing heterocycles (acridine, 1,10-phenanthroline, 2,3,5,6-tetramethylpyrazine, and hexamethylenetetramine). New structures are reported for the following three cocrystals, all in the P21/c space group: acridine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C13H9N, 1,10-phenanthroline-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C12H8N2, and 2,3,5,6-tetramethylpyrazine-1,3,5-trifluoro-2,4,6-triiodobenzene (1/1), C6F3I3·C8H12N2. (13)C and (19)F solid-state magic-angle spinning (MAS) NMR is shown to be a convenient method to characterize the structural features of the halogen-bond donor and acceptor, with chemical shifts attributable to cocrystal formation observed in the spectra of both nuclides. Cross polarization (CP) from (19)F to (13)C results in improved spectral sensitivity in characterizing the perfluorinated halogen-bond donor when compared to conventional (1)H CP. Gauge-including projector-augmented wave density functional theory (GIPAW DFT) calculations of magnetic shielding constants, along with optimization of the XRD structures, provide a final set of structures in best agreement with the experimental (13)C and (19)F chemical shifts. Data for carbons bonded to iodine remain outliers due to well-known relativistic effects.

  11. Dynamic 1H-NMR study of unusually high barrier to rotation about the partial Csbnd N double bond in N,N-dimethyl carbamoyl 5-aryloxytetrazoles

    NASA Astrophysics Data System (ADS)

    Movahedifar, Fahimeh; Modarresi-Alam, Ali Reza; Kleinpeter, Erich; Schilde, Uwe

    2017-04-01

    The synthesis of new N,N-dimethyl carbamoyl 5-aryloxytetrazoles have been reported. Their dynamic 1H-NMR via rotation about Csbnd N bonds in moiety of urea group [a; CO-NMe2 and b; (2-tetrazolyl)N-CO rotations] in the solvents CDCl3 (223-333 K) and DMSO (298-363 K) is studied. Accordingly, the free energies of activation, obtained 16.5 and 16.9 kcal mol-1 respectively, attributed to the conformational isomerization about the Me2Nsbnd Cdbnd O bond (a rotation). Moreover, a and b barrier to rotations in 5-((4-methylphenoxy)-N,N-dimethyl-2H-tetrazole-2-carboxamide (P) also were computed at level of B3LYP using 6-311++G** basis set. The optimized geometry parameters are in good agreement with X-ray structure data. The computation of energy barrier for a and b was determined 16.9 and 2.5 kcal mol-1, respectively. The former is completely in agreement with the result obtained via dynamic NMR. X-ray structure analysis data demonstrate that just 2-acylated tetrazole was formed in the case of 5-(p-tolyloxy)-N,N-dimethyl-2H-tetrazole-2-carboxamide. X-ray data also revealed a planar trigonal orientation of the Me2N group which is coplanar to carbonyl group with the partial double-bond Csbnd N character. It also demonstrates the synperiplanar position of Cdbnd O group with tetrazolyl ring. On average, in solution the plane containing carbonyl bond is almost perpendicular to the plane of the tetrazolyl ring (because of steric effects as confirmed by B3LYP/6-311++G**) while the plane containing Me2N group is coplanar with carbonyl bond which is in contrast with similar urea derivatives and it demonstrates the unusually high rotational energy barrier of these compounds.

  12. The acyl nitroso Diels-Alder (ANDA) reaction of sorbate derivatives: an X-ray and 15N NMR study with an application to amino-acid synthesis.

    PubMed

    Bollans, Lee; Bacsa, John; Iggo, Jonathan A; Morris, Gareth A; Stachulski, Andrew V

    2009-11-07

    We present a study of the acyl nitroso Diels-Alder (ANDA) reaction of sorbate esters and sorbic alcohol derivatives, using alkoxycarbonyl nitroso dienophiles. An optimisation of the reaction conditions for ethyl sorbate is first presented, and the product is used in an efficient synthesis of 5-methylornithine. Structure-reactivity trends in sorbic alcohol (E,E-2,4-hexadien-1-ol) and its acylated analogues are then discussed. We present single-crystal X-ray structural proof for key adducts in both series and present in detail a novel HMBC/HSQC ((1)H-(15)N) criterion for ready distinction of regioisomers arising from such ANDA reactions.

  13. The conformational stability, solvation and the assignments of the experimental infrared, Raman, (1)H and (13)C NMR spectra of the local anesthetic drug lidocaine.

    PubMed

    Badawi, Hassan M; Förner, Wolfgang; Ali, Shaikh A

    2015-05-05

    The structure, vibrational and (1)H and (13)C NMR spectra of the local anesthetic drug lidocaine were investigated by the B3LYP/6-311G(∗∗) calculations. The molecule was predicted to have the non-planar cis (NCCN∼0°) structures being about 2-6kcal/mol lower in energy than the corresponding trans (NCCN∼180°) forms. The calculated NCCN (9.6°) and CNCC (-132.2°) torsional angles were in a good qualitative agreement with the reported X-ray angles (3.1 and 13.0°, -102.67 and -77.9°, respectively, for H-bonded dimers). The Gibbs energy of solution of lidocaine in formamide, water, dimethylsulfoxide, acetonitrile, methanol, ethanol and chloroform solutions was estimated at the B3LYP level. The predicted affinity of lidocaine toward the alcohols, acetonitrile and chloroform solutions was in excellent agreement with the reported experimental solubility of the drug in organic solvents. The analysis of the observed vibrational spectra is consistent with the presence of lidocaine in only one conformation at room temperature. The (1)H and (13)C NMR spectra of lidocaine were interpreted by experimental and DFT calculated chemical shifts of the drug. The RMSD between experimental and theoretical (1)H and (13)C chemical shifts for lidocaine is 0.47 and 8.26ppm, respectively.

  14. The conformational stability, solvation and the assignments of the experimental infrared, Raman, 1H and 13C NMR spectra of the local anesthetic drug lidocaine

    NASA Astrophysics Data System (ADS)

    Badawi, Hassan M.; Förner, Wolfgang; Ali, Shaikh A.

    2015-05-01

    The structure, vibrational and 1H and 13C NMR spectra of the local anesthetic drug lidocaine were investigated by the B3LYP/6-311G∗∗ calculations. The molecule was predicted to have the non-planar cis (NCCN ∼ 0°) structures being about 2-6 kcal/mol lower in energy than the corresponding trans (NCCN ∼ 180°) forms. The calculated NCCN (9.6°) and CNCC (-132.2°) torsional angles were in a good qualitative agreement with the reported X-ray angles (3.1 and 13.0°, -102.67 and -77.9°, respectively, for H-bonded dimers). The Gibbs energy of solution of lidocaine in formamide, water, dimethylsulfoxide, acetonitrile, methanol, ethanol and chloroform solutions was estimated at the B3LYP level. The predicted affinity of lidocaine toward the alcohols, acetonitrile and chloroform solutions was in excellent agreement with the reported experimental solubility of the drug in organic solvents. The analysis of the observed vibrational spectra is consistent with the presence of lidocaine in only one conformation at room temperature. The 1H and 13C NMR spectra of lidocaine were interpreted by experimental and DFT calculated chemical shifts of the drug. The RMSD between experimental and theoretical 1H and 13C chemical shifts for lidocaine is 0.47 and 8.26 ppm, respectively.

  15. The structure investigations of dehydroacetic acid and 1,8-diaminonaphthalene condensation product by NMR, MS, and X-ray measurements

    NASA Astrophysics Data System (ADS)

    Kołodziej, B.; Morawiak, M.; Kamieński, B.; Schilf, W.

    2016-05-01

    A new unexpected product of condensation reaction of 1,8-diaminonaphthalene (DAN) and carbonyl compound (here: dehydroacetic acid (dha)) was synthesized. Discussion about the molecular structure of possible products of this reaction was done on the base of NMR studies. The structure of the titled product in both DMSO solution and in the solid state was resolved by analysis of its spectral data (X-ray structure analysis, multinuclear NMR in solution and solid state spectra) and MS measurements. The presented studies provided clear evidence that the titled product exists in diluted DMSO solution as the mixture of two kinetic free ionic species whereas in concentrated DMSO solution as well as in the solid state this system forms associated ionic pairs bonded together by hydrogen bonds.

  16. Applications of high-resolution 1H solid-state NMR.

    PubMed

    Brown, Steven P

    2012-02-01

    This article reviews the large increase in applications of high-resolution (1)H magic-angle spinning (MAS) solid-state NMR, in particular two-dimensional heteronuclear and homonuclear (double-quantum and spin-diffusion NOESY-like exchange) experiments, in the last five years. These applications benefit from faster MAS frequencies (up to 80 kHz), higher magnetic fields (up to 1 GHz) and pulse sequence developments (e.g., homonuclear decoupling sequences applicable under moderate and fast MAS). (1)H solid-state NMR techniques are shown to provide unique structural insight for a diverse range of systems including pharmaceuticals, self-assembled supramolecular structures and silica-based inorganic-organic materials, such as microporous and mesoporous materials and heterogeneous organometallic catalysts, for which single-crystal diffraction structures cannot be obtained. The power of NMR crystallography approaches that combine experiment with first-principles calculations of NMR parameters (notably using the GIPAW approach) are demonstrated, e.g., to yield quantitative insight into hydrogen-bonding and aromatic CH-π interactions, as well as to generate trial three-dimensional packing arrangements. It is shown how temperature-dependent changes in the (1)H chemical shift, linewidth and DQ-filtered signal intensity can be analysed to determine the thermodynamics and kinetics of molecular level processes, such as the making and breaking of hydrogen bonds, with particular application to proton-conducting materials. Other applications to polymers and biopolymers, inorganic compounds and bioinorganic systems, paramagnetic compounds and proteins are presented. The potential of new technological advances such as DNP methods and new microcoil designs is described.

  17. Identification of fucans from four species of sea cucumber by high temperature 1H NMR

    NASA Astrophysics Data System (ADS)

    Wu, Nian; Chen, Shiguo; Ye, Xingqian; Li, Guoyun; Yin, Li'ang; Xue, Changhu

    2014-10-01

    Acidic polysaccharide, which has various biological activities, is one of the most important components of sea cucumber. In the present study, crude polysaccharide was extracted from four species of sea cucumber from three different geographical zones, Pearsonothuria graeffei ( Pg) from Indo-Pacific, Holothuria vagabunda ( Hv) from Norwegian Coast, Stichopus tremulu ( St) from Western Indian Ocean, and Isostichopus badionotu ( Ib) from Western Atlantic. The polysaccharide extract was separated and purified with a cellulose DEAE anion-exchange column to obtain corresponding sea cucumber fucans (SC-Fucs). The chemical property of these SC-Fucs, including molecular weight, monosaccharide composition and sulfate content, was determined. Their structure was compared simply with fourier infrared spectrum analyzer and identified with high temperature 1H nuclear magnetic resonance spectrum analyzer (NMR) and room temperature 13C NMR. The results indicated that Fuc- Pg obtained from the torrid zone mainly contained 2,4-O-disulfated and non-sulfated fucose residue, whereas Fuc- Ib from the temperate zone contained non-, 2-O- and 2,4-O-disulfated fucose residue; Fuc- St from the frigid zone and Fuc- Hv from the torrid zone contained mainly non-sulfated fucose residue. The proton of SC-Fucs was better resolved via high temperature 1H NMR than via room temperature 1H NMR. The fingerprint of sea cucumber in different sea regions was established based on the index of anomer hydrogen signal in SC-Fucs. Further work will help to understand whether there exists a close relationship between the geographical area of sea cucumber and the sulfation pattern of SC-Fucs.

  18. (1)H nuclear magnetic resonance (NMR) as a tool to measure dehydration in mice.

    PubMed

    Li, Matthew; Vassiliou, Christophoros C; Colucci, Lina A; Cima, Michael J

    2015-08-01

    Dehydration is a prevalent pathology, where loss of bodily water can result in variable symptoms. Symptoms can range from simple thirst to dire scenarios involving loss of consciousness. Clinical methods exist that assess dehydration from qualitative weight changes to more quantitative osmolality measurements. These methods are imprecise, invasive, and/or easily confounded, despite being practiced clinically. We investigate a non-invasive, non-imaging (1)H NMR method of assessing dehydration that attempts to address issues with existing clinical methods. Dehydration was achieved by exposing mice (n = 16) to a thermally elevated environment (37 °C) for up to 7.5 h (0.11-13% weight loss). Whole body NMR measurements were made using a Bruker LF50 BCA-Analyzer before and after dehydration. Physical lean tissue, adipose, and free water compartment approximations had NMR values extracted from relaxation data through a multi-exponential fitting method. Changes in before/after NMR values were compared with clinically practiced metrics of weight loss (percent dehydration) as well as blood and urine osmolality. A linear correlation between tissue relaxometry and both animal percent dehydration and urine osmolality was observed in lean tissue, but not adipose or free fluids. Calculated R(2) values for percent dehydration were 0.8619 (lean, P < 0.0001), 0.5609 (adipose, P = 0.0008), and 0.0644 (free fluids, P = 0.3445). R(2) values for urine osmolality were 0.7760 (lean, P < 0.0001), 0.5005 (adipose, P = 0.0022), and 0.0568 (free fluids, P = 0.3739). These results suggest that non-imaging (1)H NMR methods are capable of non-invasively assessing dehydration in live animals.

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

    PubMed Central

    2015-01-01

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

  20. Metabolomic Investigations of American Oysters Using 1H-NMR Spectroscopy

    PubMed Central

    Tikunov, Andrey P.; Johnson, Christopher B.; Lee, Haakil; Stoskopf, Michael K.; Macdonald, Jeffrey M.

    2010-01-01

    The Eastern oyster (Crassostrea virginica) is a useful, robust model marine organism for tissue metabolism studies. Its relatively few organs are easily delineated and there is sufficient understanding of their functions based on classical assays to support interpretation of advanced spectroscopic approaches. Here we apply high-resolution proton nuclear magnetic resonance (1H NMR)-based metabolomic analysis to C. virginica to investigate the differences in the metabolic profile of different organ groups, and magnetic resonance imaging (MRI) to non-invasively identify the well separated organs. Metabolites were identified in perchloric acid extracts of three portions of the oyster containing: (1) adductor muscle, (2) stomach and digestive gland, and (3) mantle and gills. Osmolytes dominated the metabolome in all three organ blocks with decreasing concentration as follows: betaine > taurine > proline > glycine > ß-alanine > hypotaurine. Mitochondrial metabolism appeared most pronounced in the adductor muscle with elevated levels of carnitine facilitating ß-oxidation, and ATP, and phosphoarginine synthesis, while glycogen was elevated in the mantle/gills and stomach/digestive gland. A biochemical schematic is presented that relates metabolites to biochemical pathways correlated with physiological organ functions. This study identifies metabolites and corresponding 1H NMR peak assignments for future NMR-based metabolomic studies in oysters. PMID:21116407

  1. Magic angle spinning NMR of proteins: high-frequency dynamic nuclear polarization and (1)H detection.

    PubMed

    Su, Yongchao; Andreas, Loren; Griffin, Robert G

    2015-01-01

    Magic angle spinning (MAS) NMR studies of amyloid and membrane proteins and large macromolecular complexes are an important new approach to structural biology. However, the applicability of these experiments, which are based on (13)C- and (15)N-detected spectra, would be enhanced if the sensitivity were improved. Here we discuss two advances that address this problem: high-frequency dynamic nuclear polarization (DNP) and (1)H-detected MAS techniques. DNP is a sensitivity enhancement technique that transfers the high polarization of exogenous unpaired electrons to nuclear spins via microwave irradiation of electron-nuclear transitions. DNP boosts NMR signal intensities by factors of 10(2) to 10(3), thereby overcoming NMR's inherent low sensitivity. Alternatively, it permits structural investigations at the nanomolar scale. In addition, (1)H detection is feasible primarily because of the development of MAS rotors that spin at frequencies of 40 to 60 kHz or higher and the preparation of extensively (2)H-labeled proteins.

  2. Characterization of D-glucaric acid using NMR, x-ray crystal structure, and MM3 molecular modeling analyses

    Technology Transfer Automated Retrieval System (TEKTRAN)

    D-glucaric acid was characterized in solution by comparing NMR spectra from the isotopically unlabeled molecule with those from D-glucaric acid labeled with deuterium or carbon-13 atoms. The NMR studies provided unequivocal assignments for all carbon atoms and non-hydroxyl protons of the molecule. ...

  3. 1H to 13C Energy Transfer in Solid State NMR Spectroscopy of Natural Organic Systems

    NASA Astrophysics Data System (ADS)

    Berns, Anne E.; Conte, Pellegrino

    2010-05-01

    Cross polarization (CP) magic angle spinning (MAS) 13C-NMR spectroscopy is a solid state NMR technique widely used to study chemical composition of organic materials with low or no solubility in the common deuterated solvents used to run liquid state NMR experiments. Based on the magnetization transfer from abundant nuclei (with spin of 1 -2) having a high gyromagnetic ratio (γ), such as protons, to the less abundant 13C nuclei with low γ values, 13C-CPMAS NMR spectroscopy is often applied in environmental chemistry to obtain quantitative information on the chemical composition of natural organic matter (NOM) (Conte et al., 2004), although its quantitative assessment is still matter of heavy debates. Many authors (Baldock et al., 1997; Conte et al., 1997, 2002; Dria et al., 2002; Kiem et al., 2000; Kögel-Knabner, 2000; Preston, 2001), reported that the application of appropriate instrument setup as well as the use of special pulse sequences and correct spectra elaboration may provide signal intensities that are directly proportional to the amount of nuclei creating a NMR signal. However, many other papers dealt with the quantitative unsuitability of 13C-CPMAS NMR spectroscopy. Among those, Mao et al. (2000), Smernik and Oades (2000 a,b), and Preston (2001) reported that cross-polarized NMR techniques may fail in a complete excitation of the 13C nuclei. In fact, the amount of observable carbons via 13C-CPMAS NMR spectroscopy appeared, in many cases, lower than that measured by a direct observation of the 13C nuclei. As a consequence, cross-polarized NMR techniques may provide spectra where signal distribution may not be representative of the quantitative distribution of the different natural organic matter components. Cross-polarization is obtained after application of an initial 90° x pulse on protons and a further spin lock pulse (along the y axis) having a fixed length (contact time) for both nuclei (1H and 13C) once the Hartmann-Hahn condition is matched

  4. [Study on three different species tibetan medicine sea buckthorn by 1H-NMR-based metabonomics].

    PubMed

    Su, Yong-Wen; Tan, Er; Zhang, Jing; You, Jia-Li; Liu, Yue; Liu, Chuan; Zhou, Xiang-Dong; Zhang, Yi

    2014-11-01

    The 1H-NMR fingerprints of three different species tibetan medicine sea buckthorn were established by 1H-HMR metabolomics to find out different motablism which could provide a new method for the quality evaluation of sea buckthorn. The obtained free induction decay (FID) signal will be imported into MestReNova software and into divide segments. The data will be normalized and processed by principal component analysis and.partial least squares discriminant analysis to perform pattern recognition. The results showed that 25 metabolites belonging to different chemical types were detected from sea buckthorn,including flavonoids, triterpenoids, amino acids, carbohydrates, fatty acids, etc. PCA and PLS-DA analysis showed three different varietiest of sea buckthorn that can be clearly separated by the content of L-quebrachitol, malic acid and some unidentified sugars, which can be used as the differences metabolites of three species of sea buckthorn. 1H-NMR-based metabonomies method had a holistic characteristic with sample preparation and handling. The results of this study can offer an important reference for the species identification and quality control of sea buckthorn.

  5. Nanoliter-volume 1H NMR detection using periodic stopped-flow capillary electrophoresis.

    PubMed

    Olson, D L; Lacey, M E; Webb, A G; Sweedler, J V

    1999-08-01

    Recent advances in the analysis of nanoliter volumes using 1H NMR microcoils have led to the application of microcoils as detectors for capillary electrophoresis (CE). Custom NMR probes consisting of 1-mm-long solenoidal microcoils are fabricated from 50-micron diameter wire wrapped around capillaries to create nanoliter-volume detection cells. For geometries in which the capillary and static magnetic field are not parallel, the electrophoretic current induces a magnetic field gradient which degrades the spectroscopic information obtainable from CE/NMR. To reduce this effect and allow longer analyte observation times, the electrophoretic voltage is periodically interrupted so that 1-min high-resolution NMR spectra are obtained for every 15 s of applied voltage. The limits of detection (LODs; based on S/N = 3) for CE/NMR for arginine are 57 ng (330 pmol; 31 mM) and for triethylamine (TEA) are 9 ng (88 pmol; 11 mM). Field-amplified stacking is used for sample preconcentration. As one example, a 290-nL injection of a mixture of arginine and TEA both at 50 mM (15 nmol of each injected) is stacked severalfold for improved concentration LODs while achieving a separation efficiency greater than 50,000. Dissolving a sample in a mixture of 10% H2O/90% D2O allows H2O to serve as the nearly ideal neutral tracer and allows direct observation of the parabolic and flat flow profiles associated with gravimetric and electrokinetic injection, respectively. The unique capabilities of CE and the rich spectral information provided by NMR spectroscopy combine to yield a valuable analytical tool, especially in the study of mass-limited samples.

  6. Survey and qualification of internal standards for quantification by 1H NMR spectroscopy.

    PubMed

    Rundlöf, Torgny; Mathiasson, Marie; Bekiroglu, Somer; Hakkarainen, Birgit; Bowden, Tim; Arvidsson, Torbjörn

    2010-09-05

    In quantitative NMR (qNMR) selection of an appropriate internal standard proves to be crucial. In this study, 25 candidate compounds considered to be potent internal standards were investigated with respect to the ability of providing unique signal chemical shifts, purity, solubility, and ease of use. The (1)H chemical shift (delta) values, assignments, multiplicities and number of protons (for each signal), appropriateness (as to be used as internal standards) in four different deuterated solvents (D(2)O, DMSO-d(6), CD(3)OD, CDCl(3)) were studied. Taking into account the properties of these 25 internal standards, the most versatile eight compounds (2,4,6-triiodophenol, 1,3,5-trichloro-2-nitrobenzene, 3,4,5-trichloropyridine, dimethyl terephthalate, 1,4-dinitrobenzene, 2,3,5-triiodobenzoic acid, maleic acid and fumaric acid) were qualified using both differential scanning calorimetry (DSC) and NMR spectroscopy employing highly pure acetanilide as the reference standard. The data from these two methods were compared as well as utilized in the quality assessment of the compounds as internal standards. Finally, the selected internal standards were tested and evaluated in a real case of quantitative NMR analysis of a paracetamol pharmaceutical product.

  7. Automatic 1H-NMR Screening of Fatty Acid Composition in Edible Oils

    PubMed Central

    Castejón, David; Fricke, Pascal; Cambero, María Isabel; Herrera, Antonio

    2016-01-01

    In this work, we introduce an NMR-based screening method for the fatty acid composition analysis of edible oils. We describe the evaluation and optimization needed for the automated analysis of vegetable oils by low-field NMR to obtain the fatty acid composition (FAC). To achieve this, two scripts, which automatically analyze and interpret the spectral data, were developed. The objective of this work was to drive forward the automated analysis of the FAC by NMR. Due to the fact that this protocol can be carried out at low field and that the complete process from sample preparation to printing the report only takes about 3 min, this approach is promising to become a fundamental technique for high-throughput screening. To demonstrate the applicability of this method, the fatty acid composition of extra virgin olive oils from various Spanish olive varieties (arbequina, cornicabra, hojiblanca, manzanilla, and picual) was determined by 1H-NMR spectroscopy according to this protocol. PMID:26891323

  8. Assessing Heterogeneity of Osteolytic Lesions in Multiple Myeloma by 1H HR-MAS NMR Metabolomics

    PubMed Central

    Tavel, Laurette; Fontana, Francesca; Garcia Manteiga, Josè Manuel; Mari, Silvia; Mariani, Elisabetta; Caneva, Enrico; Sitia, Roberto; Camnasio, Francesco; Marcatti, Magda; Cenci, Simone; Musco, Giovanna

    2016-01-01

    Multiple myeloma (MM) is a malignancy of plasma cells characterized by multifocal osteolytic bone lesions. Macroscopic and genetic heterogeneity has been documented within MM lesions. Understanding the bases of such heterogeneity may unveil relevant features of MM pathobiology. To this aim, we deployed unbiased 1H high-resolution magic-angle spinning (HR-MAS) nuclear magnetic resonance (NMR) metabolomics to analyze multiple biopsy specimens of osteolytic lesions from one case of pathological fracture caused by MM. Multivariate analyses on normalized metabolite peak integrals allowed clusterization of samples in accordance with a posteriori histological findings. We investigated the relationship between morphological and NMR features by merging morphological data and metabolite profiling into a single correlation matrix. Data-merging addressed tissue heterogeneity, and greatly facilitated the mapping of lesions and nearby healthy tissues. Our proof-of-principle study reveals integrated metabolomics and histomorphology as a promising approach for the targeted study of osteolytic lesions. PMID:27809247

  9. 1H-NMR-based metabolomic study on toxicity of methomyl and methidathion in fish.

    PubMed

    Yoon, Dahye; Kim, Siwon; Lee, Minji; Yoon, Changshin; Kim, Suhkmann

    2016-12-01

    A (1)H-nuclear magnetic resonance (NMR) spectroscopy with multivariate analysis was applied to detect the toxicity of antiacetylcholinesterase insecticides, methomyl (methyl (1E)-N-(methylcarbamoyloxy)ethanimidothioate) and methidathion (3-(dimethoxyphosphinothioyl sulfanylmethyl)-5-methoxy-1,3,4-thiadiazol-2-one), using zebrafish (Danio rerio) and Chinese bleak (Aphyocypris chinensis). Generally, methomyl and methidathion have been believed not to highly accumulate in fish tissues. However, these pesticides showed their toxicity by altering patterns of whole-body metabolites in neurotransmitter balance, energy metabolism, oxidative stress, and muscle maintenance in low concentrations. We used Pearson correlation analysis to contextualize the metabolic markers in pesticide treated groups. We observed that the positive correlations of choline with acetate and betaine in untreated control were shifted to null correlations showing acetylcholinesterase specific toxicity. This research demonstrated the applicability and potential of NMR metabolomics in detecting toxic effects of insecticide with a modicum of concentrations in aquatic environment.

  10. Experimental and calculated 1H, 13C, 15N NMR spectra of famotidine

    NASA Astrophysics Data System (ADS)

    Barańska, M.; Czarniecki, K.; Proniewicz, L. M.

    2001-05-01

    Famotidine, 3-[[[2-[(aminoiminomethyl)amino]-4-thiazolyl]methyl]thio]- N-(aminosulfonyl), is a histamine H 2-receptor blocker that has been used mainly for the treatment of peptic ulcers and the Zollinger-Ellison syndrome. Its NMR spectra in different solvents were reported earlier; however, detailed interpretation has not been done thus far. In this work, experimental 1H, 13C and 15N NMR spectra of famotidine dissolved in DMSO-d 6 are shown. The assignment of observed chemical shifts is based on quantum chemical calculation at the Hartree-Fock/6-31G ∗ level. The geometry optimization of the famotidine molecule with two internal hydrogen bonds, i.e. [N(3)-H(23)⋯N(9) and N(3)⋯H(34)-N(20)], is done by using the B3LYP method with the 6-31G ∗ basis set.

  11. Structural analysis of complex saponins of Balanites aegyptiaca by 800 MHz 1H NMR spectroscopy.

    PubMed

    Staerk, Dan; Chapagain, Bishnu P; Lindin, Therese; Wiesman, Zeev; Jaroszewski, Jerzy W

    2006-10-01

    The main saponin (1) present in the mesocarp of Balanites aegyptiaca fruit is a mixture of 22R and 22S epimers of 26-(O-beta-D-glucopyranosyl)-3-beta-[4-O-(beta-D-glucopyranosyl)-2-O-(alpha-L-rhamnopyranosyl)-beta-D-glucopyranosyloxy]-22,26-dihydroxyfurost-5-ene. This structure differs from a previously reported saponin isolated from this source by the site of attachment of the rhamnosyl residue, and presumably represents a structural revision of the latter. The main saponin (2) present in the kernel is a xylopyranosyl derivative of 1. The use of high-field NMR enabled the practically complete assignment of 1H and 13C chemical shifts of these complex saponins, existing as a mixture of C-22 epimers. Moreover, the work represents a new approach to structural elucidation of saponins: direct preparative-scale HPLC-RID of crude extracts followed by high-field NMR investigations supported by ESI-MSn.

  12. 1H, 13C and 15N NMR assignments of phenazopyridine derivatives.

    PubMed

    Burgueño-Tapia, Eleuterio; Mora-Pérez, Yolanda; Morales-Ríos, Martha S; Joseph-Nathan, Pedro

    2005-03-01

    Phenazopyridine hydrochloride (1), a drug in clinical use for many decades, and some derivatives were studied by one- and two-dimensional (1)H, (13)C and (15)N NMR methodology. The assignments, combined with DFT calculations, reveal that the preferred protonation site of the drug is the pyridine ring nitrogen atom. The chemoselective acetylation of phenazopyridine (2) and its influence on the polarization of the azo nitrogen atoms were evidenced by the (15)N NMR spectra. Molecular calculations of the phenazopyridines 2-4 show that the pyridine and phenyl groups are oriented in an antiperiplanar conformation with intramolecular hydrogen bonding between the N-b atom and the C-2 amino group preserving the E-azo stereochemistry.

  13. X-ray Absorption Near Edge Structure Spectroscopy to Resolve the in Vivo Chemistry of the Redox-Active Indazolium trans-[Tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019)

    PubMed Central

    2013-01-01

    Indazolium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (1, KP1019) and its analogue sodium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (2, KP1339) are promising redox-active anticancer drug candidates that were investigated with X-ray absorption near edge structure spectroscopy. The analysis was based on the concept of the coordination charge and ruthenium model compounds representing possible coordinations and oxidation states in vivo. 1 was investigated in citrate saline buffer (pH 3.5) and in carbonate buffer (pH 7.4) at 37 °C for different time intervals. Interaction studies on 1 with glutathione in saline buffer and apo-transferrin in carbonate buffer were undertaken, and the coordination of 1 and 2 in tumor tissues was studied too. The most likely coordinations and oxidation states of the compound under the above mentioned conditions were assigned. Microprobe X-ray fluorescence of tumor thin sections showed the strong penetration of ruthenium into the tumor tissue, with the highest concentrations near blood vessels and in the edge regions of the tissue samples. PMID:23282017

  14. X-ray absorption near edge structure spectroscopy to resolve the in vivo chemistry of the redox-active indazolium trans-[Tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019).

    PubMed

    Hummer, Alfred A; Heffeter, Petra; Berger, Walter; Filipits, Martin; Batchelor, David; Büchel, Gabriel E; Jakupec, Michael A; Keppler, Bernhard K; Rompel, Annette

    2013-02-14

    Indazolium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (1, KP1019) and its analogue sodium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (2, KP1339) are promising redox-active anticancer drug candidates that were investigated with X-ray absorption near edge structure spectroscopy. The analysis was based on the concept of the coordination charge and ruthenium model compounds representing possible coordinations and oxidation states in vivo. 1 was investigated in citrate saline buffer (pH 3.5) and in carbonate buffer (pH 7.4) at 37 °C for different time intervals. Interaction studies on 1 with glutathione in saline buffer and apo-transferrin in carbonate buffer were undertaken, and the coordination of 1 and 2 in tumor tissues was studied too. The most likely coordinations and oxidation states of the compound under the above mentioned conditions were assigned. Microprobe X-ray fluorescence of tumor thin sections showed the strong penetration of ruthenium into the tumor tissue, with the highest concentrations near blood vessels and in the edge regions of the tissue samples.

  15. [1H-NMR studies of the ACTH-like immunoregulatory peptides].

    PubMed

    Khristoforov, V S; Kutyshenko, V P; Abramov, V M; Zav'ialov, V P

    1997-01-01

    A comparative study of the conformational and dynamics properties of the ACTH-like linear peptides, sequences of which correspond to amino acid residues 11-20 of the heavy chain of human immunoglobulin G1 Eu, residues 78-85 of human pro-interleukin-1 alpha and site 10-18 of human ACTH, was performed in aqueous solution and dimethylsulfoxide by 1H-NMR spectroscopy at 400 MHz. The peptides were shown to possess an unordered unfolded flexible conformation in aqueous solution. The revealed structural and dynamic features of the peptides are discussed together with biological activity of this class of compounds.

  16. 1H NMR investigation of self-association of vanillin in aqueous solution

    NASA Astrophysics Data System (ADS)

    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. High-resolution /sup 1/H NMR study of the solution structure of alamethicin

    SciTech Connect

    Esposito, G.; Carver, J.A.; Boyd, J.; Campbell, I.D.

    1987-02-24

    A /sup 1/H NMR study of the peptide alamethicin, which forms voltage-gated ion channels in membranes, is described. The molecule was studied in methanol as a function of temperature and pH. A complete assignment of the spectra is given, including several stereospecific assignments. Alamethicin was found to have a structure substantially similar to the crystal although, in solution, the C-terminal dipeptide adopts a somewhat extended conformation. The overall conformation was insensitive to the ionization of the side chain of the ionizable group, Glu-18.

  18. Structure determination of noncanonical RNA motifs guided by 1H NMR chemical shifts

    PubMed Central

    Sripakdeevong, Parin; Cevec, Mirko; Chang, Andrew T.; Erat, Michèle C.; Ziegeler, Melanie; Zhao, Qin; Fox, George E.; Gao, Xiaolian; Kennedy, Scott D.; Kierzek, Ryszard; Nikonowicz, Edward P.; Schwalbe, Harald; Sigel, Roland K. O.; Turner, Douglas H.; Das, Rhiju

    2014-01-01

    Structured non-coding RNAs underline fundamental cellular processes, but determining their 3D structures remains challenging. We demonstrate herein that integrating NMR 1H chemical shift data with Rosetta de novo modeling can consistently return high-resolution RNA structures. On a benchmark set of 23 noncanonical RNA motifs, including 11 blind targets, Chemical-Shift-ROSETTA for RNA (CS-ROSETTA-RNA) recovered the experimental structures with high accuracy (0.6 to 2.0 Å all-heavy-atom rmsd) in 18 cases. PMID:24584194

  19. 1H and 13C NMR study on some substituted azolidine derivatives

    NASA Astrophysics Data System (ADS)

    Cerioni, Giovanni; Cristiani, Franco; Devillanova, Francesco A.; Diaz, Angelo; Verani, Gaetano

    The 1H and 13C NMR spectra carried out on R overlineN·CH 2·CH 2·X·C O (where for R = H, X = NH, NMe, NEt, CH 2, S, O; for R = Me, X = NMe, CH 2; for R = Et, X = NEt) are reported. The comparison of these results with those obtained for the thionic and selonic isologues shows that sulphur and selenium have a greater deshielding effect on the ring than oxygen. The resonance of the carbons not involved in the π system have been correlated with the σ charges calculated by the DEL RE method.

  20. 1H NMR spectral studies on the polymerization mechanism of indole and its derivatives

    NASA Astrophysics Data System (ADS)

    Xu, Jingkun; Hou, Jian; Zhou, Weiqiang; Nie, Guangming; Pu, Shouzhi; Zhang, Shusheng

    2006-03-01

    The existence of N sbnd H bond according to the hydrogen nuclear magnetic resonance ( 1H NMR) spectra of polyindole and its derivatives, such as poly(5-bromoindole), poly(5-cyanoindole), poly(5-nitroindole), poly(5-methylindole), proved polymerization of high-quality polyindoles, which were electrosynthesized from middle strong Lewis acid boron trifluoride diethyl etherate (BFEE) and its mixed electrolytes with additional diethyl ether, occurred at 2,3-position. The elongation of the conjugation length made the chemical shift of all the protons of polyindoles to lower field in comparison with those of monomers.

  1. Insight into hydrogen bonding of uranyl hydroxide layers and capsules by use of 1H magic-angle spinning NMR spectroscopy [Insight into the hydrogen bonding for uranyl hydroxides using 1H MAS NMR spectroscopy

    DOE PAGES

    Alam, Todd M.; Liao, Zuolei; Nyman, May; ...

    2016-04-27

    Solid-state 1H magic-angle spinning (MAS) NMR was used to investigate local proton environments in anhydrous [UO2(OH)2] (α-UOH) and hydrated uranyl hydroxide [(UO2)4O(OH)6·5H2O (metaschoepite). For the metaschoepite material, proton resonances of the μ2-OH hydroxyl and interlayer waters were resolved, with two-dimensional (2D) double-quantum (DQ) 1H–1H NMR correlation experiments revealing strong dipolar interactions between these different proton species. The experimental NMR results were combined with first-principles CASTEP GIPAW (gauge including projector-augmented wave) chemical shift calculations to develop correlations between hydrogen-bond strength and observed 1H NMR chemical shifts. Furthermore, these NMR correlations allowed characterization of local hydrogen-bond environments in uranyl U24 capsules andmore » of changes in hydrogen bonding that occurred during thermal dehydration of metaschoepite.« less

  2. A study on the AMACR catalysed elimination reaction and its application to inhibitor testing† †Electronic supplementary information (ESI) available: 1H NMR spectra of synthesised compounds; details of X-ray crystal structure determination of compound 35; original data for Table 1; plots of fluorescence resulting from reaction of sensors 33 and 34 with fluoride solutions. CCDC 1408401. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ob01541c Click here for additional data file. Click here for additional data file.

    PubMed Central

    Yevglevskis, Maksims; Lee, Guat L.; Sun, Jenny; Zhou, Shiyi; Sun, Xiaolong; Kociok-Köhn, Gabriele; James, Tony D.; Woodman, Timothy J.

    2016-01-01

    α-Methylacyl-CoA racemase (AMACR; P504S) catalyses a key step in the degradation of branched-chain fatty acids and is important for the pharmacological activation of Ibuprofen and related drugs. Levels of AMACR are increased in prostate and other cancers, and it is a drug target. Development of AMACR as a drug target is hampered by lack of a convenient assay. AMACR irreversibly catalyses the elimination of HF from 3-fluoro-2-methylacyl-CoA substrates, and this reaction was investigated for use as an assay. Several known inhibitors and alternative substrates reduced conversion of 3-fluoro-2-methyldecanoyl-CoA by AMACR, as determined by 1H NMR. The greatest reduction of activity was observed with known potent inhibitors. A series of novel acyl-CoA esters with aromatic side chains were synthesised for testing as chromophoric substrates. These acyl-CoA esters were converted to unsaturated products by AMACR, but their use was limited by non-enzymatic elimination. Fluoride sensors were also investigated as a method of quantifying released fluoride and thus AMACR activity. These sensors generally suffered from high background signal and lacked reproducibility under the assay conditions. In summary, the elimination reaction can be used to characterise inhibitors, but it was not possible to develop a convenient colorimetric or fluorescent assay using 3-fluoro-2-methylacyl-CoA substrates. PMID:26537174

  3. Study the chemical composition and biological outcomes resulting from the interaction of the hormone adrenaline with heavy elements: Infrared, Raman, electronic, 1H NMR, XRD and SEM studies

    NASA Astrophysics Data System (ADS)

    Ibrahim, Omar B.; Mohamed, Mahmoud A.; Refat, Moamen S.

    2014-01-01

    Heavy metal adrenaline complexes formed from the reaction of adrenaline with Al3+, Zn2+, Sn2+, Sb3+, Pb2+and Bi3+ ions in methanolic solvent at 60 °C. The final reaction products have been isolated and characterization using elemental analyses (% of carbon, hydrogen and nitrogen), conductivity measurements, mid infrared, Raman laser, UV-Vis, 1H NMR spectra, X-ray powder diffraction, scanning electron microscopy and energy-dispersive X-ray spectroscopy (EDX). Upon the spectroscopic, conductivity and elemental analyses, the stoichiometric reactions indicated that the data obtained refer to 1:2 (M:L) for Zn2+, Sn2+, Pb2+and Bi3+ complexes [Zn(Adr)2(Cl)2], [Sn(Adr)2]Cl2, [Pb(Adr)2](NO3)2 and [Bi(Adr)2(Cl)2]Cl, while the molar ratio 1:3 (M:L) for Al3+ and Sb3+ with formulas [Al(Adr)3](NO3)3 and [Sb(Adr)3]Cl3. The infrared and Raman laser spectra interpreted the mode of interactions which associated through the two phenolic groups of catechol moiety. The adrenaline chelates have been screened for their in vitro antibacterial activity against four bacteria, Gram-positive (Bacillus subtilis and Staphylococcus aureus) and Gram-negative (Escherichia coli and Pseudomonas aeruginosa) and two strains of fungus (Aspergillus flavus and Candida albicans). The metal chelates were shown to possess more antibacterial and antifungal activities than the free adrenaline chelate.

  4. Water Solvent Effect on Theoretical Evaluation of (1)H NMR Chemical Shifts: o-Methyl-Inositol Isomer.

    PubMed

    Dos Santos, Hélio F; Chagas, Marcelo A; De Souza, Leonardo A; Rocha, Willian R; De Almeida, Mauro V; Anconi, Cleber P A; De Almeida, Wagner B

    2017-04-13

    In this paper, density functional theory calculations of nuclear magnetic resonance (NMR) chemical shifts for l-quebrachitol isomer, previously studied in our group, are reported with the aim of investigating in more detail the water solvent effect on the prediction of (1)H NMR spectra. In order to include explicit water molecules, 20 water-l-quebrachitol configurations obtained from Monte Carlo simulation were selected to perform geometry optimizations using the effective fragment potential method encompassing 60 water molecules around the solute. The solvated solute optimized geometries were then used in B3LYP/6-311+G(2d,p) NMR calculations with PCM-water. The inclusion of explicit solvent in the B3LYP NMR calculations resulted in large changes in the (1)H NMR profiles. We found a remarkable improvement in the agreement with experimental NMR profiles when the explicit hydrated l-quebrachitol structure is used in B3LYP (1)H NMR calculations, yielding a mean absolute error (MAE) of only 0.07 ppm, much lower than reported previously for the gas phase optimized structure (MAE = 0.11 ppm). In addition, a very improved match between theoretical and experimental (1)H NMR spectrum measured in D2O was achieved with the new hydrated optimized l-quebrachitol structure, showing that a fine-tuning of the theoretical NMR spectra can be accomplished once solvent effects are properly considered.

  5. 1H and 13C resonance designation of antimycin A1 by two-dimensional NMR spectroscopy

    USGS Publications Warehouse

    Abidi, S.L.; Adams, B.R.

    1987-01-01

    Complete 1H and 13C resonance assignments of antimycin A1 were accomplished by two-dimensional NMR techniques, viz. 1H homonuclear COSY correlation, heteronuclear 13C-1H chemical shift correlation and long-range heteronuclear 13C-1H COLOC correlation. Antimycin A1 was found to consist of two isomeric components in a 2:1 ratio based on NMR spectroscopic evidence. The structure of the major component was newly assigned as the 8-isopentanoic acid ester. The spectra of the minor component were consistent with the known structure of antimycin A1.

  6. The elusive structure of Pd2(dba)3. Examination by isotopic labeling, NMR spectroscopy, and X-ray diffraction analysis: synthesis and characterization of Pd2(dba-Z)3 complexes.

    PubMed

    Kapdi, Anant R; Whitwood, Adrian C; Williamson, David C; Lynam, Jason M; Burns, Michael J; Williams, Thomas J; Reay, Alan J; Holmes, Jordan; Fairlamb, Ian J S

    2013-06-05

    Pd(0)2(dba)3 (dba = E,E-dibenzylidene acetone) is the most widely used Pd(0) source in Pd-mediated transformations. Pd(0)2(dba-Z)3 (Z = dba aryl substituents) complexes exhibit remarkable and differential catalytic performance in an eclectic array of cross-coupling reactions. The precise structure of these types of complexes has been confounding, since early studies in 1970s to the present day. In this study the solution and solid-state structures of Pd(0)2(dba)3 and Pd(0)2(dba-Z)3 have been determined. Isotopic labeling ((2)H and (13)C) has allowed the solution structures of the freely exchanging major and minor isomers of Pd(0)2(dba)3 to be determined at high field (700 MHz). DFT calculations support the experimentally determined major and minor isomeric structures, which show that the major isomer of Pd(0)2(dba)3 possesses bridging dba ligands found exclusively in a s-cis,s-trans conformation. For the minor isomer one of the dba ligands is found exclusively in a s-trans,s-trans conformation. Single crystal X-ray diffraction analysis of Pd(0)2(dba)3·CHCl3 (high-quality data) shows that all three dba ligands are found over two positions. NMR spectroscopic analysis of Pd(0)2(dba-Z)3 reveals that the aryl substituent has a profound effect on the rate of Pd-olefin exchange and the global stability of the complexes in solution. Complexes containing the aryl substituents, 4-CF3, 4-F, 4-t-Bu, 4-hexoxy, 4-OMe, exhibit well-resolved (1)H NMR spectra at 298 K, whereas those containing 3,5-OMe and 3,4,5-OMe exhibit broad spectra. The solid-state structures of three Pd(0)2(dba-Z)3 complexes (4-F, 4-OMe, 3,5-OMe) have been determined by single crystal X-ray diffraction methods, which have been compared with Goodson's X-ray structure of Pd(0)2(dba-4-OH)3.

  7. Synthesis and structural characterization by NMR and X-ray of new Morita-Baylis-Hillman adducts derived from 7-chloroquinoline

    NASA Astrophysics Data System (ADS)

    da Silva Caleffi, Guilherme; de Oliveira, João Paulo Gomes; da Paz Silva, Everton; Olegário, Tayná Rodrigues; Mendes, Rhuan Karlos Santos; Lima-Junior, Cláudio Gabriel; Silva, Fábio Pedrosa Lins; Martins, Felipe Terra; Vasconcellos, Mário Luiz Araújo de Almeida

    2017-04-01

    Herein we describe the design, synthesis and structural characterization by NMR and X-ray of new molecular hybrids 4a-4c containing the nitroaromatic MBHA moiety and the 7-chloroquinoline pharmacophores, linked by an aliphatic spacer as a model for antiprotozoal drugs. Firstly, the 4,7-dichloroquinoline (7) reacted with excess of ethylene glycol, through a SNAr promoted by t-BuOK, to prepare the 2-(7-chloroquinolin-4-yloxy)ethanol (6) in 98% isolated yield. Then, the novel 2-(7-chloroquinolin-4-yloxy) ethyl acrylate (5) was synthesized in 78% isolated yield by reacting the alcohol (6) with acryloyl chloride and TEA in CH2Cl2. Finally, this acrylate (5) reacted with o-nitrobenzaldehyde, m-nitrobenzaldehyde and p-nitrobenzaldehyde through Morita-Baylis-Hillman reactions promoted by DABCO at room temperature, using t-BuOH:Water (9:1) as solvent, to afford the new hybrids 4a-4c in 73-76% isolated yields. Three-dimensional structures were characterized in both monomeric and intermolecular packing by X-Ray experiments.

  8. Low resolution 1H NMR assignment of proton populations in pound cake and its polymeric ingredients.

    PubMed

    Luyts, A; Wilderjans, E; Waterschoot, J; Van Haesendonck, I; Brijs, K; Courtin, C M; Hills, B; Delcour, J A

    2013-08-15

    Based on a model system approach, five different proton populations were distinguished in pound cake crumb using one dimensional low resolution (1)H NMR spectroscopy. In free induction decay (FID) measurements, proton populations were assigned to (i) non-exchanging CH protons of crystalline starch, proteins and crystalline fat and (ii) non-exchanging CH protons of amorphous starch and gluten, which are in little contact with water. In Carr-Purcell-Meiboom-Gill (CPMG) measurements, three proton populations were distinguished. The CPMG population with the lowest mobility and the FID population with the highest mobility represent the same proton population. The two CPMG proton populations with the highest mobility were assigned to exchanging protons (i.e., protons of water, starch, gluten, egg proteins and sugar) and protons of lipids (i.e., protons of egg yolk lipids and amorphous lipid fraction of margarine) respectively. Based on their spin-lattice relaxation times (T1), two dimensional (1)H NMR spectroscopy further resolved the two proton populations with the highest mobility into three and two proton populations, respectively.

  9. (1)H-NMR-based metabolomic studies of bisphenol A in zebrafish (Danio rerio).

    PubMed

    Yoon, Changshin; Yoon, Dahye; Cho, Junghee; Kim, Siwon; Lee, Heonho; Choi, Hyeonsoo; Kim, Suhkmann

    2017-04-03

    Proton nuclear magnetic resonance ((1)H-NMR) spectroscopy was used to study the response of zebrafish (Danio rerio) to increasing concentrations of bisphenol A (4,4'-(propane-2,2-diyl)diphenol, BPA). Orthogonal partial least squares discriminant analysis (OPLS-DA) was applied to detect aberrant metabolomic profiles after 72 h of BPA exposure at all levels tested (0.01, 0.1, and 1.0 mg/L). The OPLS-DA score plots showed that BPA exposure caused significant alterations in the metabolome. The metabolomic changes in response to BPA exposure generally exhibited nonlinear patterns, with the exception of reduced levels of several metabolites, including glutamine, inosine, lactate, and succinate. As the level of BPA exposure increased, individual metabolite patterns indicated that the zebrafish metabolome was subjected to severe oxidative stress. Interestingly, ATP levels increased significantly at all levels of BPA exposure. In the present study, we demonstrated the applicability of (1)H-NMR-based metabolomics to identify the discrete nature of metabolic changes.

