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Sample records for state 13c nmr

  1. 13C solid state NMR investigation of natural resins components

    International Nuclear Information System (INIS)

    Tavares, Maria I.B.; Bathista, Andre L.B.S.; Silva, Emerson O.; Priante Filho, Nicolau; Nogueira, Jose S.

    2001-01-01

    The objective of this work is to establish and analytical methodology as a routine using solid state nuclear magnetic resonance (NMR) techniques to investigate the mainly chemical components presented in natural resins in bulk. And also to evaluate the molecular behaviour of these resins. The routine solid state techniques allow us to assign the main compounds presented in the resins. Therefore, applying specialised techniques, like variable contact time, delayed contact time, dephasing time and proton spin lattice relaxation time in the rotating frame (T 1 H ρ), more information about chemical structure and molecular dynamic is available

  2. Solid-state 13C NMR characterization of polyanilines

    International Nuclear Information System (INIS)

    Kaplan, S.

    1988-01-01

    13 C solid-state nuclear magnetic resonance measurements are reported for the leucoemeraldine base, emeraldine base, and emeraldine hydrochloride forms of polyaniline in order to characterize the structures of these three distinct polymers. Chemical shift assignments are facilitated by use of the cross-depolarization technique to distinguish carbons with and without directly bonded hydrogens. Comparison of the spectra of emeraldine base with those of leucoemeraldine base and air-oxidized leucoemeraldine (which partially converts to emeraldine base) establishes that emeraldine base is essentially an alternating copolymer of reduced 1A (-(C 6 H 4 )N(H)(C 6 H 4 )N(H)-) and oxidized 2A (-(C 6 H 4 )N double-bond(C 6 H 4 )double-bond N-) repeat units. The 8-12 ppm spectral line widths measured for both emeraldine base and leucoemeraldine base are attributed to local fluctuations in conformational and configurational geometries, a distribution in chain packing, and compositional defects. 13 C spin-echo measurements establish that the 60 ppM wide line from the conducting emeraldine hydrochloride is inhomogeneously broadened. It is postulated that this line width is due to local variations in charge density along the polymer backbone arising from polymer structural heterogeneity. 47 refs., 5 figs., 1 tab

  3. Solid state 13 C NMR quantitative study of wood tar pitches

    International Nuclear Information System (INIS)

    Prauchner, Marcos Juliano; Pasa, Vanya Marcia Duarte; Menezes, Sonia Maria Cabral de

    1999-01-01

    In this work, solid-state 13 C NMR is used with other techniques to characterize Eucalyptus tar pitches and to follow their polymerization reactions. The pitches are the residues of distillation (about 50% m;m) of the tar generated in Eucalyptus slow pyrolysis for charcoal production in metal industry

  4. Selective and extensive 13C labeling of a membrane protein for solid-state NMR investigations

    International Nuclear Information System (INIS)

    Hong, M.; Jakes, K.

    1999-01-01

    The selective and extensive 13C labeling of mostly hydrophobic amino acid residues in a 25 kDa membrane protein, the colicin Ia channel domain, is reported. The novel 13C labeling approach takes advantage of the amino acid biosynthetic pathways in bacteria and suppresses the synthesis of the amino acid products of the citric acid cycle. The selectivity and extensiveness of labeling significantly simplify the solid-state NMR spectra, reduce line broadening, and should permit the simultaneous measurement of multiple structural constraints. We show the assignment of most 13C resonances to specific amino acid types based on the characteristic chemical shifts, the 13C labeling pattern, and the amino acid composition of the protein. The assignment is partly confirmed by a 2D homonuclear double-quantum-filter experiment under magic-angle spinning. The high sensitivity and spectral resolution attained with this 13C-labeling protocol, which is termed TEASE for ten-amino acid selective and extensive labeling, are demonstrated

  5. (13)C and (15)N solid-state NMR studies on albendazole and cyclodextrin albendazole complexes.

    Science.gov (United States)

    Ferreira, M João G; García, A; Leonardi, D; Salomon, Claudio J; Lamas, M Celina; Nunes, Teresa G

    2015-06-05

    (13)C and (15)N solid-state nuclear magnetic resonance (NMR) spectra were recorded from albendazole (ABZ) and from ABZ:β-cyclodextrin, ABZ:methyl-β-cyclodextrin, ABZ:hydroxypropyl-β-cyclodextrin and ABZ:citrate-β-cyclodextrin, which were prepared by the spray-drying technique. ABZ signals were typical of a crystalline solid for the pure drug and of an amorphous compound obtained from ABZ:cyclodextrin samples. Relevant spectral differences were correlated with chemical interaction between ABZ and cyclodextrins. The number and type of complexes revealed a strong dependence on the cyclodextrin group substituent. Solid-state NMR data were consistent with the presence of stable inclusion complexes. Copyright © 2015 Elsevier Ltd. All rights reserved.

  6. Structural characterization of supramolecular assemblies by {sup 13}C spin dilution and 3D solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Habenstein, Birgit; Loquet, Antoine; Giller, Karin; Becker, Stefan; Lange, Adam, E-mail: adla@nmr.mpibpc.mpg.de [Max Planck Institute for Biophysical Chemistry, Department of NMR-based Structural Biology (Germany)

    2013-01-15

    {sup 13}C spin diluted protein samples can be produced using [1-{sup 13}C] and [2-{sup 13}C]-glucose (Glc) carbon sources in the bacterial growth medium. The {sup 13}C spin dilution results in favorable {sup 13}C spectral resolution and polarization transfer behavior. We recently reported the combined use of [1-{sup 13}C]- and [2-{sup 13}C]-Glc labeling to facilitate the structural analysis of insoluble and non-crystalline biological systems by solid-state NMR (ssNMR), including sequential assignment, detection of long-range contacts and structure determination of macromolecular assemblies. In solution NMR the beneficial properties of sparsely labeled samples using [2-{sup 13}C]-glycerol ({sup 13}C labeled C{alpha} sites on a {sup 12}C diluted background) have recently been exploited to provide a bi-directional assignment method (Takeuchi et al. in J Biomol NMR 49(1):17-26, 2011 ). Inspired by this approach and our own recent results using [2-{sup 13}C]-Glc as carbon sources for the simplification of ssNMR spectra, we present a strategy for a bi-directional sequential assignment of solid-state NMR resonances and additionally the detection of long-range contacts using the combination of {sup 13}C spin dilution and 3D NMR spectroscopy. We illustrate our results with the sequential assignment and the collection of distance restraints on an insoluble and non-crystalline supramolecular assembly, the Salmonella typhimurium type III secretion system needle.

  7. Solid-state 13C magic angle spinning NMR spectroscopy characterization of particle size structural variations in synthetic nanodiamonds

    International Nuclear Information System (INIS)

    Alam, Todd M.

    2004-01-01

    Solid-state 13 C magic angle spinning (MAS) NMR spectroscopy has been used to quantify the different carbon species observed in synthetically produced nanodiamonds. Two different diamond-like carbon species were observed using 13 C MAS NMR, which have been attributed to a highly ordered crystalline diamond phase and a disordered crystalline diamond phase. The relative ratio of these different diamond phases was found to vary with the particle size of the nanodiamond materials

  8. Experiments and strategies for the assignment of fully13 C/15N-labelled polypeptides by solid state NMR

    International Nuclear Information System (INIS)

    Straus, Suzana K.; Bremi, Tobias; Ernst, Richard R.

    1998-01-01

    High-resolution heteronuclear NMR correlation experiments and strategies are proposed for the assignment of fully 13 C/ 15 N-labelled polypeptides in the solid state. By the combination of intra-residue and inter-residue 13 C- 15 N correlation experiments with 13 C- 13 C spin-diffusion studies, it becomes feasible to partially assign backbone and side-chain resonances in solid proteins. The performance of sequences using 15 N instead of 13 C detection is evaluated regarding sensitivity and resolution for a labelled dipeptide (L-Val-L-Phe). The techniques are used for a partial assignment of the 15 N and 13 C resonances in human ubiquitin

  9. Radiation oxidation of polypropylene: A solid-state 13C NMR study using selective isotopic labeling

    International Nuclear Information System (INIS)

    Mowery, Daniel M.; Assink, Roger A.; Derzon, Dora K.; Klamo, Sara B.; Bernstein, Robert; Clough, Roger L.

    2007-01-01

    Polypropylene samples, in which the three different carbon atoms along the chain were selectively labeled with carbon-13, were subjected to radiation under inert and air atmospheres, and to post-irradiation exposure in air at various temperatures. By using solid-state 13 C NMR measurements at room temperature, we have been able to identify and quantify the oxidation products. The isotopic labeling provides insight into chemical reaction mechanisms, since oxidation products can be traced back to their positions of origin on the macromolecule. The major products include peroxides and alcohols, both formed at tertiary carbon sites along the chain. Other products include methyl ketones, acids, esters, peresters, and hemiketals formed from reaction at the tertiary carbon, together with in-chain ketones and esters from reaction at the secondary chain carbon. No evidence is found of products arising from reactions at the methyl side chain. Significant temperature-dependent differences are apparent; for example much higher yields of chain-end methyl ketones, which are the indicator product of chain scission, are generated for both elevated temperature irradiation and for post-irradiation treatment at elevated temperatures. Time-dependent plots of yields of the various oxidation products have been obtained under a wide range of conditions, including the post-irradiation oxidation of a sample at room temperature in air that has been monitored for 2 years. Radiation-oxidation products of polypropylene are contrasted to products measured for 13 C-labeled polyethylene in an earlier investigation: the peroxides formed in irradiated polypropylene are remarkably longer lived, the non-peroxidic products are significantly different, and the overall ratios of oxidation products in polypropylene change relatively little as a function of the extent of oxidation

  10. Solid state CP/MAS 13C n.m.r. analysis of particle size and density fractions of soil incubated with uniformly labelled 13C-glucose

    International Nuclear Information System (INIS)

    Baldock, J.A.; Oades, J.M.

    1990-01-01

    A soil incubated for 34 days in the absence (control) and presence (treated) of uniformly labelled 13 C-glucose was dispersed using an ultrasonic probe and fractionated by sedimentation in water and a polytungstate solution of density 2.0 Mg m -3 . Solid state CP/MAS 13 C n.m.r. (cross polarization/magic angle spinning 13 C nuclear magnetic resonance) spectroscopy was used to characterize the chemical structure of the native soil organic carbon and the residual substrate carbon in the fractions of the control and treated soils. To obtain quantitative results it was essential to determine the spin lattice relaxation time in a rotating frame of the individual carbon types in the spectra as the relaxation behaviour of the native organic material in the clay fraction was different from that of the residual substrate carbon. The residual substrate carbon was found to accumulate in predominantly alkyl and O-alkyl structures in both fractions. However, significant amounts of acetal and carboxyl carbon were also observed in the clay fraction. Little if any aromatic or phenolic carbon was synthesized by the soil microorganisms utilizing substrate carbon. Dipolar dephasing CP/MAS 13 C n.m.r. experiments were also performed and allowed the proportion of each type of carbon which was protonated and nonprotonated to be estimated. Essentially all of the O-alkyl and acetal carbon, 25-40% of the aromatic carbon and 66-80% of the alkyl carbon was protonated in the fractions isolated from the treated soil. 24 refs., 4 figs., 2 tabs

  11. Solid-state /sup 13/C NMR study of cured resorcinol-formaldehyde resins

    Energy Technology Data Exchange (ETDEWEB)

    Lippmaa, H.; Samoson, A.

    1988-08-01

    The curing process generally follows the pattern observed in the stage of prepolymer formation. Catalysts (NaOH, hexa, Mg(OCOCH/sub 3/)/sub 2/) that have no substantial influence on the isomeric composition of the resorcinol-formaldehyde prepolymers, do not affect the isomeric composition of the cured resins to any significant extent either. Isomeric composition of the cured resins depends mostly on the presence of water during the curing process, necessary for depolymerisation of the added paraformaldehyde. Curing in the melt leads to enhanced 2-substitution in the 1,3-dihydroxybenzene rings. In the /sup 13/C NMR spectra of cured powdered samples, the tendency of 5-methylresorcinol to form oligomers with a higher degree of 2-substitution than resorcinol is clearly apparent. Polycondensation process continues in the powdered resins after initial curing until complete consumption of all formaldehyde. Curing of phenol-formaldehyde resols proceeds through intermediate dimethylene ether formation.

  12. Contribution of exogenous substrates to acetyl coenzyme A: Measurement by 13C NMR under non-steady-state conditions

    International Nuclear Information System (INIS)

    Malloy, C.R.; Jeffrey, F.M.H.; Thompson, J.R.; Sherry, A.D.

    1990-01-01

    A method is presented for the rapid determination of substrate selection in a manner that is not restricted to conditions of metabolic and isotopic steady state. Competition between several substrates can be assessed directly and continuously in a single experiment, allowing the effect of interventions to be studied. It is shown that a single proton-decoupled 13 C NMR spectrum of glutamate provides a direct measure of the contribution of exogenous 13 C-labeled substrates to acetyl-CoA without measurement of oxygen consumption and that steady-state conditions need not apply. Two sets of experiments were performed: one in which a metabolic steady state but a non-steady-state 13 C distribution was achieved and another in which both metabolism and labeling were not at steady state. In the first group, isolated rat hearts were supplied with [1,2- 13 C]acetate, [3- 13 C]lactate, and unlabeled glucose. 13 C NMR spectra of extracts from hearts perfused under identical conditions for 5 or 30 min were compared. In spite of significant differences in the spectra, the measured contributions of acetate, lactate, and unlabeled sources to acetyl-CoA were the same. In the second set of experiments, the same group of labeled substrates was used in a regional ischemia model in isolated rabbit hearts to show regional differences in substrate utilization under both metabolic and isotopic non steady state. The time resolution of these measurements may not be limited by technical contraints but by the rate of carbon flux in the citric acid cycle. Although this technique is demonstrated for the heart, it is applicable to all tissues

  13. Structural properties of carbon nanotubes derived from 13C NMR

    KAUST Repository

    Abou-Hamad, E.; Babaa, M.-R.; Bouhrara, M.; Kim, Y.; Saih, Y.; Dennler, S.; Mauri, F.; Basset, Jean-Marie; Goze-Bac, C.; Wå gberg, T.

    2011-01-01

    We present a detailed experimental and theoretical study on how structural properties of carbon nanotubes can be derived from 13C NMR investigations. Magic angle spinning solid state NMR experiments have been performed on single- and multiwalled

  14. Curing reactions of bismaleimide resins catalyzed by triphenylphosphine. High resolution solid-state 13C NMR study

    International Nuclear Information System (INIS)

    Shibahara, Sumio; Enoki, Takashi; Yamamoto, Takahisa; Motoyoshiya, Jiro; Hayashi, Sadao.

    1996-01-01

    The curing reactions of bismaleimide resins consisted of N,N'-4,4'-diphenylmethanebismaleimide (BMI) and o,o'-diallylbisphenol-A (DABA) in the presence of triphenylphosphine (TPP) as a catalyst were investigated. DSC measurements showed that the catalytic effect of TPP on the curing reaction of BMI was more in the presence of DABA than in its absence. In order to explore this curing reaction, N-phenylmaleimide (PMI) and o-allylphenol (AP) were selected as model compounds. The products of the PMI/TPP system were oligomers and polymers of PMI, whereas the main product of the PMI/AP/TPP system was the PMI trimer which had the five-membered ring formed via the phosphonium ylide intermediate. In these model reactions, 13 C NMR was found to be useful to distinguish between trimerization and polymerization of PMI. On the basis of the results of the model reactions, the curing reactions of bismaleimide resins were investigated by high resolution solid state 13 C NMR techniques. In the BMI/TPP system, maleimides polymerize above 175degC, but the polymerization does not proceed at 120degC. On the other hand, maleimides trimerize above 120degC in the presence of DABA and TPP. The mechanism of the trimerization is briefly discussed. (author)

  15. Identification of aquatically available carbon from algae through solution-state NMR of whole (13)C-labelled cells.

    Science.gov (United States)

    Akhter, Mohammad; Dutta Majumdar, Rudraksha; Fortier-McGill, Blythe; Soong, Ronald; Liaghati-Mobarhan, Yalda; Simpson, Myrna; Arhonditsis, George; Schmidt, Sebastian; Heumann, Hermann; Simpson, André J

    2016-06-01

    Green algae and cyanobacteria are primary producers with profound impact on food web functioning. Both represent key carbon sources and sinks in the aquatic environment, helping modulate the dissolved organic matter balance and representing a potential biofuel source. Underlying the impact of algae and cyanobacteria on an ecosystem level is their molecular composition. Herein, intact (13)C-labelled whole cell suspensions of Chlamydomonas reinhardtii, Chlorella vulgaris and Synechocystis were studied using a variety of 1D and 2D (1)H/(13)C solution-state nuclear magnetic resonance (NMR) spectroscopic experiments. Solution-state NMR spectroscopy of whole cell suspensions is particularly relevant as it identifies species that are mobile (dissolved or dynamic gels), 'aquatically available' and directly contribute to the aquatic carbon pool upon lysis, death or become a readily available food source on consumption. In this study, a wide range of metabolites and structural components were identified within the whole cell suspensions. In addition, significant differences in the lipid/triacylglyceride (TAG) content of green algae and cyanobacteria were confirmed. Mobile species in algae are quite different from those in abundance in 'classic' dissolved organic matter (DOM) indicating that if algae are major contributors to DOM, considerable selective preservation of minor components (e.g. sterols) or biotransformation would have to occur. Identifying the metabolites and dissolved components within algal cells by NMR permits future studies of carbon transfer between species and through the food chain, whilst providing a foundation to better understand the role of algae in the formation of DOM and the sequestration/transformation of carbon in aquatic environments.

  16. Molecular composition of recycled organic wastes, as determined by solid-state {sup 13}C NMR and elemental analyses

    Energy Technology Data Exchange (ETDEWEB)

    Eldridge, S.M., E-mail: simon.eldridge@dpi.nsw.gov.au [Environmental Futures Centre, School of Environment, Griffith University, Nathan, QLD 4111 (Australia); NSW Department of Primary Industries, Bruxner Highway, Wollongbar, NSW 2477 (Australia); Chen, C.R. [Environmental Futures Centre, School of Environment, Griffith University, Nathan, QLD 4111 (Australia); Xu, Z.H. [Environmental Futures Centre, School of Biomolecular and Physical Sciences, Griffith University, Nathan, QLD 4111 (Australia); Nelson, P.N. [School of Earth and Environmental Sciences, James Cook University, Cairns, QLD 4870 (Australia); Boyd, S.E. [Environmental Futures Centre, School of Biomolecular and Physical Sciences, Griffith University, Nathan, QLD 4111 (Australia); Meszaros, I. [Formerly NSW Department of Primary Industries, Richmond, NSW 2753 (Australia); Chan, K.Y. [Graduate School of Environment, Macquarie University, North Ryde, NSW 2109 (Australia); Formerly NSW Department of Primary Industries, Richmond, NSW 2753 (Australia)

    2013-11-15

    Highlights: • Model estimated the molecular C components well for most RO wastes. • Molecular nature of organic matter in RO wastes varied widely. • Molecular composition by NMR modelling preferable to extraction techniques. • Some model shortcomings in estimating molecular composition of biochars. • Waste molecular composition important for carbon/nutrient outcomes in soil. - Abstract: Using solid state {sup 13}C NMR data and elemental composition in a molecular mixing model, we estimated the molecular components of the organic matter in 16 recycled organic (RO) wastes representative of the major materials generated in the Sydney basin area. Close correspondence was found between the measured NMR signal intensities and those predicted by the model for all RO wastes except for poultry manure char. Molecular nature of the organic matter differed widely between the RO wastes. As a proportion of organic C, carbohydrate C ranged from 0.07 to 0.63, protein C from <0.01 to 0.66, lignin C from <0.01 to 0.31, aliphatic C from 0.09 to 0.73, carbonyl C from 0.02 to 0.23, and char C from 0 to 0.45. This method is considered preferable to techniques involving imprecise extraction methods for RO wastes. Molecular composition data has great potential as a predictor of RO waste soil carbon and nutrient outcomes.

  17. The influence of feedstock and production temperature on biochar carbon chemistry: A solid-state 13C NMR study

    International Nuclear Information System (INIS)

    McBeath, Anna V.; Smernik, Ronald J.; Krull, Evelyn S.; Lehmann, Johannes

    2014-01-01

    Solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy was used to evaluate the carbon chemistry of twenty-six biochars produced from eleven different feedstocks at production temperatures ranging from 350 °C to 600 °C. Carbon-13 NMR spectra were acquired using both cross-polarisation (CP) and direct polarisation (DP) techniques. Overall, the corresponding CP and DP spectra were similar, although aromaticity was slightly higher and observability much higher when DP was used. The relative size and purity of the aromatic ring structures (i.e. aromatic condensation) were also gauged using the ring current technique. Both aromaticity and aromatic condensation increased with increasing production temperature, regardless of the feedstock source. However, there were clear differences in these two measures for biochars produced at the same temperature but from different feedstocks. Based on a relationship previously established in a long-term incubation study between aromatic condensation and the mean residence time (MRT) of biochar, the MRT of the biochars was estimated to range from 1400 years. This study demonstrates how the combination of feedstock composition and production temperature influences the composition of aromatic domains in biochars, which in turn is likely to be related to their recalcitrance and ultimately their carbon sequestration value. -- Highlights: • Sensitive NMR techniques were used to gauge differences in biochar carbon chemistry. • Varying pyrolysis conditions influences biochars recalcitrant properties. • The MRT of contrasting biochars varies considerably from 1400 years

  18. Molecular composition of recycled organic wastes, as determined by solid-state 13C NMR and elemental analyses

    International Nuclear Information System (INIS)

    Eldridge, S.M.; Chen, C.R.; Xu, Z.H.; Nelson, P.N.; Boyd, S.E.; Meszaros, I.; Chan, K.Y.

    2013-01-01

    Highlights: • Model estimated the molecular C components well for most RO wastes. • Molecular nature of organic matter in RO wastes varied widely. • Molecular composition by NMR modelling preferable to extraction techniques. • Some model shortcomings in estimating molecular composition of biochars. • Waste molecular composition important for carbon/nutrient outcomes in soil. - Abstract: Using solid state 13 C NMR data and elemental composition in a molecular mixing model, we estimated the molecular components of the organic matter in 16 recycled organic (RO) wastes representative of the major materials generated in the Sydney basin area. Close correspondence was found between the measured NMR signal intensities and those predicted by the model for all RO wastes except for poultry manure char. Molecular nature of the organic matter differed widely between the RO wastes. As a proportion of organic C, carbohydrate C ranged from 0.07 to 0.63, protein C from <0.01 to 0.66, lignin C from <0.01 to 0.31, aliphatic C from 0.09 to 0.73, carbonyl C from 0.02 to 0.23, and char C from 0 to 0.45. This method is considered preferable to techniques involving imprecise extraction methods for RO wastes. Molecular composition data has great potential as a predictor of RO waste soil carbon and nutrient outcomes

  19. Assessing the extent of decomposition of natural organic materials using solid-state 13C NMR spectroscopy

    International Nuclear Information System (INIS)

    Baddock, J.A.; Oades, J.M.; Nelson, P.N.; Skene, T.M.; Golchin, A.; Clarke, P.

    1997-01-01

    Solid-state 13 C nuclear magnetic resonance (NMR) spectroscopy has become an important tool for examining the chemical structure of natural organic materials and the chemical changes associated with decomposition. In this paper, solid-state 13 C NMR data pertaining to changes in the chemical composition of a diverse range of natural organic materials, including wood, peat, composts, forest litter layers, and organic materials in surface layers of mineral soils, were reviewed with the objective of deriving an index of the extent of decomposition of such organic materials based on changes in chemical composition. Chemical changes associated with the decomposition of wood varied considerably and were dependent on a strong interaction between the species of wood examined and the species composition of the microbial decomposer community, making the derivation of a single general index applicable to wood decomposition unlikely. For the remaining forms of natural organic residues, decomposition was almost always associated with an increased content of alkyl C and a decreased content of O-alkyl C. The concomitant increase and decrease in alkyl and O-alkyl C contents, respectively, suggested that the ratio of alkyl to O-alkyl carbon (A/O-A ratio) may provide a sensitive index of the extent of decomposition. Contrary to the traditional view that humic substances with an aromatic core accumulate as decomposition proceeds, changes in the aromatic region were variable and suggested a relationship with the activity of lignin-degrading fungi. The A/O-A ratio did appear to provide a sensitive index of extent of decomposition provided that its use was restricted to situations where the organic materials were derived from a common starting material. In addition, the potential for adsorption of highly decomposable materials on mineral soil surfaces and the impacts which such an adsorption may have on bioavailability required consideration when the A/O-A ratio was used to assess the

  20. Carbonaceous species (coke) characterization in zeolites by solid state {sup 13} C NMR; Caracterizacao de especies carbonaceas (coque) em zeolitos por RMN de {sup 13} C estado solido (CP/MAS)

    Energy Technology Data Exchange (ETDEWEB)

    Mota, Claudio J.A.; Menezes, Sonia C [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

    1992-12-31

    This work applies solid state {sup 13} C NMR for characterization of carbonaceous species (coke) deposited on zeolites after contact with n-hexane at 370 deg C. The results have shown two types of carbon: saturated (sp{sup 3}) and unsaturated (sp{sup 2}) 4 refs., 4 tabs.

  1. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state 13C NMR and solution 31P NMR spectroscopy

    International Nuclear Information System (INIS)

    Liu, Shasha; Zhu, Yuanrong; Meng, Wei; He, Zhongqi; Feng, Weiying; Zhang, Chen; Giesy, John P.

    2016-01-01

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state 13 C NMR and solution 31 P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH 3 and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH 3 and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid 13 C NMR and solution 31 P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

  2. Sparse "1"3C labelling for solid-state NMR studies of P. pastoris expressed eukaryotic seven-transmembrane proteins

    International Nuclear Information System (INIS)

    Liu, Jing; Liu, Chang; Fan, Ying; Munro, Rachel A.; Ladizhansky, Vladimir; Brown, Leonid S.; Wang, Shenlin

    2016-01-01

    We demonstrate a novel sparse "1"3C labelling approach for methylotrophic yeast P. pastoris expression system, towards solid-state NMR studies of eukaryotic membrane proteins. The labelling scheme was achieved by co-utilizing natural abundance methanol and specifically "1"3C labelled glycerol as carbon sources in the expression medium. This strategy improves the spectral resolution by 1.5 fold, displays site-specific labelling patterns, and has advantages for collecting long-range distance restraints for structure determination of large eukaryotic membrane proteins by solid-state NMR.

  3. Evaluation of natural rubber from IAC series clones by solid state {sup 13}C NMR; Avaliacao da borracha natural de clones da serie IAC por {sup 13}C RMN no estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Martins, Maria A.; Moreno, Rogerio M.B.; Goncalves, Paulo S. [Instituto Agronomico de Campinas, SP (Brazil). Centro de Cafe e Plantas Tropicais. Programa Seringueira]. E-mails: paulog@iac.sp.gov.br; mariaalice@cnpdia.embrapa.br; Forato, Lucimara A.; Colnago, Luiz A.; Mattoso, Luiz H.C. [EMBRAPA Instrumentacao Agropecuaria, Sao Carlos, SP (Brazil)]. E-mail: colnago@cnpdia.embrapa.br; forato@cnpdia.embrapa.br; rogerio@cnpdia.embrapa.br; mattoso@cnpdia.embrapa.br; Job, Aldo E. [Universidade Estadual Paulista (UNESP), Presidente Prudente, SP (Brazil). Departamento de Fisica, Quimica e Biologia

    2005-07-01

    Agronomic Institute (IAC) and EMBRAPA Agricultural Instrumentation (EMBRAPA/CNPDIA) have been studied Hevea species in order to increase the production of the natural rubber and to develop new clones more appropriated to Brazil's soil and climate. Structural characterization of natural rubber [Hevea brasiliensis (Willd. ex Adr. de Juss.) Muell. - Arg.] from new clones of the IAC series (IAC 300, 301, 302, 303, 35, 40, and 56) and from RRIM 600 clone has been studied by high-resolution solid-state {sup 13}C NMR and by single pulse technique. The results have shown that the application of solid-state {sup 13}C NMR using the single pulse technique is a powerful tool to study natural rubber. The spectra obtained through this technique confirmed that natural rubber from all clones studied are cis-1,4-polyisoprene (author) form.(author)

  4. Analysis of the mechanical properties and characterization by solid state 13 C NMR of recycled EVA copolymer/silica composites

    International Nuclear Information System (INIS)

    Stael, Giovanni Chaves; Rocha, Marisa Cristina Guimaraes

    2005-01-01

    The incorporation of micrometer sized silica particles on poly (ethylene-co-vinyl acetate) - EVA - residues from the footwear industry was evaluated. The effects of the processing parameters - temperature and mixing ratio - on the mechanical behavior of molded plates of neat recycled EVA and EVA/silica composites were also investigated. The mechanical properties measured by the tensile test, the fractographic analysis by scanning electron microscopy (SEM), and the 13 C Nuclear Magnetic Resonance (NMR) showed a reduced EVA to silica compatibility. Therefore, incorporation of untreated silica to recycled EVA copolymer produced a slight decrease on the mechanical performance of EVA/silica composites in respect to neat EVA copolymer. The NMR analysis also shows that the crosslinking process on recycled EVA may be occurring at the carbonyl group. (author)

  5. Analysis of the mechanical properties and characterization by solid state 13C NMR of recycled EVA copolymer/silica composites

    Directory of Open Access Journals (Sweden)

    Giovanni Chaves Stael

    2005-09-01

    Full Text Available The incorporation of micrometer sized silica particles on poly (ethylene-co-vinyl acetate - EVA - residues from the footwear industry was evaluated. The effects of the processing parameters - temperature and mixing ratio - on the mechanical behavior of molded plates of neat recycled EVA and EVA/silica composites were also investigated. The mechanical properties measured by the tensile test, the fractographic analysis by scanning electron microscopy (SEM, and the 13C Nuclear Magnetic Resonance (NMR showed a reduced EVA to silica compatibility. Therefore, incorporation of untreated silica to recycled EVA copolymer produced a slight decrease on the mechanical performance of EVA/silica composites in respect to neat EVA copolymer. The NMR analysis also shows that the crosslinking process on recycled EVA may be occurring at the carbonyl group.

  6. XRD and solid state 13C-NMR evaluation of the crystallinity enhancement of 13C-labeled bacterial cellulose biosynthesized by Komagataeibacter xylinus under different stimuli: A comparative strategy of analyses.

    Science.gov (United States)

    Meza-Contreras, Juan C; Manriquez-Gonzalez, Ricardo; Gutiérrez-Ortega, José A; Gonzalez-Garcia, Yolanda

    2018-05-22

    The production and crystallinity of 13 C bacterial cellulose (BC) was examined in static culture of Komagataeibacter xylinus with different chemical and physical stimuli: the addition of NaCl or cloramphenicol as well as exposure to a magnetic field or to UV light. Crystalline BC biosynthesized under each stimulus was studied by XRD and solid state 13 C NMR analyses. All treatments produced BC with enhanced crystallinity over 90% (XRD) and 80% (NMR) compared to the control (83 and 76%, respectively) or to Avicel (77 and 62%, respectively). The XRD data indicated that the crystallite size was 80-85 Å. Furthermore, changes on the allomorphs (I α and I β ) ratio tendency of BC samples addressed to the stimuli were estimated using the C4 signal from 13 C NMR data. These results showed a decrease of the allomorph I α (3%) when BC was biosynthesized with UV light and chloramphenicol compared to control (58.79%). In contrast, the BC obtained with NaCl increased up to 60.31% of the I α allomorph ratio. Copyright © 2018 Elsevier Ltd. All rights reserved.

  7. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Liu, Shasha [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhu, Yuanrong, E-mail: zhuyuanrong07@mails.ucas.ac.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Meng, Wei, E-mail: mengwei@craes.org.cn [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); He, Zhongqi [USDA-ARS Southern Regional Research Center, 1100 Robert E Lee Blvd, New Orleans, LA 70124 (United States); Feng, Weiying [College of Water Sciences, Beijing Normal University, Beijing 100875 (China); State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Zhang, Chen [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Giesy, John P. [State Key Laboratory of Environment Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing 100012 (China); Department of Biomedical and Veterinary Biosciences and Toxicology Centre, University of Saskatchewan, Saskatoon, Saskatchewan (Canada)

    2016-02-01

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state {sup 13}C NMR and solution {sup 31}P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O–C–O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH{sub 3} and COO/N–C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH{sub 3} and COO/N–C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. - Highlights: • WEOM derived from aquatic macrophytes was characterized. • C and P in WEOM were characterized by solid {sup 13}C NMR and solution {sup 31}P NMR. • Degradation and transformation of macrophyte-derived C and P were investigated. • Macrophyte-derived WEOM are important source for bioavailable nutrients in lakes.

  8. Identifying inter-residue resonances in crowded 2D {sup 13}C-{sup 13}C chemical shift correlation spectra of membrane proteins by solid-state MAS NMR difference spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Miao Yimin; Cross, Timothy A. [Florida State University, Department of Chemistry and Biochemistry (United States); Fu Riqiang, E-mail: rfu@magnet.fsu.edu [National High Magnet Field Lab (United States)

    2013-07-15

    The feasibility of using difference spectroscopy, i.e. subtraction of two correlation spectra at different mixing times, for substantially enhanced resolution in crowded two-dimensional {sup 13}C-{sup 13}C chemical shift correlation spectra is presented. With the analyses of {sup 13}C-{sup 13}C spin diffusion in simple spin systems, difference spectroscopy is proposed to partially separate the spin diffusion resonances of relatively short intra-residue distances from the longer inter-residue distances, leading to a better identification of the inter-residue resonances. Here solid-state magic-angle-spinning NMR spectra of the full length M2 protein embedded in synthetic lipid bilayers have been used to illustrate the resolution enhancement in the difference spectra. The integral membrane M2 protein of Influenza A virus assembles as a tetrameric bundle to form a proton-conducting channel that is activated by low pH and is essential for the viral lifecycle. Based on known amino acid resonance assignments from amino acid specific labeled samples of truncated M2 sequences or from time-consuming 3D experiments of uniformly labeled samples, some inter-residue resonances of the full length M2 protein can be identified in the difference spectra of uniformly {sup 13}C labeled protein that are consistent with the high resolution structure of the M2 (22-62) protein (Sharma et al., Science 330(6003):509-512, 2010)

  9. Mechanism of formation of humus coatings on mineral surfaces 3. Composition of adsorbed organic acids from compost leachate on alumina by solid-state 13C NMR

    Science.gov (United States)

    Wershaw, R. L.; Llaguno, E.C.; Leenheer, J.A.

    1996-01-01

    The adsorption of compost leachate DOC on alumina is used as a model for elucidation of the mechanism of formation of natural organic coatings on hydrous metal oxide surfaces in soils and sediments. Compost leachate DOC is composed mainly of organic acid molecules. The solid-state 13C NMR spectra of these organic acids indicate that they are very similar in composition to aquatic humic substances. Changes in the solid-state 13C NMR spectra of compost leachate DOC fractions adsorbed on alumina indicate that the DOC molecules are most likely adsorbed on metal oxide surfaces through a combination of polar and hydrophobic interaction mechanisms. This combination of polar and hydrophobic mechanism leads to the formation of bilayer coatings of the leachate molecules on the oxide surfaces.

  10. Polymeric proanthocyanidins 13C NMR studies of procyanidins

    Science.gov (United States)

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

    1982-01-01

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

  11. Slow molecular dynamics in the β relaxation of semicrystalline polymers studied by pure exchange 13C solid state NMR

    International Nuclear Information System (INIS)

    Azevedo, Eduardo R. de; Becker-Guedes, Fabio; Bonagamba, Tito J.; Schmidt-Rohr, Klaus; Iowa State University, Ames, IA

    2001-01-01

    The dynamics in the amorphous regions of semicrystalline polymers exert important influences on mechanical properties, but have been notoriously difficult to characterize. Two new solid-state NMR techniques, PUREX (pure exchange) and CODEX (center band-only detection of exchange) NMR, make it possible to analyze the molecular motions near the glass transition in the amorphous regions of semicrystalline polymers. This is achieved by selectively suppressing the otherwise dominant signals of the static segments in the crystallites. We have applied both NMR techniques to study the slow motions near the glass transition in semicrystalline polymers (β relaxation) and in fully amorphous samples for reference. The studied polymers were isotactic poly(1-butene) (iPB1) (form I), syndiotactic and atactic polypropylenes (sPP, and aPP, respectively), as well as polyisobutylene (PIB). We have analyzed the geometry and time scale of the slow molecular motion for all samples and determined the apparent activation energies. (author)

  12. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state (13)C NMR and solution (31)P NMR spectroscopy.

    Science.gov (United States)

    Liu, Shasha; Zhu, Yuanrong; Meng, Wei; He, Zhongqi; Feng, Weiying; Zhang, Chen; Giesy, John P

    2016-02-01

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state (13)C NMR and solution (31)P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O-C-O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH3 and COO/N-C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH3 and COO/N-C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes. Copyright © 2015 Elsevier B.V. All rights reserved.

  13. Characteristics and degradation of carbon and phosphorus from aquatic macrophytes in lakes: Insights from solid-state 13C NMR and solution 31P NMR spectroscopy

    Science.gov (United States)

    LIU, S. S.; Zhu, Y.; Meng, W.; Wu, F.

    2016-12-01

    Water extractable organic matter (WEOM) derived from macrophytes plays an important role in biogeochemical cycling of nutrients, including carbon (C), nitrogen (N) and phosphorus (P) in lakes. However, reports of their composition and degradation in natural waters are scarce. Therefore, compositions and degradation of WEOM derived from six aquatic macrophytes species of Tai Lake, China, were investigated by use of solid-state 13C NMR and solution 31P NMR spectroscopy. Carbohydrates were the predominant constituents of WEOM fractions, followed by carboxylic acid. Orthophosphate (ortho-P) was the dominant form of P (78.7% of total dissolved P) in the water extracts, followed by monoester P (mono-P) (20.6%) and little diester P (0.65%). The proportion of mono-P in total P species increased with the percentage of O-alkyl and O-C-O increasing in the WEOM, which is likely due to degradation and dissolution of biological membranes and RNA from aquatic plants. Whereas the proportion of mono-P decreased with alkyl-C, NCH/OCH3 and COO/N-C=O increasing, which may be owing to the insoluble compounds including C functional groups of alkyl-C, NCH/OCH3 and COO/N-C=O, such as aliphatic biopolymers, lignin and peptides. Based on the results of this study and information in the literature about water column and sediment, we propose that WEOM, dominated by polysaccharides, are the most labile and bioavailable component in debris of macrophytes. Additionally, these WEOMs would also be a potential source for bioavailable organic P (e.g., RNA, DNA and phytate) for lakes.

  14. Characterization of water in hydrated Bombyx mori silk fibroin fiber and films by 2H NMR relaxation and 13C solid state NMR.

    Science.gov (United States)

    Asakura, Tetsuo; Isobe, Kotaro; Kametani, Shunsuke; Ukpebor, Obehi T; Silverstein, Moshe C; Boutis, Gregory S

    2017-03-01

    The mechanical properties of Bombyx mori silk fibroin (SF), such as elasticity and tensile strength, change remarkably upon hydration. However, the microscopic interaction with water is not currently well understood on a molecular level. In this work, the dynamics of water molecules interacting with SF was studied by 2 H solution NMR relaxation and exchange measurements. Additionally, the conformations of hydrated [3- 13 C]Ala-, [3- 13 C]Ser-, and [3- 13 C]Tyr-SF fibers and films were investigated by 13 C DD/MAS NMR. Using an inverse Laplace transform algorithm, we were able to identify four distinct components in the relaxation times for water in SF fiber. Namely, A: bulk water outside the fiber, B: water molecules trapped weakly on the surface of the fiber, C: bound water molecules located in the inner surface of the fiber, and D: bound water molecules located in the inner part of the fiber were distinguishable. In addition, four components were also observed for water in the SF film immersed in methanol for 30s, while only two components for the film immersed in methanol for 24h. The effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and non-crystalline domains of 13 C selectively labeled SF, respectively, could be determined independently. Our measurements provide new insight relating the characteristics of water and the hydration structure of silk, which are relevant in light of current interest in the design of novel silk-based biomaterials. The mechanical properties of Bombyx mori silk fibroin (SF) change remarkably upon hydration. However, the microscopic interaction between SF and water is not currently well understood on a molecular level. We were able to identify four distinct components in the relaxation times for water in SF fiber by 2 H solution NMR relaxation and exchange measurements. In addition, the effects of hydration on the conformation of Ser and Tyr residues in the site-specific crystalline and

  15. 13C-NMR assignment, structure, and dynamics of deoxyoligonucleotides

    International Nuclear Information System (INIS)

    Zanatta, N.; Borer, P.N.; Levy, G.C.

    1986-01-01

    The unique spectral properties of 13 C-NMR for studying nucleic acids and some of the important features of 13 C-NMR in oligonucleotide studies are demostrated. The main difficulty in studying oligonucleotides by 13 C-NMR and recent improvements in NMR instrumentation and advances in oligonucleotide synthesis are presented. The high resolution 13 C-NMR spectra, T 1 relaxation times and NOEs were measured for duplex of the self-complementary oligo-DNAs: d(CG) 3 and d(GGTATACC) are studied. The target of this study is to developed a systematic 13 C-NMR spectral assignment and to investigate the structure and dynamics of these two sequences by this techniques. (M.J.C.) [pt

  16. Chemical and nanometer-scale structure of kerogen and its change during thermal maturation investigated by advanced solid-state 13C NMR spectroscopy

    Science.gov (United States)

    Mao, J.; Fang, X.; Lan, Y.; Schimmelmann, A.; Mastalerz, Maria; Xu, L.; Schmidt-Rohr, K.

    2010-01-01

    We have used advanced and quantitative solid-state nuclear magnetic resonance (NMR) techniques to investigate structural changes in a series of type II kerogen samples from the New Albany Shale across a range of maturity (vitrinite reflectance R0 from 0.29% to 1.27%). Specific functional groups such as CH3, CH2, alkyl CH, aromatic CH, aromatic C-O, and other nonprotonated aromatics, as well as "oil prone" and "gas prone" carbons, have been quantified by 13C NMR; atomic H/C and O/C ratios calculated from the NMR data agree with elemental analysis. Relationships between NMR structural parameters and vitrinite reflectance, a proxy for thermal maturity, were evaluated. The aromatic cluster size is probed in terms of the fraction of aromatic carbons that are protonated (???30%) and the average distance of aromatic C from the nearest protons in long-range H-C dephasing, both of which do not increase much with maturation, in spite of a great increase in aromaticity. The aromatic clusters in the most mature sample consist of ???30 carbons, and of ???20 carbons in the least mature samples. Proof of many links between alkyl chains and aromatic rings is provided by short-range and long-range 1H-13C correlation NMR. The alkyl segments provide most H in the samples; even at a carbon aromaticity of 83%, the fraction of aromatic H is only 38%. While aromaticity increases with thermal maturity, most other NMR structural parameters, including the aromatic C-O fractions, decrease. Aromaticity is confirmed as an excellent NMR structural parameter for assessing thermal maturity. In this series of samples, thermal maturation mostly increases aromaticity by reducing the length of the alkyl chains attached to the aromatic cores, not by pronounced growth of the size of the fused aromatic ring clusters. ?? 2010 Elsevier Ltd. All rights reserved.

  17. Comparison of Australasian tertiary coals based on resolution- enhanced solid-state /sup 13/C NMR spectra

    Energy Technology Data Exchange (ETDEWEB)

    Newman, R H; Davenport, S J

    1986-04-01

    /sup 13/C solid-state nuclear magnetic resonance spectroscopy was used to characterize 32 low-rank coals from New Zealand and Australia. A combination of high magnetic field (4.7 T) and resolution enhancement was used to extract spectral details beyond those seen in published spectra of coals of similar rank. Signal heights were used to characterize organic functional distributions. The spectra showed close similarities between Australian brown coals and low-rank New Zealand subbituminous coals, particularly those mined in the North Island. The spectra of New Zealand lignites all showed stronger signals from cellulose, methoxyl groups and phenols. Almost all of the New Zealand coals showed a relatively strong signal from polymethylene chains, compared with the Australian brown coals. This led to a prediction of higher alkene yields from pyrolysis of the New Zealand coals. Variations in phenolic substitution patterns were attributed to variations in the relative proportions of tannins and lignins in the depositional environments.