  10. The molecular structure and vibrational, (1)H and (13)C NMR spectra of lidocaine hydrochloride monohydrate.

    PubMed

    Badawi, Hassan M; Förner, Wolfgang; Ali, Shaikh A

    2016-01-05

    The structure, vibrational and NMR spectra of the local anesthetic drug lidocaine hydrochloride monohydrate salt were investigated by B3LYP/6-311G(∗∗) calculations. The lidocaine·HCl·H2O salt is predicted to have the gauche structure as the predominant form at ambient temperature with NCCN and CNCC torsional angles of 110° and -123° as compared to 10° and -64°, respectively in the base lidocaine. The repulsive interaction between the two N-H bonds destabilized the gauche structure of lidocaine·HCl·H2O salt. The analysis of the observed vibrational spectra is consistent with the presence of the lidocaine salt in only one gauche conformation at room temperature. The (1)H and (13)C NMR spectra of lidocaine·HCl·H2O were interpreted by experimental and DFT calculated chemical shifts of the lidocaine salt. The RMSD between experimental and theoretical (1)H and (13)C chemical shifts for lidocaine·HCl·H2O is 2.32 and 8.21ppm, respectively.

  11. Authentication of beef versus horse meat using 60 MHz 1H NMR spectroscopy.

    PubMed

    Jakes, W; Gerdova, A; Defernez, M; Watson, A D; McCallum, C; Limer, E; Colquhoun, I J; Williamson, D C; Kemsley, E K

    2015-05-15

    This work reports a candidate screening protocol to distinguish beef from horse meat based upon comparison of triglyceride signatures obtained by 60 MHz (1)H NMR spectroscopy. Using a simple chloroform-based extraction, we obtained classic low-field triglyceride spectra from typically a 10 min acquisition time. Peak integration was sufficient to differentiate samples of fresh beef (76 extractions) and horse (62 extractions) using Naïve Bayes classification. Principal component analysis gave a two-dimensional "authentic" beef region (p=0.001) against which further spectra could be compared. This model was challenged using a subset of 23 freeze-thawed training samples. The outcomes indicated that storing samples by freezing does not adversely affect the analysis. Of a further collection of extractions from previously unseen samples, 90/91 beef spectra were classified as authentic, and 16/16 horse spectra as non-authentic. We conclude that 60 MHz (1)H NMR represents a feasible high-throughput approach for screening raw meat.

  12. Toxicity assessment of Arisaematis Rhizoma in rats by a (1)H NMR-based metabolomics approach.

    PubMed

    Dong, Ge; Wang, Junsong; Guo, Pingping; Wei, Dandan; Yang, Minghua; Kong, Lingyi

    2015-02-01

    Arisaematis Rhizoma (AR), a famous traditional Chinese medicine, has been widely used in Asia over thousands of years. Documented with noticeable toxicity in ancient books, AR has been used to treat various diseases in the clinic. Therefore, it is important to assess the toxicity of AR dynamically and holistically. In this study, a (1)H NMR-based metabolomics approach complemented with serum chemistry and histopathology has been applied to investigate the toxicity of AR. Rats were intragastrically administered with AR (0, 0.5 and 1 g kg(-1) body weight) for 30 days, and serum and urine samples were collected. Their (1)H NMR profiles were analyzed by multivariate pattern recognition techniques to denote metabolic variations induced by AR, and 13 metabolites in urine and 6 metabolites in serum were significantly altered, which suggested that disturbances in energy metabolism, perturbation of the gut microflora environment, membrane damage, folate deficiency and injury of kidneys are produced by AR. Histopathology showed a slight vacuolization of the glomerular matrix and edema of renal tubular epithelial cells in kidneys of AR administered rats, which were evidenced by increased levels of blood urea nitrogen and creatinine in serum chemistry. Our results indicated that oral administration of crude AR was found to induce slight renal toxicity. Therefore, precautions should be made to monitor the potential nephrotoxicity of AR in clinical use. The metabolomics approach provided a promising tool for the study and better understanding of TCM-induced toxicity dynamically and holistically.

  13. UV-visible and (1)H-(15)N NMR spectroscopic studies of colorimetric thiosemicarbazide anion sensors.

    PubMed

    Farrugia, Kristina N; Makuc, Damjan; Podborska, Agnieszka; Szaciłowski, Konrad; Plavec, Janez; Magri, David C

    2015-02-14

    Four model thiosemicarbazide anion chemosensors containing three N-H bonds, substituted with phenyl and/or 4-nitrophenyl units, were synthesised and studied for their anion binding abilities with hydroxide, fluoride, acetate, dihydrogen phosphate and chloride. The anion binding properties were studied in DMSO and 9 : 1 DMSO-H2O by UV-visible absorption and (1)H/(13)C/(15)N NMR spectroscopic techniques and corroborated with DFT studies. Significant changes were observed in the UV-visible absorption spectra with all anions, except for chloride, accompanied by dramatic colour changes visible to the naked eye. These changes were determined to be due to the deprotonation of the central N-H proton and not due to hydrogen bonding based on (1)H/(15)N NMR titration studies with acetate in DMSO-d6-0.5% water. Direct evidence for deprotonation was confirmed by the disappearance of the central thiourea proton and the formation of acetic acid. DFT and charge distribution calculations suggest that for all four compounds the central N-H proton is the most acidic. Hence, the anion chemosensors operate by a deprotonation mechanism of the central N-H proton rather than by hydrogen bonding as is often reported.

  14. Authentication of beef versus horse meat using 60 MHz 1H NMR spectroscopy

    PubMed Central

    Jakes, W.; Gerdova, A.; Defernez, M.; Watson, A.D.; McCallum, C.; Limer, E.; Colquhoun, I.J.; Williamson, D.C.; Kemsley, E.K.

    2015-01-01

    This work reports a candidate screening protocol to distinguish beef from horse meat based upon comparison of triglyceride signatures obtained by 60 MHz 1H NMR spectroscopy. Using a simple chloroform-based extraction, we obtained classic low-field triglyceride spectra from typically a 10 min acquisition time. Peak integration was sufficient to differentiate samples of fresh beef (76 extractions) and horse (62 extractions) using Naïve Bayes classification. Principal component analysis gave a two-dimensional “authentic” beef region (p = 0.001) against which further spectra could be compared. This model was challenged using a subset of 23 freeze–thawed training samples. The outcomes indicated that storing samples by freezing does not adversely affect the analysis. Of a further collection of extractions from previously unseen samples, 90/91 beef spectra were classified as authentic, and 16/16 horse spectra as non-authentic. We conclude that 60 MHz 1H NMR represents a feasible high-throughput approach for screening raw meat. PMID:25577043

  15. Metabolomic by 1H NMR spectroscopy differentiates "Fiano di Avellino" white wines obtained with different yeast strains.

    PubMed

    Mazzei, Pierluigi; Spaccini, Riccardo; Francesca, Nicola; Moschetti, Giancarlo; Piccolo, Alessandro

    2013-11-13

    We employed (1)H NMR spectroscopy to examine the molecular profile of a white "Fiano di Avellino" wine obtained through fermentation by either a commercial or a selected autochthonous Saccharomyces cerevisiae yeast starter. The latter was isolated from the same grape variety used in the wine-making process in order to strengthen the relationship between wine molecular quality and its geographical origin. (1)H NMR spectra, where water and ethanol signals were suppressed by a presaturated T1-edited NMR pulse sequence, allowed for definition of the metabolic content of the two differently treated wines. Elaboration of NMR spectral data by multivariate statistical analyses showed that the two different yeasts led to significant diversity in the wine metabolomes. Our results indicate that metabolomics by (1)H NMR spectroscopy combined with multivariate statistical analysis enables wine differentiation as a function of yeast species and other wine-making factors, thereby contributing to objectively relate wine quality to the terroir.

  16. Qualitative and Quantitative Control of Carbonated Cola Beverages Using 1H NMR Spectroscopy

    PubMed Central

    2012-01-01

    1H Nuclear magnetic resonance (NMR) spectroscopy (400 MHz) was used in the context of food surveillance to develop a reliable analytical tool to differentiate brands of cola beverages and to quantify selected constituents of the soft drinks. The preparation of the samples required only degassing and addition of 0.1% of TSP in D2O for locking and referencing followed by adjustment of pH to 4.5. The NMR spectra obtained can be considered as “fingerprints” and were analyzed by principal component analysis (PCA). Clusters from colas of the same brand were observed, and significant differences between premium and discount brands were found. The quantification of caffeine, acesulfame-K, aspartame, cyclamate, benzoate, hydroxymethylfurfural (HMF), sulfite ammonia caramel (E 150D), and vanillin was simultaneously possible using external calibration curves and applying TSP as internal standard. Limits of detection for caffeine, aspartame, acesulfame-K, and benzoate were 1.7, 3.5, 0.8, and 1.0 mg/L, respectively. Hence, NMR spectroscopy combined with chemometrics is an efficient tool for simultaneous identification of soft drinks and quantification of selected constituents. PMID:22356160

  17. 1H-HRMAS NMR study of smoked Atlantic salmon (Salmo salar).

    PubMed

    Castejón, David; Villa, Palmira; Calvo, Marta M; Santa-María, Guillermo; Herraiz, Marta; Herrera, Antonio

    2010-09-01

    High-resolution magic angle spinning (HRMAS) NMR spectroscopic data of smoked Atlantic salmon (Salmo salar) were fully assigned by combination of one- and two-dimensional-HRMAS experiments. Complete representative spectra, obtained after few minutes of analysis time, revealed a large number of minor and major compounds in the sample. The methodology is limited by the low sensitivity of NMR, and therefore HRMAS only enables the determination of the most relevant components. These were fatty acids (FAs), carbohydrates, nucleoside derivatives, osmolytes, amino acids, dipeptides and organic acids. For the first time, spectra were resolved sufficiently to allow semiquantitative determination in intact muscle of the highly polyunsaturated FA 22:6 omega-3. Additionally, the feasibility of (1)H-HRMAS NMR metabolite profiling was tested to identify some bioactive compounds during storage. This profiling was carried out by the non-destructive and direct analysis (i.e. without requiring sample preparation and multiple step procedures) of intact salmon muscle. The proposed procedure can be applied to a large number of samples with high throughput due to the short time of analysis and quick evaluation of the data.

  18. Solid state structure by X-ray and 13C CP/MAS NMR of new 5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarins

    NASA Astrophysics Data System (ADS)

    Ostrowska, Kinga; Maciejewska, Dorota; Dobrzycki, Łukasz; Socha, Pawel

    2016-05-01

    5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarin (1) and 6-acetyl-5-[2-(N,N-dimethylamino)ethoxy]-4,7-dimethylcoumarin (2), structurally related, were synthesized using both conventional and microwave-assisted approach. An impact of acetyl groups on the molecular structure of coumarin derivatives has been examined. Crystals of 2 were investigated using single crystal and powder X-ray diffraction techniques. Compound 2 crystallizes forming two polymorphs (denoted as 2_1 and 2_2), both belonging to P21/c space group. Both polymorphs are comparably stable and can be formed simultaneously during crystallization process. The solid state structure was also analysed using the fully resolved 13C CP/MAS NMR. The double signals with the intensity ratio of about 1:1 which were observed in the 13C CP/MAS NMR spectrum of compound 1 must arise due to the presence of two conformers of 1. In contrast, NMR spectrum recorded for powder mixture of two polymorphs of compound 2 displays no signal splitting. This is related to structural similarities of molecules in both polymorphs.

  19. Thermal degradation in a trimodal poly(dimethylsiloxane) network studied by (1)H multiple quantum NMR.

    PubMed

    Giuliani, Jason R; Gjersing, Erica L; Chinn, Sarah C; Jones, Ticora V; Wilson, Thomas S; Alviso, Cynthia T; Herberg, Julie L; Pearson, Mark A; Maxwell, Robert S

    2007-11-15

    Thermal degradation of a filled, cross-linked siloxane material synthesized from poly(dimethylsiloxane) chains of three different average molecular weights and with two different cross-linking species has been studied by (1)H multiple quantum (MQ) NMR methods. Multiple domains of polymer chains were detected by MQ NMR exhibiting residual dipolar coupling () values of 200 and 600 Hz, corresponding to chains with high average molecular weight between cross-links and chains with low average molecular weight between cross-links or near the multifunctional cross-linking sites. Characterization of the values and changes in distributions present in the material were studied as a function of time at 250 degrees C and indicate significant time-dependent degradation. For the domains with low , a broadening in the distribution was observed with aging time. For the domain with high , increases in both the mean and the width in were observed with increasing aging time. Isothermal thermal gravimetric analysis reveals a 3% decrease in weight over 20 h of aging at 250 degrees C. Degraded samples also were analyzed by traditional solid-state (1)H NMR techniques, and off-gassing products were identified by solid-phase microextraction followed by gas chromatography-mass spectrometry. The results, which will be discussed here, suggest that thermal degradation proceeds by complex competition between oxidative chain scissioning and postcuring cross-linking that both contribute to embrittlement.

  20. Thermal degradation in a trimodal PDMS network by 1H Multiple Quantum NMR

    SciTech Connect

    Giuliani, J R; Gjersing, E L; Chinn, S C; Jones, T V; Wilson, T S; Alviso, C T; Herberg, J L; Pearson, M A; Maxwell, R S

    2007-06-06

    Thermal degradation of a filled, crosslinked siloxane material synthesized from PDMS chains of three different average molecular weights and with two different crosslinking species has been studied by {sup 1}H Multiple Quantum (MQ) NMR methods. Multiple domains of polymer chains were detected by MQ NMR exhibiting Residual Dipolar Coupling (<{Omega}{sub d}>) values of 200 Hz and 600 Hz, corresponding to chains with high average molecular weight between crosslinks and chains with low average molecular weight between crosslinks or near the multifunctional crosslinking sites. Characterization of the <{Omega}{sub d}> values and changes in <{Omega}{sub d}> distributions present in the material were studied as a function of time at 250 C and indicates significant time dependent degradation. For the domains with low <{Omega}{sub d}>, a broadening in the distribution was observed with aging time. For the domain with high <{Omega}{sub d}>, increases in both the mean <{Omega}{sub d}> and the width in <{Omega}{sub d}> were observed with increasing aging time. Isothermal Thermal Gravimetric Analysis (TGA) reveals a 3% decrease in weight over 20 hours of aging at 250 C. Degraded samples also were analyzed by traditional solid state {sup 1}H NMR techniques and offgassing products were identified by Solid Phase MicroExtraction followed by Gas Chromatography-Mass Spectrometry (SPME GC-MS). The results, which will be discussed here, suggest that thermal degradation proceeds by complex competition between oxidative chain scissioning and post-curing crosslinking that both contribute to embrittlement.

  1. Determination of polydimethylsiloxanes by 1H-NMR in wine and edible oils.

    PubMed

    Mojsiewicz-Pieńkowska, K; Jamrógiewicz, Z; Łukasiak, J

    2003-05-01

    Fourier transform (1)H-nuclear magnetic resonance (NMR) spectroscopy was suitable for the quantitative determination of polydimethylsiloxanes (PDMS) in wine and edible oil samples. This approach offers highly specific qualitative and quantitative analysis due to silicone-specific location of proton signals linked to carbon atoms located directly next to silicon atoms (0-0.5 ppm), as well as a different location of signals in the range for different organosilicon structures. The method can be used for the control of PDMS at regulatory limits in foodstuffs (10 mg kg(-1)) using hexamethyldisiloxane (HDMS) as an internal standard. Samples were prepared by extraction under suitable conditions to separate the analyte, and with analyte enrichment before (1)H-NMR analysis. Analytical procedures were developed to permit the determination of PDMS at 0.06 mg kg(-1) in wine and at 6 mg kg(-1) in edible oils samples using readily available NMR instrumentation. It was, however, possible to lower the limit of detection to 6 microg kg(-1) for wine and to 60 microg kg(-1) for edible oils using a higher field instrument (500 MHz). Relative standard deviations (S(r)) were obtained for wine (0.028) and for oil samples (0.043), which when compared with values obtained for samples spiked with PDMS (0.021) indicated that the sample preparation was the main factor determining the precision of the method. The average recovery rates for PDMS were 97 and 95% for wine and edible oils, respectively. PDMS was detected in four brands of Italian wine, with Chianti-Rafaello containing the highest concentration (0.35 mg kg(-1)), and in four types of edible oils, highest concentration (11.9 mg kg(-1)) being found in Italian corn oil. None of the levels of PDMS found in the food samples exceeded the permissible standards laid down by the Codex Alimentarius Commission (10 mg kg(-1)), with the exception of the one corn oil sample.

  2. Identification of bioactive metabolites dihydrocanadensolide, Kojic acid, and vanillic acid in soy sauce using GC-MS, NMR spectroscopy, and single-crystal X-ray diffraction.

    PubMed

    Li, Ying; Teng, Zi; Parkin, Kirk L; Wang, Qin; Zhang, Qingli; Luo, Wei; Ma, Deyun; Zhao, Mouming

    2014-08-20

    Microbial transformations of intrinsic substrates offer immense potential for generating new bioactive compounds in fermented food products. The aim of this work was to characterize the secondary metabolites in soy sauce, one of the oldest fermented condiments. Ethyl acetate extract (EAE) of soy sauce was separated using flash column chromatography, crystallized, and analyzed by nuclear magnetic resonance (NMR), single-crystal X-ray diffraction (SC-XRD), and mass spectroscopy. Dihydrocanadensolide (DHC), an antiulcer agent, was identified in a food for the first time. The natural stereostructure of DHC, which remained controversial for several decades, was determined as (3S,3aS,6R,6aR)-6-butyl-3-methyltetrahydrofuro[3,4-b]furan-2,4-dione using SC-XRD analysis. Kojic acid (KA) and vanillic acid (VA) were also identified from EAE as bioactive metabolic products of fungi and yeasts. Moreover, a new polymorphic form of KA was determined by SC-XRD.

  3. Crystal structure of silica-ZSM-12 by the combined use of high-resolution solid-state MAS NMR spectroscopy and synchrotron x-ray powder diffraction

    SciTech Connect

    Fyfe, C.A.; Kokotailo, G.T. ); Gies, H.; Marler, B. ); Cox, D.E. )

    1990-05-03

    The crystal structure of the synthetic zeolite silica-ZSM-12, 56 SiO{sub 2}, has been solved by the combined use of high-resolution solid-state MAS NMR spectroscopy and high-resolution synchrotron X-ray powder diffraction ZSM-12 crystallizes in the monoclinic space group C2/c with a{sub 0} = 24.863 {angstrom}, b{sub 0} = 5.012 {angstrom}, c{sub 0} = 24.328 {angstrom}, and {beta} = 107.7{degree}. The zeolite host structure is built from corner-linked SiO{sub 4} tetrahedra to give a three-dimensional 4-connected net. The pores of the structure are one-dimensional channels that do not intersect, with 12-membered ring pore openings of approximately 5.6 {times} 7.7 {angstrom}. The structure of ZSM-12 is frequently twinned with (100) as the twin plane, which indicates a new zeolite structure type.

  4. Interplay between structure and dynamics in chitosan films investigated with solid-state NMR, dynamic mechanical analysis, and X-ray diffraction.

    PubMed

    Gartner, Carmiña; López, Betty Lucy; Sierra, Ligia; Graf, Robert; Spiess, Hans W; Gaborieau, Marianne

    2011-04-11

    Modern solid-state NMR techniques, combined with X-ray diffraction, revealed the molecular origin of the difference in mechanical properties of self-associated chitosan films. Films cast from acidic aqueous solutions were compared before and after neutralization, and the role of the counterion (acetate vs Cl(-)) was investigated. There is a competition between local structure and long-range order. Hydrogen bonding gives good mechanical strength to neutralized films, which lack long-range organization. The long-range structure is better defined in films cast from acidic solutions in which strong electrostatic interactions cause rotational distortion around the chitosan chains. Plasticization by acetate counterions enhances long-range molecular organization and film flexibility. In contrast, Cl(-) counterions act as a defect and impair the long-range organization by immobilizing hydration water. Molecular motion and proton exchange are restricted, resulting in brittle films despite the high moisture content.

  5. Structural features of cytochromes P450 and ligands that affect drug metabolism as revealed by X-ray crystallography and NMR.

    PubMed

    Gay, Sean C; Roberts, Arthur G; Halpert, James R

    2010-09-01

    Cytochromes P450 (P450s) play a major role in the clearance of drugs, toxins, and environmental pollutants. Additionally, metabolism by P450s can result in toxic or carcinogenic products. The metabolism of pharmaceuticals by P450s is a major concern during the design of new drug candidates. Determining the interactions between P450s and compounds of very diverse structures is complicated by the variability in P450-ligand interactions. Understanding the protein structural elements and the chemical attributes of ligands that dictate their orientation in the P450 active site will aid in the development of effective and safe therapeutic agents. The goal of this review is to describe P450-ligand interactions from two perspectives. The first is the various structural elements that microsomal P450s have at their disposal to assume the different conformations observed in X-ray crystal structures. The second is P450-ligand dynamics analyzed by NMR relaxation studies.

  6. NMR studies of chiral P,S-chelate platinum, rhodium, and iridium complexes and the X-ray structure of a palladium(II) allyl derivative

    SciTech Connect

    Albinati, A.; Eckert, J.; Pregosin, P.; Ruegger, H.; Salzmann, R.; Stoessel, C.

    1997-02-18

    Several Rh(I), Ir(III), and Pt(II) complexes of the chiral P,S-bidentate ligand 2 have been prepared and characterized. Detailed two-dimensional NMR studies show that (i) the boat-type chelate ring and the stereogenic sulfur center can invert rapidly at ambient temperature and (ii) the sulfur donor may dissociate, essentially destroying the chiral pocket. The solid-state structure of [Pt({eta}{sup 3}-C{sub 3}H{sub 5})(2)]PF{sub 6} (3) has been determined and the sulfur substituent shown to have an axial orientation. The six-membered chelate ring takes up a boat-like conformation. As shown by an X-ray diffraction study for 3, and via incoherent inelastic neutron scattering (IINS) measurements for the Pd analog, 4, the OH group is remote from the metal atom. 42 refs., 11 figs., 6 tabs.

  7. Leveraging NMR and X-ray Data of the Free Ligands to Build Better Drugs Targeting Angiotensin II Type 1 G-Protein Coupled Receptor.

    PubMed

    Kellici, Tahsin F; Ntountaniotis, Dimitrios; Kritsi, Eftichia; Zervou, Maria; Zoumpoulakis, Panagiotis; Potamitis, Constantinos; Durdagi, Serdar; Salmas, Ramin Ekhteiari; Ergun, Gizem; Gokdemir, Ebru; Halabalaki, Maria; Gerothanassis, Ioannis P; Liapakis, George; Tzakos, Andreas; Mavromoustakos, Thomas

    2016-01-01

    The angiotensin II type 1 receptor (AT1R) has been recently crystallized. A new era has emerged for the structure-based rational drug design and the synthesis of novel AT1R antagonists. In this critical review, the X-ray crystallographic data of commercially available AT1R antagonists in free form are analyzed and compared with the conformational analysis results obtained using a combination of NMR spectroscopy and Molecular Modeling. The same AT1R antagonists are docked and compared in terms of their interactions in their binding site using homology models and the crystallized AT1R receptor. Various aspects derived from these comparisons regarding rational drug design are outlined.

  8. Monitoring the on-line titration of enantiomeric omeprazole employing continuous-flow capillary microcoil 1H NMR spectroscopy.

    PubMed

    Hentschel, Petra; Holtin, Karsten; Steinhauser, Lisa; Albert, Klaus

    2012-12-01

    The titration of the (S)-enantiomer of omeprazole with the (R)-enantiomer in chloroform-d(1) is monitored by continuous-flow capillary microcoil (1)H NMR spectroscopy employing a microcoil with a detection volume of 1.5 µl. The observed changes of the (1)H NMR chemical shifts indicate the formation of a heterochiral (R,S) dimer of omeprazole via its sulfinyl group and the NH group of the benzimidazole ring.

  9. Structure and conformation of 2,3-diethoxycarbonyl-1-methylpyridinium iodide studied by NMR, FTIR, Raman, X-ray diffraction and DFT methods.

    PubMed

    Barczyński, P; Ratajczak-Sitarz, M; Nowaczyk, Ł; Katrusiak, A; Dega-Szafran, Z; Komasa, A; Szafran, M

    2013-11-01

    Computational and spectroscopic properties of 2,3-diethoxycarbonyl-1-methylpyridinium iodide, 1, were studied. The crystal structure of 1 was analyzed by X-ray diffraction. Molecular geometry of title compound has been calculated using the density functional theory (DFT) at B3LYP/6-311G(d,p) level of theory and was compared with the experimental data. Iodide anion interacts electrostatically with the positively charged pyridinium nitrogen atom and via weak CH⋯I(-) hydrogen bonds. In crystals the N-methyl and ethoxycarbonyl groups are disordered in two orientations. The structures of 2 (in vacuum), 3 (in CHCl3) and 4 (in DMSO) optimized by the B3LYP/6-311G(d,p) approach are different than that in crystal 1. The experimental (13)C and (1)H chemical shifts (δexp) of the investigated ester in CDCl3 and DMSO-d6 correlate linearly with GIAO/B3LYP/6-311G(d,p) magnetic isotropic shielding constants calculated according to the screening solvation model (COSMO), δexp=a+b σcalc. The FTIR and Raman spectra of the solid compound are consisted with the X-ray structure.

  10. (1)H NMR spectroscopy for profiling complex carbohydrate mixtures in non-fractionated beer.

    PubMed

    Petersen, Bent O; Nilsson, Mathias; Bøjstrup, Marie; Hindsgaul, Ole; Meier, Sebastian

    2014-05-01

    A plethora of biological and biotechnological processes involve the enzymatic remodelling of carbohydrates in complex mixtures whose compositions affect both the processes and products. In the current study, we employed high-resolution (1)H NMR spectroscopy for the analysis of cereal-derived carbohydrate mixtures as exemplified on six beer samples of different styles. Structural assignments of more than 50 carbohydrate moieties were obtained using (1)H1-(1)H2 groups as structural reporters. Spectroscopically resolved carbohydrates include more than ''20 different'' small carbohydrates with more than 38 isomeric forms in addition to cereal polysaccharide fragments with suspected organoleptic and prebiotic function. Structural motifs at the cleavage sites of starch, β-glucan and arabinoxylan fragments were identified, showing different extent and specificity of enzymatic polysaccharide cleavage during the production of different beer samples. Diffusion ordered spectroscopy supplied independent size information for the characterisation and identification of polysaccharide fragments, indicating the presence especially of high molecular weight arabinoxylan fragments in the final beer.

  11. Vicinal 1H-1H NMR coupling constants from density functional theory as reliable tools for stereochemical analysis of highly flexible multichiral center molecules.

    PubMed

    López-Vallejo, Fabian; Fragoso-Serrano, Mabel; Suárez-Ortiz, Gloria Alejandra; Hernández-Rojas, Adriana C; Cerda-García-Rojas, Carlos M; Pereda-Miranda, Rogelio

    2011-08-05

    A protocol for stereochemical analysis, based on the systematic comparison between theoretical and experimental vicinal (1)H-(1)H NMR coupling constants, was developed and applied to a series of flexible compounds (1-8) derived from the 6-heptenyl-5,6-dihydro-2H-pyran-2-one framework. The method included a broad conformational search, followed by geometry optimization at the DFT B3LYP/DGDZVP level, calculation of the vibrational frequencies, thermochemical parameters, magnetic shielding tensors, and the total NMR spin-spin coupling constants. Three scaling factors, depending on the carbon atom hybridizations, were found for the (1)H-C-C-(1)H vicinal coupling constants: f((sp3)-(sp3)) = 0.910, f((sp3)-(sp2)) = 0.929, and f((sp2)-(sp2))= 0.977. A remarkable correlation between the theoretical (J(pre)) and experimental (1)H-(1)H NMR (J(exp)) coupling constants for spicigerolide (1), a cytotoxic natural product, and some of its synthetic stereoisomers (2-4) demonstrated the predictive value of this approach for the stereochemical assignment of highly flexible compounds containing multiple chiral centers. The stereochemistry of two natural 6-heptenyl-5,6-dihydro-2H-pyran-2-ones (14 and 15) containing diverse functional groups in the heptenyl side chain was also analyzed by application of this combined theoretical and experimental approach, confirming its reliability. Additionally, a geometrical analysis for the conformations of 1-8 revealed that weak hydrogen bonds substantially guide the conformational behavior of the tetraacyloxy-6-heptenyl-2H-pyran-2-ones.

  12. Response to the Letter to the Editor regarding "Determination of the fatty acid profile by 1H-NMR spectroscopy."

    Technology Transfer Automated Retrieval System (TEKTRAN)

    In expansion of previous work (G. Knothe, J.A. Kenar, Determination of the fatty acid profile by 1H-NMR spectroscopy, Eur. J. Lipid Sci. Technol. 2004, 106, 88-96), an additional approach is discussed for quantitating saturated fatty acids in the fatty acid profiles of common vegetable oils by 1H-NM...

  13. Discovering [superscript 13]C NMR, [superscript 1]H NMR, and IR Spectroscopy in the General Chemistry Laboratory through a Sequence of Guided-Inquiry Exercises

    ERIC Educational Resources Information Center

    Iler, H. Darrell; Justice, David; Brauer, Shari; Landis, Amanda

    2012-01-01

    This sequence of three guided-inquiry labs is designed for a second-semester general chemistry course and challenges students to discover basic theoretical principles associated with [superscript 13]C NMR, [superscript 1]H NMR, and IR spectroscopy. Students learn to identify and explain basic concepts of magnetic resonance and vibrational…

  14. Nanostructures of Mg0.65Ti0.35Dx studied with x-ray diffraction, neutron diffraction, and magic-angle-spinning H2 NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Srinivasan, S.; Magusin, P. C. M. M.; Kalisvaart, W. P.; Notten, P. H. L.; Cuevas, F.; Latroche, M.; van Santen, R. A.

    2010-02-01

    Magnesium transition-metal alloys have a high hydrogen-storage capacity and show improved hydrogen-uptake and -release kinetics compared to magnesium alone. In the present study we have investigated the structure of bulk magnesium-titanium deuteride Mg0.65Ti0.35Dx prepared via mechanical alloying and gas-phase deuterium absorption by combined use of x-ray diffraction (XRD), neutron diffraction, and magic-angle-spinning H2 nuclear magnetic resonance (NMR). The initial ball-milled alloy has two XRD-distinct Mg and Ti fcc phases. Even after prolonged exposure to deuterium gas at 75 bar and 175°C the materials with and without palladium catalyst are only partly deuterated. Deuterium loading causes the formation of, on the one hand, bct (rutile) MgD2 nanodomains with interdispersed TiDy layers and, on the other hand, a separate fcc (fluorite) TiDz phase. The TiDy phase is XRD invisible, but shows clearly up at a H2 NMR shift of -43ppm between the shift of MgD2 (3 ppm) and the Knight shift of the TiDz phase (-143ppm) . Exchange NMR indicates complete deuterium exchange at 25°C between the MgD2 and TiDy phase within 1 s, as consistent with intimate contacts between these phases. Combined analysis of the XRD and NMR peak areas suggests that the deuterium concentrations y and z in the TiDy and TiDz domains are about 1.5 and 2.0, respectively. Comparing the intrinsic cell parameters of rutile MgH2 and fluorite TiH2 , we propose that stabilization of the mixed nanocomposite may arise from a coherent coupling between the crystal structures of the rutile MgD2 nanodomains and the thin layers of fcc TiDy .

  15. Solution behavior and complete sup 1 H and sup 13 C NMR assignments of the coenzyme B sub 12 derivative (5 prime -deoxyadenosyl)cobinamide using modern 2D NMR experiments, including 600-MHz sup 1 H NMR data

    SciTech Connect

    Pagano, T.G.; Yohannes, P.G.; Marzilli, L.G. ); Hay, B.P.; Scott, J.R.; Finke, R.G. )

    1989-02-15

    Two-dimensional (2D) NMR methods have been used to assign completely the {sup 1}H and {sup 13}C NMR spectra of the (5{prime}-deoxyadenosyl)cobinamide cation (AdoCbi{sup +}) in D{sub 2}O. Most of the {sup 1}H spectral assignments were made by using 2D homonuclear shift correlation spectroscopy (COSY), homonuclear Hartmann-Hahn spectroscopy (HOHAHA), absorption-mode (phase sensitive) 2D nuclear Overhauser effect (NOE) spectroscopy, and spin-locked NOE spectroscopy (also called ROESY, for rotating-frame Overhauser enhancement spectroscopy). Most of the protonated carbon resonances were assigned by using {sup 1}H-detected heteronuclear multiple-quantum coherence (HMQC) spectroscopy. The nonprotonated carbon resonances, as well as the remaining unassigned {sup 1}H and {sup 13}C NMR signals, were assigned from long-range {sup 1}H-{sup 13}C connectivities determined from {sup 1}H-detected multiple-bond heteronuclear multiple-quantum coherence spectroscopy (HMBC). Comparison of the {sup 13}C chemical shifts and {sup 1}H NOEs of AdoCbi{sup +} with those of coenzyme B{sup 12} ((5{prime}-deoxyadenosyl)cobalamin) and its benzimidazole-protonated, base-off form indicates that the electronic properties and structure of AdoCbi{sup +} are similar to that of coenzyme B{sup 12} in the protonated, base-off form. The {sup 13}C chemical shifts of most of the carbons of AdoCbi{sup +} do not vary significantly from those of base-off, benzimidazole-protonated coenzyme B{sup 12}, indicating that the electronic environment of the corrin ring is also similar in both compounds. However, significant differences in the chemical shifts of some of the corresponding carbons of the b, d, e, and f corrin side chains in AdoCbi{sup +} and in base-off, benzimidazole-protonated coenzyme B{sub 12} indicate that the positions of these side chains may be different in AdoCbi{sup +} compared to base-off coenzyme B{sup 12}.

  16. DFT calculations of 1H and 13C NMR chemical shifts in transition metal hydrides.

    PubMed

    del Rosal, I; Maron, L; Poteau, R; Jolibois, F

    2008-08-14

    Transition metal hydrides are of great interest in chemistry because of their reactivity and their potential use as catalysts for hydrogenation. Among other available techniques, structural properties in transition metal (TM) complexes are often probed by NMR spectroscopy. In this paper we will show that it is possible to establish a viable methodological strategy in the context of density functional theory, that allows the determination of 1H NMR chemical shifts of hydride ligands attached to transition metal atoms in mononuclear systems and clusters with good accuracy with respect to experiment. 13C chemical shifts have also been considered in some cases. We have studied mononuclear ruthenium complexes such as Ru(L)(H)(dppm)2 with L = H or Cl, cationic complex [Ru(H)(H2O)(dppm)2]+ and Ru(H)2(dppm)(PPh3)2, in which hydride ligands are characterized by a negative 1H NMR chemical shift. For these complexes all calculations are in relatively good agreement compared to experimental data with errors not exceeding 20% except for the hydrogen atom in Ru(H)2(dppm)(PPh3)2. For this last complex, the relative error increases to 30%, probably owing to the necessity to take into account dynamical effects of phenyl groups. Carbonyl ligands are often encountered in coordination chemistry. Specific issues arise when calculating 1H or 13C NMR chemical shifts in TM carbonyl complexes. Indeed, while errors of 10 to 20% with respect to experiment are often considered good in the framework of density functional theory, this difference in the case of mononuclear carbonyl complexes culminates to 80%: results obtained with all-electron calculations are overall in very satisfactory agreement with experiment, the error in this case does not exceed 11% contrary to effective core potentials (ECPs) calculations which yield errors always larger than 20%. We conclude that for carbonyl groups the use of ECPs is not recommended, although their use could save time for very large systems, for

  17. Composition of beer by 1H NMR spectroscopy: effects of brewing site and date of production.

    PubMed

    Almeida, Cláudia; Duarte, Iola F; Barros, António; Rodrigues, João; Spraul, Manfred; Gil, Ana M

    2006-02-08

    A principal component analysis (PCA) of 1H NMR spectra of beers differing in production site (A, B, C) and date is described, to obtain information about composition variability. First, lactic and pyruvic acids contents were found to vary significantly between production sites, good reproducibility between dates being found for site A but not for sites B and C beers. Second, site B beers were clearly distinguished by the predominance of linear dextrins, while A and C beers were richer in branched dextrins. Carbohydrate reproducibility between dates is poorer for site C with dextrin branching degree varying significantly. Finally, all production sites were successfully distinguished by their contents in adenosine/inosine, uridine, tyrosine/tyrosol, and 2-phenylethanol, reproducibility between dates being again poorer for site C. Interpretation of the above compositional differences is discussed in terms of the biochemistry taking place during brewing, and possible applications of the method in brewing process control are envisaged.

  18. 1H NMR study of the complexation of aromatic drugs with dimethylxanthine derivatives

    NASA Astrophysics Data System (ADS)

    Hernandez Santiago, A. A.; Gonzalez Flores, M.; Rosas Castilla, S. A.; Cervantes Tavera, A. M.; Gutierrez Perez, R.; Khomich, V. V.; Ovchinnikov, D. V.; Parkes, H. G.; Evstigneev, M. P.

    2012-02-01

    With an aim of searching efficient interceptors of aromatic drugs, the self- and hetero-association of dimethylxanthine derivatives with different structures, selected according to Strategy 1 (variation of the position of methyl groups) and Strategy 2 (variation of the length of sbnd (CH2)nsbnd COOH group), with aromatic drug molecules: Ethidium Bromide, Proflavine and Daunomycin, were studied using 1H NMR spectroscopy. It was found that the association proceeds in a form of stacking-type complexation and its energetics is relatively independent on the structure of the dimethylxanthines. However, on average, the dimethylxanthines possess higher hetero-association constant and, hence, higher interceptor ability as compared to the trimethylxanthine, Caffeine, used during the past two decades as a typical interceptor molecule.

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

    PubMed

    Li, Chenghong

    2013-09-05

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

  20. Quantitative 1H NMR: Development and Potential of an Analytical Method – an Update

    PubMed Central

    Pauli, Guido F.; Gödecke, Tanja; Jaki, Birgit U.; Lankin, David C.

    2012-01-01

    Covering the literature from mid-2004 until the end of 2011, this review continues a previous literature overview on quantitative 1H NMR (qHNMR) methodology and its applications in the analysis of natural products (NPs). Among the foremost advantages of qHNMR is its accurate function with external calibration, the lack of any requirement for identical reference materials, a high precision and accuracy when properly validated, and an ability to quantitate multiple analytes simultaneously. As a result of the inclusion of over 170 new references, this updated review summarizes a wealth of detailed experiential evidence and newly developed methodology that supports qHNMR as a valuable and unbiased analytical tool for natural product and other areas of research. PMID:22482996

  1. Cloud point, fluorimetric and 1H NMR studies of ibuprofen-polymer systems

    NASA Astrophysics Data System (ADS)

    Khan, Iqrar Ahmad; Anjum, Kahkashan; Koya, P. Ajmal; Qadeer, Atiytul; Kabir-ud-Din

    2014-01-01

    Influence of six polymers viz. hydroxyethyl cellulose (HEC), hydroxypropyl methyl cellulose (HPMC), polyethylene glycol (PEG), polyvinyl pyrrolidone (PVP), sodium carboxy methyl cellulose (NaCMC) and dextran sulfate (DxS) on solution properties of amphiphilic drug ibuprofen (IBF) has been described in this work. As only HPMC showed the clouding behavior (among the polymers employed herein), its cloud point (CP) was studied in detail in presence of varying amounts of IBF containing different fixed concentrations of inorganic salts (NaCl, NaNO3, Na2SO4, KBr and KNO3). Presence of all these salts had CP reducing effect. By means of steady state fluorescence quenching studies, average aggregation number of IBF aggregates (Nagg) in the presence of varying amounts of the mentioned polymers were evaluated and discussed. 1H NMR studies show that the magnitude of chemical shifts (δ) varies with the nature of the polymer.

  2. (1) H-NMR with Multivariate Analysis for Automobile Lubricant Comparison.

    PubMed

    Kim, Siwon; Yoon, Dahye; Lee, Dong-Kye; Yoon, Changshin; Kim, Suhkmann

    2017-02-23

    Identification of suspected automobile-related lubricants could provide valuable information in forensic cases. We examined that automobile lubricants might exhibit the chemometric characteristics to their individual usages. To compare the degree of clustering in the plots, we co-plotted general industrial oils that were highly dissimilar with automobile lubricants in additive compositions. (1) H-NMR spectroscopy was used with multivariate statistics as a tool for grouping, clustering, and identification of automobile lubricants in laboratory conditions. We analyzed automobile lubricants including automobile engine oils, automobile transmission oils, automobile gear oils, and motorcycle oils. In contrast to the general industrial oils, automobile lubricants showed relatively high tendencies of clustering to their usages. Our pilot study demonstrated that the comparison of known and questioned samples to their usages might be possible in forensic fields.

  3. A subzero 1H NMR relaxation investigation of water dynamics in tomato pericarp.

    PubMed

    Foucat, Loïc; Lahaye, Marc

    2014-09-01

    (1)H NMR relaxation times (T1 and T2) were measured at low field (0.47 T) in pericarp tissues of three tomato genotypes (Ferum, LA0147 and Levovil) at subzero temperature (-20 °C) and two ripening stages (mature green and red). The unfrozen water dynamics was characterised by two T1 and three T2 components. The relaxation time values and their associated relative populations allowed differentiating the ripening stage of only LA0147 and Levovil lines. But the three genotypes were unequivocally discriminated at the red ripe stage. The unfrozen water distribution was discussed in terms of specific interactions, especially with sugars, in relation with their osmoprotectant effects.

  4. Essential Parameters for Structural Analysis and Dereplication by 1H NMR Spectroscopy

    PubMed Central

    2015-01-01

    The present study demonstrates the importance of adequate precision when reporting the δ and J parameters of frequency domain 1H NMR (HNMR) data. Using a variety of structural classes (terpenoids, phenolics, alkaloids) from different taxa (plants, cyanobacteria), this study develops rationales that explain the importance of enhanced precision in NMR spectroscopic analysis and rationalizes the need for reporting Δδ and ΔJ values at the 0.1–1 ppb and 10 mHz level, respectively. Spectral simulations paired with iteration are shown to be essential tools for complete spectral interpretation, adequate precision, and unambiguous HNMR-driven dereplication and metabolomic analysis. The broader applicability of the recommendation relates to the physicochemical properties of hydrogen (1H) and its ubiquity in organic molecules, making HNMR spectra an integral component of structure elucidation and verification. Regardless of origin or molecular weight, the HNMR spectrum of a compound can be very complex and encode a wealth of structural information that is often obscured by limited spectral dispersion and the occurrence of higher order effects. This altogether limits spectral interpretation, confines decoding of the underlying spin parameters, and explains the major challenge associated with the translation of HNMR spectra into tabulated information. On the other hand, the reproducibility of the spectral data set of any (new) chemical entity is essential for its structure elucidation and subsequent dereplication. Handling and documenting HNMR data with adequate precision is critical for establishing unequivocal links between chemical structure, analytical data, metabolomes, and biological activity. Using the full potential of HNMR spectra will facilitate the general reproducibility for future studies of bioactive chemicals, especially of compounds obtained from the diversity of terrestrial and marine organisms. PMID:24895010

  5. Age-Related 1H NMR Characterization of Cerebrospinal Fluid in Newborn and Young Healthy Piglets

    PubMed Central

    Barone, Francesca; Elmi, Alberto; Romagnoli, Noemi; Bacci, Maria Laura

    2016-01-01

    When it comes to neuroscience, pigs represent an important animal model due to their resemblance with humans’ brains for several patterns including anatomy and developmental stages. Cerebrospinal fluid (CSF) is a relatively easy-to-collect specimen that can provide important information about neurological health and function, proving its importance as both a diagnostic and biomedical monitoring tool. Consequently, it would be of high scientific interest and value to obtain more standard physiological information regarding its composition and dynamics for both swine pathology and the refinement of experimental protocols. Recently, proton nuclear magnetic resonance (1H NMR) spectroscopy has been applied in order to analyze the metabolomic profile of this biological fluid, and results showed the technique to be highly reproducible and reliable. The aim of the present study was to investigate in both qualitative and quantitative manner the composition of Cerebrospinal Fluid harvested form healthy newborn (5 days old-P5) and young (30-P30 and 50-P50 days old) piglets using 1H NMR Spectroscopy, and to analyze any possible difference in metabolites concentration between age groups, related to age and Blood-Brain-Barrier maturation. On each of the analyzed samples, 30 molecules could be observed above their limit of quantification, accounting for 95–98% of the total area of the spectra. The concentrations of adenine, tyrosine, leucine, valine, 3-hydroxyvalerate, 3-methyl-2-oxovalerate were found to decrease between P05 and P50, while the concentrations of glutamine, creatinine, methanol, trimethylamine and myo-inositol were found to increase. The P05-P30 comparison was also significant for glutamine, creatinine, adenine, tyrosine, leucine, valine, 3-hydroxyisovalerate, 3-methyl-2-oxovalerate, while for the P30-P50 comparison we found significant differences for glutamine, myo-inositol, leucine and trimethylamine. None of these molecules showed at P30 concentrations

  6. (1)H NMR-based metabolomic approach for understanding the fermentation behaviors of wine yeast strains.

    PubMed

    Son, Hong-Seok; Hwang, Geum-Sook; Kim, Ki Myong; Kim, Eun-Young; van den Berg, Frans; Park, Won-Mok; Lee, Cherl-Ho; Hong, Young-Shick

    2009-02-01

    (1)H NMR spectroscopy coupled with multivariate statistical analysis was used for the first time to investigate metabolic changes in musts during alcoholic fermentation and wines during aging. Three Saccharomyces cerevisiae yeast strains (RC-212, KIV-1116, and KUBY-501) were also evaluated for their impacts on the metabolic changes in must and wine. Pattern recognition (PR) methods, including PCA, PLS-DA, and OPLS-DA scores plots, showed clear differences for metabolites among musts or wines for each fermentation stage up to 6 months. Metabolites responsible for the differentiation were identified as valine, 2,3-butanediol (2,3-BD), pyruvate, succinate, proline, citrate, glycerol, malate, tartarate, glucose, N-methylnicotinic acid (NMNA), and polyphenol compounds. PCA scores plots showed continuous movements away from days 1 to 8 in all musts for all yeast strains, indicating continuous and active fermentation. During alcoholic fermentation, the highest levels of 2,3-BD, succinate, and glycerol were found in musts with the KIV-1116 strain, which showed the fastest fermentation or highest fermentative activity of the three strains, whereas the KUBY-501 strain showed the slowest fermentative activity. This study highlights the applicability of NMR-based metabolomics for monitoring wine fermentation and evaluating the fermentative characteristics of yeast strains.

  7. 1H NMR relaxation of water: a probe for surfactant adsorption on kaolin.

    PubMed

    Totland, Christian; Lewis, Rhiannon T; Nerdal, Willy

    2011-11-01

    In this study, (1)H NMR is used to investigate properties of sodium dodecyl sulfate (SDS), tetradecyl trimethyl ammonium bromide (TTAB), and dodecyl trimethyl ammonium bromide (DTAB) adsorbed on kaolin by NMR T(1) and T(2) measurements of the water proton resonance. The results show that adsorbed surfactants form a barrier between sample water and the paramagnetic species present on the clay surface, thus significantly increasing the proton T(1) values of water. This effect is attributed to the amount of adsorbed surfactants and the arrangement of the surfactant aggregates. The total surface area covered by the cationic (DTAB and TTAB) and anionic (SDS) surfactants could be estimated from the water T(1) data and found to correspond to the fractions of negatively and positively charged surface area, respectively. For selected samples, the amount of paramagnetic species on the clay surface was reduced by treatment with hydrofluoric (HF) acid. For these samples, T(1) and T(2) measurements were taken in the temperature range 278-338 K, revealing detailed information on molecular mobility and nuclear exchange for the sample water that is related to surfactant behavior both on the surface and in the aqueous phase.

  8. 1H NMR-based metabolic profiling for evaluating poppy seed rancidity and brewing.

    PubMed

    Jawień, Ewa; Ząbek, Adam; Deja, Stanisław; Łukaszewicz, Marcin; Młynarz, Piotr

    2015-12-01

    Poppy seeds are widely used in household and commercial confectionery. The aim of this study was to demonstrate the application of metabolic profiling for industrial monitoring of the molecular changes which occur during minced poppy seed rancidity and brewing processes performed on raw seeds. Both forms of poppy seeds were obtained from a confectionery company. Proton nuclear magnetic resonance (1H NMR) was applied as the analytical method of choice together with multivariate statistical data analysis. Metabolic fingerprinting was applied as a bioprocess control tool to monitor rancidity with the trajectory of change and brewing progressions. Low molecular weight compounds were found to be statistically significant biomarkers of these bioprocesses. Changes in concentrations of chemical compounds were explained relative to the biochemical processes and external conditions. The obtained results provide valuable and comprehensive information to gain a better understanding of the biology of rancidity and brewing processes, while demonstrating the potential for applying NMR spectroscopy combined with multivariate data analysis tools for quality control in food industries involved in the processing of oilseeds. This precious and versatile information gives a better understanding of the biology of these processes.

  9. Combined Analysis of Stable Isotope, (1)H NMR, and Fatty Acid To Verify Sesame Oil Authenticity.

    PubMed

    Kim, Jeongeun; Jin, Gyungsu; Lee, Yunhee; Chun, Hyang Sook; Ahn, Sangdoo; Kim, Byung Hee

    2015-10-14

    The aim of this study was to verify the authenticity of sesame oils using combined analysis of stable isotope ratio, (1)H NMR spectroscopy, and fatty acid profiles of the oils. Analytical data were obtained from 35 samples of authentic sesame oils and 29 samples of adulterated sesame oils currently distributed in Korea. The orthogonal projection to latent structure discriminant analysis technique was used to select variables that most effectively verify the sesame oil authenticity. The variables include δ(13)C value, integration values of NMR peaks that signify the CH3 of n-3 fatty acids, CH2 between two C═C, protons from sesamin/sesamolin, and 18:1n-9, 18:3n-3, 18:2t, and 18:3t content values. The authenticity of 65 of 70 blind samples was correctly verified by applying the range of the eight variables found in the authentic sesame oil samples, suggesting that triple analysis is a useful approach to verify sesame oil authenticity.

  10. 1H HR-MAS NMR of carotenoids in aqueous samples and raw vegetables.

    PubMed

    Miglietta, M L; Lamanna, R

    2006-07-01

    Carotenoids are linear C40 tetraterpenoid hydrocarbons and represent a wide category of natural pigments. They are components of the pigment system of chloroplasts and are involved in the primary light absorption and the photon canalization of photosynthesis. Moreover, they also behave as quenchers of singlet oxygen, protecting cells and organisms against lipid peroxidation. Carotenoids have a strong lipophilic character and are usually analyzed in organic solvents. However, because of their biological activity, the characterization of these compounds in an aqueous environment or in the natural matrix is very important. One of the most important dietary carotenoids is beta-carotene, which has been extensively studied both in vivo and in model systems, but because of the low concentration and strong interaction with the biological matrix, beta-carotene has never been observed by NMR in solid aqueous samples.In the present work, a model system has been developed for the detection and identification of beta-carotene in solid aqueous samples by 1H HR-MAS NMR. The efficiency of the model has led to the identification of beta-carotene in a raw vegetable matrix.

  11. Complete 1H and 13C NMR assignments of six saponins from Sapindus trifoliatus.

    PubMed

    Grover, Rajesh K; Roy, Abhijeet D; Roy, Raja; Joshi, S K; Srivastava, Vandita; Arora, Sudershan K

    2005-12-01

    Complete 1H and 13C spectral assignments are reported for six saponins from the pericarp of Sapindus trifoliatus (Hindi name: Reetha) collected from Madhya Pradesh and Maharashtra, India, using only 1D and 2D NMR methods. The structures of the compounds were elucidated as hederagenin 3-O-(3-O-acetyl-beta-D-xylopyranosyl)-(1-3)-alpha-L-rhamnopyranosyl-(1-2)-alpha-L-ara-binopyranoside, hederagenin 3-O-(4-O-acetyl-beta-D-xylop-yranosyl)-(1-3)-alpha-L-rhamnopyranosyl-(1-2)-alpha-L-arabinop-yranoside, hederagenin 3-O-(3,4-O-diacetyl-beta-D-xylopy-ranosyl)-(1-3)-alpha-L-rhamnopyranosyl-(1-2)-alpha-L-arabinopy-ranoside, hederagenin 3-O-(3,4-O-diacetyl-alpha-L-arabinop-yranosyl)-(1-3)-alpha-L-rhamnopyranosyl-(1-2)-alpha-L-arabinop-yranoside, hederagenin 3-O-(beta-D-xylopyranosyl)-(1-3)-alpha-L-rhamnopyranosyl-(1-2)-alpha-L-arabinopyranoside and he-deragenin 3-O-(alpha-L-arabinopyranosyl)-(1-3)-alpha-L-rhamno-pyranosyl-(1-2)-alpha-L-arabinopyranoside. It is concluded that saponins of this complexity approach the limit of structural complexity, which can be solved by NMR alone, precisely and quickly.

  12. Secondary structure determination of human. beta. -endorphin by /sup 1/H NMR spectroscopy

    SciTech Connect

    Lichtarge, O.; Jardetzky, O.; Li, C.H.

    1987-09-08

    The /sup 1/H NMR spectra of human ..beta..-endorphin indicate that the peptide exists in random-coil form in aqueous solution but becomes helical in mixed solvent. Thermal denaturation NMR experiments show that in water there is no transition between 24 and 75/sup 0/C, while a slow noncooperative thermal unfolding is observed in a 60% methanol-40% water mixed solvent in the same temperature range. These findings are consistent with circular dichroism studies by other workers concluding that ..beta..-endorphin is a random coil in water but that it forms 50% ..cap alpha..-helix or more in mixed solvents. The peptide in the mixed water-methanol solvent was further studied by correlated spectroscopy (COSY) and nuclear Overhauser effect spectroscopy (NOESY) experiments. These allow a complete set of assignments to be made and establish two distinct stretches over which the solvent induces formation of ..cap alpha..-helices: the first occurs between Tyr-1 and Thr-12 and the second between Leu-14 and extending to Lys-28. There is evidence that the latter is capped by a turn occurring between Lys-28 and Glu-31. These helices form at the enkephalin receptor binding site, which is at the amino terminus, and at the morphine receptor binding site, located at the carboxyl terminus. The findings suggest that these two receptors may specifically recognize ..cap alpha..-helices.

  13. 1H NMR characterization of a hen ovalbumin tyrosinamide N-linked oligosaccharide library.

    PubMed

    Corradi Da Silva, M L; Stubbs, H J; Tamura, T; Rice, K G

    1995-04-20

    A library of 15 N-linked oligosaccharide structures was prepared from ovalbumin and characterized using high-field NMR and mass spectrometry. The oligosaccharides were enzymatically released from ovalbumin glycopeptides, and the reducing ends were reacted with ammonium bicarbonate to form oligosaccharide-glycosylamines. These reacted with Boc-tyrosine-N-hydroxysuccinimide ester, resulting in a mixture of tyrosinamide-oligosaccharides. The Boc group was removed to expose an amine terminus which enhanced the resolution of tyrosinamide-oligosaccharides when chromatographed on reverse-phase HPLC. Ten major and five minor oligosaccharides were purified on a micromole scale and characterized using 1H NMR and FAB-MS. The structures include high-mannose, hybrid, and complex oligosaccharides possessing from two to five antenna, providing the most complete definition of ovalbumin N-linked oligosaccharides to date. The resulting library is well suited to biological studies due to the presence of a single terminal tyrosine residue on each oligosaccharide that allows radioiodination or the attachment of additional probes to these glycoconjugates prior to biological studies.

  14. Rapid determination of coenzyme Q10 in food supplements using 1H NMR spectroscopy.

    PubMed

    Monakhova, Yulia B; Ruge, Ingrid; Kuballa, Thomas; Lerch, Christiane; Lachenmeier, Dirk W

    2013-01-01

    A methodology utilizing 1H NMR spectroscopy has been developed to measure the concentration of coenzyme Q10 (CoQ10) in dietary supplements. For sample preparation, a very simple dilution with deuterated chloroform and addition of internal standard is sufficient. CoQ10 produces a distinct peak of the CH groups in the isoprene side chain of the molecule in the δ 5.15 - 5.05 ppm range, where it can be distinguished from other matrix compounds. The method was shown to be of adequate sensitivity with a limit of detection (LOD) of 7.8 mg/L, to control the CoQ10 content in the majority of the products. The precision expressed as relative standard deviation was around 5 %; linearity was observed from 14 to 2000 mg/L (R = 0.99). The developed methodology was applied for the analysis of 21 food supplements (capsules, tablets, and liquid products). On the basis of the labeled amounts, only two products contained substantially lower concentrations of CoQ10 (57 % and 51 %). All other concentrations varied between 83 % and 190 % with respect to labeling. The developed NMR method may be used by quality assurance laboratories for routine control of CoQ10 products.

  15. 15N, 17O NMR and X-ray diffraction study of mesoionic 1,2,3,4-thiatriazolium-5-olate and its ethylated derivative

    NASA Astrophysics Data System (ADS)

    Jaźiwińsk, J.; Staszewska, O.; Staszewski, P.; Stefaniak, L.; Wiench, J. W.; Webb, G. A.

    1999-02-01

    Two mesoionic compounds with oxygenous exocyclic groups: 3-phenyl-1,2,3,4-thiatriazolium-5-olate 1 and its ethylated derivative 2 were investigated by means of 15N, 17O NMR and X-ray diffraction techniques. The exocyclic C5-O6 bond of thiatriazole 1 [1.224(3) Å] has a strong double bond character. Bond lengths in the thiatriazole ring are intermediate between single and double bond values except for S1-C5 [1.800(2) Å] which is close to a single Csp 3-S bond. The C5-O6 bond is significantly longer for the ethylated derivative 2 [1.314(4) Å]. The ethyl group attached to O6 is located in the trans position in relation to the ring S1 atom. The experimental data are compared with the results of ab initio molecular orbital calculations. The calculated absolute nuclear shieldings, chemical shifts and charge densities, in spite of some limitations, can be useful as an aid to signal assignments and for an understanding of the NMR parameters.

  16. Organic solute changes with acidification in Lake Skjervatjern as shown by 1H-NMR spectroscopy

    USGS Publications Warehouse

    Malcolm, R.L.; Hayes, T.

    1994-01-01

    1H-NMR spectroscopy has been found to be a useful tool to establish possible real differences and trends between all natural organic solute fractions (fulvic acids, humic acids, and XAD-4 acids) after acid-rain additions to the Lake Skjervatjern watershed. The proton NMR technique used in this study determined the spectral distribution of nonexchangeable protons among four peaks (aliphatic protons; aliphatic protons on carbon ?? or attached to electronegative groups; protons on carbons attached to O or N heteroatoms; and aromatic protons). Differences of 10% or more in the respective peak areas were considered to represent a real difference. After one year of acidification, fulvic acids decreased 13% (relative) in Peak 3 protons on carbon attached to N and O heteratoms and exhibited a decrease in aromatic protons between 27% and 31%. Humic acids also exhibited an 11% relative decrease in aromatic protons as a result of acidification. After one year of acidification, real changes were shown in three of the four proton assignments in XAD-4 acids. Peak 1 aliphatic protons increased by 14% (relative), Peak 3 protons on carbons attached to O and N heteroatoms decreased by 13% (relative), and aromatic protons (Peak 4) decreased by 35% (relative). Upon acidification, there was a trend in all solutes for aromatic protons to decrease and aliphatic protons to increase. The natural variation in organic solutes as shown in the Control Side B of the lake from 1990 to 1991 is perhaps a small limitation to the same data interpretations of acid rain changes at the Lake Skjervatjern site, but the proton NMR technique shows great promise as an independent scientific tool to detect and support other chemical techniques in establishing organic solute changes with different treatments (i.e., additions of acid rain).

  17. Spatially localized sup 1 H NMR spectra of metabolites in the human brain

    SciTech Connect

    Hanstock, C.C. ); Rothman, D.L.; Jue, T.; Shulman, R.G. ); Prichard, J.W. )

    1988-03-01

    Using a surface coil, the authors have obtained {sup 1}H NMR spectra from metabolites in the human brain. Localization was achieved by combining depth pulses with image-selected in vivo spectroscopy magnetic field gradient methods. {sup 1}H spectra in which total creatine (3.03 ppm) has a signal/noise ratio of 95:1 were obtained in 4 min from 14 ml of brain. A resonance at 2.02 ppm consisting predominantly of N-acetylaspartate was measured relative to the creatine peak in gray and white matter, and the ratio was lower in the white matter. The spin-spin relaxation times of N-acetylaspartate and creatine were measured in white and gray matter and while creatine relaxation times were the same in both, the N-acetylaspartate relaxation time was longer in white matter. Lactate was detected in the normoxic brain and the average of three measurements was {approx}0.5 mM from comparison with the creatine plus phosphocreatine peak, which was assumed to be 10.5 mM.

  18. Towards high resolution ^1H NMR spectra of tannin colloidal aggregates

    NASA Astrophysics Data System (ADS)

    Mirabel, M.; Glories, Y.; Pianet, I.; Dufourc, E. J.

    1999-10-01

    The time dependent colloidal formation of tannins in hydro-alcoholic medium has been studied by 1H-NMR. Line broadening observed with time can be cancelled by making use of magic angle sample spinning (MASS) thus yielding sharp lines that allow structural studies. We used as an example catechin, a constitutive monomer of Bordeaux young red wine tannins. Chemical shift variations of polyphenol protons allow monitoring the time course of aggregation. La formation de tanins colloïdaux au cours du temps, en milieu hydroalcoolique, a été suivie par RMN-^1H. Un élargissement marqué des résonances est observé et peut être supprimé par la rotation de l'échantillon à l'angle magique ce qui ouvre tout un champ d'études structurales sur ces composés colloïdaux. L'exemple proposé est celui de la catéchine, monomère constitutif de tannins présents en grande quantité dans les vins rouges jeunes de Bordeaux. Des variations du déplacement chimique de certains protons polyphénoliques permettent de suivre l'évolution temporelle de l'agrégation.

  19. 1H Photo-CIDNP Enhancements in Heteronuclear Correlation NMR Spectroscopy

    PubMed Central

    Sekhar, Ashok; Cavagnero, Silvia

    2009-01-01

    Photochemically induced dynamic nuclear polarization (photo-CIDNP) is usually employed as a probe of solvent exposure, in biomolecular NMR. The potential of the photo-CIDNP effect for sensitivity enhancement, however, remains poorly explored. Here, we introduce 1H-photo-CIDNP in heteronuclear correlation spectroscopy at low laser irradiation power (1 W), and compare the sensitivity of various 1H-Photo-CIDNP-enhanced- (HPE) 1H◻15N heteronuclear correlation pulse sequences, including HSQC, HMQC, and SOFAST-HMQC, in terms of their ability to detect the Trp indole Hε1 resonance. Both Trp and the Trp-containing protein apoHmpH were analyzed using flavin mononucleotide as photosensitizer in aqueous solutions either containing or lacking urea. We find that 1H◻15N photo-CIDNP-SOFAST-HMQC, denoted here as HPE-SOFAST-HMQC, yields a two-fold higher signal-to-noise per unit time than the parent SOFAST-HMQC for the solvent-exposed Trp of urea-unfolded apoHmpH. Thus, HPE-SOFAST-HMQC is the most sensitive heteronuclear correlation pulse sequence for the detection of solvent-exposed Trp. PMID:19462951

  20. 1H-NMR characterization of poly(ethylene glycol) and polydimethylsiloxane copolymer

    NASA Astrophysics Data System (ADS)

    Zainuddin, Ain Athirah; Othaman, Rizafizah; Noor, Wan Syaidatul Aqma Wan Mohd; Anuar, Farah Hannan

    2016-11-01

    This paper describes the synthesis and characterization of poly(ethylene glycol) (PEG) and polydimethylsiloxane (PDMS) copolymers. The copolymers were synthesized by reacting hydroxyl group (-OH) of poly(ethylene glycol) (PEG) and polydimetylsiloxane (PDMS) with isocyanate group (R-N=C=O) of 1,6-hexamethylene diisocyanate (HMDI). The reaction was carried out at room temperature. The copolymers were synthesized in three different compositions which differ in molar ratios of PEG to PDMS. The ratios (PEG:PDMS) used were 2:6. 3:5 and 4:4. The formation of the copolymers was characterized by 1H Nuclear Magnetic Resonance (1H-NMR) for structural determination. The presence of proton signal at 4.80 ppm which belongs to the proton of urethane group indicates the formation of urethane links. The formation of urethane links showed that two homopolymers were linked together by HMDI to form longer copolymer chains. It is worth to note that the sequence of PEG and PDMS along the copolymer chain is random.

  1. A novel one-pot synthesis of heterocyclic compound (4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-7(6H)-one): Structural (X-ray and DFT) and spectroscopic (FT-IR, NMR, UV-Vis and Mass) characterization Studies

    NASA Astrophysics Data System (ADS)

    Özdemir, Mecit; Sönmez, Mehmet; Şen, Fatih; Dinçer, Muharrem; Özdemir, Namık

    2015-02-01

    In this study, the title compound named as 4-benzoyl-5-phenyl-2-(pyridin-2-yl)-3,3a-dihydropyrazolo[1,5-c]pyrimidin-7(6H)-one (C24H18N4O2) was both experimentally and theoretically investigated. The compound was synthesized and characterized by FT-IR, NMR (1H NMR, 13C NMR and HETCOR-NMR), Mass spectroscopies and single-crystal X-ray diffraction methods. The compound crystallizes in the monoclinic space group P21/n with a = 6.1402 (3) Å, b = 21.4470 (15) Å, c = 15.0049 (8) Å and β = 97.407 (4)°. The molecular geometry was obtained from the X-ray structure determination optimized using density functional theory (DFT/B3LYP) method with the 6-31+G(d, p) basis set in ground state. From the optimized structure, geometric parameters, vibrational wavenumbers and chemical shifts of molecule were obtained. Experimental measurements were compared with its corresponding the calculated data. An excellent harmony between the two data was ascertained. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMOs) and non-linear optical (NLO) properties of the title molecule were investigated by theoretical calculations at the B3LYP/6-31+G(d, p) level.

  2. Crystal structure and theoretical study of IR and 1H and 13C NMR spectra of cordatin, a natural product with antiulcerogenic activity

    NASA Astrophysics Data System (ADS)

    Brasil, Davi S. B.; Alves, Cláudio N.; Guilhon, Giselle M. S. P.; Muller, Adolfo H.; Secco, Ricardo De S.; Peris, Gabriel; Llusar, Rosa

    Cordatin is a furan diterpenoid with a clerodane skeleton isolated from Croton palanostigma Klotzsch (Euphorbiaceae). This natural product shows significant antiulcerogenic activity, similar to cimetidine (Tagamet®), a compound used for the treatment of peptic ulcers. The crystal structure of cordatin was obtained by X-ray diffraction and its geometrical parameters were compared with theoretical calculations at the B3LYP theory level. The IR and NMR (1H and 13C chemical shifts and coupling constants) spectra were obtained and compared with the theoretical calculations. The B3LYP theory level, with the 6-31G(d,p) and 6-311G(d,p) basis set, provided IR absorption values close to the experimental data. Moreover, theoretical NMR parameters obtained in both gas phase and chloroform solvent at the B3PW91/DGDZVP, B3LYP/6-311+G(2d,p), and B3PW91/6-311+G(2d,p) levels showed good correlations with the experimental results.

  3. X-ray structure, NMR and stability-in-solution study of 6-(furfurylamino)-9-(tetrahydropyran-2-yl)purine - A new active compound for cosmetology

    NASA Astrophysics Data System (ADS)

    Walla, Jan; Szüčová, Lucie; Císařová, Ivana; Gucký, Tomáš; Zatloukal, Marek; Doležal, Karel; Greplová, Jarmila; Massino, Frank J.; Strnad, Miroslav

    2010-06-01

    The crystal and molecular structure of 6-(furfurylamino)-9-(tetrahydropyran-2-yl)purine ( 1) was determined at 150(2) K. The compound crystallizes in monoclinic P2 1/ c space group with a = 10.5642(2), b = 13.6174(3), c = 10.3742(2) Å, V = 1460.78(5) Å 3, Z = 4, R( F) = for 3344 unique reflections. The purine moiety and furfuryl ring are planar and the tetrahydropyran-2-yl is disordered in the ratio 1:3, probably due to the chiral carbon atom C(17). The individual 1H and 13C NMR signals were assigned by 2D correlation experiments such as 1H- 1H COSY and ge-2D HSQC. Stability-in-solution was determined in methanol/water in acidic pH (3-7).

  4. X-ray Structure Analysis of Indazolium trans-[Tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019) Bound to Human Serum Albumin Reveals Two Ruthenium Binding Sites and Provides Insights into the Drug Binding Mechanism

    PubMed Central

    2016-01-01

    Ruthenium(III) complexes are promising candidates for anticancer drugs, especially the clinically studied indazolium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (KP1019) and its analogue sodium trans-[tetrachlorobis(1H-indazole)ruthenate(III)] (NKP-1339). Several studies have emphasized the likely role of human serum proteins in the transportation and accumulation of ruthenium(III) complexes in tumors. Therefore, the interaction between KP1019 and human serum albumin was investigated by means of X-ray crystallography and inductively coupled plasma mass spectrometry (ICP-MS). The structural data unambiguously reveal the binding of two ruthenium atoms to histidine residues 146 and 242, which are both located within well-known hydrophobic binding pockets of albumin. The ruthenium centers are octahedrally coordinated by solvent molecules revealing the dissociation of both indazole ligands from the ruthenium-based drug. However, a binding mechanism is proposed indicating the importance of the indazole ligands for binding site recognition and thus their indispensable role for the binding of KP1019. PMID:27196130

  5. Keto-enol tautomerism of (E)-2-[(3,4-dimethylphenylimino)methyl]-4-nitrophenol: Synthesis, X-ray, FT-IR, UV-Vis, NMR and quantum chemical characterizations

    NASA Astrophysics Data System (ADS)

    Özek Yıldırım, Arzu; Yıldırım, M. Hakkı; Albayrak Kaştaş, Çiǧdem

    2017-01-01

    (E)-2-((3,4-dimethylphenylimino)methyl)-4-nitrophenol, which is a new Schiff base compound, was synthesized and characterized by experimental and computational methods. Molecular geometry, harmonic oscillator model of aromaticity (HOMA) indices, intra- and inter-molecular interactions in the crystal structure were determined by using single crystal X-ray diffraction technique. The optimized structures, which are obtained by Gaussian and Slater type orbitals, were compared to experimental structures to determine how much correlation is found between the experimental and the calculated properties. Intramolecular and hyperconjugative interactions of bonds have been found by Natural Bond Orbital analysis. The experimental infrared spectrum of the compound has been analyzed in detail by the calculated infrared spectra and Potential Energy Distribution analysis. To find out about the correlation between the solvent polarity and the enol-keto equilibrium, experimental UV-Visible spectra of the compound were obtained in benzene, CHCl3, EtOH and DMSO solvents. In these solvents, the UV-Vis spectra and relaxed potential energy surface scan (PES) calculations have been performed to get more insight into the equilibrium dynamics. Solvent effects in UV-Vis and PES calculations have been taken into account by using Polarizable Continuum Modelling method. 1H and 13C NMR spectra of the compound (in DMSO) were analyzed. The computational study of nonlinear optical properties shows that the compound can be used for the development of nonlinear optical materials.

  6. Cosmic x ray physics

    NASA Technical Reports Server (NTRS)

    Mccammon, Dan; Cox, D. P.; Kraushaar, W. L.; Sanders, W. T.

    1990-01-01

    The annual progress report on Cosmic X Ray Physics is presented. Topics studied include: the soft x ray background, proportional counter and filter calibrations, the new sounding rocket payload: X Ray Calorimeter, and theoretical studies.

  7. Cosmic x ray physics

    NASA Technical Reports Server (NTRS)

    Mccammon, Dan; Cox, D. P.; Kraushaar, W. L.; Sanders, W. T.

    1991-01-01

    The annual progress report on Cosmic X Ray Physics for the period 1 Jan. to 31 Dec. 1990 is presented. Topics studied include: soft x ray background, new sounding rocket payload: x ray calorimeter, and theoretical studies.

  8. Chest X-Ray

    MedlinePlus

    ... by Image/Video Gallery Your radiologist explains chest x-ray. Transcript Welcome to Radiology Info dot org! Hello, ... you about chest radiography also known as chest x-rays. Chest x-rays are the most commonly performed ...

  9. Joint x-ray

    MedlinePlus

    X-ray - joint; Arthrography; Arthrogram ... x-ray technologist will help you position the joint to be x-rayed on the table. Once in place, pictures are taken. The joint may be moved into other positions for more ...

  10. 1H NMR to investigate metabolism and energy supply in rhesus macaque sperm.

    PubMed

    Lin, Ching-Yu; Hung, Pei-hsuan; VandeVoort, Catherine A; Miller, Marion G

    2009-07-01

    Sperm ATP is derived primarily from either glycolysis or mitochondrial oxidative phosphorylation. In the present studies, (1)H NMR spectroscopy was used to characterize the metabolite profile in primate sperm treated either with alpha-chlorohydrin (ACH), a known inhibitor of sperm glycolysis or pentachlorophenol (PCP), an uncoupler of oxidative phosphorylation. Sperm were collected from monkeys in the fall and spring, washed and incubated with either the media control, ACH (0.5mM) or PCP (50 microM). Using principal components analysis, PC1 scores plot indicated that the greatest level of variance was found between fall and spring samples and not chemical-treated samples. However, PC4 scores plot did show a consistent effect of ACH treatment. From the PC1 loadings plot, metabolites contributing to the seasonal differences were higher levels of formate in the fall and higher levels of carnitine and acetylcarnitine in the spring as well as possible differences in lipoprotein content. The PC4 loadings plot indicated that ACH treatment decreased lactate and ATP consistent with inhibition of glycolysis. Carnitine also was decreased and acetylcarnitine increased although the latter was not statistically significant. With PCP-treated sperm, no difference between control and treated samples could be discerned suggesting either that primate sperm are insensitive to uncoupling agents or that glycolysis played the more important role in maintaining sperm ATP levels. Overall, NMR studies may prove useful in the development of metabolomic markers that signal sperm metabolic impairments and have the potential to provide useful biomarkers for reproductive health.

  11. 1H-NMR analysis provides a metabolomic profile of patients with multiple sclerosis

    PubMed Central

    Cocco, Eleonora; Murgia, Federica; Lorefice, Lorena; Barberini, Luigi; Poddighe, Simone; Frau, Jessica; Fenu, Giuseppe; Coghe, Giancarlo; Murru, Maria Rita; Murru, Raffaele; Del Carratore, Francesco; Atzori, Luigi

    2015-01-01

    Objective: To investigate the metabolomic profiles of patients with multiple sclerosis (MS) and to define the metabolic pathways potentially related to MS pathogenesis. Methods: Plasma samples from 73 patients with MS (therapy-free for at least 90 days) and 88 healthy controls (HC) were analyzed by 1H-NMR spectroscopy. Data analysis was conducted with principal components analysis followed by a supervised analysis (orthogonal partial least squares discriminant analysis [OPLS-DA]). The metabolites were identified and quantified using Chenomx software, and the receiver operating characteristic (ROC) curves were calculated. Results: The model obtained with the OPLS-DA identified predictive metabolic differences between the patients with MS and HC (R2X = 0.615, R2Y = 0.619, Q2 = 0.476; p < 0.001). The differential metabolites included glucose, 5-OH-tryptophan, and tryptophan, which were lower in the MS group, and 3-OH-butyrate, acetoacetate, acetone, alanine, and choline, which were higher in the MS group. The suitability of the model was evaluated using an external set of samples. The values returned by the model were used to build the corresponding ROC curve (area under the curve of 0.98). Conclusion: NMR metabolomic analysis was able to discriminate different metabolic profiles in patients with MS compared with HC. With the exception of choline, the main metabolic changes could be connected to 2 different metabolic pathways: tryptophan metabolism and energy metabolism. Metabolomics appears to represent a promising noninvasive approach for the study of MS. PMID:26740964

  12. Application of 1H NMR for the characterisation of cocoa beans of different geographical origins and fermentation levels.

    PubMed

    Caligiani, Augusta; Palla, Luigi; Acquotti, Domenico; Marseglia, Angela; Palla, Gerardo

    2014-08-15

    This study reports for the first time the use of (1)H NMR technique combined with chemometrics to study the metabolic profile of cocoa (Theobroma cacao L.) beans of different varieties, origin and fermentation levels. Results of PCA applied to cocoa bean (1)H NMR dataset showed that the main factor influencing the cocoa bean metabolic profile is the fermentation level. In fact well fermented brown beans form a group clearly separated from unfermented, slaty, and underfermented, violet, beans, independently of the variety or geographical origin. Considering only well fermented beans, the metabolic profile obtained by (1)H NMR permitted to discriminate between some classes of samples. The National cocoa of Ecuador, known as Arriba, showed the most peculiar characteristics, while the samples coming from the African region showed some similar traits. The dataset obtained, representative of all the classes of soluble compounds of cocoa, was therefore useful to characterise fermented cocoa beans as a function of their origin and fermentation level.

  13. Fatty acids profile of Sacha Inchi oil and blends by 1H NMR and GC-FID.

    PubMed

    Vicente, Juarez; de Carvalho, Mario Geraldo; Garcia-Rojas, Edwin E

    2015-08-15

    This study aimed at the characterization of blends of Sacha Inchi oil (SIO) with different ratios of SO (soybean oil) and CO (corn oil) by nuclear magnetic resonance ((1)H NMR), compared with the data obtained by gas chromatography with a flame ionization detector (GC-FID). The (1)H NMR and GC-FID data from different ratios of SIO were adjusted by a second order polynomial equation. The two techniques were highly correlated (R(2) values ranged from 0.995 to 0.999), revealing that (1)H NMR is an efficient methodology for the quantification of omega-3 fatty acids in oils rich in omega-6 fatty acids or vice versa such as SO and CO and, on the other hand, can be used to quantify ω-6 in oils rich in ω-3, such as SIO.

  14. Dipolar cross-relaxation modulates signal amplitudes in the 1H NMR spectrum of hyperpolarized [ 13C]formate

    NASA Astrophysics Data System (ADS)

    Merritt, Matthew E.; Harrison, Crystal; Mander, William; Malloy, Craig R.; Dean Sherry, A.

    2007-12-01

    The asymmetry in the doublet of a spin coupled to hyperpolarized 13C has been used previously to measure the initial polarization of 13C. We tested the hypothesis that a single observation of the 1H NMR spectrum of hyperpolarized 13C formate monitors 13C polarization. Depending on the microwave frequency during the polarization process, in-phase or out-of-phase doublets were observed in the 1H NMR spectrum. Even in this simple two-spin system, 13C polarization was not reflected in the relative area of the JCH doublet components due to strong heteronuclear cross-relaxation. The Solomon equations were used to model the proton signal as a function of time after polarization and to estimate 13C polarization from the 1H NMR spectra.

  15. 1H NMR determination of beta-N-methylamino-L-alanine (L-BMAA) in environmental and biological samples.

    PubMed

    Moura, Sidnei; Ultramari, Mariah de Almeida; de Paula, Daniela Mendes Louzada; Yonamine, Mauricio; Pinto, Ernani

    2009-04-01

    A nuclear magnetic resonance (1H NMR) method for the determination of beta-N-methylamino-L-alanine (L-BMAA) in environmental aqueous samples was developed and validated. L-BMAA is a neurotoxic modified amino acid that can be produced by cyanobacteria in aqueous environments. This toxin was extracted from samples by means of solid-phase extraction (SPE) and identified and quantified by 1H NMR without further derivatization steps. The lower limit of quantification (LLOQ) was 5 microg/mL. Good inter and intra-assay precision was also observed (relative standard deviation <8.5%) with the use of 4-nitro-DL-phenylalanine as an internal standard (IS). This method of 1H NMR analysis is not time consuming and can be readily utilized to monitor L-BMAA and confirm its presence in environmental and biological samples.

  16. Combination of 1H NMR and chemometrics to discriminate manuka honey from other floral honey types from Oceania.

    PubMed

    Spiteri, Marc; Rogers, Karyne M; Jamin, Eric; Thomas, Freddy; Guyader, Sophie; Lees, Michèle; Rutledge, Douglas N

    2017-02-15

    Manuka honey is a product produced essentially in New Zealand, and has been widely recognised for its antibacterial properties and specific taste. In this study, 264 honeys from New Zealand and Australia were analysed using proton NMR spectroscopy coupled with chemometrics. Known manuka markers, methylglyoxal and dihydroxyacetone, have been characterised and quantified, together with a new NMR marker, identified as being leptosperin. Manuka honey profiling using 1H NMR is shown to be a possible alternative to chromatography with the added advantage that it can measure methylglyoxal (MGO), dihydroxyacetone (DHA) and leptosperin simultaneously. By combining the information from these three markers, we established a model to estimate the proportion of manuka in a given honey. Markers of other botanical origins were also identified, which makes 1H NMR a convenient and efficient tool, complementary to pollen analysis, to control the botanical origin of Oceania honeys.

  17. Probing Structure Property Relationships in Complex Engineering Silicones by 1H NMR

    SciTech Connect

    Chinn, S C; Gjersing, E L; Maxwell, R S; Eastwood, E; Bowen, D; Stephens, T

    2006-07-14

    It is generally accepted that the properties of polymeric materials are controlled by the network structure and the reactions by which they have been constructed. These properties include the bulk moduli at creation, but also the properties as a function of age during use. In order to interpret mechanical properties and predict the time dependent changes in these properties, detailed knowledge of the effect of structural changes must be obtained. The degree and type of crosslinking, the molecular weight between crosslinks, the number of elastically ineffective chains (loops, dangling chain ends, sol-fraction) must be characterized. A number of theoretical and experimental efforts have been reported in the last few years on model networks prepared by endlinking reactions and the relationships of those structures with the ultimate mechanical properties. A range of experimental methods have been used to investigate structure including rheometric, scattering, infrared, {sup 29}Si MAS and CPMAS, {sup 1}H relaxation measurements, and recently {sup 1}H multiple quantum methods. Characterization of the growth of multiple quantum coherences have recently been shown to provide detailed insight into silicone network structure by the ability to selective probe the individual components of the polymer network, such as the polymer-filler interface or network chains. We have employed recently developed MQ methods to investigate the structure-property relationships in a series of complex, endlinked filled-PDMS blends. Here, a systematic study of the relationship between the molecular formulation, as dictated by the amount and type of crosslinks present and by the remaining network chains, and the segmental dynamics as observed by MQ NMR was performed.

  18. Complete assignments of 1H and 13C NMR data for three new arylnaphthalene lignan from Justicia procumbens.

    PubMed

    Liu, Guorui; Wu, Jun; Si, Jianyong; Wang, Junmei; Yang, Meihua

    2008-03-01

    Three new arylnaphthalene lignans, named neojusticin C (1), procumbenoside C (2) and procumbenoside D (3), have been isolated from the whole plant of Justicia procumbens, together with three known ones, justicidinoside B (4), justicidinoside C (5), and diphyllin-1-O-beta-D-apiofuranoside (6). The complete assignments of 1H and 13C NMR data for three new lignans were first obtained by means of 2D NMR techniques, including HSQC and HMBC.

  19. 1H-NMR metabolite profiles of different strains of Plasmodium falciparum

    PubMed Central

    Teng, Rongwei; Lehane, Adele M.; Winterberg, Markus; Shafik, Sarah H.; Summers, Robert L.; Martin, Rowena E.; van Schalkwyk, Donelly A.; Junankar, Pauline R.; Kirk, Kiaran

    2014-01-01

    Although efforts to understand the basis for inter-strain phenotypic variation in the most virulent malaria species, Plasmodium falciparum, have benefited from advances in genomic technologies, there have to date been few metabolomic studies of this parasite. Using 1H-NMR spectroscopy, we have compared the metabolite profiles of red blood cells infected with different P. falciparum strains. These included both chloroquine-sensitive and chloroquine-resistant strains, as well as transfectant lines engineered to express different isoforms of the chloroquine-resistance-conferring pfcrt (P. falciparum chloroquine resistance transporter). Our analyses revealed strain-specific differences in a range of metabolites. There was marked variation in the levels of the membrane precursors choline and phosphocholine, with some strains having >30-fold higher choline levels and >5-fold higher phosphocholine levels than others. Chloroquine-resistant strains showed elevated levels of a number of amino acids relative to chloroquine-sensitive strains, including an approximately 2-fold increase in aspartate levels. The elevation in amino acid levels was attributable to mutations in pfcrt. Pfcrt-linked differences in amino acid abundance were confirmed using alternate extraction and detection (HPLC) methods. Mutations acquired to withstand chloroquine exposure therefore give rise to significant biochemical alterations in the parasite. PMID:25405893

  20. Quantification of acesulfame potassium in processed foods by quantitative 1H NMR.

    PubMed

    Ohtsuki, Takashi; Sato, Kyoko; Abe, Yutaka; Sugimoto, Naoki; Akiyama, Hiroshi

    2015-01-01

    Acesulfame potassium (AceK), a high-intensity and non-caloric artificial sweetener, is used in various processed foods as a food additive. In this study, we established and validated a method for determining the AceK content in various processed foods by solvent extraction and quantitative (1)H NMR, using a certified reference material as the internal standard. In the recovery test, the proposed method gave satisfactory recoveries (88.4-99.6%) and repeatabilities (0.6-5.6%) for various processed foods. The limit of quantification was confirmed as 0.13 g kg(-1), which was sufficiently low for the purposes of monitoring AceK levels. In the analysis of commercially processed foods containing AceK, all AceK contents determined by the proposed method were in good agreement with those obtained by a conventional method based on dialysis and HPLC. Moreover, this method can achieve rapid quantification and yields analytical data with traceability to the International System of Units (SI) without the need for an authentic analyte standard. Therefore, the proposed method is a useful and practical tool for the determination of AceK in processed foods.

  1. Biochemical effects of venlafaxine on astrocytes as revealed by (1)H NMR-based metabolic profiling.

    PubMed

    Sun, Lu; Fang, Liang; Lian, Bin; Xia, Jin-Jun; Zhou, Chan-Juan; Wang, Ling; Mao, Qiang; Wang, Xin-Fa; Gong, Xue; Liang, Zi-Hong; Bai, Shun-Jie; Liao, Li; Wu, Yu; Xie, Peng

    2017-01-31

    As a serotonin-norepinephrine reuptake inhibitor [SNRI], venlafaxine is one of the most commonly prescribed clinical antidepressants, with a broad range of antidepressant effects. Accumulating evidence shows that venlafaxine may target astrocytes to exert its antidepressant activity, although the underlying pharmacological mechanisms remained largely unknown. Here, we used a (1)H nuclear magnetic resonance (NMR)-based metabonomics method coupled with multivariate statistical analysis to characterize the metabolic profiling of astrocytes treated with venlafaxine to explore the potential mechanism of its antidepressant effect. In total, 31 differential metabolites involved in energy, amino acid and lipid metabolism were identified. Ingenuity pathway analysis was used to identify the predicted pathways and biological functions with venlafaxine and fluoxetine. The most significantly altered network was "amino acid metabolism, cellular growth and proliferation", with a score above 20. Certain metabolites (lysine, tyrosine, glutamate, methionine, ethanolamine, fructose-6-phosphate, and phosphorylethanolamine) are involved in and play a central role in this network. Collectively, the biological effects of venlafaxine on astrocytes provide us with the further understanding of the mechanisms by which venlafaxine treats major depressive disorder.

  2. Tissue metabolic profiling of lymph node metastasis of colorectal cancer assessed by 1H NMR.

    PubMed

    Zhang, Hailong; Qiao, Liang; Li, Xiaopeng; Wan, Yang; Yang, Li; Wang, Huijuan

    2016-12-01

    Lymph node metastasis is a decisive prognostic and therapeutic staging factor for colorectal cancer (CRC), which is one of the most prevalent types of cancer and a malignant tumor. The metabolic profiling of tissue samples from a large cohort of lymph node non‑metastatic CRC patients (n=73), lymph node metastatic CRC patients (n=52) and normal controls (n=41) was performed using 1H nuclear magnetic resonance (NMR) together with multivariate statistical analyses. Excellent separation was obtained between CRC patients and normal controls, and CRC patients were also perfectly classified according to lymph node metastasis. Forty‑two distinguishing metabolites were identified, which revealed disturbance of glycolysis, glutaminolysis, fatty acid metabolism, choline metabolism and amino acids, suggesting that cellular functions in energy production, macromolecular synthesis, oxidative stress and immune escape of cancer cells are affected in CRC. In total, 10 tissue metabolites were significantly disturbed between non‑metastatic and metastatic CRC patients. The present study firstly staged CRC patients by lymph node metastasis by metabolomic approach. The identified metabolites may be associated with the neoplasia, invasion and metastasis of the tumor. The results suggest the promising application of these metabolites in clinical therapy, and further understanding of the related mechanism warrants further investigation.

  3. Resolution Improvements in in Vivo1H NMR Spectra with Increased Magnetic Field Strength

    NASA Astrophysics Data System (ADS)

    Gruetter, Rolf; Weisdorf, Sally A.; Rajanayagan, Vasantham; Terpstra, Melissa; Merkle, Hellmut; Truwit, Charles L.; Garwood, Michael; Nyberg, Scott L.; Ugurbil, Kâmil

    1998-11-01

    The measurement of cerebral metabolites using highly homologous localization techniques and similar shimming methods was performed in the human brain at 1.5 and 4 T as well as in the dog and rat brain at 9.4 T. In rat brain, improved resolution was achieved by shimming all first- and second-order shim coils using a fully adiabatic FASTMAP sequence. The spectra showed a clear improvement in spectral resolution for all metabolite resonances with increased field strength. Changes in cerebral glutamine content were clearly observed at 4 T compared to 1.5 T in patients with hepatic encephalopathy. At 9.4 T, glutamine H4 at 2.46 ppm was fully resolved from glutamate H4 at 2.37 ppm, as was the potential resonance from γ-amino-butyric acid at 2.30 ppm and N-acetyl-aspartyl-glutamate at 2.05 ppm. Singlet linewidths were found to be as low as 6 Hz (0.015 ppm) at 9.4 T, indicating a substantial decrease in ppm linewidth with field strength. Furthermore, the methylene peak of creatine was partially resolved from phosphocreatine, indicating a close to 1:1 relationship in gray matter. We conclude that increasing the magnetic field strength increases spectral resolution also for1H NMR, which can lead to more than linear sensitivity gains.

  4. Relativistic force field: parametric computations of proton-proton coupling constants in (1)H NMR spectra.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2014-09-05

    Spin-spin coupling constants in (1)H NMR carry a wealth of structural information and offer a powerful tool for deciphering molecular structures. However, accurate ab initio or DFT calculations of spin-spin coupling constants have been very challenging and expensive. Scaling of (easy) Fermi contacts, fc, especially in the context of recent findings by Bally and Rablen (Bally, T.; Rablen, P. R. J. Org. Chem. 2011, 76, 4818), offers a framework for achieving practical evaluation of spin-spin coupling constants. We report a faster and more precise parametrization approach utilizing a new basis set for hydrogen atoms optimized in conjunction with (i) inexpensive B3LYP/6-31G(d) molecular geometries, (ii) inexpensive 4-31G basis set for carbon atoms in fc calculations, and (iii) individual parametrization for different atom types/hybridizations, not unlike a force field in molecular mechanics, but designed for the fc's. With the training set of 608 experimental constants we achieved rmsd <0.19 Hz. The methodology performs very well as we illustrate with a set of complex organic natural products, including strychnine (rmsd 0.19 Hz), morphine (rmsd 0.24 Hz), etc. This precision is achieved with much shorter computational times: accurate spin-spin coupling constants for the two conformers of strychnine were computed in parallel on two 16-core nodes of a Linux cluster within 10 min.

  5. The (1)H NMR structure of bovine Pb(2+)-osteocalcin and implications for lead toxicity.

    PubMed

    Dowd, T L; Li, L; Gundberg, C M

    2008-11-01

    Structural information on the effect of Pb(2+) on proteins under physiologically relevant conditions is largely unknown. We have previously shown that low levels of lead increased the amount of osteocalcin bound to hydroxyapatite (BBA 1535:153). This suggested that lead induced a more compact structure in the protein. We have determined the 3D structure of Pb(2+)-osteocalcin (49 amino acids), a bone protein from a target tissue, using (1)H 2D NMR techniques. Lead, at a stoichiometry of only 1:1, induced a similar fold in the protein as that induced by Ca(2+) at a stoichiometry of 3:1. The structure consisted of an unstructured N-terminus and an ordered C-terminal consisting of a hydrophobic core (residues 16-49). The genetic algorithm-molecular dynamics simulation predicted the lead ion was coordinated by the Gla 24 and Gla 21 residues. It is proposed that mineral binding occurs via uncoordinated Gla oxygen ions binding to calcium in hydroxyapatite. A comparison of Pb(2+)- and Ca(2+)-osteocalcin suggests Pb(2+), at a lower stoichiometry, may induce similar conformational changes in proteins and subsequent molecular processes normally controlled by calcium alone. This may contribute to a molecular mechanism of lead toxicity for calcium binding proteins. Lead exposure may alter the amount of mineral bound osteocalcin and contribute to abnormal bone remodeling.

  6. Polypharmacotherapy in rheumatology: 1H NMR analysis of binding of phenylbutazone and methotrexate to serum albumin

    NASA Astrophysics Data System (ADS)

    Maciążek-Jurczyk, M.; Sułkowska, A.; Równicka-Zubik, J.; Bojko, B.; Szkudlarek-Haśnik, A.; Knopik, M.; Sułkowski, W. W.

    2011-05-01

    The influence of phenylbutazone (Phe) and methotrexate (MTX) on binding of MTX and Phe to human (HSA) and bovine (BSA) serum albumin in the low-affinity binding sites is investigated. The strength and kind of interactions between serum albumin (SA) and drugs used in combination therapy were found using 1H NMR spectroscopy. A stoichiometric molar ratios for Phe-SA and MTX-SA complexes are 36:1 and 31:1, respectively. It appeared these molar ratios are higher for the ternary systems than it were in the binary ones. The presence of the additional drug (MTX or Phe) causes the increase of an affinity of albumin towards Phe and MTX. It was found that the aliphatic groups of MTX are more resistant to the influence of Phe on the MTX-SA complex than the aromatic rings. The results showed the important impact of another drug (MTX or Phe) on the affinity of SA towards Phe and MTX in the low-affinity binding sites. This work is a subsequent part of the spectroscopic study on Phe-MTX-SA interactions (Maciążek-Jurczyk, 2009 [1]).

  7. Enantioseparation of cetirizine by chromatographic methods and discrimination by 1H-NMR.

    PubMed

    Taha, Elham A; Salama, Nahla N; Wang, Shudong

    2009-03-01

    Cetirizine is an antihistaminic drug used to prevent and treat allergic conditions. It is currently marketed as a racemate. The H1-antagonist activity of cetirizine is primarily due to (R)-levocetirizine. This has led to the introduction of (R)-levocetirizine into clinical practice, and the chiral switching is expected to be more selective and safer. The present work represents three methods for the analysis and chiral discrimination of cetirizine. The first method was based on the enantioseparation of cetirizine on silica gel TLC plates using different chiral selectors as mobile phase additives. The mobile phase enabling successful resolution was acetonitrile-water 17: 3, (v/v) containing 1 mM of chiral selector, namely hydroxypropyl-beta-cyclodextrin, chondroitin sulphate or vancomycin hydrochloride. The second method was a validated high performance liquid chromatography (HPLC), based on stereoselective separation of cetirizine and quantitative determination of its eutomer (R)-levocetirizine on a monolithic C18 column using hydroxypropyl-beta-cyclodextrin as a chiral mobile phase additive. The resolved peaks of (R)-levocetirizine and (S)-dextrocetirizine were confirmed by further mass spectrometry. The third method used a (1)H-NMR technique to characterize cetirizine and (R)-levocetirizine. These methods are selective and accurate, and can be easily applied for chiral discrimination and determination of cetirizine in drug substance and drug product in quality control laboratory. Moreover, chiral purity testing of (R)-levocetirizine can also be monitored by the chromatographic methods.

  8. 1H NMR Spectroscopy and MVA Analysis of Diplodus sargus Eating the Exotic Pest Caulerpa cylindracea

    PubMed Central

    De Pascali, Sandra A.; Del Coco, Laura; Felline, Serena; Mollo, Ernesto; Terlizzi, Antonio; Fanizzi, Francesco P.