  18. 13C and 31P NMR studies of myocardial metabolism

    International Nuclear Information System (INIS)

    Laughlin, M.R.

    1988-01-01

    The fluxes through two enzyme systems have been measured in perfused or in in vivo heart using NMR: phosphocreatine kinase, and glycogen synthase and phosphorylase. The rates of synthesis and degradation of glycogen were monitored in vivo in fed, fasted, and diabetic rat heart during infusions of 13 C-1-glucose and insulin using proton-decoupled 13 C-NMR at 1.9 and 4.7 tesla. The enzyme activities of glycogen synthase and glycogen phosphorylase were also measured in this tissue which had been freeze clamped at the end of the experiment, for comparison with the synthetic rates. For normal fed, fasted, and diabetic animals, synthesis rates were 0.28, 0.16, and 0.15 μmol/min.gww respectively. Glycogen synthase i activity was 0.23, 0.14, and 0.14 μmol/min.gww in these hearts at the end of the experiment, when measured at appropriate substrate and activator concentrations, and follow activation time courses that are consistent with being the main rate determinant for net synthesis in all cases. Turnover of glycogen was studied by observing the preformed 13 C-1-glycogen signal during infusion of 12 C-glucose and insulin, and was found to be close to zero. Extracted phosphorylase a activity was approximately ten times that of synthase i under these circumstances. In order to fully interpret the turnover studies, glycogenolysis of preformed 13 C-glycogen was observed after a bolus of glucagon. The glycogen had either been synthesized from 13 C-1-glucose for a single hour, or during an hour of 13 C-glucose and a subsequent hour of 12 C-glucose infusion. The author observed that breakdown follows an exponential time course related to the phosphorylase a activation state and that the last synthesized glycogen breaks down at the rate of 2.5 μmol/min.gww, five times faster than that synthesized an hour earlier

  19. Direct 13C NMR Detection in HPLC Hyphenation Mode

    DEFF Research Database (Denmark)

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

    2012-01-01

    Solid phase extraction (SPE) was introduced as a crucial step in the HPLC-SPE-NMR technique to enable online analyte enrichment from which proton-detected NMR experiments on submicrogram amounts from complex mixtures were possible. However, the significance of direct-detected (13)C NMR experiments...... application of HPLC-SPE-NMR analysis using direct-detected (13)C NMR spectra. HPLC column loading, accumulative SPE trappings, and the effect of different elution solvents were evaluated and optimized. A column loading of approximately 600 mug of a prefractionated triterpenoid mixture, six trappings...

  20. Solid-State (13)C NMR Delineates the Architectural Design of Biopolymers in Native and Genetically Altered Tomato Fruit Cuticles.

    Science.gov (United States)

    Chatterjee, Subhasish; Matas, Antonio J; Isaacson, Tal; Kehlet, Cindie; Rose, Jocelyn K C; Stark, Ruth E

    2016-01-11

    Plant cuticles on outer fruit and leaf surfaces are natural macromolecular composites of waxes and polyesters that ensure mechanical integrity and mitigate environmental challenges. They also provide renewable raw materials for cosmetics, packaging, and coatings. To delineate the structural framework and flexibility underlying the versatile functions of cutin biopolymers associated with polysaccharide-rich cell-wall matrices, solid-state NMR spectra and spin relaxation times were measured in a tomato fruit model system, including different developmental stages and surface phenotypes. The hydrophilic-hydrophobic balance of the cutin ensures compatibility with the underlying polysaccharide cell walls; the hydroxy fatty acid structures of outer epidermal cutin also support deposition of hydrophobic waxes and aromatic moieties while promoting the formation of cell-wall cross-links that rigidify and strengthen the cuticle composite during fruit development. Fruit cutin-deficient tomato mutants with compromised microbial resistance exhibit less efficient local and collective biopolymer motions, stiffening their cuticular surfaces and increasing their susceptibility to fracture.

  1. Whole-core analysis by 13C NMR

    International Nuclear Information System (INIS)

    Vinegar, H.J.; Tutunjian, P.N.; Edelstein, W.A.; Roemer, P.B.

    1991-01-01

    This paper reports on a whole-core nuclear magnetic resonance (NMR) system that was used to obtain natural abundance 13 C spectra. The system enables rapid, nondestructive measurements of bulk volume of movable oil, aliphatic/aromatic ratio, oil viscosity, and organic vs. carbonate carbon. 13 C NMR can be used in cores where the 1 H NMR spectrum is too broad to resolve oil and water resonances separately. A 5 1/4-in. 13 C/ 1 H NMR coil was installed on a General Electric (GE) CSI-2T NMR imager/spectrometer. With a 4-in.-OD whole core, good 13 C signal/noise ratio (SNR) is obtained within minutes, while 1 H spectra are obtained in seconds. NMR measurements have been made of the 13 C and 1 H density of crude oils with a wide range of API gravities. For light- and medium-gravity oils, the 13 C and 1 H signal per unit volume is constant within about 3.5%. For heavy crudes, the 13 C and 1 H density measured by NMR is reduced by the shortening of spin-spin relaxation time. 13 C and 1 H NMR spin-lattice relaxation times were measured on a suite of Cannon viscosity standards, crude oils (4 to 60 degrees API), and alkanes (C 5 through C 16 ) with viscosities at 77 degrees F ranging from 0.5 cp to 2.5 x 10 7 cp. The 13 C and 1 H relaxation times show a similar correlation with viscosity from which oil viscosity can be estimated accurately for viscosities up to 100 cp. The 13 C surface relaxation rate for oils on water-wet rocks is very low. Nonproton decoupled 13 C NMR is shown to be insensitive to kerogen; thus, 13 C NMR measures only the movable hydrocarbon content of the cores. In carbonates, the 13 C spectrum also contains a carbonate powder pattern useful in quantifying inorganic carbon and distinguishing organic from carbonate carbon

  2. 13C-NMR of diterpenes with pimarane skeleton

    International Nuclear Information System (INIS)

    Garcez, W.S.; Pereira, A.L.; Silva Queiroz, P.P. da; Silva, R.S. da; Valente, L.M.M.; Peixoto, E.M.; Cunha Pinto, A. da

    1981-01-01

    The effect of substituent groups on the chemical shift of carbons using nuclear magnetic resonance spectra of carbon 13 ( 13 C-NMR) is discussed. Diterpenes having pimarane skeleton, isolated from plants of Velloziaceae family are analysed. (ARHC) [pt

  3. CP/MAS 13C NMR characterization of the isomeric states and intermolecular packing in tris(8-hydroxyquinoline) aluminum(III) (Alq3).

    Science.gov (United States)

    Kaji, Hironori; Kusaka, Yasunari; Onoyama, Goro; Horii, Fumitaka

    2006-04-05

    The isomeric states and intermolecular packing of tris(8-hydroxyquinoline) aluminum(III) (Alq(3)) in the alpha-, gamma-, and delta-crystalline forms and in the amorphous state, which are important for understanding the light-emitting and electron-transport properties, have been analyzed by CP/MAS (13)C NMR. This simple NMR experiment shows that the isomeric state of alpha- and amorphous Alq(3) is meridional, whereas that of gamma- and delta-Alq(3) is facial. In the amorphous Alq(3), the inclusion of facial isomers has been under debate. Our experiments show that meridional isomers are dominant in the amorphous Alq(3), although the existence of facial isomers cannot be completely denied. The local structure of amorphous Alq(3) is similar to that of alpha-Alq(3) and is significantly different from those of gamma- and delta-Alq(3). Among these Alq(3) samples, the effect of intermolecular interaction is not found only for gamma-Alq(3). This finding can explain the good solvent solubility of gamma-Alq(3), compared with the other crystalline forms. It is also shown that the structures are locally disordered not only for amorphous Alq(3) but also for alpha-Alq(3), although clear X-ray diffraction peaks are observed for alpha-Alq(3). In contrast, the local structures of gamma- and delta-Alq(3) are well defined. A clear relation is found between the spectral patterns of CP/MAS (13)C NMR and the fluorescence wavelengths; the samples, which consist of facial isomers, show blue-shifted fluorescence compared with those of meridionals.

  4. Distinct solvent- and temperature-dependent packing arrangements of anti-parallel β-sheet polyalanines studied with solid-state 13C NMR and MD simulation.

    Science.gov (United States)

    Kametani, Shunsuke; Tasei, Yugo; Nishimura, Akio; Asakura, Tetsuo

    2017-08-09

    Polyalanine (polyA) sequences are well known as the simplest sequence that naturally forms anti-parallel β-sheets and constitute a key element in the structure of spider and wild silkworm silk fibers. We have carried out a systematic analysis of the packing of anti-parallel β-sheets for (Ala) n , n = 5, 6, 7 and 12, using primarily 13 C solid-state NMR and MD simulation. HFIP and TFA are frequently used as the dope solvents for recombinant silks, and polyA was solidified from both HFIP and TFA solutions by drying. An analysis of Ala Cβ peaks in the 13 C CP/MAS NMR spectra indicated that polyA from HFIP was mainly rectangular but polyA from TFA was mainly staggered. The transition from the rectangular to the staggered arrangement in (Ala) 6 was observed for the first time from the change in the Ala Cβ peak through heat treatment at 200 °C for 4 h. The removal of the bound water was confirmed by thermal analysis. This transition could be reproduced by MD simulation of (Ala) 6 molecules at 200 °C after removal of the bound water molecules. In this way, the origin of the stability of the different packing arrangements of polyA was clarified.

  5. Solid state 13C NMR analysis of shales and coals from Laramide Basins. Final report, March 1, 1995--March 31, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Miknis, F.P.; Jiao, Z.S.; Zhao, Hanqing; Surdam, R.C.

    1998-12-31

    This Western Research Institute (WRI) jointly sponsored research (JSR) project augmented and complemented research conducted by the University of Wyoming Institute For Energy Research for the Gas Research Institute. The project, {open_quotes}A New Innovative Exploitation Strategy for Gas Accumulations Within Pressure Compartments,{close_quotes} was a continuation of a project funded by the GRI Pressure Compartmentalization Program that began in 1990. That project, {open_quotes}Analysis of Pressure Chambers and Seals in the Powder River Basin, Wyoming and Montana,{close_quotes} characterized a new class of hydrocarbon traps, the discovery of which can provide an impetus to revitalize the domestic petroleum industry. In support of the UW Institute For Energy Research`s program on pressure compartmentalization, solid-state {sup 13}C NMR measurements were made on sets of shales and coals from different Laramide basins in North America. NMR measurements were made on samples taken from different formations and depths of burial in the Alberta, Bighorn, Denver, San Juan, Washakie, and Wind River basins. The carbon aromaticity determined by NMR was shown to increase with depth of burial and increased maturation. In general, the NMR data were in agreement with other maturational indicators, such as vitrinite reflectance, illite/smectite ratio, and production indices. NMR measurements were also obtained on residues from hydrous pyrolysis experiments on Almond and Lance Formation coals from the Washakie Basin. These data were used in conjunction with mass and elemental balance data to obtain information about the extent of carbon aromatization that occurs during artificial maturation. The data indicated that 41 and 50% of the original aliphatic carbon in the Almond and Lance coals, respectively, aromatized during hydrous pyrolysis.

  6. Structural properties of carbon nanotubes derived from 13C NMR

    KAUST Repository

    Abou-Hamad, E.

    2011-10-10

    We present a detailed experimental and theoretical study on how structural properties of carbon nanotubes can be derived from 13C NMR investigations. Magic angle spinning solid state NMR experiments have been performed on single- and multiwalled carbon nanotubes with diameters in the range from 0.7 to 100 nm and with number of walls from 1 to 90. We provide models on how diameter and the number of nanotube walls influence NMR linewidth and line position. Both models are supported by theoretical calculations. Increasing the diameter D, from the smallest investigated nanotube, which in our study corresponds to the inner nanotube of a double-walled tube to the largest studied diameter, corresponding to large multiwalled nanotubes, leads to a 23.5 ppm diamagnetic shift of the isotropic NMR line position δ. We show that the isotropic line follows the relation δ = 18.3/D + 102.5 ppm, where D is the diameter of the tube and NMR line position δ is relative to tetramethylsilane. The relation asymptotically tends to approach the line position expected in graphene. A characteristic broadening of the line shape is observed with the increasing number of walls. This feature can be rationalized by an isotropic shift distribution originating from different diamagnetic shielding of the encapsulated nanotubes together with a heterogeneity of the samples. Based on our results, NMR is shown to be a nondestructive spectroscopic method that can be used as a complementary method to, for example, transmission electron microscopy to obtain structural information for carbon nanotubes, especially bulk samples.

  7. Application of 13C-labeling and 13C-13C COSY NMR experiments in the structure determination of a microbial natural product.

    Science.gov (United States)

    Kwon, Yun; Park, Sunghyouk; Shin, Jongheon; Oh, Dong-Chan

    2014-08-01

    The elucidation of the structures of complex natural products bearing many quaternary carbons remains challenging, even in this advanced spectroscopic era. (13)C-(13)C COSY NMR spectroscopy shows direct couplings between (13)C and (13)C, which comprise the backbone of a natural product. Thus, this type of experiment is particularly useful for natural products bearing consecutive quaternary carbons. However, the low sensitivity of (13)C-based NMR experiments, due to the low natural abundance of the (13)C nucleus, is problematic when applying these techniques. Our efforts in the (13)C labeling of a microbial natural product, cyclopiazonic acid (1), by feeding (13)C-labeled glucose to the fungal culture, enabled us to acquire (13)C-(13)C COSY NMR spectra on a milligram scale that clearly show the carbon backbone of the compound. This is the first application of (13)C-(13)C COSY NMR experiments for a natural product. The results suggest that (13)C-(13)C COSY NMR spectroscopy can be routinely used for the structure determination of microbial natural products by (13)C-enrichment of a compound with (13)C-glucose.

  8. Chemical structure changes in coals after low-temperature oxidation and demineralization by acid treatment as revealed by high resolution solid state 13C NMR

    International Nuclear Information System (INIS)

    Tekely, P.; Nicole, D.; Delpuech, J.-J.; Totino, E.; Muller, J.F.

    1987-01-01

    13 C CP/MAS NMR has been used for characterization of chemical structure changes in coals after low-temperature oxidation and prolonged demineralization by acid treatment. In both cases the changes take place mainly in the aliphatic part of coal molecules. 21 refs.; 3 figs.; 2 tabs

  9. 13C-NMR spectra and bonding situation in ketenimines

    International Nuclear Information System (INIS)

    Firl, J.; Runge, W.; Hartmann, W.; Utikal, H.P.

    1975-01-01

    13 C-NMR spectra of a series of substituted ketenimines are reported. The terminal carbon resonances are found at unusual high fields between delta 37 and 78, while the central carbon signals appear around delta 189 - 196. On the basis of these results, the bonding situation in ketenimines has been discussed. (auth.)

  10. Structural Characterization of Febuxostat/l-Pyroglutamic Acid Cocrystal Using Solid-State 13C-NMR and Investigational Study of Its Water Solubility

    Directory of Open Access Journals (Sweden)

    Ji-Hun An

    2017-12-01

    Full Text Available Febuxostat (FB is a poorly water-soluble drug that belongs to BCS class II. The drug is employed for the treatment of inflammatory disease arthritis urica (gout, and the free base, FB form-A, is most preferred for drug formulation. In order to achieve a goal of improving the water solubility of FB form-A, this study was carried out using the cocrystallization technique called the liquid-assisted grinding method to produce FB cocrystals. Here, five amino acids containing amine (NH, oxygen (O, and hydroxyl (OH functional groups, and possessing difference of pKa less than 3 with FB, were selected as coformers. Then, solvents including methanol, ethanol, isopropyl alcohol, n-hexane, dichloromethane, and acetone were used for the cocrystal screening. As a result, a cocrystal was obtained when acetone and l-pyroglutamic acid (PG of 0.5 eq. were employed as solvent and coformer, respectively. The ratio of 2:1, which is the ratio of FB to PG within FB-PG cocrystal, was predicted by means of solid-state CP/MAS 13C-NMR, solution-state NMR (1H, 13C, and 2D and FT-IR. Moreover, Powder X-ray Diffraction (PXRD, Differential Scanning Calorimetry (DSC, and Thermogravimetric Analysis (TGA were used to investigate the characteristics of FB-PG cocrystal. In addition, comparative solubility tests between FB-PG cocrystal and FB form-A were conducted in deionized water and under simulated gastrointestinal pH (1.2, 4, and 6.8 conditions. The result revealed that FB-PG cocrystal has a solubility of four-fold higher than FB form-A in deionized water and two-fold and five-fold greater than FB form-A at simulated gastrointestinal pH 1.2 and pH 4, respectively. Besides, solubilities of FB-PG cocrystal and FB form-A at pH 6.8 were similar to the results measured in deionized water. Therefore, it is postulated that FB-PG cocrystal has a potential overcoming the limitations related to the low aqueous solubility of FB form-A. Accordingly, FB-PG cocrystal is suggested as an

  11. Residue specific hydration of primary cell wall potato pectin identified by solid-state 13C single-pulse MAS and CP/MAS NMR spectroscopy

    DEFF Research Database (Denmark)

    Larsen, Flemming Hofmann; Chrestensen, Inge Byg; Damager, Iben

    2011-01-01

    Hydration of rhamnogalacturonan-I (RG-I) derived from potato cell wall was analyzed by 13C single-pulse (SP) magic-angle-spinning (MAS) and 13C cross-polarization (CP) MAS nuclear magnetic resonance (NMR) and supported by 2H SP/MAS NMR experiments. The study shows that the arabinan side chains...... hydrate more readily than the galactan side chains and suggests that the overall hydration properties can be controlled by modifying the ratio of these side chains. Enzymatic modification of native (NA) RG-I provided samples with reduced content of arabinan (sample DA), galactan (sample DG), or both side...... chains (sample DB). Results of these samples suggested that hydration properties were determined by the length and character of the side chains. NA and DA exhibited similar hydration characteristics, whereas DG and DB were difficult to hydrate because of the less hydrophilic properties of the rhamnose...

  12. Liquid state sup1H and sup13C-NMR studies on polymerisation reaction of 2,2'-difurfuryloxy-2- silapropane

    International Nuclear Information System (INIS)

    Rusli bin Omar

    1994-01-01

    The purpose of this study was to prepare the copolymer of 2,2'-difurfuryloxy-2-silapropane (DFS) and 1,1'-(methylenedi-4, 1-phenylene) bismaleimide (BM). DFS was prepared at 0 degC through the reaction of 2 moles of furfuryl alcohol (FA) with 1 mole of dichlorodimethylsilane (DCMS) in the presence of pyridine and chloroform as a solvent. The formation of this compound was characterized by the sup1H and sup13C-NMR spectroscopy and mass spectrometry. DFS has the ability to undergo the Diels-Alder reaction. The furan end groups of DFS could react with dienophile groups of other materials. The adduct of DFS-BM was prepared by the reaction of DFS with BM at room temperature (18degC) in chloroform (CDClsub3). Characterization of the adduct was carried out through a study of the sup1H and sup13C-NMR spectra of the adduct

  13. Effects of cooking on the cell walls (dietary fiber) of 'Scarlet Warren' winter squash ( Cucurbita maxima ) studied by polysaccharide linkage analysis and solid-state (13)C NMR.

    Science.gov (United States)

    Ratnayake, R M Sunil; Sims, Ian M; Newman, Roger H; Melton, Laurence D

    2011-07-13

    Cell wall polysaccharides of 'Scarlet Warren' winter squash ( Cucurbita maxima ) were investigated before and after thermal processing. Linkage analysis of polysaccharides was done by gas chromatography coupled to mass spectrometry (GC-MS). The linkage analysis showed the cell wall polysaccharide compositions of raw and cooked squash were similar. The total pectic polysaccharides (galacturonan, rhamnogalacturonan, arabinan, and arabinogalactan) contents of the cell walls of both raw and cooked squash were 39 mol %. The amounts of pectic polysaccharides and xyloglucan in the cell walls of squash showed little alteration on heating. The cellulose content of the raw and cooked cell walls was relatively high at 47 mol %, whereas the xyloglucan content was low at 4 mol %. Solid-state (13)C nuclear magnetic resonance (NMR) spectroscopy techniques were used to examine the molecular motion of the polysaccharides in the cell walls. The mobility of highly flexible galactan depends on the water content of the sample, but no difference was seen between raw and cooked samples. Likewise, the mobility of semimobile pectic polysaccharides was apparently unaltered by cooking. No change was detected in the rigid cellulose microfibrils on cooking.

  14. Early diagenesis of mangrove leaves in a tropical estuary: Bulk chemical characterization using solid-state 13C NMR and elemental analyses

    Science.gov (United States)

    Benner, Ronald; Hatcher, Patrick G.; Hedges, John I.

    1990-07-01

    Changes in the chemical composition of mangrove ( Rhizophora mangle) leaves during decomposition in tropical estuarine waters were characterized using solid-state 13C nuclear magnetic resonance (NMR) and elemental (CHNO) analysis. Carbohydrates were the most abundant components of the leaves accounting for about 50 wt% of senescent tissues. Tannins were estimated to account for about 20 wt% of leaf tissues, and lipid components, cutin, and possibly other aliphatic biopolymers in leaf cuticles accounted for about 15 wt%. Carbohydrates were generally less resistant to decomposition than the other constituents and decreased in relative concentration during decomposition. Tannins were of intermediate resistance to decomposition and remained in fairly constant proportion during decomposition. Paraffinic components were very resistant to decomposition and increased in relative concentration as decomposition progressed. Lignin was a minor component of all leaf tissues. Standard methods for the colorimetric determination of tannins (Folin-Dennis reagent) and the gravimetric determination of lignin (Klason lignin) were highly inaccurate when applied to mangrove leaves. The N content of the leaves was particularly dynamic with values ranging from 1.27 wt% in green leaves to 0.65 wt% in senescent yellow leaves attached to trees. During decomposition in the water the N content initially decreased to 0.51 wt% due to leaching, but values steadily increased thereafter to 1.07 wt% in the most degraded leaf samples. The absolute mass of N in the leaves increased during decomposition indicating that N immobilization was occurring as decomposition progressed.

  15. Identifying oil/marine snow associations in mesocosm simulations of the Deepwater Horizon oil spill event using solid-state 13C NMR spectroscopy.

    Science.gov (United States)

    Hatcher, Patrick G; Obeid, Wassim; Wozniak, Andrew S; Xu, Chen; Zhang, Saijin; Santschi, Peter H; Quigg, Antonietta

    2018-01-01

    The Deepwater Horizon oil spill stimulated the release of marine snow made up of dead/living plankton/bacteria and their exopolymeric polysaccharide substances (EPS), termed marine oil snow (MOS), promoting rapid removal of oil from the water column into sediments near the well site. Mesocosm simulations showed that Macondo surrogate oil readily associates with the marine snow. Quantitative solid-state 13 C NMR readily distinguishes this oil from naturally formed marine snow and reveals that adding the dispersant Corexit enhances the amount of oil associated with the MOS, thus contributing to rapid removal from the water column. Solvent extraction of MOS removes the oil-derived compounds for analysis by one and two-dimensional GC/MS and evaluation of potential transformations they undergo when associated with the EPS. The results reveal that the oil associated with EPS is subjected to rapid transformation, in a matter of days, presumably by bacteria and fungi associated with EPS. Copyright © 2017 Elsevier Ltd. All rights reserved.

  16. Analysis of the mechanical properties and characterization by solid state {sup 13} C NMR of recycled EVA copolymer/silica composites

    Energy Technology Data Exchange (ETDEWEB)

    Stael, Giovanni Chaves [Observatorio Nacional, Rio de Janeiro, RJ (Brazil)]. E-mail: stael@on.br; Rocha, Marisa Cristina Guimaraes [Universidade do Estado do Rio de Janeiro, Nova Friburgo, RJ (Brazil). Instituto Politecnico; Menezes, Sonia Maria Cabral de [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas. Quimica; D' Almeida, Jose Roberto Morais; Ruiz, Naira Machado da Silva [Pontificia Universidade Catolica do Rio de Janeiro, RJ (Brazil)

    2005-07-15

    The incorporation of micrometer sized silica particles on poly (ethylene-co-vinyl acetate) - EVA - residues from the footwear industry was evaluated. The effects of the processing parameters - temperature and mixing ratio - on the mechanical behavior of molded plates of neat recycled EVA and EVA/silica composites were also investigated. The mechanical properties measured by the tensile test, the fractographic analysis by scanning electron microscopy (SEM), and the {sup 13} C Nuclear Magnetic Resonance (NMR) showed a reduced EVA to silica compatibility. Therefore, incorporation of untreated silica to recycled EVA copolymer produced a slight decrease on the mechanical performance of EVA/silica composites in respect to neat EVA copolymer. The NMR analysis also shows that the crosslinking process on recycled EVA may be occurring at the carbonyl group. (author)

  17. Structure determination of uniformly {sup 13}C, {sup 15}N labeled protein using qualitative distance restraints from MAS solid-state {sup 13}C-NMR observed paramagnetic relaxation enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Tamaki, Hajime [Hokkaido University, Graduate School of Life Science (Japan); Egawa, Ayako [Osaka University, Institute for Protein Research (Japan); Kido, Kouki [Hokkaido University, Graduate School of Life Science (Japan); Kameda, Tomoshi [National Institute of Advanced Industrial Science and Technology, Biotechnology Research Institute for Drug Discovery (Japan); Kamiya, Masakatsu; Kikukawa, Takashi; Aizawa, Tomoyasu [Hokkaido University, Faculty of Advanced Life Science (Japan); Fujiwara, Toshimichi [Osaka University, Institute for Protein Research (Japan); Demura, Makoto, E-mail: demura@sci.hokudai.ac.jp [Hokkaido University, Faculty of Advanced Life Science (Japan)

    2016-01-15

    Magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) is a powerful method for structure determination of insoluble biomolecules. However, structure determination by MAS solid-state NMR remains challenging because it is difficult to obtain a sufficient amount of distance restraints owing to spectral complexity. Collection of distance restraints from paramagnetic relaxation enhancement (PRE) is a promising approach to alleviate this barrier. However, the precision of distance restraints provided by PRE is limited in solid-state NMR because of incomplete averaged interactions and intermolecular PREs. In this report, the backbone structure of the B1 domain of streptococcal protein G (GB1) has been successfully determined by combining the CS-Rosetta protocol and qualitative PRE restraints. The derived structure has a Cα RMSD of 1.49 Å relative to the X-ray structure. It is noteworthy that our protocol can determine the correct structure from only three cysteine-EDTA-Mn{sup 2+} mutants because this number of PRE sites is insufficient when using a conventional structure calculation method based on restrained molecular dynamics and simulated annealing. This study shows that qualitative PRE restraints can be employed effectively for protein structure determination from a limited conformational sampling space using a protein fragment library.

  18. Acid-base interactions and secondary structures of poly-L-lysine probed by 15N and 13C solid state NMR and Ab initio model calculations.

    Science.gov (United States)

    Dos, Alexandra; Schimming, Volkmar; Tosoni, Sergio; Limbach, Hans-Heinrich

    2008-12-11

    The interactions of the 15N-labeled amino groups of dry solid poly-L-lysine (PLL) with various halogen and oxygen acids HX and the relation to the secondary structure have been studied using solid-state 15N and 13C CPMAS NMR spectroscopy (CP = cross polarization and MAS = magic angle spinning). For comparison, 15N NMR spectra of an aqueous solution of PLL were measured as a function of pH. In order to understand the effects of protonation and hydration on the 15N chemical shifts of the amino groups, DFT and chemical shielding calculations were performed on isolated methylamine-acid complexes and on periodic halide clusters of the type (CH3NH3(+)X(-))n. The combined experimental and computational results reveal low-field shifts of the amino nitrogens upon interaction with the oxygen acids HX = HF, H2SO4, CH3COOH, (CH3)2POOH, H3PO4, HNO3, and internal carbamic acid formed by reaction of the amino groups with gaseous CO2. Evidence is obtained that only hydrogen-bonded species of the type (Lys-NH2***H-X)n are formed in the absence of water. 15N chemical shifts are maximum when H is located in the hydrogen bond center and then decrease again upon full protonation, as found for aqueous solution at low pH. By contrast, halogen acids interact in a different way. They form internal salts of the type (Lys-NH3(+)X(-))n via the interaction of many acid-base pairs. This salt formation is possible only in the beta-sheet conformation. By contrast, the formation of hydrogen-bonded complexes can occur both in beta-sheet domains as well as in alpha-helical domains. The 15N chemical shifts of the protonated ammonium groups increase when the size of the interacting halogen anions is increased from chloride to iodide and when the number of the interacting anions is increased. Thus, the observed high-field 15N shift of ammonium groups upon hydration is the consequence of replacing interacting halogen atoms by oxygen atoms.

  19. Supressão das anomalias de fase e batimentos laterais em espectros de RMN 13c obtidos com a sequência de precessão livre no estado estacionário Suppression of phase anomalies and sidebands on 13c NMR spectra obtained with the steady-state free precession sequence

    Directory of Open Access Journals (Sweden)

    Poliana Macedo dos Santos

    2010-01-01

    Full Text Available The Steady-State Free Precession (SSFP sequence has been widely used in low-field and low-resolution imaging NMR experiments to increase the signal-to-noise ratio (s/n of the signals. Here, we analyzed the Scrambled Steady State - SSS and Unscrambled Steady State - USS sequences to suppress phase anomalies and sidebands of the 13C NMR spectrum acquired in the SSFP regime. The results showed that the application of the USS sequence allowed a uniform distribution of the time interval between pulses (Tp, in the established time range, allowing a greater suppression of phase anomalies and sidebands, when compared with the SSS sequence.

  20. 13C-NMR chemical shift databases as a quick tool to evaluate structural models of humic substances

    DEFF Research Database (Denmark)

    Nyrop Albers, Christian; Hansen, Poul Erik

    2010-01-01

    Models for humic and fulvic acids are discussed based on 13C liquid state NMR spectra combined with results from elemental analysis and titration studies. The analysis of NMR spectra is based on a full reconstruction of the NMR spectrum done with help of 13C-NMR data bases by adding up chemical...... side missing structural elements in the models can be suggested. A number of proposed structures for humic and fulvic acids are discussed based on the above analysis....

  1. Solid-state NMR detection of 14N-13C dipolar couplings between amino acid side groups provides constraints on amyloid fibril architecture.

    Science.gov (United States)

    Middleton, David A

    2011-02-01

    Solid-state nuclear magnetic resonance (SSNMR) is a powerful technique for the structural analysis of amyloid fibrils. With suitable isotope labelling patterns, SSNMR can provide constraints on the secondary structure, alignment and registration of β-strands within amyloid fibrils and identify the tertiary and quaternary contacts defining the packing of the β-sheet layers. Detection of (14)N-(13)C dipolar couplings may provide potentially useful additional structural constraints on β-sheet packing within amyloid fibrils but has not until now been exploited for this purpose. Here a frequency-selective, transfer of population in double resonance SSNMR experiment is used to detect a weak (14)N-(13)C dipolar coupling in amyloid-like fibrils of the peptide H(2)N-SNNFGAILSS-COOH, which was uniformly (13)C and (15)N labelled across the four C-terminal amino acids. The (14)N-(13)C interatomic distance between leucine and asparagine side groups is constrained between 2.4 and 3.8 Å, which allows current structural models of the β-spine arrangement within the fibrils to be refined. This procedure could be useful for the general structural analysis of other proteins in condensed phases and environments, such as biological membranes. Copyright © 2011 John Wiley & Sons, Ltd.

  2. Quantitative comparison of structure and dynamics of elastin following three isolation schemes by 13C solid state NMR and MALDI mass spectrometry.

    Science.gov (United States)

    Papaioannou, A; Louis, M; Dhital, B; Ho, H P; Chang, E J; Boutis, G S

    2015-05-01

    Methods for isolating elastin from fat, collagen, and muscle, commonly used in the design of artificial elastin based biomaterials, rely on exposing tissue to harsh pH levels and temperatures that usually denature many proteins. At present, a quantitative measurement of the modifications to elastin following isolation from other extracellular matrix constituents has not been reported. Using magic angle spinning (13)C NMR spectroscopy and relaxation methodologies, we have measured the modification in structure and dynamics following three known purification protocols. Our experimental data reveal that the (13)C spectra of the hydrated samples appear remarkably similar across the various purification methods. Subtle differences in the half maximum widths were observed in the backbone carbonyl suggesting possible structural heterogeneity across the different methods of purification. Additionally, small differences in the relative signal intensities were observed between purified samples. Lyophilizing the samples results in a reduction of backbone motion and reveals additional differences across the purification methods studied. These differences were most notable in the alanine motifs indicating possible changes in cross-linking or structural rigidity. The measured correlation times of glycine and proline moieties are observed to also vary considerably across the different purification methods, which may be related to peptide bond cleavage. Lastly, the relative concentration of desmosine cross-links in the samples quantified by MALDI mass spectrometry is reported. Copyright © 2015 Elsevier B.V. All rights reserved.

  3. {sup 13} C-NMR of mesquite gum

    Energy Technology Data Exchange (ETDEWEB)

    Andrade, Cristina T; Garcia, Rosangela B [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas

    1992-12-31

    Mesquite and guar gums are galactomannans extracted from the seeds of Proposis Juliflora and Cyamopsis tetragonolobus, respectively. An experimental sample of mesquite gum and a commercial sample of guar gum were partially depolymerized by ultrasonic radiation and the produce analysed by high resolution {sup 13} C-NMR spectroscopy. The different carbon lines were resolved and their assignments were done as those reported in the literature. The galactose to mannose ratios (G/M) were estimated from the relative peak areas of the C-1 lines as G/M=61 for mesquite and G/M=0.54 for guar gum. The next nearest-neighbour probabilities (diad frequencies) of the D-galactosyl substitution to the D-mannose backbone were evaluated by integrating C-4 mannose splitted peaks. (author) 9 refs., 2 figs., 2 tabs.

  4. Distinguishing tautomerism in the crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide using DFT-D calculations and {sup 13}C solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Li, Xiaozhou; Bond, Andrew D.; Johansson, Kristoffer E.; Van de Streek, Jacco, E-mail: jacco.vandestreek@sund.ku.dk [Department of Pharmacy, University of Copenhagen, Universitetsparken 2, Copenhagen DK-2100 (Denmark)

    2014-08-01

    The crystal structure of (Z)-N-(5-ethyl-2,3-di-hydro-1,3,4-thiadiazol-2-ylidene) -4-methylbenzenesulfonamide contains an imine tautomer, rather than the previously reported amine tautomer. The tautomers can be distinguished using dispersion-corrected density functional theory calculations and by comparison of calculated and measured {sup 13}C solid-state NMR spectra. The crystal structure of the title compound, C{sub 11}H{sub 13}N{sub 3}O{sub 2}S{sub 2}, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated {sup 13}C solid-state NMR spectra [Hangan et al. (2010 ▶). Acta Cryst. B66, 615–621]. The mol@@ecule is tautomeric, and was reported as an amine tautomer [systematic name: N-(5-ethyl-1,3,4-thia@@diazol-2-yl)-p-toluene@@sulfonamide], rather than the correct imine tautomer. The protonation site on the mol@@ecule’s 1,3,4-thia@@diazole ring is indicated by the inter@@molecular contacts in the crystal structure: N—H⋯O hydrogen bonds are established at the correct site, while the alternative protonation site does not establish any notable inter molecular inter@@actions. The two tautomers provide essentially identical Rietveld fits to laboratory PXRD data, and therefore they cannot be directly distinguished in this way. However, the correct tautomer can be distinguished from the incorrect one by previously reported qu@@anti@@tative criteria based on the extent of structural distortion on optimization of the crystal structure using dispersion-corrected density functional theory (DFT-D) calculations. Calculation of the {sup 13}C SS-NMR spectrum based on the correct imine tautomer also provides considerably better agreement with the measured {sup 13}C SS-NMR spectrum.

  5. 13C CPMAS NMR Studies of Anthocyanidins and their Glucosides

    International Nuclear Information System (INIS)

    Wolniak, M.; Wawer, I.

    2005-01-01

    Anthocyanins are responsible for red, purple or blue colours of flower petals and can be found in red or black fruits and berries. Many foods, especially red grapes and wines, aronia or blueberries contain large amounts of anthocyanins. Their health beneficial effects are related to antioxidant and radical scavenging properties. Structural analysis of anthocyanins by NMR are few, owing to the difficulty in obtaining analysable spectra for unstable, interconverting compounds, available in small amounts. Compounds studied by us were isolated from fruits and berries. 13 C CPMAS NMR spectra were recorded on a Bruker DSX-400 spectrometer for solid chlorides of: cyanidin, cyanidin 3-O-glucoside, cyanidin 3,5-O-diglucoside, pelargonidin and pelargonidin 3-O-glucoside. Dipolar dephased and short contact pulse sequences were used as an aid in the assignment of resonances in CPMAS spectra of solids. Inspection of the spectra indicates that anthocyanidins are in the form of flavylium (cationic) and not in form of the chalcone.: the resonance of C2 appears at ca. 160 ppm and C3 at ca. 135 ppm, whereas C ring opening produces C2 = O, for which chemical shift of ca. 180 ppm can be expected. A comparison of experimental (CPMAS) and predicted (GIAO DFT) shielding constants for cyanidin provided information about the orientation of OH groups, twist angle of aromatic ring B and the localization of the chloride anion.(author)

  6. Alpha Resonant States in 13C

    International Nuclear Information System (INIS)

    Rodrigues, M. R. D.; Borello-Lewin, T.; Horodynski-Matsushigue, L. B.; Duarte, J. L. M.; Rodrigues, C. L.; Souza, M. A.; Miyake, H.; Cunsolo, A.; Cappuzzello, F.; Ukita, G. M.

    2011-01-01

    The 9 Be( 6 Li,d) 13 C reaction was used to investigate alpha resonant states in 13 C up to 15 MeV of excitation. The reaction was measured at a bombarding energy of 25.5 MeV employing the Sao Paulo Pelletron-Enge-Spectrograph facility and the nuclear emulsion detection technique. An energy resolution of 50 keV was obtained. Several narrow alpha resonant states not previously measured were detected, in particular the one at the (3α+n) threshold populated by an L = 2 transfer, revealing a 9 Be+α component for the 1/2 - cluster state candidate at this threshold. Experimental angular distributions are presented in comparison with DWBA predictions.

  7. Determination of the Tautomeric Equilibria of Pyridoyl Benzoyl -Diketones in the Liquid and Solid State through the use of Deuterium Isotope Effects on 1H and 13C NMR Chemical Shifts and Spin Coupling Constants

    DEFF Research Database (Denmark)

    Hansen, Poul Erik; Borisov, Eugeny V.; Lindon, John C.

    2015-01-01

    The tautomeric equilibria for 2-pyridoyl-, 3-pyridoyl-, and 4-pyridoyl-benzoyl methane have been investigated using deuterium isotope effects on 1H and 13C chemical shifts both in the liquid and the solid state. Equilibria are established both in the liquid and the solid state. In addition......, in the solution state the 2-bond and 3-bond J(1H–13C) coupling constants have been used to confirm the equilibrium positions. The isotope effects due to deuteriation at the OH position are shown to be superior to chemical shift in determination of equilibrium positions of these almost symmetrical -pyridoyl......-benzoyl methanes. The assignments of the NMR spectra are supported by calculations of the chemical shifts at the DFT level. The equilibrium positions are shown to be different in the liquid and the solid state. In the liquid state the 4-pyridoyl derivative is at the B-form (C-1 is OH), whereas the 2-and 3-pyridoyl...

  8. Carbon-13 solid state NMR studies in the aromatization of residual coals from hydropyrolised cellulose; Estudo por {sup 13} C RMN em estado solido da aromatizacao em carvoes residuais de celulose hidropirolisada

    Energy Technology Data Exchange (ETDEWEB)

    Rocha, J.D.; Luengo, C.A. [Universidade Estadual de Campinas, SP (Brazil). Inst. de Fisica; Snape, C.A. [Dept. Pure and Apllied Chemistry, Glasgow (United Kingdom)

    1997-12-31

    Pure cellulose was pyrolyzed is a fixed-bed reactor under hydrogen pressure (hydropyrolysis). Residual chars were collected and analysed by solid state nmr {sup 13} C (CP-MAS) and elemental. Hydrophyrolysis parameters such as final temperature in the range of 300 to 520 deg C and hydrogen pressure from 5 to 100 atm gave different char samples. CP-MAS spectra were obtained in a BRUKER MSL-100 spectrometer. The results showed that the aromatic and aliphatic fractions had strong dependence with temperature and no influence with pressure. Elemental analysis indicated the carbon content increased more with temperature than the pressure increasing. (author) 6 refs., 2 figs., 2 tabs.

  9. NMR structure analysis of uniformly 13C-labeled carbohydrates.

    Science.gov (United States)

    Fontana, Carolina; Kovacs, Helena; Widmalm, Göran

    2014-06-01

    In this study, a set of nuclear magnetic resonance experiments, some of them commonly used in the study of (13)C-labeled proteins and/or nucleic acids, is applied for the structure determination of uniformly (13)C-enriched carbohydrates. Two model substances were employed: one compound of low molecular weight [(UL-(13)C)-sucrose, 342 Da] and one compound of medium molecular weight ((13)C-enriched O-antigenic polysaccharide isolated from Escherichia coli O142, ~10 kDa). The first step in this approach involves the assignment of the carbon resonances in each monosaccharide spin system using the anomeric carbon signal as the starting point. The (13)C resonances are traced using (13)C-(13)C correlations from homonuclear experiments, such as (H)CC-CT-COSY, (H)CC-NOESY, CC-CT-TOCSY and/or virtually decoupled (H)CC-TOCSY. Based on the assignment of the (13)C resonances, the (1)H chemical shifts are derived in a straightforward manner using one-bond (1)H-(13)C correlations from heteronuclear experiments (HC-CT-HSQC). In order to avoid the (1) J CC splitting of the (13)C resonances and to improve the resolution, either constant-time (CT) in the indirect dimension or virtual decoupling in the direct dimension were used. The monosaccharide sequence and linkage positions in oligosaccharides were determined using either (13)C or (1)H detected experiments, namely CC-CT-COSY, band-selective (H)CC-TOCSY, HC-CT-HSQC-NOESY or long-range HC-CT-HSQC. However, due to the short T2 relaxation time associated with larger polysaccharides, the sequential information in the O-antigen polysaccharide from E. coli O142 could only be elucidated using the (1)H-detected experiments. Exchanging protons of hydroxyl groups and N-acetyl amides in the (13)C-enriched polysaccharide were assigned by using HC-H2BC spectra. The assignment of the N-acetyl groups with (15)N at natural abundance was completed by using HN-SOFAST-HMQC, HNCA, HNCO and (13)C-detected (H)CACO spectra.

  10. Theoretical predictions of the two-dimensional solid-state NMR spectra: a case study of the 13C-1H correlations in metergoline

    Czech Academy of Sciences Publication Activity Database

    Czernek, Jiří; Brus, Jiří

    2013-01-01

    Roč. 586, 24 October (2013), s. 56-60 ISSN 0009-2614 Institutional support: RVO:61389013 Keywords : NMR * shielding * metergoline Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.991, year: 2013

  11. Metabolic pathways for ketone body production. 13C NMR spectroscopy of rat liver in vivo using 13C-multilabeled fatty acids

    International Nuclear Information System (INIS)

    Pahl-Wostl, C.; Seelig, J.