    2015-01-01

    The green alga Caulerpa cylindracea is a non-autochthonous and invasive species that is severely affecting the native communities in the Mediterranean Sea. Recent researches show that the native edible fish Diplodus sargus actively feeds on this alga and cellular and physiological alterations have been related to the novel alimentary habits. The complex effects of such a trophic exposure to the invasive pest are still poorly understood. Here we report on the metabolic profiles of plasma from D. sargus individuals exposed to C. cylindracea along the southern Italian coast, using 1H NMR spectroscopy and multivariate analysis (Principal Component Analysis, PCA, Orthogonal Partial Least Square, PLS, and Orthogonal Partial Least Square Discriminant Analysis, OPLS-DA). Fish were sampled in two seasonal periods from three different locations, each characterized by a different degree of algal abundance. The levels of the algal bisindole alkaloid caulerpin, which is accumulated in the fish tissues, was used as an indicator of the trophic exposure to the seaweed and related to the plasma metabolic profiles. The profiles appeared clearly influenced by the sampling period beside the content of caulerpin, while the analyses also supported a moderate alteration of lipid and choline metabolism related to the Caulerpa-based diet. PMID:26058009

  9. 1H NMR spectra of humic and fulvic acids and their peracetic oxidation products

    NASA Astrophysics Data System (ADS)

    Ruggiero, P.; Interesse, F. S.; Cassidei, L.; Sciacovelli, O.

    1980-04-01

    1H NMR spectra of humic (HA) and fulvic (FA) acids and their oxidative degradation products are reported. The HA shows the presence of -( CH2) n - CH3 ( n > 6) chemical fragments belonging to n-alkanes and/or n-fatty acids physically adsorbed onto the macromolecule structure. These fragments are absent in the FA fraction. Both humic fractions reveal the presence of similar amounts of aromatic protons which partly undergo exchange phenomena. The importance of this experimental observation is discussed. Oxidative degradation seems to cause partial cleavage of aromatic rings, more pronounced in the FA than in the HA. The degraded FA shows a higher total acidity and a higher phenolic OH content than the degraded HA. Both degraded fractions display some sharp singlet signals at 1.9 and 3.9 ppm arising from protons belonging to repetitive chemical fragments probably formed during the oxidation reaction. Tentative assignments of these signals are given. A general analysis of the HA and FA degraded spectra seems to indicate that the chemical fragments which undergo peracetic oxidation are substantially similar. The extent of oxidation of the two humic fractions is different. The HA degradation products reveal the presence of oligomeric structures, whereas the degraded FA appears less resistant to the oxidizing agent.

  10. Testing the limits of sensitivity in a solid-state structural investigation by combined X-ray powder diffraction, solid-state NMR, and molecular modelling.

    PubMed

    Filip, Xenia; Borodi, Gheorghe; Filip, Claudiu

    2011-10-28

    A solid state structural investigation of ethoxzolamide is performed on microcrystalline powder by using a multi-technique approach that combines X-ray powder diffraction (XRPD) data analysis based on direct space methods with information from (13)C((15)N) solid-state Nuclear Magnetic Resonance (SS-NMR) and molecular modeling. Quantum chemical computations of the crystal were employed for geometry optimization and chemical shift calculations based on the Gauge Including Projector Augmented-Wave (GIPAW) method, whereas a systematic search in the conformational space was performed on the isolated molecule using a molecular mechanics (MM) approach. The applied methodology proved useful for: (i) removing ambiguities in the XRPD crystal structure determination process and further refining the derived structure solutions, and (ii) getting important insights into the relationship between the complex network of non-covalent interactions and the induced supra-molecular architectures/crystal packing patterns. It was found that ethoxzolamide provides an ideal case study for testing the accuracy with which this methodology allows to distinguish between various structural features emerging from the analysis of the powder diffraction data.

  11. Dynamic equilibrium between closed and partially closed states of the bacterial Enzyme I unveiled by solution NMR and X-ray scattering

    PubMed Central

    Venditti, Vincenzo; Schwieters, Charles D.; Grishaev, Alexander; Clore, G. Marius

    2015-01-01

    Enzyme I (EI) is the first component in the bacterial phosphotransferase system, a signal transduction pathway in which phosphoryl transfer through a series of bimolecular protein–protein interactions is coupled to sugar transport across the membrane. EI is a multidomain, 128-kDa homodimer that has been shown to exist in two conformational states related to one another by two large (50–90°) rigid body domain reorientations. The open conformation of apo EI allows phosphoryl transfer from His189 located in the N-terminal domain α/β (EINα/β) subdomain to the downstream protein partner bound to the EINα subdomain. The closed conformation, observed in a trapped phosphoryl transfer intermediate, brings the EINα/β subdomain into close proximity to the C-terminal dimerization domain (EIC), thereby permitting in-line phosphoryl transfer from phosphoenolpyruvate (PEP) bound to EIC to His189. Here, we investigate the solution conformation of a complex of an active site mutant of EI (H189A) with PEP. Simulated annealing refinement driven simultaneously by solution small angle X-ray scattering and NMR residual dipolar coupling data demonstrates unambiguously that the EI(H189A)–PEP complex exists in a dynamic equilibrium between two approximately equally populated conformational states, one corresponding to the closed structure and the other to a partially closed species. The latter likely represents an intermediate in the open-to-closed transition. PMID:26305976

  12. Synthesis, solid-state NMR, and X-ray powder diffraction characterization of group 12 coordination polymers, including the first example of a C-mercuriated pyrazole.

    PubMed

    Masciocchi, Norberto; Galli, Simona; Alberti, Enrica; Sironi, Angelo; Di Nicola, Corrado; Pettinari, Claudio; Pandolfo, Luciano

    2006-10-30

    Cadmium and mercury acetates have been reacted with pyrazole (Hpz) and 3,5-dimethylpyrazole (Hdmpz), affording distinct mixed-ligand species, selectively prepared upon slightly modifying the reaction conditions. Two polymorphs of [{Cd(mu-ac)2(Hpz)2}n], as well as the [{Cd(mu-ac)2(Hdmpz)2}n] species (Hac = acetic acid), were obtained by solution chemistry, while the two-dimensional [{Cd3(mu3-ac)4(mu-pz)2(Hpz)2}n] and [{Cd(mu-ac)(mu-pz)}n] polymers were prepared upon controlled thermal treatment of one of the [{Cd(mu-ac)2(Hpz)2}n] forms. Two mercury derivatives, [{Hg3(mu-ac)3(mu-pz)3}n] and [{Hg(ac)(mu-dmpz)}n], were also prepared, the latter containing one-dimensional chains of Hg(II) ions bridged by C-mercuriated Hdmpz ligands. All their crystal structures (but one) were determined by powder diffraction methods using conventional X-ray laboratory equipment, supported by 13C CPMAS NMR measurements. The latter method helped in assigning a C-metalated nature to an amorphous material of [Hg(ac)(pz)] formula, obtained by employing EtOH as a solvent. A few other Hdmpz-containing cadmium acetates were also prepared, but their polyphasic nature, evidenced by diffraction methods, hampered their complete structural characterization.

  13. Structural Features of Cytochromes P450 and Ligands that Affect Drug Metabolism as Revealed by X-ray Crystallography and NMR

    PubMed Central

    Gay, Sean C.; Roberts, Arthur G.; Halpert, James R.

    2010-01-01

    SUMMARY Cytochromes P450 (P450s) play a major role in the clearance of drugs, toxins, and environmental pollutants. Additionally, metabolism by P450s can result in toxic or carcinogenic products. The metabolism of pharmaceuticals by P450s is a major concern during the design of new drug candidates. Determining the interactions between P450s and compounds of very diverse structures is complicated by the variability in P450-ligand interactions. Understanding the protein structural elements and the chemical attributes of ligands that dictate their orientation in the P450 active site will aid in the development of effective and safe therapeutic agents. The goal of this review is to describe P450-ligand interactions from two perspectives. The first is the various structural elements that microsomal P450s have at their disposal to assume the different conformations observed in X-ray crystal structures. The second is P450-ligand dynamics analyzed by NMR relaxation studies. PMID:21103389

  14. Microphase structure of poly(N-isopropylacrylamide) hydrogels as seen by small- and wide-angle X-ray scattering and pulsed field gradient NMR.

    PubMed

    László, Krisztina; Guillermo, Armel; Fluerasu, Andrei; Moussaïd, Abdellatif; Geissler, Erik

    2010-03-16

    Above the lower critical solution temperature T(c) (ca. 34 degrees C), poly(N-isopropylacrylamide) hydrogels become weakly hydrophobic and undergo microphase separation. Macroscopic deswelling, however, is extraordinarily slow, the out-of equilibrium state of the gel being conserved for many days. In this article the structure of the microphase-separated state above T(c) is probed by small-angle X-ray scattering and by pulsed field gradient NMR of the protons of water, both in the water phase and in the polymer-rich phase. Above T(c) the gel comprises two microphases, separated by smooth interfaces. The cavities occupied by the water phase form a connected network. The diffusion rate of the water molecules in this phase varies from one cavity to another and can be described by a Gaussian distribution. Water molecules belonging to the polymer-rich phase are also mobile, but their self-diffusion coefficient D is greatly diminished. Absence of compartmentalization of the water phase implies that the slow deswelling rate of the gel is not due to trapping of the water phase.

  15. Determination of glucan phosphorylation using heteronuclear 1H, 13C double and 1H, 13C, 31P triple-resonance NMR spectra.

    PubMed

    Schmieder, Peter; Nitschke, Felix; Steup, Martin; Mallow, Keven; Specker, Edgar

    2013-10-01

    Phosphorylation and dephosphorylation of starch and glycogen are important for their physicochemical properties and also their physiological functions. It is therefore desirable to reliably determine the phosphorylation sites. Heteronuclear multidimensional NMR-spectroscopy is in principle a straightforward analytical approach even for complex carbohydrate molecules. With heterogeneous samples from natural sources, however, the task becomes more difficult because a full assignment of the resonances of the carbohydrates is impossible to obtain. Here, we show that the combination of heteronuclear (1) H,(13) C and (1) H,(13) C,(31) P techniques and information derived from spectra of a set of reference compounds can lead to an unambiguous determination of the phosphorylation sites even in heterogeneous samples.

  16. Using magnetic coupling to implement 1H, 19F, 13C experiments in routine high resolution NMR probes

    NASA Astrophysics Data System (ADS)

    Bowyer, Paul; Finnigan, Jim; Marsden, Brian; Taber, Bob; Zens, Albert

    2015-12-01

    We report in this paper the design of 1H, 19F, 13C circuitry using magnetic coupling which can do on demand experiments where one of the three nuclei is observed and the other two are decoupled. The implementation of this circuitry in routine NMR probes is compared with capacitive coupling methods where it was found that by using magnetic coupling the performance of the routine NMR probe was not impacted by the addition of this circuitry. It is surmised that using this type of circuitry would be highly desirable for those chemists doing routine 19F NMR.

  17. Complete assignments of 1H and 13C NMR data for seven arylnaphthalide lignans from Justicia procumbens.

    PubMed

    Yang, Meihua; Wu, Jun; Cheng, Fan; Zhou, Yuan

    2006-07-01

    Three new arylnaphthalide lignans named 6'-hydroxy justicidin A (1), 6'-hydroxy justicidin B (2) and 6'-hydroxy justicidin C (3) have been isolated from the whole plant of Justicia procumbens, together with four known ones, neojusticin A (4), chinensinaphthol methyl ester (5), isodiphyllin (6) and taiwanin C (7). The complete assignments of 1H and 13C NMR chemical shifts for the new lignans and the 13C NMR chemical shifts for the known lignans were obtained for the first time by means of 2D NMR techniques, including HSQC and HMBC.

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

    PubMed

    Askenasy, Nadir; Navon, Gil

    2005-04-01

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

  19. Quantitative and qualitative 1H, 13C, and 15N NMR spectroscopic investigation of the urea-formaldehyde resin synthesis.

    PubMed

    Steinhof, Oliver; Kibrik, Éléonore J; Scherr, Günter; Hasse, Hans

    2014-04-01

    Urea-formaldehyde resins are bulk products of the chemical industry. Their synthesis involves a complex reaction network. The present work contributes to its elucidation by presenting results from detailed NMR spectroscopic studies with different methods. Besides (1)H NMR and (13)C NMR, (15)N NMR spectroscopy is also applied. (15)N-enriched urea was used for the investigations. A detailed NMR signal assignment and a model of the reaction network of the hydroxymethylation step of the synthesis are presented. Because of its higher spectral dispersion and the fact that all key reactions directly involve the nitrogen centers, (15)N NMR provides a much larger amount of detail than do (1)H and (13)C NMR spectroscopy. Symmetric and asymmetric dimethylol urea can be clearly distinguished and separated from monomethylol urea, trimethylol urea, and methylene-bridged urea. The existence of hemiformals of methylol urea is confirmed. 1,3,5-Oxadiazinan-4-on (uron) and its derivatives were not found in the reaction mixtures investigated here but were prepared via alternative routes. The molar ratios of formaldehyde to urea were 1, 2, and 4, the pH values 7.5 and 8.5, and the reaction temperature 60 °C.

  20. Complete assignment of the (1)H and (13)C NMR spectra of cis and trans isonucleoside derivatives of purine with a tetrahydropyran ring.

    PubMed

    Besada, Pedro; Costas, Tamara; Terán, Carmen

    2010-06-01

    (1)H and (13)C NMR chemical shifts of cis and trans isonucleoside analogues of purine in which the furanose moiety is substituted by a tetrahydropyran ring were completely assigned using one- and two-dimensional NMR experiments that include NOE, DEPT, COSY and HSQC. The significant (1)H and (13)C NMR signals differentiating between the cis and trans stereoisomers were compared.

  1. Studies of Secondary Melanoma on C57BL/6J Mouse Liver Using 1H NMR Metabolomics

    SciTech Connect

    Feng, Ju; Isern, Nancy G.; Burton, Sarah D.; Hu, Jian Z.

    2013-10-31

    NMR metabolomics, consisting of solid state high resolution (hr) magic angle spinning (MAS) 1H NMR (1H hr-MAS), liquid state high resolution 1H-NMR, and principal components analysis (PCA) has been used to study secondary metastatic B16-F10 melanoma in C57BL/6J mouse liver . The melanoma group can be differentiated from its control group by PCA analysis of the absolute concentrations or by the absolute peak intensities of metabolites from either 1H hr-MAS NMR data on intact liver tissues or liquid state 1H-NMR spectra on liver tissue extracts. In particular, we found that the absolute concentrations of alanine, glutamate, creatine, creatinine, fumarate and cholesterol are elevated in the melanoma group as compared to controls, while the absolute concentrations of succinate, glycine, glucose, and the family of linear lipids including long chain fatty acids, total choline and acylglycerol are decreased. The ratio of glycerophosphocholine to phosphocholine is increased by about 1.5 fold in the melanoma group, while the absolute concentration of total choline is actually lower in melanoma mice. These results suggest the following picture in secondary melanoma metastasis: Linear lipid levels are decreased by beta oxidation in the melanoma group, which contributes to an increase in the synthesis of cholesterol, and also provides an energy source input for TCA cycle. These findings suggest a link between lipid oxidation, the TCA cycle and the hypoxia-inducible factors (HIF) signal pathway in tumor metastases. Thus this study indicates that the metabolic profile derived from NMR analysis can provide a valuable bio-signature of malignancy and cell hypoxia in metastatic melanoma.

  2. Robust algorithms for automated chemical shift calibration of 1D 1H NMR spectra of blood serum.

    PubMed

    Pearce, Jake T M; Athersuch, Toby J; Ebbels, Timothy M D; Lindon, John C; Nicholson, Jeremy K; Keun, Hector C

    2008-09-15

    In biofluid NMR spectroscopy, the frequency of each resonance is typically calibrated by addition of a reference compound such as 3-(trimethylsilyl)-propionic acid- d 4 (TSP) to the sample. However biofluids such as serum cannot be referenced to TSP, due to shifts resonance caused by binding to macromolecules in solution. In order to overcome this limitation we have developed algorithms, based on analysis of derivative spectra, to locate and calibrate (1)H NMR spectra to the alpha-glucose anomeric doublet. We successfully used these algorithms to calibrate 77 serum (1)H NMR spectra and demonstrate the greater reproducibility of the calculated chemical-shift corrections ( r = 0.97) than those generated by manual alignment ( r = 0.8-0.88). Hence we show that these algorithms provide robust and reproducible methods of calibrating (1)H NMR of serum, plasma, or any biofluid in which glucose is abundant. Precise automated calibration of complex biofluid NMR spectra is an important tool in large-scale metabonomic or metabolomic studies, where hundreds or even thousands of spectra may be analyzed in high-resolution by pattern recognition analysis.

  3. 1H and 13C NMR signal assignments of a novel Baeyer-Villiger originated diterpene lactone.

    PubMed

    Vieira, Henriete S; Takahashi, Jacqueline A; Gunatilaka, A A Leslie; Boaventura, Maria Amélia D

    2006-02-01

    A highly rearranged novel dilactone was the single product isolated from Baeyer-Villiger oxidation of a norketone prepared from grandiflorenic acid, a natural kaurane diterpene. The complete 1H and 13C NMR assignment is presented for this novel compound that showed discrete in vitro antibacterial activity.

  4. 1H, 13C and 15N NMR assignments of a calcium-binding protein from Entamoeba histolytica.

    PubMed

    Verma, Deepshikha; Bhattacharya, Alok; Chary, Kandala V R

    2016-04-01

    We report almost complete sequence specific (1)H, (13)C and (15)N NMR assignments of a 150-residue long calmodulin-like calcium-binding protein from Entamoeba histolytica (EhCaBP6), as a prelude to its structural and functional characterization.

  5. LC-MS and 1H NMR as an improved dereplication tool to identify antifungal diterpenoids from Sagittaria latifolia

    Technology Transfer Automated Retrieval System (TEKTRAN)

    A dereplication strategy using a combination of liquid chromatography-mass spectrometry (LC-MS) and proton nuclear magnetic resonance spectroscopy (1H NMR) to facilitate compound identification towards antifungal natural product discovery is presented. This analytical approach takes advantage of th...

  6. Quality evaluation and prediction of Citrullus lanatus by 1H NMR-based metabolomics and multivariate analysis.

    PubMed

    Tarachiwin, Lucksanaporn; Masako, Osawa; Fukusaki, Eiichiro

    2008-07-23

    (1)H NMR spectrometry in combination with multivariate analysis was considered to provide greater information on quality assessment over an ordinary sensory testing method due to its high reliability and high accuracy. The sensory quality evaluation of watermelon (Citrullus lanatus (Thunb.) Matsum. & Nakai) was carried out by means of (1)H NMR-based metabolomics. Multivariate analyses by partial least-squares projections to latent structures-discrimination analysis (PLS-DA) and PLS-regression offered extensive information for quality differentiation and quality evaluation, respectively. The impact of watermelon and rootstock cultivars on the sensory qualities of watermelon was determined on the basis of (1)H NMR metabolic fingerprinting and profiling. The significant metabolites contributing to the discrimination were also identified. A multivariate calibration model was successfully constructed by PLS-regression with extremely high reliability and accuracy. Thus, (1)H NMR-based metabolomics with multivariate analysis was considered to be one of the most suitable complementary techniques that could be applied to assess and predict the sensory quality of watermelons and other horticultural plants.

  7. Application of (1)h NMR profiling to assess seed metabolomic diversity. A case study on a soybean era population.

    PubMed

    Harrigan, George G; Skogerson, Kirsten; MacIsaac, Susan; Bickel, Anna; Perez, Tim; Li, Xin

    2015-05-13

    (1)H NMR spectroscopy offers advantages in metabolite quantitation and platform robustness when applied in food metabolomics studies. This paper provides a (1)H NMR-based assessment of seed metabolomic diversity in conventional and glyphosate-resistant genetically modified (GM) soybean from a genetic lineage representing ∼35 years of breeding and differing yield potential. (1)H NMR profiling of harvested seed allowed quantitation of 27 metabolites, including free amino acids, sugars, and organic acids, as well as choline, O-acetylcholine, dimethylamine, trigonelline, and p-cresol. Data were analyzed by canonical discriminant analysis (CDA) and principal variance component analysis (PVCA). Results demonstrated that (1)H NMR spectroscopy was effective in highlighting variation in metabolite levels in the genetically diverse sample set presented. The results also confirmed that metabolite variability is influenced by selective breeding and environment, but not genetic modification. Therefore, metabolite variability is an integral part of crop improvement that has occurred for decades and is associated with a history of safe use.

  8. Extraction and [superscript 1]H NMR Analysis of Fats from Convenience Foods: A Laboratory Experiment for Organic Chemistry

    ERIC Educational Resources Information Center

    Hartel, Aaron M.; Moore, Amy C.

    2014-01-01

    The extraction and analysis of fats from convenience foods (crackers, cookies, chips, candies) has been developed as an experiment for a second-year undergraduate organic chemistry laboratory course. Students gravimetrically determine the fat content per serving and then perform a [superscript 1]H NMR analysis of the recovered fat to determine the…

  9. Microscale Synthesis and (super 1)H NMR Analysis of Zn(super II) and Ni(super II) Tetraphenylporphyrins

    ERIC Educational Resources Information Center

    Saucedo, Laura; Mink, Larry M.

    2005-01-01

    A multisection undergraduate laboratory involving the microscale synthesis and spectroscopic analysis of unmetalled porphyrins and their corresponding metalloporphyins is described. The microscale synthesis involving the isolation of the metalloporphyrins as solids and their corresponding (super 1)H NMR spectra are presented.

  10. Flow tracing microparticle sensors designed for enhanced X-ray contrast.

    PubMed

    Lee, Sang Joon; Jung, Sung Yong; Ahn, Sungsook

    2010-03-15

    In applying the X-ray particle image velocimetry (PIV) technique to biofluid flows, the most pivotal prerequisite is suitable flow tracing sensors which should be detected effectively by the X-ray imaging system. In this study, to design those flow tracing sensors, X-ray contrast agent Iopamidol was encapsulated into the poly(vinyl alcohol) (PVA) microparticles crosslinked by glutaraldehyde (GA). The characteristics of the fabricated particle sensors were determined by optical microscopy, scanning electron microscopy, dynamic light scattering, laser Doppler electrophoresis and nuclear magnetic resonance spectroscopy ((1)H NMR). The amount of Iopamidol in the microparticles was measured using the energy dispersive X-ray spectroscopy (EDS) and (1)H NMR. The physical properties of the PVA microparticles are effectively controlled in terms of the average particle size, degree of crosslinking, degree of swelling and encapsulation efficiency of Iopamidol. By changing the amount of crosslinker, the degree of crosslinking and the efficiency of the Iopamidol encapsulation reached to the optimal. To some extent, the zeta-potential of the PVA microparticles is increased in less ionic media where the particles can effectively repel each other prohibiting aggregation. The X-ray absorption ability of the designed tracing sensors was examined by a synchrotron X-ray imaging technique. The X-ray absorption coefficients of the particle sensors were expressed by an exponential law assuming the spherical shape of the microparticles. The X-ray contrast agent, Iopamidol, was successfully encapsulated into the bio-compatible and bio-degradable PVA. With the controlled physical properties of the flow tracing sensors designed in this study, the particle sensors exhibit excellent X-ray absorption contrast fairly applicable in biological systems.

  11. A thorough study on the use of quantitative 1H NMR in Rioja red wine fermentation processes.

    PubMed

    López-Rituerto, Eva; Cabredo, Susana; López, Martina; Avenoza, Alberto; Busto, Jesús H; Peregrina, Jesús M

    2009-03-25

    In this study, we focused our attention on monitoring the levels of important metabolites of wine during the alcoholic and malolactic fermentation processes by quantitative nuclear magnetic resonance (qNMR). Therefore, using (1)H NMR, the method allows the simultaneous quantification of ethanol, acetic, malic, lactic, and succinic acids, and the amino acids proline and alanine, besides the ratio proline/arginine through fermentation of must of grapes corresponding to the Tempranillo variety. Each (1)H NMR spectrum gives direct and visual information concerning these metabolites, and the effectiveness of each process was assessed and compared by carrying out analyses using infrared spectroscopy to ethanol and acetic acid. The quantitative data were explained with the aid of chemometric algorithms.

  12. Bonding in hard and elastic amorphous carbon nitride films investigated using 15N, 13C, and 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Gammon, W. J.; Hoatson, G. L.; Holloway, B. C.; Vold, R. L.; Reilly, A. C.

    2003-11-01

    The nitrogen bonding in hard and elastic amorphous carbon nitride (a-CNx) films is examined with 15N, 13C, and 1H nuclear magnetic resonance (NMR) spectroscopy. Films were deposited by dc magnetron sputtering, in a pure nitrogen discharge on Si(001) substrates at 300 °C. Nanoindentation tests revealed an elastic recovery of 80%, a hardness of 5 GPa, and an elastic modulus of 47 GPa. The NMR results show that nitrogen bonding in this material is consistent with sp2 hybridized nitrogen incorporated in an aromatic carbon environment. The data also indicate that the a-CNx prepared for this study has very low hydrogen content and is hydrophilic. Specifically, analysis of 15N and 13C cross polarization magic angle spinning and 1H NMR experiments suggests that water preferentially protonates nitrogen sites.

  13. Metabonomic signature analysis of cervical carcinoma and precancerous lesions in women by 1H NMR spectroscopy

    PubMed Central

    HASIM, AYSHAMGUL; ALI, MAYINUER; MAMTIMIN, BATUR; MA, JUN-QI; LI, QIAO-ZHI; ABUDULA, ABULIZI

    2012-01-01

    1H nuclear magnetic resonance (NMR)-based metabonomics has been used to characterize the metabolic profiles of cervical intraepithelial neoplasia (CIN) and cervical squamous cell carcinoma (CSCC). Principal component analysis (PCA) and orthogonal partial least-squares discriminant analysis (OPLS-DA) were used to model the systematic variation related to patients with CIN or CSCC with healthy controls. Potential metabolic biomarkers were identified using database comparisons, and the one-way analysis of variance (ANOVA) test was used to examine the significance of the metabolites. Compared with plasma obtained from the healthy controls, plasma from patients with CIN had higher levels of very-low density lipoprotein (VLDL), acetone, unsaturated lipid and carnitine, together with lower levels of creatine, lactate, isoleucine, leucine, valine, alanine, glutamine, histidine, glycine, acetylcysteine, myo-inositol, choline and glycoprotein. Plasma from patients with CSCC had higher levels of acetate and formate, together with lower levels of creatine, lactate, isoleucine, leucine, valine, alanine, glutamine, histidine and tyrosine compared with the plasma of the healthy controls. In addition, compared with the plasma of patients with CIN, the plasma of CSCC patients had higher levels of acetate, formate, lactate, isoleucine, leucine, valine, alanine, glutamine, histidine, tyrosine, acetylcysteine, myo-inositol, glycoprotein, α-glucose and β-glucose, together with lower levels of acetone, unsaturated lipid and carnitine. Moreover, the profiles showed high feasibility and specificity by statistical analysis with OPLS-DA compared to the Thinprep cytology test (TCT) by setting the histopathological outcome as standard. The metabolic profile obtained for cervical cancer is significant, even for the precancerous disease. This suggests a systemic metabolic response to cancer, which may be used to identify potential early diagnostic biomarkers of the cancer and to establish

  14. Evaluation of 1H NMR metabolic profiling using biofluid mixture design.

    PubMed

    Athersuch, Toby J; Malik, Shahid; Weljie, Aalim; Newton, Jack; Keun, Hector C

    2013-07-16

    A strategy for evaluating the performance of quantitative spectral analysis tools in conditions that better approximate background variation in a metabonomics experiment is presented. Three different urine samples were mixed in known proportions according to a {3, 3} simplex lattice experimental design and analyzed in triplicate by 1D (1)H NMR spectroscopy. Fifty-four urinary metabolites were subsequently quantified from the sample spectra using two methods common in metabolic profiling studies: (1) targeted spectral fitting and (2) targeted spectral integration. Multivariate analysis using partial least-squares (PLS) regression showed the latent structure of the spectral set recapitulated the experimental mixture design. The goodness-of-prediction statistic (Q(2)) of each metabolite variable in a PLS model was calculated as a metric for the reliability of measurement, across the sample compositional space. Several metabolites were observed to have low Q(2) values, largely as a consequence of their spectral resonances having low s/n or strong overlap with other sample components. This strategy has the potential to allow evaluation of spectral features obtained from metabolic profiling platforms in the context of the compositional background found in real biological sample sets, which may be subject to considerable variation. We suggest that it be incorporated into metabolic profiling studies to improve the estimation of matrix effects that confound accurate metabolite measurement. This novel method provides a rational basis for exploiting information from several samples in an efficient manner and avoids the use of multiple spike-in authentic standards, which may be difficult to obtain.

  15. Detection of cerebral NAD(+) by in vivo (1)H NMR spectroscopy.

    PubMed

    de Graaf, Robin A; Behar, Kevin L

    2014-07-01

    Nicotinamide adenine dinucleotide (NAD(+)) plays a central role in cellular metabolism both as a coenzyme for electron-transfer enzymes as well as a substrate for a wide range of metabolic pathways. In the current study NAD(+) was detected on rat brain in vivo at 11.7T by 3D localized (1)H MRS of the NAD(+) nicotinamide protons in the 8.7-9.5 ppm spectral region. Avoiding water perturbation was critical to the detection of NAD(+) as strong, possibly indirect cross-relaxation between NAD(+) and water would lead to a several-fold reduction of the NAD(+) intensity in the presence of water suppression. Water perturbation was minimized through the use of localization by adiabatic spin-echo refocusing (LASER) in combination with frequency-selective excitation. The NAD(+) concentration in the rat cerebral cortex was determined at 296 ± 28 μm, which is in good agreement with recently published (31) P NMR-based results as well as results from brain extracts in vitro (355 ± 34 μm). The T1 relaxation time constants of the NAD(+) nicotinamide protons as measured by inversion recovery were 280 ± 65 and 1136 ± 122 ms in the absence and presence of water inversion, respectively. This confirms the strong interaction between NAD(+) nicotinamide and water protons as observed during water suppression. The T2 relaxation time constants of the NAD(+) nicotinamide protons were determined at 60 ± 13 ms after confounding effects of scalar coupling evolution were taken into account. The simplicity of the MR sequence together with the robustness of NAD(+) signal detection and quantification makes the presented method a convenient choice for studies on NAD(+) metabolism and function. As the method does not critically rely on magnetic field homogeneity and spectral resolution it should find immediate applications in rodents and humans even at lower magnetic fields.

  16. Selective excitation enables assignment of proton resonances and (1)H-(1)H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy.

    PubMed

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of (1)H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as (13)C or (15)N. In this method, after the initial preparation of proton magnetization and cross-polarization to (13)C nuclei, transverse magnetization of desired (13)C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific (13)C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of (1)H-(1)H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  17. Selective excitation enables assignment of proton resonances and 1H-1H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-01

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of 1H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as 13C or 15N. In this method, after the initial preparation of proton magnetization and cross-polarization to 13C nuclei, transverse magnetization of desired 13C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific 13C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of 1H-1H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  18. Selective excitation enables assignment of proton resonances and {sup 1}H-{sup 1}H distance measurement in ultrafast magic angle spinning solid state NMR spectroscopy

    SciTech Connect

    Zhang, Rongchun; Ramamoorthy, Ayyalusamy

    2015-07-21

    Remarkable developments in ultrafast magic angle spinning (MAS) solid-state NMR spectroscopy enabled proton-based high-resolution multidimensional experiments on solids. To fully utilize the benefits rendered by proton-based ultrafast MAS experiments, assignment of {sup 1}H resonances becomes absolutely necessary. Herein, we propose an approach to identify different proton peaks by using dipolar-coupled heteronuclei such as {sup 13}C or {sup 15}N. In this method, after the initial preparation of proton magnetization and cross-polarization to {sup 13}C nuclei, transverse magnetization of desired {sup 13}C nuclei is selectively prepared by using DANTE (Delays Alternating with Nutations for Tailored Excitation) sequence and then, it is transferred to bonded protons with a short-contact-time cross polarization. Our experimental results demonstrate that protons bonded to specific {sup 13}C atoms can be identified and overlapping proton peaks can also be assigned. In contrast to the regular 2D HETCOR experiment, only a few 1D experiments are required for the complete assignment of peaks in the proton spectrum. Furthermore, the finite-pulse radio frequency driven recoupling sequence could be incorporated right after the selection of specific proton signals to monitor the intensity buildup for other proton signals. This enables the extraction of {sup 1}H-{sup 1}H distances between different pairs of protons. Therefore, we believe that the proposed method will greatly aid in fast assignment of peaks in proton spectra and will be useful in the development of proton-based multi-dimensional solid-state NMR experiments to study atomic-level resolution structure and dynamics of solids.

  19. Chiral trimethylsilylated C2-symmetrical diamines as phosphorous derivatizing agents for the determination of the enantiomeric excess of chiral alcohols by 1H NMR

    PubMed Central

    Chauvin, Anne-Sophie; Alexakis, Alexandre

    2006-01-01

    The use of organophosphorus derivatising agents, prepared from C2 symmetric trimethylsilylated diamines, for the 1H NMR and 31P NMR determination of the enantiomeric composition of chiral alcohols is described. PMID:16566844

  20. Synthesis, structural, and spectroscopic (FT-IR, NMR, and UV) Characterization of 1-(Cyclohexylmethyl)-2-(pyridin-2-yl)-1 H-benzo[ d]imidazole by experimental techniques and quantum chemical calculations

    NASA Astrophysics Data System (ADS)

    Özdemir, Namık; Dayan, Osman; Demirmen, Selin

    2016-05-01

    The title compound ( II), 1-(cyclohexylmethyl)-2-(pyridin-2-yl)-1 H-benzo[ d]imidazole (C19H21N3), was synthesized via N-alkylation of 2-(pyridin-2-yl)-1 H-benzo[ d]imidazole ( I). Both compounds I and II were characterized by IR, NMR and UV-vis spectroscopy. Solid-state structure of compound II was determined by single-crystal X-ray diffraction technique. Furthermore, quantum chemical calculations employing density functional theory (DFT/B3LYP) method with the 6-311++ G( d, p) basis set were performed for the theoretical characterization of the molecular and spectroscopic features of the compounds. Using the TD-DFT method, electronic absorption spectra of the compounds have been predicted at same level. When the obtained results were compared with the experimental findings, it is seen that theoretical results support the experimental data and a good agreement exists between them.

  1. 1H NMR, 13C NMR and mass spectral studies of some Schiff bases derived from 3-amino-1,2,4-triazole.

    PubMed

    Issa, Y M; Hassib, H B; Abdelaal, H E

    2009-11-01

    Heterocyclic Schiff bases derived from 3-amino-1,2,4-triazole and different substituted aromatic aldehydes are prepared and subjected to (1)H NMR, (13)C NMR and mass spectral analyses. (1)H NMR spectra in DMSO exhibit a sharp singlet within the 9.35-8.90ppm region which corresponds to the azomethine proton. The position of this signal is largely dependent on the nature of the substituents on the benzal moiety. It is observed that the shape, position and the integration value of the signal of the aromatic proton of the triazole ring ((5)C) are clearly affected by the rate of exchange, relaxation time, concentration of solution as well as the solvent used. (13)C NMR is taken as substantial support for the results reached from (1)H NMR studies. The mass spectral results are taken as a tool to confirm the structure of the investigated compounds. The base peak (100%), mostly the M-1 peak, indicates the facile loss of hydrogen radical. The fragmentation pattern of the unsubstituted Schiff base is taken as the general scheme. Differences in the other schemes result from the effect of the electronegativity of the substituents attached to the aromatic ring.

  2. Comprehensive quantum chemical and spectroscopic (FTIR, FT-Raman, 1H, 13C NMR) investigations of O-desmethyltramadol hydrochloride an active metabolite in tramadol - An analgesic drug

    NASA Astrophysics Data System (ADS)

    Arjunan, V.; Santhanam, R.; Marchewka, M. K.; Mohan, S.

    2014-03-01

    O-desmethyltramadol is one of the main metabolites of tramadol widely used clinically and has analgesic activity. The FTIR and FT-Raman spectra of O-desmethyl tramadol hydrochloride are recorded in the solid phase in the regions 4000-400 cm-1 and 4000-100 cm-1, respectively. The observed fundamentals are assigned to different normal modes of vibration. Theoretical studies have been performed as its hydrochloride salt. The structure of the compound has been optimised with B3LYP method using 6-31G** and cc-pVDZ basis sets. The optimised bond length and bond angles are correlated with the X-ray data. The experimental wavenumbers were compared with the scaled vibrational frequencies determined by DFT methods. The IR and Raman intensities are determined with B3LYP method using cc-pVDZ and 6-31G(d,p) basic sets. The total electron density and molecular electrostatic potential surfaces of the molecule are constructed by using B3LYP/cc-pVDZ method to display electrostatic potential (electron + nuclei) distribution. The electronic properties HOMO and LUMO energies were measured. Natural bond orbital analysis of O-desmethyltramadol hydrochloride has been performed to indicate the presence of intramolecular charge transfer. The 1H and 13C NMR chemical shifts of the molecule have been anlysed.

  3. A closer look at the nitrogen next door: 1H-15N NMR methods for glycosaminoglycan structural characterization

    NASA Astrophysics Data System (ADS)

    Langeslay, Derek J.; Beni, Szabolcs; Larive, Cynthia K.

    2012-03-01

    Recently, experimental conditions were presented for the detection of the N-sulfoglucosamine (GlcNS) NHSO3- or sulfamate 1H and 15N NMR resonances of the pharmaceutically and biologically important glycosaminoglycan (GAG) heparin in aqueous solution. In the present work, we explore further the applicability of nitrogen-bound proton detection to provide structural information for GAGs. Compared to the detection of 15N chemical shifts of aminosugars through long-range couplings using the IMPACT-HNMBC pulse sequence, the more sensitive two-dimensional 1H-15N HSQC-TOCSY experiments provided additional structural data. The IMPACT-HNMBC experiment remains a powerful tool as demonstrated by the spectrum measured for the unsubstituted amine of 3-O-sulfoglucosamine (GlcN(3S)), which cannot be observed with the 1H-15N HSQC-TOCSY experiment due to the fast exchange of the amino group protons with solvent. The 1H-15N HSQC-TOCSY NMR spectrum reported for the mixture of model compounds GlcNS and N-acetylglucosamine (GlcNAc) demonstrate the broad utility of this approach. Measurements for the synthetic pentasaccharide drug Arixtra® (Fondaparinux sodium) in aqueous solution illustrate the power of this NMR pulse sequence for structural characterization of highly similar N-sulfoglucosamine residues in GAG-derived oligosaccharides.

  4. Unambiguous Metabolite Identification in High-Throughput Metabolomics by Hybrid 1H-NMR/ESI-MS1 Approach

    SciTech Connect

    2016-10-18

    The invention improves accuracy of metabolite identification by combining direct infusion ESI-MS with one-dimensional 1H-NMR spectroscopy. First, we apply a standard 1H-NMR metabolite identification protocol by matching the chemical shift, J-coupling and intensity information of experimental NMR signals against the NMR signals of standard metabolites in a metabolomics reference libraries. This generates a list of candidate metabolites. The list contains both false positive and ambiguous identifications. The software tool (the invention) takes the list of candidate metabolites, generated from NMRbased metabolite identification, and then calculates, for each of the candidate metabolites, the monoisotopic mass-tocharge (m/z) ratios for each commonly observed ion, fragment and adduct feature. These are then used to assign m/z ratios in experimental ESI-MS spectra of the same sample. Detection of the signals of a given metabolite in both NMR and MS spectra resolves the ambiguities, and therefore, significantly improves the confidence of the identification.

  5. 1H-detected solid-state NMR of proteins entrapped in bioinspired silica: a new tool for biomaterials characterization

    PubMed Central

    Ravera, Enrico; Cerofolini, Linda; Martelli, Tommaso; Louka, Alexandra; Fragai, Marco; Luchinat, Claudio

    2016-01-01

    Proton-detection in solid-state NMR, enabled by high magnetic fields (>18 T) and fast magic angle spinning (>50 kHz), allows for the acquisition of traditional 1H-15N experiments on systems that are too big to be observed in solution. Among those, proteins entrapped in a bioinspired silica matrix are an attractive target that is receiving a large share of attention. We demonstrate that 1H-detected SSNMR provides a novel approach to the rapid assessment of structural integrity in proteins entrapped in bioinspired silica. PMID:27279168

  6. 1H-detected solid-state NMR of proteins entrapped in bioinspired silica: a new tool for biomaterials characterization

    NASA Astrophysics Data System (ADS)

    Ravera, Enrico; Cerofolini, Linda; Martelli, Tommaso; Louka, Alexandra; Fragai, Marco; Luchinat, Claudio

    2016-06-01

    Proton-detection in solid-state NMR, enabled by high magnetic fields (>18 T) and fast magic angle spinning (>50 kHz), allows for the acquisition of traditional 1H-15N experiments on systems that are too big to be observed in solution. Among those, proteins entrapped in a bioinspired silica matrix are an attractive target that is receiving a large share of attention. We demonstrate that 1H-detected SSNMR provides a novel approach to the rapid assessment of structural integrity in proteins entrapped in bioinspired silica.

  7. X-Ray Lasers

    ERIC Educational Resources Information Center

    Chapline, George; Wood, Lowell

    1975-01-01

    Outlines the prospects of generating coherent x rays using high-power lasers and indentifies problem areas in their development. Indicates possible applications for coherent x rays in the fields of chemistry, biology, and crystallography. (GS)

  8. X-ray (image)

    MedlinePlus

    X-rays are a form of ionizing radiation that can penetrate the body to form an image on ... will be shades of gray depending on density. X-rays can provide information about obstructions, tumors, and other ...

  9. Bone x-ray

    MedlinePlus

    ... not being scanned. Alternative Names X-ray - bone Images Skeleton Skeletal spine Osteogenic sarcoma - x-ray References ... urac.org). URAC's accreditation program is an independent audit to verify that A.D.A.M. follows ...

  10. X-ray

    MedlinePlus

    ... think you might be pregnant. Alternative Names Radiography Images X-ray X-ray References Geleijns J, Tack ... urac.org). URAC's accreditation program is an independent audit to verify that A.D.A.M. follows ...

  11. Extremity x-ray

    MedlinePlus

    ... sensitive to the risks of an x-ray. Images X-ray References Kelly DM. Congenital anomalies of ... urac.org). URAC's accreditation program is an independent audit to verify that A.D.A.M. follows ...

  12. X-Ray Toolkit

    SciTech Connect

    2015-10-20

    Radiographic Image Acquisition & Processing Software for Security Markets. Used in operation of commercial x-ray scanners and manipulation of x-ray images for emergency responders including State, Local, Federal, and US Military bomb technicians and analysts.

  13. MAS (1)H NMR Probes Freezing Point Depression of Water and Liquid-Gel Phase Transitions in Liposomes.

    PubMed

    Mandal, Abhishek; van der Wel, Patrick C A

    2016-11-01

    The lipid bilayer typical of hydrated biological membranes is characterized by a liquid-crystalline, highly dynamic state. Upon cooling or dehydration, these membranes undergo a cooperative transition to a rigidified, more-ordered, gel phase. This characteristic phase transition is of significant biological and biophysical interest, for instance in studies of freezing-tolerant organisms. Magic-angle-spinning (MAS) solid-state NMR (ssNMR) spectroscopy allows for the detection and characterization of the phase transitions over a wide temperature range. In this study we employ MAS (1)H NMR to probe the phase transitions of both solvent molecules and different hydrated phospholipids, including tetraoleoyl cardiolipin (TOCL) and several phosphatidylcholine lipid species. The employed MAS NMR sample conditions cause a previously noted substantial reduction in the freezing point of the solvent phase. The effect on the solvent is caused by confinement of the aqueous solvent in the small and densely packed MAS NMR samples. In this study we report and examine how the freezing point depression also impacts the lipid phase transition, causing a ssNMR-observed reduction in the lipids' melting temperature (Tm). The molecular underpinnings of this phenomenon are discussed and compared with previous studies of membrane-associated water phases and the impact of membrane-protective cryoprotectants.

  14. Diagnosis of cerebral cryptococcoma using a computerized analysis of 1H NMR spectra in an animal model.

    PubMed

    Dzendrowskyj, Theresa E; Dolenko, Brion; Sorrell, Tania C; Somorjai, Rajmund L; Malik, Richard; Mountford, Carolyn E; Himmelreich, Uwe

    2005-06-01

    Viable cryptococci load in biopsy material from an animal model of cerebral cryptococcoma were correlated with 1H NMR spectra and metabolite profiles. A statistical classification strategy was applied to distinguish among high-resolution 1H NMR spectra acquired from cryptococcomas, glioblastomas, and normal brain tissue. The overall classification accuracy was 100% when a genetic-algorithm-based optimal region selection preceded the development of linear discriminant analysis-based classifiers. The method remained robust despite differences in the microbial load of the cryptococcoma group when harvested at different time points. These results indicate the feasibility of the method for diagnosis without isolation of the pathogenic microorganism and its potential for in vivo diagnosis based on computerized analysis of magnetic resonance spectra.

  15. The origin of molecular mobility during biomass pyrolysis as revealed by in situ (1)H NMR spectroscopy.

    PubMed

    Dufour, Anthony; Castro-Diaz, Miguel; Brosse, Nicolas; Bouroukba, Mohamed; Snape, Colin

    2012-07-01

    The thermochemical conversion of lignocellulosic biomass feedstocks offers an important potential route for the production of biofuels and value-added green chemicals. Pyrolysis is the first phenomenon involved in all biomass thermochemical processes and it controls to a major extent the product composition. The composition of pyrolysis products can be affected markedly by the extent of softening that occurs. In spite of extensive work on biomass pyrolysis, the development of fluidity during the pyrolysis of biomass has not been quantified. This paper provides the first experimental investigation of proton mobility during biomass pyrolysis by in situ (1)H NMR spectroscopy. The origin of mobility is discussed for cellulose, lignin and xylan. The effect of minerals on cellulose mobility is also investigated. Interactions between polymers in the native biomass network are revealed by in situ (1)H NMR analysis.

  16. A study by (1)H NMR on the influence of some factors affecting lipid in vitro digestion.

    PubMed

    Nieva-Echevarría, Bárbara; Goicoechea, Encarnación; Manzanos, María J; Guillén, María D

    2016-11-15

    This article focuses on the impact of several experimental factors, including gastric acidification, intestinal transit time, presence of gastric lipase, sample/digestive fluids ratio, concentration and nature of the enzymes in intestinal juice, and bile concentration, on the extent of in vitro lipolysis when using a static model that simulates human digestion processes in mouth, stomach and small intestine. The study was carried out by Proton Nuclear Magnetic Resonance ((1)H NMR). This technique provides a complete molecular picture of lipolysis, evidencing for the first time, whether preferential hydrolysis of certain glycerides over others occurs. A lipolysis degree similar to that reported in vivo was reached by varying certain variables within a physiological range; among them, bile concentration was found to be crucial. The holistic view of this (1)H NMR study provides information of paramount importance to design sound in vitro digestion models to determine the bioaccessibility and bioavailability of lipophilic compounds.

  17. FT-IR and {sup 1}H NMR characterization of the products of an ethylene inverse diffusion flame

    SciTech Connect

    Santamaria, Alexander; Mondragon, Fanor; Molina, Alejandro; Marsh, Nathan D.; Eddings, Eric G.; Sarofim, Adel F.

    2006-07-15

    Knowledge of the chemical structure of young soot and its precursors is very useful in the understanding of the paths leading to soot particle inception. This paper presents analyses of the chemical functional groups, based on FT-IR and {sup 1}H NMR spectroscopy of the products obtained in an ethylene inverse diffusion flame. The trends in the data indicate that the soluble fraction of the soot becomes progressively more aromatic and less aliphatic as the height above the burner increases. Results from {sup 1}H NMR spectra of the chloroform-soluble soot samples taken at different heights above the burner corroborate the infrared results based on proton chemical shifts (Ha, H{alpha}, H{beta}, and H{gamma}). The results indicate that the aliphatic {beta} and {gamma} hydrogens suffered the most drastic reduction, while the aromatic character increased considerably with height, particularly in the first half of the flame. (author)

  18. In vitro interaction of selected phospholipid species with mercuric chloride using Fourier transform sup 1 H-NMR

    SciTech Connect

    Shinada, Masayuki; Muto, Hajime; Takizawa, Yukio )

    1991-09-01

    Many studies on the mercury toxicities have been accumulated since the outbreak of Minamata Disease.' There have been few reports on the reaction mechanisms of mercurials with phospholipids which substantially locate in biological membranes, although the interactions of nucleotides or nucleosides with mercurials have been reported. Recently, the study on the interaction of mercuric chloride (HgCl{sub 2}) with amino polar heads of model membranes containing phosphatidylserine (PS) and phosphatidylethanolamine (PE) has been reported, as the results from the fluorescence polarization analysis using 1,6-diphenyl-1,3,5-hexatriene. The authors demonstrate here the interactions of dioleoylphosphatidylethanolamine (DOPE) and dioleoylphosphatidylcholine (DOPC) with HgCl{sub 2}, using Fourier transform {sup 1}H-NMR ({sup 1}H-FT-NMR).