    1986-01-01

    The hormonal regulation of ketogenesis in the liver of living rat has been studied noninvasively with 13 C nuclear magnetic resonance. The spatial selection for the liver was better than 90%, with extrahepatic adipose tissue contribution only a very small amount of signal. The metabolic activities of the liver were investigated by infusion of 13 C-labeled butyrate in the jugular vein of the anesthetized rat. The rate of butyrate infusion was chosen to be close to the maximum oxidative capacity of the rat liver, and the 13 C signal intensities were enhanced by using doubly labeled [1,3- 13 C]butyrate as a substrate. Different 13 C NMR spectra and hence different metabolites were observed depending on the hormonal state of the animal. The 13 C NMR studies demonstrate that even when rate of acetyl-CoA production are high, the disposal of this compound is not identical in fasted and diabetic animals. This supports previous suggestions that the redox state of the mitochondrion represents the most important factor in regulation. For a given metabolic state of the animal, different signal intensities were obtained depending on whether butyrate was labeled at C-1, C-3, or C-1,3. From the ratios of incorporation of 13 C label into the carbons of 3-hydroxybutyrate, it could be estimated that a large fraction of butyrate evaded β-oxidation to acetyl-CoA but was converted directly to acetoacetyl-CoA. 13 C-labeled glucose could be detected in vivo in the liver of diabetic rats

  12. Computer-aided structure analysis. Structure identification by infrared and /sup 13/C NMR measurements

    Energy Technology Data Exchange (ETDEWEB)

    Szalontai, G; Simon, Z; Csapo, Z; Farkas, M; Pfeifer, Gy [Nehezvegyipari Kutato Intezet, Veszprem (Hungary)

    1980-01-01

    The results obtained from the computer-aided interpretation of /sup 13/C NMR and IR spectra using the artificial intelligence approach are presented. In its present state the output of the system is a list of functional groups which are resonable candidates for the final structural isomers. The input requires empirical formula, /sup 13/C NMR data (off resonance data also) and IR spectral data. The confirmation of the presence of a functional group is based on comparison of the experimental data with the spectral properties of functional groups stored in a property matrix. If the molecular weight of the compounds studied is less or equal 500, the output contains usually 1.5-2.5 times more groups than really present, in most cases without the loss of the real ones.

  13. Solid state {sup 13}C NMR study on the synthesis of graphite oxide from different graphitic precursors; Estudo atravéS de RMN de {sup 13}C no estado sólido sobre a síntese de oxido de grafite utilizando diferentes precursores grafíticos

    Energy Technology Data Exchange (ETDEWEB)

    Vieira, Mariana A.; Frasson, Carolina Maria R.; Costa, Tainara Luiza G.; Cipriano, Daniel F.; Schettino Junior, Miguel A.; Cunha, Alfredo G.; Freitas, Jair C.C., E-mail: marianaarpini@hotmail.com [Universidade Federal do Espírito Santo (UFES), Vitória, ES (Brazil). Lab. de Materiais Carbonosos e Cerâmicos

    2017-10-15

    The influence of the structural and microstructural characteristics of graphitic precursors on the production of graphite oxide (GO) is investigated in the present work. Six different graphitic precursors were used to produce GO following a modified Hummers method, namely: natural graphite, commercial lubricant graphite, milled graphite, graphite flakes, high-purity graphite and graphite recycled from Li-ion batteries. The products were characterized by X-ray diffraction (XRD), thermogravimetry, solid-state {sup 13}C nuclear magnetic resonance (NMR) and scanning electron microscopy (SEM). {sup 13}C NMR spectra revealed the presence of epoxy, hydroxyl, carbonyl and lactol groups in the synthesized GOs. However, the oxidation degree of each product was found to be dependent on the average crystallite size (Lc) and particle size of the graphitic precursors, with the best GO samples being produced from the milled graphite and the graphite recycled from ion-Li batteries. These results were rationalized in terms of the structural and microstructural differences among the graphitic precursors, as revealed by the XRD patterns and SEM images, evidencing the importance of the correct choice of the precursor aiming the achievement of a well-developed structure for the GO product. (author)

  14. Analysis of commercial proanthocyanidins. Part 4: solid state (13)C NMR as a tool for in situ analysis of proanthocyanidin tannins, in heartwood and bark of quebracho and acacia, and related species.

    Science.gov (United States)

    Reid, David G; Bonnet, Susan L; Kemp, Gabre; van der Westhuizen, Jan H

    2013-10-01

    (13)C NMR is an effective method of characterizing proanthocyanidin (PAC) tannins in quebracho (Schinopsis lorentzii) heartwood and black wattle (Acacia mearnsii) bark, before and after commercial extraction. The B-rings of the constituent flavan-3-ols, catechols (quebracho) or pyrogallols (wattle), are recognized in unprocessed source materials by "marker" signals at ca. 118 or 105ppm, respectively. NMR allows the minimum extraction efficiency to be calculated; ca. 30%, and ca. 80%, for quebracho heartwood and black wattle bark, respectively. NMR can also identify PAC tannin (predominantly robinetinidin), and compare tannin content, in bark from other acacia species; tannin content decreases in the order A. mearnsii, Acacia pycnantha (87% of A. mearnsii), Acacia dealbata and Acacia decurrens (each 74%) and Acacia karroo (30%). Heartwood from an underexploited PAC tannin source, Searsia lancea, taxonomically close to quebracho, shows abundant profisetinidin and catechin PACs. NMR offers the advantage of being applicable to source materials in their native state, and has potential applications in optimizing extraction processes, identification of tannin sources, and characterization of tannin content in cultivar yield improvement programmes. Copyright © 2013 Elsevier Ltd. All rights reserved.

  15. 13C and 29Si NMR as a probe to investigate polysiloxanes used in dental applications

    International Nuclear Information System (INIS)

    Silva, Naira Machado da; Tavares, Maria Ines B.

    2001-01-01

    The properties of dental mould polymeric materials are strongly influenced by the chemical structure of both the polymer and the catalyst used in the crosslink reaction between them. In order to characterize and suggest some modifications on the materials interfacial interactions, mixtures of Polymer-catalyst were prepared. The polymer and the catalyst chemical structures were obtained by 13 C, 1 H and 129 Si NMR analysis in solution state. From the solution NMR results it was obtained the structure of the polymer and the catalyst and also the kind of the crosslink reaction taken. The CPMAS 1 '3C NMR analysis in the solid state were used to identify chemical structure of the polymeric dental moulded sample. (author)

  16. 13C NMR and EPR spectroscopic evaluation of oil shale mined soil recuperation

    International Nuclear Information System (INIS)

    Santos, J.V. dos; Mangrich, A.S.; Pereira, B.F.; Pillon, C.N.; Bonagamba, T.J.

    2013-01-01

    In this work, native forest soil (NFS) organic matter (SOM) sample and SOM samples from a neighboring forest soil area of an oil shale mine which is being rehabilitated for thirty years (RFS) were analyzed. X-band electron paramagnetic resonance (EPR) and solid-state 13 C nuclear magnetic resonance (NMR) spectroscopies were used to evaluate the soil reclamation of the Brazilian oil shale mining process. Two-dimensional heterospectral correlation studies of the results obtained from EPRand 13 C NMR were used to obtain information about SOM structures and their interactions with residual paramagnetic metal ion. The signal of the residual metallic oxycation, VO 2+ correlated positively with uronic acid-type hydrophilic organic structures, determined from the 13 C NMR spectra, and correlated negatively with the organic free radical (OFR) signal associated with oxygen atoms (g = 2.0042). The hydrophobic aromatic structures correlate positively with the EPR OFR signal associated with carbon atoms (g = 2.0022). The data from the two spectroscopic magnetic techniques show that the used recuperation process is effective. (author)

  17. {sup 13}C NMR and EPR spectroscopic evaluation of oil shale mined soil recuperation

    Energy Technology Data Exchange (ETDEWEB)

    Santos, J.V. dos, E-mail: mangrich@ufpr.br [Universidade Federal do Parana (UFPR), Curitiba, PR (Brazil); Mangrich, A.S. [Instituto Nacional de Ciencia e Tecnologia: Energia e Ambiente, Salvador, BA (Brazil); Pereira, B.F. [EMBRAPA Clima Temperado, Pelotas, RS (Brazil); Pillon, C.N. [EMBRAPA Clima Temperado, Pelotas, RS (Brazil). Estacao Experimental Cascata; Novotny, E.H. [EMBRAPA Solos, Rio de Janeiro, RJ (Brazil); Bonagamba, T.J. [Universidade de Sao Paulo (USP), Sao Carlos, SP (Brazil). Instituto de Fisica; Abbt-Braun, G.; Frimmel, F.H. [Engler-Bunte-Institut, Universitaet Karlsruhe, TH (Germany)

    2013-02-15

    In this work, native forest soil (NFS) organic matter (SOM) sample and SOM samples from a neighboring forest soil area of an oil shale mine which is being rehabilitated for thirty years (RFS) were analyzed. X-band electron paramagnetic resonance (EPR) and solid-state {sup 13}C nuclear magnetic resonance (NMR) spectroscopies were used to evaluate the soil reclamation of the Brazilian oil shale mining process. Two-dimensional heterospectral correlation studies of the results obtained from EPRand {sup 13}C NMR were used to obtain information about SOM structures and their interactions with residual paramagnetic metal ion. The signal of the residual metallic oxycation, VO{sup 2+} correlated positively with uronic acid-type hydrophilic organic structures, determined from the {sup 13}C NMR spectra, and correlated negatively with the organic free radical (OFR) signal associated with oxygen atoms (g = 2.0042). The hydrophobic aromatic structures correlate positively with the EPR OFR signal associated with carbon atoms (g = 2.0022). The data from the two spectroscopic magnetic techniques show that the used recuperation process is effective. (author)

  18. Conformational analysis of capsaicin using 13C, 15N MAS NMR, GIAO DFT and GA calculations

    Science.gov (United States)

    Siudem, Paweł; Paradowska, Katarzyna; Bukowicki, Jarosław

    2017-10-01

    Capsaicin produced by plants from genus Capsicum exerts multiple pharmacological effects and has found applications in food and pharmaceutical industry. The alkaloid was studied by a combined approach: solid-state NMR, GA conformational search and GIAO DFT methods. The 13C CPMAS NMR spectra were recorded using variable contact time and dipolar dephasing experiments. The results of cross-polarization (CP) kinetics, such as TCP values and long T1ρH (100-200 ms), indicated that the capsaicin molecule is fairly mobile, especially at the end of the aliphatic chain. The15N MAS NMR spectrum showed one narrow signal at -255 ppm. Genetic algorithm (GA) search with multi modal optimization was used to find low-energy conformations of capsaicin. Theoretical GIAO DFT calculations were performed using different basis sets to characterize five selected conformations. 13C CPMAS NMR was used as a validation method and the experimental chemical shifts were compared with those calculated for selected stable conformers. Conformational analysis suggests that the side chain can be bent or extended. A comparison of the experimental and the calculated chemical shifts indicates that solid capsaicin does not have the same structure as those established by PWXRD.

  19. Optimized strategy of 1H and 13C solid-state NMR methods to investigate water dynamics in soil organic matter as well as the influence of crystallinity of poly(methylene) segments

    Science.gov (United States)

    Bertmer, Marko; Jaeger, Alexander; Schwarz, Jette; Schaumann, Gabriele

    2010-05-01

    Water plays a crucial role in soil organic matter (SOM) having various different functions such as transport of material, elution of ,e. g., pollutants in soil, and also the sequestration of humic substances. Furthermore, the generation and quantification of hydrophilic and hydrophobic regions in soil has several effects on SOM which can also include the storage amount and time of certain material, especially chemical pollutants. The importance of water in soil is also documented by the multitude of scientific approaches to characterize soils including diffusion NMR to study the water channel structure in soil. Our focus is on the study of water dynamics and soil structure to elucidate mechanisms of physicochemical aging. The approach uses the application of various solid-state NMR techniques - including 1H and 13C NMR - to get a multitude of information on SOM. In non-rotating samples, 1H lines are usually very broad and unstructured. Nevertheless, this rather simple technique allows for a differentiation of 1H containing chemicals based on their dynamics in soil. This includes rather solid soil components and solid as well as mobile water molecules. Based on an optimized 1H solid-state NMR strategy to study soil material together with a straightforward lineshape analysis, a series of soils and peats are characterized. Although even 1H NMR with sample spinning (MAS) often gives only limited information on different structures, we present results on the application of 2D 1H-1H phase-modulated Lee-Goldburg sequences (PMLG), that show already at medium spinning speeds the separation of functional groups. Their quantification can be correlated with sample composition, type of sample conditioning, and other parameters such as cation type or concentration and heat treatment. We are especially interested to correlate NMR data with DSC measurements based on a certain heat treatment of the soils. Our proposed model describes the presence of water in soil as a matrix

  20. Influence of the nature of soil organic matter on the sorption behaviour of pentadecane as determined by PLS analysis of mid-infrared DRIFT and solid-state {sup 13}C NMR spectra

    Energy Technology Data Exchange (ETDEWEB)

    Clark Ehlers, G.A. [Institute of Environmental Biotechnology, Department IFA-Tulln, University of Natural Resources and Applied Life Sciences, Vienna, Konrad Lorenz Str. 20, Tulln A-3430 (Austria); Forrester, Sean T. [CSIRO Land and Water, Waite Rd, Urrbrae SA 5064 (Australia); Scherr, Kerstin E. [Institute of Environmental Biotechnology, Department IFA-Tulln, University of Natural Resources and Applied Life Sciences, Vienna, Konrad Lorenz Str. 20, Tulln A-3430 (Austria); Loibner, Andreas P., E-mail: andreas.loibner@boku.ac.a [Institute of Environmental Biotechnology, Department IFA-Tulln, The University of Natural Resources and Applied Life Sciences, Vienna, Konrad Lorenz Str. 20, Tulln A-3430 (Austria); Janik, Les J. [CSIRO Land and Water, Waite Rd, Urrbrae SA 5064 (Australia)

    2010-01-15

    The nature of soil organic matter (SOM) functional groups associated with sorption processes was determined by correlating partitioning coefficients with solid-state {sup 13}C nuclear magnetic resonance (NMR) and diffuse reflectance mid-infrared (DRIFT) spectral features using partial least squares (PLS) regression analysis. Partitioning sorption coefficients for n-pentadecane (n-C{sub 15}) were determined for three alternative models: the Langmuir model, the dual distributed reactive domain model (DRDM) and the Freundlich model, where the latter was found to be the most appropriate. NMR-derived constitutional descriptors did not correlate with Freundlich model parameters. By contrast, PLS analysis revealed the most likely nature of the functional groups in SOM associated with n-C{sub 15} sorption coefficients (K{sub F}) to be aromatic, possibly porous soil char, rather than aliphatic organic components for the presently investigated soils. High PLS cross-validation correlation suggested that the model was robust for the purpose of characterising the functional group chemistry important for n-C{sub 15} sorption. - NMR/IR spectroscopy and chemometrics reveal the aromatic fraction of soil organic matter being responsible for alkane sorption.

  1. 13C nuclear magnetic resonance data of lanosterol derivatives—Profiling the steric topology of the steroid skeleton via substituent effects on its 13C NMR

    Science.gov (United States)

    Dias, Jerry Ray; Gao, Hongwu

    2009-12-01

    The 13C NMR spectra of over 24 tetracyclic triterpenoid derivatives have been structurally analyzed. The 13C NMR chemical shifts allow one to probe the steric topology of the rigid steroid skeleton and inductive effects of its substituents. Use of deuterium labeling in chemical shift assignment and B-ring aromatic terpenoids are also featured.

  2. Acetylenes bearing Aromatic Terminal Groups. : II 13C-NMR Spectra of Monosubstituted Diphenylacetylenes

    OpenAIRE

    野本, 健雄; Nomoto, Takeo

    1986-01-01

    Six monosubstituted diphenylacetylenes, p-X-C6H4-C≡C-C6H5 1 (Ⅹ=NMe2, NH2, OMe, Cl, and NO2), were synthesized, and 13C-NMR spectra of their acetylenic carbons were measured. Hammett plots of the chemical shifts of the acetylenic α-13C and β-13C (against substituent constants σ) respectively showed a linear relationship, eXCept for β-13C on NMe2 and NH2 groups. The effects of substituents on 13C-Chemical shifts of diphenylacetylenes and effeciency of the C≡C bonds in transmitting the substitue...

  3. 1H, 15N and 13C NMR Assignments of Mouse Methionine Sulfoxide Reductase B2

    Science.gov (United States)

    Breivik, Åshild S.; Aachmann, Finn L.; Sal, Lena S.; Kim, Hwa-Young; Del Conte, Rebecca; Gladyshev, Vadim N.; Dikiy, Alexander

    2011-01-01

    A recombinant mouse methionine-r-sulfoxide reductase 2 (MsrB2ΔS) isotopically labeled with 15N and 15N/13C was generated. We report here the 1H, 15N and 13C NMR assignments of the reduced form of this protein. PMID:19636904

  4. Intracellular PHB conversion in a type II methanotroph studied by 13 C NMR

    NARCIS (Netherlands)

    Vecherskaya, M.; Dijkema, C.; Stams, A.J.M.

    2001-01-01

    Poly-g-hydroxybutyrate (PHB) formation under aerobic conditions via incorporation of [13C-2]acetate as a cosubstrate and its intracellular degradation under anaerobic conditions in a Type II methanotroph was studied by 13C NMR. During PHB synthesis in the presence of labelled acetate, low levels of

  5. Aspects of reaction of N-oxide radical with ethers in 13C NMR spectrum

    International Nuclear Information System (INIS)

    Kolodziejski, W.

    1980-01-01

    The stable radical N-oxide 2,2,6,6-tetramethylpiperidine was dissolved in ethers. The 13 C NMR spectra were recorded in the temperature 313K at the frequency 22,625 MHz on the spectrometers with Fourier transformation. The dissolution of the radical in ether caused the contact shifts in NMR spectra. The shifts were measured. (A.S.)

  6. 13C and 31P NMR study of gluconeogenesis: utilization of 13C-labeled substrates by perfused liver from streptozotocin-diabetic and untreated rats

    International Nuclear Information System (INIS)

    Cohen, S.M.

    1987-01-01

    The metabolism of 13 C-labeled substrates was followed by 13 C and 31 P NMR in perfused liver from the streptozotocin-treated rat model of insulin-dependent diabetes. Comparison was made with perfused liver from untreated littermates, fasted either 24 or 12 h. The major routes of pyruvate metabolism were followed by a 13 C NMR approach that provided for the determination of the metabolic fate of several substances simultaneously. The rate of gluconeogenesis was 2-4-fold greater and β-hydroxybutyrate production was 50% greater in liver from the chronically diabetic rats as compared with the control groups. Large differences in the distribution of 13 C label in hepatic alanine were measured between diabetic and control groups. The biosyntheses of 13 C-labeled glutathione and N-carbamoylaspartate were monitored in time-resolved 13 C NMR spectra of perfused liver. Assignments for the resonances of glutathione and N-carbamoylaspartate were made with the aid of 13 C NMR studies of perchloric acid extracts of the freeze-clamped livers. 13 C NMR spectroscopy of the perfusates provided a convenient, rapid assay of the rate of oxidation of [2- 13 C]ethanol, the hepatic output of [2- 13 ]acetaldehyde, and the accumulation of [2- 13 C]acetate in the perfusate. By 31 P NMR spectroscopy, carbamoyl phosphate was measured in all diabetic livers and an unusual P,P'-diesterified pyrophosphate was observed in one-fourth of the diabetic livers examined. Neither of these phosphorylated metabolites was detected in control liver. Both 13 C and 31 P NMR were useful in defining changes in hepatic metabolism in experimental diabetes

  7. Detailed {sup 1}H and {sup 13}C NMR spectral data assignment for two dihydrobenzofuran neolignans

    Energy Technology Data Exchange (ETDEWEB)

    Medeiros, Talita C.T.; Dias, Herbert J.; Crotti, Antônio E.M., E-mail: millercrotti@ffclrp.usp.br [Universidade de São Paulo (USP), Ribeirão Preto, SP (Brazil). Faculdade de Filosofia, Ciências e Letras. Departamento de Química

    2016-07-01

    In this work we present a complete proton ({sup 1}H) and carbon 13 ({sup 13}C) nuclear magnetic resonance (NMR) spectral analysis of two synthetic dihydrofuran neolignans (±)-trans-dehydrodicoumarate dimethyl ester and (±)-trans-dehydrodiferulate dimethyl ester. Unequivocal assignments were achieved by 1 H NMR, proton decoupled {sup 13}C ({sup 13}C{"1H}) NMR spectra, gradient-selected correlation spectroscopy (gCOSY), J-resolved, gradient-selected heteronuclear multiple quantum coherence (gHMQC), gradient-selected heteronuclear multiple bond coherence (gHMBC) and nuclear Overhauser effect spectroscopy (NOESY) experiments. All hydrogen coupling constants were measured, clarifying all the hydrogen signals multiplicities. Computational methods were also used to simulate the {sup 1}H and {sup 13}C chemical shifts and showed good agreement with the trans configuration of the substituents at C{sub 7} and C{sub 8}. (author)

  8. Detailed 1H and 13C NMR spectral data assignment for two dihydrobenzofuran neolignans

    International Nuclear Information System (INIS)

    Medeiros, Talita C.T.; Dias, Herbert J.; Crotti, Antônio E.M.

    2016-01-01

    In this work we present a complete proton ( 1 H) and carbon 13 ( 13 C) nuclear magnetic resonance (NMR) spectral analysis of two synthetic dihydrofuran neolignans (±)-trans-dehydrodicoumarate dimethyl ester and (±)-trans-dehydrodiferulate dimethyl ester. Unequivocal assignments were achieved by 1 H NMR, proton decoupled 13 C ( 13 C{ 1 H}) NMR spectra, gradient-selected correlation spectroscopy (gCOSY), J-resolved, gradient-selected heteronuclear multiple quantum coherence (gHMQC), gradient-selected heteronuclear multiple bond coherence (gHMBC) and nuclear Overhauser effect spectroscopy (NOESY) experiments. All hydrogen coupling constants were measured, clarifying all the hydrogen signals multiplicities. Computational methods were also used to simulate the 1 H and 13 C chemical shifts and showed good agreement with the trans configuration of the substituents at C 7 and C 8 . (author)

  9. Robust refocusing of 13C magnetization in multidimensional NMR experiments by adiabatic fast passage pulses

    International Nuclear Information System (INIS)

    Zweckstetter, Markus; Holak, Tad A.

    1999-01-01

    We show that adiabatic fast passage (AFP) pulses are robust refocusing elements of transverse 13 C magnetization in multidimensional NMR experiments. A pair of identical AFP pulses can refocus selected parts or a complete 13 C chemical shift range in 13 C spectra. In the constant time 13 C- 1 H HSQC, replacement of attenuated rectangular pulses by selective AFP pulses results in a sensitivity enhancement of up to a factor of 1.8. In the 3D CBCA(CO)NH the signal-to-noise ratio is increased by a factor of up to 1.6

  10. A First Laboratory Utilizing NMR for Undergraduate Education: Characterization of Edible Fats and Oils by Quantitative [superscript 13]C NMR

    Science.gov (United States)

    Fry, Charles G.; Hofstetter, Heike; Bowman, Matthew D.

    2017-01-01

    Quantitative [superscript 13]C NMR provides a straightforward method of analyzing edible oils in undergraduate chemistry laboratories. [superscript 13]C spectra are relatively easy to understand, and are much simpler to analyze and workup than corresponding [superscript 1]H spectra. Average chain length, degree of saturation, and average…

  11. {sup 13}C-NMR studies on disulfide bond isomerization in bovine pancreatic trypsin inhibitor (BPTI)

    Energy Technology Data Exchange (ETDEWEB)

    Takeda, Mitsuhiro [Kumamoto University, Department of Structural BioImaging, Faculty of Life Sciences (Japan); Miyanoiri, Yohei [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan); Terauchi, Tsutomu [Tokyo Metropolitan University, Graduate School of Science and Engineering (Japan); Kainosho, Masatsune, E-mail: kainosho@tmu.ac.jp [Nagoya University, Structural Biology Research Center, Graduate School of Science (Japan)

    2016-09-15

    Conformational isomerization of disulfide bonds is associated with the dynamics and thus the functional aspects of proteins. However, our understanding of the isomerization is limited by experimental difficulties in probing it. We explored the disulfide conformational isomerization of the Cys14–Cys38 disulfide bond in bovine pancreatic trypsin inhibitor (BPTI), by performing an NMR line-shape analysis of its Cys carbon peaks. In this approach, 1D {sup 13}C spectra were recorded at small temperature intervals for BPTI samples selectively labeled with site-specifically {sup 13}C-enriched Cys, and the recorded peaks were displayed in the order of the temperature after the spectral scales were normalized to a carbon peak. Over the profile of the line-shape, exchange broadening that altered with temperature was manifested for the carbon peaks of Cys14 and Cys38. The Cys14–Cys38 disulfide bond reportedly exists in equilibrium between a high-populated (M) and two low-populated states (m{sub c14} and m{sub c38}). Consistent with the three-site exchange model, biphasic exchange broadening arising from the two processes was observed for the peak of the Cys14 α-carbon. As the exchange broadening is maximized when the exchange rate equals the chemical shift difference in Hz between equilibrating sites, semi-quantitative information that was useful for establishing conditions for {sup 13}C relaxation dispersion experiments was obtained through the carbon line-shape profile. With respect to the m{sub c38} isomerization, the {sup 1}H-{sup 13}C signals at the β-position of the minor state were resolved from the major peaks and detected by exchange experiments at a low temperature.

  12. Study of solid chemical evolution in torrefaction of different biomasses through solid-state "1"3C cross-polarization/magic angle spinning NMR (nuclear magnetic resonance) and TGA (thermogravimetric analysis)

    International Nuclear Information System (INIS)

    Rodriguez Alonso, Elvira; Dupont, Capucine; Heux, Laurent; Da Silva Perez, Denilson; Commandre, Jean-Michel; Gourdon, Christophe

    2016-01-01

    The objective of this work is to compare mass loss and chemical evolution of the solid phase, versus time, during dynamic torrefaction of different types of biomass. For this purpose, two experiments, ThermoGravimetric Analysis and solid-state "1"3C Cross-Polarization/Magic Angle Spinning Nuclear Magnetic Resonance, were run on four representative biomasses. Overall mass loss and chemical evolution of the solid phase were followed, respectively, as a function of temperature and time. Thanks to this coupled information, it was shown that the knowledge of both solid mass loss and chemical evolution is necessary to characterize torrefaction severity. Moreover, biomasses containing higher proportions of xylan lost mass faster than those containing lower proportions. Lignin showed a protecting role towards cellulose, which would lead to a faster degradation of non-woody biomasses in comparison with woody biomasses. Three parameters would have an influence on solid chemical evolution during torrefaction: xylan content in hemicellulose, lignin content in biomass, and cellulose crystallinity. - Highlights: • Torrefaction of four biomasses was studied with TGA and solid-state NMR. • Both solid mass loss and chemical evolution characterize torrefaction severity. • Biomasses containing a higher proportion of xylan lose mass faster. • Lignin shows a stronger protecting role in degradation of woody biomasses. • Xylan, lignin and crystalline cellulose values influence solid chemical evolution.

  13. 13C NMR for the assessment of human brain glucose metabolism in vivo

    International Nuclear Information System (INIS)

    Beckman, N.; Seelig, J.; Turkalj, I.; Keller, U.

    1991-01-01

    Proton-decoupled 13 C NMR spectra of the human head were obtained during hyperglycemic glucose clamping using intravenous infusions of [1- 13 C]glucose in normal volunteers. In addition to 13 C signals of mobile lipids, a variety of new metabolite resonances could be resolved for the first time in the human brain. At an enrichment level of 20% [1- 13 C]glucose, the signals of α- and β-glucose at 92.7 and 96.6 ppm, respectively, could be detected in the human brain after only an infusion period of 15 minutes. The spatial localization of the different regions of interest was confirmed by 13 C NMR spectroscopic imaging with a time resolution of 9 minutes. Increasing the enrichment level to 99% [1- 13 C]glucose not only improved the time resolution but allowed the detection of metabolic breakdown products of [1- 13 C]glucose. The time course of 13 C label incorporation into the C 2 , C 3 , and C 4 resonances of glutamate/glutamine and into lactate could be recorded in the human brain. These results suggest the possibility of obtaining time-resolved, spatially selective, and chemically specific information on the human body

  14. Changes in Lignin and Polysaccharide Components in 13 Cultivars of Rice Straw following Dilute Acid Pretreatment as Studied by Solution-State 2D 1H-13C NMR

    Science.gov (United States)

    Teramura, Hiroshi; Sasaki, Kengo; Oshima, Tomoko; Aikawa, Shimpei; Matsuda, Fumio; Okamoto, Mami; Shirai, Tomokazu; Kawaguchi, Hideo; Ogino, Chiaki; Yamasaki, Masanori; Kikuchi, Jun; Kondo, Akihiko

    2015-01-01

    A renewable raw material, rice straw is pretreated for biorefinery usage. Solution-state two-dimensional (2D) 1H-13 C hetero-nuclear single quantum coherence (HSQC) nuclear magnetic resonance (NMR) spectroscopy, was used to analyze 13 cultivars of rice straw before and after dilute acid pretreatment, to characterize general changes in the lignin and polysaccharide components. Intensities of most (15 of 16) peaks related to lignin aromatic regions, such as p-coumarate, guaiacyl, syringyl, p-hydroxyphenyl, and cinnamyl alcohol, and methoxyl, increased or remained unchanged after pretreatment. In contrast, intensities of most (11 of 13) peaks related to lignin aliphatic linkages or ferulate decreased. Decreased heterogeneity in the intensities of three peaks related to cellulose components in acid-insoluble residues resulted in similar glucose yield (0.45–0.59 g/g-dry biomass). Starch-derived components showed positive correlations (r = 0.71 to 0.96) with glucose, 5-hydroxymethylfurfural (5-HMF), and formate concentrations in the liquid hydrolysates, and negative correlations (r = –0.95 to –0.97) with xylose concentration and acid-insoluble residue yield. These results showed the fate of lignin and polysaccharide components by pretreatment, suggesting that lignin aromatic regions and cellulose components were retained in the acid insoluble residues and starch-derived components were transformed into glucose, 5-HMF, and formate in the liquid hydrolysate. PMID:26083431

  15. Detection of human muscle glycogen by natural abundance 13C NMR

    International Nuclear Information System (INIS)

    Avison, M.J.; Rothman, D.L.; Nadel, E.; Shulman, R.G.

    1988-01-01

    Natural abundance 13 C nuclear magnetic resonance spectroscopy was used to detect signals from glycogen in the human gastrocnemius muscle. The reproducibility of the measurement was demonstrated, and the ability to detect dynamic changes was confirmed by measuring a decrease in muscle glycogen levels after exercise and its subsequent repletion. Single frequency gated 1 H decoupling was used to obtain decoupled natural abundance 13 C NMR spectra of the C-1 position of muscle glycogen

  16. Cyclohexanecarbonitriles: Assigning Configurations at Quaternary Centers From 13C NMR CN Chemical Shifts.1

    Science.gov (United States)

    Wei, Guoqing

    2009-01-01

    13C NMR chemical shifts of the nitrile carbon in cyclohexanecarbonitriles directly correlate with the configuration of the quaternary, nitrile-bearing stereocenter. Comparing 13C NMR chemical shifts for over 200 cyclohexanecarbonitriles reveals that equatorially oriented nitriles resonate 3.3 ppm downfield, on average, from their axial counterparts. Pairs of axial/equatorial diastereomers varying only at the nitrile-bearing carbon consistently exhibit downfield shifts of δ 0.4–7.2 for the equatorial nitrile carbon, even in angularly substituted decalins and hydrindanes. PMID:19348434

  17. Evidencing of collagen polypeptide sequences responsible of hydration by means of 13 C NMR spectra

    International Nuclear Information System (INIS)

    Trandafir, Viorica; Georgescu, Mariana; Albu, Bujor; Popescu, G.; Akutsu, Hiroshi; Nechifor, Gheorghe

    2000-01-01

    The aim of these studies is to prepare biomaterials of high biocompatibility to the human body, provided for a long lifetime. Among these important biomaterials also accounts the collagen, with a large application area in medicine, pharmaceutics, cosmetics, etc. Collagen biomaterials of various hydration levels (between 23 - 83%) were prepared by a particular technique, using a matrix of 23% initial humidity. In order to investigate the structural and conformational changes from the collagen macromolecules by denaturation - renaturation, hydration - dehydration, the high-resolution 13 C - NMR solid state and also pore size distribution analysis were carried out. The collagen biomaterials can be made in a large range of shapes and can have structures of mimesis, close to those of the live tissues, when hydrated. (authors)

  18. Microstructure study of ethylene, propylene and 1-decene terpolymers by 13C-NMR

    International Nuclear Information System (INIS)

    Ferreira, Marcio; Escher, Fernanda Nunes; Galland, Griselda Barrera

    2001-01-01

    Terpolymers of ethylene-propylene-1-decene with different composition of monomers were obtained using the metallocenes catalyst rac-EtInd 2 ZrCl 2 . The complete 13 C-NMR characterization of these terpolymers was done qualitatively and quantitatively. Chemical shifts, carbon assignments and corresponding integrals for each triad sequence are presented. (author)

  19. Configurations and conformations in acyclic, unsaturated hydrocarbons. A 13C NMR study

    NARCIS (Netherlands)

    Haan, de J.W.; Ven, van de L.J.M.

    1973-01-01

    13C NMR (CMR) spectra of a number of di- and trisubstituted ethylenes have been measured. Very consistent values are found for the differential shieldings of allylic carbons in a number of linear, (Z)- and (E)-disubstituted ethylenes. The discrepancies between the several structural elements are

  20. 13C NMR spectra and bonding situation of the B-C bond in alkynylboranes

    International Nuclear Information System (INIS)

    Yamamoto, Yoshinori; Moritani, Ichiro

    1975-01-01

    13 C NMR spectra of boron substituted alkynes reveal that the β-carbon is deshielded by ca. 21 ppm by a B(O-n-C 4 H 9 ) 2 group. This clearly indicates the presence of a B-C π-bonding in alkynylboranes. (auth.)

  1. (1 H, 13 C and 31 P) NMR of phosphonic acid derivatives

    International Nuclear Information System (INIS)

    Campos, Valdevino; Costa, Valentim E. Uberti

    1991-01-01

    In the last years the development of phosphates analogues in the medical and agricultural pesticides has being very expressive. 1 H, 13 C and mainly 31 P NMR are used for stereochemical and conformational analysis, and reactivity studies on the compounds resulting from those chemical processes

  2. Occurrence, biological activities and 13C NMR data of amides from Piper (Piperaceae

    Directory of Open Access Journals (Sweden)

    Jeferson C. do Nascimento

    2012-01-01

    Full Text Available This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae. Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled 13C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts.

  3. Occurrence, biological activities and 13C NMR data of amides from Piper (Piperaceae)

    International Nuclear Information System (INIS)

    Nascimento, Jeferson C. do; Paula, Vanderlucia F. de; David, Jorge M.; David, Juceni P.

    2012-01-01

    This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae). Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled 13 C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts. (author)

  4. Occurrence, biological activities and {sup 13}C NMR data of amides from Piper (Piperaceae)

    Energy Technology Data Exchange (ETDEWEB)

    Nascimento, Jeferson C. do; Paula, Vanderlucia F. de [Universidade Estadual do Sudoeste da Bahia, Jequie, BA (Brazil). Dept. de Quimica e Exatas; David, Jorge M. [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Inst. de Quimica; David, Juceni P., E-mail: jmdavid@ufba.br [Universidade Federal da Bahia (UFBA), Salvador, BA (Brazil). Fac. de Farmacia

    2012-07-01

    This manuscript describes an update review with up to 285 references concerning the occurrence of amides from a variety of species of the genus Piper (Piperaceae). Besides addressing occurrence, this review also describes the biological activities attributed to extracts and pure compounds, a compiled {sup 13}C NMR data set, the main correlations between structural and NMR spectroscopic data of these compounds, and employment of hyphened techniques such as LC-MS, GC-MS and NMR for analysis of amides from biological samples and crude Piper extracts. (author)

  5. Authentication of the origin of vanillin using quantitative natural abundance 13C NMR.

    Science.gov (United States)

    Tenailleau, Eve J; Lancelin, Pierre; Robins, Richard J; Akoka, Serge

    2004-12-29

    The use of 13C isotopic distribution as an efficient means to determine the origin of vanillin has been substantiated. Using quantitative 13C NMR, the 13C/12C ratios at all eight carbon positions can be exploited. On a set of 21 samples of vanillin from five different origins, complete discrimination can be achieved. It is shown that, for many purposes, a rapid analysis in which only five sites are used is sufficient. However, improved discrimination using all eight sites is preferable to differentiate between different methods of production from natural ferulic acid or between natural and lignin-derived vanillin on the basis of the 13C/12C ratios characteristic of different origins. The C1 and C8 positions are demonstrated to be the most significant sites for discrimination using principle component analysis. However, aromatic carbon positions make an essential contribution, notably in differentiating between natural and lignin-derived vanillin.

  6. Identification of natural metabolites in mixture: a pattern recognition strategy based on (13)C NMR.

    Science.gov (United States)

    Hubert, Jane; Nuzillard, Jean-Marc; Purson, Sylvain; Hamzaoui, Mahmoud; Borie, Nicolas; Reynaud, Romain; Renault, Jean-Hugues

    2014-03-18

    Because of their highly complex metabolite profile, the chemical characterization of bioactive natural extracts usually requires time-consuming multistep purification procedures to achieve the structural elucidation of pure individual metabolites. The aim of the present work was to develop a dereplication strategy for the identification of natural metabolites directly within mixtures. Exploiting the polarity range of metabolites, the principle was to rapidly fractionate a multigram quantity of a crude extract by centrifugal partition extraction (CPE). The obtained fractions of simplified chemical composition were subsequently analyzed by (13)C NMR. After automatic collection and alignment of (13)C signals across spectra, hierarchical clustering analysis (HCA) was performed for pattern recognition. As a result, strong correlations between (13)C signals of a single structure within the mixtures of the fraction series were visualized as chemical shift clusters. Each cluster was finally assigned to a molecular structure with the help of a locally built (13)C NMR chemical shift database. The proof of principle of this strategy was achieved on a simple model mixture of commercially available plant secondary metabolites and then applied to a bark extract of the African tree Anogeissus leiocarpus Guill. & Perr. (Combretaceae). Starting from 5 g of this genuine extract, the fraction series was generated by CPE in only 95 min. (13)C NMR analyses of all fractions followed by pattern recognition of (13)C chemical shifts resulted in the unambiguous identification of seven major compounds, namely, sericoside, trachelosperogenin E, ellagic acid, an epimer mixture of (+)-gallocatechin and (-)-epigallocatechin, 3,3'-di-O-methylellagic acid 4'-O-xylopyranoside, and 3,4,3'-tri-O-methylflavellagic acid 4'-O-glucopyranoside.

  7. Quantitative analysis of deuterium using the isotopic effect on quaternary {sup 13}C NMR chemical shifts

    Energy Technology Data Exchange (ETDEWEB)

    Darwish, Tamim A., E-mail: tamim.darwish@ansto.gov.au [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); Yepuri, Nageshwar Rao; Holden, Peter J. [National Deuteration Facility, Australian Nuclear Science and Technology Organisation, Locked Bag 21, Kirrawee DC, NSW 2232 (Australia); James, Michael [Australian Synchrotron, 800 Blackburn Road, Clayton, Victoria 3168 (Australia)

    2016-07-13

    Quantitative analysis of specifically deuterated compounds can be achieved by a number of conventional methods, such as mass spectroscopy, or by quantifying the residual {sup 1}H NMR signals compared to signals from internal standards. However, site specific quantification using these methods becomes challenging when dealing with non-specifically or randomly deuterated compounds that are produced by metal catalyzed hydrothermal reactions in D{sub 2}O, one of the most convenient deuteration methods. In this study, deuterium-induced NMR isotope shifts of quaternary {sup 13}C resonances neighboring deuterated sites have been utilized to quantify the degree of isotope labeling of molecular sites in non-specifically deuterated molecules. By probing {sup 13}C NMR signals while decoupling both proton and deuterium nuclei, it is possible to resolve {sup 13}C resonances of the different isotopologues based on the isotopic shifts and the degree of deuteration of the carbon atoms. We demonstrate that in different isotopologues, the same quaternary carbon, neighboring partially deuterated carbon atoms, are affected to an equal extent by relaxation. Decoupling both nuclei ({sup 1}H, {sup 2}H) resolves closely separated quaternary {sup 13}C signals of the different isotopologues, and allows their accurate integration and quantification under short relaxation delays (D1 = 1 s) and hence fast accumulative spectral acquisition. We have performed a number of approaches to quantify the deuterium content at different specific sites to demonstrate a convenient and generic analysis method for use in randomly deuterated molecules, or in cases of specifically deuterated molecules where back-exchange processes may take place during work up. - Graphical abstract: The relative intensities of quaternary {sup 13}C {"1H,"2H} resonances are equal despite the different relaxation delays, allowing the relative abundance of the different deuterated isotopologues to be calculated using NMR fast

  8. Direct 13C-detected NMR experiments for mapping and characterization of hydrogen bonds in RNA

    International Nuclear Information System (INIS)

    Fürtig, Boris; Schnieders, Robbin; Richter, Christian; Zetzsche, Heidi; Keyhani, Sara; Helmling, Christina; Kovacs, Helena; Schwalbe, Harald

    2016-01-01

    In RNA secondary structure determination, it is essential to determine whether a nucleotide is base-paired and not. Base-pairing of nucleotides is mediated by hydrogen bonds. The NMR characterization of hydrogen bonds relies on experiments correlating the NMR resonances of exchangeable protons and can be best performed for structured parts of the RNA, where labile hydrogen atoms are protected from solvent exchange. Functionally important regions in RNA, however, frequently reveal increased dynamic disorder which often leads to NMR signals of exchangeable protons that are broadened beyond 1 H detection. Here, we develop 13 C direct detected experiments to observe all nucleotides in RNA irrespective of whether they are involved in hydrogen bonds or not. Exploiting the self-decoupling of scalar couplings due to the exchange process, the hydrogen bonding behavior of the hydrogen bond donor of each individual nucleotide can be determined. Furthermore, the adaption of HNN-COSY experiments for 13 C direct detection allows correlations of donor–acceptor pairs and the localization of hydrogen-bond acceptor nucleotides. The proposed 13 C direct detected experiments therefore provide information about molecular sites not amenable by conventional proton-detected methods. Such information makes the RNA secondary structure determination by NMR more accurate and helps to validate secondary structure predictions based on bioinformatics.

  9. Comparison of soil organic carbon speciation using C NEXAFS and CPMAS 13C NMR spectroscopy.

    Science.gov (United States)

    Prietzel, Jörg; Müller, Svenja; Kögel-Knabner, Ingrid; Thieme, Jürgen; Jaye, Cherno; Fischer, Daniel

    2018-07-01

    We compared synchrotron-based C near-edge X-ray absorption fine structure (NEXAFS) and CPMAS 13 C nuclear magnetic resonance (NMR) spectroscopy with respect to their precision and accuracy to quantify different organic carbon (OC) species in defined mixtures of soil organic matter source compounds. We also used both methods to quantify different OC species in organic surface horizons of a Histic Leptosol as well as in mineral topsoil and subsoil horizons of two soils with different parent material, stage of pedogenesis, and OC content (Cambisol: 15-30 OC mgg -1 , Podzol: 0.9-7 OC mgg -1 ). CPMAS 13 C NMR spectroscopy was more accurate and precise (mean recovery of different C functional groups 96-103%) than C NEXAFS spectroscopy (mean recovery 92-113%). For organic surface and topsoil samples, NMR spectroscopy consistently yielded larger O-alkyl C percentages and smaller alkyl C percentages than C NEXAFS spectroscopy. For the Cambisol subsoil samples both methods performed well and showed similar C speciation results. NEXAFS spectroscopy yielded excellent spectra with a high signal-to-noise ratio also for OC-poor Podzol subsoil samples, whereas this was not the case for CPMAS 13 C NMR spectroscopy even after sample treatment with HF. Our results confirm the analytical power of CPMAS 13 C NMR spectroscopy for a reliable quantitative OC speciation in soils with >10mgOCg -1 . Moreover, they highlight the potential of synchrotron-based C NEXAFS spectroscopy as fast, non-invasive method to semi-quantify different C functional groups in soils with low C content (0.9-10mgg -1 ). Copyright © 2018 Elsevier B.V. All rights reserved.