  19. Metabolite profiling of Clinacanthus nutans leaves extracts obtained from different drying methods by 1H NMR-based metabolomics

    NASA Astrophysics Data System (ADS)

    Hashim, Noor Haslinda Noor; Latip, Jalifah; Khatib, Alfi

    2016-11-01

    The metabolites of Clinacanthus nutans leaves extracts and their dependence on drying process were systematically characterized using 1H nuclear magnetic resonance spectroscopy (NMR) multivariate data analysis. Principal component analysis (PCA) and partial least square-discriminant analysis (PLS-DA) were able to distinguish the leaves extracts obtained from different drying methods. The identified metabolites were carbohydrates, amino acid, flavonoids and sulfur glucoside compounds. The major metabolites responsible for the separation in PLS-DA loading plots were lupeol, cycloclinacosides, betulin, cerebrosides and choline. The results showed that the combination of 1H NMR spectroscopy and multivariate data analyses could act as an efficient technique to understand the C. nutans composition and its variation.

  20. Characterizing Covalently Sidewall-Functionalized SWCNTs by using 1H NMR Spectroscopy

    PubMed Central

    Nelson, Donna J.; Kumar, Ravi

    2013-01-01

    Unambiguous evidence for covalent sidewall functionalization of single-walled carbon nanotubes (SWCNTs) has been a difficult task, especially for nanomaterials in which slight differences in functionality structure produce significant changes in molecular characteristics. Nuclear magnetic resonance (NMR) spectroscopy provides clear information about the structural skeleton of molecules attached to SWCNTs. In order to establish the generality of proton NMR as an analytical technique for characterizing covalently functionalized SWCNTs, we have obtained and analyzed proton NMR data of SWCNT-substituted benzenes across a variety of para substituents. Trends obtained for differences in proton NMR chemical shifts and the impact of o-, p-, and m-directing effects of electrophilic aromatic substituents on phenyl groups covalently bonded to SWCNTs are discussed. PMID:24009779

  1. Improving the efficiency of quantitative (1)H NMR: an innovative external standard-internal reference approach.

    PubMed

    Huang, Yande; Su, Bao-Ning; Ye, Qingmei; Palaniswamy, Venkatapuram A; Bolgar, Mark S; Raglione, Thomas V

    2014-01-01

    The classical internal standard quantitative NMR (qNMR) method determines the purity of an analyte by the determination of a solution containing the analyte and a standard. Therefore, the standard must meet the requirements of chemical compatibility and lack of resonance interference with the analyte as well as a known purity. The identification of such a standard can be time consuming and must be repeated for each analyte. In contrast, the external standard qNMR method utilizes a standard with a known purity to calibrate the NMR instrument. The external standard and the analyte are measured separately, thereby eliminating the matter of chemical compatibility and resonance interference between the standard and the analyte. However, the instrumental factors, including the quality of NMR tubes, must be kept the same. Any deviations will compromise the accuracy of the results. An innovative qNMR method reported herein utilizes an internal reference substance along with an external standard to assume the role of the standard used in the traditional internal standard qNMR method. In this new method, the internal reference substance must only be chemically compatible and be free of resonance-interference with the analyte or external standard whereas the external standard must only be of a known purity. The exact purity or concentration of the internal reference substance is not required as long as the same quantity is added to the external standard and the analyte. The new method reduces the burden of searching for an appropriate standard for each analyte significantly. Therefore the efficiency of the qNMR purity assay increases while the precision of the internal standard method is retained.

  2. Hydrocarbon type analysis of jet fuels by /sup 1/H and /sup 13/C NMR

    SciTech Connect

    Netzel, D.A.; Hunter, P.M.

    1981-05-01

    This report describes the application of NMR spectroscopy to the chemical characterization without prior chromatographic separation of jet fuels and various fuel blends containing varying amounts of paraffinic and aromatic constituents. Equations are derived by which the total percent paraffins and aromatics as well as percent monoaromatics and diaromatics can be calculated. Computer programs for the various calculations are included. The results obtained by NMR are compared to those obtained by MS.

  3. Light induced E-Z isomerization in a multi-responsive organogel: elucidation from (1)H NMR spectroscopy.

    PubMed

    Mondal, Sanjoy; Chakraborty, Priyadarshi; Bairi, Partha; Chatterjee, Dhruba P; Nandi, Arun K

    2015-07-07

    A multiresponsive organogel of (E)-N'-(anthracene-10-ylmethylene)-3,4,5-tris(dodecyloxy)benzohydrazide (I) showed a decrease of fluorescence intensity, decrease in mechanical strength and a change in gel morphology on irradiation with a wavelength of 365 nm. This is attributed to the E-Z isomerization across the C=N bond of I as evidenced from (1)H NMR spectroscopy.

  4. Method of Continuous Variation: Characterization of Alkali Metal Enolates Using 1H and 19F NMR Spectroscopies

    PubMed Central

    2015-01-01

    The method of continuous variation in conjunction with 1H and 19F NMR spectroscopies was used to characterize lithium and sodium enolates solvated by N,N,N′,N′-tetramethylethyldiamine (TMEDA) and tetrahydrofuran (THF). A strategy developed using lithium enolates was then applied to the more challenging sodium enolates. A number of sodium enolates solvated by TMEDA or THF afford exclusively tetramers. Evidence suggests that TMEDA chelates sodium on cubic tetramers. PMID:24915602

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

    PubMed

    Nieuwendaal, Ryan C

    2016-01-01

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

  6. Identification of isomeric dicaffeoylquinic acids from Eleutherococcus senticosus using HPLC-ESI/TOF/MS and 1H-NMR methods.

    PubMed

    Tolonen, Ari; Joutsamo, Topi; Mattlla, Sampo; Kämäräinen, Terttu; Jalonen, Jorma

    2002-01-01

    Liquid chromatography-electrospray time-of-flight mass spectrometry (HPLC-ESI/TOF/MS) and a novel NMR technique, developed to maximise the sensitivity obtained from the standard NMR spectrometer, have been applied to the identification of the phenolic constituents of Eleutherococcus senticosus. In addition, molecular modelling and dihedral bond angle calculations based on the vicinal 3JHH-coupling constants have been used in the unambiguous assignment of signals in the 1H-NMR spectra. 5'-O-Caffeoylquinic acid and three isomeric compounds, 1',5'-O-dicaffeoylquinic acid, 3',5'-O-dicaffeoylquinic acid and 4',5'-O-dicaffeoylquinic acid, have been isolated and identified from a sample. The isolation and structure determination of the latter two compounds are reported for the first time from this plant.

  7. Sinus x-ray

    MedlinePlus

    Paranasal sinus radiography; X-ray - sinuses ... sinus x-ray is taken in a hospital radiology department. Or the x-ray may be taken ... Brown J, Rout J. ENT, neck, and dental radiology. In: Adam A, Dixon AK, Gillard JH Schaefer- ...

  8. Hand x-ray

    MedlinePlus

    X-ray - hand ... A hand x-ray is taken in a hospital radiology department or your health care provider's office by an ... technician. You will be asked to place your hand on the x-ray table, and keep it ...

  9. Qualitative and quantitative analyses of Compound Danshen extract based on (1)H NMR method and its application for quality control.

    PubMed

    Yan, Kai-Jing; Chu, Yang; Huang, Jian-Hua; Jiang, Miao-Miao; Li, Wei; Wang, Yue-Fei; Huang, Hui-Yong; Qin, Yu-Hui; Ma, Xiao-Hui; Zhou, Shui-Ping; Sun, Henry; Wang, Wei

    2016-11-30

    In this study, a new approach using (1)H NMR spectroscopy combined with chemometrics method was developed for qualitative and quantitative analyses of extracts of Compound Danshen Dripping Pills (CDDP). For the qualitative analysis, some metabolites presented in Compound Danshen extract (CDE, extraction intermediate of CDDP) were detected, including phenolic acids, saponins, saccharides, organic acids and amino acids, by the proposed (1)H NMR method, and metabolites profiles were further analyzed by selected chemometrics algorithms to define the threshold values for product quality evaluation. Moreover, three main phenolic acids (danshensu, salvianolic acid B, and procatechuic aldehyde) in CDE were determined simultaneously, and method validation in terms of linearity, precision, repeatability, accuracy, and stability of the dissolved target compounds in solution was performed. The average recoveries varied between 84.20% and 110.75% while the RSDs were below 6.34% for the three phenolic acids. This (1)H NMR method offers an integral view of the extract composition, allows the qualitative and quantitative analysis of CDDP, and has the potential to be a supplementary tool to UPLC/HPLC for quality assessment of Chinese herbal medicines.

  10. Molecular characterization of dissolved organic matter in glacial ice: coupling natural abundance 1H NMR and fluorescence spectroscopy.

    PubMed

    Pautler, Brent G; Woods, Gwen C; Dubnick, Ashley; Simpson, André J; Sharp, Martin J; Fitzsimons, Sean J; Simpson, Myrna J

    2012-04-03

    Glaciers and ice sheets are the second largest freshwater reservoir in the global hydrologic cycle, and the onset of global climate warming has necessitated an assessment of their contributions to sea-level rise and the potential release of nutrients to nearby aquatic environments. In particular, the release of dissolved organic matter (DOM) from glacier melt could stimulate microbial activity in both glacial ecosystems and adjacent watersheds, but this would largely depend on the composition of the material released. Using fluorescence and (1)H NMR spectroscopy, we characterize DOM at its natural abundance in unaltered samples from a number of glaciers that differ in geographic location, thermal regime, and sample depth. Parallel factor analysis (PARAFAC) modeling of DOM fluorophores identifies components in the ice that are predominantly proteinaceous in character, while (1)H NMR spectroscopy reveals a mixture of small molecules that likely originate from native microbes. Spectrofluorescence also reveals a terrestrial contribution that was below the detection limits of NMR; however, (1)H nuclei from levoglucosan was identified in Arctic glacier ice samples. This study suggests that the bulk of the DOM from these glaciers is a mixture of biologically labile molecules derived from microbes.

  11. Mechanisms of humic acids degradation by white rot fungi explored using 1H NMR spectroscopy and FTICR mass spectrometry.

    PubMed

    Grinhut, Tzafrir; Hertkorn, Norbert; Schmitt-Kopplin, Philippe; Hadar, Yitzhak; Chen, Yona

    2011-04-01

    Enzymatic activities involved in decay processes of natural aromatic macromolecules, such as humic acids (HA) and lignin by white rot fungi, have been widely investigated. However, the physical and chemical analysis of degradation products of these materials has not been intensively explored. Fourier transform cyclotron resonance mass spectrometry (FTICR MS) and 1H NMR as well as CHNOS and size exclusion chromatography were employed to study the mechanisms of HA degradation by Trametes sp. M23 and Phanerochaete sp. Y6. Size exclusion chromatography analyses demonstrate and provide evidence for HA breakdown into low MW compounds. The 1H NMR analysis revealed oxidation, a decrease in the aromatic content, and an indication of demethylation of the HA during biodegradation. Evidence for oxidation was also obtained using CHNOS. Analysis of FTICR MS results using a new software program developed by our group (David Mass Sort) revealed consecutive series of masses suggesting biochemical degradation trends such as oxidation, aromatic cleavage, and demethylation. These results are in agreement with the 1H NMR analysis and with the suggested role of the ligninolytic system leading to HA degradation.

  12. Complete 1H and 13C NMR assignments and Z/E-stereoconfiguration determination of isomers of 1,4-diketone derivatives.

    PubMed

    Xu, Guohua; Yin, Guodong; Guo, Wenbo; Wu, Anxin; Cui, Yanfang

    2008-01-01

    Complete 1H and 13C NMR assignments and Z/E-stereoconfiguration determination for a series of new isomers of 1,4-diketone derivatives obtained via self-sorting tandem reaction were accomplished by means of one- and two-dimentional NMR experiments including 1H, 13C, gCOSY, gHSQC, gHMBC, and NOESY.

  13. Metabolic Characterization of Advanced Liver Fibrosis in HCV Patients as Studied by Serum 1H-NMR Spectroscopy.

    PubMed

    Embade, Nieves; Mariño, Zoe; Diercks, Tammo; Cano, Ainara; Lens, Sabela; Cabrera, Diana; Navasa, Miquel; Falcón-Pérez, Juan M; Caballería, Joan; Castro, Azucena; Bosch, Jaume; Mato, José M; Millet, Oscar

    2016-01-01

    Several etiologies result in chronic liver diseases including chronic hepatitis C virus infection (HCV). Despite its high incidence and the severe economic and medical consequences, liver disease is still commonly overlooked due to the lack of efficient non-invasive diagnostic methods. While several techniques have been tested for the detection of fibrosis, the available biomarkers still present severe limitations that preclude their use in clinical diagnostics. Liver diseases have also been the subject of metabolomic analysis. Here, we demonstrate the suitability of 1H NMR spectroscopy for characterizing the metabolism of liver fibrosis induced by HCV. Serum samples from HCV patients without fibrosis or with liver cirrhosis were analyzed by NMR spectroscopy and the results were submitted to multivariate and univariate statistical analysis. PLS-DA test was able to discriminate between advanced fibrotic and non-fibrotic patients and several metabolites were found to be up or downregulated in patients with cirrhosis. The suitability of the most significantly regulated metabolites was validated by ROC analysis. Our study reveals that choline, acetoacetate and low-density lipoproteins are the most informative biomarkers for predicting cirrhosis in HCV patients. Our results demonstrate that statistical analysis of 1H-NMR spectra is able to distinguish between fibrotic and non-fibrotic patients suffering from HCV, representing a novel diagnostic application for NMR spectroscopy.

  14. Synthesis, spectral characterization, single crystal X-ray diffraction and DFT studies of 4-((2,4,5-triphenyl-1H-imidazol-1-yl)methyl)pyridine derivatives

    NASA Astrophysics Data System (ADS)

    Rajkumar, R.; Kamaraj, A.; Bharanidharan, S.; Saleem, H.; Krishnasamy, K.

    2015-03-01

    We have synthesized a series of novel 4-((2,4,5-triphenyl-1H-imidazol-1-yl)methyl)pyridine derivatives. The structures of these compounds were confirmed by IR, HR-MS, 1H and 13C NMR spectra. The compound 5g was also confirmed by single crystal XRD. The geometry of the synthesized compounds 5a-5g were examined by density functional theory (DFT) method at B3LYP/6-31G(d,p) level. The optimized geometrical parameters obtained by DFT calculation are in good agreement with single crystal XRD data. The HOMO-LUMO energies describes charge transfer takes place within the molecule. Furthermore, Mulliken and NBO charges were also calculated. The stability and charge delocalization of the molecule were also studied by natural bond orbital (NBO) analysis. Compound 5g exhibited good non linear optical activity and was 20 times greater than that of urea. In addition, molecular electrostatic potential map (MEP) was studied for predicting the reactive sites.

  15. Application of quantitative 1H NMR for the calibration of protoberberine alkaloid reference standards.

    PubMed

    Wu, Yan; He, Yi; He, Wenyi; Zhang, Yumei; Lu, Jing; Dai, Zhong; Ma, Shuangcheng; Lin, Ruichao

    2014-03-01

    Quantitative nuclear magnetic resonance spectroscopy (qNMR) has been developed into an important tool in the drug analysis, biomacromolecule detection, and metabolism study. Compared with mass balance method, qNMR method bears some advantages in the calibration of reference standard (RS): it determines the absolute amount of a sample; other chemical compound and its certified reference material (CRM) can be used as internal standard (IS) to obtain the purity of the sample. Protoberberine alkaloids have many biological activities and have been used as reference standards for the control of many herbal drugs. In present study, the qNMR methods were developed for the calibration of berberine hydrochloride, palmatine hydrochloride, tetrahydropalmatine, and phellodendrine hydrochloride with potassium hydrogen phthalate as IS. Method validation was carried out according to the guidelines for the method validation of Chinese Pharmacopoeia. The results of qNMR were compared with those of mass balance method and the differences between the results of two methods were acceptable based on the analysis of estimated measurement uncertainties. Therefore, qNMR is an effective and reliable analysis method for the calibration of RS and can be used as a good complementarity to the mass balance method.

  16. Probing hydrogen bonding in cocrystals and amorphous dispersions using (14)N-(1)H HMQC solid-state NMR.

    PubMed

    Tatton, Andrew S; Pham, Tran N; Vogt, Frederick G; Iuga, Dinu; Edwards, Andrew J; Brown, Steven P

    2013-03-04

    Cocrystals and amorphous solid dispersions have generated interest in the pharmaceutical industry as an alternative to more established solid delivery forms. The identification of intermolecular hydrogen bonding interactions in a nicotinamide palmitic acid cocrystal and a 50% w/w acetaminophen-polyvinylpyrrolidone solid dispersion are reported using advanced solid-state magic-angle spinning (MAS) NMR methods. The application of a novel (14)N-(1)H HMQC experiment, where coherence transfer is achieved via through-space couplings, is shown to identify specific hydrogen bonding motifs. Additionally, (1)H isotropic chemical shifts and (14)N electric field gradient (EFG) parameters, both accessible from (14)N-(1)H HMQC experiments, are shown to be sensitive to changes in hydrogen bonding geometry. Numerous indicators of molecular association are accessible from this experiment, including NH cross-peaks occurring from intermolecular hydrogen bonds and changes in proton chemical shifts or electric field gradient parameters. First-principles calculations using the GIPAW approach that yield accurate estimates of isotropic chemical shifts, and EFG parameters were used to assist in assignment. It is envisaged that (14)N-(1)H HMQC solid state NMR experiments could become a valuable screening technique of solid delivery forms in the pharmaceutical industry.

  17. Differential protonation and dynamic structure of doxylamine succinate in solution using 1H and 13C NMR.

    PubMed

    Somashekar, B S; Nagana Gowda, G A; Ramesha, A R; Khetrapal, C L

    2004-07-01

    A protonation and dynamic structural study of doxylamine succinate, a 1:1 salt of succinic acid with dimethyl-[2-(1-phenyl-1-pyridin-2-yl-ethoxy)ethyl]amine, in solution using one- and two-dimensional 1H and 13C NMR experiments at variable temperature and concentration is presented. The two acidic protons of the salt doxylamine succinate are in 'intermediate' exchange at room temperature, as evidenced by the appearance of a broad signal. This signal evolves into two distinct signals below about -30 degrees C. A two-dimensional 1H-1H double quantum filtered correlation experiment carried out at -55 degrees C shows protonation of one of the acidic protons to the dimethylamine nitrogen. A two-dimensional rotating frame 1H-1H NOE experiment at the same temperature reveals that the other proton remains with the succinate moiety. Comparison of the 1H and 13C chemical shifts and the 13C T1 relaxation times of the salt with those of the free base further substantiate the findings.

  18. Nondestructive Quantification of Local Plasticizer Concentration in PVC by (1)H NMR Relaxometry.

    PubMed

    Adams, Alina; Kwamen, Rance; Woldt, Benjamin; Graß, Michael

    2015-12-01

    The properties of plasticized poly(vinyl chloride) (PVC) , one of the most important polymers today, are strongly dictated by the concentration of plasticizer. Yet, it has been impossible to quantify this concentration at different positions inside a PVC product without its destruction because of a lack of suitable analytical methods. Thus, this paper introduces a simple, fast, and efficient way to determine truly nondestructively the concentration of plasticizer in PVC by single-sided nuclear magnetic resonance (NMR). With the help of correlation curves between the concentration of plasticizer inside nonaged PVC samples and the corresponding volume-averaged NMR parameters, single-sided NMR allows the quantification of the local concentration of plasticizer in aged PVC plates at different depths by spatially resolved relaxation measurements. The presented approach represents a fundamental step toward in situ characterization of plasticized PVC.

  19. Glycerin-Induced Conformational Changes in Bombyx mori Silk Fibroin Film Monitored by 13C CP/MAS NMR and 1H DQMAS NMR

    PubMed Central

    Asakura, Tetsuo; Endo, Masanori; Hirayama, Misaki; Arai, Hiroki; Aoki, Akihiro; Tasei, Yugo

    2016-01-01

    In order to improve the stiff and brittle characteristics of pure Bombyx mori (B. mori) silk fibroin (SF) film in the dry state, glycerin (Glyc) has been used as a plasticizer. However, there have been very limited studies on the structural characterization of the Glyc-blended SF film. In this study, 13C Cross Polarization/Magic Angle Spinning nuclear magnetic resonance (CP/MAS NMR) was used to monitor the conformational changes in the films by changing the Glyc concentration. The presence of only 5 wt % Glyc in the film induced a significant conformational change in SF where Silk I* (repeated type II β-turn and no α-helix) newly appeared. Upon further increase in Glyc concentration, the percentage of Silk I* increased linearly up to 9 wt % Glyc and then tended to be almost constant (30%). This value (30%) was the same as the fraction of Ala residue within the Silk I* form out of all Ala residues of SF present in B. mori mature silkworm. The 1H DQMAS NMR spectra of Glyc-blended SF films confirmed the appearance of Silk I* in the Glyc-blended SF film. A structural model of Glyc-SF complex including the Silk I* form was proposed with the guidance of the Molecular Dynamics (MD) simulation using 1H–1H distance constraints obtained from the 1H Double-Quantum Magic Angle Spinning (DQMAS) NMR spectra. PMID:27618034

  20. Gelified Biofluids for High-Resolution Magic Angle Spinning (1)H NMR Analysis: The Case of Urine.

    PubMed

    Takis, Panteleimon G; Tenori, Leonardo; Ravera, Enrico; Luchinat, Claudio

    2017-01-17

    In this letter, we propose an alternative, effective protocol for metabolomic characterization of biofluids based on their gelification and subsequent application of high-resolution magic angle spinning (HRMAS) (1)H nuclear magnetic resonance (NMR). The sample handling is very rapid and reproducible, and much less than 40 μL of neat urine are needed to obtain a sample. Our results indicate that the HRMAS spectra of gelified urine encompass all metabolites in the NMR fingerprint, as observed by solution NMR. The proposed approach can be efficiently integrated into the NMR based metabolomics analyses routines: multivariate statistical analysis of both solution and HRMAS data produced very similar statistical models, with high classification accuracy. One of the key advantages offered by the gelification approach is the improved short-term (up to 24 h) preservation of nonfrozen HRMAS NMR gel urine samples compared to the solution samples, which could lead to an alternative way for transportation or domestic collection of biofluids, without the need of cold-storage and reducing the risks of leakage.

  1. 1H NMR studies distinguish the water soluble metabolomic profiles of untransformed and RAS-transformed cells

    PubMed Central

    Marks, Vered; Munoz, Anisleidys; Rai, Priyamvada

    2016-01-01

    Metabolomic profiling is an increasingly important method for identifying potential biomarkers in cancer cells with a view towards improved diagnosis and treatment. Nuclear magnetic resonance (NMR) provides a potentially noninvasive means to accurately characterize differences in the metabolomic profiles of cells. In this work, we use 1H NMR to measure the metabolomic profiles of water soluble metabolites extracted from isogenic control and oncogenic HRAS-, KRAS-, and NRAS-transduced BEAS2B lung epithelial cells to determine the robustness of NMR metabolomic profiling in detecting differences between the transformed cells and their untransformed counterparts as well as differences among the RAS-transformed cells. Unique metabolomic signatures between control and RAS-transformed cell lines as well as among the three RAS isoform-transformed lines were found by applying principal component analysis to the NMR data. This study provides a proof of principle demonstration that NMR-based metabolomic profiling can robustly distinguish untransformed and RAS-transformed cells as well as cells transformed with different RAS oncogenic isoforms. Thus, our data may potentially provide new diagnostic signatures for RAS-transformed cells. PMID:27330862

  2. High-Frequency (1)H NMR Chemical Shifts of Sn(II) and Pb(II) Hydrides Induced by Relativistic Effects: Quest for Pb(II) Hydrides.

    PubMed

    Vícha, Jan; Marek, Radek; Straka, Michal

    2016-10-17

    The role of relativistic effects on (1)H NMR chemical shifts of Sn(II) and Pb(II) hydrides is investigated by using fully relativistic DFT calculations. The stability of possible Pb(II) hydride isomers is studied together with their (1)H NMR chemical shifts, which are predicted in the high-frequency region, up to 90 ppm. These (1)H signals are dictated by sizable relativistic contributions due to spin-orbit coupling at the heavy atom and can be as large as 80 ppm for a hydrogen atom bound to Pb(II). Such high-frequency (1)H NMR chemical shifts of Pb(II) hydride resonances cannot be detected in the (1)H NMR spectra with standard experimental setup. Extended (1)H NMR spectral ranges are thus suggested for studies of Pb(II) compounds. Modulation of spin-orbit relativistic contribution to (1)H NMR chemical shift is found to be important also in the experimentally known Sn(II) hydrides. Because the (1)H NMR chemical shifts were found to be rather sensitive to the changes in the coordination sphere of the central metal in both Sn(II) and Pb(II) hydrides, their application for structural investigation is suggested.

  3. (1)H and (13)C NMR chemical shifts of methacrylate molecules associated with DMPC and/or DPPC liposomes.

    PubMed

    Fujisawa, Seiichiro; Ishihara, Mariko; Kadoma, Yoshinori

    2005-01-01

    In the light of recent developments, changes in (1)H and (13)C NMR chemical shifts of methacrylate molecule associated with DMPC (L-alpha dimyristoylphosphatidylcholine) or DPPC (L-alpha-dipalmitoylphosphatidylcholine) liposomes as a model for mimic native lipid bilayers were studied at 30, 37, and 52 degrees C. The chemical shifts of 3Ha, 3C, and 4C resonances in methacrylates (see Fig. 2) were greatly shifted higher field, suggesting the methacrylate molecule-lipid bilayer interaction. Comparison of the findings with methyl methacrylate (MMA), ethylene dimethacrylate (EDMA), and triethyleneglycol dimethacrylate (TEGDMA) revealed that the interaction of dimethacrylates (EDMA, TEGDMA) was greater than monomethacrylate, MMA. Their interaction with DMPC liposomes was also judged by a differential scanning calorimetry (DSC), indicating that the interaction was characterized by decreasing the enthalpy, entropy, and transition co-operativity. The evidence of the upfield NMR-shifts for methacrylate molecules was also judged by the descriptors such as the reactivity (HOMO-LUMO energy) and the electrostatic function (partial charges) between methacrylate molecules and DPPC, calculated by a PM 3 semiempirical MO method. The upfield NMR shifts were considerably well interpreted from the descriptors. NMR screening technique in methacrylates to phospholipid targets would be highly valuable in biomaterial developments. Figure 2 Changes in (1)H and (13)C NMR chemical shifts of methacrylate molecule associated with DMPC or DPPC liposomes. DMPC liposomes/MMA (1:1, molar ratio) and DMPC/TEGDMA (1:1) liposomes were measured at 30 degrees C. In DPPC liposome system, the rippled gel phase was measured at 30 degrees C, whereas the liquid crystalline phase for MMA and for both EDMA and TEGDMA were measured at 52 degrees C and 37 degrees C, respectively.

  4. Hydrogen Atomic Positions of O-H···O Hydrogen Bonds in Solution and in the Solid State: The Synergy of Quantum Chemical Calculations with ¹H-NMR Chemical Shifts and X-ray Diffraction Methods.

    PubMed

    Siskos, Michael G; Choudhary, M Iqbal; Gerothanassis, Ioannis P

    2017-03-07

    The exact knowledge of hydrogen atomic positions of O-H···O hydrogen bonds in solution and in the solid state has been a major challenge in structural and physical organic chemistry. The objective of this review article is to summarize recent developments in the refinement of labile hydrogen positions with the use of: (i) density functional theory (DFT) calculations after a structure has been determined by X-ray from single crystals or from powders; (ii) ¹H-NMR chemical shifts as constraints in DFT calculations, and (iii) use of root-mean-square deviation between experimentally determined and DFT calculated ¹H-NMR chemical shifts considering the great sensitivity of ¹H-NMR shielding to hydrogen bonding properties.

  5. In vivo1H NMR spectroscopy of the human brain at 9.4 T: Initial results

    NASA Astrophysics Data System (ADS)

    Deelchand, Dinesh Kumar; Moortele, Pierre-François Van de; Adriany, Gregor; Iltis, Isabelle; Andersen, Peter; Strupp, John P.; Thomas Vaughan, J.; Uğurbil, Kâmil; Henry, Pierre-Gilles

    2010-09-01

    In vivo proton NMR spectroscopy allows non-invasive detection and quantification of a wide range of biochemical compounds in the brain. Higher field strength is generally considered advantageous for spectroscopy due to increased signal-to-noise and increased spectral dispersion. So far 1H NMR spectra have been reported in the human brain up to 7 T. In this study we show that excellent quality short echo time STEAM and LASER 1H NMR spectra can be measured in the human brain at 9.4 T. The information content of the human brain spectra appears very similar to that measured in the past decade in rodent brains at the same field strength, in spite of broader linewidth in human brain. Compared to lower fields, the T1 relaxation times of metabolites were slightly longer while T2 relaxation values of metabolites were shorter (<100 ms) at 9.4 T. The linewidth of the total creatine (tCr) resonance at 3.03 ppm increased linearly with magnetic field (1.35 Hz/T from 1.5 T to 9.4 T), with a minimum achievable tCr linewidth of around 12.5 Hz at 9.4 T. At very high field, B0 microsusceptibility effects are the main contributor to the minimum achievable linewidth.

  6. Analysis of amorphous solid dispersions using 2D solid-state NMR and (1)H T(1) relaxation measurements.

    PubMed

    Pham, Tran N; Watson, Simon A; Edwards, Andrew J; Chavda, Manisha; Clawson, Jacalyn S; Strohmeier, Mark; Vogt, Frederick G

    2010-10-04

    Solid-state NMR (SSNMR) can provide detailed structural information about amorphous solid dispersions of pharmaceutical small molecules. In this study, the ability of SSNMR experiments based on dipolar correlation, spin diffusion, and relaxation measurements to characterize the structure of solid dispersions is explored. Observation of spin diffusion effects using the 2D (1)H-(13)C cross-polarization heteronuclear correlation (CP-HETCOR) experiment is shown to be a useful probe of association between the amorphous drug and polymer that is capable of directly proving glass solution formation. Dispersions of acetaminophen and indomethacin in different polymers are examined using this approach, as well as (1)H double-quantum correlation experiments to probe additional structural features. (1)H-(19)F CP-HETCOR serves a similar role for fluorinated drug molecules such as diflunisal in dispersions, providing a rapid means to prove the formation of a glass solution. Phase separation is detected using (13)C, (19)F, and (23)Na-detected (1)H T(1) experiments in crystalline and amorphous solid dispersions that contain small domains. (1)H T(1) measurements of amorphous nanosuspensions of trehalose and dextran illustrate the ability of SSNMR to detect domain size effects in dispersions that are not glass solutions via spin diffusion effects. Two previously unreported amorphous solid dispersions involving up to three components and containing voriconazole and telithromycin are analyzed using these experiments to demonstrate the general applicability of the approach.

  7. Comprehensive non-targeted analysis of contaminated groundwater of a former ammunition destruction site using 1H-NMR and HPLC-SPE-NMR/TOF-MS.

    PubMed

    Godejohann, Markus; Heintz, Lea; Daolio, Cristina; Berset, Jean-Daniel; Muff, Daniel

    2009-09-15

    The aim of the present study was to explore the capabilities of the combination of 1H NMR (proton nuclear magnetic resonance) mixture analysis and HPLC-SPE-NMR/TOF-MS (high-performance liquid chromatography coupled to solid-phase extraction and nuclear magnetic resonance and time-of-flight mass spectrometry) for the characterization of xenobiotic contaminants in groundwater samples. As an example, solid-phase extracts of two groundwater samples taken from a former ammunition destruction site in Switzerland were investigated. 1H NMR spectra of postcolumn SPE enriched compounds, together with accurate mass measurements, allowed the structural elucidation of unknowns. This untargeted approach allowed us to identify expected residues of explosives such as 2,4,6-trinitrotoluene (2,4,6-TNT), Hexogen (RDX) and Octogen (HMX), degradation products of TNT (1,3,5-trinitrobenzene (1,3,5-TNB), 2-amino-4,6-dinitrotoluene (2-A-4,6-DNT), 3,5-dinitrophenol (3,5-DNP), 3,5-dinitroaniline (3,5-DNA), 2,6-dinitroanthranite, and 2-Hydroxy-4,6-dinitrobenzonitrile), benzoic acid, Bisphenol A (a known endocrine disruptor compound), and some toxicologically relevant additives for propelling charges: Centralite I (1,3-diethyl-1,3-diphenylurea), DPU (N,N-diphenylurethane), N,N-diphenylcarbamate (Acardite II), and N-methyl-N-phenylurethane. To our knowledge, this is the first report of the presence of these additives in environmental samples. Extraction recoveries for Centralite I and DPU have been determined. Contaminants identified by our techniques were quantified based on HPLC-UV (HPLC-ultraviolet detection) and 1H NMR mixture analysis. The concentrations of the contaminants ranged between 0.1 and 48 microg/L assuming 100% recovery for the SPE step.

  8. (1)H NMR spectroscopy and chemometrics evaluation of non-thermal processing of orange juice.

    PubMed

    Alves Filho, Elenilson G; Almeida, Francisca D L; Cavalcante, Rosane S; de Brito, Edy S; Cullen, Patrick J; Frias, Jesus M; Bourke, Paula; Fernandes, Fabiano A N; Rodrigues, Sueli

    2016-08-01

    This study evaluated the effect of atmospheric cold plasma and ozone treatments on the key compounds (sugars, amino acids and short chain organic acids) in orange juice by NMR and chemometric analysis. The juice was directly and indirectly exposed to atmospheric cold plasma field at 70kV for different treatment time (15, 30, 45 and 60sec). For ozone processing different loads were evaluated. The Principal Component Analysis shown that the groups of compounds are affected differently depending on the processing. The ozone was the processing that more affected the aromatic compounds and atmospheric cold plasma processing affected more the aliphatic compounds. However, these variations did not result in significant changes in orange juice composition as a whole. Thus, NMR data and chemometrics were suitable to follow quality changes in orange juice processing by atmospheric cold plasma and ozone.

  9. {sup 1}H NMR relaxometry as an indicator of setting and water depletion during cement hydration

    SciTech Connect

    Wang, Biyun; Faure, Paméla; Thiéry, Mickaël; Baroghel-Bouny, Véronique

    2013-03-15

    Proton nuclear magnetic resonance relaxometry has been used to detect setting and microstructure evolution during cement hydration. NMR measurements were performed since casting, during setting and until hardening (from 0 to 3 days). The mobility of water molecules was assessed by an analysis focused on the diagram of longitudinal relaxation time T{sub 1} generated by an Inversion Recovery sequence. The initial stiffening of the solid network was identified by an analysis of the relaxation rate 1/T{sub 1}. The kinetics of water depletion was investigated by using a simple one-pulse acquisition sequence. In parallel, conventional techniques (Vicat needle and temperature monitoring), as well as numerical simulations of hydration, were used to complement and validate these NMR results. Cement pastes and mortars with different water-to-cement ratios made of grey or white OPCs were tested. Furthermore, the effects of the addition of sand, super-plasticizer and silica fume on the hydration kinetics were investigated.

  10. 13C and 1H NMR (Nuclear Magnetic Resonance) studies of solid polyolefines

    NASA Technical Reports Server (NTRS)

    Cudby, M. E. A.; Harris, R. K.; Metcalfe, K.; Packer, K. J.; Smith, P. W. R.

    1983-01-01

    The basis of H-1 and C-13 high-resolution NMR investigations of solid polymers is outlined. The C-13 NMR spectra of solid syndiotactic and isotactic polypropene are discussed and their interpretation in terms of conformation and chain-packing effects are reviewed. The effects of decreasing temperature on the C-13 high-resolution spectrum of an annealed sample of isotactic polypropene is described and interpreted in terms of the crystal structure. The question of the proportion of the sample giving rise to C-13 signals is addressed and some results reported. The main cause for observing only part of the total sample is shown to be the H-1 rotating frame spin-lattice relaxation behavior. The H-1 spin-lattice relaxation and spectral characteristics of a number of polyolefin samples are summarized and the role of spin-diffusion discussed.

  11. Metabolomics in Lung Inflammation: A High Resolution 1H NMR Study of Mice Exposed to Silica Dust

    PubMed Central

    Hu, Jian Zhi; Rommereim, Donald N.; Minard, Kevin R.; Woodstock, Angie; Harrer, Bruce J.; Wind, Robert A.; Phipps, Richard P.; Sime, Patricia J.

    2010-01-01

    Here we report the first 1H NMR metabolomics studies on excised lungs and bronchoalveolar lavage fluid (BALF) from mice exposed to crystalline silica. High resolution 1H NMR metabolic profiling on intact excised lungs was performed using slow magic angle sample spinning (slow-MAS) 1H PASS (phase altered spinning sidebands) at a sample spinning rate of 80 Hz. Metabolic profiling on BALF was completed using fast magic angle spinning at 2kHz. Major findings are that the relative concentrations of choline, phosphocholine (PC) and glycerophosphocholine(GPC) were statistically significantly increased in silica-exposed mice compared to sham controls, indicating an altered membrane choline phospholipids metabolism (MCPM). The relative concentrations of glycogen/glucose, lactate and creatine were also statistically significantly increased in mice exposed to silica dust, suggesting that cellular energy pathways were affected by silica dust. Elevated levels of glycine, lysine, glutamate, proline and 4-hydroxyproline were also increased in exposed mice, suggesting the activation of a collagen pathway. Furthermore, metabolic profiles in mice exposed to silica dust were found to be spatially heterogeneous, in consistent with regional inflammation revealed by in vivo magnetic resonance imaging (MRI). PMID:20020862

  12. 1H NMR study of the phase transitions of trissarcosine calcium chloride single crystals at low temperature

    NASA Astrophysics Data System (ADS)

    Lee, Kyuhong; Lee, Moohee; Lee, Kwang Sei; Lim, Ae Ran

    2005-10-01

    The 1H NMR line-width and spin lattice relaxation time T1 of TSCC single crystals were studied. Variations in the temperature dependence of the spin lattice relaxation time were observed near 65 and 130 K, indicating drastic alterations of the spin dynamics at the phase transition temperatures. The changes in the temperature dependence of T1 near 65 and 130 K correspond to phase transitions of the crystal. The anomalous decrease in T1 around 130 K is due to the critical slowing down of the soft mode. The abrupt change in relaxation time at 65 K is associated with a structural phase transition. The proton spin lattice relaxation time of this crystal also has a minimum value in the vicinity of 185 K, which is governed by the reorientation of the CH3 groups of the sarcosine molecules. From this result, we conclude that the two phase transitions at 65 and 130 K can be discerned from abrupt variations in the 1H NMR relaxation behavior, and that 1H nuclei play important roles in the phase transitions of the TSCC single crystal.

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

    PubMed

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

    2006-07-01

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

  14. Communication: molecular dynamics and (1)H NMR of n-hexane in liquid crystals.

    PubMed

    Weber, Adrian C J; Burnell, E Elliott; Meerts, W Leo; de Lange, Cornelis A; Dong, Ronald Y; Muccioli, Luca; Pizzirusso, Antonio; Zannoni, Claudio

    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.

  15. Communication: Molecular dynamics and {sup 1}H NMR of n-hexane in liquid crystals

    SciTech Connect

    Weber, Adrian C. J.; Burnell, E. Elliott; Meerts, W. Leo; Lange, Cornelis A. de; Dong, Ronald Y.; Muccioli, Luca Pizzirusso, Antonio Zannoni, Claudio

    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.

  16. Degradation Kinetics and Mechanism of Lithospermic Acid under Low Oxygen Condition Using Quantitative 1H NMR with HPLC-MS

    PubMed Central

    Pan, Jianyang; Gong, Xingchu; Qu, Haibin

    2016-01-01

    A novel quantitative 1H NMR (Q-NMR) combined with HPLC-MS method has been proposed for investigating the degradation process of traditional Chinese medicine (TCM) components. Through this method, in-situ monitoring of dynamics degradation process of lithospermic acid (LA), one of the popular polyphenolic acids in TCM, was realized under low oxygen condition. Additionally, this methodology was proved to be simple, rapid and specific. Degradation kinetic runs have been carried out to systematically investigate the effects of two key environmental factors, initial pH values and temperatures. Eight main degradation products of LA were detected, seven of which were tentatively structural elucidated with the help of both NMR and LC-MS in this work and salvianolic acid A (Sal A) was the primary degradation product of LA. A possible degradation pathway of LA was proposed, subsequently. The results showed that the degradation of LA followed pseudo-first-order kinetics. The apparent degradation kinetic constants increased as the initial pH value of the phosphate buffer increased. Under the given conditions, the rate constants of overall degradation as a function of temperature obeyed the Arrhenius equation. Our results proved that the Q-NMR combined with HPLC-MS method can be one of the most promising techniques for investigating degradation process of active components in TCM. PMID:27776128

  17. Classification of Coffee Beans by GC-C-IRMS, GC-MS, and 1H-NMR

    PubMed Central

    Arana, Victoria Andrea; Esseiva, Pierre; Pazos, Diego

    2016-01-01

    In a previous work using 1H-NMR we reported encouraging steps towards the construction of a robust expert system for the discrimination of coffees from Colombia versus nearby countries (Brazil and Peru), to assist the recent protected geographical indication granted to Colombian coffee in 2007. This system relies on fingerprints acquired on a 400 MHz magnet and is thus well suited for small scale random screening of samples obtained at resellers or coffee shops. However, this approach cannot easily be implemented at harbour's installations, due to the elevated operational costs of cryogenic magnets. This limitation implies shipping the samples to the NMR laboratory, making the overall approach slower and thereby more expensive and less attractive for large scale screening at harbours. In this work, we report on our attempt to obtain comparable classification results using alternative techniques that have been reported promising as an alternative to NMR: GC-MS and GC-C-IRMS. Although statistically significant information could be obtained by all three methods, the results show that the quality of the classifiers depends mainly on the number of variables included in the analysis; hence NMR provides an advantage since more molecules are detected to obtain a model with better predictions. PMID:27516919

  18. Identification and quantification of major steviol glycosides in Stevia rebaudiana purified extracts by 1H NMR spectroscopy.

    PubMed

    Pieri, Valerio; Belancic, Andrea; Morales, Susana; Stuppner, Hermann

    2011-05-11

    The use of (1)H NMR spectroscopy for the characterization of Stevia rebaudiana extracts is presented. The developed method allows qualitative and quantitative determination of the major steviol glycosides in purified extracts and fractions obtained from various stages of the purification process. Moreover, it proved to be a powerful tool to differentiate between glycosides which are naturally occurring in the stevia plant and artifacts formed in the course of the manufacturing process. Identification of steviol glycosides was achieved by the use of 2D NMR techniques, whereas quantification is based on qHNMR using anthracene as internal standard. The solvent mixture pyridine-d(5)-DMSO-d(6) (6:1) enabled satisfactory separation of the signals to be integrated. Validation of the method was performed in terms of specificity, precision, accuracy, linearity, robustness, and stability. Quantitative results were compared to those obtained with the JECFA HPLC-UV method and were found to be in reasonable agreement. NMR analysis does not rely on the use of reference compounds and enables significantly faster analysis compared to HPLC-UV. Thus, NMR represents a feasible alternative to HPLC-based methods for the quality control of Stevia rebaudiana extracts.

  19. Combining 1H NMR spectroscopy and multivariate regression techniques to quantitatively determine falsification of porcine heparin with bovine species.

    PubMed

    Monakhova, Yulia B; Diehl, Bernd W K

    2015-11-10

    (1)H NMR spectroscopy was used to distinguish pure porcine heparin and porcine heparin blended with bovine species and to quantify the degree of such adulteration. For multivariate modelling several statistical methods such as partial least squares regression (PLS), ridge regression (RR), stepwise regression with variable selection (SR), stepwise principal component regression (SPCR) were utilized for modeling NMR data of in-house prepared blends (n=80). The models were exhaustively validated using independent test and prediction sets. PLS and RR showed the best performance for estimating heparin falsification regarding its animal origin with the limit of detection (LOD) and root mean square error of validation (RMSEV) below 2% w/w and 1% w/w, respectively. Reproducibility expressed in coefficients of variation was estimated to be below 10% starting from approximately 5% w/w of bovine adulteration. Acceptable calibration model was obtained by SPCR, by its application range was limited, whereas SR is least recommended for heparin matrix. The developed method was found to be applicable also to heparinoid matrix (not purified heparin). In this case root mean square of prediction (RMSEP) and LOD were approximately 7% w/w and 8% w/w, respectively. The simple and cheap NMR method is recommended for screening of heparin animal origin in parallel with official NMR test of heparin authenticity and purity.

  20. Quantification of Human Brain Metabolites from in Vivo1H NMR Magnitude Spectra Using Automated Artificial Neural Network Analysis

    NASA Astrophysics Data System (ADS)

    Hiltunen, Yrjö; Kaartinen, Jouni; Pulkkinen, Juhani; Häkkinen, Anna-Maija; Lundbom, Nina; Kauppinen, Risto A.

    2002-01-01

    Long echo time (TE=270 ms) in vivo proton NMR spectra resembling human brain metabolite patterns were simulated for lineshape fitting (LF) and quantitative artificial neural network (ANN) analyses. A set of experimental in vivo1H NMR spectra were first analyzed by the LF method to match the signal-to-noise ratios and linewidths of simulated spectra to those in the experimental data. The performance of constructed ANNs was compared for the peak area determinations of choline-containing compounds (Cho), total creatine (Cr), and N-acetyl aspartate (NAA) signals using both manually phase-corrected and magnitude spectra as inputs. The peak area data from ANN and LF analyses for simulated spectra yielded high correlation coefficients demonstrating that the peak areas quantified with ANN gave similar results as LF analysis. Thus, a fully automated ANN method based on magnitude spectra has demonstrated potential for quantification of in vivo metabolites from long echo time spectroscopic imaging.

  1. Study of the Cardiotoxicity of Venenum Bufonis in Rats using an 1H NMR-Based Metabolomics Approach

    PubMed Central

    Wang, Junsong; Guo, Pingping; Li, Minghui; Yang, Minghua; Kong, Lingyi

    2015-01-01

    Venenum Bufonis, a well-known traditional Chinese medicine, has been widely used in Asia and has gained popularity in Western countries over the last decade. Venenum Bufonis has obvious side effects that have been observed in clinical settings, but few studies have reported on its cardiotoxicity. In this work, the cardiotoxicity of Venenum Bufonis was investigated using a 11H NMR-based metabolomics approach. The 1H NMR profiles of the serum, myocardial extracts and liver extracts of specific-pathogen-free rats showed that Venenum Bufonis produced significant metabolic perturbations dose-dependently with a distinct time effect, peaking at 2 hr after dosing and attenuating gradually. Clinical chemistry, electrocardiographic recordings, and histopathological evaluation provided additional evidence of Venenum Bufonis-induced cardiac damage that complemented and supported the metabolomics findings. The combined results demonstrated that oxidative stress, mitochondrial dysfunction, and energy metabolism perturbations were associated with the cardiac damage that results from Venenum Bufonis. PMID:25781638

  2. (1)H NMR spectroscopy-guided isolation of new sucrose esters from Physalis alkekengi var. franchetii and their antibacterial activity.

    PubMed

    Zhang, Chuan-Yang; Luo, Jian-Guang; Liu, Rui-Huan; Lin, Ru; Yang, Ming-Hua; Kong, Ling-Yi

    2016-10-01

    Ten new sucrose esters, physakengoses A-J (1-10), were isolated from the aerial parts of Physalis alkekengi var. franchetii under the guidance of (1)H NMR spectroscopy. Their structures were determined by spectroscopic analyses (HRESIMS, 1D and 2D NMR, and ESIMS) and chemical methods. These new compounds were tested for antibacterial activities against Staphylococcus aureus, Bacillus subtilis, Pseudomonas aeruginosa and Escherichia coli. Among them, compounds 2 and 5-8 showed potent inhibitory effects against test strains with MIC values ranging from 3.5 to 14.9μg/mL. These findings may indicate that the P. alkekengi var. franchetii has potential application as an ingredient in pharmaceuticals.

  3. 1H NMR analysis of complexation of hydrotropic agents nicotinamide and caffeine with aromatic biologically active molecules in aqueous solution

    NASA Astrophysics Data System (ADS)

    Lantushenko, Anastasia O.; Mukhina, Yulia V.; Veselkov, Kyrill A.; Davies, David B.; Veselkov, Alexei N.

    2004-07-01

    NMR spectroscopy has been used to elucidate the molecular mechanism of solubilization action of hydrotropic agents nicotinamide (NA) and caffeine (CAF). Hetero-association of NA with riboflavine-mononucleotide (FMN) and CAF with low soluble in aqueous solution synthetic analogue of antibiotic actinomycin D, actinocyl-bis-(3-dimethylaminopropyl) amine (Actill), has been investigated by 500 MHz 1H NMR spectroscopy. Concentration and temperature dependences of proton chemical shifts have been analysed in terms of a statistical-thermodynamic model of indefinite self- and heteroassociation of aromatic molecules. The obtained results enable to conclude that NA-FMN and CAF-Actill intermolecular complexes are mainly stabilized by the stacking interactions of the aromatic chromophores. Hetero-association of the investigated molecules plays an important role in solubilization of aromatic drugs by hydrotropic agents nicotinamide and caffeine.