  10. 1H-NMR/13C-NMR studies of branched structures in PVC obtained at atmospheric pressure

    International Nuclear Information System (INIS)

    Braun, D.; Holzer, G.; Hjertberg, T.

    1981-01-01

    The 1 H-NMR-spectra of raw poly (vinyl cloride) obtained at atmospheric pressure (U-PVC) have revealed the presence of high concentrations of branches. The content of labile chlorine was determined by reaction with phenole in order to estimate the branch points with tertiary chlorine. The branch length of reductively dehalogenated U-PVC by 13 C-NMR analysis have provided evidence for both short chain branches including chloromethyl groups and 2.4-dichloro-n-butyl groups and long chain branching. For a number of U-polymers the total amount of branching ranges from 7.5 to 13.5/1000 C. The 13 C-NMR measurements point to a ratio of methyl/butyl branches of 1:1 and short chains/long chains of 6:1. (orig.)

  11. Determination of fructose metabolic pathways in normal and fructose-intolerant children: A 13C NMR study using [U-13C]fructose

    International Nuclear Information System (INIS)

    Gopher, A.; Lapidot, A.; Vaisman, N.; Mandel, H.

    1990-01-01

    An inborn deficiency in the ability of aldolase B to split fructose 1-phosphate is found in humans with hereditary fructose intolerance (HFI). A stable isotope procedure to elucidate the mechanism of conversion of fructose to glucose in normal children and in HFI children has been developed. A constant infusion of D-[U- 13 C]fructose was given nasogastrically to control and to HFI children. Hepatic fructose conversion to glucose was estimated by examination of 13 C NMR spectra of plasma glucose. Significantly lower values (∼3-fold) for fructose conversion to glucose were obtained for the HFI patients as compared to the controls. A quantitative determination of the metabolic pathways of fructose conversion to glucose was derived from 13 C NMR measurement of plasma [ 13 C]glucose isotopomer populations. The finding of isotopomer populations of three adjacent 13 C atoms at glucose C-4 ( 13 C 3 - 13 C 4 - 13 C 5 ) suggests that there is a direct pathway from fructose, by-passing fructose-1-phosphate aldolase, to fructose 1,6-bisphosphate. The metabolism of fructose by fructose-1-phosphate aldolase activity accounts for only ∼50% of the total amount of hepatic fructose conversion to glucose. In view of the marked decline by 67% in synthesis of glucose from fructose in HFI subjects found in this study, the extent of [ 13 C]glucose formation from a trace amount of [U- 13 C]fructose infused into the patient can be used as a safe and noninvasive diagnostic test for inherent faulty fructose metabolism

  12. Conformational analysis of 9,10-dihydroanthracenes. Molecular mechanics calculations and /sup 13/C NMR

    Energy Technology Data Exchange (ETDEWEB)

    Rabideau, P.W.; Mooney, J.L.; Lipkowitz, K.B.

    1986-12-24

    The conformational analyses of 9, 10-dihydroanthracene and several of its methylated and ethylated derivatives are studied by empirical force field calculations (MM2 and MMPI). The computational results are considered in light of previous and current carbon NMR data. Model compounds are examined which involve fixed, planar, and boat-shaped conformations about the central ring, and these /sup 13/C NMR data are then compared with flexible systems. It is concluded that carbon chemical shifts and carbon-hydrogen coupling constants are consistent with the results of molecular mechanics calculations which indicate a greater tendency for planarity around the central ring than previously considered.

  13. Protolytic properties of polyamine wasp toxin analogues studied by 13C NMR spectroscopy

    DEFF Research Database (Denmark)

    Strømgaard, Kristian; Piazzi, Lorna; Olsen, Christian A

    2006-01-01

    Acid-base properties of the natural polyamine wasp toxin PhTX-433 (1) and seven synthetic analogues [PhTX-343 (2), PhTX-334 (3), PhTX-443 (4), PhTX-434 (5), PhTX-344 (6), PhTX-444 (7), and PhTX-333 (8)], each having four protolytic sites, were characterized by 13C NMR spectroscopy. Nonlinear......, multiparameter, simultaneous fit of all chemical shift data obtained from the NMR titration curves yielded macroscopic pKa values as well as intrinsic chemical shift data of all differently protonated macrospecies. Analyses of the chemical shift data demonstrated strong interactions between all four sites...

  14. /sup 13/C NMR spectra and electron conduction in 4-substituted diphenylamines

    Energy Technology Data Exchange (ETDEWEB)

    Filimonov, V.D.; Kogan, R.M.; Tverdokhlebova, N.E.; Shcherbakov, V.V.; Kushnarev, D.F.; Kalabin, G.A.

    1986-07-10

    The /sup 13/C NMR spectra were recorded for a series of 4-X-diphenylamines, and correlations equations relating the /sup 13/C NMR chemical shifts of the C/sup 1/ and C/sup 4/ positions to the electronic characteristics of the substituent X were obtained. It was established that the conduction of the substituted ring in the 4-X-diphenylamines is practically the same as in 4-X-biphenyls. Joint analysis of the spectral characteristics of the diphenylamines, biphenyls, N-substituted anilines, and carbazoles made it possible to conclude that the increased transmission characteristics of the diphenylamines are determined by the conformational mobility of the two benzene rings and by the unidirectional effect of changes in the introduction and resonance factors with variation in the substituent X.

  15. NMR study of the 1-13C glucose colon bacterial metabolism

    International Nuclear Information System (INIS)

    Briet, F.; Flourie, B.; Pochart, P.; Rambaud, J.C.; Desjeux, J.F.; Dallery, L.; Grivet, J.P.

    1994-01-01

    The aim of the study is to examine in-vitro and by nuclear magnetic resonance the biological pathways for the fermentation of the 1- 13 C labelled glucose (99 atoms percent) by human colon bacteria. The preparation of the bacterial suspension and the glucose degradation kinetics are presented; the NMR analysis sensitivity and quantification features are discussed and results are presented. 2 figs., 1 ref

  16. Changes in chemical composition of litter during decomposition: a review of published 13C NMR spectra

    Czech Academy of Sciences Publication Activity Database

    Cepáková, Šárka; Frouz, Jan

    2015-01-01

    Roč. 15, č. 3 (2015), s. 805-815 ISSN 0718-9516 Grant - others:GAJU(CZ) GAJU/04-146/2013P; GA ČR(CZ) GAP504/12/1288 Program:GA Institutional support: RVO:60077344 Keywords : 13C CPMAS NMR * litter decomposition * litter quality * soil organic matter Subject RIV: DF - Soil Science Impact factor: 1.600, year: 2015

  17. 13C NMR and stereochestry of 1-β-phenylethylcyclohexanol derivatives obtained by synthesis

    International Nuclear Information System (INIS)

    Antunes, O.A.C.; Braz Filho, R.

    1986-01-01

    1-β-Phenylethylcyclohexanol derivatives substituted in position 2 have been synthesized and analysed by 13 C-NMR spectroscopy. Their stereochemistry have been considered as cis (hydroxyl in C-1 and substituent in C-2) which is in agreement with the pertinent literature. Derivatives obtained were 2-β-phenylethyl-2-allycyclohexanol, 1-β-phenylethyl-2-methylcyclohexanol, 7a-β-phenylethylperhy-drobenzo (b) furan, and 1-β-phenylethyl-2-β-hydroxyethylcyclohexanol. (author) [pt

  18. (13)C-(15)N correlation via unsymmetrical indirect covariance NMR: application to vinblastine.

    Science.gov (United States)

    Martin, Gary E; Hilton, Bruce D; Blinov, Kirill A; Williams, Antony J

    2007-12-01

    Unsymmetrical indirect covariance processing methods allow the derivation of hyphenated 2D NMR data from the component 2D spectra, potentially circumventing the acquisition of the much lower sensitivity hyphenated 2D NMR experimental data. Calculation of HSQC-COSY and HSQC-NOESY spectra from GHSQC, COSY, and NOESY spectra, respectively, has been reported. The use of unsymmetrical indirect covariance processing has also been applied to the combination of (1)H- (13)C GHSQC and (1)H- (15)N long-range correlation data (GHMBC, IMPEACH, or CIGAR-HMBC). The application of unsymmetrical indirect covariance processing to spectra of vinblastine is now reported, specifically the algorithmic extraction of (13)C- (15)N correlations via the unsymmetrical indirect covariance processing of the combination of (1)H- (13)C GHSQC and long-range (1)H- (15)N GHMBC to produce the equivalent of a (13)C- (15)N HSQC-HMBC correlation spectrum. The elimination of artifact responses with aromatic solvent-induced shifts (ASIS) is shown in addition to a method of forecasting potential artifact responses through the indirect covariance processing of the GHSQC spectrum used in the unsymmetrical indirect covariance processing.

  19. Calculation of the 13C NMR shieldings of the C0 2 complexes of aluminosilicates

    Science.gov (United States)

    Tossell, J. A.

    1995-04-01

    13C NMR shieldings have been calculated using the random-phase-approximation, localized-orbital local-origins version of ab initio coupled Hartree-Fuck perturbation theory for CO 2 and and for several complexes formed by the reaction of CO 2 with molecular models for aluminosilicate glasses, H 3TOT'H3 3-n, T,T' = Si,Al. Two isomeric forms of the CO 2-aluminosilicate complexes have been considered: (1) "CO 2-like" complexes, in which the CO 2 group is bound through carbon to a bridging oxygen and (2) "CO 3-like" complexes, in which two oxygens of a central CO 3 group form bridging bonds to the two TH 3 groups. The CO 2-like isomer of CO 2-H 3SiOSiH 3 is quite weakly bonded and its 13C isotropic NMR shielding is almost identical to that in free CO 2. As Si is progressively replaced by Al in the - H terminated aluminosilicate model, the CO 2-like isomers show increasing distortion from the free CO 2 geometry and their 13C NMR shieldings decrease uniformly. The calculated 13C shielding value for H 3AlO(CO 2)AlH 3-2 is only about 6 ppm larger than that calculated for point charge stabilized CO 3-2. However, for a geometry of H 3SiO(CO 2) AlH 3-1, in which the bridging oxygen to C bond length has been artificially increased to that found in the - OH terminated cluster (OH) 3SiO(CO 2)Al(OH) 3-1, the calculated 13C shielding is almost identical to that for free CO 2. The CO 3-like isomers of the CO 2-aluminosili-cate complexes show carbonate like geometries and 13C NMR shieldings about 4-9 ppm larger than those of carbonate for all T,T' pairs. For the Si,Si tetrahedral atom pair the CO 2-like isomer is more stable energetically, while for the Si,Al and Al,Al cases the CO 3-like isomer is more stable. Addition of Na + ions to the CO 3-2 or H 3AlO(CO 2)AlH 3-2 complexes reduces the 13C NMR shieldings by about 10 ppm. Complexation with either Na + or CO 2 also reduces the 29Si NMR shieldings of the aluminosilicate models, while the changes in 27Al shielding with Na + or CO 2

  20. Quantitative evaluation of the biosynthetic pathways leading to δ-aminolevulinic acid from the Shemin precursor glycine via the C5 pathway in Arthrobacter hyalinus by analysis of 13C-labeled coproporphyrinogen III biosynthesized from [2-13C]glycine, [1-13C]acetate, and [2-13C]acetate using 13C NMR spectroscopy

    International Nuclear Information System (INIS)

    Katsumi Iida

    2013-01-01

    The biosynthetic pathways leading to δ-aminolevulinic acid (ALA) from the Shemin precursor glycine via the C5 pathway in Arthrobacter hyalinus were quantitatively evaluated by means of feeding experiments with [2- 13 C]glycine, sodium [1- 13 C]acetate, and sodium [2- 13 C]acetate, followed by analysis of the labeling patterns of coproporphyrinogen III (Copro'gen III) (biosynthesized from ALA) using 13 C NMR spectroscopy. Two biosynthetic pathways leading to ALA from glycine via the C5 pathway were identified: i.e., transformation of glycine to l-serine catalyzed by glycine hydroxymethyltransferase, and glycine synthase-catalyzed catabolism of glycine to N 5 , N 10 -methylene-tetrahydrofolic acid (THF), which reacts with another molecule of glycine to afford l-serine. l-Serine is transformed to acetyl-CoA via pyruvic acid. Acetyl-CoA enters the tricarboxylic acid cycle, affording 2-oxoglutaric acid, which in turn is transformed to l-glutamic acid. The l-glutamic acid enters the C5 pathway, affording ALA in A. hyalinus. A 13 C NMR spectroscopic comparison of the labeling patterns of Copro'gen III obtained after feeding of [2- 13 C]glycine, sodium [1- 13 C]acetate, and sodium [2- 13 C]acetate showed that [2- 13 C]glycine transformation and [2- 13 C]glycine catabolism in A. hyalinus proceed in the ratio of 52 and 48 %. The reaction of [2- 13 C]glycine and N 5 , N 10 -methylene-THF, that of glycine and N 5 , N 10 -[methylene- 13 C]methylene-THF generated from the [2- 13 C]glycine catabolism, and that of [2- 13 C]glycine and N 5 , N 10 -[methylene- 13 C]methylene-THF transformed the fed [2- 13 C]glycine to [1- 13 C]acetyl-CoA, [2- 13 C]acetyl-CoA, and [1,2- 13 C 2 ]acetyl-CoA in the ratios of 42, 37, and 21 %, respectively. These labeled acetyl-CoAs were then incorporated into ALA. Our results provide a quantitative picture of the pathways of biosynthetic transformation to ALA from glycine in A. hyalinus. (author)

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

    NARCIS (Netherlands)

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

    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

  2. Complete 1H and 13C NMR assignments and anti fungal activity of two 8-hydroxy flavonoids in mixture

    International Nuclear Information System (INIS)

    Johann, Susana; Smania Junior, Artur; Branco, Alexsandro

    2007-01-01

    A mixture of the two new flavonols 8-hydroxy-3, 4', 5, 6, 7-pentamethoxyflavone (1) and 8-hydroxy-3, 3', 4', 5, 6, 7-hexamethoxyflavone (2) was isolated from a commercial sample of Citrus aurantifolia. An array of one- ( 1 H NMR, { 1 H} -13 C NMR, and APT -13 C NMR) and two-dimensional NMR techniques (COSY, NOESY, HMQC and HMBC) was used to achieve the structural elucidation and the complete 1 H and 13 C chemical shift assignments of these natural compounds. In addition, the antifungal activity of these compounds against phytopathogenic and human pathogenic fungi was investigated. (author)

  3. 13C NMR Chemical Shifts of the Triclinic and Monoclinic Crystal forms of Valinomycin

    International Nuclear Information System (INIS)

    Kameda, Tsunenori; McGeorge, Gary; Orendt, Anita M.; Grant, David M.

    2004-01-01

    Two different crystalline polymorphs of valinomycin, the triclinic and monoclinic forms, have been studied by high resolution, solid state 13 C CP-MAS NMR spectroscopy. Although the two polymorphs of the crystal are remarkably similar, there are distinct differences in the isotropic chemical shifts between the two spectra. For the triclinic form, the carbon chemical shift tensor components for the alpha carbons adjacent to oxygen in the lactic acid and hydroxyisovaleric acid residues and the ester carbonyls of the valine residue were obtained using the FIREMAT experiment. From the measured components, it was found that the behavior of the isotropic chemical shift, δ iso , for valine residue ester carbonyl carbons is predominately influenced by the intermediate component, δ 22 . Additionally it was found that the smallest shift component, δ 33 , for the L-lactic acid (L-Lac) and D-α-hydroxyisovaleric acid (D-Hyi) C α -O carbon was significantly displaced depending upon the nature of individual amino acid residues, and it is the δ 33 component that governs the behavior of δ iso in these alpha carbons

  4. Computational characterization of 13C NMR lineshapes of carbon dioxide in structure 1 clathrate hydrates

    Energy Technology Data Exchange (ETDEWEB)

    Dornan, P.; Woo, T.K. [Ottawa Univ., ON (Canada). Dept. of Chemistry

    2008-07-01

    Nonspherical large cages in structure one clathrates impose non-uniform motion of nonspherical guest molecules and anisotropic lineshapes in nuclear magnetic resonance (NMR) spectra of the guest. This paper presented a general method for calculating the chemical shift lineshape anisotropy of guest molecules in clathrate hydrate compounds from molecular dynamics simulations for the case of weak host, guest dipolar coupling. In order to calculate the cage chemical shielding tensors and the NMR lineshape produced by each guest molecule, the study involved the use of orientational distributions from molecular dynamics simulation along with time and powder angle averaging. The total predicted lineshape anisotropy was calculated from the superposition of the lineshapes of all guests. The approach was applied to calculate the temperature dependent 13C NMR lineshape anisotropy of carbon dioxide in structure 1 clathrates. The paper presented the computational methodology and results and discussion. It was concluded that the resulting lineshapes were in good agreement with the experimental 13C NMR spectrum at each temperature. The method provided a uniform procedure to calculate the lineshapes at different temperatures and no prior assumptions about the nature of the motion of the guest in cages was required. 37 refs., 2 tabs., 3 figs.

  5. Molecular motion of micellar solutes: a 13C NMR relaxation study

    International Nuclear Information System (INIS)

    Stark, R.E.; Kasakevich, M.L.; Granger, J.W.

    1982-01-01

    A series of simple NMR relaxation experiments have been performed on nitrobenzene and aniline dissolved in the ionic detergents sodium dodecyl sulfate (SDS) and hexadecyltrimethylammonium bromide (CTAB). Using 13 C relaxation rates at various molecular sites, and comparing data obtained in organic media with those for micellar solutions, the viscosity at the solubilization site was estimated and a detailed picture of motional restrictions imposed by the micellar enviroment was derived. Viscosities of 8 to 17 cp indicate a rather fluid environment for solubilized nitrobenzene; both additives exhibit altered motional preferences in CTAB solutions only. As an aid in interpretation of the NMR data, quasi-elastic light scattering and other physical techniques have been used to evaluate the influence of organic solutes on micellar size and shape. The NMR methods are examined critically in terms of their general usefulness for studies of solubilization in detergent micelles. 48 references

  6. Pectins from apple pomace - characterization by 13C and 1H NMR spectroscopy

    International Nuclear Information System (INIS)

    Marcon, M.V.; Carneiro, P.I.B.; Wosiacki, G.; Beleski-Carneiro, E.; Petkowicz, C.L.O.

    2005-01-01

    Pectins were extracted from apple pomace flour with 5% (w/v) aqueous citric acid solutions under different time and temperature according to an experimental design (factorial 2 2 with triplicate of central point). Monosaccharide composition of fractions was determined by colorimetric analysis and gas chromatography. The structure of pectins was studied by NMR spectroscopy. The degree of esterification (DE=30.5-55.9), determined by FT-IR spectroscopy, was indirectly correlated with increasing temperature and time of extraction, showing that drastic conditions for extraction promote hydrolysis of esterified units. High content of galacturonic acid is consistent with the smooth region of the polysaccharide. 13 C and 1 H NMR spectroscopy confirmed the presence of uronic acids in the free and methyl ester forms. NMR data also showed the presence of arabinan and galactan as side chains. (author)

  7. Combined chemometric analysis of (1)H NMR, (13)C NMR and stable isotope data to differentiate organic and conventional milk.

    Science.gov (United States)

    Erich, Sarah; Schill, Sandra; Annweiler, Eva; Waiblinger, Hans-Ulrich; Kuballa, Thomas; Lachenmeier, Dirk W; Monakhova, Yulia B

    2015-12-01

    The increased sales of organically produced food create a strong need for analytical methods, which could authenticate organic and conventional products. Combined chemometric analysis of (1)H NMR-, (13)C NMR-spectroscopy data, stable-isotope data (IRMS) and α-linolenic acid content (gas chromatography) was used to differentiate organic and conventional milk. In total 85 raw, pasteurized and ultra-heat treated (UHT) milk samples (52 organic and 33 conventional) were collected between August 2013 and May 2014. The carbon isotope ratios of milk protein and milk fat as well as the α-linolenic acid content of these samples were determined. Additionally, the milk fat was analyzed by (1)H and (13)C NMR spectroscopy. The chemometric analysis of combined data (IRMS, GC, NMR) resulted in more precise authentication of German raw and retail milk with a considerably increased classification rate of 95% compared to 81% for NMR and 90% for IRMS using linear discriminate analysis. Copyright © 2015 Elsevier Ltd. All rights reserved.

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

    Science.gov (United States)

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

    2016-01-21

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

  9. Metabolic engineering applications of in vivo 31P and 13C NMR studies of Saccharomyces cerevisiae

    International Nuclear Information System (INIS)

    Shanks, J.V.

    1989-01-01

    With intent to quantify NMR measurements as much as possible, analysis techniques of the in vivo 31 P NMR spectrum are developed. A systematic procedure is formulated for estimating the relative intracellular concentrations of the sugar phosphates in S. cerevisiae from the 31 P NMR spectrum. In addition, in vivo correlation of inorganic phosphate chemical shift with the chemical shifts of 3-phosphoglycerate, β-fructose 1,6-diphosphate, fructose 6-phosphate, and glucose 6-phosphate are determined. Also, a method was developed for elucidation of the cytoplasmic and vacuolar components of inorganic phosphate in the 31 P NMR spectrum of S. cerevisiae. An in vivo correlation relating the inorganic phosphate chemical shift of the vacuole with the chemical shift of the resonance for pyrophosphate and the terminal phosphate of polyphosphate (PP 1 ) is established. Transient measurements provided by 31 P NMR are applied to reg1 mutant and standard strains. 31 P and 13 C NMR measurements are used to analyze the performance of recombinant strains in which the glucose phosphorylation step had been altered

  10. Degradation of mangrove tissues by arboreal termites (Nasutitermes acajutlae) and their role in the mangrove C cycle (Puerto Rico): Chemical characterization and organic matter provenance using bulk δ13C, C/N, alkaline CuO oxidation-GC/MS, and solid-state 13C NMR

    Science.gov (United States)

    Vane, Christopher H.; Kim, Alexander W.; Moss-Hayes, Vicky; Snape, Colin E.; Diaz, Miguel Castro; Khan, Nicole S.; Engelhart, Simon E.; Horton, Benjamin P.

    2013-08-01

    Arboreal termites are wood decaying organisms that play an important role in the first stages of C cycling in mangrove systems. The chemical composition of Rhizophora mangle, Avicennia germinans, and Laguncularia racemosa leaf, stem, and pneumatophore tissues as well as associated sediments was compared to that of nests of the termite Nasutitermes acajutlae. Nests gave δ13C values of -26.1 to -27.2‰ (±0.1) and C/N of 43.3 (±2.0) to 98.6 (±16.2) which were similar to all stem and pneumatophores but distinct from mangrove leaves or sediments. Organic matter processed by termites yielded lignin phenol concentrations (Λ, lambda) that were 2-4 times higher than stem or pneumatophores and 10-20 times higher than that of leaves or sediments, suggesting that the nests were more resistant to biodegradation than the mangrove vegetation source. 13C NMR revealed that polysaccharide content of mangrove tissues (50-69% C) was higher than that of the nests (46-51% C). Conversely, lignin accounted for 16.2-19.6% C of nest material, a threefold increase relative to living mangrove tissues; a similar increase in aromatic methoxyl content was also observed in the nests. Lipids (aliphatic and paraffinic moieties) were also important but rather variable chemical components of all three mangrove species, representing between 13.5 and 28.3% of the C content. Termite nests contained 3.14 Mg C ha-1 which represents approximately 2% of above ground C storage in mangroves, a value that is likely to increase upon burial due to their refractory chemical composition.

  11. 13C NMR and relaxation studies of the nanomagnet Mn12-acetate

    Science.gov (United States)

    Achey, Randall M.; Kuhns, Philip L.; Reyes, Arneil P.; Moulton, William G.; Dalal, Naresh S.

    2001-08-01

    The nanomagnet [Mn12O12(CH3COO)16(H2O)4].2CH3COOH.4H2O, also known as Mn12, has been synthesized with 13C labeling at the CH3 groups, and investigated by 13C NMR at fields up to 23 T. Using oriented samples, it is possible to resolve four distinct 13C peaks at room temperature, located on both sides of the unshifted Larmor frequency. These peaks were assigned to the four hyperfine-shifted, magnetically inequivalent sets of 13CH3 groups in the Mn12 lattice, based on a comparison with the crystal structure and point-dipole and spin-density calculations. These results establish that the unpaired electron spin density of the S=10 system in this cluster extends over the entire molecular framework, not just the core. These results are discussed in relationship to inelastic neutron scattering measurements. The temperature and field dependence of the 13C nuclear-spin-lattice-relaxation time T1 on the least shifted peak was measured. A single weakly field-dependent minimum at about 60 K is observed in the temperature dependence of the measured T1. The relaxation mechanism responsible for the T1 minimum is ascribed mainly to hindered rotation of the methyl group of the acetate ligand at higher temperature, and to electronic spin fluctuations at lower temperature.

  12. Iminium ion chemistry of mitosene DNA alkylating agents. Enriched 13C NMR and isolation studies.

    Science.gov (United States)

    Ouyang, A; Skibo, E B

    2000-05-16

    Described herein is a study of the reductive alkylation chemistry of mitosene antitumor agents. We employed a 13C-enriched electrophilic center to probe the fate of the iminium ion resulting from reductive activation. The 13C-labeled center permitted the identification of complex products resulting from alkylation reactions. In the case of DNA reductive alkylation, the type and number of alkylation sites were readily assessed by 13C NMR. Although there has been much excellent work done in the area of mitosene chemistry and biochemistry, the present study provides a number of new findings: (1) The major fate of the iminium ion is head-to-tail polymerization, even in dilute solutions. (2) Dithionite reductive activation results in the formation of mitosene sulfite esters as well as the previously observed sulfonate adducts. (3) The mitosene iminium ion alkylates the adenosine 6-amino group as well as the guanosine 2-amino group. The identification of the latter adduct was greatly facilitated by the 13C-label at the electrophilic center. (4) The mitosene iminium ion alkylates DNA at both nitrogen and oxygen centers without any apparent base selectivity. The complexity of mitosene reductive alkylation of DNA will require continued adduct isolation studies.

  13. Analysis of Hydroperoxides in Solid Polyethylene by MAS (13)C NMR and EPR

    International Nuclear Information System (INIS)

    ASSINK, ROGER A.; CELINA, MATHIAS C.; DUNBAR, TIMOTHY D.; ALAM, TODD M.; CLOUGH, ROGER LEE; GILLEN, KENNETH T.

    1999-01-01

    13 C-enriched polyethylene was subjected to γ-irradiation in the presence of air at 25 and 80 C for total doses ranging from 71 to 355 kGy. Significant quantities of hydroperoxides were detected in the 25 C irradiated sample by 13 C magic angle spinning NMR spectroscopy. This method of detection was performed on the solid polymer and required no chemical derivatization or addition of solvent. The chemical stability and subsequent products of the hydroperoxide species were studied by annealing the irradiated samples in air at temperatures ranging from 22 to 110 C. A time-temperature superposition analysis provided an activation energy of 108 kJ/mol for the hydroperoxide decomposition process. The primary products of hydroperoxide decomposition were ketones and secondary alcohols with lesser amounts of acids and esters. EPR measurements suggest that the reactive hydroperoxide species reside in the amorphous phase of polyethylene, consistent with degradation occurring in the amorphous phase

  14. Direct observation of glycogen synthesis in human muscle with 13C NMR

    International Nuclear Information System (INIS)

    Jue, T.; Rothman, D.L.; Shulman, G.I.; Tavitian, B.A.; DeFronzo, R.A.; Shulman, R.G.

    1989-01-01

    On the basis of previous indirect measurements, skeletal muscle has been implicated as the major site of glucose uptake and it has been suggested that muscle glycogen formation is the dominant pathway. However, direct measurements of the rates of glycogen synthesis have not been possible by previous techniques. The authors have developed 13 C NMR methods to measure directly the rate of human muscle glycogen formation from infused, isotopically labeled [1- 13 C]glucose. They show that under conditions of imposed hyperglycemia and hyperinsulinemia, a majority of the infused glucose was converted to muscle glycogen in a normal man. This directly shows that muscle is the major site of glucose disposal under these conditions, and provides quantitation of the glucose flux to muscle glycogen

  15. Monovacancy paramagnetism in neutron-irradiated graphite probed by 13C NMR.

    Science.gov (United States)

    Zhang, Z T; Xu, C; Dmytriieva, D; Molatta, S; Wosnitza, J; Wang, Y T; Helm, M; Zhou, Shengqiang; Kühne, H

    2017-10-20

    We report on the magnetic properties of monovacancy defects in neutron-irradiated graphite, probed by 13 C nuclear magnetic resonance spectroscopy. The bulk paramagnetism of the defect moments is revealed by the temperature dependence of the NMR frequency shift and spectral linewidth, both of which follow a Curie behavior, in agreement with measurements of the macroscopic magnetization. Compared to pristine graphite, the fluctuating hyperfine fields generated by the defect moments lead to an enhancement of the 13 C nuclear spin-lattice relaxation rate [Formula: see text] by about two orders of magnitude. With an applied magnetic field of 7.1 T, the temperature dependence of [Formula: see text] below about 10 K can well be described by a thermally activated form, [Formula: see text], yielding a singular Zeeman energy of ([Formula: see text]) meV, in excellent agreement with the sole presence of polarized, non-interacting defect moments.

  16. Application of 13C NMR spectroscopy to characterize organic chemical components of decomposing coarse woody debris from different climatic regions

    Directory of Open Access Journals (Sweden)

    Takuya Hishinuma

    2015-04-01

    Full Text Available Solid-state 13C nuclear magnetic resonance (NMR spectroscopy was applied to coarse woody debris (CWD in different stages of decomposition and collected from forest floor of a subtropical, a cool temperate, and a subalpine forest in Japan. The purpose was to test its applicability to characterize organic chemical composition of CWD of broad-leaved and coniferous trees from different climatic conditions. O-alkyl-C, mainly representing carbohydrates, was the predominant component of CWD at the three sites, accounting for 43.5-58.1% of the NMR spectra. Generally, the relative area under the signals for aromatic-C and phenolic-C, mainly representing lignin, increased, whereas the relative area for O-alkyl-C decreased, as the decay class advanced. The relative area under NMR chemical shift regions was significantly correlated with the chemical properties examined with proximate analyses. That is, O-alkyl-C and di-O-alkyl-C NMR signal areas were positively correlated with the volumetric density of CWD and the content of total carbohydrates. Methoxyl-C, aromatic-C, phenolic-C, carboxyl-C, and carbonyl-C were positively correlated with the contents of acid-unhydrolyzable residues (lignin, tannins, and cutin and nitrogen. Lignin-C calculated from NMR signals increased, and polysaccharide-C decreased, with the decay class of CWD at the three study sites. A review of previous studies on 13C NMR spectroscopy for decomposing CWD suggested further needs of its application to broad-leaved trees from tropical and subtropical regions.

  17. Estimation of glucose carbon recycling in children with glycogen storage disease: A 13C NMR study using [U-13C]glucose

    International Nuclear Information System (INIS)

    Kalderon, B.; Korman, S.H.; Gutman, A.; Lapidot, A.

    1989-01-01

    A stable isotope procedure to estimate hepatic glucose carbon recycling and thereby elucidate the mechanism by which glucose is produced in patients lacking glucose 6-phosphatase is described. A total of 10 studies was performed in children with glycogen storage disease type I (GSD-I) and type III (GSD-III) and control subjects. A primed dose-constant nasogastric infusion of D-[U- 13 C]glucose or an infusion diluted with nonlabeled glucose solution was administered following different periods of fasting. Hepatic glucose carbon recycling was estimated from 13 C NMR spectra. The values obtained for GSD-I patients coincided with the standard [U- 13 C]glucose dilution curve. These results indicate that the plasma glucose of GSD-I subjects comprises only a mixture of 99% 13 C-enriched D-[U- 13 C]glucose and unlabeled glucose but lacks any recycled glucose. Significantly different glucose carbon recycling values were obtained for two GSD-III patients in comparison to GSD-I patients. The results eliminate a mechanism for glucose production in GSD-I children involving gluconeogenesis. However, glucose release by amylo-1,6-glucosidase activity would result in endogenous glucose production of non- 13 C-labeled and nonrecycled glucose carbon, as was found in this study. In GSD-III patients gluconeogenesis is suggested as the major route for endogenous glucose synthesis. The contribution of the triose-phosphate pathway in these patients has been determined

  18. Morphological study of chitin from Xiphopenaeus kroyeri exoskeletons by using atomic force microscopy (AFM) and CPMAS {sup 13} C NMR; Estudo morfologico de quitina da exocuticula de Xiphopenaeus kroyeri por AFM e por CPMAS {sup 13} C NMR

    Energy Technology Data Exchange (ETDEWEB)

    Silva, K.M.; Tavares, M.I.; Andrade, C.T. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Macromoleculas; Simao, R.A. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Coordenacao dos Programas de Pos-graduacao de Engenharia. Programa de Engenharia Metalurgica e de Materiais

    1999-07-01

    A sample of {alpha} chitin was isolated from exoskeletons of Xiphopenaeus kroyeri. This sample ws dissolved in phosphoric acid and recovered as a fibrous precipitate. Atomic force microscopy was used in noncontact mode to obtain images of the native chitin sample. Different morphological features were observed, including rigid rod crystals 200-300 nm wide. Solid state {sup 13} C NMR techniques were used to investigate chitin samples, and revealed molecular order in both samples. The differences observed in the proton spin-lattice relaxation times in the rotating frame, T{sup H1}{sub p} were attributed to the formation of hydrogen bonds in preferential sites in the samples. (author)

  19. Trans and surface membrane bound zervamicin IIB: 13C-MAOSS-NMR at high spinning speed

    International Nuclear Information System (INIS)

    Raap, J.; Hollander, J.; Ovchinnikova, T. V.; Swischeva, N. V.; Skladnev, D.; Kiihne, S.

    2006-01-01

    Interactions between 15 N-labelled peptides or proteins and lipids can be investigated using membranes aligned on a thin polymer film, which is rolled into a cylinder and inserted into the MAS-NMR rotor. This can be spun at high speed, which is often useful at high field strengths. Unfortunately, substrate films like commercially available polycarbonate or PEEK produce severe overlap with peptide and protein signals in 13 C-MAOSS NMR spectra. We show that a simple house hold foil support allows clear observation of the carbonyl, aromatic and C α signals of peptides and proteins as well as the ester carbonyl and choline signals of phosphocholine lipids. The utility of the new substrate is validated in applications to the membrane active peptide zervamicin IIB. The stability and macroscopic ordering of thin PC10 bilayers was compared with that of thicker POPC bilayers, both supported on the household foil. Sidebands in the 31 P-spectra showed a high degree of alignment of both the supported POPC and PC10 lipid molecules. Compared with POPC, the PC10 lipids are slightly more disordered, most likely due to the increased mobilities of the shorter lipid molecules. This mobility prevents PC10 from forming stable vesicles for MAS studies. The 13 C-peptide peaks were selectively detected in a 13 C-detected 1 H-spin diffusion experiment. Qualitative analysis of build-up curves obtained for different mixing times allowed the transmembrane peptide in PC10 to be distinguished from the surface bound topology in POPC. The 13 C-MAOSS results thus independently confirms previous findings from 15 N spectroscopy [Bechinger, B., Skladnev, D.A., Ogrel, A., Li, X., Rogozhkina, E.V., Ovchinnikova, T.V., O'Neil, J.D.J. and Raap, J. (2001) Biochemistry, 40, 9428-9437]. In summary, application of house hold foil opens the possibility of measuring high resolution 13 C-NMR spectra of peptides and proteins in well ordered membranes, which are required to determine the secondary and

  20. Regioselectivity of tributyltin ether mediated alkylations. A 119Sn and 13C NMR study

    International Nuclear Information System (INIS)

    Cruzado, C.; Bernabe, M.; Martin-Lomas, M.

    1989-01-01

    The 119 Sn and 13 C NMR spectra of the stannylated species resulting from the treatment of conformationally rigid polyhydroxylated compounds with bis(tributyltin) oxide have been determined and the effect of N-methylimidazole, added as catalyst in tributyltin ether mediated regioselective alkylations, has been investigated. The observed signal intensity changes, upfield shifts, signal broadenings, and the results of variable temperature experiments have been interpreted as indicative of the selective formation of pentacoordinated tin species, involving conveniently disposed adjacent hydroxyl groups, on addition of the catalyst. On these bases, a mechanistic hypothesis for the observed regioselectivity of N-methylimidazole-catalyzed tributyltin ether mediated benzylations is proposed. 13 references, 5 tables

  1. 13C NMR investigation of the structure of cationic carbonyls in transition metal zeolites

    International Nuclear Information System (INIS)

    Ben Taarit, Y.

    1979-01-01

    13 C NMR spectroscopy was used to investigate the nature of carbon monoxide adsorbed on transition metal ions hosted in a synthetic faujastite type zeolite. The adsorbed CO species was characterised by a highly shielded carbon nucleus. Using the Pople approximation for the paramagnetic shielding term, the observed chemical shift was rationalised assuming the formation of a cationic carbonyl species with an appreciable electronic transfer from the carbon lone pair to the transition metal ion and negligible π back-bonding if at all. (Auth.)

  2. 1H and 13C NMR spectral data of new saponins from Cordia piauhiensis.

    Science.gov (United States)

    Santos, Renata P; Silveira, Edilberto R; Uchôa, Daniel Esdras de A; Pessoa, Otília Deusdênia L; Viana, Francisco Arnaldo; Braz-Filho, Raimundo

    2007-08-01

    Two new bidesmoside triterpenoid saponins were isolated from stems of Cordia piauhiensis. Their structures, characterized as 3-O-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl pomolic acid 28-O-beta-D-glucopyranosyl ester (1) and 3-O-alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl oleanolic acid 28-O-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl ester (2), were unequivocally established after extensive NMR (1H, 13C, DEPT 135 degrees, COSY, HSQC, HMBC, TOCSY, and NOESY) studies. Copyright 2007 John Wiley & Sons, Ltd.

  3. Two-dimensional NMR spectroscopy of 13C methanol at less than 5 μT

    Science.gov (United States)

    Shim, Jeong Hyun; Lee, Seong-Joo; Hwang, Seong-min; Yu, Kwon-Kyu; Kim, Kiwoong

    2014-09-01

    Two-dimensional (2D) spectroscopy is one of the most significant applications of nuclear magnetic resonance (NMR). Here, we demonstrate that the 2D NMR can be performed even at a low magnetic field of less than 5 μT, which is ten times less than the Earth’s magnetic field. The pulses used in the experiment were composed of circularly polarized fields for coherent as well as wideband excitations. Since the excitation band covers the entire spectral range, the simplest two-pulse sequence delivered the full 2D spectrum. At 5 μT, methanol with 13C enriched up to 99% belongs to a strongly coupled regime, and thus its 2D spectrum exhibits complicated spectral correlations, which can be exploited as a fingerprint in chemical analysis. In addition, we show that, with compressive sensing, the acquisition of the 2D spectrum can be accelerated to take only 45% of the overall duration.

  4. Characterization of two minor saponins from Cordia piauhiensis by 1H and 13C NMR spectroscopy.

    Science.gov (United States)

    Santos, Renata P; Silveira, Edilberto R; Lemos, Telma Leda G; Viana, Francisco Arnaldo; Braz-Filho, Raimundo; Pessoa, Otília Deusdênia L

    2005-06-01

    A careful NMR analysis with full assignment of the 1H and 13C spectral data for two minor saponins isolated from stems of Cordia piauhiensis is reported. These saponins were isolated by high-performance liquid chromatography and characterized as 3beta-O-[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl]pomolic acid 28-O-[beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl] ester (1) and 3beta-O-[alpha-L-rhamnopyranosyl-(1 --> 2)-beta-D-glucopyranosyl]oleanolic acid 28-O-[beta-D-xylopyranosyl-(1 --> 2)-beta-D-glucopyranosyl-(1 --> 6)-beta-D-glucopyranosyl] ester (2). Their structures were established using a combination of 1D and 2D (1H, 1H-COSY, TOCSY, NOESY, gs-HMQC and gs-HMBC) NMR techniques, electrospray ionization mass spectrometry and chemical evidence. Copyright 2005 John Wiley & Sons, Ltd.

  5. Study of the metabolism of 13C labeled substrates by 13C NMR spectroscopy of intact cells, tissues, and organs

    International Nuclear Information System (INIS)

    Matwiyoff, N.A.; London, R.E.; Hutson, J.Y.

    1982-01-01

    Carbon-13 nuclear magnetic resonance spectroscopy, in conjunction with carbon-13 labeling, has become an important analytical technique for the study of biological systems and biologically important molecules. The growing list of its well established applications to isolated molecules in solution includes the investigation of: metabolic pathways; the microenvironments of ligands bound to proteins; the architecture and dynamics of macromolecules; the structures of coenzymes and other natural products; and the mechanisms of reactions. Recently interest has been reawakened in the use of the technique for the study of metabolic pathways and structural components in intact organelles, cells, and tissues. The promise and problems in the use of 13 C labeling in such investigations can be illustrated by the results on suspensions of the yeast, Candida utilis

  6. Morphological study of chitin from Xiphopenaeus kroyeri exoskeletons by using atomic force microscopy (AFM) and CPMAS 13 C NMR

    International Nuclear Information System (INIS)

    Silva, K.M.; Tavares, M.I.; Andrade, C.T.; Simao, R.A.

    1999-01-01

    A sample of α chitin was isolated from exoskeletons of Xiphopenaeus kroyeri. This sample ws dissolved in phosphoric acid and recovered as a fibrous precipitate. Atomic force microscopy was used in noncontact mode to obtain images of the native chitin sample. Different morphological features were observed, including rigid rod crystals 200-300 nm wide. Solid state 13 C NMR techniques were used to investigate chitin samples, and revealed molecular order in both samples. The differences observed in the proton spin-lattice relaxation times in the rotating frame, T H1 p were attributed to the formation of hydrogen bonds in preferential sites in the samples. (author)

  7. Magnetization and 13C NMR spin-lattice relaxation of nanodiamond powder

    Energy Technology Data Exchange (ETDEWEB)

    Levin, E.M.; Fang, X.W.; Bud' ko, S.L.; Straszheim, W.E.; McCallum, R.W.; Schmidt-Rohr, K.

    2008-02-15

    The bulk magnetization at temperatures of 1.8-400 K and in magnetic fields up to 70 kOe, the ambient temperature {sup 13}C NMR spin-lattice relaxation, T{sub 1,c}, and the elemental composition of three nanodiamond powder samples have been studied. The total magnetization of nanodiamond can be explained in terms of contributions from (1) the diamagnetic effect of carbon, (2) the paramagnetic effect of unpaired electrons present in nanodiamond grains, and (3) ferromagnetic-like and (4) superparamagnetic contributions from Fe-containing particles detected in spatially resolved energy-dispersive spectroscopy. Contributions (1) and (2) are intrinsic to nanodiamond, while contributions (3) and (4) arise from impurities naturally present in detonation nanodiamond samples. {sup 13}C NMR T{sub 1,c} relaxation would be unaffected by the presence of the ferromagnetic particles with the bulk magnetization of {approx} 0.01 emu/g at 300 K. Thus, a reduction of T{sub 1,c} by 3 orders of magnitude compared to natural and synthetic microdiamonds confirms the presence of unpaired electrons in the nanodiamond grains. The spin concentration in nanodiamond powder corresponds to {approx}30 unpaired electrons per {approx}4.6 nm diameter nanodiamond grain.

  8. Sup(13)C NMR studies of glucose disposal in normal and non-insulin-dependent diabetic humans

    International Nuclear Information System (INIS)

    Shulman, G.I.; Rothman, D.L.; Shulman, R.G.

    1990-01-01

    To examine the extent to which the defect in insulin action in subjects with non-insulin-dependent diabetes mellitus (NIDDM) can be accounted for by impairment of muscle glycogen synthesis, we performed combined hyperglycemic-hyperinsulinemic clamp studies with [ 13 C]glucose in five subjects with NIDDM and in six age- and weight-matched healthy subjects. The rate of incorporation of intravenously infused [1- 13 C]glucose into muscle glycogen was measured directly in the gastrocnemius muscle by means of a nuclear magnetic resonance (NMR) spectrometer with a 15.5 min time resolution and a 13 C surface coil. The steady-state plasma concentrations of insulin and glucose were similar in both study groups. The mean (±SE) rate of glycogen synthesis, as determined by 13 C NMR, was 78±28 and 183±39 μmol-glucosyl units (kg muscle tissue (wet mass)) -1 min -1 in the diabetic and normal subjects, respectively. The mean glucose uptake was markedly reduced in the diabetic as compared with the normal subjects. The mean rate of non-oxidative glucose metabolism was 22±4 μmol kg -1 min -1 in the diabetic subjects and 42±4 μmol kg -1 min -1 in the normal subjects. When these rates are extrapolated to apply to the whole body, the synthesis of muscle glycogen would account for most of the total-body glucose uptake and all of the non-oxidative glucose metabolism in both normal and diabetic subjects. We conclude that muscle glycogen synthesis is the principal pathway of glucose disposal in both normal and diabetic subjects and that defects in muscle glycogen synthesis have a dominant role in the insulin resistance that occurs in persons with NIDDM. (author)

  9. 13C and 31P NMR [Nuclear Magnetic Resonance] studies of prostate tumor metabolism

    International Nuclear Information System (INIS)

    Sillerud, L.O.; Halliday, K.R.; Freyer, J.P; Griffey, R.H.; Fenoglio-Preiser, C.

    1989-01-01

    The current research on prostate cancer by NMR spectroscopy and microscopy will most significantly contribute to tumor diagnosis and characterization only if sound biochemical models of tumor metabolism are established and tested. Prior searches focused on universal markers of malignancy, have to date, revealed no universal markers by any method. It is unlikely that NMRS will succeed where other methods have failed, however, NMR spectroscopy does provide a non-invasive means to analyze multiple compounds simultaneously in vivo. In order to fully evaluate the ability of NMRS to differentiate non-malignant from malignant tissues it is necessary to determine sufficient multiple parameters from specific, well-diagnosed, histological tumor types that, in comparison to normal tissue and non-neoplastic, non-normal pathologies from which the given neoplasm must be differentiated, one has enough degrees of freedom to make a mathematically and statistically significant determination. Confounding factors may consist of tumor heterogeneity arising from regional variations in differentiation, ischemia, necrosis, hemorrhage, inflammation and the presence of intermingled normal tissue. One related aspect of our work is the development of { 13 C}- 1 H metabolic imaging of 13 C for metabolic characterization, with enhanced spatial localization (46). This should markedly extend the range of potential clinical NMR uses because the spatial variation in prostate metabolism may prove to be just as important in tumor diagnoses as bulk (volume-averaged) properties themselves. It is our hope that NMRS and spectroscopic imaging will reveal a sound correlation between prostate metabolism and tumor properties that will be clinically straightforward and useful for diagnosis

  10. The ratio of acetate-to-glucose oxidation in astrocytes from a single 13C NMR spectrum of cerebral cortex.

    Science.gov (United States)

    Marin-Valencia, Isaac; Hooshyar, M Ali; Pichumani, Kumar; Sherry, A Dean; Malloy, Craig R

    2015-01-01

    The (13) C-labeling patterns in glutamate and glutamine from brain tissue are quite different after infusion of a mixture of (13) C-enriched glucose and acetate. Two processes contribute to this observation, oxidation of acetate by astrocytes but not neurons, and preferential incorporation of α-ketoglutarate into glutamate in neurons, and incorporation of α-ketoglutarate into glutamine in astrocytes. The acetate:glucose ratio, introduced previously for analysis of a single (13) C NMR spectrum, provides a useful index of acetate and glucose oxidation in the brain tissue. However, quantitation of relative substrate oxidation at the cell compartment level has not been reported. A simple mathematical method is presented to quantify the ratio of acetate-to-glucose oxidation in astrocytes, based on the standard assumption that neurons do not oxidize acetate. Mice were infused with [1,2-(13) C]acetate and [1,6-(13) C]glucose, and proton decoupled (13) C NMR spectra of cortex extracts were acquired. A fit of those spectra to the model indicated that (13) C-labeled acetate and glucose contributed approximately equally to acetyl-CoA (0.96) in astrocytes. As this method relies on a single (13) C NMR spectrum, it can be readily applied to multiple physiologic and pathologic conditions. Differences in (13) C labeling of brain glutamate and glutamine have been attributed to metabolic compartmentation. The acetate:glucose ratio, introduced for description of a (13) C NMR (nuclear magnetic resonance) spectrum, is an index of glucose and acetate oxidation in brain tissue. A simple mathematical method is presented to quantify the ratio of acetate-to-glucose oxidation in astrocytes from a single NMR spectrum. As kinetic analysis is not required, the method is readily applicable to analysis of tissue extracts. α-KG = alpha-ketoglutarate; CAC = citric acid cycle; GLN = glutamine; GLU = glutamate. © 2014 International Society for Neurochemistry.

  11. Antiferromagnetic Ordering in Quasi-Triangular Localized Spin System, β'-Et2Me2P[Pd(dmit)2]2, Studied by 13C NMR

    Science.gov (United States)

    Otsuka, Kei; Iikubo, Hideaki; Kogure, Takayuki; Takano, Yoshiki; Hiraki, Ko-ichi; Takahashi, Toshihiro; Cui, Hengbo; Kato, Reizo

    2014-05-01

    We performed 13C NMR measurements of a selectively 13C isotope-labeled single-crystal sample of a frustrated spin system, β'-Et2Me2P[Pd(dmit)2]2. A long-range antiferromagnetic (AF) ordering below 17 K was confirmed by the observation of NMR spectrum broadening and well split resonance lines at lower temperatures. NMR spectra in the AF state can be well explained by a two sublattice model. From the analysis of the angular dependence of the NMR spectrum, we clarified the magnetic structure in the AF state, where the easy and hard axes are the crystallographic c*- and b-axes, respectively, and the effective localized moments are quite small, ˜0.28 μB/dimer. This suggests a strong quantum fluctuation effect due to magnetic frustrations in a quasi-triangular spin-1/2 system.

  12. Heteronuclear three-dimensional NMR spectroscopy. Natural abundance 13C chemical shift editing of 1H-1H COSY spectra

    International Nuclear Information System (INIS)

    Fesik, S.W.; Gampe, R.T. Jr.; Zuiderweg, E.R.P.

    1989-01-01

    It has been demonstrated that heteronuclear 3D NMR spectroscopy can be effectively applied to small molecules with 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

  13. A 13C NMR Study of 7-Norbornadienyl Cation by Modified Hammett-Brown Equation

    International Nuclear Information System (INIS)

    Park, Jeong Kyu; Shin, Jung Hyu

    1999-01-01

    A series of the para-substituted 7-aryl-norbornadienyl cation (3) was prepared in FSO 3 H/SO 2 ClF solution at -100 .deg. C and their 13 C NMR shifts were measured at -80 .deg. C. The plots of the chemical shifts (changes in chemical shifts) of cationic carbon, Δδ C+ , against our calculated new substituent constant, σ c+ s, gave an excellent correlation (r = 0.994), with a p c+ value of 12.63. These results indicate that the new substituent onstants, σ c+ s, can be successfully employed to compare the relative charge demand of the carbonium ion by π- and πσ-participation

  14. {sup 13}C NMR spectral data and molecular descriptors to predict the antioxidant activity of flavonoids

    Energy Technology Data Exchange (ETDEWEB)

    Fernandes, Mariane Balerine; Muramatsu, Eric [Universidade de Sao Paulo (USP). Ribeirao Preto, SP (Brazil). Fac. de Ciencias Farmauceuticas; Emereciano, Vicente de Paula [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica; Scotti, Marcus Tullius [Universidade Federal da Paraiba (UFPA), Joao Pessoa, PA (Brazil). Centro de Ciencias Aplicadas e Educacao; Scotti, Luciana; Tavares, Josean Fechine; Silva, Marcelo Sobral da [Universidade Federal da Paraiba (UFPA), Joao Pessoa, PA (Brazil). Lab. de Tecnologia Farmaceutica

    2011-04-15

    Tissue damage due to oxidative stress is directly linked to development of many, if not all, human morbidity factors and chronic diseases. In this context, the search for dietary natural occurring molecules with antioxidant activity, such as flavonoids, has become essential. In this study, we investigated a set of 41 flavonoids (23 flavones and 18 flavonols) analyzing their structures and biological antioxidant activity. The experimental data were submitted to a QSAR (quantitative structure-activity relationships) study. NMR {sup 13}C data were used to perform a Kohonen self-organizing map study, analyzing the weight that each carbon has in the activity. Additionally, we performed MLR (multilinear regression) using GA (genetic algorithms) and molecular descriptors to analyze the role that specific carbons and substitutions play in the activity. (author)

  15. 1H-13C NMR-based profiling of biotechnological starch utilization

    DEFF Research Database (Denmark)

    Sundekilde, Ulrik K.; Meier, Sebastian

    2016-01-01

    Starch is used in food-and non-food 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 1H-13C 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 down-stream process output such as ethanol production from starch. Thus, high...

  16. Complete {sup 1}H and {sup 13}C NMR structural assignments for a group of four goyazensolide-type furanoheliangolides

    Energy Technology Data Exchange (ETDEWEB)

    Soares, Ana Carolina Ferreira; Silva, Aline Nazare; Matos, Priscilla Mendonca; Silva, Eder Henrique da; Heleno, Vladimir Constantino Gomes [Universidade de Franca, Franca, SP (Brazil). Nucleo de Pesquisas em Ciencias Exatas e Tecnologicas; Lopes, Norberto Peporine; Lopes, Joao Luis Callegari [Universidade de Sao Paulo (FCFRP/USP), Ribeirao Preto, SP (Brazil). Fac. de Ciencias Farmaceuticas de Ribeirao Preto. Dept. de Quimica e Fisica; Sass, Daiane Cristina, E-mail: vheleno_05@yahoo.com.br [Universidade de Sao Paulo (FFCLRP/USP), Ribeirao Preto, SP (Brazil). Fac. de Filosofia, Ciencias e Letras de Ribeirao Preto. Dept. de Quimica

    2012-07-01

    Four goyazensolide-type sesquiterpene lactones - lychnofolide, centratherin, goyazensolide and goyazensolide acetate - were thoroughly studied by NMR experimental techniques. {sup 1}H NMR, {sup 13}C NMR {l_brace}{sup 1}H{r_brace}, COSY, HMQC, HMBC, J-res. and NOE experiments were performed to provide the needed structural information. Complete and unequivocal assignment, including the determination of all multiplicities, was obtained for each structure and the data collections are presented in tables (author)

  17. Acetate and bicarbonate assimilation and metabolite formation in Chlamydomonas reinhardtii: a 13C-NMR study.

    Directory of Open Access Journals (Sweden)

    Himanshu Singh

    Full Text Available Cellular metabolite analyses by (13C-NMR showed that C. reinhardtii cells assimilate acetate at a faster rate in heterotrophy than in mixotrophy. While heterotrophic cells produced bicarbonate and CO2aq, mixotrophy cells produced bicarbonate alone as predominant metabolite. Experiments with singly (13C-labelled acetate ((13CH(3-COOH or CH(3-(13COOH supported that both the (13C nuclei give rise to bicarbonate and CO2(aq. The observed metabolite(s upon further incubation led to the production of starch and triacylglycerol (TAG in mixotrophy, whereas in heterotrophy the TAG production was minimal with substantial accumulation of glycerol and starch. Prolonged incubation up to eight days, without the addition of fresh acetate, led to an increased TAG production at the expense of bicarbonate, akin to that of nitrogen-starvation. However, such TAG production was substantially high in mixotrophy as compared to that in heterotrophy. Addition of mitochondrial un-coupler blocked the formation of bicarbonate and CO2(aq in heterotrophic cells, even though acetate uptake ensued. Addition of PSII-inhibitor to mixotrophic cells resulted in partial conversion of bicarbonate into CO2(aq, which were found to be in equilibrium. In an independent experiment, we have monitored assimilation of bicarbonate via photoautotrophy and found that the cells indeed produce starch and TAG at a much faster rate as compared to that in mixotrophy and heterotrophy. Further, we noticed that the accumulation of starch is relatively more as compared to TAG. Based on these observations, we suggest that acetate assimilation in C. reinhardtii does not directly lead to TAG formation but via bicarbonate/CO2(aq pathways. Photoautotrophic mode is found to be the best growth condition for the production of starch and TAG and starch in C. reinhardtii.

  18. Monovacancy paramagnetism in neutron-irradiated graphite probed by 13C NMR.

    Science.gov (United States)

    Zhang, Zhi Tao; Xu, C; Dmytriieva, Daryna; Molatta, Sebastian; Wosnitza, J; Wang, Y T; Helm, Manfred; Zhou, Shengqiang; Kuehne, Hannes

    2017-09-18

    We report on the magnetic properties of monovacancy defects in neutron-irradiated graphite, probed by $^{13}$C nuclear magnetic resonance spectroscopy. The bulk paramagnetism of the defect moments is revealed by the temperature dependence of the NMR frequency shift and spectral linewidth, both of which follow a Curie behavior, in agreement with measurements of the macroscopic magnetization. Compared to pristine graphite, the fluctuating hyperfine fields generated by the defect moments lead to an enhancement of the $^{13}$C nuclear spin-lattice relaxation rate $1/T_{1}$ by about two orders of magnitude. With an applied magnetic field of 7.1 T, the temperature dependence of $1/T_{1}$ below about 10 K can well be described by a thermally activated form, $1/T_{1}\\propto\\exp(-\\Delta/k_{B}T)$, yielding a singular Zeeman energy of ($0.41\\pm0.01$) meV, in excellent agreement with the sole presence of polarized, non-interacting defect moments. © 2017 IOP Publishing Ltd.

  19. Mono terpenes characterization by {sup 1} H and {sup 13} C-1 NMR; Caracterizacao de monoterpenos por RMN - {sup 1} H e de {sup 13} C-1

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, Martha T. de [Universidade Federal Fluminense, Niteroi, RJ (Brazil). Dept. de Fisico-Quimica; Silveira, Carmen L.P. [Universidade Federal Fluminense, Niteroi, RJ (Brazil). Dept. de Quimica Organica; Mcchesney, James D [Mississippi Univ., University, MS (United States). Research Inst. of Pharmaceutical Sciences

    1992-12-31

    Artemisinine, a new lactone sesquiterpene containing one peroxide binding, is the main anti malarial agent obtained from the Artemisia annua L. Viewing to obtain a simple synthetic route for artemisinic acid preparation, which is the key intermediary for total synthesis of this type of anti malarial agent, R-carvone has been chosen as starting material. The S-carvone was used as model for reaction optimization and preparation of derivatives to be used for NMR studies. The main objective of this work is the signalling of the {sup 13} C and {sup 1} H NMR spectra, using the 2 D-COSY and 2 D-Hector spectra 4 refs., 3 figs., 1 tab

  20. Optimized slice-selective 1H NMR experiments combined with highly accurate quantitative 13C NMR using an internal reference method

    Science.gov (United States)

    Jézéquel, Tangi; Silvestre, Virginie; Dinis, Katy; Giraudeau, Patrick; Akoka, Serge

    2018-04-01

    Isotope ratio monitoring by 13C NMR spectrometry (irm-13C NMR) provides the complete 13C intramolecular position-specific composition at natural abundance. It represents a powerful tool to track the (bio)chemical pathway which has led to the synthesis of targeted molecules, since it allows Position-specific Isotope Analysis (PSIA). Due to the very small composition range (which represents the range of variation of the isotopic composition of a given nuclei) of 13C natural abundance values (50‰), irm-13C NMR requires a 1‰ accuracy and thus highly quantitative analysis by 13C NMR. Until now, the conventional strategy to determine the position-specific abundance xi relies on the combination of irm-MS (isotopic ratio monitoring Mass Spectrometry) and 13C quantitative NMR. However this approach presents a serious drawback since it relies on two different techniques and requires to measure separately the signal of all the carbons of the analyzed compound, which is not always possible. To circumvent this constraint, we recently proposed a new methodology to perform 13C isotopic analysis using an internal reference method and relying on NMR only. The method combines a highly quantitative 1H NMR pulse sequence (named DWET) with a 13C isotopic NMR measurement. However, the recently published DWET sequence is unsuited for samples with short T1, which forms a serious limitation for irm-13C NMR experiments where a relaxing agent is added. In this context, we suggest two variants of the DWET called Multi-WET and Profiled-WET, developed and optimized to reach the same accuracy of 1‰ with a better immunity towards T1 variations. Their performance is evaluated on the determination of the 13C isotopic profile of vanillin. Both pulse sequences show a 1‰ accuracy with an increased robustness to pulse miscalibrations compared to the initial DWET method. This constitutes a major advance in the context of irm-13C NMR since it is now possible to perform isotopic analysis with high

  1. Unified integration intervals for the structural characterization of oil, coal or fractions there of by 1h NMR and 13c NMR

    International Nuclear Information System (INIS)

    Avella, Eliseo; Fierro, Ricardo

    2010-01-01

    Based on an analysis of publications reported between 1972 and 2006, it became clear that there are inaccuracies in the limits of the ranges of integration that the authors assigned to signals in nuclear magnetic resonance (NMR) to the structural characterization of petroleum, coals and their derived fractions, from their hydrogen (1H NMR) and carbon (13C NMR) spectra. Consequently, consolidated limits were determined for the integration of 1H NMR spectra and 13C NMR of these samples using a statistical treatment applied to the limits of integration intervals already published. With these unified limits, correlation NMR charts were developed that are useful for the allocation of the integral at such intervals, and at smaller intervals defined in terms of the intersection between different assignments. Also raised equations needed to establish the integral attributable to specific fragments in an attempt to make a more accurate structural characterization from NMR spectra of oil, coal or fractions derived.

  2. Effects of insulin on perfused liver from streptozotocin-diabetic and untreated rats: 13C NMR assay of pyruvate kinase flux

    International Nuclear Information System (INIS)

    Cohen, S.M.

    1987-01-01

    The effects of insulin in vitro on perfused liver from streptozotocin-diabetic rats and their untreated littermates during gluconeogenesis from either [3- 13 C]alanine + ethanol or [2- 13 C]pyruvate + NH 4 Cl + ethanol were studied by 13 C NMR. A 13 C NMR determination of the rate of pyruvate kinase flux under steady-state conditions of active gluconeogenesis was developed; this assay includes a check on the reuse of recycled pyruvate. The preparations studied provided gradations of pyruvate kinase flux within the confines of the assay's requirement of active gluconeogenesis. By this determination, the rate of pyruvate kinase flux was 0.74 +/- 0.04 of the gluconeogenic rate in liver from 24-h-fasted controls; in liver from 12-h fasted controls, relative pyruvate kinase flux increased to 1.0 +/- 0.2. In diabetic liver, this flux was undetectable by the authors NMR method. Insulin's hepatic influence in vitro was greatest in the streptozotocin model of type 1 diabetes: upon treatment of diabetic liver with 7 nM insulin in vitro, a partial reversal of many of the differences noted between diabetic and control liver was demonstrated by 13 C NMR. A major effect of insulin in vitro upon diabetic liver was the induction of a large increase in the rate of pyruvate kinase flux, bringing relative and absolute fluxes up to the levels measured in 24-h-fasted controls. By way of comparison, the effects of ischemia on diabetic liver were studied by 13 C NMR to test whether changes in allosteric effectors under these conditions could also increase pyruvate kinase flux. A large increase in this activity was demonstrated in ischemic diabetic liver

  3. 13C NMR relaxation times of hepatic glycogen in vitro and in vivo

    International Nuclear Information System (INIS)

    Zang, Lihsin; Laughlin, M.R.; Rothman, D.L.; Shulman, R.G.

    1990-01-01

    The field dependence of relaxation times of the C-1 carbon of glycogen was studied in vitro by natural-abundance 13 C NMR. T 1 is strongly field dependent, while T 2 does not change significantly with magnetic field. T 1 and T 2 were also measured for rat hepatic glycogen enriched with [1- 13 C]glucose in vivo at 4.7 T, and similar relaxation times were observed as those obtained in vitro at the same field. The in vitro values of T 1 were 65 ± 5 ms at 2.1 T, 142 ± 10 ms at 4.7 T, and 300 ± 10 ms at 8.4 T, while T 2 values were 6.7 ± 1 ms at 2.1 T, 9.4 ± 1 ms at 4.7 T, and 9.5 ± 1 ms at 8.4 T. Calculations based on the rigid-rotor nearest-neighbor model give qualitatively good agreement with the T 1 field dependence with a best-fit correlation time of 6.4 x 10 -9 s, which is significantly smaller than τ M , the estimated overall correlation time for the glycogen molecule (ca. 10 -5 s). A more accurate fit of T 1 data using a modified Lipari and Szabo approach indicates that internal fast motions dominate the T 1 relaxation in glycogen. On the other hand, the T 2 relaxation is dominated by the overall correlation time τ M while the internal motions are almost but not completely unrestricted

  4. Comparison of IRMS and NMR spectrometry for the determination of intramolecular 13C isotope composition: application to ethanol.

    Science.gov (United States)

    Gilbert, Alexis; Hattori, Ryota; Silvestre, Virginie; Wasano, Nariaki; Akoka, Serge; Hirano, Satoshi; Yamada, Keita; Yoshida, Naohiro; Remaud, Gérald S

    2012-09-15

    Isotopic (13)C NMR is a relatively recent technique which allows the determination of intramolecular (13)C isotope composition at natural abundance. It has been used in various scientific fields such as authentication, counterfeiting or plant metabolism. Although its precision has already been evaluated, the determination of its trueness remains still challenging. To deal with that issue, a comparison with another normalized technique must be achieved. In this work, we compare the intramolecular (13)C isotope distribution of ethanol from different origins obtained using both Isotope Ratio Mass Spectrometry (IRMS) and Nuclear Magnetic Resonance (NMR) spectrometry techniques. The IRMS approach consists of the oxidation of ethanol to acetic acid followed by the degradation of the latter for the analysis of each fragments formed. We show here that the oxidation of ethanol to acetic acid does not bring any significant error on the determination of the site-specific δ(13)C (δ(13)C(i)) of ethanol using the IRMS approach. The difference between the data obtained for 16 samples from different origins using IRMS and NMR approaches is not statistically significant and remains below 0.3‰. These results are encouraging for the future studies using isotopic NMR, especially in combination with the IRMS approach. Copyright © 2012. Published by Elsevier B.V.

  5. Styrylpyrylium Salts: 1H and 13C NMR High-Resolution Spectroscopy (1D and 2D

    Directory of Open Access Journals (Sweden)

    Jean Claude W. Ouédraogo

    2010-01-01

    Full Text Available 1H and 13C NMR high-resolution spectroscopy (1D and 2D (1H, 1H-COSY, HSQC, HMBC for four styrylpyrylium perchlorates were carried out and signal attributions are reported. Chemical shifts observed on 13C NMR spectra for the styrylpyrylium salts were compared with net atomic charge for carbon obtained by AM1 semiempirical calculations. The position of the styryl group present low effect on chemical shifts for carbon atoms, while the presence of methyl group led to the unshielding of the substituted carbon.

  6. Spectrally edited 2D 13Csbnd 13C NMR spectra without diagonal ridge for characterizing 13C-enriched low-temperature carbon materials

    Science.gov (United States)

    Johnson, Robert L.; Anderson, Jason M.; Shanks, Brent H.; Fang, Xiaowen; Hong, Mei; Schmidt-Rohr, Klaus

    2013-09-01

    Two robust combinations of spectral editing techniques with 2D 13Csbnd 13C NMR have been developed for characterizing the aromatic components of 13C-enriched low-temperature carbon materials. One method (exchange with protonated and nonprotonated spectral editing, EXPANSE) selects cross peaks of protonated and nearby nonprotonated carbons, while the other technique, dipolar-dephased double-quantum/single-quantum (DQ/SQ) NMR, selects signals of bonded nonprotonated carbons. Both spectra are free of a diagonal ridge, which has many advantages: Cross peaks on the diagonal or of small intensity can be detected, and residual spinning sidebands or truncation artifacts associated with the diagonal ridge are avoided. In the DQ/SQ experiment, dipolar dephasing of the double-quantum coherence removes protonated-carbon signals; this approach also eliminates the need for high-power proton decoupling. The initial magnetization is generated with minimal fluctuation by combining direct polarization, cross polarization, and equilibration by 13C spin diffusion. The dipolar dephased DQ/SQ spectrum shows signals from all linkages between aromatic rings, including a distinctive peak from polycondensed aromatics. In EXPANSE NMR, signals of protonated carbons are selected in the first spectral dimension by short cross polarization combined with dipolar dephasing difference. This removes ambiguities of peak assignment to overlapping signals of nonprotonated and protonated aromatic carbons, e.g. near 125 ppm. Spin diffusion is enhanced by dipolar-assisted rotational resonance. Before detection, Csbnd H dipolar dephasing by gated decoupling is applied, which selects signals of nonprotonated carbons. Thus, only cross peaks due to magnetization originating from protonated C and ending on nearby nonprotonated C are retained. Combined with the chemical shifts deduced from the cross-peak position, this double spectral editing defines the bonding environment of aromatic, COO, and Cdbnd O carbons

  7. 13C-NMR-Based Metabolomic Profiling of Typical Asian Soy Sauces

    Directory of Open Access Journals (Sweden)

    Ghulam Mustafa Kamal

    2016-09-01

    Full Text Available It has been a strong consumer interest to choose high quality food products with clear information about their origin and composition. In the present study, a total of 22 Asian soy sauce samples have been analyzed in terms of 13C-NMR spectroscopy. Spectral data were analyzed by multivariate statistical methods in order to find out the important metabolites causing the discrimination among typical soy sauces from different Asian regions. It was found that significantly higher concentrations of glutamate in Chinese red cooking (CR soy sauce may be the result of the manual addition of monosodium glutamate (MSG in the final soy sauce product. Whereas lower concentrations of amino acids, like leucine, isoleucine and valine, observed in CR indicate the different fermentation period used in production of CR soy sauce, on the other hand, the concentration of some fermentation cycle metabolites, such as acetate and sucrose, can be divided into two groups. The concentrations of these fermentation cycle metabolites were lower in CR and Singapore Kikkoman (SK, whereas much higher in Japanese shoyu (JS and Taiwan (China light (TL, which depict the influence of climatic conditions. Therefore, the results of our study directly indicate the influences of traditional ways of fermentation, climatic conditions and the selection of raw materials and can be helpful for consumers to choose their desired soy sauce products, as well as for researchers in further authentication studies about soy sauce.

  8. Metabolic Effects of Hypoxia in Colorectal Cancer by 13C NMR Isotopomer Analysis

    Directory of Open Access Journals (Sweden)

    Ana M. Abrantes

    2014-01-01

    Full Text Available 13C NMR isotopomer analysis was used to characterize intermediary metabolism in three colorectal cancer cell lines (WiDr, LS1034, and C2BBe1 and determine the “metabolic remodeling” that occurs under hypoxia. Under normoxia, the three colorectal cancer cell lines present high rates of lactate production and can be seen as “Warburg” like cancer cells independently of substrate availability, since such profile was dominant at both high and low glucose media contents. The LS1034 was the less glycolytic of the three cell lines and was the most affected by the event of hypoxia, raising abruptly glucose consumption and lactate production. The other two colorectal cell lines, WiDr and C2BBe1, adapted better to hypoxia and were able to maintain their oxidative fluxes even at the very low levels of oxygen. These differential metabolic behaviors of the three colorectal cell lines show how important an adequate knowledge of the “metabolic remodeling” that follows a given cancer treatment is towards the correct (redesign of therapeutic strategies against cancer.

  9. Prototropic tautomerism of 5-nitrobenzimidazole derivatives in {sup 1}H, {sup 13}C and {sup 15}N NMR spectra; Tautomeria prototropowa pochodnych 5-nitrobenzimidazolu w widmach {sup 1}H, {sup 13}C, {sup 15}N NMR

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-12-31

    NMR spectra of 5-nitrobenzimidazole derivatives in DMSO solution show the fast exchange of protons. The line broadening in {sup 1}H,{sup 13}C and {sup 15}N spectra have been observed. The interpretation of the spectra has been done basing on chemical shifts values and couplings between nuclei in the investigated derivatives. 3 refs, 2 figs, 3 tabs.

  10. NMR studies of bent DNA using {sup 13}C-enriched samples

    Energy Technology Data Exchange (ETDEWEB)

    Zimmer, D.P.; Crothers, D.M. [Yale Univ., New Haven, CT (United States)

    1994-12-01

    Bending of the DNA double helix can be brought about by introducing runs of adenines (A-tracts) in phase with the helical repeat of the DNA. The requirements for bending of DNA by A-tracts are that the length of the A-tract be greater than 3 base pairs and that the A-tracts must be in phase with the helical repeat (every 10 or 11 bp). Other factors, such as the number of adenines in the run, flanking sequences, and whether the A-tracts are phased with respect to the 5{prime}A or the 3{prime}A, have effects upon the degree of bending as assayed by electrophoretic mobility on native polyacrylamide gels. There are a number of models for bending A-tract DNA. The junction-bending model postulates that the structure of A-tracts is similar to the fiber diffraction structure of poly A, in which there is a significant degree of base pair tilt with respect to the helix axis. In this model, bending occurs at the junction between the A-tract and the B-form helix to allow favorable stacking interactions to occur. The bend of the helix could arise as a result of some other perturbation of B-form DNA by A-tracts, such as propeller twist; bending also could be due to a combination of factors. Our goal is to find the structural features of A-tracts responsible for bending of the helix by performing NMR on oligonucleotides containing A-tracts to obtain higher resolution structural data. One of the problems encountered in NMR structure determination of nucleic acids and other macromolecules is the assignment of resonances to nuclei. This procedure can be greatly facilitated through the use of {sup 13}C-enriched nucleic acid samples. We are developing a technique for the enzymatic synthesis of labeled DNA for NMR. The technique we are developing is similar to RNA labeling techniques already in use. The technique involves growth of methylotrophic bacteria on {sup 13}CH{sub 3}OH.

  11. Study of lignin standard-substances type biphenyl by {sup 13} C NMR; Estudo de substancias-modelo de lignina do tipo bifenila, por RMN de {sup 13} C

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Marcia Alves; Drumond, Mariza Guimaraes; Veloso, Dorila Pilo [Minas Gerais Univ., Belo Horizonte, MG (Brazil). Dept. de Quimica

    1995-12-31

    Lignins structural study by NMR has utilized standard-substances spectral comparative analysis. This work has present relaxation time studies for lignin standard-substance, and {sup 13} C NMR chemical shift values were also shown and compared for several compounds. NMR spectra were commented besides experimental data analysis 2 figs., 4 tabs.

  12. Structure of Selected Derivates of p-Hydroxy Cynamonic Acid According to 13C CP MAS NMR and DFT Calculation

    International Nuclear Information System (INIS)

    Pisklak, D.M.; Wawer, I.; Tkaczyk, M.

    2005-01-01

    Derivatives of p-hydroxy cynamonic acid are widely occurring in fruits, vegetables, tea and coffee. They exhibit strong antioxidant activity due to the presence of phenolic group. Epidemiological, biological and biochemical data support health beneficial role of this group of compounds and anticarcinogenic, antimutagenic and antiinflamatory effects have been reported. The most common caffeic acid contributes significantly to the total polyphenol intake and has been suggested to play a role in the apparent association between the regular consumption of polyphenol-rich food and beverages, and the prevetion of inflammatory and proliferative diseases. 13 C MAS NMR spectra were recorded on a BRUKER DSX 400 spectrometer at 400,13. Powder samples were spun in a 4 mm rotor at 10 kHz ( 13 C). Signals were assigned:- By comparison with solution spectra; - Using dipolar dephasing and variable contact time experiments; - Confirmed by DFT calculations of shielding constants. The differences in chemical shifts between solution and solid state spectra are due to the formation of intramolecular and intermolecular hydrogen bonds, including C-OH...OC within cyclic dimers. (author)

  13. Residue-specific membrane location of peptides and proteins using specifically and extensively deuterated lipids and {sup 13}C-{sup 2}H rotational-echo double-resonance solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Xie Li; Ghosh, Ujjayini; Schmick, Scott D.; Weliky, David P., E-mail: weliky@chemistry.msu.edu [Michigan State University, Department of Chemistry (United States)

    2013-01-15

    Residue-specific location of peptides in the hydrophobic core of membranes was examined using {sup 13}C-{sup 2}H REDOR and samples in which the lipids were selectively deuterated. The transmembrane topology of the KALP peptide was validated with this approach with substantial dephasing observed for deuteration in the bilayer center and reduced or no dephasing for deuteration closer to the headgroups. Insertion of {beta} sheet HIV and helical and {beta} sheet influenza virus fusion peptides into the hydrophobic core of the membrane was validated in samples with extensively deuterated lipids.

  14. Optimization of amino acid type-specific 13C and 15N labeling for the backbone assignment of membrane proteins by solution- and solid-state NMR with the UPLABEL algorithm

    International Nuclear Information System (INIS)

    Hefke, Frederik; Bagaria, Anurag; Reckel, Sina; Ullrich, Sandra Johanna; Dötsch, Volker; Glaubitz, Clemens; Güntert, Peter

    2011-01-01

    We present a computational method for finding optimal labeling patterns for the backbone assignment of membrane proteins and other large proteins that cannot be assigned by conventional strategies. Following the approach of Kainosho and Tsuji (Biochemistry 21:6273–6279 (1982)), types of amino acids are labeled with 13 C or/and 15 N such that cross peaks between 13 CO(i – 1) and 15 NH(i) result only for pairs of sequentially adjacent amino acids of which the first is labeled with 13 C and the second with 15 N. In this way, unambiguous sequence-specific assignments can be obtained for unique pairs of amino acids that occur exactly once in the sequence of the protein. To be practical, it is crucial to limit the number of differently labeled protein samples that have to be prepared while obtaining an optimal extent of labeled unique amino acid pairs. Our computer algorithm UPLABEL for optimal unique pair labeling, implemented in the program CYANA and in a standalone program, and also available through a web portal, uses combinatorial optimization to find for a given amino acid sequence labeling patterns that maximize the number of unique pair assignments with a minimal number of differently labeled protein samples. Various auxiliary conditions, including labeled amino acid availability and price, previously known partial assignments, and sequence regions of particular interest can be taken into account when determining optimal amino acid type-specific labeling patterns. The method is illustrated for the assignment of the human G-protein coupled receptor bradykinin B2 (B 2 R) and applied as a starting point for the backbone assignment of the membrane protein proteorhodopsin.

  15. Glycerin-Induced Conformational Changes in Bombyx mori Silk Fibroin Film Monitored by (13)C CP/MAS NMR and ¹H DQMAS NMR.

    Science.gov (United States)

    Asakura, Tetsuo; Endo, Masanori; Hirayama, Misaki; Arai, Hiroki; Aoki, Akihiro; Tasei, Yugo

    2016-09-09

    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, (13)C 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.

  16. Biosynthetic studies of the glycopeptide teicoplanin by 1H and 13C NMR

    DEFF Research Database (Denmark)

    Heydorn, Arne; Petersen, Bent O.; Duus, Jens Øllgaard

    2000-01-01

    The biosynthesis of the glycopeptide antibiotic teicoplanin was studied by growing a teicoplanin producing strain of Actinoplanes teichomyceticus (ATCC 31121) on glucose containing either 34.0% [1-13C]glucose or 9.7% [U- 13C]glucose. The fractional enrichment pattern of teicoplanin produced in th...

  17. Direct {sup 13}C-detected NMR experiments for mapping and characterization of hydrogen bonds in RNA

    Energy Technology Data Exchange (ETDEWEB)

    Fürtig, Boris, E-mail: fuertig@nmr.uni-frankfurt.de; Schnieders, Robbin; Richter, Christian; Zetzsche, Heidi; Keyhani, Sara; Helmling, Christina [Johann Wolfgang Goethe Universität Frankfurt, Center for Biomolecular Magnetic Resonance (BMRZ), Institute of Organic Chemistry and Chemical Biology (Germany); Kovacs, Helena [Bruker BioSpin (Switzerland); Schwalbe, Harald, E-mail: schwalbe@nmr.uni-frankfurt.de [Johann Wolfgang Goethe Universität Frankfurt, Center for Biomolecular Magnetic Resonance (BMRZ), Institute of Organic Chemistry and Chemical Biology (Germany)

    2016-03-15

    In RNA secondary structure determination, it is essential to determine whether a nucleotide is base-paired and not. Base-pairing of nucleotides is mediated by hydrogen bonds. The NMR characterization of hydrogen bonds relies on experiments correlating the NMR resonances of exchangeable protons and can be best performed for structured parts of the RNA, where labile hydrogen atoms are protected from solvent exchange. Functionally important regions in RNA, however, frequently reveal increased dynamic disorder which often leads to NMR signals of exchangeable protons that are broadened beyond {sup 1}H detection. Here, we develop {sup 13}C direct detected experiments to observe all nucleotides in RNA irrespective of whether they are involved in hydrogen bonds or not. Exploiting the self-decoupling of scalar couplings due to the exchange process, the hydrogen bonding behavior of the hydrogen bond donor of each individual nucleotide can be determined. Furthermore, the adaption of HNN-COSY experiments for {sup 13}C direct detection allows correlations of donor–acceptor pairs and the localization of hydrogen-bond acceptor nucleotides. The proposed {sup 13}C direct detected experiments therefore provide information about molecular sites not amenable by conventional proton-detected methods. Such information makes the RNA secondary structure determination by NMR more accurate and helps to validate secondary structure predictions based on bioinformatics.

  18. 13C-NMR reveals glycerol as an unexpected major metabolite of the protozoan parasite Trichomonas vaginalis

    International Nuclear Information System (INIS)

    Chapman, A.; Lloyd, D.; Linstead, D.J.; Williams, J.

    1985-01-01

    13 C-NMR has been used to study the kinetics of the formation of metabolites from [l- 13 C]glucose in intact cells of Trichomonas vaginalis during anaerobic incubation. As well as the expected metabolites lactate and acetate, this technique revealed glycerol as an additional major product, present in amounts equimolar with acetate. The formation of glycerol is readily explained in terms of the need to maintain redox balance. This protozoan now joins the small group of organisms which are known to produce glycerol as a result of normal metabolic activities. (Auth.)

  19. Effect of pressure on the short-range structure and speciation of carbon in alkali silicate and aluminosilicate glasses and melts at high pressure up to 8 GPa: 13C, 27Al, 17O and 29Si solid-state NMR study

    Science.gov (United States)

    Kim, Eun Jeong; Fei, Yingwei; Lee, Sung Keun

    2018-03-01

    Despite the pioneering efforts to explore the nature of carbon in carbon-bearing silicate melts under compression, experimental data for the speciation and the solubility of carbon in silicate melts above 4 GPa have not been reported. Here, we explore the speciation of carbon and pressure-induced changes in network structures of carbon-bearing silicate (Na2O-3SiO2, NS3) and sodium aluminosilicate (NaAlSi3O8, albite) glasses quenched from melts at high pressure up to 8 GPa using multi-nuclear solid-state NMR. The 27Al triple quantum (3Q) MAS NMR spectra for carbon-bearing albite melts revealed the pressure-induced increase in the topological disorder around 4 coordinated Al ([4]Al) without forming [5,6]Al. These structural changes are similar to those in volatile-free albite melts at high pressure, indicating that the addition of CO2 in silicate melts may not induce any additional increase in the topological disorder around Al at high pressure. 13C MAS NMR spectra for carbon-bearing albite melts show multiple carbonate species, including [4]Si(CO3)[4]Si, [4]Si(CO3)[4]Al, [4]Al(CO3)[4]Al, and free CO32-. The fraction of [4]Si(CO3)[4]Al increases with increasing pressure, while those of other bridging carbonate species decrease, indicating that the addition of CO2 may enhance mixing of Si and Al at high pressure. A noticeable change is not observed for 29Si NMR spectra for the carbon-bearing albite glasses with varying pressure at 1.5-6 GPa. These NMR results confirm that the densification mechanisms established for fluid-free, polymerized aluminosilicate melts can be applied to the carbon-bearing albite melts at high pressure. In contrast, the 29Si MAS NMR spectra for partially depolymerized, carbon-bearing NS3 glasses show that the fraction of [5,6]Si increases with increasing pressure at the expense of Q3 species ([4]Si species with one non-bridging oxygen as the nearest neighbor). The pressure-induced increase in topological disorder around Si is evident from an

  20. Studies on /sup 13/C-NMR spectroscopy of carbohydrates. Application of selective deuteration

    Energy Technology Data Exchange (ETDEWEB)

    Mizutani, Kenji; Kajita, Hitomi; Tashima, Takako; Tanaka, Osamu (Hiroshima Univ. (Japan). School of Medicine)

    1982-10-01

    /C-NMR signal-assignments of the above oligo- and polysaccharides were substantiated or revised as shown in Tables.

  1. 1H and 13C NMR studies of palladium(2) and platinium(2) complexes with S-Methyl-L-Cysteine

    International Nuclear Information System (INIS)

    Allain, A.; Jezowska-Trzebiatowska, B.; Kozlowski, H.

    1979-01-01

    Our recent 1 H NMR studies on Pd(2)-S-Methyl-L-Cysteine(SMC) complexes have shown that the use of a conformational analysis to establish the complexed species existing in solution may provide clearer results than considering the proton chemical shift only. However, the use of the vicinal coupling constant of ABC spectrum of αCH-βCH 2 proton unit to estimate the rotational isomer fractions, may contain some ambiguity, especially on the proton assignment of the methylene group. For this reason 13 C NMR method has been applied to study these systems. (author)

  2. An improved synthesis of α-13C glycine and heteronuclear NMR studies of its incorporation into thioredoxin

    International Nuclear Information System (INIS)

    Wishart, D.S.; Sykes, B.D.; Richards, F.M.

    1992-01-01

    We present an improved method to easily prepare gram quantities of α- 13 C glycine beginning from K 13 CN. The four step synthesis involves the production of an N, N-diphenyl-cyanoformamidine intermediate through the coupling of cyanide to N, N-diphenylcarbodiimide. Subsequent reduction by LiAlH 4 and hydrolysis of the resulting amidine produces fully enriched α- 13 C labelled glycine with a 45-50% yield. This relatively fast and simple synthesis uses only commonly available compounds and requires no special equipment, making the process easy to perform in any well equipped biochemistry laboratory. We further demonstrate that the product may be used, without extensive purification, to specifically label bacterially expressed proteins (E. coli thioredoxin) through standard biosynthetic procedures. We also show that the 13 C glycine-labelled protein may be readily analyzed using commonly available heteronuclear NMR techniques. Complete assignments for all 9 glycines of native E. coli thoredoxin are presented. (Author)

  3. Solubilization and localization of weakly polar lipids in unsonicated egg phosphatidylcholine: A 13C MAS NMR study

    International Nuclear Information System (INIS)

    Hamilton, J.A.; Fujito, D.T.; Hammer, C.F.

    1991-01-01

    The weakly polar lipids cholesteryl ester, triacylglycerol, and diacylglycerol incorporate to a limited extent into the lamellar structure of small unilamellar vesicles. The localization of the carbonyl group(s) at the aqueous interface was detected by [ 13 C]carbonyl chemical shift changes relative to the neat unhydrated lipid. This study uses 13 C NMR to investigate the interactions of thes lipids with unsonicated (multilamellar) phosphatidylcholine, a model system for cellular membranes and surfaces of emulsion particles with low curvature. Magic angle spinning reduced the broad lines of the unsonicated dispersions to narrow lines comparable to those from sonicated dispersions. [ 13 C]Carbonyl chemical shifts revealed incorporation of the three lipids into the lamellar structure of the unsonicated phospholipids and a partial hydration of the carbonyl groups similar to that observed in small vesicles. Other properties of interfacial weakly polar lipids in multilayers were similar to those in small unilamellar bilayers. There is thus a general tendency of weakly polar lipids to incorparate at least to a small extent into the lamellar structure of phospholipids and take on interfacial properties that are distinct from their bulk-phase properties. This pool of surface-located lipid is likely to be directly involved in enzymatyic transformations and protein-mediated transport. The 13 C magic angle spinning NMR method may be generally useful for determining the orientation of molecules in model membranes

  4. Partial least squares modeling of combined infrared, 1H NMR and 13C NMR spectra to predict long residue properties of crude oils

    NARCIS (Netherlands)

    de Peinder, P.; Visser, T.; Petrauskas, D.D.; Salvatori, F.; Soulimani, F.; Weckhuysen, B.M.