  4. Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal syringates

    NASA Astrophysics Data System (ADS)

    Świsłocka, Renata

    2013-07-01

    In this work the influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the syringic acid (4-hydroxy-3,5-dimethoxybenzoic acid) was studied. This paper presents spectroscopic vibrations (FT-IR, FT-Raman) and NMR (1H and 13C) study of the series of alkali metal syringates from lithium to cesium syringates. Characteristic shifts of band wavenumbers and changes in band intensities along the metal series were observed. Optimized geometrical structures of the studied compounds were calculated by the B3LYP method using the 6-311++G∗∗ basis set. Aromaticity indices, atomic charges, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and NMR spectra were obtained. The calculated parameters were compared to experimental characteristics of studied compounds.

  5. Two-dimensional sup 1 H NMR studies on HPr protein from Staphylococcus aureus: Complete sequential assignments and secondary structure

    SciTech Connect

    Kalbitzer, H.R.; Neidig, K.P. ); Hengstenberg, W. )

    1991-11-19

    Complete sequence-specific assignments of the {sup 1}H NMR spectrum of HPr protein from Staphylococcus aureus were obtained by two-dimensional NMR methods. Important secondary structure elements that can be derived from the observed nuclear Overhauser effects are a large antiparallel {beta}-pleated sheet consisting of four strands, A, B, C, D, a segment S{sub AB} consisting of an extended region around the active-center histidine (His-15) and an {alpha}-helix, a half-turn between strands B and C, a segment S{sub CD} which shows no typical secondary structure, and the {alpha}-helical, C-terminal segment S{sub term}. These general structural features are similar to those found earlier in HPr proteins from different microorganisms such as Escherichia coli, Bacillus subtilis, and Streptococcus faecalis.

  6. A physical picture of atomic motions within the Dickerson DNA dodecamer in solution derived from joint ensemble refinement against NMR and large-angle X-ray scattering data.

    PubMed

    Schwieters, Charles D; Clore, G Marius

    2007-02-06

    The structure and dynamics of the Dickerson DNA dodecamer [5'd(CGCGAATTCGCG)2] in solution have been investigated by joint simulated annealing refinement against NMR and large-angle X-ray scattering data (extending from 0.25 to 3 A-1). The NMR data comprise an extensive set of hetero- and homonuclear residual dipolar coupling and 31P chemical shift anisotropy restraints in two alignment media, supplemented by NOE and 3J coupling data. The NMR and X-ray scattering data cannot be fully ascribed to a single structure representation, indicating the presence of anisotropic motions that impact the experimental observables in different ways. Refinement with ensemble sizes (Ne) of >or=2 to represent the atomic motions reconciles all the experimental data within measurement error. Cross validation against both the dipolar coupling and X-ray scattering data suggests that the optimal ensemble size required to account for the current data is 4. The resulting ensembles permit one to obtain a detailed view of the conformational space sampled by the dodecamer in solution and permit one to analyze fluctuations in helicoidal parameters, sugar puckers, and BI-BII backbone transitions and to obtain quantitative metrics of atomic motion such as generalized order parameters and thermal B factors. The calculated order parameters are in good agreement with experimental order parameters obtained from 13C relaxation measurements. Although DNA behaves as a relatively rigid rod with a persistence length of approximately 150 bp, dynamic conformational heterogeneity at the base pair level is functionally important since it readily permits optimization of intermolecular protein-DNA interactions.

  7. X-ray binaries

    NASA Technical Reports Server (NTRS)

    1976-01-01

    Satellite X-ray experiments and ground-based programs aimed at observation of X-ray binaries are discussed. Experiments aboard OAO-3, OSO-8, Ariel 5, Uhuru, and Skylab are included along with rocket and ground-based observations. Major topics covered are: Her X-1, Cyg X-3, Cen X-3, Cyg X-1, the transient source A0620-00, other possible X-ray binaries, and plans and prospects for future observational programs.

  8. 1H NMR assignments of apo calcyclin and comparative structural analysis with calbindin D9k and S100 beta.

    PubMed Central

    Potts, B. C.; Carlström, G.; Okazaki, K.; Hidaka, H.; Chazin, W. J.

    1996-01-01

    The homodimeric S100 protein calcyclin has been studied in the apo state by two-dimensional 1H NMR spectroscopy. Using a combination of scalar correlation and NOE experiments, sequence-specific 1H NMR assignments were obtained for all but one backbone and > 90% of the side-chain resonances. To our knowledge, the 2 x 90 residue (20 kDa) calcyclin dimer is the largest protein system for which such complete assignments have been made by purely homonuclear methods. Sequential and medium-range NOEs and slowly exchanging backbone amide protons identified directly the four helices and the short antiparallel beta-type interaction between the two binding loops that comprise each subunit of the dimer. Further analysis of NOEs enabled the unambiguous assignment of 556 intrasubunit distance constraints, 24 intrasubunit hydrogen bonding constraints, and 2 x 26 intersubunit distance constraints. The conformation of the monomer subunit was refined by distance geometry and restrained molecular dynamics calculations using the intrasubunit constraints only. Calculation of the dimer structure starting from this conformational ensemble has been reported elsewhere. The extent of structural homology among the apo calcyclin subunit, the monomer subunit of apo S100 beta, and monomeric apo calbindin D9k has been examined in detail by comparing 1H NMR chemical shifts and secondary structures. This analysis was extended to a comprehensive comparison of the three-dimensional structures of the calcyclin monomer subunit and calbindin D9k, which revealed greater similarity in the packing of their hydrophobic cores than was anticipated previously. Together, these results support the hypothesis that all members of the S100 family have similar core structures and similar modes of dimerization. Analysis of the amphiphilicity of Helix IV is used to explain why calbindin D9k is monomeric, but full-length S100 proteins form homodimers. PMID:8931135

  9. Probing phosphorylation by non-mammalian isoprenoid biosynthetic enzymes using (1)H-(31)P-(31)P correlation NMR spectroscopy.

    PubMed

    Majumdar, Ananya; Shah, Meha H; Bitok, J Kipchirchir; Hassis-LeBeau, Maria E; Freel Meyers, Caren L

    2009-09-01

    The biogenesis of isopentenyl pyrophosphate (IPP) and dimethylallyl pyrophosphate (DMAPP) is accomplished by the methylerythritol phosphate (MEP) pathway in plants, bacteria and parasites, making it a potential target for the development of anti-infective agents and herbicides. The biosynthetic enzymes comprising this pathway catalyze intriguing chemical transformations on diphosphate scaffolds, offering an opportunity to generate novel analogs in this synthetically challenging compound class. Such a biosynthetic approach to generating new diphosphate analogs may involve transformation through discrete diphosphate species, presenting unique challenges in structure determination and characterization of unnatural enzyme-generated diphosphate products produced in tandem. We have developed (1)H-(31)P-(31)P correlation NMR spectroscopy techniques for the direct characterization of crude MEP pathway enzyme products at low concentrations (200 microM to 5 mM) on a room temperature (non-cryogenic) NMR probe. Coupling the 100% natural abundance of the (31)P nucleus with the high intrinsic sensitivity of proton NMR, (1)H-(31)P-(31)P correlation spectroscopy is particularly useful for characterization of unnatural diphosphate enzyme products in the MEP pathway. As proof of principle, we demonstrate the rapid characterization of natural enzyme products of the enzymes IspD, E and F in tandem enzyme incubations. In addition, we have characterized several unnatural enzyme products using this technique, including new products of cytidyltransferase IspD bearing erythritol, glycerol and ribose components. The results of this study indicate that IspD may be a useful biocatalyst and highlight (1)H-(31)P-(31)P correlation spectroscopy as a valuable tool for the characterization of other unnatural products in non-mammalian isoprenoid biosynthesis.

  10. GFT projection NMR for efficient (1)H/ (13)C sugar spin system identification in nucleic acids.

    PubMed

    Atreya, Hanudatta S; Sathyamoorthy, Bharathwaj; Jaipuria, Garima; Beaumont, Victor; Varani, Gabriele; Szyperski, Thomas

    2012-12-01

    A newly implemented G-matrix Fourier transform (GFT) (4,3)D HC(C)CH experiment is presented in conjunction with (4,3)D HCCH to efficiently identify (1)H/(13)C sugar spin systems in (13)C labeled nucleic acids. This experiment enables rapid collection of highly resolved relay 4D HC(C)CH spectral information, that is, shift correlations of (13)C-(1)H groups separated by two carbon bonds. For RNA, (4,3)D HC(C)CH takes advantage of the comparably favorable 1'- and 3'-CH signal dispersion for complete spin system identification including 5'-CH. The (4,3)D HC(C)CH/HCCH based strategy is exemplified for the 30-nucleotide 3'-untranslated region of the pre-mRNA of human U1A protein.

  11. Conformation of some N,N'-arylalkyl thioureas by 1H-NMR and infrared spectral analysis

    NASA Astrophysics Data System (ADS)

    Sudha, L. V.; Sathyanarayana, D. N.

    Several N,N'-arylalkyl thioureas were examined with 1H-NMR and i.r. spectra in order to study the conformation of the -NHCSNH- group. The influence of temperature and substituents on the chemical shift of the NH protons has been investigated. Formation of a strong intramolecular hydrogen bond stabilizes the trans—cis conformation for most systems, while for the others the prevalence of different rotational isomers can be postulated. The influence of the steric effect on hydrogen bonding and molecular conformation is discussed.

  12. Hydrogen cluster/network in tobermorite as studied by multiple-quantum spin counting {sup 1}H NMR

    SciTech Connect

    Mogami, Yuuki; Yamazaki, Satoru; Matsuno, Shinya; Matsui, Kunio; Noda, Yasuto; Takegoshi, K.

    2014-12-15

    Proton multiple-quantum (MQ) spin-counting experiment has been employed to study arrangement of hydrogen atoms in 9 Å/11 Å natural/synthetic tobermorites. Even though all tobermorite samples give similar characterless, broad static-powder {sup 1}H NMR spectra, their MQ spin-counting spectra are markedly different; higher quanta in 11 Å tobermorite do not grow with the MQ excitation time, while those in 9 Å one do. A statistical analysis of the MQ results recently proposed [26] is applied to show that hydrogens align in 9 Å tobermorite one dimensionally, while in 11 Å tobermorite they exist as a cluster of 5–8 hydrogen atoms.

  13. 31P{1H}NMR and carbonyl force constants of unsymmetrical bidentate phosphine complexes of group (VI) metal carbonyls

    NASA Astrophysics Data System (ADS)

    Jesu Raj, Joe Gerald; Pathak, Devendra Deo; Kapoor, Pramesh N.

    2015-05-01

    In our present work we report synthesis of an unsymmetrical diphos ligand, 1-diphenylphosphino-2-di-m-tolylphosphinoethane and its coordinate complexes with group (VI) metal carbonyls such as Cr(CO)6 Mo(CO)6 and W(CO)6. The synthesized ligand and its complexes have been completely characterized by elemental analyses, FTIR, 1HNMR, 31P{1H}NMR and FAB mass spectrometry methods. Special emphasis has been given to calculations of carbonyl force constants. Based on the spectroscopic evidences it has been confirmed that these metal carbonyl complexes with the ditertiary phosphine ligand showed cis geometry in their molecular structure.

  14. Whole Blood Metabolomics by (1)H NMR Spectroscopy Provides a New Opportunity To Evaluate Coenzymes and Antioxidants.

    PubMed

    Nagana Gowda, G A; Raftery, Daniel

    2017-03-30

    Conventional human blood metabolomics employs serum or plasma and provides a wealth of metabolic information therein. However, this approach lacks the ability to measure and evaluate important metabolites such as coenzymes and antioxidants that are present at high concentrations in red blood cells. As an important alternative to serum/plasma metabolomics, we show here that a simple (1)H NMR experiment can simultaneously measure coenzymes and antioxidants in extracts of whole human blood, in addition to the nearly 70 metabolites that were shown to be quantitated in serum/plasma recently [ Anal. Chem. 2015 , 87 , 706 - 715 ]. Coenzymes of redox reactions: oxidized/reduced nicotinamide adenine dinucleotide (NAD(+) and NADH) and nicotinamide adenine dinucleotide phosphate (NADP(+) and NADPH); coenzymes of energy including adenosine triphosphate (ATP), adenosine diphosphate (ADP), and adenosine monophosphate (AMP); and antioxidants, the sum of oxidized and reduced glutathione (GSSG and GSH) can be measured with essentially no additional effort. A new method was developed for detecting many of these unstable species without affecting other blood/blood plasma metabolites. The identities of coenzymes and antioxidants in blood NMR spectra were established combining 1D/2D NMR techniques, chemical shift databases, pH measurements and, finally, spiking with authentic compounds. This is the first study to report identification of major coenzymes and antioxidants and quantify them, simultaneously, with the large pool of other metabolites in human blood using NMR spectroscopy. Considering that the levels of coenzymes and antioxidants represent a sensitive measure of cellular functions in health and numerous diseases, the NMR method presented here potentially opens a new chapter in the metabolomics of blood.

  15. Method development and validation: quantitation of telmisartan bulk drug and its tablet formulation by (1) H NMR spectroscopy.

    PubMed

    Jadeja, Yashwantsinh; Chomal, Bhagyawanti; Patel, Madhavi; Jebaliya, Hetal; Khunt, Ranjan; Shah, Anamik

    2016-12-14

    The quantitative NMR (qNMR) spectroscopy is nowadays a new tool for the determination of pharmaceutical potent biologically active molecules in bulk drug and its tablet formulation than the other analytical techniques. Herein, qNMR method was developed for an anti-hypertensive drug, telmisartan in bulk drug and its tablet formulation. The precise method was developed by using malononitrile as an internal standard. The methylene signal of telmisartan appeared at δ = 5.46 ppm (singlet) relative to the signal of malononitrile at δ = 3.59 ppm (singlet) in CDCl3 , as an NMR solvent. The development and validation of the method were carried out as per International Conference on Harmonization guidelines. The method was found to be linear (r(2)  = 0.9999) for 0.5 to 3.5 mg/ml in the drug concentration range. The relative standard deviation for accuracy and precession was not more than 2.0%. The sensitivity of the method was carried out by limit of detection and a limit of quantification, at 0.05 and 0.2 mg/ml, respectively, concentration. The robustness of the method was studied by changing parameters as well as different solvent manufacturer company. The result shows that method was accurately developed for quantification of telmisartan in pharmaceutical dosage form. The developed method by (1) H NMR spectroscopy is comparatively easy and more precise with respect to the other analytical tools. Copyright © 2016 John Wiley & Sons, Ltd.

  16. Synthesis, NMR characterisation and X-ray structures of mixed chalcogenido PNP ligands containing tellurium: crystal structures of SeiPr2PNP(H)iPr2 and [NaN(EPiPr2)2]infinity (E = Se, Te).

    PubMed

    Robertson, Stuart D; Chivers, Tristram

    2008-04-07

    Reaction of HN(PiPr2)2 with one equivalent of selenium in hexane at room temperature yields the monoselenide as the P-H tautomer Se=PiPr2-N=P(H)iPr2 (2b). Deprotonation of 2b with n butyllithium in the presence of TMEDA at -78 degrees C followed by addition of tellurium produces the air-sensitive, mixed chalcogenido complex [(TMEDA)Li(SePiPr2)(TePiPr2)N] (8Li) in >97% purity after recrystallisation. Similarly, deprotonation of Te=PiPr2-N=P(H)iPr2 (2c), followed by addition of sulfur, gives the sulfur analogue [(TMEDA)Li(SPiPr2)(TePiPr2)N] (7Li) in >99% purity. The symmetrical complexes [(TMEDA)Li(SePiPr2)2N] (4Li) and [(TMEDA)Li(TePiPr2)2N] (5Li) are produced by similar methods. Compounds 2b, 4Li, 5Li, 7Li and 8Li were characterised in solution by multinuclear (1H, 31P, 77Se and 125Te) NMR spectroscopy and their solid-state structures were determined by X-ray crystallography. The X-ray crystal structures of the polymeric chains [NaN(EPiPr2)2]infinity (4Na, E = Se and 5Na, E = Te) are also reported.

  17. 1H-2H cross-polarization NMR in fast spinning solids by adiabatic sweeps

    NASA Astrophysics Data System (ADS)

    Wi, Sungsool; Schurko, Robert; Frydman, Lucio

    2017-03-01

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

  18. Localized 1H NMR spectroscopy in fifty cases of newly diagnosed intracranial tumors

    SciTech Connect

    Demaerel, P.; Johannik, K.; Van Hecke, P.; Van Ongeval, C.; Verellen, S.; Marchal, G.; Wilms, G.; Plets, C.; Goffin, J.; Van Calenbergh, F. )

    1991-01-01

    Fifty patients with newly diagnosed, untreated intracranial tumors were examined with 1H nuclear magnetic resonance single-volume spectroscopy (MRS) using a 1.5 T whole-body MR system. Prior to the MRS, contrast enhanced MR and/or CT imaging studies were carried out. Histological verification was obtained in all patients except one. All tumor spectra revealed distinct abnormalities as compared with the normal brain spectra. Although most meningiomas showed a rather characteristic spectral pattern, generally features specific for the various tumor types were not observed. For instance, though a strong lactic acid signal was seen in most malignant tumors, this signal was also evident in five benign neoplasms.

  19. A combined approach for characterisation of fresh and brined vine leaves by X-ray powder diffraction, NMR spectroscopy and direct infusion high resolution mass spectrometry.

    PubMed

    Rizzuti, Antonino; Caliandro, Rocco; Gallo, Vito; Mastrorilli, Piero; Chita, Giuseppe; Latronico, Mario

    2013-12-01

    X-ray powder diffraction was combined, for the first time, with Nuclear Magnetic Resonance spectroscopy and direct infusion mass spectrometry to characterise fresh and brined grape leaves. Covariance analysis of data generated by the three techniques was performed with the aim to correlate information deriving from the solid part with those obtained for soluble metabolites. The results obtained indicate that crystalline components can be correlated to the metabolites contained in the grape leaves, paving the way to the use of X-ray diffraction analysis for food fingerprinting purposes. Moreover it was ascertained that, differently from most of the metabolites present in the fresh vine leaves, linolenic acid (an omega-3-fatty acid) and quercetin-3-O-glucuronide (a polyphenol metabolite) do not undergo sensible degradation during the brining process, which is used as preservative method for the grape leaves.

  20. 1H and 19 F NMR Study of Cation and Anion Motions in Guanidinium Hexafluorozirconate

    NASA Astrophysics Data System (ADS)

    Grottel, M.; Kozak, A.; Pająk, Z.

    1996-09-01

    Proton and fluorine NMR second moments and spin-lattice relaxation times of polycrystalline guanidinium hexafluorozirconate and its deuterated analogue were studied in laboratory (60 MHz) and rotating (H1 = 20 G) frames over a wide range of temperature. An analysis of the experimental results enabled us to reveal a dynamical inequivalence of two crystallographically independent cations and an unexpected high mobility of nonspherical anion dimers. A comparison of the ions dynamics in 2:1 complex studied with the guanidinium 1:1 and 3:1 complexes has shown a significant contribution of the hydrogen bonds to the potential barriers hindering the anion reorientations. At low temperatures a proton motion in the hydrogen bond and at 400 K a solid-solid phase transition have been discerned.

  1. (1)H NMR metabolomics to study the effects of diazepam on anisatin induced convulsive seizures.

    PubMed

    Li, Pei; Wei, Dan-Dan; Wang, Jun-Song; Yang, Ming-Hua; Kong, Ling-Yi

    2016-01-05

    The anticonvulsive properties of diazepam have been extensively studied, mainly focusing on the γ-amino butyrate (GABA) system. The aim of this investigation was to integrally analyze the metabolic events related to neuroprotection of diazepam on anisatin-induced convulsive seizures by a NMR-based metabolomic approach combined with histopathological examination and behavior examination. Multivariate analysis on metabolic profiles of the piriform cortex and cerebellum of mice revealed that diazepam could relieve mice suffering from the convulsive seizures by recovering destructed neurotransmitter and neuromodulator metabolism, ameliorating oxidative stress, alleviating the disturbance in energy, amino acid and nucleic acid metabolism in anisatin intoxicated mice. This integrated metabolomics study provided a powerful and highly effective approach to elucidate therapeutic effects and assessed the safety of diazepam. This study should be helpful for our understanding of convulsive seizures, and provide a holistic view of the treatment effects of benzodiazepine on convulsive seizures.

  2. High-Resolution Microcoil ^1H-NMR for Mass-Limited, Nanoliter-Volume Samples

    NASA Astrophysics Data System (ADS)

    Olson, Dean L.; Peck, Timothy L.; Webb, Andrew G.; Magin, Richard L.; Sweedler, Jonathan V.

    1995-12-01

    High-resolution, proton nuclear magnetic resonance (NMR) spectra of 5-nanoliter samples have been obtained with much higher mass sensitivity [signal-to-noise ratio (S/N) per micromole] than with traditional methods. Arginine and sucrose show a mean sensitivity enhancement of 130 compared to 278-microliter samples run in a 5-millimeter tube in a conventional, commercial probe. This can reduce data acquisition time by a factor of >16,000 or reduce the needed sample mass by a factor of about 130. A linewidth of 0.6 hertz was achieved on a 300-megahertz spectrometer by matching the magnetic susceptibility of the medium that surrounds the detection cell to that of the copper coil. For sucrose, the limit of detection (defined at S/N = 3) was 19 nanograms (56 picomoles) for a 1-minute data acquisition. This technique should prove useful with mass-limited samples and for use as a detector in capillary separations.

  3. Molecular degradation of ancient documents revealed by 1H HR-MAS NMR spectroscopy

    PubMed Central

    Corsaro, Carmelo; Mallamace, Domenico; Łojewska, Joanna; Mallamace, Francesco; Pietronero, Luciano; Missori, Mauro

    2013-01-01

    For centuries mankind has stored its knowledge on paper, a remarkable biomaterial made of natural cellulose fibers. However, spontaneous cellulose degradation phenomena weaken and discolorate paper over time. The detailed knowledge of products arising from cellulose degradation is essential in understanding deterioration pathways and in improving durability of cultural heritage. In this study, for the first time, products of cellulose degradation were individually detected in solid paper samples by means of an extremely powerful proton HR-MAS NMR set-up, in combination to a wise use of both ancient and, as reference, artificially aged paper samples. Carboxylic acids, in addition to more complex dicarboxylic and hydroxy-carboxylic acids, were found in all samples studied. Since these products can catalyze further degradation, their knowledge is fundamental to improve conservation strategies of historical documents. Furthermore, the identification of compounds used in ancient production techniques, also suggests for artifacts dating, authentication and provenance. PMID:24104201

  4. X-Ray

    MedlinePlus

    ... of gray. For some types of X-ray tests, a contrast medium — such as iodine or barium — is introduced into your body to provide greater detail on the images. X-ray technology is used to examine many parts of the ...

  5. Chest X-Ray

    MedlinePlus Videos and Cool Tools

    ... Site Index A-Z Spotlight Recently posted: Anal Cancer Facet Joint Block Video: Lung Cancer Screening Video: Upper GI Tract X-ray Video: ... of lung conditions such as pneumonia, emphysema and cancer. A chest x-ray requires no special preparation. ...

  6. X-ray Spectrometry.

    ERIC Educational Resources Information Center

    Markowicz, Andrzej A.; Van Grieken, Rene E.

    1984-01-01

    Provided is a selective literature survey of X-ray spectrometry from late 1981 to late 1983. Literature examined focuses on: excitation (photon and electron excitation and particle-induced X-ray emission; detection (wavelength-dispersive and energy-dispersive spectrometry); instrumentation and techniques; and on such quantitative analytical…

  7. X-ray beamsplitter

    DOEpatents

    Ceglio, Natale M.; Stearns, Daniel S.; Hawryluk, Andrew M.; Barbee, Jr., Troy W.

    1989-01-01

    An x-ray beamsplitter which splits an x-ray beam into two coherent parts by reflecting and transmitting some fraction of an incident beam has applications for x-ray interferometry, x-ray holography, x-ray beam manipulation, and x-ray laser cavity output couplers. The beamsplitter is formed of a wavelength selective multilayer thin film supported by a very thin x-ray transparent membrane. The beamsplitter resonantly transmits and reflects x-rays through thin film interference effects. A thin film is formed of 5-50 pairs of alternate Mo/Si layers with a period of 20-250 A. The support membrane is 10-200 nm of silicon nitride or boron nitride. The multilayer/support membrane structure is formed across a window in a substrate by first forming the structure on a solid substrate and then forming a window in the substrate to leave a free-standing structure over the window.

  8. Dental x-rays

    MedlinePlus

    ... X-rays are a form of high energy electromagnetic radiation. The x-rays penetrate the body to form ... for detecting cavities, unless the decay is very advanced and deep. Many ... The amount of radiation given off during the procedure is less than ...

  9. X-ray beamsplitter

    DOEpatents

    Ceglio, N.M.; Stearns, D.G.; Hawryluk, A.M.; Barbee, T.W. Jr.

    1987-08-07

    An x-ray beamsplitter which splits an x-ray beam into two coherent parts by reflecting and transmitting some fraction of an incident beam has applications for x-ray interferometry, x-ray holography, x-ray beam manipulation, and x-ray laser cavity output couplers. The beamsplitter is formed of a wavelength selective multilayer thin film supported by a very thin x-ray transparent membrane. The beamsplitter resonantly transmits and reflects x-rays through thin film interference effects. A thin film is formed of 5--50 pairs of alternate Mo/Si layers with a period of 20--250 A. The support membrane is 10--200 nm of silicon nitride or boron nitride. The multilayer/support membrane structure is formed across a window in a substrate by first forming the structure on a solid substrate and then forming a window in the substrate to leave a free-standing structure over the window. 6 figs.

  10. Urea's effect on the ribonuclease A catalytic efficiency: a kinetic, 1H NMR and molecular orbital study.

    PubMed

    Almarza, Jorge; Rincón, Luis; Bahsas, Alí; Pinto, María Angela; Brito, Francisco

    2013-02-01

    Understanding of protein-urea interactions is one of the greatest challenges to modern structural protein chemistry. Based in enzyme kinetics experiments and (1)H NMR spectroscopic analysis we proposed that urea, at low concentrations, directly interacts with the protonated histidines of the active center of RNase A, following a simple model of competitive inhibition. These results were supported by theoretical analysis based on the frontier molecular orbital theory and suggest that urea might establish a favorable interaction with the cationic amino acids. Our experimental evidence and theoretical analysis indicate that the initials steps of the molecular mechanism of Urea-RNase A interaction passes through the establishment of a three center four electron adduct. Also, our results would explain the observed disruption of the (1)H NMR signals corresponding to H12 and H119 (involved in catalysis) of the RNase A studied in the presence of urea. Our interaction model of urea-amino acids (cationic) can be extended to explain the inactivation of other enzymes with cationic amino acids at the active site.

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

    SciTech Connect

    Ross, J.B.A.; Schwartz, G.P.; Laws, W.R. ); Wyssbrod, H.R.; Porter, R.A. ); Michaels, C.A. )

    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.

  12. Analysis of the electronic, IR, and 1H NMR spectra of conjugated oligomers based on 4,4'-triphenylamine vinylene

    NASA Astrophysics Data System (ADS)

    Baryshnikov, G. V.; Minaeva, V. A.; Minaev, B. F.; Sun, V.-H.; Grigoras, M.

    2016-09-01

    Two types of conjugated oligomers based on 4,4'-triphenylamine vinylene have been synthesized and characterized by the methods of IR, UV-visible, and 1H NMR spectroscopy. The corresponding spectra have also been simulated theoretically at the density functional theory level with application of the B3LYP and BMK hybrid exchange-correlation functionals. A comparative analysis of the experimental and theoretical spectra of polymers and oligomers has revealed regularities of the manifestation of spectral signals depending on the conjugation chain length and the presence of a substituent in the triphenylamine core. It has been established, in particular, that the absolute intensity of IR bands satisfies a linear dependence with increase in the degree of polymerization; however, no frequency shift is observed at the same time. The position of the main peak in electron absorption spectra demonstrates the bathochromic shift with an increase in the oligomeric chain length due to the narrowing of the energy gap between the boundary molecular orbitals. Based on the theoretical estimation of the hydrogen atoms chemical shifts, the signals of various protons types in the strongly broadened experimental 1H NMR spectra of the bis-(4-iodine phenyl)-phenylamine and N,N-bis-(4-iodine phenyl)-4'-(phenylethynyl)-phenylamine polymerization products have also been identified.

  13. (1)H NMR-based metabolomics of Daphnia magna responses after sub-lethal exposure to triclosan, carbamazepine and ibuprofen.

    PubMed

    Kovacevic, Vera; Simpson, André J; Simpson, Myrna J

    2016-09-01

    Pharmaceuticals and personal care products are a class of emerging contaminants that are present in wastewater effluents, surface water, and groundwater around the world. There is a need to determine rapid and reliable bioindicators of exposure and the toxic mode of action of these contaminants to aquatic organisms. (1)H nuclear magnetic resonance (NMR)-based metabolomics in combination with multivariate statistical analysis was used to determine the metabolic profile of Daphnia magna after exposure to a range of sub-lethal concentrations of triclosan (6.25-100μg/L), carbamazepine (1.75-14mg/L) and ibuprofen (1.75-14mg/L) for 48h. Sub-lethal triclosan exposure suggested a general oxidative stress condition and the branched-chain amino acids, glutamine, glutamate, and methionine emerged as potential bioindicators. The aromatic amino acids, serine, glycine and alanine are potential bioindicators for sub-lethal carbamazepine exposure that may have altered energy metabolism. The potential bioindicators for sub-lethal ibuprofen exposure are serine, methionine, lysine, arginine and leucine, which showed a concentration-dependent response. The differences in the metabolic changes were related to the dissimilar modes of toxicity of triclosan, carbamazepine and ibuprofen. (1)H NMR-based metabolomics gave an improved understanding of how these emerging contaminants impact the keystone species D. magna.

  14. (1)H NMR at Larmor frequencies down to 3Hz by means of Field-Cycling techniques.

    PubMed

    Kresse, B; Becher, M; Privalov, A F; Hofmann, M; Rössler, E A; Vogel, M; Fujara, F

    2017-04-01

    Field-Cycling (FC) NMR experiments were carried out at (1)H Larmor frequencies down to about 3Hz. This could be achieved by fast switching a high polarizing magnetic field down to a low evolution field which is tilted with respect to the polarization field. Then, the low frequency Larmor precession of the nuclear spin magnetization about this evolution field is registered by means of FIDs in a high detection field. The crucial technical point of the experiment is the stabilization of the evolution field, which is achieved by compensating for temporal magnetic field fluctuations of all three spatial components. The paper reports on some other basic low field experiments such as the simultaneous measurement of the Larmor frequency and the spin-lattice relaxation time in such small fields as well as the irradiation of oscillating transversal magnetic field pulses at very low frequencies as a novel method for field calibration in low field FC NMR. The potential of low field FC is exemplified by the (1)H relaxation dispersion of water at frequencies below about 2kHz stemming from the slow proton exchange process.

  15. Adsorption mechanism at the molecular level between polymers and uremic octapeptide by the 2D 1H NMR Technique.

    PubMed

    Li, Guohua; Li, Jihong; Wang, Wei; Yang, Mei; Zhang, Yuanwei; Sun, Pingchuan; Yuan, Zhi; He, Binglin; Yu, Yaoting

    2006-06-01

    To remove uremic octapeptide from the blood stream of uremic patients, various modified polyacylamide cross-linked absorbents were prepared. Adsorption experiments showed these absorbents have significant differences in adsorption capacity to the target peptide. In this paper, two-dimension proton nuclear magnetic resonance (2D 1H NMR) spectroscopy was used to investigate the interaction mechanism between the peptide and the adsorbents. Because of the insolubility of the absorbent, some soluble linear polymers with the same functional groups as the absorbents were employed as the model adsorbents in 2D 1H NMR. The preferred binding site for the peptide and polymers was identified to be at the C-terminal carboxyl group of the octapeptide via chemical shift perturbation effects. In this study, we found that hydrogen bonding, electrostatic, and hydrophobic interactions all play a role in the interaction force but had different contributions. Especially, the great chemical shift changes of the aromatic amino acid residues (Trp) during the interaction between butyl-modified polyacrylamide and octapeptide suggested the hydrophobic interaction, incorporated with the electrostatic force, played an important role in the binding reaction in aqueous solutions. This information not only rationally explained the results of the adsorption experiments, but also identified the effective binding site and mechanism, and shall provide a structural basis for designing better affinity-type adsorbents for the target peptide.

  16. Regression formulas for density functional theory calculated 1H and 13C NMR chemical shifts in toluene-d8.

    PubMed

    Konstantinov, Ivan A; Broadbelt, Linda J

    2011-11-10

    This study aimed at investigating the performance of a series of basis sets, density functional theory (DFT) functionals, and the IEF-PCM solvation model in the accurate calculation of (1)H and (13)C NMR chemical shifts in toluene-d(8). We demonstrated that, on a test set of 37 organic species with various functional moieties, linear scaling significantly improved the calculated shifts and was necessary to obtain more accurate results. Inclusion of a solvation model produced larger deviations from the experimental data as compared to the gas-phase calculations. Moreover, we did not find any evidence that very large basis sets were necessary to reproduce the experimental NMR data. Ultimately, we recommend the use of the BMK functional. For the (1)H shifts the use of the 6-311G(d) basis set gave linearly scaled mean unsigned (MU) and root-mean-square (rms) errors of 0.15 ppm and 0.21 ppm, respectively. For the calculation of the (13)C chemical shifts the 6-31G(d) basis set produced MUE of 1.82 ppm and RMSE of 3.29 ppm.

  17. LC-MS- and (1)H NMR Spectroscopy-Guided Identification of Antifungal Diterpenoids from Sagittaria latifolia.

    PubMed

    Ravu, Ranga Rao; Jacob, Melissa R; Jeffries, Cynthia; Tu, Ying; Khan, Shabana I; Agarwal, Ameeta K; Guy, R Kiplin; Walker, Larry A; Clark, Alice M; Li, Xing-Cong

    2015-09-25

    Antifungal screening of small-molecule natural product libraries showed that a column fraction (CF) derived from the plant extract of Sagittaria latifolia was active against the fungal pathogen Cryptococcus neoformans. Dereplication analysis by liquid chromatography-mass spectrometry (LC-MS) and proton nuclear magnetic resonance spectroscopy ((1)H NMR) indicated the presence of new compounds in this CF. Subsequent fractionation of the plant extract resulted in the identification of two new isopimaradiene-type diterpenoids, 1 and 2. The structures of 1 and 2 were determined by chemical methods and spectroscopic analysis as isopimara-7,15-dien-19-ol 19-O-α-l-arabinofuranoside and isopimara-7,15-dien-19-ol 19-O-α-l-(5'-acetoxy)arabinofuranoside, respectively. Compound 1 exhibited IC50 values of 3.7 and 1.8 μg/mL, respectively, against C. neoformans and C. gattii. Its aglycone, isopimara-7,15-dien-19-ol (3), resulting from acid hydrolysis of 1, was also active against the two fungal pathogens, with IC50 values of 9.2 and 6.8 μg/mL, respectively. This study demonstrates that utilization of the combined LC-MS and (1)H NMR analytical tools is an improved chemical screening approach for hit prioritization in natural product drug discovery.

  18. Development and Validation of Quantitative (1)H NMR Spectroscopy for the Determination of Total Phytosterols in the Marine Seaweed Sargassum.

    PubMed

    Zhang, Xiu-Li; Wang, Cong; Chen, Zhen; Zhang, Pei-Yu; Liu, Hong-Bing

    2016-08-10

    Knowledge of phytosterol (PS) contents in marine algae is currently lacking compared to those in terrestrial plants. The present studies developed a quantitative (1)H NMR method for the determination of the total PSs in Sargassum. The characteristic proton signal H-3α in PSs was used for quantification, and 2,3,4,5-tetrachloro-nitrobenzene was used as an internal standard. Seaweed samples could be recorded directly after total lipid extraction and saponification. The results showed that the PS contents in Sargassum fusiforme (788.89-2878.67 mg/kg) were significantly higher than those in Sargassum pallidum (585.33-1596.00 mg/kg). The variable contents in both species suggested that fixed raw materials are very important for future research and development. Orthogonal projection to latent structures discriminant analysis was carried out in the spectral region of δ 3.00-6.50 in the (1)H NMR spectrum. S. fusiforme and S. pallidum could be separated well, and the key sterol marker was fucosterol.

  19. Effect of 1,10-phenanthroline aromaticity in carboxylic acids:1H NMR spectroscopy, GIAO calculations and thermodynamic properties

    NASA Astrophysics Data System (ADS)

    Machado, Camila M. B.; Santos, Vanessa F. C.; Belarmino, Marcia K. D. L.; França, José A. A.; Moura, Gustavo L. C.; Lima, Nathalia B. D.

    2016-08-01

    Hydrogen bonding represents a class of chemical interactions, which are directly responsible for several physical properties, such as: energetic stabilities, boiling points, vibrational modes, bond lengths, etc. In this article, we examine from the point of view of 1H NMR spectroscopy and GIAO calculations, the effects associated with the process of formation of the hydrogen bonds as they appear in the chemical shifts of the acidic hydrogens in the complexes between nitrogenated compounds, PHEN, BIPY and DIBIPY, and carboxylic acids, HOOCH, HOOCCH3 and HOOCC6H5. All computational simulations were performed using the quantum chemical methods B3LYP/6-31++G(d,p) and ωB97X-D/def2-TZVP. The 1H NMR spectroscopy results showed that, in both cases, the hydrogen nucleus of the OH group is the most affected in the process of hydrogen bond formation. For the complexes involving PHEN we observed that the hydrogen nucleus is more strongly shielded when compared with this signal in the corresponding complexes involving BIPY and DIBIPY.

  20. The effect of standardized food intake on the association between BMI and 1H-NMR metabolites

    PubMed Central

    Schutte, Bianca A. M.; van den Akker, Erik B.; Deelen, Joris; van de Rest, Ondine; van Heemst, Diana; Feskens, Edith J. M.; Beekman, Marian; Slagboom, P. Eline

    2016-01-01

    Multiple studies have shown that levels of 1H-NMR metabolites are associated with disease and risk factors of disease such as BMI. While most previous investigations have been performed in fasting samples, meta-analysis often includes both cohorts with fasting and non-fasting blood samples. In the present study comprising 153 participants (mean age 63 years; mean BMI 27 kg/m2) we analyzed the effect of a standardized liquid meal (SLM) on metabolite levels and how the SLM influenced the association between metabolites and BMI. We observed that many metabolites, including glycolysis related metabolites, multiple amino acids, LDL diameter, VLDL and HDL lipid concentration changed within 35 minutes after a standardized liquid meal (SLM), similarly for all individuals. Remarkable, however, is that the correlations of metabolite levels with BMI remained highly similar before and after the SLM. Hence, as exemplified with the disease risk factor BMI, our results suggest that the applicability of 1H-NMR metabolites as disease biomarkers depends on the standardization of the fasting status rather than on the fasting status itself. Future studies are required to investigate the dependency of metabolite biomarkers for other disease risk factors on the fasting status. PMID:27966583

  1. 1H, 13C NMR and DFT Study of Hydrogen Bonding in Imidazolium-based Ionic Liquids.

    PubMed

    Balevičius, Vytautas; Gdaniec, Zofia; Džiaugys, Lukas; Kuliešius, Feliksas; Maršalka, Arūnas

    2011-09-01

    The ionic liquid 1-decyl-3-methyl-imidazolium bromide [C10mim][Br], the neat material, and also dissolved (~0.01 mole fraction) in various dielectric media (acetonitrile, benzene, chloroform, dichloromethane, methanol, 2-butanol and H2O) was studied using 1H and 13C NMR spectroscopy. The most important interaction in this compound is considered to be the Br-...H-C2+ hydrogen bond, which is formed between the anions and cations. The obtained results show that dielectric medium influence mostly the behavior of the Br-...H-C2+ bridge proton. The changes observed in 1H and 13C NMR spectra of [C10mim][Br] with increasing solvents polarity and temperature can be explained applying the model of the lengthening of the H2...Br- bond with the accompanying thickening of the solvation shell of bromine anion and C2-H bond contraction. The short-range order effects related to the configuration of neighboring dipoles of solvent molecules are more important for the solvation ability of small anions than the bulk solvent field effect. However, the solvents, molecules of which tend to associate via hydrogen bonding, can significantly affect the dynamics of anions.

  2. (1)H NMR and GC-MS based metabolomics reveal nano-Cu altered cucumber (Cucumis sativus) fruit nutritional supply.

    PubMed

    Zhao, Lijuan; Hu, Jerry; Huang, Yuxiong; Wang, Hongtao; Adeleye, Adeyemi; Ortiz, Cruz; Keller, Arturo A

    2017-01-01

    It is imperative to study the interaction of nanoparticles residuals with crop plants in agricultural soils, due to the increased application of nanotechnology in agriculture. So far, a few studies have focused on the impact of nanoparticles on fruit quality and nutritional supply. In this work, a thorough and comprehensive analysis of metabolite changes of cucumber fruits from plants under nano-Cu stress was possible through the use of both (1)H NMR and GC-MS. The results of supervised partial least-squares discriminant analysis from both platforms showed that cucumber fruit extracts samples were clearly grouped based on the nano-Cu level in soil. This indicates that the fruit metabolite profile was influenced by exposure to nano-Cu. GC-MS data showed concentrations of some sugars, organic acids, amino acids, and fatty acids were increased or decreased by nano-Cu. Several metabolites, such as methylnicotinamide (MNA), trigonelline, imidazole, quinolinate were only detected and quantified by (1)H NMR. Our results showed that combining the two platforms provided a comprehensive understanding about the metabolites (nutrient supply) changes in cucumber fruits impacted by exposure to nano-Cu.

  3. Metabolic fingerprinting of Leontopodium species (Asteraceae) by means of 1H NMR and HPLC–ESI-MS

    PubMed Central

    Safer, Stefan; Cicek, Serhat S.; Pieri, Valerio; Schwaiger, Stefan; Schneider, Peter; Wissemann, Volker; Stuppner, Hermann

    2011-01-01

    The genus Leontopodium, mainly distributed in Central and Eastern Asia, consists of ca. 34–58 different species. The European Leontopodium alpinum, commonly known as Edelweiss, has a long tradition in folk medicine. Recent research has resulted in the identification of prior unknown secondary metabolites, some of them with interesting biological activities. Despite this, nearly nothing is known about the Asian species of the genus. In this study, we applied proton nuclear magnetic resonance (1H NMR) spectroscopy and liquid chromatography–mass spectrometry (LC–MS) metabolic fingerprinting to reveal insights into the metabolic patterns of 11 different Leontopodium species, and to conclude on their taxonomic relationship. Principal component analysis (PCA) of 1H NMR fingerprints revealed two species groups. Discriminators for these groups were identified as fatty acids and sucrose for group A, and ent-kaurenoic acid and derivatives thereof for group B. Five diterpenes together with one sesquiterpene were isolated from Leontopodium franchetii roots; the compounds were described for the first time for L. franchetii: ent-kaur-16-en-19-oic acid, methyl-15α-angeloyloxy-ent-kaur-16-en-19-oate, methyl-ent-kaur-16-en-19-oate, 8-acetoxymodhephene, 19-acetoxy-ent-kaur-16-ene, methyl-15β–angeloyloxy-16,17-epoxy-ent-kauran-19-oate. In addition, differences in the metabolic profile between collected and cultivated species could be observed using a partial least squares-discriminant analysis (PLS-DA). PCA of the LC–MS fingerprints revealed three groups. Discriminating signals were compared to literature data and identified as two bisabolane derivatives responsible for discrimination of group A and C, and one ent-kaurenoic acid derivative, discriminating group B. A taxonomic relationship between a previously unidentified species and L. franchetii and Leontopodium sinense could be determined by comparing NMR fingerprints. This finding supports recent molecular data

  4. Solubilization of flurbiprofen within non-ionic Tween 20 surfactant micelles: a 19F and 1H NMR study.

    PubMed

    Saveyn, Pieter; Cocquyt, Ellen; Zhu, Wuxin; Sinnaeve, Davy; Haustraete, Katrien; Martins, José C; Van der Meeren, Paul

    2009-07-14

    The solubilization of the poorly water soluble anti-inflammatory drug flurbiprofen in non-ionic Tween 20 surfactant micellar solutions was studied by both (19)F and (1)H NMR spectroscopy in an acidic environment. These non-destructive techniques allowed us to investigate the effect of temperature cycling in situ. Using (19)F NMR, an increased solubilisation capacity was observed as the temperature increased. This effect became more pronounced above the cloud point, which was reduced by more than 30 degrees C in the presence of an excess of flurbiprofen. Upon clouding, peak splitting was observed in the (19)F spectrum, which indicates that two pools of solubilised flurbiprofen exist that are in slow exchange on the NMR frequency timescale. The clouding and solubilization processes were found to be reversible, albeit with slow kinetics. Based on chemical shift differences of both Tween 20 and flurbiprofen, as well as NOESY experiments, the flurbiprofen was found to be accumulated within the palisade layer of the Tween 20 micelles.

  5. Predicting paramagnetic 1H NMR chemical shifts and state-energy separations in spin-crossover host-guest systems.

    PubMed

    Isley, William C; Zarra, Salvatore; Carlson, Rebecca K; Bilbeisi, Rana A; Ronson, Tanya K; Nitschke, Jonathan R; Gagliardi, Laura; Cramer, Christopher J

    2014-06-14

    The behaviour of metal-organic cages upon guest encapsulation can be difficult to elucidate in solution. Paramagnetic metal centres introduce additional dispersion of signals that is useful for characterisation of host-guest complexes in solution using nuclear magnetic resonance (NMR). However, paramagnetic centres also complicate spectral assignment due to line broadening, signal integration error, and large changes in chemical shifts, which can be difficult to assign even for known compounds. Quantum chemical predictions can provide information that greatly facilitates the assignment of NMR signals and identification of species present. Here we explore how the prediction of paramagnetic NMR spectra may be used to gain insight into the spin crossover (SCO) properties of iron(II)-based metal organic coordination cages, specifically examining how the structure of the local metal coordination environment affects SCO. To represent the tetrahedral metal-organic cage, a model system is generated by considering an isolated metal-ion vertex: fac-ML3(2+) (M = Fe(II), Co(II); L = N-phenyl-2-pyridinaldimine). The sensitivity of the (1)H paramagnetic chemical shifts to local coordination environments is assessed and utilised to shed light on spin crossover behaviour in iron complexes. Our data indicate that expansion of the metal coordination sphere must precede any thermal SCO. An attempt to correlate experimental enthalpies of SCO with static properties of bound guests shows that no simple relationship exists, and that effects are likely due to nuanced dynamic response to encapsulation.