    2009-01-01

    Research has been carried out to determine the potential of partial least squares (PLS) modeling of mid-infrared (IR) spectra of crude oils combined with the corresponding 1H and 13C nuclear magnetic resonance (NMR) data, to predict the long residue (LR) properties of these substances. The study

  5. Retrobiosynthetic NMR studies with 13C-labeled glucose. Formation of gallic acid in plants and fungi

    International Nuclear Information System (INIS)

    Werner, I.; Bacher, A.; Eisenreich, W.

    1997-01-01

    The biosynthesis of gallic acid was studied in cultures of the fungus Phycomyces blakesleeanus and in leaves of the tree Rhus typhina. Fungal cultures were grown with [1-13C]glucose or with a mixture of unlabeled glucose and [U-13C6]glucose. Young leaves of R. typhina were kept in an incubation chamber and were supplied with a solution containing a mixture of unlabeled glucose and [U-13C6]glucose via the leaf stem. Isotope distributions in isolated gallic acid and aromatic amino acids were analyzed by one-dimensional 1H and 13C NMR spectroscopy. A quantitative analysis of the complex isotopomer composition of metabolites was obtained by deconvolution of the 13C13C coupling multiplets using numerical simulation methods. This approach required the accurate analysis of heavy isotope chemical shift effects in a variety of different isotopomers and the analysis of long range 13C13C coupling constants. The resulting isotopomer patterns were interpreted using a retrobiosynthetic approach based on a comparison between the isotopomer patterns of gallic acid and tyrosine. The data show that both in the fungus and in the plant all carbon atoms of gallic acid are biosynthetically equivalent to carbon atoms of shikimate. Notably, the carboxylic group of gallic acid is derived from the carboxylic group of an early intermediate of the shikimate pathway and not from the side chain of phenylalanine or tyrosine. It follows that the committed precursor of gallic acid is an intermediate of the shikimate pathway prior to prephenate or arogenate, most probably 5-dehydroshikimate. A formation of gallic acid via phenylalanine, the lignin precursor, caffeic acid, or 3,4, 5-trihydroxycinnamic acid can be ruled out as major pathways in the fungus and in young leaves of R. typhina. The incorporation of uniformly 13C-labeled glucose followed by quantitative NMR analysis of isotopomer patterns is suggested as a general method for biosynthetic studies. As shown by the plant experiment, this

  6. Compositional differences among Chinese soy sauce types studied by (13)C NMR spectroscopy coupled with multivariate statistical analysis.

    Science.gov (United States)

    Kamal, Ghulam Mustafa; Wang, Xiaohua; Bin Yuan; Wang, Jie; Sun, Peng; Zhang, Xu; Liu, Maili

    2016-09-01

    Soy sauce a well known seasoning all over the world, especially in Asia, is available in global market in a wide range of types based on its purpose and the processing methods. Its composition varies with respect to the fermentation processes and addition of additives, preservatives and flavor enhancers. A comprehensive (1)H NMR based study regarding the metabonomic variations of soy sauce to differentiate among different types of soy sauce available on the global market has been limited due to the complexity of the mixture. In present study, (13)C NMR spectroscopy coupled with multivariate statistical data analysis like principle component analysis (PCA), and orthogonal partial least square-discriminant analysis (OPLS-DA) was applied to investigate metabonomic variations among different types of soy sauce, namely super light, super dark, red cooking and mushroom soy sauce. The main additives in soy sauce like glutamate, sucrose and glucose were easily distinguished and quantified using (13)C NMR spectroscopy which were otherwise difficult to be assigned and quantified due to serious signal overlaps in (1)H NMR spectra. The significantly higher concentration of sucrose in dark, red cooking and mushroom flavored soy sauce can directly be linked to the addition of caramel in soy sauce. Similarly, significantly higher level of glutamate in super light as compared to super dark and mushroom flavored soy sauce may come from the addition of monosodium glutamate. The study highlights the potentiality of (13)C NMR based metabonomics coupled with multivariate statistical data analysis in differentiating between the types of soy sauce on the basis of level of additives, raw materials and fermentation procedures. Copyright © 2016 Elsevier B.V. All rights reserved.

  7. Determination of the percentage of quitine desacetilation reaction by solid state carbon-13 NMR; Determinacao do porcentual de reacao de desacetilacao de quitina por RMN {sup 13} C no estado solido

    Energy Technology Data Exchange (ETDEWEB)

    Ferracin, Ricardo J. [Sao Carlos Univ., SP (Brazil). Centro de Caracterizacao e Desenvolvimento; Cass, Quezia B.; Bassi, Ana L. [Sao Carlos Univ., SP (Brazil). Lab. de Sintese Organica

    1997-12-31

    Quitine is a bi-polymer largely found in invertebrates. As most compounds of this class are insoluble in common organic solvents, the des-acetylation percentile was obtained by carbon-13 solid state nuclear magnetic resonance. The methodology is presented. Results are presented 3 refs., 1 figs.

  8. A 13C{31P} REDOR NMR Investigation of the Role of Glutamic Acid Residues in Statherin-Hydroxyapatite Recognition

    Science.gov (United States)

    Ndao, Moise; Ash, Jason T.; Breen, Nicholas F.; Goobes, Gil; Stayton, Patrick S.; Drobny, Gary P.

    2011-01-01

    The side chain carboxyl groups of acidic proteins found in the extra-cellular matrix (ECM) of mineralized tissues play a key role in promoting or inhibiting the growth of minerals such as hydroxyapatite (HAP), the principal mineral component of bone and teeth. Among the acidic proteins found in the saliva is statherin, a 43-residue tyrosine-rich peptide that is a potent lubricant in the salivary pellicle and an inhibitor of both HAP crystal nucleation and growth. Three acidic amino acids – D1, E4, and E5 – are located in the N-terminal 15 amino acid segment, with a fourth amino acid, E26, located outside the N-terminus. We have utilized 13C{31P} REDOR NMR to analyze the role played by acidic amino acids in the binding mechanism of statherin to the HAP surface by measuring the distance between the δ-carboxyl 13C spins of the three glutamic acid side chains of statherin (residues E4, E5, E26) and 31P spins of the phosphate groups at the HAP surface. 13C{31P} REDOR studies of glutamic-5-13C acid incorporated at positions E4 and E26 indicate a 13C–31P distance of more than 6.5 Å between the side chain carboxyl 13C spin of E4 and the closest 31P in the HAP surface. In contrast, the carboxyl 13C spin at E5 has a much shorter 13C–31P internuclear distance of 4.25±0.09 Å, indicating that the carboxyl group of this side chain interacts directly with the surface. 13C T1ρ and slow-spinning MAS studies indicate that the motions of the side chains of E4 and E5 are more restricted than that of E26. Together, these results provide further insight into the molecular interactions of statherin with HAP surfaces. PMID:19678690

  9. General method of preparation of uniformly 13C, 15N-labeled DNA fragments for NMR analysis of DNA structures

    International Nuclear Information System (INIS)

    Rene, Brigitte; Masliah, Gregoire; Zargarian, Loussine; Mauffret, Olivier; Fermandjian, Serge

    2006-01-01

    Summary 13 C, 15 N labeling of biomolecules allows easier assignments of NMR resonances and provides a larger number of NMR parameters, which greatly improves the quality of DNA structures. However, there is no general DNA-labeling procedure, like those employed for proteins and RNAs. Here, we describe a general and widely applicable approach designed for preparation of isotopically labeled DNA fragments that can be used for NMR studies. The procedure is based on the PCR amplification of oligonucleotides in the presence of labeled deoxynucleotides triphosphates. It allows great flexibility thanks to insertion of a short DNA sequence (linker) between two repeats of DNA sequence to study. Size and sequence of the linker are designed as to create restriction sites at the junctions with DNA of interest. DNA duplex with desired sequence and size is released upon enzymatic digestion of the PCR product. The suitability of the procedure is validated through the preparation of two biological relevant DNA fragments

  10. Experimental and DFT evaluation of the 1H and 13C NMR chemical shifts for calix[4]arenes

    Science.gov (United States)

    Guzzo, Rodrigo N.; Rezende, Michelle Jakeline Cunha; Kartnaller, Vinicius; Carneiro, José Walkimar de M.; Stoyanov, Stanislav R.; Costa, Leonardo Moreira da

    2018-04-01

    The density functional theory is employed to determine the efficiency of 11 exchange-correlation (XC) functionals to compute the 1H and 13C NMR chemical shifts of p-tert-butylcalix[4]arene (ptcx4, R1 = C(CH3)3) and congeners using the 6-31G(d,p) basis set. The statistical analysis shows that B3LYP, B3PW91 and PBE1PBE are the best XC functionals for the calculation of 1H chemical shifts. Moreover, the best results for the 13C chemical shifts are obtained using the LC-WPBE, M06-2X and wB97X-D functionals. The performance of these XC functionals is tested for three other calix[4]arenes: p-sulfonic acid calix[4]arene (sfxcx4 - R1 = SO3H), p-nitro-calix[4]arene (ncx4, R1 = NO2) and calix[4]arene (cx4 - R1 = H). For 1H chemical shifts B3LYP, B3PW91 and PBE1PBE yield similar results, although B3PW91 shows more consistency in the calculated error for the different structures. For 13C NMR chemical shifts, the XC functional that stood out as best is LC-WPBE. Indeed, the three functionals selected for each of 1H and 13C show good accuracy and can be used in future studies involving the prediction of 1H and 13C chemical shifts for this type of compounds.

  11. Sensitivity enhancement of 13C nuclei in 2D J-resolved NMR spectroscopy using a recycled-flow system

    International Nuclear Information System (INIS)

    Ha, S.T.K.; Lee, R.W.K.; Wilkins, C.L.

    1987-01-01

    Recycled-flow nuclear magnetic resonance for sensitivity enhancement in 1/2 spin nuclei has been reported previously, achieving several-fold signal enhancement. The success of the method depends upon premagnetization of nuclei prior to flowing into the detector region, obviating the need for delays following data acquisition to allow spin-lattice relaxation and reduce experiment time. The actual gains of sensitivity enhancement for 13 C- 1 H 2D J-resolved NMR using a recycled-flow method are evaluated. Possible enhancements for two types of J-resolved measurements, namely, one-bond 13 C- 1 H and long range J-resolved spectroscopy, are estimated using a simple Carr-Purcell spin-echo approach to quantify the 13 C signals. The pulse sequence is simply 90 0 -t /sub 1/2/-180 0 -t/sub 1/2/-AT-t/sub d/, where t/sub 1/2/ is half the evolution time, AT is the acquisition time, and t/sub d/ the experiment repetition time. In a static 2D NMR experiment, t/sub d/ usually must be the same order of the longest spin-lattice relaxation time (T 1 ) of nuclei. Quantitative measurements using a recycled-flow system indicate t/dub d/ can be reduced to a fraction of T 1 ; hence significant time savings can be achieved. Time-savings of between 2 and 25 can be anticipated for 2D spectroscopy under flow measurement conditions used in the present study. Other types of 2D NMR spectroscopy (autocorrelation and double quantum NMR) are discussed

  12. Characterizing crystal disorder of trospium chloride: a comprehensive,(13) C CP/MAS NMR, DSC, FTIR, and XRPD study.

    Science.gov (United States)

    Urbanova, Martina; Sturcova, Adriana; Brus, Jiri; Benes, Hynek; Skorepova, Eliska; Kratochvil, Bohumil; Cejka, Jan; Sedenkova, Ivana; Kobera, Libor; Policianova, Olivia; Sturc, Antonin

    2013-04-01

    Analysis of C cross-polarization magic angle spinning (CP/MAS) nuclear magnetic resonance (NMR), differential scanning calorimetry (DSC), Fourier transform infrared (FTIR), and X-ray powder diffraction data of trospium chloride (TCl) products crystallized from different mixtures of water-ethanol [φ(EtOH) = 0.5-1.0] at various temperatures (0°C, 20°C) and initial concentrations (saturated solution, 30%-50% excess of solvent) revealed extensive structural variability of TCl. Although (13) C CP/MAS NMR spectra indicated broad variety of structural phases arising from molecular disorder, temperature-modulated DSC identified presence of two distinct components in the products. FTIR spectra revealed alterations in the hydrogen bonding network (ionic hydrogen bond formation), whereas the X-ray diffraction reflected unchanged unit cell parameters. These results were explained by a two-component character of TCl products in which a dominant polymorphic form is accompanied by partly separated nanocrystalline domains of a secondary phase that does not provide clear Bragg reflections. These phases slightly differ in the degree of molecular disorder, in the quality of crystal lattice and hydrogen bonding network. It is also demonstrated that, for the quality control of such complex products, (13) C CP/MAS NMR spectroscopy combined with factor analysis (FA) can satisfactorily be used for categorizing the individual samples: FA of (13) C CP/MAS NMR spectra found clear relationships between the extent of molecular disorder and crystallization conditions. © 2013 Wiley Periodicals, Inc. and the American Pharmacists Association J Pharm Sci 102:1235-1248, 2013. Copyright © 2013 Wiley Periodicals, Inc.

  13. In vivo NMR analysis of incorporation of [2-13C] glycine into silk fibroin

    International Nuclear Information System (INIS)

    Asakura, Tetsuo; Nagashima, Mariko; Demura, Makoto; Osanai, Minoru.

    1990-01-01

    The biosynthetic mechanism of silk fibroin in silkworms, Bombyx mori, is unique because this fibrous protein composed mainly of glycine, alanine and serine is produced very rapidly in large quantity in the posterior silk glands. It is very meaningful to investigate into the biosynthesis of silk protein under nondestructive condition by in vivo NMR and C-13 labeling techniques. The sugar metabolism related to the production of silk fibroin was analyzed by monitoring the change in the C-13 labeled peaks in the NMR spectra for silkworms. In this paper, the monitoring of the 2-(C-13) glycine metabolism in Bombyx mori by the C-13 NMR in vivo is reported. In particular, the in vivo transport of glycine from the midgut to the posterior silk gland was measured, and the rate constants were determined with the course of the peak intensity in the C-13 NMR spectra. It is possible to discuss quantitatively the in vivo production of silk fibroin with these rate constants. The experiment and the results are reported. The in vivo C-13 NMR spectra of a 5 day old, 5th instar larva of Bombyx mori after the oral administration of 2-(C-13) glycine are shown. The significant increase of the peak intensity occurred. (K.I.)

  14. Experimental (FT-IR, FT-Raman, 1H, 13C NMR) and theoretical study of alkali metal 2-aminobenzoates

    Science.gov (United States)

    Samsonowicz, M.; Świsłocka, R.; Regulska, E.; Lewandowski, W.

    2008-09-01

    The influence of lithium, sodium, potassium, rubidium and cesium on the electronic system of the 2-aminobenzoic acid was studied by the methods of molecular spectroscopy. The vibrational (FT-IR, FT-Raman) and NMR ( 1H and 13C) spectra for 2-aminobenzoic acid and its alkali metal salts were recorded. The assignment of vibrational spectra was done on the basis of literature data, theoretical calculations and our previous experience. Characteristic shifts of bands and changes in intensities of bands along the metal series were observed. The changes of chemical shifts of protons ( 1H NMR) and carbons ( 13C NMR) in the series of studied alkali metal 2-aminobenzoates were observed too. Optimized geometrical structures of studied compounds were calculated by B3LYP method using 6-311++G ∗∗ basis set. Geometric aromaticity indices, dipole moments and energies were also calculated. The theoretical wavenumbers and intensities of IR and Raman spectra were obtained. The calculated parameters were compared to experimental characteristic of studied compounds.

  15. Characterization of threonine side chain dynamics in an antifreeze protein using natural abundance {sup 13}C NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Daley, Margaret E.; Sykes, Brian D. [University of Alberta, Department of Biochemistry, CIHR Group in Protein Structure and Function and Protein Engineering Network of Centres of Excellence (Canada)

    2004-06-15

    The dynamics of threonine side chains of the Tenebrio molitor antifreeze protein (TmAFP) were investigated using natural abundance {sup 13}C NMR. In TmAFP, the array of threonine residues on one face of the protein is responsible for conferring its ability to bind crystalline ice and inhibit its growth. Heteronuclear longitudinal and transverse relaxation rates and the {sup 1}H-{sup 13}C NOE were determined in this study. The C{alpha}H relaxation measurements were compared to the previously measured {sup 15}N backbone parameters and these are found to be in agreement. For the analysis of the threonine side chain motions, the model of restricted rotational diffusion about the {chi}{sub 1} dihedral angle was employed [London and Avitabile (1978) J. Am. Chem. Soc., 100, 7159-7165]. We demonstrate that the motion experienced by the ice binding threonine side chains is highly restricted, with an approximate upper limit of less than {+-}25 deg.

  16. Characterization of threonine side chain dynamics in an antifreeze protein using natural abundance 13C NMR spectroscopy

    International Nuclear Information System (INIS)

    Daley, Margaret E.; Sykes, Brian D.

    2004-01-01

    The dynamics of threonine side chains of the Tenebrio molitor antifreeze protein (TmAFP) were investigated using natural abundance 13 C NMR. In TmAFP, the array of threonine residues on one face of the protein is responsible for conferring its ability to bind crystalline ice and inhibit its growth. Heteronuclear longitudinal and transverse relaxation rates and the 1 H- 13 C NOE were determined in this study. The CαH relaxation measurements were compared to the previously measured 15 N backbone parameters and these are found to be in agreement. For the analysis of the threonine side chain motions, the model of restricted rotational diffusion about the χ 1 dihedral angle was employed [London and Avitabile (1978) J. Am. Chem. Soc., 100, 7159-7165]. We demonstrate that the motion experienced by the ice binding threonine side chains is highly restricted, with an approximate upper limit of less than ±25 deg

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

    Energy Technology Data Exchange (ETDEWEB)

    LeMaster, D.M. [Northwestern Univ., Evanston, IL (United States)

    1994-12-01

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

  18. 1H and 13C NMR spectral assignments of four dammarane triterpenoids from carnauba wax.

    Science.gov (United States)

    Cysne, Juliana de Brito; Braz-Filho, Raimundo; Assunção, Marcus Vinícius; Uchoa, Daniel E de Andrade; Silveira, Edilberto R; Pessoa, Otília Deusdênia L

    2006-06-01

    The phytochemical investigation of carnauba wax led to the isolation of three new dammarane triterpenoids 1, 2 and 4, together with the known triterpene 3. The structures of the new compounds were determined by 1D and 2D NMR spectroscopy and by comparison with published data for closely related compounds. 2006 John Wiley & Sons, Ltd.

  19. Chemotaxonomy of three genera of the Annonaceae family using self-organizing maps and 13C NMR data of diterpenes

    International Nuclear Information System (INIS)

    Scotti, Luciana; Tavares, Josean Fechine; Silva, Marcelo Sobral da; Falcao, Emanuela Viana; Silva, Luana de Morais e; Soares, Gabriela Cristina da Silva; Scotti, Marcus Tullius

    2012-01-01

    The Annonaceae family is distributed throughout Neotropical regions of the world. In Brazil, it covers nearly all natural formations particularly Annona, Xylopia and Polyalthia and is characterized chemically by the production of sources of terpenoids (mainly diterpenes), alkaloids, steroids, polyphenols and, flavonoids. Studies from 13 C NMR data of diterpenes related with their botanical occurrence were used to generate self-organizing maps. Results corroborate those in the literature obtained from morphological and molecular data for three genera and the model can be used to project other diterpenes. Therefore, the model produced can predict which genera are likely to contain a compound. (author)

  20. Acid-base equilibrium in aqueous solutions of 1,3-dimethylbarbituric acid as studied by 13C NMR spectroscopy

    Science.gov (United States)

    Gryff-Keller, A.; Kraska-Dziadecka, A.

    2011-12-01

    13C NMR spectra of 1,3-dimethylbarbituric acid in aqueous solutions of various acidities and for various solute concentrations have been recorded and interpreted. The spectra recorded at pH = 2 and below contain the signals of the neutral solute molecule exclusively, while the ones recorded at pH = 7 and above only the signals of the appropriate anion, which has been confirmed by theoretical GIAO-DFT calculations. The signals in the spectra recorded for solutions of pH pH variation have been observed for the parent barbituric acid.

  1. Identification and quantitative determination of carbohydrates in ethanolic extracts of two conifers using 13C NMR spectroscopy.

    Science.gov (United States)

    Duquesnoy, Emilie; Castola, Vincent; Casanova, Joseph

    2008-04-07

    We developed a method for the direct identification and quantification of carbohydrates in raw vegetable extracts using (13)C NMR spectroscopy without any preliminary step of precipitation or reduction of the components. This method has been validated (accuracy, precision and response linearity) using pure compounds and artificial mixtures before being applied to authentic ethanolic extracts of pine needles, pine wood and pine cones and fir twigs. We determined that carbohydrates represented from 15% to 35% of the crude extracts in which pinitol was the principal constituent accompanied by arabinitol, mannitol, glucose and fructose.

  2. Applications of artificial intelligence techniques to organic chemistry. Study on 13C NMR of steroids using computer

    International Nuclear Information System (INIS)

    Lins, A.P.; Furlan, M.; Gastmans, G.P.; Emerenciano, V.P.

    1991-01-01

    This work describes the utilization of two groups of programs in searching for characteristic signals of NMR 13 C steroidal compounds. The first group of programs used data bases with the spectral data and a methodology that enables the choice and the search of substructures. The chemical shifts and multiplicities for each specific substructure are used as rules to identify different types and subtypes of steroidal compounds. The second one was built to apply the rules formulated by the first group of programs and to foresee any skeletal based on a spectral analysis. (author)

  3. Structural characteristics of marine sedimentary humic acids by CP/MAS sup(13)C NMR spectroscopy

    Digital Repository Service at National Institute of Oceanography (India)

    Sardessai, S.; Wahidullah, S.

    quino- nes or semiquinones which exhibit 13C resonance at around 195 ppm. Free radicals of semiquinone type have been reported from the aquatic environment [2]. Spectra of all the four samples show absorption at 195 ppm. The total acidity of marine..., significant resonance at 55 ppm (8.9) from aromatic methoxy carbon suggests that phenol is present mostly as methyl ether and not as free phenol. The signal at 55 ppm is also attributed to aliphatic carbon adjacent to the amino functional group as in amino...

  4. Measurement of soil carbon oxidation state and oxidative ratio by 13C nuclear magnetic resonance

    Science.gov (United States)

    Hockaday, W.C.; Masiello, C.A.; Randerson, J.T.; Smernik, R.J.; Baldock, J.A.; Chadwick, O.A.; Harden, J.W.

    2009-01-01

    The oxidative ratio (OR) of the net ecosystem carbon balance is the ratio of net O2 and CO2 fluxes resulting from photosynthesis, respiration, decomposition, and other lateral and vertical carbon flows. The OR of the terrestrial biosphere must be well characterized to accurately estimate the terrestrial CO2 sink using atmospheric measurements of changing O2 and CO2 levels. To estimate the OR of the terrestrial biosphere, measurements are needed of changes in the OR of aboveground and belowground carbon pools associated with decadal timescale disturbances (e.g., land use change and fire). The OR of aboveground pools can be measured using conventional approaches including elemental analysis. However, measuring the OR of soil carbon pools is technically challenging, and few soil OR data are available. In this paper we test three solid-state nuclear magnetic resonance (NMR) techniques for measuring soil OR, all based on measurements of the closely related parameter, organic carbon oxidation state (Cox). Two of the three techniques make use of a molecular mixing model which converts NMR spectra into concentrations of a standard suite of biological molecules of known C ox. The third technique assigns Cox values to each peak in the NMR spectrum. We assess error associated with each technique using pure chemical compounds and plant biomass standards whose Cox and OR values can be directly measured by elemental analyses. The most accurate technique, direct polarization solid-state 13C NMR with the molecular mixing model, agrees with elemental analyses to ??0.036 Cox units (??0.009 OR units). Using this technique, we show a large natural variability in soil Cox and OR values. Soil Cox values have a mean of -0.26 and a range from -0.45 to 0.30, corresponding to OR values of 1.08 ?? 0.06 and a range from 0.96 to 1.22. We also estimate the OR of the carbon flux from a boreal forest fire. Analysis of soils from nearby intact soil profiles imply that soil carbon losses associated

  5. Analysis of neuron–astrocyte metabolic cooperation in the brain of db/db mice with cognitive decline using 13C NMR spectroscopy

    OpenAIRE

    Zheng, Hong; Zheng, Yongquan; Wang, Dan; Cai, Aimin; Lin, Qiuting; Zhao, Liangcai; Chen, Minjiang; Deng, Mingjie; Ye, Xinjian; Gao, Hongchang

    2016-01-01

    Type 2 diabetes has been linked to cognitive impairment, but its potential metabolic mechanism is still unclear. The present study aimed to explore neuron–astrocyte metabolic cooperation in the brain of diabetic (db/db, BKS.Cg-m+/+ Leprdb/J) mice with cognitive decline using 13C NMR technique in combination with intravenous [2-13C]-acetate and [3-13C]-lactate infusions. We found that the 13C-enrichment from [2-13C]-acetate into tricarboxylic acid cycle intermediate, succinate, was significant...

  6. 13C CP MAS NMR and GIAO-CHF/DFT calculations of flavonoids: Morin, kaempferol, tricin, genistein, formononetin and 3,7-dihydroxyflavone

    Science.gov (United States)

    Zielińska, Agnieszka; Paradowska, Katarzyna; Jakowski, Jacek; Wawer, Iwona

    2008-02-01

    13C CP MAS NMR spectra of the flavonoids: morin, kaempferol, 3,7-dihydroxyflavone, tricin and isoflavones: genistein and formononetin were recorded to characterize solid-state conformations. Intramolecular hydrogen bonds forming five-, six- and seven-membered rings are present in the two morin molecules in the crystals - their 13C resonances have been assigned with the aid of the calculated shielding constants. Linear relationships between the calculated shielding constants σDFT (ppm) and chemical shifts ( δCPMAS, ppm) were obtained for all studied compounds. Higher correlation coefficients suggest that the conformation with "clockwise" orientation of both OH groups is more probable in the solid 3,7-dihydroxyflavone, whereas in the solid formononetin the OH and OCH 3 substituents are directed "anticlockwise". The barrier to the rotation of phenyl ring B decreases in the order: morin (2'-OH, 3-OH) > kaempferol (3-OH) > tricin.

  7. {sup 13}C-Methyl isocyanide as an NMR probe for cytochrome P450 active sites

    Energy Technology Data Exchange (ETDEWEB)

    McCullough, Christopher R.; Pullela, Phani Kumar [Marquette University, Chemical Proteomics Facility at Marquette, Department of Chemistry (United States); Im, Sang-Choul; Waskell, Lucy [University of Michigan and VA Medical Center, Department of Anesthesiology (United States); Sem, Daniel S. [Marquette University, Chemical Proteomics Facility at Marquette, Department of Chemistry (United States)], E-mail: Daniel.sem@marquette.edu

    2009-03-15

    The cytochromes P450 (CYPs) play a central role in many biologically important oxidation reactions, including the metabolism of drugs and other xenobiotic compounds. Because they are often assayed as both drug targets and anti-targets, any tools that provide: (a) confirmation of active site binding and (b) structural data, would be of great utility, especially if data could be obtained in reasonably high throughput. To this end, we have developed an analog of the promiscuous heme ligand, cyanide, with a {sup 13}CH{sub 3}-reporter attached. This {sup 13}C-methyl isocyanide ligand binds to bacterial (P450cam) and membrane-bound mammalian (CYP2B4) CYPs. It can be used in a rapid 1D experiment to identify binders, and provides a qualitative measure of structural changes in the active site.

  8. Use of proton-enhanced, natural abundance /sup 13/C NMR to study the molecular dynamics of model and biological membranes

    Energy Technology Data Exchange (ETDEWEB)

    Cornell, B A [Commonwealth Scientific and Industrial Research Organization, North Ryde (Australia). Div. of Food Research; Keniry, M [Sydney Univ. (Australia). Dept. of Physical Chemistry; Hiller, R G [Macquarie Univ., North Ryde (Australia). School of Biological Sciences; Smith, R [La Trobe Univ., Bundoora (Australia). Dept. of Biochemistry

    1980-06-16

    Proton-enhanced NMR of the natural abundance /sup 13/C nuclei is used to study the lipid mobility in dispersions containing cholesterol, the polypeptide gramicidin A, and in membrane proparations derived from spinach chloroplasts and bovine brain myelin.

  9. Two flavonoids from Iboza riparia and the unambiguous assignments of the 1H and 13C NMR signals of their methoxyle groups

    International Nuclear Information System (INIS)

    Haider, A.; Matida, A.; Zelnik, R.

    1988-01-01

    Two rare flavonoids, salvigenin and cirsimaritin, were isolated from the leaves of Iboza riparia. The 1 H and 13 C NMR spectra as well as non-quaternary carbon signals shift are analysed. (M.J.C.) [pt

  10. NMR study of conjugation effects. 15. /sup 13/C-/sup 13/C spin-spin coupling constants in phenylalkyl ether

    Energy Technology Data Exchange (ETDEWEB)

    Kalabin, G.A. (Siberian Branch of the Academy of Sciences of the USSR); Krivdin, L.B.; Trofimov, B.A.

    1982-07-20

    In order to elucidate the /sup 13/C-/sup 13/-C SSCC (spin-spin coupling constants) segment with the electronic excitations induced by the R group, a series of phenyl alkyl ethers, PhOAlk, where Alk = Me(I), Et(II), i-Pr(III), and t-Bu(IV), were studied. This series was chosen because in studying the /sup 13/C CS in monosubstituted benzenes it was observed that the intensity of the ..pi..-electron interaction of the unshared electron pairs of oxygen with the ..pi.. system of the benzene ring was practically the same in some compounds, but increased by 30% in others. This is related to the fact that the latter is characterized by an average noncoplanar conformation, with a dihedral angle between the benzene-ring plane and the C-O-C bond of approx. 45/sup 0/, whereas some compounds have an angle < 20/sup 0/. The reason for the difference is significant steric interaction of the alkyl hydrogens with the o-position of the ring. Thus, consideration of the /sup 13/C-/sup 13/C SSCC of a series of quite similar compounds, especially when compared to the whole set of such SSCC for other monosubstituted benzenes, shows that their relationship to the structure of the substituent R is extremely complex.

  11. Evolution of organic matter during composting of different organic wastes assessed by CPMAS 13C NMR spectroscopy

    International Nuclear Information System (INIS)

    Caricasole, P.; Provenzano, M.R.; Hatcher, P.G.; Senesi, N.

    2011-01-01

    In this paper, the evolution of organic matter (OM) during composting of different mixtures of various organic wastes was assessed by means of chemical analyses and CPMAS 13 C NMR spectroscopy measured during composting. The trends of temperatures and C/N ratios supported the correct evolution of the processes. The CPMAS 13 C NMR spectra of all composting substrates indicated a reduction in carbohydrates and an increase in aromatic, phenolic, carboxylic and carbonylic C which suggested a preference by microorganisms for easily degradable C molecules. The presence of hardly degradable pine needles in one of the substrates accounted for the lowest increase in alkyl C and the lowest reduction in carbohydrates and carboxyl C as opposite to another substrate characterized by the presence of a highly degradable material such as spent yeast from beer production, which showed the highest increase of the alkyl C/O-alkyl C ratio. The highest increase of COOH deriving by the oxidative degradation of cellulose was shown by a substrate composed by about 50% of plant residues. The smallest increases in alkyl C/O-alkyl C ratio and in polysaccharides were associated to the degradation of proteins and lipids which are major components of sewage sludge. Results obtained were related to the different composition of fresh organic substrates and provided evidence of different OM evolution patterns as a function of the initial substrate composition.

  12. A 13C-NMR study of mutant hemoglobins with altered oxygen affinity

    International Nuclear Information System (INIS)

    Smith, M.L.; Norden, B.; Edlund, U.; Paul, K.-G.

    1986-01-01

    The 13 CO-NMR spectra of carbonylhemoglobins Saint Mande (β 102Asn → Tyr), Malmo (β 97His → Gln), Hotel Dieu (β 99Asp → Gly) and A o have been determined. The positions of the 13 CO resonances for hemoglobins A o , Malmo and Hotel Dieu were similar indicating similar ligand environments for all. The 13 CO resonance for the β-subunit of Saint Mande was upfield-shifted compared to the others. This is evidence that structural changes at the β102 position directly affect iron-ligand bonding as well as quaternary structure. (Auth.)

  13. 1H and 13C NMR assignments for two new cordiaquinones from roots of Cordia leucocephala.

    Science.gov (United States)

    Diniz, Jaécio Carlos; Viana, Francisco Arnaldo; Oliveira, Odaci Fernandes; Maciel, Maria Aparecida M; Torres, Maria da Conceição de Menezes; Braz-Filho, Raimundo; Silveira, Edilberto R; Pessoa, Otília Deusdênia L

    2009-02-01

    From the roots of Cordia leucocephala (Boraginaceae), two new meroterpenoid naphthoquinones, 6-[10-(12,12-dimethyl-13alpha-hydroxy-16-methenyl-cyclohexyl)ethyl]-1,4-naphthalenedione (cordiaquinone L) and 5-methyl-6-[10-(12,12-dimethyl-13beta-hydroxy-16-methenyl-cyclohexyl)methyl-1,4-naphthalenedione (cordiaquinone M) were isolated. Their structures were elucidated after detailed 1D and 2D NMR (COSY, HSQC, HMBC and NOESY) data analyses and comparison with literature data for analogous compounds. 2008 John Wiley & Sons, Ltd.

  14. Methodology for the identification of tri-terpenes mixtures components by {sup 13} C NMR; Metodologia para identificao dos componentes de misturas de triterpenos por RMN de {sup 13} C

    Energy Technology Data Exchange (ETDEWEB)

    Olea, Roberto S.G.

    1991-12-31

    This work describes a methodology for the identification of tri terpenes complex mixtures by {sup 13} C NMR. The use of {sup 13} C NMR techniques, such as obtention of noise decoupled spectra, DEPT 135 and DEPT 90 sequences, allowed the identification of components of triterpene mixtures with identical functionality through comparison of observed {sup 13} C NMR chemical shifts with {sup 13} C NMR chemical shifts reported in the literature. The method proved to be specially helpful in the identification of triterpenes by analysis of chemical shifts assignable to doubly bonded carbons, since the particular position of such double bonds is characteristic of some triterpene skeletons. Application of this methodology indicated the presence of bauerenol, {alpha}-amyrin and {beta}-amyrin in Acmanthera latifolis Griseb. (Malpighiaceae); of germanicone, lupenone, {alpha}-amyrenone and {beta}-amyrenone in Alibertia macrophylla A. Rich. (Rubiaceae); of {alpha}-amyrin acetate, lupeol acetate and {beta}-amyrin acetate in Vernonia polyanthes Schreb. (Asteraceae); {alpha}-amyrenone, {beta}-amyrenone, boehmerone, friedelin, lupenone, {alpha}-amyrin, {beta}-amyrin and glutinol in Scoparia dulcis L. (Scrophulariaceae). (author). 37 refs., 93 figs.

  15. Methodology for the identification of tri-terpenes mixtures components by {sup 13} C NMR; Metodologia para identificao dos componentes de misturas de triterpenos por RMN de {sup 13} C

    Energy Technology Data Exchange (ETDEWEB)

    Olea, Roberto S.G.

    1990-12-31

    This work describes a methodology for the identification of tri terpenes complex mixtures by {sup 13} C NMR. The use of {sup 13} C NMR techniques, such as obtention of noise decoupled spectra, DEPT 135 and DEPT 90 sequences, allowed the identification of components of triterpene mixtures with identical functionality through comparison of observed {sup 13} C NMR chemical shifts with {sup 13} C NMR chemical shifts reported in the literature. The method proved to be specially helpful in the identification of triterpenes by analysis of chemical shifts assignable to doubly bonded carbons, since the particular position of such double bonds is characteristic of some triterpene skeletons. Application of this methodology indicated the presence of bauerenol, {alpha}-amyrin and {beta}-amyrin in Acmanthera latifolis Griseb. (Malpighiaceae); of germanicone, lupenone, {alpha}-amyrenone and {beta}-amyrenone in Alibertia macrophylla A. Rich. (Rubiaceae); of {alpha}-amyrin acetate, lupeol acetate and {beta}-amyrin acetate in Vernonia polyanthes Schreb. (Asteraceae); {alpha}-amyrenone, {beta}-amyrenone, boehmerone, friedelin, lupenone, {alpha}-amyrin, {beta}-amyrin and glutinol in Scoparia dulcis L. (Scrophulariaceae). (author). 37 refs., 93 figs.

  16. ({sup 1} H, {sup 13} C and {sup 31} P) NMR of phosphonic acid derivatives; Ressonancia magnetica nuclear ({sup 1} H, {sup 13} C, {sup 31} P) de derivados do acido fosfonico

    Energy Technology Data Exchange (ETDEWEB)

    Campos, Valdevino; Costa, Valentim E. Uberti [Rio Grande do Sul Univ., Porto Alegre, RS (Brazil). Inst. de Quimica

    1992-12-31

    In the last years the development of phosphates analogues in the medical and agricultural pesticides has being very expressive. {sup 1} H, {sup 13} C and mainly {sup 31} P NMR are used for stereochemical and conformational analysis, and reactivity studies on the compounds resulting from those chemical processes 2 refs., 4 figs., 1 tab.

  17. Intermolecular Interactions in Crystalline Theobromine as Reflected in Electron Deformation Density and (13)C NMR Chemical Shift Tensors.

    Science.gov (United States)

    Bouzková, Kateřina; Babinský, Martin; Novosadová, Lucie; Marek, Radek

    2013-06-11

    An understanding of the role of intermolecular interactions in crystal formation is essential to control the generation of diverse crystalline forms which is an important concern for pharmaceutical industry. Very recently, we reported a new approach to interpret the relationships between intermolecular hydrogen bonding, redistribution of electron density in the system, and NMR chemical shifts (Babinský et al. J. Phys. Chem. A, 2013, 117, 497). Here, we employ this approach to characterize a full set of crystal interactions in a sample of anhydrous theobromine as reflected in (13)C NMR chemical shift tensors (CSTs). The important intermolecular contacts are identified by comparing the DFT-calculated NMR CSTs for an isolated theobromine molecule and for clusters composed of several molecules as selected from the available X-ray diffraction data. Furthermore, electron deformation density (EDD) and shielding deformation density (SDD) in the proximity of the nuclei involved in the proposed interactions are calculated and visualized. In addition to the recently reported observations for hydrogen bonding, we focus here particularly on the stacking interactions. Although the principal relations between the EDD and CST for hydrogen bonding (HB) and stacking interactions are similar, the real-space consequences are rather different. Whereas the C-H···X hydrogen bonding influences predominantly and significantly the in-plane principal component of the (13)C CST perpendicular to the HB path and the C═O···H hydrogen bonding modulates both in-plane components of the carbonyl (13)C CST, the stacking modulates the out-of-plane electron density resulting in weak deshielding (2-8 ppm) of both in-plane principal components of the CST and weak shielding (∼ 5 ppm) of the out-of-plane component. The hydrogen-bonding and stacking interactions may add to or subtract from one another to produce total values observed experimentally. On the example of theobromine, we demonstrate

  18. Characterization and Comparison of Fast Pyrolysis Bio-oils from Pinewood, Rapeseed Cake, and Wheat Straw Using 13C NMR and Comprehensive GC × GC

    NARCIS (Netherlands)

    Negahdar, Leila; Gonzalez-Quiroga, Arturo; Otyuskaya, Daria; Toraman, Hilal E.; Liu, Li; Jastrzebski, Johann T B H; Van Geem, Kevin M.; Marin, Guy B.; Thybaut, Joris W.; Weckhuysen, Bert M.

    2016-01-01

    Fast pyrolysis bio-oils are feasible energy carriers and a potential source of chemicals. Detailed characterization of bio-oils is essential to further develop its potential use. In this study, quantitative 13C nuclear magnetic resonance (13C NMR) combined with comprehensive two-dimensional gas

  19. Positional enrichment by proton analysis (PEPA). A one-dimensional "1H-NMR approach for "1"3C stable isotope tracer studies in metabolomics

    International Nuclear Information System (INIS)

    Vinaixa, Maria; Yanes, Oscar; Rodriguez, Miguel A.; Capellades, Jordi; Aivio, Suvi; Stracker, Travis H.; Gomez, Josep; Canyellas, Nicolau

    2017-01-01

    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 "1"3C-satellite peaks using 1D-"1H-NMR spectra. In comparison with "1"3C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of "1"3C 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 "1H-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. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  20. Positional enrichment by proton analysis (PEPA). A one-dimensional {sup 1}H-NMR approach for {sup 13}C stable isotope tracer studies in metabolomics

    Energy Technology Data Exchange (ETDEWEB)

    Vinaixa, Maria; Yanes, Oscar [Department of Electronic Engineering-Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Rodriguez, Miguel A.; Capellades, Jordi [Universitat Rovira i Virgili, Spanish Biomedical Research Center in Diabetes and Associated Metabolic Disorders (CIBERDEM), Reus (Spain); Aivio, Suvi; Stracker, Travis H. [Institute for Research in Biomedicine (IRB Barcelona), Barcelona Institute of Science and Technology (Spain); Gomez, Josep; Canyellas, Nicolau [Department of Electronic Engineering-, Universitat Rovira i Virgili, Tarragona (Spain)

    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 {sup 13}C-satellite peaks using 1D-{sup 1}H-NMR spectra. In comparison with {sup 13}C-NMR, TOCSY and HSQC, PEPA improves sensitivity, accelerates the elucidation of {sup 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 {sup 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. (copyright 2017 The Authors. Published by Wiley-VCH Verlag GmbH and Co. KGaA.)

  1. Skeletal and chlorine effects on 13C-NMR chemical shifts of chlorinated polycyclic systems

    Directory of Open Access Journals (Sweden)

    Costa V.E.U.

    1999-01-01

    Full Text Available In order to establish a comparative analysis of chemical shifts caused by ring compression effects or by the presence of a chlorine atom on strained chlorinated carbons, a series of the chlorinated and dechlorinated polycyclic structures derived from "aldrin" (5 and "isodrin" (14 was studied. Compounds were classified in four different groups, according to their conformation and number of ring such as: endo-exo and endo-endo tetracyclics, pentacyclics and hexacyclics. The 13C chemical shift comparison between the chlorinated and dechlorinated compounds showed that when C-9 and C-10 are olefinic carbons, it occurs a shielding of 0.5-2.4 ppm for endo-endo tetracyclics and of 4.7-7.6 ppm for endo-exo tetracyclic. The chemical shift variation for C-11 reaches 49-53 ppm for endo-exo and endo-endo tetracyclics, 54 ppm for pentacyclic and 56-59 ppm for hexacyclic compounds. From these data, it was possible to observe the influence of ring compression on the chemical shifts.

  2. Plant Resources, 13C-NMR Spectral Characteristic and Pharmacological Activities of Dammarane-Type Triterpenoids

    Directory of Open Access Journals (Sweden)

    Jingya Ruan

    2016-08-01

    Full Text Available Dammarane-type triterpenoids (DTT widely distribute in various medicinal plants. They have generated a great amount of interest in the field of new drug research and development. Generally, DTT are the main bioactive ingredients abundant in Araliaceae plants, such as Panax ginseng, P. japonicas, P. notoginseng, and P. quinquefolium. Aside from Araliaceae, DTT also distribute in other families, including Betulaceae, Cucurbitaceae, Meliaceae, Rhamnaceae, and Scrophulariaceae. Until now, about 136 species belonging to 46 families have been reported to contain DTT. In this article, the genus classifications of plant sources of the botanicals that contain DTT are reviewed, with particular focus on the NMR spectral features and pharmacological activities based on literature reports, which may be benefit for the development of new drugs or food additives.

  3. Structural characterization of heat treated pitch by solid state /sup 13/C nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Sfihi, H.; Tougne, P.; Legrand, A.P.; Couderc, P.; Saint-Romain, J.L.

    1988-12-01

    The objective of this paper is to determine structural parameters (aromaticity factor, fractions of protonated and non-protonated aromatic carbons) of some pitches, and to follow their evolution as a function of the heat treatment duration. For such a determination, /sup 13/C-/sup 1/H cross polarization combined with magic angle spinning and dipolar dephasing (CP/MAS/DD) NMR was used. 15 refs., 4 figs., 1 tab.

  4. Complexation of rhodium(II) tetracarboxylates with aliphatic diamines in solution: 1H and 13C NMR and DFT investigations.

    Science.gov (United States)

    Jaźwiński, Jarosław; Sadlej, Agnieszka

    2013-10-01

    The complexation of rhodium(II) tetraacetate, tetrakistrifluoroaceate and tetrakisoctanoate with a set of diamines (ethane-1,diamine, propane-1,3-diamine and nonane-1,9-diamine) and their N,N'-dimethyl and N,N,N',N'-tetramethyl derivatives in chloroform solution has been investigated by (1) H and (13) C NMR spectroscopy and density functional theory (DFT) modelling. A combination of two bifunctional reagents, diamines and rhodium(II) tetracarboxylates, yielded insoluble coordination polymers as main products of complexation and various adducts in the solution, being in equilibrium with insoluble material. All diamines initially formed the 2 : 1 (blue), (1 : 1)n oligomeric (red) and 1 : 2 (red) axial adducts in solution, depending on the reagents' molar ratio. Adducts of primary and secondary diamines decomposed in the presence of ligand excess, the former via unstable equatorial complexes. The complexation of secondary diamines slowed down the inversion at nitrogen atoms in NH(CH3 ) functional groups and resulted in the formation of nitrogenous stereogenic centres, detectable by NMR. Axial adducts of tertiary diamines appeared to be relatively stable. The presence of long aliphatic chains in molecules (adducts of nonane-1,9-diamines or rhodium(II) tetrakisoctanoate) increased adduct solubility. Hypothetical structures of the equatorial adduct of rhodium(II) tetraacetate with ethane-1,2-diamine and their NMR parameters were explored by means of DFT calculations. Copyright © 2013 John Wiley & Sons, Ltd.

  5. Polysaccharides of algae. Pt. 37. Characterization of hybrid structure of substituted agarose from Polysiphonia morrowii (Rhodophyta, Rhodomelaceae) using. beta. -agarase and /sup 13/C-NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Usov, A.I.; Ivanova, E.G.

    1987-09-01

    Structure of gel-forming galactan from Polysiphonia morrowii was analysed using bacterial ..beta..-agarase and /sup 13/C-nuclear magnetic resonance (/sup 13/C-NMR) spectroscopy. The polysaccharide was shown to contain: a) blocks composed of agarobiose residues, partly 6-O-methylated and 6-sulfated, which are sensitive to enzymolysis; b) extended blocks composed of agarobiose 6-sulfate residues, which are resistant to ..beta..-agarase action. The latter blocks contain also ..beta..-D-galactopyranosyl-(1->4)-..cap alpha..-L-galactopyranose 6.6'-disulfate residues (biogenetic precursors of agarobiose 6-sulfate), which are hardly detectable by /sup 13/C-NMR spectrum of the starting polysaccharide. Action of alkali on the enzyme-resistant fraction afforded a polysaccharide preparation having /sup 13/C-NMR spectrum of agarose 6-sulfate.

  6. Application of unsymmetrical indirect covariance NMR methods to the computation of the (13)C (15)N HSQC-IMPEACH and (13)C (15)N HMBC-IMPEACH correlation spectra.

    Science.gov (United States)

    Martin, Gary E; Hilton, Bruce D; Irish, Patrick A; Blinov, Kirill A; Williams, Antony J

    2007-10-01

    Utilization of long-range (1)H--(15)N heteronuclear chemical shift correlation has continually grown in importance since the first applications were reported in 1995. More recently, indirect covariance NMR methods have been introduced followed by the development of unsymmetrical indirect covariance processing methods. The latter technique has been shown to allow the calculation of hyphenated 2D NMR data matrices from more readily acquired nonhyphenated 2D NMR spectra. We recently reported the use of unsymmetrical indirect covariance processing to combine (1)H--(13)C GHSQC and (1)H--(15)N GHMBC long-range spectra to yield a (13)C--(15)N HSQC-HMBC chemical shift correlation spectrum that could not be acquired in a reasonable period of time without resorting to (15)N-labeled molecules. We now report the unsymmetrical indirect covariance processing of (1)H--(13)C GHMBC and (1)H--(15)N IMPEACH spectra to afford a (13)C--(15)N HMBC-IMPEACH spectrum that has the potential to span as many as six to eight bonds. Correlations for carbon resonances long-range coupled to a protonated carbon in the (1)H--(13)C HMBC spectrum are transferred via the long-range (1)H--(15)N coupling pathway in the (1)H--(15)N IMPEACH spectrum to afford a much broader range of correlation possibilities in the (13)C--(15)N HMBC-IMPEACH correlation spectrum. The indole alkaloid vincamine is used as a model compound to illustrate the application of the method. (c) 2007 John Wiley & Sons, Ltd.

  7. 13C n.m.r. study of solvation mechanisms in the radiation-induced polymerization of vinyl ethers

    International Nuclear Information System (INIS)

    Deffieux, A.; Subira, F.; Stannett, V.T.

    1984-01-01

    A 13 C n.m.r. study of the microstructure of ethyl vinyl ether (EVE) and isopropyl vinyl ether (IPVE) polymers prepared under various experimental conditions and using chemical or γ-ray initiation has been made. Long stereo-sequence assignments were conducted for poly EVE allowing determination of the configurational statistics of propagation in the radiation-induced polymerization of EVE in low polar solvents. Stereo-sequence intensities are found in good agreement with the Markovian model. The results are considered as further support for the occurrence of a specific interaction between the growing active centres and the polymer chains. In the case of IPVE polymers much more important overlappings of the resonance patterns are observed thus preventing any similar detailed study. (author)

  8. Fatty acid synthesis in Xylella fastidiosa: correlations between genome studies, 13C NMR data, and molecular models

    International Nuclear Information System (INIS)

    Osiro, Denise; Muniz, Joao Renato C.; Coleta Filho, Helvecio Della; Alves de Sousa, Alessandra; Machado, Marcos Antonio; Garratt, Richard C.; Colnago, Luiz Alberto

    2004-01-01

    Xylella fastidiosa was the first plant pathogen to have its complete genome sequence elucidated. Routine database analyses suggested that two enzymes essential for fatty acid synthesis were missing, one of these is the holo-acyl-carrier-protein synthase. However, here we demonstrate, using 13 C NMR spectroscopy, that X. fastidiosa is indeed able to synthesize fatty acids from acetate via an apparently conventional metabolic pathway. We further identify a gene product HetI, an alternative phosphopantetheinyl transferase, which we propose to fill the missing link. Homology modeling of HetI shows conservation of the Coenzyme A binding site suggesting it to be an active enzyme and reveals several interesting structural features when compared with the surfactin synthase-activating enzyme, on which the model was built. These include a simplified topology due to N- and C-terminal deletions and the observation of a novel serine ladder

  9. Glutamine synthetase activity in solanaceous cell suspensions accumulating alkaloids or not. 13C NMR and enzymatic assay

    International Nuclear Information System (INIS)

    Mesnard, F.; Marty, D.; Monti, J.P.; Gillet-Manceau, F.; Fliniaux, M.A.

    1999-01-01

    The metabolism of labelled pyruvate followed by 13 C NMR and the measure of glutamine synthetase (GS) showed, according to previous results, a high activity of this enzyme in suspension cells of Nicotiana plumbaginifolia. This activity could derive glutamate from the alkaloid synthesizing pathways. However, a recent work showed that the rate of the GS gene transcription was inversely proportional to the Gln/Glu ratio. The measures of Gln and Glu concentrations in Nicotiana plumbaginifolia cells revealed that high GS activity correlates with the weak value of Gln/Glu ratio. Therefore, the hypothesis of GS dysfunction for the non-biosynthesis of alkaloids in N. plumbaginifolia suspension cells can be discarded. This conclusion is strengthened by the results obtained when using a GS inhibitor. (author)

  10. 13C-NMR Study on Structure Evolution Characteristics of High-Organic-Sulfur Coals from Typical Chinese Areas

    Directory of Open Access Journals (Sweden)

    Qiang Wei

    2018-02-01

    Full Text Available The structure evolution characteristics of high-organic-sulfur (HOS coals with a wide range of ranks from typical Chinese areas were investigated using 13C-CP/MAS NMR. The results indicate that the structure parameters that are relevant to coal rank include CH3 carbon (fal*, quaternary carbon, CH/CH2 carbon + quaternary carbon (falH, aliphatic carbon (falC, protonated aromatic carbon (faH, protonated aromatic carbon + aromatic bridgehead carbon (faH+B, aromaticity (faCP, and aromatic carbon (farC. The coal structure changed dramatically in the first two coalification jumps, especially the first one. A large number of aromatic structures condensed, and aliphatic structures rapidly developed at the initial stage of bituminous coal accompanied by remarkable decarboxylation. Compared to ordinary coals, the structure evolution characteristics of HOS coals manifest in three ways: First, the aromatic CH3 carbon, alkylated aromatic carbon (faS, aromatic bridgehead carbon (faB, and phenolic ether (faP are barely relevant to rank, and abundant organic sulfur has an impact on the normal evolution process of coal. Second, the average aromatic cluster sizes of some super-high-organic-sulfur (SHOS coals are not large, and the extensive development of cross bonds and/or bridged bonds form closer connections among the aromatic fringes. Moreover, sulfur-containing functional groups are probably significant components in these linkages. Third, a considerable portion of “oxygen-containing functional groups” in SHOS coals determined by 13C-NMR are actually sulfur-containing groups, which results in the anomaly that the oxygen-containing structures increase with coal rank.

  11. Complete {sup 1}H and {sup 13}C NMR assignments and anti fungal activity of two 8-hydroxy flavonoids in mixture

    Energy Technology Data Exchange (ETDEWEB)

    Johann, Susana; Smania Junior, Artur [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Microbiologia e Parasitologia. Lab. de Antibioticos; Pizzolatti, Moacir G. [Universidade Federal de Santa Catarina (UFSC), Florianopolis, SC (Brazil). Dept. de Quimica; Schripsema, Jan; Braz-Filho, Raimundo [Universidade Estadual do Norte Fluminense (UENF), Campos dos Goytacazes, RJ (Brazil). Setor de Quimica de Produtos Naturais. Lab. de Quimica e Funcao de Proteinas e Peptideos (LQFPP); Branco, Alexsandro [Universidade Estadual de Feira de Santana, BA (Brazil). Dept. de Saude. Lab. de Fitoquimica]. E-mail: branco@uefs.br

    2007-06-15

    A mixture of the two new flavonols 8-hydroxy-3, 4', 5, 6, 7-pentamethoxyflavone (1) and 8-hydroxy-3, 3', 4', 5, 6, 7-hexamethoxyflavone (2) was isolated from a commercial sample of Citrus aurantifolia. An array of one- ({sup 1}H NMR, {l_brace}{sup 1}H{r_brace} {sup -13}C NMR, and APT{sup -13}C NMR) and two-dimensional NMR techniques (COSY, NOESY, HMQC and HMBC) was used to achieve the structural elucidation and the complete {sup 1}H and {sup 13}C chemical shift assignments of these natural compounds. In addition, the antifungal activity of these compounds against phytopathogenic and human pathogenic fungi was investigated. (author)

  12. Cerebral glucose metabolism and the glutamine cycle as detected by in vivo and in vitro 13C NMR spectroscopy.

    Science.gov (United States)

    García-Espinosa, María A; Rodrigues, Tiago B; Sierra, Alejandra; Benito, Marina; Fonseca, Carla; Gray, Heather L; Bartnik, Brenda L; García-Martín, María L; Ballesteros, Paloma; Cerdán, Sebastián

    2004-01-01

    We review briefly 13C NMR studies of cerebral glucose metabolism with an emphasis on the roles of glial energetics and the glutamine cycle. Mathematical modeling analysis of in vivo 13C turnover experiments from the C4 carbons of glutamate and glutamine are consistent with: (i) the glutamine cycle being the major cerebral metabolic route supporting glutamatergic neurotransmission, (ii) glial glutamine synthesis being stoichiometrically coupled to glycolytic ATP production, (iii) glutamine serving as the main precursor of neurotransmitter glutamate and (iv) glutamatergic neurotransmission being supported by lactate oxidation in the neurons in a process accounting for 60-80% of the energy derived from glucose catabolism. However, more recent experimental approaches using inhibitors of the glial tricarboxylic acid (TCA) cycle (trifluoroacetic acid, TFA) or of glutamine synthase (methionine sulfoximine, MSO) reveal that a considerable portion of the energy required to support glutamine synthesis is derived from the oxidative metabolism of glucose in the astroglia and that a significant amount of the neurotransmitter glutamate is produced from neuronal glucose or lactate rather than from glial glutamine. Moreover, a redox switch has been proposed that allows the neurons to use either glucose or lactate as substrates for oxidation, depending on the relative availability of these fuels under resting or activation conditions, respectively. Together, these results suggest that the coupling mechanisms between neuronal and glial metabolism are more complex than initially envisioned.

  13. Detection of tannins in modern and fossil barks and in plant residues by high-resolution solid-state /sup 13/C nuclear magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Wilson, M A; Hatcher, P G

    1988-01-01

    Bark samples isolated from brown coal deposits in Victoria, Australia, and buried wood from Rhizophora mangle have been studied by high-resolution solid-state nuclear magnetic resonance (NMR) techniques. Dipolar dephasing /sup 13/C NMR appears to be a useful method of detecting the presence of tannins in geochemical samples including barks, buried woods, peats and leaf litter. It is shown that tannins are selectively preserved in bark during coalification to the brown coal stage. 28 refs., 9 figs., 1 tab.

  14. Detection of tannins in modern and fossil barks and in plant residues by high-resolution solid-state 13C nuclear magnetic resonance

    Science.gov (United States)

    Wilson, M.A.; Hatcher, P.G.

    1988-01-01

    Bark samples isolated from brown coal deposits in Victoria, Australia, and buried wood from Rhizophora mangle have been studies by high-resolution solid-state nuclear magnetic resonance (NMR) techniques. Dipolar dephasing 13C NMR appears to be a useful method of detecting the presence of tannins in geochemical samples including barks, buried woods, peats and leaf litter. It is shown that tannins are selectively preserved in bark during coalification to the brown coal stage. ?? 1988.

  15. 13C spin relaxation measurements in RNA: Sensitivity and resolution improvement using spin-state selective correlation experiments

    International Nuclear Information System (INIS)

    Boisbouvier, Jerome; Brutscher, Bernhard; Simorre, Jean-Pierre; Marion, Dominique

    1999-01-01

    A set of new NMR pulse sequences has been designed for the measurement of 13 C relaxation rate constants in RNA and DNA bases: the spin-lattice relaxation rate constant R(C z ), the spin-spin relaxation rate constant R(C + ), and the CSA-dipolar cross-correlated relaxation rate constant Γ C,CH xy . The use of spin-state selective correlation techniques provides increased sensitivity and spectral resolution. Sensitivity optimised C-C filters are included in the pulse schemes for the suppression of signals originating from undesired carbon isotopomers. The experiments are applied to a 15% 13 C-labelled 33-mer RNA-theophylline complex. The measured R(C + )/Γ C,CH xy ratios indicate that 13 C CSA tensors do not vary significantly for the same type of carbon (C 2 , C 6 , C 8 ), but that they differ from one type to another. In addition, conformational exchange effects in the RNA bases are detected as a change in the relaxation decay of the narrow 13 C doublet component when varying the spacing of a CPMG pulse train. This new approach allows the detection of small exchange effects with a higher precision compared to conventional techniques

  16. Effect of chronic hypoglycaemia on glucose concentration and glycogen content in rat brain: a localized 13C NMR study

    OpenAIRE

    Lei, Hongxia; Gruetter, Rolf

    2006-01-01

    While chronic hypoglycaemia has been reported to increase unidirectional glucose transport across the blood-brain barrier (BBB) and to increase GLUT1 expression at the endothelium, the effect on steady-state brain d-glucose and brain glycogen content is currently unknown. Brain glucose and glycogen concentrations were directly measured in vivo using localized 13C magnetic resonance spectroscopy (MRS) following 12-14 days of hypoglycaemia. Brain glucose content was significantly increased by 4...

  17. 13C-detected NMR experiments for automatic resonance assignment of IDPs and multiple-fixing SMFT processing

    International Nuclear Information System (INIS)

    Dziekański, Paweł; Grudziąż, Katarzyna; Jarvoll, Patrik; Koźmiński, Wiktor; Zawadzka-Kazimierczuk, Anna

    2015-01-01

    Intrinsically disordered proteins (IDPs) have recently attracted much interest, due to their role in many biological processes, including signaling and regulation mechanisms. High-dimensional 13 C direct-detected NMR experiments have proven exceptionally useful in case of IDPs, providing spectra with superior peak dispersion. Here, two such novel experiments recorded with non-uniform sampling are introduced, these are 5D HabCabCO(CA)NCO and 5D HNCO(CA)NCO. Together with the 4D (HACA)CON(CA)NCO, an extension of the previously published 3D experiments (Pantoja-Uceda and Santoro in J Biomol NMR 59:43–50, 2014. doi: 10.1007/s10858-014-9827-1 10.1007/s10858-014-9827-1 ), they form a set allowing for complete and reliable resonance assignment of difficult IDPs. The processing is performed with sparse multidimensional Fourier transform based on the concept of restricting (fixing) some of spectral dimensions to a priori known resonance frequencies. In our study, a multiple-fixing method was developed, that allows easy access to spectral data. The experiments were tested on a resolution-demanding alpha-synuclein sample. Due to superior peak dispersion in high-dimensional spectrum and availability of the sequential connectivities between four consecutive residues, the overwhelming majority of resonances could be assigned automatically using the TSAR program

  18. Quality of spelt pasta enriched with eggs and identification of eggs using 13C MAS NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    Filipović Jelena S.

    2015-01-01

    Full Text Available This paper deals with the characteristics of spelt pasta enriched with eggs. Eggs were added to spelt farina in the quantity of 0, 124 or 248 g/kg (equivalent to 0, 3 or 6 eggs, respectively. Post-hoc Tukey’s HSD test at 95% confidence limit showed significant differences between various samples. Relatively low coefficients of variation have been obtained for each applied assay (1.25-12.42%, which confirmed the high accuracy measurements and statistically significant results. Standard score analysis is applied for accessing the contribution of eggs content to spelt pasta quality. Maximum scores regarding quality (0.89 and chemical characteristics (0.70, have been obtained for 6 eggs spelt pasta formulation. It is also shown that the presence of eggs in pasta can be clearly confirmed by 13C MAS NMR spectroscopy. Simultaneous increase in area of peak positioned at 29.5 and 176 ppm is directly associated with the increase in the content of added eggs in the corresponding samples. Pertinent data point at positive contribution of eggs to the spelt pasta and also that NMR spectrum can be used in the egg quantity control. [Projekat Ministarstva nauke Republike Srbije, br. TRI 46005 i br. TR 31029

  19. In situ measurement of magnesium carbonate formation from CO2 using static high-pressure and -temperature 13C NMR.

    Science.gov (United States)

    Surface, J Andrew; Skemer, Philip; Hayes, Sophia E; Conradi, Mark S

    2013-01-02

    We explore a new in situ NMR spectroscopy method that possesses the ability to monitor the chemical evolution of supercritical CO(2) in relevant conditions for geological CO(2) sequestration. As a model, we use the fast reaction of the mineral brucite, Mg(OH)(2), with supercritical CO(2) (88 bar) in aqueous conditions at 80 °C. The in situ conversion of CO(2) into metastable and stable carbonates is observed throughout the reaction. After more than 58 h of reaction, the sample was depressurized and analyzed using in situ Raman spectroscopy, where the laser was focused on the undisturbed products through the glass reaction tube. Postreaction, ex situ analysis was performed on the extracted and dried products using Raman spectroscopy, powder X-ray diffraction, and magic-angle spinning (1)H-decoupled (13)C NMR. These separate methods of analysis confirmed a spatial dependence of products, possibly caused by a gradient of reactant availability, pH, and/or a reaction mechanism that involves first forming hydroxy-hydrated (basic, hydrated) carbonates that convert to the end-product, anhydrous magnesite. This carbonation reaction illustrates the importance of static (unmixed) reaction systems at sequestration-like conditions.

  20. Organic matter characterization during the anaerobic digestion of different biomasses by means of CPMAS 13C NMR spectroscopy

    International Nuclear Information System (INIS)

    Tambone, Fulvia; Adani, Fabrizio; Gigliotti, Giovanni; Volpe, Daniela; Fabbri, Claudio; Provenzano, Maria Rosaria

    2013-01-01

    The aim of this work was to characterize ingestates and their corresponding digestates obtained in two full-scale biogas production plants processing a) mixtures of organic wastes in co-digestion, and b) pig slurry in order to assess the organic matter transformation during anaerobic digestion by means of chemical analysis and 13 CPMAS-NMR spectroscopy. Results proved that digestates obtained by different organic substrates exhibited significant chemical differences related to the different initial composition of substrates. We proposed the use of the aliphaticity index in order to highlight the different chemical nature of ingestates and their corresponding digestates. In order to verify whether the AD process leads to stabilized final products regardless the initial composition of biomass in view of a possible agronomical use of digestate, a comparison of CPMAS 13 C NMR data of a number of ingestates and digestates available in literature was carried out. Results indicated that most of the aromatic structures present in the substrate tend to degrade during the process and that anaerobic digestion proceeds through preferential degradation of carbohydrates such as cellulose and hemicellulose and, as a consequence, concentration of more chemically recalcitrant aliphatic molecules occurs. -- Highlights: ► We studied anaerobic digestion by means of chemical analysis and 13 CPMAS-NMR spectroscopy. ► Significant chemical differences in digestates were highlighted. ► We proposed the use of the aliphaticity index in order to differentiate digestates. ► Most of the aromatic structures tend to degrade. ► Carbohydrates are degraded and recalcitrant aliphatic molecules concentrate

  1. NMR 1H,13C, 15N backbone and 13C side chain resonance assignment of the G12C mutant of human K-Ras bound to GDP.

    Science.gov (United States)

    Sharma, Alok K; Lee, Seung-Joo; Rigby, Alan C; Townson, Sharon A

    2018-05-02

    K-Ras is a key driver of oncogenesis, accounting for approximately 80% of Ras-driven human cancers. The small GTPase cycles between an inactive, GDP-bound and an active, GTP-bound state, regulated by guanine nucleotide exchange factors and GTPase activating proteins, respectively. Activated K-Ras regulates cell proliferation, differentiation and survival by signaling through several effector pathways, including Raf-MAPK. Oncogenic mutations that impair the GTPase activity of K-Ras result in a hyperactivated state, leading to uncontrolled cellular proliferation and tumorogenesis. A cysteine mutation at glycine 12 is commonly found in K-Ras associated cancers, and has become a recent focus for therapeutic intervention. We report here 1 H N, 15 N, and 13 C resonance assignments for the 19.3 kDa (aa 1-169) human K-Ras protein harboring an oncogenic G12C mutation in the GDP-bound form (K-RAS G12C-GDP ), using heteronuclear, multidimensional NMR spectroscopy. Backbone 1 H- 15 N correlations have been assigned for all non-proline residues, except for the first methionine residue.

  2. Characterizing crystal disorder of trospium chloride: a comprehensive, 13C CP/MAS NMR, DSC, FTIR, and XRPD study

    Czech Academy of Sciences Publication Activity Database

    Urbanová, Martina; Šturcová, Adriana; Brus, Jiří; Beneš, Hynek; Skořepová, E.; Kratochvíl, B.; Čejka, J.; Šeděnková, Ivana; Kobera, Libor; Policianová, Olivia; Šturc, A.

    2013-01-01

    Roč. 102, č. 4 (2013), s. 1235-1248 ISSN 0022-3549 R&D Projects: GA ČR GPP106/11/P426 Institutional support: RVO:61389013 Keywords : trospium chloride * solid state NMR * factor analysis Subject RIV: FR - Pharmacology ; Medidal Chemistry Impact factor: 3.007, year: 2013

  3. Solid state NMR study of cumbaru flour

    International Nuclear Information System (INIS)

    Nogueira, Jose S.; Bathista, Andre L.B.S.; Silva, Emerson O.; Priante Filho, Nicolau; Tavares, Maria I.B.

    2001-01-01

    The polysaccharide obtained by seed of Dipteryx alata Vog, has been characterised by 13 C solid state, using the basic routine techniques, like MAS and CPMAS and by the proton spin-lattice relaxation time in the rotating frame parameter (T 1 H ρ). Knowing that the chemical structure and molecular dynamic are extremely necessary route to obtain information on the polysaccharides, this work contributes to the classification of the seed containing in the cumbaru fruit to get response on its application. To obtain the initial responses for our purposes some solid state NMR techniques were chosen. The CPMAS 13 C NMR spectrum of the polysaccharide was investigated to know if it has some crystallinity. The MAS 13 C NMR spectrum showed the presence of domains with distinct molecular mobility, because these domains will differ basically in the distribution size and chain packing. The variable contact time experiment was used to analyse the distribution form of 13 C decays, which give us more information about sample heterogeneity. The T 1 H ρHr values were obtained from the variable contact time and by delayed contact time experiment, because these parameter indicate the order of polysaccharides. From the values of this parameter, we found that this polysaccharide is completely non-ordered. (author)

  4. Microstructural Analysis of Carbonyl Signal in the 13C NMR Spectra of Methyl Methacrylate - n-Butyl Acrylate Copolymer

    International Nuclear Information System (INIS)

    Bujak, P.; Matlengiewicz, M.

    2005-01-01

    Microstructural information on acrylic copolymers, i.e. distribution of the comonomers along the macromolecular chain and their stereochemical arrangement (tacticity) can be derived from 13 C NMR, analyzing the splitting of their carbonyl signal. In the 100 MHz 13 C NMR spectrum of poly(methyl methacrylate-co-n-butyl acrylate), PMMA-nBA, the carbonyl signal at 174-178,5 ppm is clearly split into the lines of configurational-compositional pentads. This splitting is slightly different in different solvents, hence, recording of the same sample in different solvents may reveal differences important to correct assignment of individual sequences, since their probabilities (intensities) remain the same, while the chemical shift can vary in different solvents. If we would like to perform a complete analysis at this level we have to determine the distribution of 272 individual pentads. The outermost lines in the carbonyl signal of the copolymer can be assigned to the sequences of pure composition by simple comparison with the spectra of respective homopolymers. The rest of the inner lines cannot be easily attributed, therefore, a series of copolymer samples of different composition were synthesized in order to observe the different heterosequences, since depending on copolymer composition, different signals representing individual sequences, assume different relative intensities. To confirm the correctness of proposed attribution a simulation of the carbonyl signal can be performed. It is therefore necessary to know the intensities and positions of individual signals, representing individual compositional-configurational pentads. Calculation of the intensity of the lines can be performed assuming Bernoullian and/or Markov statistics, separately for compositional and configurational sequences and verifying the overall distribution of the individual probabilities. The position of the individual lines cannot be straightforwardly determined, therefore, we have adopted an

  5. Other compounds isolated from Simira glaziovii and the {sup 1}H and {sup 13}C NMR chemical shift assignments of new 1-epi-castanopsol

    Energy Technology Data Exchange (ETDEWEB)

    Araujo, Marcelo F. de; Vieira, Ivo J. Curcino [Universidade Federal Rural do Rio de Janeiro, Seropedica, RJ (Brazil). Dept. de Quimica; Braz-Filho, Raimundo [Universidade Estadual do Norte Fluminense (UENF), Campos dos Goytacases, RJ (Brazil). Centro de Ciencias Tecnologicas. Lab. de Ciencias Quimicas; Carvalho, Mario G. de, E-mail: mgeraldo@ufrrj.br [Universidade Federal do Rio de Janeiro (NPPN/UFRJ), RJ (Brazil). Centro de Ciencias da Saude. Nucleo de Pesquisa em Produtos Naturais

    2012-07-01

    A new triterpene, 1-epi-castanopsol, besides eleven known compounds: sitosterol, stigmasterol, campesterol, lupeol, lupenone, simirane B, syringaresinol, scopoletin, isofraxidin, 6,7,8-trimethoxycoumarin and harman, were isolated from the wood of Simira glaziovii. The structures of the known compounds were defined by 1D, 2D {sup 1}H, {sup 13}C NMR spectra data analyses and comparison with literature data. The detailed spectral data analyses allowed the definition of the structure of the new 1-epi isomer of castanopsol and performance of {sup 1}H and {sup 13}C NMR chemical shift assignments. (author)

  6. Other compounds isolated from Simira glaziovii and the 1H and 13C NMR chemical shift assignments of new 1-epi-castanopsol

    International Nuclear Information System (INIS)

    Araujo, Marcelo F. de; Vieira, Ivo J. Curcino; Braz-Filho, Raimundo; Carvalho, Mario G. de

    2012-01-01

    A new triterpene, 1-epi-castanopsol, besides eleven known compounds: sitosterol, stigmasterol, campesterol, lupeol, lupenone, simirane B, syringaresinol, scopoletin, isofraxidin, 6,7,8-trimethoxycoumarin and harman, were isolated from the wood of Simira glaziovii. The structures of the known compounds were defined by 1D, 2D 1 H, 13 C NMR spectra data analyses and comparison with literature data. The detailed spectral data analyses allowed the definition of the structure of the new 1-epi isomer of castanopsol and performance of 1 H and 13 C NMR chemical shift assignments. (author)

  7. Use of 13NMR to delineate the mode of association or binding of 13C-labeled pollutants with humic materials

    International Nuclear Information System (INIS)

    Bortiatynski, J.M.; Minard, R.D.; Hatcher, P.G.

    1993-01-01

    13 C NMR has recently been shown to be a powerful technique for the examination of the covalent binding of pollutants to humic materials when the latter are enriched with 13 C. Enhanced signals are observed for the carbons that are highly enriched with 13 C while the remaining signals due to naturally abundant 13 C form unlabeled pollutant carbons or humic substances are at the baseline noise level. If covalent bonding and/or non covalent associations take place at or near the site of the 13 C label(s), the nature of the bonding or association can be discerned and the adsorption coefficients can be calculated. In this paper, the authors present the results of such binding studies which demonstrate the great potential of this technique

  8. Sub-minute kinetics of human red cell fumarase: 1 H spin-echo NMR spectroscopy and 13 C rapid-dissolution dynamic nuclear polarization.

    Science.gov (United States)

    Shishmarev, Dmitry; Wright, Alan J; Rodrigues, Tiago B; Pileio, Giuseppe; Stevanato, Gabriele; Brindle, Kevin M; Kuchel, Philip W

    2018-03-01

    Fumarate is an important probe of metabolism in hyperpolarized magnetic resonance imaging and spectroscopy. It is used to detect the release of fumarase in cancer tissues, which is associated with necrosis and drug treatment. Nevertheless, there are limited reports describing the detailed kinetic studies of this enzyme in various cells and tissues. Thus, we aimed to evaluate the sub-minute kinetics of human red blood cell fumarase using nuclear magnetic resonance (NMR) spectroscopy, and to provide a quantitative description of the enzyme that is relevant to the use of fumarate as a probe of cell rupture. The fumarase reaction was studied using time courses of 1 H spin-echo and 13 C-NMR spectra. 1 H-NMR experiments showed that the fumarase reaction in hemolysates is sufficiently rapid to make its kinetics amenable to study in a period of approximately 3 min, a timescale characteristic of hyperpolarized 13 C-NMR spectroscopy. The rapid-dissolution dynamic nuclear polarization (RD-DNP) technique was used to hyperpolarize [1,4- 13 C]fumarate, which was injected into concentrated hemolysates. The kinetic data were analyzed using recently developed FmR α analysis and modeling of the enzymatic reaction using Michaelis-Menten equations. In RD-DNP experiments, the decline in the 13 C-NMR signal from fumarate, and the concurrent rise and fall of that from malate, were captured with high spectral resolution and signal-to-noise ratio, which allowed the robust quantification of fumarase kinetics. The kinetic parameters obtained indicate the potential contribution of hemolysis to the overall rate of the fumarase reaction when 13 C-NMR RD-DNP is used to detect necrosis in animal models of implanted tumors. The analytical procedures developed will be applicable to studies of other rapid enzymatic reactions using conventional and hyperpolarized substrate NMR spectroscopy. Copyright © 2018 John Wiley & Sons, Ltd.

  9. New organic single crystal of (benzylthio)acetic acid: Synthesis, crystal structure, spectroscopic (ATR-FTIR, 1H and 13C NMR) and thermal characterization

    Science.gov (United States)

    Sienkiewicz-Gromiuk, Justyna; Tarasiuk, Bogdan; Mazur, Liliana

    2016-04-01

    (Benzylthio)acetic acid (Hbta) was synthesized with 78% yield from benzyl chloride and thiourea as substrates. Well-shaped crystals of Hbta were grown by slow solvent evaporation technique from pure methanol. The compound was investigated by single-crystal X-ray and powder diffraction techniques and was also characterized by other analytical methods, like ATR-FTIR, 1H and 13C NMR and TG/DSC. The acid molecule adopts bent conformation in the solid state. The crystal structure of Hbta is stabilized by numerous intermolecular interactions, including O-H···O, C-H···O, C-H···S and C-H···π contacts. Thermal decomposition of the obtained material takes place above 150 °C.

  10. Study of the direct detection of crosslinking in hydrocarbons by 13C-NMR. II. Identification of crosslink in model compound and application to irradiate paraffins

    International Nuclear Information System (INIS)

    Bennett, R.L.; Keller, A.; Stejny, H.H.; Murray, M.

    1976-01-01

    A 13 C-NMR investigation was carried out in aid of direct detection of crosslinks in hydrocarbons with the future objective of studying radiation-induced crosslinking in polyethylene by a direct method. The resonance signal due to a tertiary carbon atom appropriate to a crosslink far remote from molecular ends has been identified in a definitive manner with the aid of the H-shaped model compound 1,1,2,2-tetra(tridecyl)ethane synthetized in Part I of this study. This identification was then put to use in the examination of the irradiated linear paraffins n-hexadecane and n-eicosane, where it enabled the detection of radiation-induced crosslinks. This crosslinking could then be associated with corresponding changes in molecular weight (dimer, trimer formation) as revealed by discrete peaks in the gel-permeation chromatograms of the same samples and randomness of the crosslinking process in the liquid state of these compounds being inferred

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

    Science.gov (United States)

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

    2011-05-01

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

  12. Investigation of α-cluster states in 13C via the (6Li,d) reaction

    CERN Document Server

    Rodrigues, M R D; Horodynski-Matsushigue, L B; Cunsolo, A; Cappuzzello, F; Duarte, J L M; Rodrigues, C L; Ukita, G M; Souza, M A; Miyake, H

    2010-01-01

    The 9Be(6Li,d)13C reaction was used to investigate possible α-cluster states in 13C. The reaction was measured at 25.5 MeV incident energy, employing the São Paulo Pelletron-Enge-Spectrograph facility and the nuclear emulsion detection technique. Ten out of sixteen known levels of 13C, up to 11 MeV of excitation, were observed and, due to the much improved energy resolution of 50 keV, at least three doublets could be resolved. This work presents a preliminary analysis of five of the most intensely populated states, also in comparison with the results of former transfer studies.

  13. Sesquiterpenoids in subtribe Centaureinae (Cass.) Dumort (tribe Cardueae, Asteraceae): distribution, (13)C NMR spectral data and biological properties.

    Science.gov (United States)

    Bruno, Maurizio; Bancheva, Svetlana; Rosselli, Sergio; Maggio, Antonella

    2013-11-01

    Asteraceae Bercht. & J. Presl is one of the biggest and most economically important plant families. The taxonomy and phylogeny of Asteraceae is rather complex and according to the latest and most reliable taxonomic classification of Panero & Funk, based on the analysis of nine chloroplast regions, the family is divided into 12 subfamilies and 35 tribes. One of the largest tribes of Asteraceae is Cardueae Cass. with four subtribes (Carlininae, Echinopinae, Carduinae and Centaureinae) and more than 2500 species. Susanna & Garcia-Jacas have organized the genera of Centaureinae (about 800 species) into seven informal groups, which recent molecular studies have confirmed: 1. Basal genera; 2. Volutaria group; 3. Rhaponticum group; 4. Serratula group; 5. Carthamus group; 6. Crocodylium group; 7. Centaurea group. This review summarizes reports on sesquiterpenoids from the Centaureinae subtribe of the Asteraceae family, as well as the (13)C NMR spectral data described in the literature. It further reviews studies concerning the biological activities of these metabolites. For this work, literature data on sesquiterpenes from the Centaureinae subtribe were retrieved with the help of the SciFinder database and other similar data banks. All entries from 1958 until the end of 2011 were considered. This review is addressed to scientists working in the metabolomics field such as chemists, botanists, etc., the spectroscopic data reported make this work a good tool for structural elucidation, the biological section gives useful information to those who wish to study the structure activity relationships. Copyright © 2013 Elsevier Ltd. All rights reserved.

  14. Determination of the structural changes by Raman and {sup 13}C CP/MAS NMR spectroscopy on native corn starch with plasticizers

    Energy Technology Data Exchange (ETDEWEB)

    Cozar, O. [Academy of Romanian Scientists, Splaiul Independentei 54, 050094, Bucharest, Romania and National Institute of Research-Development for Machines and Installations Designed to Agriculture and Food Industry - INMA Bucureşti - Cluj-Napoca Branch (Romania); Filip, C.; Tripon, C. [National Institute for Research and Development of Isotopic and Molecular Technologies, 65-103 Donath, 400293 Cluj-Napoca (Romania); Cioica, N.; Coţa, C.; Nagy, E. M. [National Institute of Research-Development for Machines and Installations Designed to Agriculture and Food Industry - INMA Bucureşti - Cluj-Napoca Branch, RO-400458 Cluj-Napoca (Romania)

    2013-11-13

    The plasticizing - antiplasticizing effect of water and glycerol contents on native corn starch samples is investigated by FT-Raman and {sup 13}C CP/MAS NMR spectroscopy. The presence of both amorphous and crystalline structural phases was evidenced in pure native corn starch and also in the samples containing plasticizers. Among the crystalline starch structures, the A- and V- types were suggested by CP/MAS NMR spectra.

  15. 1H NMR, 13C NMR and Computational Daft Study of the Solution Structure of 2-Formylcyclohexane-1,3-Dione and its Alkali Metal Salts

    International Nuclear Information System (INIS)

    Szczecinski, P.; Gryff-Keller, A.; Molchanov, S.

    2005-01-01

    Triketones have been known for many years to be efficient inhibitors of (4-hydroxyphenyl)pyruvate dioxygenase (HPPD), an enzyme very important for plants and animals, which catalyzes the tyrosine catabolism. Inhibition of this process has been used for both herbicidal and medical purposes. The mechanism of inhibition of HPPD by triketones is still under investigation. Recently, an almost complete mechanistic model of interaction between the mentioned enzyme and its inhibitor has been proposed. However, some arguments used by the authors to rationalize the proposed mechanism cannot be accepted. Therefore further developing of the investigation in this field is justified. In the present work the solution structure of 2-formylcyclohexane-1,3-dione, a simple molecular model of HPPD inhibitors, has been investigated using 1 H and 13 C NMR spectroscopic methods and theoretical DFT-based calculations. (author)

  16. (13)C heteronuclear NMR studies of the interaction of cultured neurons and astrocytes and aluminum blockade of the preferential release of citrate from astrocytes.

    Science.gov (United States)

    Meshitsuka, Shunsuke; Aremu, David A

    2008-02-01

    Citrate has been identified as a major tricarboxylic acid (TCA) cycle constituent preferentially released by astrocytes. We undertook the present study to examine further the nature of metabolic compartmentation in central nervous system tissues using (13)C-labeled glucose and to provide new information on the influence of aluminum on the metabolic interaction between neurons and astrocytes. Metabolites released into the culture medium from astrocytes and neuron-astrocyte coculture, as well as the perchloric acid extracts of the cells were analyzed using 2D (1)H and (13)C NMR spectroscopy. Astrocytes released citrate into the culture medium and the released citrate was consumed by neurons in coculture. Citrate release by astrocytes was blocked in the presence of aluminum, with progressive accumulation of citrate within the cells. We propose citrate supply is a more efficient energy source than lactate for neurons to produce ATP, especially in the hypoglycemic state on account of it being a direct component of the TCA cycle. Astrocytes may be the cellular compartment for aluminum accumulation as a citrate complex in the brain.

  17. Detection and assignment of phosphoserine and phosphothreonine residues by {sup 13}C-{sup 31}P spin-echo difference NMR spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    McIntosh, Lawrence P., E-mail: mcintosh@chem.ubc.ca; Kang, Hyun-Seo; Okon, Mark [University of British Columbia, Department of Biochemistry (Canada); Nelson, Mary L.; Graves, Barbara J. [University of Utah, Department of Oncological Sciences, Huntsman Cancer Institute (United States); Brutscher, Bernhard [CNRS, CEA, UJF, Institut de Biologie Structurale Jean-Pierre Ebel (France)], E-mail: bernhard.brutscher@ibs.fr

    2009-01-15

    A simple NMR method is presented for the identification and assignment of phosphorylated serine and threonine residues in {sup 13}C- or {sup 13}C/{sup 15}N-labeled proteins. By exploiting modest ({approx}5 Hz) 2- and 3-bond {sup 13}C-{sup 31}P scalar couplings, the aliphatic {sup 1}H-{sup 13}C signals from phosphoserines and phosphothreonines can be detected selectively in a {sup 31}P spin-echo difference constant time {sup 1}H-{sup 13}C HSQC spectrum. Inclusion of the same {sup 31}P spin-echo element within the {sup 13}C frequency editing period of an intraHNCA or HN(CO)CA experiment allows identification of the amide {sup 1}H{sup N} and {sup 15}N signals of residues (i) for which {sup 13}C{sup {alpha}}(i) or {sup 13}C{sup {alpha}}(i - 1), respectively, are coupled to a phosphate. Furthermore, {sup 31}P resonance assignments can be obtained by applying selective low power cw {sup 31}P decoupling during the spin-echo period. The approach is demonstrated using a PNT domain containing fragment of the transcription factor Ets-1, phosphorylated in vitro at Thr38 and Ser41 with the MAP kinase ERK2.

  18. 1H, 13C and 13N chemical shifts and 1H-15N and 13C-15N heteronuclear spin-spin coupling constants n the NMR spectra of 5-substituted furfural oximes

    International Nuclear Information System (INIS)

    Popelis, Yu.Yu.; Liepin'sh, E.E.; Lukevits, E.Ya.

    1986-01-01

    The 1 H, 13 C, and 15 N NMR spectra of 15 N-enriched 5-substituted furfural oximes were investigated. It was shown that the chemical shifts of the ring atoms and the oxime group correlate satisfactorily with the F and R substituent constants, whereas their sensitivity to the effect of the substituents is lower than in monosubstituted furan derivatives. The constants of spin-spin coupling between the ring protons and the oxime group were determined. An analysis of the 1 H- 1 H spin-spin coupling constants (SSCC) on the basis of their stereospecificity indicates that the E isomers have primarily an s-trans conformation in polar dimethyl sulfoxide, whereas the Z isomers, on the other hand, have an s-cis conformation. The signs of the direct and geminal 13 C- 15 N SSCC were determined for 5-trimethylsilylfurfural oxime

  19. Analysis of neuron–astrocyte metabolic cooperation in the brain of db/db mice with cognitive decline using 13C NMR spectroscopy

    Science.gov (United States)

    Zheng, Hong; Zheng, Yongquan; Wang, Dan; Cai, Aimin; Lin, Qiuting; Zhao, Liangcai; Chen, Minjiang; Deng, Mingjie; Ye, Xinjian

    2016-01-01

    Type 2 diabetes has been linked to cognitive impairment, but its potential metabolic mechanism is still unclear. The present study aimed to explore neuron–astrocyte metabolic cooperation in the brain of diabetic (db/db, BKS.Cg-m+/+ Leprdb/J) mice with cognitive decline using 13C NMR technique in combination with intravenous [2-13C]-acetate and [3-13C]-lactate infusions. We found that the 13C-enrichment from [2-13C]-acetate into tricarboxylic acid cycle intermediate, succinate, was significantly decreased in db/db mice with cognitive decline compared with wild-type (WT, C57BLKS/J) mice, while an opposite result was obtained after [3-13C]-lactate infusion. Relative to WT mice, db/db mice with cognitive decline had significantly lower 13C labeling percentages in neurotransmitters including glutamine, glutamate, and γ-aminobutyric acid after [2-13C]-acetate infusion. However, [3-13C]-lactate resulted in increased 13C-enrichments in neurotransmitters in db/db mice with cognitive decline. This may indicate that the disturbance of neurotransmitter metabolism occurred during the development of cognitive decline. In addition, a reduction in 13C-labeling of lactate and an increase in gluconeogenesis were found from both labeled infusions in db/db mice with cognitive decline. Therefore, our results suggest that the development of cognitive decline in type 2 diabetes may be implicated to an unbalanced metabolism in neuron–astrocyte cooperation and an enhancement of gluconeogenesis. PMID:26762505

  20. Analysis of neuron-astrocyte metabolic cooperation in the brain of db/db mice with cognitive decline using 13C NMR spectroscopy.