  6. Metabolic Discrimination of Catharanthus roseus Leaves Infected by Phytoplasma Using 1H-NMR Spectroscopy and Multivariate Data Analysis1

    PubMed Central

    Choi, Young Hae; Tapias, Elisabet Casas; Kim, Hye Kyong; Lefeber, Alfons W.M.; Erkelens, Cornelis; Verhoeven, Jacobus Th.J.; Brzin, Jernej; Zel, Jana; Verpoorte, Robert

    2004-01-01

    A comprehensive metabolomic profiling of Catharanthus roseus L. G. Don infected by 10 types of phytoplasmas was carried out using one-dimensional and two-dimensional NMR spectroscopy followed by principal component analysis (PCA), an unsupervised clustering method requiring no knowledge of the data set and used to reduce the dimensionality of multivariate data while preserving most of the variance within it. With a combination of these techniques, we were able to identify those metabolites that were present in different levels in phytoplasma-infected C. roseus leaves than in healthy ones. The infection by phytoplasma in C. roseus leaves causes an increase of metabolites related to the biosynthetic pathways of phenylpropanoids or terpenoid indole alkaloids: chlorogenic acid, loganic acid, secologanin, and vindoline. Furthermore, higher abundance of Glc, Glu, polyphenols, succinic acid, and Suc were detected in the phytoplasma-infected leaves. The PCA of the 1H-NMR signals of healthy and phytoplasma-infected C. roseus leaves shows that these metabolites are major discriminating factors to characterize the phytoplasma-infected C. roseus leaves from healthy ones. Based on the NMR and PCA analysis, it might be suggested that the biosynthetic pathway of terpenoid indole alkaloids, together with that of phenylpropanoids, is stimulated by the infection of phytoplasma. PMID:15286294

  7. Metabolic Study of Breast MCF-7 Tumor Spheroids after Gamma Irradiation by 1H NMR Spectroscopy and Microimaging

    PubMed Central

    Palma, Alessandra; Grande, Sveva; Luciani, Anna Maria; Mlynárik, Vladimír; Guidoni, Laura; Viti, Vincenza; Rosi, Antonella

    2016-01-01

    Multicellular tumor spheroids are an important model system to investigate the response of tumor cells to radio- and chemotherapy. They share more properties with the original tumor than cells cultured as 2D monolayers do, which helps distinguish the intrinsic properties of monolayer cells from those induced during cell aggregation in 3D spheroids. The paper investigates some metabolic aspects of small tumor spheroids of breast cancer and their originating MCF-7 cells, grown as monolayer, by means of high–resolution (HR) 1H NMR spectroscopy and MR microimaging before and after gamma irradiation. The spectra of spheroids were characterized by higher intensity of mobile lipids, mostly neutral lipids, and glutamine (Gln) signals with respect to their monolayer cells counterpart, mainly owing to the lower oxygen supply in spheroids. Morphological changes of small spheroids after gamma-ray irradiation, such as loss of their regular shape, were observed by MR microimaging. Lipid signal intensity increased after irradiation, as evidenced in both MR localized spectra of the single spheroid and in HR NMR spectra of spheroid suspensions. Furthermore, the intense Gln signal from spectra of irradiated spheroids remained unchanged, while the low Gln signal observed in monolayer cells increased after irradiation. Similar results were observed in cells grown in hypoxic conditions. The different behavior of Gln in 2D monolayers and in 3D spheroids supports the hypothesis that a lower oxygen supply induces both an upregulation of Gln synthetase and a downregulation of glutaminases with the consequent increase in Gln content, as already observed under hypoxic conditions. The data herein indicate that 1H NMR spectroscopy can be a useful tool for monitoring cell response to different constraints. The use of spheroid suspensions seems to be a feasible alternative to localized spectroscopy since similar effects were found after radiation treatment. PMID:27200293

  8. 1H NMR Metabolic Fingerprinting to Probe Temporal Postharvest Changes on Qualitative Attributes and Phytochemical Profile of Sweet Cherry Fruit

    PubMed Central

    Goulas, Vlasios; Minas, Ioannis S.; Kourdoulas, Panayiotis M.; Lazaridou, Athina; Molassiotis, Athanassios N.; Gerothanassis, Ioannis P.; Manganaris, George A.

    2015-01-01

    Sweet cherry fruits (Prunus avium cvs. ‘Canada Giant’, ‘Ferrovia’) were harvested at commercial maturity stage and analyzed at harvest and after maintenance at room temperature (storage at ∼20°C, shelf life) for 1, 2, 4, 6, and 8 days, respectively. Fruit were initially analyzed for respiration rate, qualitative attributes and textural properties: ‘Canada Giant’ fruit were characterized by higher weight losses and stem browning index, being more intense over the late stages of shelf life period; meanwhile ‘Ferrovia’ possessed appreciably better performance even after extended shelf life period. A gradual decrease of respiration rate was monitored in both cultivars, culminated after 8 days at 20°C. The sweet cherry fruit nutraceutical profile was monitored using an array of instrumental techniques (spectrophotometric assays, HPLC, 1H-NMR). Fruit antioxidant capacity was enhanced with the progress of shelf life period, concomitant with the increased levels of total anthocyanin and of phenolic compounds. ‘Ferrovia’ fruit presented higher contents of neochlorogenic acid and p-coumaroylquinic acid throughout the shelf life period. We further developed an 1H-NMR method that allows the study of primary and secondary metabolites in a single running, without previous separation and isolation procedures. Diagnostic peaks were located in the aliphatic region for sugars and organic acids, in the aromatic region for phenolic compounds and at 8.2–8.6 ppm for anthocyanins. This NMR-based methodology provides a unifying tool for quantitative and qualitative characterization of metabolite changes of sweet cherry fruits; it is also expected to be further exploited for monitoring temporal changes in other fleshy fruits. PMID:26617616

  9. Prognosis Biomarkers of Severe Sepsis and Septic Shock by 1H NMR Urine Metabolomics in the Intensive Care Unit.

    PubMed

    Garcia-Simon, Monica; Morales, Jose M; Modesto-Alapont, Vicente; Gonzalez-Marrachelli, Vannina; Vento-Rehues, Rosa; Jorda-Miñana, Angela; Blanquer-Olivas, Jose; Monleon, Daniel

    2015-01-01

    Early diagnosis and patient stratification may improve sepsis outcome by a timely start of the proper specific treatment. We aimed to identify metabolomic biomarkers of sepsis in urine by (1)H-NMR spectroscopy to assess the severity and to predict outcomes. Urine samples were collected from 64 patients with severe sepsis or septic shock in the ICU for a (1)H NMR spectra acquisition. A supervised analysis was performed on the processed spectra, and a predictive model for prognosis (30-days mortality/survival) of sepsis was constructed using partial least-squares discriminant analysis (PLS-DA). In addition, we compared the prediction power of metabolomics data respect the Sequential Organ Failure Assessment (SOFA) score. Supervised multivariate analysis afforded a good predictive model to distinguish the patient groups and detect specific metabolic patterns. Negative prognosis patients presented higher values of ethanol, glucose and hippurate, and on the contrary, lower levels of methionine, glutamine, arginine and phenylalanine. These metabolites could be part of a composite biopattern of the human metabolic response to sepsis shock and its mortality in ICU patients. The internal cross-validation showed robustness of the metabolic predictive model obtained and a better predictive ability in comparison with SOFA values. Our results indicate that NMR metabolic profiling might be helpful for determining the metabolomic phenotype of worst-prognosis septic patients in an early stage. A predictive model for the evolution of septic patients using these metabolites was able to classify cases with more sensitivity and specificity than the well-established organ dysfunction score SOFA.

  10. Prognosis Biomarkers of Severe Sepsis and Septic Shock by 1H NMR Urine Metabolomics in the Intensive Care Unit

    PubMed Central

    Modesto-Alapont, Vicente; Gonzalez-Marrachelli, Vannina; Vento-Rehues, Rosa; Jorda-Miñana, Angela; Blanquer-Olivas, Jose; Monleon, Daniel

    2015-01-01

    Early diagnosis and patient stratification may improve sepsis outcome by a timely start of the proper specific treatment. We aimed to identify metabolomic biomarkers of sepsis in urine by 1H-NMR spectroscopy to assess the severity and to predict outcomes. Urine samples were collected from 64 patients with severe sepsis or septic shock in the ICU for a 1H NMR spectra acquisition. A supervised analysis was performed on the processed spectra, and a predictive model for prognosis (30-days mortality/survival) of sepsis was constructed using partial least-squares discriminant analysis (PLS-DA). In addition, we compared the prediction power of metabolomics data respect the Sequential Organ Failure Assessment (SOFA) score. Supervised multivariate analysis afforded a good predictive model to distinguish the patient groups and detect specific metabolic patterns. Negative prognosis patients presented higher values of ethanol, glucose and hippurate, and on the contrary, lower levels of methionine, glutamine, arginine and phenylalanine. These metabolites could be part of a composite biopattern of the human metabolic response to sepsis shock and its mortality in ICU patients. The internal cross-validation showed robustness of the metabolic predictive model obtained and a better predictive ability in comparison with SOFA values. Our results indicate that NMR metabolic profiling might be helpful for determining the metabolomic phenotype of worst-prognosis septic patients in an early stage. A predictive model for the evolution of septic patients using these metabolites was able to classify cases with more sensitivity and specificity than the well-established organ dysfunction score SOFA. PMID:26565633

  11. Metabolic profiling studies on the toxicological effects of realgar in rats by {sup 1}H NMR spectroscopy

    SciTech Connect

    Wei Lai; Liao Peiqiu; Wu Huifeng; Li Xiaojing Pei Fengkui Li Weisheng; Wu Yijie

    2009-02-01

    The toxicological effects of realgar after intragastrical administration (1 g/kg body weight) were investigated over a 21 day period in male Wistar rats using metabonomic analysis of {sup 1}H NMR spectra of urine, serum and liver tissue aqueous extracts. Liver and kidney histopathology examination and serum clinical chemistry analyses were also performed. {sup 1}H NMR spectra and pattern recognition analyses from realgar treated animals showed increased excretion of urinary Kreb's cycle intermediates, increased levels of ketone bodies in urine and serum, and decreased levels of hepatic glucose and glycogen, as well as hypoglycemia and hyperlipoidemia, suggesting the perturbation of energy metabolism. Elevated levels of choline containing metabolites and betaine in serum and liver tissue aqueous extracts and increased serum creatine indicated altered transmethylation. Decreased urinary levels of trimethylamine-N-oxide, phenylacetylglycine and hippurate suggested the effects on the gut microflora environment by realgar. Signs of impairment of amino acid metabolism were supported by increased hepatic glutamate levels, increased methionine and decreased alanine levels in serum, and hypertaurinuria. The observed increase in glutathione in liver tissue aqueous extracts could be a biomarker of realgar induced oxidative injury. Serum clinical chemistry analyses showed increased levels of lactate dehydrogenase, aspartate aminotransferase, and alkaline phosphatase as well as increased levels of blood urea nitrogen and creatinine, indicating slight liver and kidney injury. The time-dependent biochemical variations induced by realgar were achieved using pattern recognition methods. This work illustrated the high reliability of NMR-based metabonomic approach on the study of the biochemical effects induced by traditional Chinese medicine.

  12. 1H NMR-based serum metabolomics reveals erythromycin-induced liver toxicity in albino Wistar rats

    PubMed Central

    Rawat, Atul; Dubey, Durgesh; Guleria, Anupam; Kumar, Umesh; Keshari, Amit K.; Chaturvedi, Swati; Prakash, Anand; Saha, Sudipta; Kumar, Dinesh

    2016-01-01

    Introduction: Erythromycin (ERY) is known to induce hepatic toxicity which mimics other liver diseases. Thus, ERY is often used to produce experimental models of drug-induced liver-toxicity. The serum metabolic profiles can be used to evaluate the liver-toxicity and to further improve the understanding of underlying mechanism. Objective: To establish the serum metabolic patterns of Erythromycin induced hepatotoxicity in albino wistar rats using 1H NMR based serum metabolomics. Experimental: Fourteen male rats were randomly divided into two groups (n = 7 in each group): control and ERY treated. After 28 days of intervention, the metabolic profiles of sera obtained from ERY and control groups were analyzed using high-resolution 1D 1H CPMG and diffusion-edited nuclear magnetic resonance (NMR) spectra. The histopathological and SEM examinations were employed to evaluate the liver toxicity in ERY treated group. Results: The serum metabolic profiles of control and ERY treated rats were compared using multivariate statistical analysis and the metabolic patterns specific to ERY-induced liver toxicity were established. The toxic response of ERY was characterized with: (a) increased serum levels of Glucose, glutamine, dimethylamine, malonate, choline, phosphocholine and phospholipids and (b) decreased levels of isoleucine, leucine, valine, alanine, glutamate, citrate, glycerol, lactate, threonine, circulating lipoproteins, N-acetyl glycoproteins, and poly-unsaturated lipids. These metabolic alterations were found to be associated with (a) decreased TCA cycle activity and enhanced fatty acid oxidation, (b) dysfunction of lipid and amino acid metabolism and (c) oxidative stress. Conclusion and Recommendations: Erythromycin is often used to produce experimental models of liver toxicity; therefore, the established NMR-based metabolic patterns will form the basis for future studies aiming to evaluate the efficacy of anti-hepatotoxic agents or the hepatotoxicity of new drug

  13. X-ray generator

    DOEpatents

    Dawson, John M.

    1976-01-01

    Apparatus and method for producing coherent secondary x-rays that are controlled as to direction by illuminating a mixture of high z and low z gases with an intense burst of primary x-rays. The primary x-rays are produced with a laser activated plasma, and these x-rays strip off the electrons of the high z atoms in the lasing medium, while the low z atoms retain their electrons. The neutral atoms transfer electrons to highly excited states of the highly striped high z ions giving an inverted population which produces the desired coherent x-rays. In one embodiment, a laser, light beam provides a laser spark that produces the intense burst of coherent x-rays that illuminates the mixture of high z and low z gases, whereby the high z atoms are stripped while the low z ones are not, giving the desired mixture of highly ionized and neutral atoms. To this end, the laser spark is produced by injecting a laser light beam, or a plurality of beams, into a first gas in a cylindrical container having an adjacent second gas layer co-axial therewith, the laser producing a plasma and the intense primary x-rays in the first gas, and the second gas containing the high and low atomic number elements for receiving the primary x-rays, whereupon the secondary x-rays are produced therein by stripping desired ions in a neutral gas and transfer of electrons to highly excited states of the stripped ions from the unionized atoms. Means for magnetically confining and stabilizing the plasma are disclosed for controlling the direction of the x-rays.

  14. Metabolomics study of Saw palmetto extracts based on 1H NMR spectroscopy.

    PubMed

    de Combarieu, Eric; Martinelli, Ernesto Marco; Pace, Roberto; Sardone, Nicola

    2015-04-01

    Preparations containing Saw palmetto extracts are used in traditional medicine to treat benign prostatic hyperplasia. According to the European and the American Pharmacopoeias, the extract is obtained from comminuted Saw palmetto berries by a suitable extracting procedure using ethanol or supercritical carbon dioxide or a mixture of n-hexane and methylpentanes. In the present study an approach to metabolomics profiling using nuclear magnetic resonance (NMR) has been used as a finger-printing tool to assess the overall composition of the extracts. The phytochemical analysis coupled with principal component analysis (PCA) showed the same composition of the Saw palmetto extracts obtained with carbon dioxide and hexane with minor not significant differences for extracts obtained with ethanol. In fact these differences are anyhow lower than the batch-to-batch variability ascribable to the natural-occurring variability in the Saw palmetto fruits' phytochemical composition. The fingerprinting analysis combined with chemometric method, is a technique, which would provide a tool to comprehensively assess the quality control of Saw palmetto extracts.

  15. Harvest year effects on Apulian EVOOs evaluated by 1H NMR based metabolomics

    PubMed Central

    De Pascali, Sandra A.

    2016-01-01

    Nine hundred extra virgin olive oils (EVOO) were extracted from individual olive trees of four olive cultivars (Coratina, Cima di Mola, Ogliarola, Peranzana), originating from the provinces of Bari and Foggia (Apulia region, Southern Italy) and collected during two consecutive harvesting seasons (2013/14 and 2014/15). Following genetic identification of individual olive trees, a detailed Apulian EVOO NMR database was built using 900 oils samples obtained from 900 cultivar certified single trees. A study on the olive oil lipid profile was carried out by statistical multivariate analysis (Principal Component Analysis, PCA, Partial Least-Squares Discriminant Analysis, PLS-DA, Orthogonal Partial Least-Squares Discriminant Analysis, OPLS-DA). Influence of cultivar and weather conditions, such as the summer rainfall, on the oil metabolic profile have been evaluated. Mahalanobis distances and J2 criterion have been measured to assess the quality of resulting scores clusters for each cultivar in the two harvesting campaigns. The four studied cultivars showed non homogeneous behavior. Notwithstanding the geographical spread and the wide number of samples, Coratina showed a consistent behavior of its metabolic profile in the two considered harvests. Among the other three Peranzana showed the second more consistent behavior, while Cima di Mola and Ogliarola having the biggest change over the two years. PMID:27994965

  16. 1H NMR Metabolomics Study of Metastatic Melanoma in C57BL/6J Mouse Spleen

    PubMed Central

    Wang, Xuan; Hu, Mary; Feng, Ju; Liu, Maili; Hu, Jian Zhi

    2014-01-01

    Melanoma is a malignant tumor of melanocytes. Although extensive investigations have been done to study metabolic changes in primary melanoma in vivo and in vitro, little effort has been devoted to metabolic profiling of metastatic tumors in organs other than lymph nodes. In this work, NMR-based metabolomics combined with multivariate data analysis is used to study metastatic B16-F10 melanoma in C57BL/6J mouse spleen. Principal Component Analysis (PCA), an unsupervised multivariate data analysis method, is used to detect possible outliers, while Orthogonal Projection to Latent Structure (OPLS), a supervised multivariate data analysis method, is employed to find important metabolites responsible for discriminating the control and the melanoma groups. Two different strategies, i.e. spectral binning and spectral deconvolution, are used to reduce the original spectral data before statistical analysis. Spectral deconvolution is found to be superior for identifying a set of discriminatory metabolites between the control and the melanoma groups, especially when the sample size is small. OPLS results show that the melanoma group can be well separated from its control group. It is found that taurine, glutamate, aspartate, O-Phosphoethanolamine, niacinamide,ATP, lipids and glycerol derivatives are decreased statistically and significantly while alanine, malate, xanthine, histamine, dCTP, GTP, thymidine, 2′-Deoxyguanosine are statistically and significantly elevated. These significantly changed metabolites are associated with multiple biological pathways and may be potential biomarkers for metastatic melanoma in spleen. PMID:25383071

  17. Metabolomic Characterization of Nipple Aspirate Fluid by 1H NMR Spectroscopy and GC-MS

    PubMed Central

    Tredwell, Gregory D.; Miller, Jessica A.; Chow, H.-H. Sherry; Thompson, Patricia A.; Keun, Hector C.

    2015-01-01

    Nipple aspirate fluid (NAF) is a noninvasively obtained biofluid from the duct openings of the breast. NAF components are constantly secreted, metabolized, and reabsorbed by the epithelial lining of the lactiferous ducts of the breast. NAF has been studied as a potential breast tissue surrogate for the discovery of novel breast cancer risk, early detection, and treatment response biomarkers. We report the first unsupervised metabolite characterization of nipple aspirate fluid using NMR and GC-MS using convenience samples previously collected from four premenopausal and four postmenopausal women. A total of 38 metabolites were identified using the two analytical techniques, including amino acids, organic acids, fatty acids, and carbohydrates. Analytical reproducibility of metabolites in NAF by GC-MS was high across different extraction and analysis days. Overall, 31 metabolites had a coefficient of variation below 20%. By GC-MS, there were eight metabolites unique to NAF, 19 unique to plasma, and 24 shared metabolites. Correlative analysis of shared metabolites between matched NAF and plasma samples from pre- and postmenopausal women shows almost no correlations, with the exception being lactic acid, which was significantly negatively correlated (R2 = 0.57; P = 0.03). These results suggest that NAF is metabolically distinct from plasma and that the application of metabolomic strategies may be useful for future studies investigating breast cancer risk and intervention response biomarkers. PMID:24364541

  18. Complete (1)H and (13)C NMR chemical shift assignments of mono-, di-, and trisaccharides as basis for NMR chemical shift predictions of polysaccharides using the computer program casper.

    PubMed

    Roslund, Mattias U; Säwén, Elin; Landström, Jens; Rönnols, Jerk; Jonsson, K Hanna M; Lundborg, Magnus; Svensson, Mona V; Widmalm, Göran

    2011-08-16

    The computer program casper uses (1)H and (13)C NMR chemical shift data of mono- to trisaccharides for the prediction of chemical shifts of oligo- and polysaccharides. In order to improve the quality of these predictions the (1)H and (13)C, as well as (31)P when applicable, NMR chemical shifts of 30 mono-, di-, and trisaccharides were assigned. The reducing sugars gave two distinct sets of NMR resonances due to the α- and β-anomeric forms. In total 35 (1)H and (13)C NMR chemical shift data sets were obtained from the oligosaccharides. One- and two-dimensional NMR experiments were used for the chemical shift assignments and special techniques were employed in some cases such as 2D (1)H,(13)C-HSQC Hadamard Transform methodology which was acquired approximately 45 times faster than a regular t(1) incremented (1)H,(13)C-HSQC experiment and a 1D (1)H,(1)H-CSSF-TOCSY experiment which was able to distinguish spin-systems in which the target protons were only 3.3Hz apart. The (1)H NMR chemical shifts were subsequently refined using total line-shape analysis with the PERCH NMR software. The acquired NMR data were then utilized in the casper program (http://www.casper.organ.su.se/casper/) for NMR chemical shift predictions of the O-antigen polysaccharides from Klebsiella O5, Shigella flexneri serotype X, and Salmonella arizonae O62. The data were compared to experimental data of the polysaccharides from the two former strains and the lipopolysaccharide of the latter strain showing excellent agreement between predicted and experimental (1)H and (13)C NMR chemical shifts.

  19. Al coordination and water speciation in hydrous aluminosilicate glasses: direct evidence from high-resolution heteronuclear 1H-27Al correlation NMR.

    PubMed

    Xue, Xianyu; Kanzaki, Masami

    2007-02-01

    In order to shed light on the dissolution mechanisms of water in depolymerized aluminosilicate melts/glasses, a comprehensive one- (1D) and two-dimensional (2D) NMR study has been carried out on hydrous Ca- and Mg-aluminosilicate glasses of a haplobasaltic composition. The applied techniques include 1D 1H MAS NMR and 27Al-->1H cross-polarization (CP) MAS NMR, and 2D 1H NOESY and double-quantum (DQ) MAS NMR, 27Al triple-quantum (3Q) MAS NMR and 27Al-->1H heteronuclear correlation (HETCOR) and 3QMAS/HETCOR NMR. Ab initio calculations were also performed to place additional constraints on the 1H NMR characteristics of AlOH and Si(OH)Al groups. This study has revealed, for the first time, the presence of free OH (i.e. (Ca, Mg)OH), SiOH and AlOH species, in addition to molecular H2O, in hydrous glasses of a depolymerized aluminosilicate composition. The AlOH groups are mostly associated with four-coordinate Al, but some are associated with five- and six-coordinate Al.

  20. 1H and 13C NMR signal assignment of cucurbitacin derivatives from Citrullus colocynthis (L.) Schrader and Ecballium elaterium L. (Cucurbitaceae).

    PubMed

    Seger, Christoph; Sturm, Sonja; Mair, Maria-Elisabeth; Ellmerer, Ernst P; Stuppner, Hermann

    2005-06-01

    2D NMR-derived 1H and 13C NMR signal assignments of six structurally closely related cucurbitacin derivatives are presented. The investigated 2-O-beta-D-glucopyranosylcucurbitacins I, J, K, and L were obtained from Citrullus colocynthis (L.) Schrader whereas the aglyca cucurbitacin E and I were isolated from Ecballium elaterium L.

  1. Metabolic Profiling of Intact Arabidopsis thaliana Leaves during Circadian Cycle Using 1H High Resolution Magic Angle Spinning NMR

    PubMed Central

    van Schadewijk, R.; de Groot, H. J. M.; Alia, A.

    2016-01-01

    Arabidopsis thaliana is the most widely used model organism for research in plant biology. While significant advances in understanding plant growth and development have been made by focusing on the molecular genetics of Arabidopsis, extracting and understanding the functional framework of metabolism is challenging, both from a technical perspective due to losses and modification during extraction of metabolites from the leaves, and from the biological perspective, due to random variation obscuring how well the function is performed. The purpose of this work is to establish the in vivo metabolic profile directly from the Arabidopsis thaliana leaves without metabolite extraction, to reduce the complexity of the results by multivariate analysis, and to unravel the mitigation of cellular complexity by predominant functional periodicity. To achieve this, we use the circadian cycle that strongly influences metabolic and physiological processes and exerts control over the photosynthetic machinery. High resolution-magic angle spinning nuclear magnetic resonance (HR-MAS NMR) was applied to obtain the metabolic profile directly from intact Arabidopsis leaves. Combining one- and two-dimensional 1H HR-MAS NMR allowed the identification of several metabolites including sugars and amino acids in intact leaves. Multivariate analysis on HR-MAS NMR spectra of leaves throughout the circadian cycle revealed modules of primary metabolites with significant and consistent variations of their molecular components at different time points of the circadian cycle. Since robust photosynthetic performance in plants relies on the functional periodicity of the circadian rhythm, our results show that HR-MAS NMR promises to be an important non-invasive method that can be used for metabolomics of the Arabidopsis thaliana mutants with altered physiology and photosynthetic efficiency. PMID:27662620

  2. Investigation of network heterogeneities in filled, trimodal, highly functional PDMS networks by 1H Multiple Quantum NMR

    SciTech Connect

    Gjersing, E; Chinn, S; Maxwell, R S; Herberg, J; Eastwood, E; Bowen, D; Stephens, T

    2006-09-06

    The segmental order and dynamics of polymer network chains in a filled, tri-modal silicone network have been studied by static 1H Multiple Quantum (MQ) NMR methods to gain insight into the structure property relationships. The materials were synthesized with two different types of crosslinks, with functionalities of 4 and near 60. The network chains were composed of distributions of high, low, and medium molecular weight chains. Crosslinking was accomplished by standard acid catalyzed reactions. MQ NMR methods have detected domains with residual dipolar couplings (<{Omega}{sub d}>) of near 4 kRad/s and 1 kRad/s assigned to (a) the shorter polymer chains and chains near the multifunctional ({phi}=60) crosslinking sites and to (b) the longer polymer chains far from these sites. Three structural variables were systematically varied and the mechanical properties and distributions of residual dipolar couplings measured in order to gain insight in to the network structural motifs that contribute significantly to the composite properties. The partitioning of and the average values of the residual dipolar couplings for the two domains were observed to be dependent on formulation variable and provided increased insight into the mechanical properties of these materials which are unavailable from swelling and spin-echo methods. The results of this study suggest that the domains with high crosslink density contribute significantly to the high strain modulus, while the low crosslink density domains do not. This is in agreement with theories and experimental studies on silicone bimodal networks over the last 20 years. In-situ MQ-NMR of swollen sample suggests that the networks deform non-affinely, in agreement with theory. The NMR experiments shown here provide increased ability to characterize multimodal networks of typical engineering silicone materials and to gain significant insight into structure-property relationships.

  3. Investigation of network heterogeneities in filled, trimodal, highly functional PDMS networks by 1H Multiple Quantum NMR

    SciTech Connect

    Maxwell, R; Gjersing, E; Chinn, S; Giuliani, J; Herberg, J; Eastwood, E; Bowen, D; Stephens, T

    2007-03-20

    The segmental order and dynamics of polymer network chains in a filled, tri-modal silicone foam network have been studied by static 1H Multiple Quantum (MQ) NMR methods to gain insight into the structure property relationships. The foam materials were synthesized with two different types of crosslinks, with functionalities, {phi}, of 4 and near 60. The network chains were composed of distributions of high, low, and medium molecular weight chains. Crosslinking was accomplished by standard acid catalyzed reactions. MQ NMR methods have detected domains with residual dipolar couplings (<{Omega}{sub d}>) of near 4 kRad/s and 1 kRad/s assigned to (a) the shorter polymer chains and chains near the multifunctional (f=60) crosslinking sites and to (b) the longer polymer chains far from these sites. Three structural variables were systematically varied and the mechanical properties via compression and distributions of residual dipolar couplings measured in order to gain insight in to the network structural motifs that contribute significantly to the composite properties. The partitioning of and the average values of the residual dipolar couplings for the two domains were observed to be dependent on formulation variable and provided increased insight into the network structure of these materials which are unavailable from swelling and spin-echo methods. The results of this study suggest that the domains with high crosslink density contribute significantly to the high strain modulus, while the low crosslink density domains do not. This is in agreement with theories and experimental studies on silicone bimodal networks over the last 20 years. In-situ MQ-NMR of swollen sample suggests that the networks deform heterogeneously and non-affinely. The heterogeneity of the deformation process was observed to depend on the amount of the high functionality crosslinking site PMHS. The NMR experiments shown here provide increased ability to characterize multimodal networks of typical

  4. sup 1 H NMR study of renal trimethylamine responses to dehydration and acute volume loading in man

    SciTech Connect

    Avison, M.J.; Rothman, D.L.; Nixon, T.W.; Long, W.S.; Siegel, N.J. )

    1991-07-15

    The authors have used volume-localized {sup 1}H NMR spectroscopy to detect and measure changes in medullary trimethylamines (TMAs) in the human kidney in vivo. Localized water-suppressed {sup 1}H spectra were collected from a volume of interest located within the renal medulla by using a stimulated echo-based localization scheme. The principal resonances in the medullary {sup 1}H spectrum were residual water, lipid, and TMAs. The TMA line width was 7-15 Hz before filtering, and the signal-to-noise ratio was 40:1. In four normal volunteers, 15 hr of dehydration led to a significant increase in urine ismolality and decrease in body weight and an increase in medullary TMAs. A subsequent water load caused a transient water diuresis, a return to euvolemic body weight, and a significant reduction in medullary TMAs within 4 hr. These results suggest that TMAs may play an osmoregulatory role in the medulla of the normal human kidney.

  5. 1H NMR study of robustoxin, the lethal neurotoxin from the funnel web spider Atrax robustus.

    PubMed

    Temple, M D; Hinds, M G; Sheumack, D D; Howden, M E; Norton, R S

    1999-03-01

    Robustoxin, the lethal neurotoxin from the Sydney funnel web spider Atrax robustus, is a polypeptide of 42 residues cross-linked by four disulfide bonds. This paper describes the sequence-specific assignment of resonances in the 1H nuclear magnetic resonance spectrum of robustoxin in aqueous solution. Several broad backbone amide resonances were encountered in spectra recorded at 27 degrees C, making the assignments at that temperature incomplete. In spectra recorded at lower temperatures these amide resonances became sharper, but others that were sharp at 27 degrees C became broad, indicative of conformational averaging on the millisecond timescale for certain regions of the structure. Nevertheless, it was possible to establish that robustoxin contains a small, triple-stranded, antiparallel beta-sheet and several reverse turns, but no alpha-helix. These observations indicate that this toxin may adopt the inhibitor cystine knot structure found in polypeptides from a diverse range of species, including a number of spiders. Analysis of the pH dependence of the spectrum yielded pKa values for Tyr22 and Tyr25, one of the three carboxyl groups, and the Lys residues.

  6. Intrauterine fetal brain NMR spectroscopy: 1H and 31P studies in rats

    SciTech Connect

    Nakada, T.; Kwee, I.L.; Suzuki, N.; Houkin, K. )

    1989-11-01

    Fetal brain metabolism was investigated in utero noninvasively using multinuclear nuclear magnetic resonance spectroscopy in rats at two representative prenatal stages: early (17-18 days) and late (20-21 days) stages. Phosphorus-31 (31P) spectroscopy revealed that phosphocreatine is significantly lower in the early stage and increases to the level of early neonates by the late prenatal stage. Intracellular pH at the early stage was found to be strikingly high (7.52 +/- 0.21) and decreased to a level similar to that of neonates by the late stage (7.29 +/- 0.07). Phosphomonoester levels at both stages were similar to the values reported for early neonates. Water-suppressed proton (1H) spectroscopy demonstrated a distinctive in vivo fetal brain spectral pattern characterized by low levels of N-acetyl aspartate and high levels of taurine. High-resolution proton spectroscopy and homonuclear chemical-shift correlate spectroscopy of brain perchloric acid extracts confirmed these in vivo findings. In vitro 31P spectroscopy of acidified chloroform methanol extracts showed the characteristic membrane phospholipid profiles of fetal brain. The phosphatidylethanolamine (PE)-to-phosphatidylcholine (PC) ratio (PE/PC) did not show significant changes between the two stages at 0.40 +/- 0.11, a value similar to that of early neonates.

  7. X-ray crystallography

    NASA Technical Reports Server (NTRS)

    2001-01-01

    X-rays diffracted from a well-ordered protein crystal create sharp patterns of scattered light on film. A computer can use these patterns to generate a model of a protein molecule. To analyze the selected crystal, an X-ray crystallographer shines X-rays through the crystal. Unlike a single dental X-ray, which produces a shadow image of a tooth, these X-rays have to be taken many times from different angles to produce a pattern from the scattered light, a map of the intensity of the X-rays after they diffract through the crystal. The X-rays bounce off the electron clouds that form the outer structure of each atom. A flawed crystal will yield a blurry pattern; a well-ordered protein crystal yields a series of sharp diffraction patterns. From these patterns, researchers build an electron density map. With powerful computers and a lot of calculations, scientists can use the electron density patterns to determine the structure of the protein and make a computer-generated model of the structure. The models let researchers improve their understanding of how the protein functions. They also allow scientists to look for receptor sites and active areas that control a protein's function and role in the progress of diseases. From there, pharmaceutical researchers can design molecules that fit the active site, much like a key and lock, so that the protein is locked without affecting the rest of the body. This is called structure-based drug design.

  8. Change of translational-rotational coupling in liquids revealed by field-cycling 1H NMR

    NASA Astrophysics Data System (ADS)

    Meier, R.; Schneider, E.; Rössler, E. A.

    2015-01-01

    Applying the field-cycling nuclear magnetic resonance technique, the frequency dependence of the 1H spin-lattice relaxation rate, R 1 ω = T1 - 1 ω , is measured for propylene glycol (PG) which is increasingly diluted with deuterated chloroform. A frequency range of 10 kHz-20 MHz and a broad temperature interval from 220 to about 100 K are covered. The results are compared to those of experiments, where glycerol and o-terphenyl are diluted with their deuterated counter-part. Reflecting intra- as well as intermolecular relaxation, the dispersion curves R 1 ω , x (x denotes mole fraction PG) allow to extract the rotational time constant τrot(T, x) and the self-diffusion coefficient D(T, x) in a single experiment. The Stokes-Einstein-Debye (SED) relation is tested in terms of the quantity D(T, x) τrot(T, x) which provides a measure of an effective hydrodynamic radius or equivalently of the spectral separation of the translational and the rotational relaxation contribution. In contrast to o-terphenyl, glycerol and PG show a spectral separation much larger than suggested by the SED relation. In the case of PG/chloroform mixtures, not only an acceleration of the PG dynamics is observed with increasing dilution but also the spectral separation of rotational and translational relaxation contributions continuously decreases. Finally, following a behavior similar to that of o-terphenyl already at about x = 0.6; i.e., while D(T, x) τrot(T, x) in the mixture is essentially temperature independent, it strongly increases with x signaling thus a change of translational-rotational coupling. This directly reflects the dissolution of the hydrogen-bond network and thus a change of solution structure.

  9. X-ray laser

    DOEpatents

    Nilsen, Joseph

    1991-01-01

    An X-ray laser (10) that lases between the K edges of carbon and oxygen, i.e. between 44 and 23 Angstroms, is provided. The laser comprises a silicon (12) and dysprosium (14) foil combination (16) that is driven by two beams (18, 20) of intense line focused (22, 24) optical laser radiation. Ground state nickel-like dysprosium ions (34) are resonantly photo-pumped to their upper X-ray laser state by line emission from hydrogen-like silicon ions (32). The novel X-ray laser should prove especially useful for the microscopy of biological specimens.

  10. X-ray superbubbles

    NASA Technical Reports Server (NTRS)

    Cash, W.

    1983-01-01

    Four regions of the galaxy, the Cygnus Superbubble, the Eta Carina complex, the Orion/Eridanus complex, and the Gum Nebula, are discussed as examples of collective effects in the interstellar medium. All four regions share certain features, indicating a common structure. The selection effects which determine the observable X-ray properties of the superbubbles are discussed, and it is demonstrated that only a very few more in our Galaxy can be detected in X rays. X-ray observation of extragalactic superbubbles is shown to be possible but requires the capabilities of a large, high quality, AXAF class observatory.

  11. 1H NMR Metabolomics: A New Molecular Level Tool for Assessment of Organic Contaminant Bioavailability to Earthworms in Soil

    NASA Astrophysics Data System (ADS)

    McKelvie, J. R.; Wolfe, D. M.; Celejewski, M. A.; Simpson, A. J.; Simpson, M. J.

    2009-05-01

    At contaminated field sites, the complete removal of polycyclic aromatic hydrocarbons (PAHs) is rarely achieved since a portion of these compounds remain tightly bound to the soil matrix. The concentration of PAHs in soil typically decreases until a plateau is reached, at which point the remaining contaminant is considered non- bioavailable. Numerous soil extraction techniques, including cyclodextrin extraction, have been developed to estimate contaminant bioavailability. However, these are indirect methods that do not directly measure the response of organisms to chemical exposure in soil. Earthworm metabolomics offers a promising new way to directly evaluate the bioavailability and toxicity of contaminants in soil. Metabolomics involves the measurement of changes in small-molecule metabolites, including sugars and amino acids, in living organisms due to an external stress, such as contaminant exposure. The objective of this study was to compare cyclodextrin extraction of soil (a bioavailability proxy) and 1H NMR metabolomic analysis of aqueous earthworm tissue extracts as indicators of contaminant bioavailability. A 30 day laboratory experiment was conducted using phenanthrene-spiked sphagnum peat soil and the OECD recommended earthworm species for toxicity testing, Eisenia fetida. The initial phenanthrene concentration in the soil was 320 mg/kg. Rapid biodegradation of phenanthrene occurred and concentrations decreased to 16 mg/kg within 15 days. After 15 days, phenanthrene biodegradation slowed and cyclodextrin extraction of the soil suggested that phenanthrene was no longer bioavailable. Multivariate statistical analysis of the 1H NMR spectra for E. fetida tissue extracts indicated that the metabolic profile of phenanthrene exposed earthworms differed from control earthworms throughout the 30 day experiment. This suggests that the residual phenanthrene remaining in the soil after 15 days continued to elicit a metabolic response, even though it was not

  12. Miscibility of nifedipine and hydrophilic polymers as measured by (1)H-NMR spin-lattice relaxation.

    PubMed

    Aso, Yukio; Yoshioka, Sumie; Miyazaki, Tamaki; Kawanishi, Tohru; Tanaka, Kazuyuki; Kitamura, Satoshi; Takakura, Asako; Hayashi, Takashi; Muranushi, Noriyuki

    2007-08-01

    The miscibility of a drug with excipients in solid dispersions is considered to be one of the most important factors for preparation of stable amorphous solid dispersions. The purpose of the present study was to elucidate the feasibility of (1)H-NMR spin-lattice relaxation measurements to assess the miscibility of a drug with excipients. Solid dispersions of nifedipine with the hydrophilic polymers poly(vinylpyrrolidone) (PVP), hydroxypropylmethylcellulose (HPMC) and alpha,beta-poly(N-5-hydroxypentyl)-L-aspartamide (PHPA) with various weight ratios were prepared by spray drying, and the spin-lattice relaxation decay of the solid dispersions in a laboratory frame (T(1) decay) and in a rotating frame (T(1rho) decay) were measured. T(1rho) decay of nifedipine-PVP solid dispersions (3 : 7, 5 : 5 and 7 : 3) was describable with a mono-exponential equation, whereas T(1rho) decay of nifedipine-PHPA solid dispersions (3 : 7, 4 : 6 and 5 : 5) was describable with a bi-exponential equation. Because a mono-exponential T(1rho) decay indicates that the domain sizes of nifedipine and polymer in solid dispersion are less than several nm, it is speculated that nifedipine is miscible with PVP but not miscible with PHPA. All the nifedipine-PVP solid dispersions studied showed a single glass transition temperature (T(g)), whereas two glass transitions were observed for the nifedipine-PHPA solid dispersion (3 : 7), thus supporting the above speculation. For nifedipine-HPMC solid dispersions (3 : 7 and 5 : 5), the miscibility of nifedipine and HPMC could not be determined by DSC measurements due to the lack of obviously evident T(g). In contrast, (1)H-NMR spin-lattice relaxation measurements showed that nifedipine and HPMC are miscible, since T(1rho) decay of the solid dispersions (3 : 7, 5 : 5 and 7 : 3) was describable with a mono-exponential equation. These results indicate that (1)H-NMR spin-lattice relaxation measurements are useful for assessing the miscibility of a drug and an

  13. Local Water Dynamics in Coacervated Polyelectrolytes Monitored Through Dynamic Nuclear Polarization-Enhanced 1H NMR

    PubMed Central

    Kausik, Ravinath; Srivastava, Aasheesh; Korevaar, Peter A.; Stucky, Galen; Waite, J. Herbert

    2009-01-01

    We present the first study of quantifying the diffusion coefficient of interfacial water on polyelectrolyte surfaces of systems fully dispersed in bulk water under ambient conditions. Such measurements were made possible through the implementation of a recently introduced Dynamic Nuclear Polarization (DNP) technique to selectively amplify the nuclear magnetic resonance (NMR) signal of hydration water that is interacting with specifically located spin labels on polyelectrolyte surfaces. The merit of this novel capability is demonstrated in this report through the measurement of solvent microvisosity on the surface of two types of oppositely charged polyelectrolytes, when freely dissolved versus when complexed to form a liquid-liquid colloidal phase called complex coacervates. These complex coacervates were formed through electrostatic complexation between the imidazole-based cationic homopolymer poly(N-vinylimidazole) (PVIm), and anionic polypeptide polyaspartate (PAsp) in the pH range of 4.5 – 6.0, under which conditions the coacervate droplets are highly fluidic yet densely packed with polyelectrolytes. We also investigated the rotational diffusion coefficients of the spin labels covalently bound to the polyelectrolyte chains for both PVIm and PAsp, showing a 5 fold change in the rotational correlation time as well as anisotropy parameter upon coacervation, which represents a surprisingly small decrease given the high polymer concentration inside the dense microdroplets. For both DNP and ESR experiments, the polymers were covalently tagged with stable nitroxide radical spin labels (∼1 wt %) to probe the local solvent and polymer segment dynamics. We found that the surface water diffusion coefficients near uncomplexed PVIm and PAsp at pH 8 differ, and are around D∼1.3×10−9 m2 / s. In contrast, inside the complex coacervate phase, the water diffusion coefficient in the immediate vicinity of either polyelectrolyte was D∼ 0.25×10−9 m2 / s, which is about

  14. Lumbosacral spine x-ray

    MedlinePlus

    X-ray - lumbosacral spine; X-ray - lower spine ... The test is done in a hospital x-ray department or your health care provider's office by an x-ray technician. You will be asked to lie on the x-ray table ...

  15. Thoracic spine x-ray

    MedlinePlus

    Vertebral radiography; X-ray - spine; Thoracic x-ray; Spine x-ray; Thoracic spine films; Back films ... The test is done in a hospital radiology department or in the health care provider's office. You will lie on the x-ray table in different positions. If the x-ray ...

  16. Conformations and intermolecular interactions pattern in solid chloroxylenol and triclosan (API of anti-infective agents and drugs). A (35)Cl NQR, (1)H-(14)N NQDR, X-ray and DFT/QTAIM study.

    PubMed

    Latosińska, J N; Latosińska, M; Tomczak, M A; Seliger, J; Zagar, V; Maurin, J K

    2012-02-01

    Two antibacterial and antifungal agents, chloroxylenol (4-chloro-3,5-dimethyl-phenol) and triclosan (5-chloro-2-(2',4'-dichlorophenoxy)-phenol), were studied experimentally in solid state with an X-ray, (35)Cl-nuclear quadrupole resonance (NQR) and (17)O-nuclear quadrupole double resonance (NQDR) spectroscopies and, theoretically, with the density functional theory/quantum theory of atoms in molecules (DFT/QTAIM). The crystallographic structure of triclosan, which crystallises in space group P31 with one molecule in the asymmetric unit [a = 12.64100(10), b = 12.64100(10), c = 6.71630(10) Å], was solved with an X-ray and refined to a final R-factor of 2.81% at room temperature. The NQR frequencies of (35)Cl and (17)O were detected with the help of the density functional theory (DFT) assigned to particular chlorine and oxygen sites in the molecules of both compounds. The NQR frequencies at (35)Cl sites in chloroxylenol and triclosan were found to be more differentiated than frequencies at the (17)O site. The former better describes the substituent withdrawing effects connected to π-electron delocalization within the benzene rings and the influence of temperature; whereas, those at the (17)O site provide more information on O-H bond and intermolecular interactions pattern. The conformation adopted by diphenyl ether of triclosan in solid state was found to be typical of diphenyl ethers, but the opposite to those adopted when it was bound to different inhibitors. According to an X-ray study, temperature had no effect on the conformation of the diphenyl ring of triclosan, which was the same at 90 K and at room temperature (RT). The scattering of NQR frequencies reproduced by the DFT under assumption of the X-ray data at 90 K and RT is found to be a good indicator of the quality of resolution of the crystallographic structure.

  17. Electronic states and molecular dynamics of single-component molecular conductors [M (tmdt) 2] (M =Ni , Pt) studied by 13C and 1H NMR

    NASA Astrophysics Data System (ADS)

    Takagi, Rina; Miyagawa, Kazuya; Yoshimura, Masahide; Gangi, Hiro; Kanoda, Kazushi; Zhou, Biao; Idobata, Yuki; Kobayashi, Akiko

    2016-01-01

    The molecular conductors [M(tmdt) 2] (M =Ni , Pt) consisting of single molecular species are investigated with 13C NMR and 1H NMR. The temperature dependences of the 13C NMR shift and relaxation rate provide microscopic evidence for the metallic nature with appreciable electron correlations. Both compounds exhibit an anomalous frequency-dependent enhancement in the 1H nuclear spin-lattice relaxation rate in a wide temperature range. These observations signify the presence of extraordinary molecular motions with low energy excitations.

  18. Probing intermolecular interactions in a diethylcarbamazine citrate salt by fast MAS (1)H solid-state NMR spectroscopy and GIPAW calculations.

    PubMed

    Venâncio, Tiago; Oliveira, Lyege Magalhaes; Ellena, Javier; Boechat, Nubia; Brown, Steven P

    2017-03-02

    Fast magic-angle spinning (MAS) NMR is used to probe intermolecular interactions in a diethylcarbamazine salt, that is widely used as a treatment against adult worms of Wuchereria bancrofti which cause a common disease in tropical countries named filariasis. Specifically, a dihydrogen citrate salt that has improved thermal stability and solubility as compared to the free form is studied. One-dimensional (1)H, (13)C and (15)N and two-dimensional (1)H-(13)C and (14)N-(1)H heteronuclear correlation NMR experiments under moderate and fast MAS together with GIPAW (CASTEP) calculations enable the assignment of the (1)H, (13)C and (14)N/(15)N resonances. A two-dimensional (1)H-(1)H double-quantum (DQ) -single-quantum (SQ) MAS spectrum recorded with BaBa recoupling at 60kHz MAS identifies specific proton-proton proximities associated with citrate-citrate and citrate-diethylcarbamazine intermolecular interactions.

  19. Heteronuclear three-dimensional NMR spectroscopy. Natural abundance sup 13 C chemical shift editing of sup 1 H- sup 1 H COSY spectra

    SciTech Connect

    Fesik, S.W.; Gampe, R.T. Jr.; Zuiderweg, E.R.P. )

    1989-01-18

    It has been demonstrated that heteronuclear 3D NMR spectroscopy can be effectively applied to small molecules with {sup 13}C at natural abundance. A 78mM solution of the aminoglycoside, kanamycin A was used for this experiment. The heteronuclear 3D NMR spectroscopy is shown to be a useful method for resolving spectral overlap in all frequency domains. 10 refs., 2 figs.

  20. X-ray - skeleton

    MedlinePlus

    ... medlineplus.gov/ency/article/003381.htm X-ray - skeleton To use the sharing features on this page, ... ray views may be uncomfortable. If the whole skeleton is being imaged, the test usually takes 1 ...

  1. Evaluation of the effect of carvacrol on the Escherichia coli 555 metabolome by using 1H-NMR spectroscopy.

    PubMed

    Picone, Gianfranco; Laghi, Luca; Gardini, Fausto; Lanciotti, Rosalba; Siroli, Lorenzo; Capozzi, Francesco

    2013-12-15

    Cultures of Escherichia coli 555 were grown at four levels of carvacrol (0-2 mM) and the E. coli endo-metabolome was extracted and measured by (1)H NMR spectroscopy. The results show that glucose concentration is going up with concentration of carvacrol and so do formate until the highest concentration is reached, from which point it suddenly decreases. This is interpreted as if the bacteria are increasingly unable to further metabolize glucose and as if the bacteria increasingly shifts with higher levels of carvacrol toward sugar fermentation as carbon source, until the level of carvacrol reaches a level (2.00 mM), where the E. coli must give up. Additionally, the multivariate Principal Component Analysis suggests that the adaptation occurring at sub-lethal doses of carvacrol is different from that occurring at higher doses.

  2. Study of the formation of carbonyl compounds in edible oils and fats by 1H-NMR and FTIR

    NASA Astrophysics Data System (ADS)

    Moya Moreno, M. C. M.; Mendoza Olivares, D.; Amézquita López, F. J.; Peris Martínez, V.; Bosch Reig, F.

    1999-05-01

    Oils and fats start decomposing from the moment they are isolated from their natural environment. Heating accelerates oxidative rancidity and frying at high temperatures produces thermal degradation with the formation of decomposition products, such as aldehydes, ketones, free acids and hydroxilic compounds that in high levels can be harmful to human health. The decomposition products formed up to 300°C were determined by means of 1H-NMR spectroscopy and an FTIR spectroscopic method was developed for the quantification of carbonyl compounds generated during heating. The results show that there is a formation of carbonyl compounds starting at 150°C and when the sample was heated at 300°C for 40 min, the following contents (expressed as butyraldehyde mass fraction) were found: olive oil 10.5%, sunflower oil 11.3%, corn oil 3.0%, seeds oil (sunflower, safflower and canola seed) 6.6% and lard 3.5%.

  3. [Studies by means of 1H NMR spectroscopy of complex formation of aromatic biologically active compounds with antibiotic topotecan].

    PubMed

    Mosunov, A A; Kostiukov, V V; Evstigneev, M P

    2012-01-01

    The analysis of heteroassociation of antibiotic topotecan (TPT) with aromatic biologically active compounds (BAC): caffeine, mutagens ethidium bromide and proflavine, antibiotic daunomycin, vitamins flavin-mononucleotide and nicotinamide, has been carried out in the work using 1H NMR spectroscopy data. The equilibrium constants of heteroassociation and induced chemical shifts of the protons have been obtained in the complexes with BAC. It is found that the complex formation TPT-BAC has the nature of stacking of the chromophores, additionally stabilized in the case of proflavine by intermolecular hydrogen bond. Calculation of the basic components of the Gibbs free energy of the complexation reactions is carried out, and the factors which stabilize and destabilize the heterocomplexes of molecules are revealed.

  4. 13C-CPMAS and 1H-NMR study of the inclusion complexes of beta-cyclodextrin with carvacrol, thymol, and eugenol prepared in supercritical carbon dioxide.

    PubMed

    Locci, Emanuela; Lai, Simona; Piras, Alessandra; Marongiu, Bruno; Lai, Adolfo

    2004-09-01

    Beta-cyclodextrin (beta-CD) inclusion complexes with carvacrol (1), thymol (2), and eugenol (3) (components of essential oils of vegetable origin) were prepared by the supercritical CO2 technique, and their structural characterization was achieved by means of 1H-NMR in aqueous solution and 13C-CPMAS NMR in the solid state. Evidence of the formation of the inclusion complexes for all the examined systems was obtained by 1H-NMR in solution, while 2D-ROESY-NMR experiments were used to investigate the geometry of inclusion. In addition, the dynamics of these inclusion complexes in the kHz timescale was investigated by analysis of the 1H and 13C spin-lattice relaxation times in the rotating frame.

  5. Cosmic x ray physics

    NASA Technical Reports Server (NTRS)

    Mccammon, Dan; Cox, D. P.; Kraushaar, W. L.; Sanders, W. T.

    1992-01-01

    This final report covers the period 1 January 1985 - 31 March 1992. It is divided into the following sections: the soft x-ray background; proportional counter and filter calibrations; sounding rocket flight preparations; new sounding rocket payload: x-ray calorimeter; and theoretical studies. Staff, publications, conference proceedings, invited talks, contributed talks, colloquia and seminars, public service lectures, and Ph. D. theses are listed.

  6. Combining biochemical with (1)H NMR-based metabolomics approach unravels the antidiabetic activity of genipin and its possible mechanism.

    PubMed

    Shen, Xiao-Li; Liu, Huan; Xiang, Huan; Qin, Xue-Mei; Du, Guan-Hua; Tian, Jun-Sheng

    2016-09-10

    Diabetes mellitus is a typical heterogeneous metabolic disorder characterized by abnormal metabolism of carbohydrates, lipids and proteins. Genipin possesses a wide spectrum of biological activities including ameliorating effects on diabetes, but the definite mechanism of this effect remains unknown. To investigate the antidiabetic activities of genipin and explore the biochemical changes of serum endogenous metabolites on diabetic rats induced by alloxan, (1)H NMR spectroscopy coupled with multivariate data analysis was used to. All rats were randomly divided into six groups including negative control (NC) group, diabetic mellitus (DM) group, metformin hydrochloride group, high dose group of genipin, middle dose group of genipin and low dose group of genipin. Diabetes was induced by a single intraperitoneal injection of 120mg/kg body weight of alloxan. Serum samples were collected for the (1)H NMR-based metabolomics and clinical biochemical analysis. Daily oral administration of genipin (25, 50 and 100mg/kg body weight) and metformin hydrochloride (125mg/kg) for two weeks showed beneficial effects on blood glucose level (P<0.01). Significant differences in the metabolic profile as well as the result of biochemical parameters between the diabetic group and the control group were observed. The PLS-DA scores and corresponding loading plots demonstrated that genipin significantly restored the abnormal metabolic state. Detailed analysis of the altered metabolite levels indicated that genipin significantly ameliorated the disturbance in glucose metabolism, tricarboxylic acid cycle, lipid metabolism and amino acid metabolism. Genipin showed the best anti-diabetic effects at a dose of 100mg/kg in rats. This finding indicates that chemical and metabolomic approaches could be powerful tools for the investigation of the biochemical changes in pathological conditions or drug treatment.

  7. A 1H NMR study of a ternary peptide complex that mimics the interaction between troponin C and troponin I.

    PubMed Central

    Slupsky, C. M.; Shaw, G. S.; Campbell, A. P.; Sykes, B. D.

    1992-01-01

    The troponin I peptide N alpha-acetyl TnI (104-115) amide (TnIp) represents the minimum sequence necessary for inhibition of actomyosin ATPase activity of skeletal muscle (Talbot, J.A. & Hodges, R.S. 1981, J. Biol. Chem. 256, 2798-3802; Van Eyk, J.E. & Hodges, R.S., 1988, J. Biol. Chem. 263, 1726-1732; Van Eyk, J.E., Kay, C.M., & Hodges, R.S., 1991, Biochemistry 30, 9974-9981). In this study, we have used 1H NMR spectroscopy to compare the binding of this inhibitory TnI peptide to a synthetic peptide heterodimer representing site III and site IV of the C-terminal domain of troponin C (TnC) and to calcium-saturated skeletal TnC. The residues whose 1H NMR chemical shifts are perturbed upon TnIp binding are the same in both the site III/site IV heterodimer and TnC. These residues include F102, I104, F112, I113, I121, I149, D150, F151, and F154, which are all found in the C-terminal domain hydrophobic pocket and antiparallel beta-sheet region of the synthetic site III/site IV heterodimer and of TnC. Further, the affinity of TnIp binding to the heterodimer (Kd = 192 +/- 37 microM) was found to be similar to TnIp binding to TnC (48 +/- 18 microM [Campbell, A.P., Cachia, P.J., & Sykes, B.D., 1991, Biochem. Cell Biol. 69, 674-681]). The results indicate that binding of the inhibitory region of TnI is primarily to the C-terminal domain of TnC. The results also indicate how well the synthetic peptide heterodimer mimics the C-terminal domain of TnC in structure and functional interactions. PMID:1304891

  8. Quantitative Quantum Mechanical Spectral Analysis (qQMSA) of (1)H NMR spectra of complex mixtures and biofluids.

    PubMed

    Tiainen, Mika; Soininen, Pasi; Laatikainen, Reino

    2014-05-01

    The quantitative interpretation of (1)H NMR spectra of mixtures like the biofluids is a demanding task due to spectral complexity and overlap. Complications may arise also from water suppression, T2-editing, protein interactions, relaxation differences of the species, experimental artifacts and, furthermore, the spectra may contain unknown components and macromolecular background which cannot be easily separated from baseline. In this work, tools and strategies for quantitative Quantum Mechanical Spectral Analysis (qQMSA) of (1)H NMR spectra from complex mixtures were developed and systematically assessed. In the present approach, the signals of well-defined, stoichiometric components are described by a QM model, while the background is described by a multiterm baseline function and the unknown signals using optimizable and adjustable lines, regular multiplets or any spectral structures which can be composed from spectral lines. Any prior knowledge available from the spectrum can also be added to the model. Fitting strategies for weak and strongly overlapping spectral systems were developed and assessed using two basic model systems, the metabolite mixtures without and with macromolecular (serum) background. The analyses show that if the spectra are measured in high-throughput manner, the consistent absolute quantification demands some calibration to compensate the different response factors of the protons and compounds. On the other hand, the results show that also the T2-edited spectra can be measured so that they obey well the QM rules. In general, qQMSA exploits and interprets the spectral information in maximal way taking full advantage from the QM properties of the spectra and, at the same time, offers chemical confidence which means that individual components can be identified with high confidence on the basis of their accurate spectral parameters.

  9. Detection, identification and quantification by 1H NMR of adulterants in 150 herbal dietary supplements marketed for improving sexual performance.

    PubMed

    Gilard, Véronique; Balayssac, Stéphane; Tinaugus, Aurélie; Martins, Nathalie; Martino, Robert; Malet-Martino, Myriam

    2015-01-01

    One hundred and fifty dietary supplements (DS) marketed to increase sexual performance were analyzed. All these formulations were claimed to contain only natural compounds, plant extracts and/or vitamins. (1)H NMR spectroscopy was used for detecting the presence of adulterants and for their identification and quantification. Mass spectrometry was used as a complementary method for confirming the chemical structures. 61% of DS were adulterated with phosphodiesterase-5 inhibitors (PDE-5i) (27% with the PDE-5i medicines sildenafil, tadalafil and vardenafil, and 34% with their structurally modified analogues). Among them, 64% contained only one PDE-5i and 36% mixtures of two, three and even four. The amounts of PDE-5i medicines were higher than the maximum recommended dose in 25% of DS tainted with these drugs. Additional 5.5% DS included other drugs for the treatment of sexual dysfunction (yohimbine, flibanserin, phentolamine, dehydroepiandrosterone or testosterone). Some DS (2.5%) contained products (osthole, icariin) extracted from plants known to improve sexual performance. Only 31% of the samples could be considered as true herbal/natural products. A follow-up over time of several DS revealed that manufacturers make changes in the chemical composition of the formulations. Lack of quality or consistent manufacture (contamination possibly due to inadequate cleaning of the manufacturing chain, presence of impurities or degradation products, various compositions of a given DS with the same batch number, inadequate labelling) indicated poor manufacturing practices. In conclusion, this paper demonstrates the power of (1)H NMR spectroscopy as a first-line method for the detection of adulterated herbal/natural DS and the need for more effective quality control of purported herbal DS.

  10. X-ray Binaries

    NASA Astrophysics Data System (ADS)

    Lewin, Walter H. G.; van Paradijs, Jan; van den Heuvel, Edward Peter Jacobus

    1997-01-01

    Preface; 1. The properties of X-ray binaries, N. E. White, F. Nagase and A. N. Parmar; 2. Optical and ultraviolet observations of X-ray binaries J. van Paradijs and J. E. McClintock; 3. Black-hole binaries Y. Tanaka and W. H. G. Lewin; 4. X-ray bursts Walter H. G. Lewin, Jan Van Paradijs and Ronald E. Taam; 5. Millisecond pulsars D. Bhattacharya; 6. Rapid aperiodic variability in binaries M. van der Klis; 7. Radio properties of X-ray binaries R. M. Hjellming and X. Han; 8. Cataclysmic variable stars France Anne-Dominic Córdova; 9. Normal galaxies and their X-ray binary populations G. Fabbiano; 10. Accretion in close binaries Andrew King; 11. Formation and evolution of neutron stars and black holes in binaries F. Verbunt and E. P. J. van den Heuvel; 12. The magnetic fields of neutron stars and their evolution D. Bhattacharya and G. Srinivasan; 13. Cosmic gamma-ray bursts K. Hurley; 14. A catalogue of X-ray binaries Jan van Paradijs; 15. A compilation of cataclysmic binaries with known or suspected orbital periods Hans Ritter and Ulrich Kolb; References; Index.

  11. Comparative study of the complex forming ability and enantioselectivity of cyclodextrin polymers by CE and 1H NMR.

    PubMed

    Danel, Cécile; Azaroual, Nathalie; Chavaria, Cédric; Odou, Pascal; Martel, Bernard; Vaccher, Claude

    2013-02-15

    The interactions between nine drugs (baclofen, bupivacaine, chlorpheniramine, ketoconazole, paliperidone, promethazine, propranolol, risperidone and verapamil) and six cyclodextrins (α-CD, β-CD, γ-CD, HP-β-CD, HP-γ-CD and Me-β-CD) or six polymers of cyclodextrins (polyα-CD, polyβ-CD, polyγ-CD, polyHP-β-CD, polyHP-γ-CD and polyMe-β-CD) were studied by affinity capillary electrophoresis and/or (1)H NMR at pH 2.5. An exhaustive qualitative study was performed through the determination of the retardation factor. Then, four compounds and both β-CD and polyβ-CD were selected for the quantitative study of the interactions at pH 2.5 and 7.0. By comparing the results obtained with the β-CD and polyβ-CD, it appears that the apparent binding constants are up to five times higher with the polymer. The 2D-NMR results seem to indicate that the structure of the polymeric network favours the inclusion of the guest in the hydrophobic cavity of the CD units. Moreover, the poly-CDs have shown very high enantioselective abilities at both pH.

  12. Tautomeric ratio and prototropic equilibrium constants of tenoxicam, a 1H and 13C NMR theoretical and experimental study.

    PubMed

    Franco-Pérez, Marco; Moya-Hernández, Rosario; Rojas-Hernández, Alberto; Gutiérrez, Atilano; Gómez-Balderas, Rodolfo

    2011-11-24

    The determination of the micro-equilibrium prototropic constants is often a tough task when the tautomeric ratio favors one of the species or when the chemical exchange is not slow enough to allow the quantitative detection of the tautomeric species. There are just few experimental methods available to reveal the constants of the tautomeric micro-equilibriums; its applicability depends on the nature of the tautomeric system. A combination of experimental and quantum chemistry calculated (1)H and (13)C NMR chemical shifts is presented here to estimate the population of the species participating in the tautomeric equilibriums of the tenoxicam, an important anti-inflammatory drug. A multivariate fitting of a fraction-mol-weighted contribution model, for the NMR chemical shifts of the species in solution, was used to find the populations of the tautomers of tenoxicam. To consider and evaluate the effect of the solvent polarity on the tautomers' populations, experimental determinations were carried out in DMSO-d(6), in an equimolar DMSO-H(2)O mixture of deuterated solvents and in D(2)O. Additionally, by employing HYPNMR, it has been possible to refine the acid-base macroscopic constants of tenoxicam.

  13. Global Metabolic Stress of Isoeffort Continuous and High Intensity Interval Aerobic Exercise: A Comparative (1)H NMR Metabonomic Study.

    PubMed

    Zafeiridis, Andreas; Chatziioannou, Anastasia Chrysovalantou; Sarivasiliou, Haralambos; Kyparos, Antonios; Nikolaidis, Michalis G; Vrabas, Ioannis S; Pechlivanis, Alexandros; Zoumpoulakis, Panagiotis; Baskakis, Constantinos; Dipla, Konstantina; Theodoridis, Georgios A

    2016-12-02

    The overall metabolic/energetic stress that occurs during an acute bout of exercise is proposed to be the main driving force for long-term training adaptations. Continuous and high-intensity interval exercise protocols (HIIE) are currently prescribed to acquire the muscular and metabolic benefits of aerobic training. We applied (1)H NMR-based metabonomics to compare the overall metabolic perturbation and activation of individual bioenergetic pathways of three popular aerobic exercises matched for effort/strain. Nine men performed continuous, long-interval (3 min), and short-interval (30 s) bouts of exercise under isoeffort conditions. Blood was collected before and after exercise. The multivariate PCA and OPLS-DA models showed a distinct separation of pre- and postexercise samples in three protocols. The two models did not discriminate the postexercise overall metabolic profiles of the three exercise types. Analysis focused on muscle bioenergetic pathways revealed an extensive upregulation of carbohydrate-lipid metabolism and the TCA cycle in all three protocols; there were only a few differences among protocols in the postexercise abundance of molecules when long-interval bouts were performed. In conclusion, continuous and HIIE exercise protocols, when performed with similar effort/strain, induce comparable global metabolic response/stress despite their marked differences in work-bout intensities. This study highlights the importance of NMR metabonomics in comprehensive monitoring of metabolic consequences of exercise training in the blood of athletes and exercising individuals.

  14. Benzocaine complexation with p-sulfonic acid calix[n]arene: experimental ((1) H-NMR) and theoretical approaches.

    PubMed

    Arantes, Lucas M; Varejão, Eduardo V V; Pelizzaro-Rocha, Karin J; Cereda, Cíntia M S; de Paula, Eneida; Lourenço, Maicon P; Duarte, Hélio A; Fernandes, Sergio A

    2014-05-01

    The aim of this work was to study the interaction between the local anesthetic benzocaine and p-sulfonic acid calix[n]arenes using NMR and theoretical calculations and to assess the effects of complexation on cytotoxicity of benzocaine. The architectures of the complexes were proposed according to (1) H NMR data (Job plot, binding constants, and ROESY) indicating details on the insertion of benzocaine in the cavity of the calix[n]arenes. The proposed inclusion compounds were optimized using the PM3 semiempirical method, and the electronic plus nuclear repulsion energy contributions were performed at the DFT level using the PBE exchange/correlation functional and the 6-311G(d) basis set. The remarkable agreement between experimental and theoretical approaches adds support to their use in the structural characterization of the inclusion complexes. In vitro cytotoxic tests showed that complexation intensifies the intrinsic toxicity of benzocaine, possibly by increasing the water solubility of the anesthetic and favoring its partitioning inside of biomembranes.

  15. Characterization of Chinese liquor starter, "Daqu", by flavor type with 1H NMR-based nontargeted analysis.

    PubMed

    Wu, Xiao-He; Zheng, Xiao-Wei; Han, Bei-Zhong; Vervoort, Jacques; Nout, M J Robert

    2009-12-09

    "Daqu" is a fermentation starter and substrate complex that is used to initiate fermentations for the production of Chinese liquor (alcoholic spirit). Several different types of Daqu are customary used, having different flavours, i.e. light, strong, or sauce flavor. With the aim to develop objective methods to characterize and distinguish such different types of Daqu, nontargeted analyses of extracts from three typical flavor types of Daqu were carried out using (1)H nuclear magnetic resonance (NMR) spectroscopy. A significant separation of spectra of Daqu of light-flavor, strong-flavor and sauce-flavor types was achieved using principal components analysis. The separation could be attributed to higher levels of glycerol, malate, acetate and N-acetylglutamine in light-flavor Daqu; higher levels of mannitol, betaine, trimethylamine and pyroglutamate in strong-flavor Daqu; and higher levels of lactate, isoleucine, leucine, isovalerate and valine in sauce-flavor Daqu. These metabolites were regarded as the representative metabolites or biomarkers characteristic for each type of Daqu and could be associated with some of the microorganisms that have been reported in Daqu. This study highlights the application of nontargeted analysis techniques based on NMR in process research and quality control in Daqu production and liquor fermentation.

  16. 1H NMR Spectroscopy and Multivariate Analysis of Monovarietal EVOOs as a Tool for Modulating Coratina-Based Blends

    PubMed Central

    Del Coco, Laura; De Pascali, Sandra Angelica; Fanizzi, Francesco Paolo

    2014-01-01

    Coratina cultivar-based olives are very common among 100% Italian extra virgin olive oils (EVOOs). Often, the very spicy character of this cultivar, mostly due to the high polyphenols concentration, requires blending with other “sweetener” oils. In this work, monovarietal EVOO samples from the Coratina cultivar (Apulia, Italy) were investigated and compared with monovarietal EVOO from native or recently introduced Apulian (Italy) cultivars (Ogliarola Garganica, Ogliarola Barese, Cima di Mola, Peranzana, Picholine), from Calabria (Italy) (Carolea and Rossanese) and from other Mediterranean countries, such as Spain (Picual) and Greece (Kalamata and Koroneiki) by 1H NMR spectroscopy and multivariate analysis (principal component analysis (PCA)). In this regard, NMR signals could allow a first qualitative evaluation of the chemical composition of EVOO and, in particular, of its minor component content (phenols and aldehydes), an intrinsic behavior of EVOO taste, related to the cultivar and geographical origins. Moreover, this study offers an opportunity to address blended EVOOs tastes by using oils from a specific region or country of origin. PMID:28234316

  17. (1)H NMR based metabolomics approach to study the toxic effects of herbicide butachlor on goldfish (Carassius auratus).

    PubMed

    Xu, Hua-Dong; Wang, Jun-Song; Li, Ming-Hui; Liu, Yan; Chen, Ting; Jia, Ai-Qun

    2015-02-01

    Butachlor, one of the most widely used herbicides in agriculture, has been reported with high ecotoxicity to aquatic plants and animals. In this study, a (1)H NMR based metabolomics approach combined with histopathological examination and biochemical assays was applied to comprehensively investigate the toxic effects of butachlor on four important organs (gill, brain, liver and kidney) of goldfish (Carassius auratus) for the first time. After 10 days' butachlor exposure at two dosages of 3.2 and 0.64 μmol/L, fish tissues (gill, brain, liver and kidney) and serum were collected. Histopathological inspection revealed severe impairment of gill filaments and obvious cellular edema in livers and kidneys. The increase of glutathione peroxidase (GSH-Px) activity in gill and methane dicarboxylic aldehyde (MDA) level in four tissues reflected the disturbance of antioxidative system in the intoxicated goldfish. Serum lactate dehydrogenase (LDH) activity and creatinine (CRE) level were increased in butachlor exposure groups, suggesting liver and kidney injuries induced by butachlor. Orthogonal signal correction partial least-squares discriminant analysis (OSC-PLS-DA) of NMR profiles disclosed metabolic changes that were related to the toxic effects of butachlor including oxidative stress, disorder of energy metabolism and amino acids metabolism, and disturbance of neurotransmitter balance in butachlor exposed goldfish. This integrated metabolomics approach provided a molecular basis underlying the toxicity of butachlor and demonstrated that metabolomics was a powerful and highly effective approach to elucidate the toxicity and underlying mechanisms of herbicides and pesticides, applicable for their risk assessment.

  18. Rapid milk group classification by 1H NMR analysis of Le and H epitopes in human milk oligosaccharide donor samples.

    PubMed

    van Leeuwen, Sander S; Schoemaker, Ruud J W; Gerwig, Gerrit J; van Leusen-van Kan, Ellen J M; Dijkhuizen, Lubbert; Kamerling, Johannis P

    2014-08-01

    Human milk oligosaccharides (HMOs) are a major constituent of human breast milk and play an important role in reducing the risk of infections in infants. The structures of these HMOs show similarities with blood group antigens in protein glycosylation, in particular in relation to fucosylation in Lewis blood group-type epitopes, matching the maternal pattern. Previously, based on the Secretor and Lewis blood group system, four milk groups have been defined, i.e. Lewis-positive Secretors, Lewis-positive non-Secretors, Lewis-negative Secretors and Lewis-negative non-Secretors. Here, a rapid one-dimensional (1)H nuclear magnetic resonance (NMR) analysis method is presented that identifies the presence/absence of (α1-2)-, (α1-3)- and (α1-4)-linked fucose residues in HMO samples, affording the essential information to attribute different HMO samples to a specific milk group. The developed method is based on the NMR structural-reporter-group concept earlier established for glycoprotein glycans. Further evaluation of the data obtained from the analysis of 36 HMO samples shows that within each of the four milk groups the relative levels of the different fucosylation epitopes can greatly vary. The data also allow a separation of the Lewis-positive Secretor milk group into two sub-groups.

  19. Water distribution in brine salted cod (Gadus morhua) and salmon (Salmo salar): a low-field 1H NMR study.

    PubMed

    Aursand, Ida G; Gallart-Jornet, Lorena; Erikson, Ulf; Axelson, David E; Rustad, Turid

    2008-08-13

    Low-field (LF) (1)H NMR T 2 relaxation measurements were used to study changes in water distribution in lean (Atlantic cod) and fatty (Atlantic salmon) fish during salting in 15% NaCl and 25% NaCl brines. The NMR data were treated by PCA, continuous distribution analysis, and biexponential fitting and compared with physicochemical data. Two main water pools were observed in unsalted fish, T 21, with relaxation times in the range 20-100 ms, and T 22, with relaxation times in the range 100-300 ms. Pronounced changes in T 2 relaxation data were observed during salting, revealing changes in the water properties. Salting in 15% brine lead to a shift toward longer relaxation times, reflecting increased water mobility, whereas, salting in saturated brines had the opposite effect. Water mobility changes were observed earlier in the salting process for cod compared to salmon. Good linear correlations ( F

  20. (1)H-NMR-based metabolomic analysis of the effect of moderate wine consumption on subjects with cardiovascular risk factors.

    PubMed

    Vázquez-Fresno, Rosa; Llorach, Rafael; Alcaro, Francesca; Rodríguez, Miguel Ángel; Vinaixa, Maria; Chiva-Blanch, Gemma; Estruch, Ramon; Correig, Xavier; Andrés-Lacueva, Cristina

    2012-08-01

    Moderate wine consumption is associated with health-promoting activities. An H-NMR-based metabolomic approach was used to identify urinary metabolomic differences of moderate wine intake in the setting of a prospective, randomized, crossover, and controlled trial. Sixty-one male volunteers with high cardiovascular risk factors followed three dietary interventions (28 days): dealcoholized red wine (RWD) (272mL/day, polyphenol control), alcoholized red wine (RWA) (272mL/day) and gin (GIN) (100mL/day, alcohol control). After each period, 24-h urine samples were collected and analyzed by (1) H-NMR. According to the results of a one-way ANOVA, significant markers were grouped in four categories: alcohol-related markers (ethanol); gin-related markers; wine-related markers; and gut microbiota markers (hippurate and 4-hydroxphenylacetic acid). Wine metabolites were classified into two groups; first, metabolites of food metabolome: tartrate (RWA and RWD), ethanol, and mannitol (RWA); and second, biomarkers that relates to endogenous modifications after wine consumption, comprising branched-chain amino acid (BCAA) metabolite (3-methyl-oxovalerate). Additionally, a possible interaction between alcohol and gut-related biomarkers has been identified. To our knowledge, this is the first time that this approach has been applied in a nutritional intervention with red wine. The results show the capacity of this approach to obtain a comprehensive metabolome picture including food metabolome and endogenous biomarkers of moderate wine intake.

  1. Positional Enrichment by Proton Analysis (PEPA): A One-Dimensional (1) H-NMR Approach for (13) C Stable Isotope Tracer Studies in Metabolomics.

    PubMed

    Vinaixa, Maria; Rodríguez, Miguel A; Aivio, Suvi; Capellades, Jordi; Gómez, Josep; Canyellas, Nicolau; Stracker, Travis H; Yanes, Oscar

    2017-03-20

    A novel metabolomics approach for NMR-based stable isotope tracer studies called PEPA is presented, and its performance validated using human cancer cells. PEPA detects the position of carbon label in isotopically enriched metabolites and quantifies fractional enrichment by indirect determination of (13) C-satellite peaks using 1D-(1) H-NMR spectra. In comparison with (13) C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of (13) C positions in labeled metabolites and the quantification of the percentage of stable isotope enrichment. Altogether, PEPA provides a novel framework for extending the high-throughput of (1) H-NMR metabolic profiling to stable isotope tracing in metabolomics, facilitating and complementing the information derived from 2D-NMR experiments and expanding the range of isotopically enriched metabolites detected in cellular extracts.

  2. 1H and 13C NMR chemical shift assignments of spiro-cycloalkylidenehomo- and methanofullerenes by the DFT-GIAO method.

    PubMed

    Khalilov, L M; Tulyabaev, A R; Yanybin, V M; Tuktarov, A R

    2011-06-01

    The (1)H and (13)C NMR chemical shifts of spiro-cycloalkylidene[60]fullerenes were assigned using experimental NMR data and the Density Functional Theory (DFT)-Gauge Independence Of Atomic Orbitals method (GAIO) calculation method in the Perdew Burke Ernzerhof (PBE)/3z approach. The calculated values of the (13)C NMR chemical shifts adequately reproduce the experimental values at this quantum chemistry approach. Similar assignments will be helpful for (13)C NMR spectral analysis of homo- and methano[60]fullerene derivatives for structure elucidation and to determine the influence of fullerene frames on substituents and the influence of substituents on fullerene cores.

  3. Inverse nonionic microemulsion studied by means of 1H, 13C, and PGSTE NMR during silica nanoparticle synthesis.

    PubMed

    Asaro, Fioretta; Benedetti, Alvise; Savko, Nina; Pellizer, Giorgio

    2009-03-03

    The soluble species present in the reaction mixture that leads to silica nanoparticle production through the base catalyzed hydrolysis of tetraethyl orthosilicate (TEOS) and the successive condensation were investigated in situ, under the actual synthesis conditions, by means of 1H, 13C, and 29Si NMR spectroscopy. The two former nuclei, owing to higher sensitivity and their presence both in the reacting species and in the constituents of the W/O microemulsion (cyclohexane-igepal-CA-520-concentrated ammonia solution) afforded insight into the inverse microemulsion and allowed us to assess the kinetic rate of the hydrolysis step. It was verified that the microemulsion microstructure is maintained during the reaction. The characterization of the final nanoparticles was carried out by means of transmission electron microscopy (TEM). Special attention was paid to the reaction medium, and an extended assignment of the 1H and 13C resonances of the surfactant headgroup is reported together with the discussion of the changes they undergo due to the environmental modifications induced by transition from cyclohexane solution to W/O microemulsion and further to NH3 containing W/O microemulsion. The self-diffusion coefficient measurements revealed that NH3 exchanges among the inverse micelles diffusing through cyclohexane and confirmed that the preferred localization for ethanol, a byproduct of the reaction, is the bulk oil.

  4. Dynamic structures of intact chicken erythrocyte chromatins as studied by 1H-31P cross-polarization NMR.

    PubMed Central

    Akutsu, H; Nishimoto, S; Kyogoku, Y

    1994-01-01

    The dynamic properties of DNA in intact chicken erythrocyte cells, nuclei, nondigested chromatins, digested soluble chromatins, H1, H5-depleted soluble chromatins and nucleosome cores were investigated by means of single-pulse and 1H-31P cross-polarization NMR. The temperature dependence of the phosphorus chemical shift anisotropy was identical for the former three in the presence of 3 mM MgCl2, suggesting that the local higher order structure is identical for these chromatins. The intrinsic phosphorus chemical shift anisotropy of the nucleosome cores was -159 ppm. The chemical shift anisotropy of DNA in the chromatins can be further averaged by the motion of the linker DNA. The spin-lattice relaxation time in the rotating frame of the proton spins (T1p) of the nondigested chromatins was measured at various locking fields. The result was analyzed on the assumption of the isotropic motion to get a rough value of the correlation time of the motion efficient for the relaxation, which was eventually ascribed to the segmental motion of the linker DNA with restricted amplitude. The 30 nm filament structure induced by NaCl was shown to be dynamically different from that induced by MgCl2. Side-by-side compaction of 30-nm filaments was suggested to be induced in the MgCl2 concentration range higher than 0.3 mM. Biological significance of the dynamic structure was discussed in connection with the results obtained. PMID:7948693

  5. The identification of vicinally substituted cyclohexane isomers in their mixtures by 1H and 13C NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Laihia, Katri; Kolehmainen, Erkki; Nevalainen, Tapio; Kauppinen, Reijo; Vasilieva, Tamara T.; Terentiev, Alexander B.

    2000-02-01

    The radical addition reactions of organobromine compounds, XBr (X=CH 2COOMe, PhCH 2, CHBr 2 and CCl 3) with cyclohexene afforded mixtures of cis/ trans isomer pairs of 1-X-2-Br-cyclohexanes. In addition to benzyl benzoyloxy derivatives are formed also, when benzoyl peroxide is used as an initiator. Owing to the great difficulties in separating these cis/ trans isomer pairs, they are identified directly in their mixtures by NMR spectroscopy. In addition to one-dimensional (1D) 1H, proton decoupled 13C and DEPT-135, also two-dimensional (2D) 13C- 13C INADEQUATE as well as 1H- 13C HMQC experiments have been used in assigning the signals of each compound in their mixtures. The identification of each isomer was based on comparison of experimental 3JH,H coupling constants with theoretical ones based on the well-known Karplus type relationship. The more stable conformation for each isomer was estimated using the semiempirical AM1 molecular orbital method. The calculations support the isomer pair elucidations.

  6. Intermolecular triple proton and deuteron transfer in crystalline 3,5-dimethylpyrazole studied by NMR, NQR, and x-ray methods

    SciTech Connect

    Wehrle, B.; Aguilar-Parrilla, F.; Limbach, H.H. ); de la Concepcion Foces-Foces, M.; Cano, F.H. ); Elguero, J. ); Baldy, A.; Pierrot, M. ); Khurshid, M.M.T.; Larcombe-McDouall, J.B.; Smith, J.A.S. )

    1989-09-13

    A combination of {sup 13}C, {sup 15}N magnetic resonance, {sup 14}N quadrupole double resonance, and x-ray studies of solid 3,5-dimethylpyrazole between 270 and 350 K has shown that the NH...N hydrogen bond units present in the crystal are dynamically disordered, so that each nitrogen atom is on average attached to half a hydrogen atom. The molecules form discrete hydrogen-bonded cyclic trimers, in which the hydrogen atoms move in a double minimum potential energy surface which is symmetrical, to within experimental error. The experimental evidence in this temperature range is consistent with disorder by means of correlated triple hydrogen jumps with an activation energy of 45 kJ mol{sup {minus}1}. There is a large kinetic hydrogen (HHH)/deuterium (DDD) isotope effort of >20 at 299 K and equal to 8 at 347 K.

  7. The relation of the X-ray B-factor to protein dynamics: insights from recent dynamic solid-state NMR data.

    PubMed

    Reichert, Detlef; Zinkevich, Tatiana; Saalwächter, Kay; Krushelnitsky, Alexey

    2012-01-01

    In addressing the potential use of B-factors derived from X-ray scattering data of proteins for the understanding the (functional) dynamics of proteins, we present a comparison of B-factors of five different proteins (SH3 domain, Crh, GB1, ubiquitin and thioredoxin) with data from recent solid-state nuclear magnetic resonance experiments reflecting true (rotational) dynamics on well-defined timescales. Apart from trivial correlations involving mobile loop regions and chain termini, we find no significant correlation of B-factors with the dynamic data on any of the investigated timescales, concluding that there is no unique and general correlation of B-factors with the internal reorientational dynamics of proteins.

  8. Proton-detected 3D (15)N/(1)H/(1)H isotropic/anisotropic/isotropic chemical shift correlation solid-state NMR at 70kHz MAS.

    PubMed

    Pandey, Manoj Kumar; Yarava, Jayasubba Reddy; Zhang, Rongchun; Ramamoorthy, Ayyalusamy; Nishiyama, Yusuke

    2016-01-01

    Chemical shift anisotropy (CSA) tensors offer a wealth of information for structural and dynamics studies of a variety of chemical and biological systems. In particular, CSA of amide protons can provide piercing insights into hydrogen-bonding interactions that vary with the backbone conformation of a protein and dynamics. However, the narrow span of amide proton resonances makes it very difficult to measure (1)H CSAs of proteins even by using the recently proposed 2D (1)H/(1)H anisotropic/isotropic chemical shift (CSA/CS) correlation technique. Such difficulties due to overlapping proton resonances can in general be overcome by utilizing the broad span of isotropic chemical shifts of low-gamma nuclei like (15)N. In this context, we demonstrate a proton-detected 3D (15)N/(1)H/(1)H CS/CSA/CS correlation experiment at fast MAS frequency (70kHz) to measure (1)H CSA values of unresolved amide protons of N-acetyl-(15)N-l-valyl-(15)N-l-leucine (NAVL).

  9. The metabolism of 2-trifluormethylaniline and its acetanilide in the rat by 19F NMR monitored enzyme hydrolysis and 1H/19F HPLC-NMR spectroscopy.

    PubMed

    Tugnait, M; Lenz, E M; Hofmann, M; Spraul, M; Wilson, I D; Lindon, J C; Nicholson, J K

    2003-01-01

    The urinary excretion profile and identity of the metabolites of 2-trifluoromethyl aniline (2-TFMA) and 2-trifluoromethyl acetanilide (2-TFMAc), following i.p. administration to the rat at 50 mg kg(-1), were determined using a combination of 19F NMR monitored enzyme hydrolysis, SPEC-MS and 19F/1H HPLC-NMR. A total recovery of approximately 96.4% of the dose was excreted into the urine as seven metabolites. The major routes of metabolism were N-conjugation (glucuronidation), and ring-hydroxylation followed by sulphation (and to a lesser extent glucuronidation). The major metabolites excreted into the urine for both compounds were a labile N-conjugated metabolite (a postulated N-glucuronide) and a sulphated ring-hydroxylated metabolite (a postulated 4-amino-5-trifluoromethylphenyl sulphate) following dosing of 2-TFMA. These accounted for approximately 53.0 and 31.5% of the dose, respectively. This study identifies problems on sample component instability in the preparation and analysis procedures.

  10. Heterocyclization of enediynes promoted by sodium azide: a case of ambiguity of X-ray data and structure revision.

    PubMed

    Gulevskaya, Anna V; Tyaglivy, Alexander S; Pozharskii, Alexander F; Nelina-Nemtseva, Julia I; Steglenko, Dmitry V

    2014-03-21

    It has been shown that contrary to the literature data the tandem cyclization of (Z)-1-aryl-3-hexen-1,5-diynes promoted by sodium azide results in the formation of the corresponding [1,2,3]triazolo[1,5-a]pyridines, not 1H-benzotriazole derivatives. Apparently, incorrect structure elucidation made by previous investigators originates from misinterpretation of X-ray data. A number of new transformations of this type as well as X-ray and NMR experiments are discussed.

  11. The influence of membrane electrode assembly water content on the performance of a polymer electrolyte membrane fuel cell as investigated by 1H NMR microscopy.

    PubMed

    Feindel, Kirk W; Bergens, Steven H; Wasylishen, Roderick E

    2007-04-21

    The relation between the performance of a self-humidifying H(2)/O(2) polymer electrolyte membrane fuel cell and the amount and distribution of water as observed using (1)H NMR microscopy was investigated. The integrated (1)H NMR image signal intensity (proportional to water content) from the region of the polymer electrolyte membrane between the catalyst layers was found to correlate well with the power output of the fuel cell. Several examples are provided which demonstrate the sensitivity of the (1)H NMR image intensity to the operating conditions of the fuel cell. Changes in the O(2)(g) flow rate cause predictable trends in both the power density and the image intensity. Higher power densities, achieved by decreasing the resistance of the external circuit, were found to increase the water in the PEM. An observed plateau of both the power density and the integrated (1)H NMR image signal intensity from the membrane electrode assembly and subsequent decline of the power density is postulated to result from the accumulation of H(2)O(l) in the gas diffusion layer and cathode flow field. The potential of using (1)H NMR microscopy to obtain the absolute water content of the polymer electrolyte membrane is discussed and several recommendations for future research are provided.

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

    NASA Astrophysics Data System (ADS)

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

    2002-07-01

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

  13. 2D-NMR, X-ray crystallography and theoretical studies of the reaction mechanism for the synthesis of 1,5-benzodiazepines from dehydroacetic acid derivatives and o-phenylenediamines

    NASA Astrophysics Data System (ADS)

    Rabahi, Amal; Hamdi, Safouane M.; Rachedi, Yahia; Hamdi, Maamar; Talhi, Oualid; Almeida Paz, Filipe A.; Silva, Artur S. M.; Fadila, Balegroune; Malika, Hamadène; Kamel, Taïbi

    2014-03-01

    The synthesis of 1,5-benzodiazepines by the reaction of o-phenylenediamines (o-PDAs) with dehydroacetic acid DHAA [3-acetyl-4-hydroxy-6-methyl-2H-pyran-2-one] or conjugate analogues is largely reported in the literature, but still with uncontrolled stereochemistry. In this work, a comprehensive mechanistic study on the formation of some synthesized 1,5-benzodiazepine models following different organic routes is established based on liquid-state 2D NMR, single-crystal X-ray diffraction and theoretical calculations allowing the classification of two prototropic forms A (enaminopyran-2,4-dione) and B (imino-4-hydroxypyran-2-one). Evidences are presented to show that most of the reported 1,5-benzodiazepine structures arising from DHAA and derivatives preferentially adopt the (E)-enaminopyran-2,4-diones A.

  14. Investigation of structural and dynamic properties of NH 4[N(CN) 2] by means of X-ray and neutron powder diffraction as well as vibrational and solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Lotsch, Bettina V.; Senker, Jürgen; Kockelmann, Winfried; Schnick, Wolfgang

    2003-11-01

    The crystal structure, spectroscopic and thermal properties of ammonium dicyanamide NH 4[N(CN) 2] have been thoroughly investigated by means of temperature-dependent single-crystal X-ray and neutron powder diffraction, vibrational and MAS-NMR spectroscopy as well as thermoanalytical measurements. The comprehensive elucidation of structural details is of special interest with respect to the unique solid-state transformation of ammonium dicyanamide into dicyandiamide. This reaction occurs at temperatures >80°C and it represents the isolobal analogue of Wöhler's historic transformation of ammonium cyanate into urea. NH 4[N(CN) 2] crystallizes in the monoclinic space group P2 1/ c with lattice constants a=3.7913(8), b=12.412(2), c=9.113(2) Å, β=91.49(2)° and Z=4 (single-crystal X-ray data, T=200 K). The temperature dependence of the lattice constants shows anisotropic behavior, however, no evidence for phase transitions in the investigated temperature range was observed. The hydrogen positions could be localized by neutron diffraction (10-370 K), and the temperature-dependent behavior of the ammonium group has been analyzed by Rietveld refinements using anisotropic thermal displacement parameters. They were interpreted by utilizing a rigid body model and extracting the libration and translation matrices of the ammonium ion by applying the TLS formalism. The results obtained by the diffraction methods were confirmed and supplemented by vibrational spectroscopy and solid-state 15N and 13C MAS-NMR investigations.

  15. Clocking femtosecond X rays.

    PubMed

    Cavalieri, A L; Fritz, D M; Lee, S H; Bucksbaum, P H; Reis, D A; Rudati, J; Mills, D M; Fuoss, P H; Stephenson, G B; Kao, C C; Siddons, D P; Lowney, D P; Macphee, A G; Weinstein, D; Falcone, R W; Pahl, R; Als-Nielsen, J; Blome, C; Düsterer, S; Ischebeck, R; Schlarb, H; Schulte-Schrepping, H; Tschentscher, Th; Schneider, J; Hignette, O; Sette, F; Sokolowski-Tinten, K; Chapman, H N; Lee, R W; Hansen, T N; Synnergren, O; Larsson, J; Techert, S; Sheppard, J; Wark, J S; Bergh, M; Caleman, C; Huldt, G; van der Spoel, D; Timneanu, N; Hajdu, J; Akre, R A; Bong, E; Emma, P; Krejcik, P; Arthur, J; Brennan, S; Gaffney, K J; Lindenberg, A M; Luening, K; Hastings, J B

    2005-03-25

    Linear-accelerator-based sources will revolutionize ultrafast x-ray science due to their unprecedented brightness and short pulse duration. However, time-resolved studies at the resolution of the x-ray pulse duration are hampered by the inability to precisely synchronize an external laser to the accelerator. At the Sub-Picosecond Pulse Source at the Stanford Linear-Accelerator Center we solved this problem by measuring the arrival time of each high energy electron bunch with electro-optic sampling. This measurement indirectly determined the arrival time of each x-ray pulse relative to an external pump laser pulse with a time resolution of better than 60 fs rms.

  16. Simultaneous Analysis of Major Coenzymes of Cellular Redox Reactions and Energy Using ex Vivo (1)H NMR Spectroscopy.

    PubMed

    Nagana Gowda, G A; Abell, Lauren; Lee, Chi Fung; Tian, Rong; Raftery, Daniel

    2016-05-03

    Coenzymes of cellular redox reactions and cellular energy mediate biochemical reactions fundamental to the functioning of all living cells. Despite their immense interest, no simple method exists to gain insights into their cellular concentrations in a single step. We show that a simple (1)H NMR experiment can simultaneously measure oxidized and reduced forms of nicotinamide adenine dinucleotide (NAD(+) and NADH), oxidized and reduced forms of nicotinamide adenine dinucleotide phosphate (NADP(+) and NADPH), and adenosine triphosphate (ATP) and its precursors, adenosine diphosphate (ADP) and adenosine monophosphate (AMP), using mouse heart, kidney, brain, liver, and skeletal muscle tissue extracts as examples. Combining 1D/2D NMR experiments, chemical shift libraries, and authentic compound data, reliable peak identities for these coenzymes have been established. To assess this methodology, cardiac NADH and NAD(+) ratios/pool sizes were measured using mouse models with a cardiac-specific knockout of the mitochondrial Complex I Ndufs4 gene (cKO) and cardiac-specific overexpression of nicotinamide phosphoribosyltransferase (cNAMPT) as examples. Sensitivity of NAD(+) and NADH to cKO or cNAMPT was observed, as anticipated. Time-dependent investigations showed that the levels of NADH and NADPH diminish by up to ∼50% within 24 h; concomitantly, NAD(+) and NADP(+) increase proportionately; however, degassing the sample and flushing the sample tubes with helium gas halted such changes. The analysis protocol along with the annotated characteristic fingerprints for each coenzyme is provided for easy identification and absolute quantification using a single internal reference for routine use. The ability to visualize the ubiquitous coenzymes fundamental to cellular functions, simultaneously and reliably, offers a new avenue to interrogate the mechanistic details of cellular function in health and disease.

  17. Simultaneous Analysis of Major Coenzymes of Cellular Redox Reactions and Energy Using ex Vivo 1H NMR Spectroscopy

    PubMed Central

    2016-01-01

    Coenzymes of cellular redox reactions and cellular energy mediate biochemical reactions fundamental to the functioning of all living cells. Despite their immense interest, no simple method exists to gain insights into their cellular concentrations in a single step. We show that a simple 1H NMR experiment can simultaneously measure oxidized and reduced forms of nicotinamide adenine dinucleotide (NAD+ and NADH), oxidized and reduced forms of nicotinamide adenine dinucleotide phosphate (NADP+ and NADPH), and adenosine triphosphate (ATP) and its precursors, adenosine diphosphate (ADP) and adenosine monophosphate (AMP), using mouse heart, kidney, brain, liver, and skeletal muscle tissue extracts as examples. Combining 1D/2D NMR experiments, chemical shift libraries, and authentic compound data, reliable peak identities for these coenzymes have been established. To assess this methodology, cardiac NADH and NAD+ ratios/pool sizes were measured using mouse models with a cardiac-specific knockout of the mitochondrial Complex I Ndufs4 gene (cKO) and cardiac-specific overexpression of nicotinamide phosphoribosyltransferase (cNAMPT) as examples. Sensitivity of NAD+ and NADH to cKO or cNAMPT was observed, as anticipated. Time-dependent investigations showed that the levels of NADH and NADPH diminish by up to ∼50% within 24 h; concomitantly, NAD+ and NADP+ increase proportionately; however, degassing the sample and flushing the sample tubes with helium gas halted such changes. The analysis protocol along with the annotated characteristic fingerprints for each coenzyme is provided for easy identification and absolute quantification using a single internal reference for routine use. The ability to visualize the ubiquitous coenzymes fundamental to cellular functions, simultaneously and reliably, offers a new avenue to interrogate the mechanistic details of cellular function in health and disease. PMID:27043450

  18. Haemolymph from Mytilus galloprovincialis: Response to copper and temperature challenges studied by (1)H-NMR metabonomics.

    PubMed

    Digilio, Giuseppe; Sforzini, Susanna; Cassino, Claudio; Robotti, Elisa; Oliveri, Caterina; Marengo, Emilio; Musso, Davide; Osella, Domenico; Viarengo, Aldo

    2016-01-01

    Numerous studies on molluscs have been carried out to clarify the physiological roles of haemolymph serum proteins and haemocytes. However, little is known about the presence and functional role of the serum metabolites. In this study, Nuclear Magnetic Resonance (NMR) was used to assess whether changes of the metabolic profile of Mytilus galloprovincialis haemolymph may reflect alterations of the physiological status of the organisms due to environmental stressors, namely copper and temperature. Mussel haemolymph was taken from the posterior adductor muscle after a 4-day exposure to ambient (16 °C) or high temperature (24 °C) and in the absence or presence (5 μg/L, 20 μg/L, or 40 μg/L) of sublethal copper (Cu(2+)). The total glutathione (GSH) concentration in the haemolymph of both control and treated mussels was minimal, indicating the absence of significant contaminations by muscle intracellular metabolites due to the sampling procedure. In the (1)H-NMR spectrum of haemolymph, 27 metabolites were identified unambiguously. The separate and combined effects of exposure to copper and temperature on the haemolymph metabolic profile were assessed by Principal Component Analysis (PCA) and Ranking-PCA multivariate analysis. Changes of the metabolomic profile due to copper exposure at 16 °C became detectable at a dose of 20 μg/L copper. Alanine, lysine, serine, glutamine, glycogen, glucose and protein aliphatics played a major role in the classification of the metabolic changes according to the level of copper exposition. High temperature (24 °C) and high copper levels caused a coherent increase of a common set of metabolites (mostly glucose, serine, and lysine), indicating that the metabolic impairment due to high temperature is enforced by the presence of copper. Overall, the results demonstrate that, as for human blood plasma, the analysis of haemolymph metabolites represents a promising tool for the diagnosis of pollutant-induced stress syndrome in marine