    Science.gov (United States)

    Zheng, Hong; Zheng, Yongquan; Wang, Dan; Cai, Aimin; Lin, Qiuting; Zhao, Liangcai; Chen, Minjiang; Deng, Mingjie; Ye, Xinjian; Gao, Hongchang

    2017-01-01

    Type 2 diabetes has been linked to cognitive impairment, but its potential metabolic mechanism is still unclear. The present study aimed to explore neuron-astrocyte metabolic cooperation in the brain of diabetic (db/db, BKS.Cg-m +/+ Leprdb/J) mice with cognitive decline using 13 C NMR technique in combination with intravenous [2- 13 C]-acetate and [3- 13 C]-lactate infusions. We found that the 13 C-enrichment from [2- 13 C]-acetate into tricarboxylic acid cycle intermediate, succinate, was significantly decreased in db/db mice with cognitive decline compared with wild-type (WT, C57BLKS/J) mice, while an opposite result was obtained after [3- 13 C]-lactate infusion. Relative to WT mice, db/db mice with cognitive decline had significantly lower 13 C labeling percentages in neurotransmitters including glutamine, glutamate, and γ-aminobutyric acid after [2- 13 C]-acetate infusion. However, [3- 13 C]-lactate resulted in increased 13 C-enrichments in neurotransmitters in db/db mice with cognitive decline. This may indicate that the disturbance of neurotransmitter metabolism occurred during the development of cognitive decline. In addition, a reduction in 13 C-labeling of lactate and an increase in gluconeogenesis were found from both labeled infusions in db/db mice with cognitive decline. Therefore, our results suggest that the development of cognitive decline in type 2 diabetes may be implicated to an unbalanced metabolism in neuron-astrocyte cooperation and an enhancement of gluconeogenesis. © The Author(s) 2016.

  1. 12C(d,p) 13C reaction at Esub(d) = 30 MeV to the positive-parity states in 13C

    International Nuclear Information System (INIS)

    Ohnuma, H.; Hoshino, N.; Mikoshiba, O.

    1985-07-01

    The 12 C(d, p) 13 C reaction has been studied at Esub(d) = 30 MeV. All the known positive-parity states of 13 C below 10 MeV in excitation energy, including the 7/2 + and 9/2 + states, are observed in this reaction. The angular distributions for these positive-parity bound and unbound states are analyzed in CCBA frame work. The 13 C wave functions, which reproduce the resonant and non-resonant scattering of neutrons from 12 C, also give good accounts of the experimentally observed angular distributions and energy spectra of outgoing protons in the 12 C(d, p) 13 C reaction. In most cases the cross section magnitude and the angular distribution shape are primarily determined by the 0 + x j component, even if it is only a small fraction of the total wave function. An exception is the 7/2 + state, where the main contribution comes from the 2 + x dsub(5/2) component. The inclusion of the 4 + state in 12 C and the gsub(9/2) and gsub(7/2) neutron components in the n + 12 C system has very small effects on the low-spin states, but is indispensable for a good fit to the 7/2 + and 9/2 + angular distributions. The transitions to the negative-parity states, 1/2 1 - , 3/2 1 - , 5/2 - , 7/2 - and 1/2 3 - , are also observed experimentally, and analyzed by DWBA. (author)

  2. Combination of capillary GC, GC/MS and 13C-NMR for the characterization of the rhizome oil of Piper betle L. (Piperaceae) from Vietnam

    NARCIS (Netherlands)

    Thanh, L.; Dung, N.X.; Bighelli, A.; Casanova, J.; Leclercq, P.A.

    1997-01-01

    The essential oil from the rhizomes of Piper betle L. (betel), collected around Hue, was obtained in 0.20% yield. The oil was examined by a combination of capillary GC and GC/MS. 13C-NMR studies confirmed the structure assignments proposed by retention data and mass spectra of the components with a

  3. Synthesis of 24-methyl sterols sterospecifically labelled with 2H in the isopropyl methyl groups. 13C NMR spectral assignment of C-26 and C-27 resonances

    International Nuclear Information System (INIS)

    Colombo, D.; Ronchetti, F.; Toma, L.

    1990-01-01

    Through analysis of the 13 C NMR spectra of (25S)-[27- 2 H]campesterol (1) and (25R)-[26- 2 H]dihydrobrassicasterol (2), the C-26 and C-27 resonances have been unambiguously assigned; the biosynthetic applications are discussed. (author)

  4. Spectroscopic effects in 1H and 13C NMR spectra of 4,4'-di-substituted 3,3'-diquinolines sulfides

    International Nuclear Information System (INIS)

    Pluta, K.

    1994-01-01

    The 1 H and 13 C NMR spectra of 4,4'-disubstituted sulfides of 3,3'-quinolines have been studied in CDCl 3 solutions. The observed spectroscopic effects have been interpreted in terms of molecule structure and configuration. The factors being responsible for the value of spectroscopic effects have been discussed

  5. A Discovery-Based Hydrochlorination of Carvone Utilizing a Guided-Inquiry Approach to Determine the Product Structure from [superscript 13]C NMR Spectra

    Science.gov (United States)

    Pelter, Michael W.; Walker, Natalie M.

    2012-01-01

    This experiment describes a discovery-based method for the regio- and stereoselective hydrochlorination of carvone, appropriate for a 3-h second-semester organic chemistry laboratory. The product is identified through interpretation of the [superscript 13]C NMR and DEPT spectra are obtained on an Anasazi EFT-60 at 15 MHz as neat samples. A…

  6. Applications of artificial intelligence techniques to organic chemistry. Study on sup 13 C NMR of steroids using computer. Aplicacoes de tecnicas de inteligencia artificial em quimica organica. Estudo, por computador, de RMN sup 13 C de esteroides

    Energy Technology Data Exchange (ETDEWEB)

    Lins, A P [Instituto Biologico, Sao Paulo, SP (Brazil). Secao de Farmacologia; Furlan, M [UNESP, Araraquara, SP (Brazil). Inst. de Quimica; Gastmans, G P [UNESP, Guaratingueta, SP (Brazil). Inst. de Quimica e Fisica; Emerenciano, V P [Sao Paulo Univ., SP (Brazil). Inst. de Quimica

    1991-01-01

    This work describes the utilization of two groups of programs in searching for characteristic signals of NMR {sup 13}C steroidal compounds. The first group of programs used data bases with the spectral data and a methodology that enables the choice and the search of substructures. The chemical shifts and multiplicities for each specific substructure are used as rules to identify different types and subtypes of steroidal compounds. The second one was built to apply the rules formulated by the first group of programs and to foresee any skeletal based on a spectral analysis. (author).

  7. [1-13C]Glucose entry in neuronal and astrocytic intermediary metabolism of aged rats. A study of the effects of nicergoline treatment by 13C NMR spectroscopy.

    Science.gov (United States)

    Miccheli, Alfredo; Puccetti, Caterina; Capuani, Giorgio; Di Cocco, Maria Enrica; Giardino, Luciana; Calzà, Laura; Battaglia, Angelo; Battistin, Leontino; Conti, Filippo

    2003-03-14

    Age-related changes in glucose utilization through the TCA cycle were studied using [1-13C]glucose and 13C, 1H NMR spectroscopy on rat brain extracts. Significant increases in lactate levels, as well as in creatine/phosphocreatine ratios (Cr/PCr), and a decrease in N-acetyl-aspartate (NAA) and aspartate levels were observed in aged rat brains as compared to adult animals following glucose administration. The total amount of 13C from [1-13C]glucose incorporated in glutamate, glutamine, aspartate and GABA was significantly decreased in control aged rat brains as compared to adult brains. The results showed a decrease in oxidative glucose utilization of control aged rat brains. The long-term nicergoline treatment increased NAA and glutamate levels, and decreased the lactate levels as well as the Cr/PCr ratios in aged rat brains as compared to adult rats. The total amount of 13C incorporated in glutamate, glutamine, aspartate, NAA and GABA was increased by nicergoline treatment, showing an improvement in oxidative glucose metabolism in aged brains. A significant increase in pyruvate carboxylase/pyruvate dehydrogenase activity (PC/PDH) in the synthesis of glutamate in nicergoline-treated aged rats is consistent with an increase in the transport of glutamine from glia to neurons for conversion into glutamate. In adult rat brains, no effect of nicergoline on glutamate PC/PDH activity was observed, although an increase in PC/PDH activity in glutamine was, suggesting that nicergoline affects the glutamate/glutamine cycle between neurons and glia in different ways depending on the age of animals. These results provide new insights into the effects of nicergoline on the CNS.

  8. Regional origin assignment of red wines from Valencia (Spain) by (2)H NMR and (13)C IRMS stable isotope analysis of fermentative ethanol.

    Science.gov (United States)

    Giménez-Miralles, J E; Salazar, D M; Solana, I

    1999-07-01

    The use of the stable hydrogen and carbon isotope ratios of fermentative ethanol as suitable environmental fingerprints for the regional origin identification of red wines from Valencia (Spain) has been explored. Monovarietal Vitis vinifera L. cvs. Bobal, Tempranillo, and Monastrell wines have been investigated by (2)H NMR and (13)C IRMS for the natural ranges of site-specific (2)H/(1)H ratios and global delta(13)C values of ethanol over three vintage years. Statistically significant interregional and interannual (2)H and (13)C abundance differences have been noticed, which are interpreted in terms of environmental and ecophysiological factors of isotope content variation. Multivariate discriminant analysis is shown to provide a convenient means for integration of the classifying information, high discriminating abilities being demonstrated for the (2)H and (13)C fingerprints of ethanol. Reasonable differentiation results are achieved at a microregional scale in terms of geographic provenance and even grapevine genotypic features.

  9. Oligomeric complexes of some heteroaromatic ligands and aromatic diamines with rhodium and molybdenum tetracarboxylates: 13C and 15N CPMAS NMR and density functional theory studies.

    Science.gov (United States)

    Leniak, Arkadiusz; Kamieński, Bohdan; Jaźwiński, Jarosław

    2015-05-01

    Seven new oligomeric complexes of 4,4'-bipyridine; 3,3'-bipyridine; benzene-1,4-diamine; benzene-1,3-diamine; benzene-1,2-diamine; and benzidine with rhodium tetraacetate, as well as 4,4'-bipyridine with molybdenum tetraacetate, have been obtained and investigated by elemental analysis and solid-state nuclear magnetic resonance spectroscopy, (13)C and (15)N CPMAS NMR. The known complexes of pyrazine with rhodium tetrabenzoate, benzoquinone with rhodium tetrapivalate, 4,4'-bipyridine with molybdenum tetrakistrifluoroacetate and the 1 : 1 complex of 2,2'-bipyridine with rhodium tetraacetate exhibiting axial-equatorial ligation mode have been obtained as well for comparison purposes. Elemental analysis revealed 1 : 1 complex stoichiometry of all complexes. The (15)N CPMAS NMR spectra of all new complexes consist of one narrow signal, indicating regular uniform structures. Benzidine forms a heterogeneous material, probably containing linear oligomers and products of further reactions. The complexes were characterized by the parameter complexation shift Δδ (Δδ = δcomplex  - δligand). This parameter ranged from around -40 to -90 ppm in the case of heteroaromatic ligands, from around -12 to -22 ppm for diamines and from -16 to -31 ppm for the complexes of molybdenum tetracarboxylates with 4,4'-bipyridine. The experimental results have been supported by a density functional theory computation of (15)N NMR chemical shifts and complexation shifts at the non-relativistic Becke, three-parameter, Perdew-Wang 91/[6-311++G(2d,p), Stuttgart] and GGA-PBE/QZ4P levels of theory and at the relativistic scalar and spin-orbit zeroth order regular approximation/GGA-PBE/QZ4P level of theory. Nucleus-independent chemical shifts have been calculated for the selected compounds. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Characterization of organic matter in sediment cores of the Todos os Santos Bay, Bahia, Brazil, by elemental analysis and 13C NMR

    International Nuclear Information System (INIS)

    Costa, A.B.; Novotny, E.H.; Bloise, A.C.; Azevedo, E.R. de; Bonagamba, T.J.; Zucchi, M.R.; Santos, V.L.C.S.; Azevedo, A.E.G.

    2011-01-01

    Highlights: → The impact of human activity on the sediments of Todos os Santos Bay in Brazil was evaluated by EA and 13 C NMR. → This article reports a study of six sediment cores collected at different depths and regions. → The elemental profiles of cores suggest an abrupt change in the sedimentation regime, corresponds to about 50 years ago, coinciding with the implantation of major onshore industrial projects. → The results presented illustrate several important aspects of environmental impact of human activity on this bay. - Abstract: The impact of human activity on the sediments of Todos os Santos Bay in Brazil was evaluated by elemental analysis and 13 C Nuclear Magnetic Resonance ( 13 C NMR). This article reports a study of six sediment cores collected at different depths and regions of Todos os Santos Bay. The elemental profiles of cores collected on the eastern side of Frades Island suggest an abrupt change in the sedimentation regime. Autoregressive Integrated Moving Average (ARIMA) analysis corroborates this result. The range of depths of the cores corresponds to about 50 years ago, coinciding with the implantation of major onshore industrial projects in the region. Principal Component Analysis of the 13 C NMR spectra clearly differentiates sediment samples closer to the Subae estuary, which have high contents of terrestrial organic matter, from those closer to a local oil refinery. The results presented in this article illustrate several important aspects of environmental impact of human activity on this bay.

  11. Determination of the anomeric specificity of the Escherichia coli CTP:CMP-3-deoxy-D-manno-octulosonate cytidylyltransferase by 13C NMR spectroscopy

    International Nuclear Information System (INIS)

    Kohlbrenner, W.E.; Fesik, S.W.

    1985-01-01

    [99%, 1- 13 C]- and [90%, 2- 13 C]3-deoxy-D-manno-octulosonic acid (KDO) were prepared enzymatically and used to determine the anomeric specificity of the CTP:CMP-3-deoxy-D-manno-octulosonate cytidylyl transferase (CMP-KDO synthetase) by 13 C NMR spectroscopy. Addition of CMP-KDO synthetase to reaction mixtures containing either 1- 13 C- or 2- 13 C-labeled KDO resulted in rapid CMP-KDO formation which was accompanied by a substantial decrease in the 13 C-enriched resonances of the beta-pyranose form of KDO relative to the resonances of other KDO species in solution, demonstrating that the beta-pyranose is the preferred substrate. Concomitant with the production of CMP-KDO was the appearance of peaks at 174.3 and 101.4 ppm when [1- 13 C]- and [2- 13 C]KDO, respectively, were used as substrates. The correspondence of these resonances to the enriched carbons in CMP-KDO was confirmed by the expected 3-bond (3JP,C-1 = 6.9 Hz) and 2-bond coupling (2JP,C-2 = 8.3 Hz) between the labeled carbons and the ketosidically linked phosphoryl group. A large coupling (3J = 5.7 Hz) was observed in proton-coupled spectra of CMP-[1- 13 C]KDO between carbon 1 and the axial proton at carbon 3 of KDO. The magnitude of this coupling constant supports a diaxial relationship between these two groups and, along with chemical shift data, indicates that KDO retains the beta-configuration when linked in CMP-KDO

  12. Total assignment of 1 H and 13 C NMR of Cordiachrome C, a terpenoid benzoquinone from Cordia trichotoma

    International Nuclear Information System (INIS)

    Alencar, Jane Eire; Pessoa, Otilia Deusdenia Loiola; Lemos, Tlema Leda Gomes de; Silveira, Edilberto Rocha; Braz Filho, Raimundo

    1999-01-01

    1 D and 2 D NMR techniques were applied for establishing of the complete assignment of hydrogen and carbon-13 NMR of cordiachrome C. Th results were also used to confirm 1 H NMR data already published, as well as to define the relative stereochemistry, which has not been completely established for cordiachrome C, previously isolated from C. millenii

  13. Total assignment of {sup 1} H and {sup 13} C NMR of Cordiachrome C, a terpenoid benzoquinone from Cordia trichotoma

    Energy Technology Data Exchange (ETDEWEB)

    Alencar, Jane Eire; Pessoa, Otilia Deusdenia Loiola; Lemos, Tlema Leda Gomes de; Silveira, Edilberto Rocha [Ceara Univ., Fortaleza, CE (Brazil). Dept. de Quimica Organica e Inorganica; Braz Filho, Raimundo [Universidade Estadual do Norte Fluminense (UENF), Campos dos Goytacazes, RJ (Brazil). Setor de Quimica de Produtos Naturais

    1999-05-01

    1 D and 2 D NMR techniques were applied for establishing of the complete assignment of hydrogen and carbon-13 NMR of cordiachrome C. Th results were also used to confirm {sup 1} H NMR data already published, as well as to define the relative stereochemistry, which has not been completely established for cordiachrome C, previously isolated from C. millenii.

  14. 13C NMR and XPS characterization of anion adsorbent with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse

    International Nuclear Information System (INIS)

    Cao, Wei; Wang, Zhenqian; Zeng, Qingling; Shen, Chunhua

    2016-01-01

    Highlights: • 13 C NMR and XPS were successfully used to characterize quaternary ammonium groups in the surface of crop straw based anion adsorbents. • The results obtained from different kinds of crop straw material clearly confirmed the presence of quaternary ammonium groups. • The composition of C-groups and N-groups also were determined by curving fitting of high-resolution XPS C1 and N1 spectra. - Abstract: Despite amino groups modified crop straw has been intensively studied as new and low-cost adsorbent for removal of anionic species from water, there is still a lack of clear characterization for amino groups, especially quaternary ammonium groups in the surface of crop straw. In this study, we used 13 C NMR and XPS technologies to characterize adsorbents with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse. 13 C NMR spectra clearly showed the presence of quaternary ammonium groups in lignocelluloses structure of modified crop straw. The increase of nitrogen observed in XPS survey spectra also indicated the existence of quaternary ammonium group in the surface of the adsorbents. The curve fitting of high-resolution XPS N1s and C1s spectra were conducted to probe the composition of nitrogen and carbon contained groups, respectively. The results showed the proportion of quaternary ammonium group significantly increased in the prepared adsorbent’s surface that was dominated by methyl/methylene, hydroxyl, quaternary ammonium, ether and carbonyl groups. This study proved that 13 C NMR and XPS could be successfully utilized for characterization of quaternary ammonium modified crop straw adsorbents.

  15. {sup 13}C NMR and XPS characterization of anion adsorbent with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse

    Energy Technology Data Exchange (ETDEWEB)

    Cao, Wei, E-mail: weicao@hqu.edu.cn; Wang, Zhenqian; Zeng, Qingling; Shen, Chunhua

    2016-12-15

    Highlights: • {sup 13}C NMR and XPS were successfully used to characterize quaternary ammonium groups in the surface of crop straw based anion adsorbents. • The results obtained from different kinds of crop straw material clearly confirmed the presence of quaternary ammonium groups. • The composition of C-groups and N-groups also were determined by curving fitting of high-resolution XPS C1 and N1 spectra. - Abstract: Despite amino groups modified crop straw has been intensively studied as new and low-cost adsorbent for removal of anionic species from water, there is still a lack of clear characterization for amino groups, especially quaternary ammonium groups in the surface of crop straw. In this study, we used {sup 13}C NMR and XPS technologies to characterize adsorbents with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse. {sup 13}C NMR spectra clearly showed the presence of quaternary ammonium groups in lignocelluloses structure of modified crop straw. The increase of nitrogen observed in XPS survey spectra also indicated the existence of quaternary ammonium group in the surface of the adsorbents. The curve fitting of high-resolution XPS N1s and C1s spectra were conducted to probe the composition of nitrogen and carbon contained groups, respectively. The results showed the proportion of quaternary ammonium group significantly increased in the prepared adsorbent’s surface that was dominated by methyl/methylene, hydroxyl, quaternary ammonium, ether and carbonyl groups. This study proved that {sup 13}C NMR and XPS could be successfully utilized for characterization of quaternary ammonium modified crop straw adsorbents.

  16. 13C NMR and XPS characterization of anion adsorbent with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse

    Science.gov (United States)

    Cao, Wei; Wang, Zhenqian; Zeng, Qingling; Shen, Chunhua

    2016-12-01

    Despite amino groups modified crop straw has been intensively studied as new and low-cost adsorbent for removal of anionic species from water, there is still a lack of clear characterization for amino groups, especially quaternary ammonium groups in the surface of crop straw. In this study, we used 13C NMR and XPS technologies to characterize adsorbents with quaternary ammonium groups prepared from rice straw, corn stalk and sugarcane bagasse. 13C NMR spectra clearly showed the presence of quaternary ammonium groups in lignocelluloses structure of modified crop straw. The increase of nitrogen observed in XPS survey spectra also indicated the existence of quaternary ammonium group in the surface of the adsorbents. The curve fitting of high-resolution XPS N1s and C1s spectra were conducted to probe the composition of nitrogen and carbon contained groups, respectively. The results showed the proportion of quaternary ammonium group significantly increased in the prepared adsorbent's surface that was dominated by methyl/methylene, hydroxyl, quaternary ammonium, ether and carbonyl groups. This study proved that 13C NMR and XPS could be successfully utilized for characterization of quaternary ammonium modified crop straw adsorbents.

  17. One-azabicyclic compounds. 22. Stereochemistry and /sup 13/C NMR spectra of salts of pyrrolizidine and its homologs with protonic acids

    Energy Technology Data Exchange (ETDEWEB)

    Subbotin, O.A.; Skvortsov, I.M.

    1986-06-01

    /sup 13/C NMR spectra were obtained for pyrrolizidinium salts and their homologs and their signals were assigned. With the exception of highly strained cis-3,8-H-cis-5,8-H-3,5-dimethylpyrrolizidine (VI), all the bases studied upon their direct mixing with CF/sub 3/CO/sub 2/H form salts only with cis-fused rings in the cation. Mixtures of salts with cis- and trans-fused pyrrolizidinium fragments are formed upon the reaction of cis-3,8-H-methyl- (III) and cis-3,8-H-cis-5,8-H-3,5-dimethylpyrrolizidine (VI) under conditions close to those for kinetically-controlled amine protonation. The /sup 13/C NMR spectra of the isomeric pyrrolizidinium salts obtained as a result of the absorption of base VI by sulfuric acid were used to evaluate the conformational equilibrium in the starting compound VI. The /sup 13/C NMR chemical shifts of unsubstituted trans-fused pyrrolizidinium salts were predicted.

  18. 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.

    Science.gov (United States)

    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. Copyright © 2011 Elsevier B.V. All rights reserved.

  19. 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: international collaborative study report.

    Science.gov (United States)

    Thomas, Freddy; Jamin, Eric

    2009-09-01

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

  20. 2H NMR and 13C-IRMS analyses of acetic acid from vinegar, 18O-IRMS analysis of water in vinegar: International collaborative study report

    International Nuclear Information System (INIS)

    Thomas, Freddy; Jamin, Eric

    2009-01-01

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

  1. Relaxation-compensated difference spin diffusion NMR for detecting {sup 13}C–{sup 13}C long-range correlations in proteins and polysaccharides

    Energy Technology Data Exchange (ETDEWEB)

    Wang, Tuo; Williams, Jonathan K. [Massachusetts Institute of Technology, Department of Chemistry (United States); Schmidt-Rohr, Klaus [Brandeis University, Department of Chemistry (United States); Hong, Mei, E-mail: meihong@mit.edu [Massachusetts Institute of Technology, Department of Chemistry (United States)

    2015-02-15

    The measurement of long-range distances remains a challenge in solid-state NMR structure determination of biological macromolecules. In 2D and 3D correlation spectra of uniformly {sup 13}C-labeled biomolecules, inter-residue, inter-segmental, and intermolecular {sup 13}C–{sup 13}C cross peaks that provide important long-range distance constraints for three-dimensional structures often overlap with short-range cross peaks that only reflect the covalent structure of the molecule. It is therefore desirable to develop new approaches to obtain spectra containing only long-range cross peaks. Here we show that a relaxation-compensated modification of the commonly used 2D {sup 1}H-driven spin diffusion (PDSD) experiment allows the clean detection of such long-range cross peaks. By adding a z-filter to keep the total z-period of the experiment constant, we compensate for {sup 13}C T{sub 1} relaxation. As a result, the difference spectrum between a long- and a scaled short-mixing time spectrum show only long-range correlation signals. We show that one- and two-bond cross peaks equalize within a few tens of milliseconds. Within ∼200 ms, the intensity equilibrates within an amino acid residue and a monosaccharide to a value that reflects the number of spins in the local network. With T{sub 1} relaxation compensation, at longer mixing times, inter-residue and inter-segmental cross peaks increase in intensity whereas intra-segmental cross-peak intensities remain unchanged relative to each other and can all be subtracted out. Without relaxation compensation, the difference 2D spectra exhibit both negative and positive intensities due to heterogeneous T{sub 1} relaxation in most biomolecules, which can cause peak cancellation. We demonstrate this relaxation-compensated difference PDSD approach on amino acids, monosaccharides, a crystalline model peptide, a membrane-bound peptide and a plant cell wall sample. The resulting difference spectra yield clean multi-bond, inter

  2. Relaxation-compensated difference spin diffusion NMR for detecting 13C–13C long-range correlations in proteins and polysaccharides

    International Nuclear Information System (INIS)

    Wang, Tuo; Williams, Jonathan K.; Schmidt-Rohr, Klaus; Hong, Mei

    2015-01-01

    The measurement of long-range distances remains a challenge in solid-state NMR structure determination of biological macromolecules. In 2D and 3D correlation spectra of uniformly 13 C-labeled biomolecules, inter-residue, inter-segmental, and intermolecular 13 C– 13 C cross peaks that provide important long-range distance constraints for three-dimensional structures often overlap with short-range cross peaks that only reflect the covalent structure of the molecule. It is therefore desirable to develop new approaches to obtain spectra containing only long-range cross peaks. Here we show that a relaxation-compensated modification of the commonly used 2D 1 H-driven spin diffusion (PDSD) experiment allows the clean detection of such long-range cross peaks. By adding a z-filter to keep the total z-period of the experiment constant, we compensate for 13 C T 1 relaxation. As a result, the difference spectrum between a long- and a scaled short-mixing time spectrum show only long-range correlation signals. We show that one- and two-bond cross peaks equalize within a few tens of milliseconds. Within ∼200 ms, the intensity equilibrates within an amino acid residue and a monosaccharide to a value that reflects the number of spins in the local network. With T 1 relaxation compensation, at longer mixing times, inter-residue and inter-segmental cross peaks increase in intensity whereas intra-segmental cross-peak intensities remain unchanged relative to each other and can all be subtracted out. Without relaxation compensation, the difference 2D spectra exhibit both negative and positive intensities due to heterogeneous T 1 relaxation in most biomolecules, which can cause peak cancellation. We demonstrate this relaxation-compensated difference PDSD approach on amino acids, monosaccharides, a crystalline model peptide, a membrane-bound peptide and a plant cell wall sample. The resulting difference spectra yield clean multi-bond, inter-residue and intermolecular correlation peaks

  3. Analysis of mercerization process based on the intensity change of deconvoluted resonances of 13C CP/MAS NMR: Cellulose mercerized under cooling and non-cooling conditions

    International Nuclear Information System (INIS)

    Miura, Kento; Nakano, Takato

    2015-01-01

    The area intensity change of C1, C4, and C6 in spectrum obtained by 13 C CP/MAS NMR and the mutual relationship between their changes were examined for cellulose samples treated with various concentrations of aqueous NaOH solutions under non-cooling and cooling conditions. The area intensity of C1-up and C6-down changed cooperatively with that of C4-down which corresponds to the crystallinity of samples: “-up” and “-down” are the up- and down- field component in a splitting peak of NMR spectrum, respectively. The intensity change of C1-up starts to decrease with decreasing in that of C4-down after that of C6-down is almost complete. These changes were more clearly observed for samples treated under cooling condition. It can be suggested that their characteristic change relates closely to the change in conformation of cellulose chains by induced decrystallization and the subsequent crystallization of cellulose II, and presumed that their changes at microscopic level relate to the macroscopic morphological changes such as contraction along the length of cellulose chains and recovery along the length. - Highlight: • Samples were mercerized at various NaOH concentrations under non-cooling and cooling. • The intensity change of C1 starts immediately after that of C6 is complete. • The creation of cell-II starts when decrystallization proceeds to a certain state. • This change relates closely to the change in conformation of cellulose chains. • The above change is more clearly found for samples treated under cooling

  4. Carbon-13 composition of bulk dry wines by irm-EA/MS and irm-13C NMR: An indicator of vine water status

    Directory of Open Access Journals (Sweden)

    Guyon Francois

    2017-01-01

    Full Text Available Measurements performed on a set of 32 authentic wines (not submitted to any oenological treatment and their ethanol, recovered by distillation, show high correlation between δ13C of bulk wine and its ethanol. These measurements were performed by isotope ratio monitoring by mass spectrometry coupled to an elemental analyzer (irm-EA/MS. Then a series of wines produced by vines of which water status was assessed during the growing season with predawn leaf water potential measurements, was studied by irm-EA/MS. As expected δ13C is correlated to vine water status conditions, as a result of stomatal closure. The ethanol of these specific wines was also analyzed by isotope ratio monitoring and by nuclear magnetic resonance (irm-13C NMR to determine carbon-13 composition on the two specific sites of the ethanol skeleton. If these measurements confirm the correlation between 13C composition and vine growth conditions, the 13C stereospecific information does not make vine water status assessment more precise.

  5. In vivo assessment of intracellular redox state in rat liver using hyperpolarized [1-13 C]Alanine.

    Science.gov (United States)

    Park, Jae Mo; Khemtong, Chalermchai; Liu, Shie-Chau; Hurd, Ralph E; Spielman, Daniel M

    2017-05-01

    The intracellular lactate to pyruvate concentration ratio is a commonly used tissue assay biomarker of redox, being proportional to free cytosolic [NADH]/[NAD + ]. In this study, we assessed the use of hyperpolarized [1- 13 C]alanine and the subsequent detection of the intracellular products of [1- 13 C]pyruvate and [1- 13 C]lactate as a useful substrate for assessing redox levels in the liver in vivo. Animal experiments were conducted to measure in vivo metabolism at baseline and after ethanol infusion. A solution of 80-mM hyperpolarized [1- 13 C]alanine was injected intravenously at baseline (n = 8) and 45 min after ethanol infusion (n = 4), immediately followed by the dynamic acquisition of 13 C MRS spectra. In vivo rat liver spectra showed peaks from [1- 13 C] alanine and the products of [1- 13 C]lactate, [1- 13 C]pyruvate, and 13 C-bicarbonate. A significantly increased 13 C-lactate/ 13 C-pyruvate ratio was observed after ethanol infusion (8.46 ± 0.58 at baseline versus 13.58 ± 0.69 after ethanol infusion; P alanine is presented, with the validity of the proposed 13 C-pyruvate/ 13 C-lactate metric tested using an ethanol challenge to alter liver redox state. Magn Reson Med 77:1741-1748, 2017. © 2017 International Society for Magnetic Resonance in Medicine. © 2017 International Society for Magnetic Resonance in Medicine.

  6. The anomalous substituent effect of the ethyl group in the 13 C NMR and IR data of some aliphatic nitriles

    International Nuclear Information System (INIS)

    Garcia, Janaina C.; Barbarini, Jose E.; Rittner, Roberto; Rocco, Silvana A.; Tormena, Claudio F.

    1999-01-01

    This work reports a full assignment of 13 C and 1 H chemical shifts for some aliphatic nitriles from acetonitrile to octanonitrile and the observed shieldings for the carbon cyano group are correlated with the ν CN and with the electronic and steric parameters

  7. Synthesis of ring-13C-labelled and ring-demethylated retinals

    International Nuclear Information System (INIS)

    Courtin, J.M.L.

    1988-01-01

    Efficient synthetic schemes are described for the preparation of the required mono- and di- 13 C labelled retinals based on simple 13 C labelled starting materials. Results from solid-state 13 C-NMR spectroscopic studies of the various ring- 13 C labelled bacteriorhodopsins and rhodopsins are discussed. 404 refs.; 74 figs.; 16 tabs

  8. Internal motion time scales of a small, highly stable and disulfide-rich protein: A 15N, 13C NMR and molecular dynamics study

    International Nuclear Information System (INIS)

    Guenneugues, Marc; Gilquin, Bernard; Wolff, Nicolas; Menez, Andre; Zinn-Justin, Sophie

    1999-01-01

    Motions of the backbone CαHα and threonine CβHβ bonds of toxin α were investigated using natural abundance 13C NMR and molecular dynamics. Measurement of the 13C longitudinal and transverse relaxation rates employed ACCORDION techniques together with coherence selection by pulsed field gradients and sensitivity enhancement through the use of preservation of equivalent pathway, thus allowing a considerable reduction of the required spectrometer time. 13C R1, R2, 1H → 13C NOE were obtained, as well as the variations of R1ρ(90 deg.) as a function of the rf field strength. These data were compared to those recorded by 1H and 15N NMR on a labelled sample of the toxin [Guenneugues et al. (1997) Biochemistry, 36, 16097-16108]. Both sets of data showed that picosecond to nanosecond time scale motions are well correlated to the secondary structure of the protein. This was further reinforced by the analysis of a 1 ns molecular dynamics simulation in water. Several CαHα and threonine CβHβ experimentally exhibit fast motions with a correlation time longer than 500 ps, that cannot be sampled along the simulation. In addition, the backbone exhibits motions on the microsecond to millisecond time scale on more than half of its length. Thus, toxin α, a highly stable protein (Tm=75 deg. C at acidic pH) containing 61 amino acids and 4 disulfides, shows important internal motions on time scales ranging from 0.1-0.5 ps, to 10-100 ps, 1 ns, and about 30 μs to 10 ms

  9. Soil nitrogen mineralisation and organic matter composition revealed by 13C NMR spectroscopy under repeated prescribed burning in eucalypt forests of south-east Queensland

    International Nuclear Information System (INIS)

    Guinto, D. F.; Saffigna, P. G.; Xu, Z. H.; House, A. P. N.; Perera, M. C. S.

    1999-01-01

    The effects of burning on in situ extractable nitrogen (NH + 4 -N+NO - 3 -N) and net N mineralisation following scheduled fuel reduction burns in repeatedly burnt dry and wet sclerophyll forest sites in south-east Queensland were assessed. In addition, soil organic matter composition in the wet sclerophyll site was assessed by 13 C NMR spectroscopy. The results showed that at the dry sclerophyll site, extractable N and net N mineralisation for 1 year were largely unaffected by burning, while at the wet sclerophyll site, these parameters decreased. 13 C NMR analysis of soil samples from the wet sclerophyll site revealed that there was a significant reduction in the proportion of O-alkyl (alkoxy/carbohydrate) C with increasing burning frequency. Statistically significant effects on the other chemical shift regions were not detected. The ratio of alkyl C to O-alkyl C, a proposed index of organic matter decomposition, increased with increasing burning frequency. A high ratio of alkyl C to O-alkyl C suggests low amounts of carbohydrates relative to waxes and cutins, which could in turn lead to slower mineralisation. The findings are in accord with this hypothesis. There were significant linear relationships between cumulative N mineralisation for 1 year and the proportions of alkyl C and O-alkyl C, and the ratio of alkyl C/O-alkyl C. Thus, in addition to reductions in substrate quantity (low organic C and total N for burnt soils), there was also an alteration of substrate quality as revealed by 13 C NMR spectroscopy which is reflected in low N mineralisation. Copyright (1999) CSIRO Publishing

  10. 1H and 13C NMR Chemical Shift Assignments and Conformational Analysis for the Two Diastereomers of the Vitamin K Epoxide Reductase Inhibitor Brodifacoum

    International Nuclear Information System (INIS)

    Cort, John R.; Cho, Herman M.

    2009-01-01

    Proton and 13C NMR chemical shift assignments and 1H-1H scalar couplings for the two diastereomers of the vitamin K epoxide reductase (VKOR) inhibitor brodifacoum have been determined from acetone solutions containing both diastereomers. Data were obtained from homo- and heteronuclear correlation spectra acquired at 1H frequencies of 750 and 900 MHz over a 268-303 K temperature range. Conformations inferred from scalar coupling and 1-D NOE measurements exhibit large differences between the diastereomers. Pacific Northwest National Laboratory is operated by Battelle for the US Department of Energy.

  11. Oxidative stress-induced metabolic changes in mouse C2C12 myotubes studied with high-resolution 13C, 1H, and 31P NMR spectroscopy

    DEFF Research Database (Denmark)

    Straadt, Ida K; Young, Jette F; Petersen, Bent O

    2010-01-01

    In this study, stress in relation to slaughter was investigated in a model system by the use of (13)C, (1)H, and (31)P nuclear magnetic resonance (NMR) spectroscopy for elucidating changes in the metabolites in C2C12 myotubes exposed to H(2)O(2)-induced stress. Oxidative stress resulted in lower...... to lower levels of the unlabeled ((12)C) lactate were identified in the (1)H spectra after stress exposure. These data indicate an increase in de novo synthesis of alanine, concomitant with a release of lactate from the myotubes to the medium at oxidative stress conditions. The changes in the metabolite...

  12. Chemotaxonomy of three genera of the Annonaceae family using self-organizing maps and {sup 13}C NMR data of diterpenes

    Energy Technology Data Exchange (ETDEWEB)

    Scotti, Luciana; Tavares, Josean Fechine; Silva, Marcelo Sobral da [Universidade Federal da Paraiba (UFPB), Joao Pessoa, PB (Brazil). Dept. de Ciencias Farmaceuticas; Falcao, Emanuela Viana; Silva, Luana de Morais e; Soares, Gabriela Cristina da Silva; Scotti, Marcus Tullius, E-mail: mtscotti@ccae.ufpb.br [Universidade Federal da Paraiba (UFPB), Rio Tinto, PB (Brazil). Dept. de Engenharia e Meio Ambiente

    2012-07-01

    The Annonaceae family is distributed throughout Neotropical regions of the world. In Brazil, it covers nearly all natural formations particularly Annona, Xylopia and Polyalthia and is characterized chemically by the production of sources of terpenoids (mainly diterpenes), alkaloids, steroids, polyphenols and, flavonoids. Studies from {sup 13}C NMR data of diterpenes related with their botanical occurrence were used to generate self-organizing maps. Results corroborate those in the literature obtained from morphological and molecular data for three genera and the model can be used to project other diterpenes. Therefore, the model produced can predict which genera are likely to contain a compound. (author)

  13. /sup 1/H- and /sup 13/C-NMR spectroscopic study of glucose metabolism in eggs of Angiostrongylus cantonensis during their development

    Energy Technology Data Exchange (ETDEWEB)

    Takahashi, M.; Kato, K.; Ohsaka, A.; Nishina, M.; Hori, E.; Matsushita, K.

    1987-02-01

    /sup 1/H- and /sup 13/C-nuclear magnetic resonance (NMR) spectroscopy was used to study aerobic glucose metabolism in eggs of Angiostrongylus cantonensis in an NCTC-109 medium supplemented with fetal calf serum. Without any pretreatment of the spent medium, we were able to identify and quantitate, by NMR, the end-products of glucose metabolism in eggs after cultivation for 2, 4, and 8 days. We demonstrated that A. cantonensis eggs took up glucose rapidly; among the major end products were found lactic acid, acetic acid and alanine. The eggs are parasitic in a sense that the energy metabolism in them is dependent mainly upon the energy source present in outer medium.

  14. Dynamics of the carbohydrate chains attached to the Fc portion of immunoglobulin G as studied by NMR spectroscopy assisted by selective 13C labeling of the glycans

    International Nuclear Information System (INIS)

    Yamaguchi, Yoshiki; Kato, Koichi; Shindo, Mitsuru; Aoki, Shin; Furusho, Kumiko; Koga, Kenji; Takahashi, Noriko; Arata, Yoji; Shimada, Ichio

    1998-01-01

    A systematic method for 13 C labeling of the glycan of immunoglobulin G for NMR study has been developed. A mouse immunoglobulin of subclass IgG2b has been used for the experiment. On the basis of chemical shift and linewidth data, it has been concluded that (1) the mobility of the carbohydrate chain in IgG2b is comparable to that of the backbone polypeptide chain with the exception of the galactose residue at the nonreducing end of the Man α 1-3 branch, which is extremely mobile and (2) agalactosylation does not induce any significant change in the mobility. The results obtained indicate that even in the agalactosyl form the glycans are buried in the protein. Biological significance of the NMR results obtained is also briefly discussed

  15. Fate of [15N]glycine in peat as determined by 13C and 15N CP-MAS NMR spectroscopy

    International Nuclear Information System (INIS)

    Benzing-Purdie, L.M.; Cheshire, M.V.; Williams, B.L.; Sparling, G.P.; Ratcliffe, C.I.; Ripmeester, J.A.

    1986-01-01

    Peat samples, nonsterile, sterilized by γ irradiation or autoclaving, were incubated with [ 15 N]glycine for a period of 6 months. The 13 C NMR data showed the established trend of increased humification with decreasing particle size and that autoclaving had significantly disturbed the humification-particle size distribution. The 15 N CP-MAS NMR spectra showed the presence of [ 15 N]glycine in all fractions after incubation. 15 NH 4 + , a result of either biological or chemical deamination, was one of the main products in the nonsterile peat series. The 15 N spectra also showed resonances corresponding to amine, secondary amide, and pyrrole-type nitrogen and the presence of glycine derivatives and melanoidins. The results presented give the first spectroscopic evidence of the possible involvement of the Maillard reaction in the humification process

  16. NMR characterization of HtpG, the E. coli Hsp90, using sparse labeling with 13C-methyl alanine.

    Science.gov (United States)

    Pederson, Kari; Chalmers, Gordon R; Gao, Qi; Elnatan, Daniel; Ramelot, Theresa A; Ma, Li-Chung; Montelione, Gaetano T; Kennedy, Michael A; Agard, David A; Prestegard, James H

    2017-07-01

    A strategy for acquiring structural information from sparsely isotopically labeled large proteins is illustrated with an application to the E. coli heat-shock protein, HtpG (high temperature protein G), a 145 kDa dimer. It uses 13 C-alanine methyl labeling in a perdeuterated background to take advantage of the sensitivity and resolution of Methyl-TROSY spectra, as well as the backbone-centered structural information from 1 H- 13 C residual dipolar couplings (RDCs) of alanine methyl groups. In all, 40 of the 47 expected crosspeaks were resolved and 36 gave RDC data. Assignments of crosspeaks were partially achieved by transferring assignments from those made on individual domains using triple resonance methods. However, these were incomplete and in many cases the transfer was ambiguous. A genetic algorithm search for consistency between predictions based on domain structures and measurements for chemical shifts and RDCs allowed 60% of the 40 resolved crosspeaks to be assigned with confidence. Chemical shift changes of these crosspeaks on adding an ATP analog to the apo-protein are shown to be consistent with structural changes expected on comparing previous crystal structures for apo- and complex- structures. RDCs collected on the assigned alanine methyl peaks are used to generate a new solution model for the apo-protein structure.

  17. Pre-physical treatment: an important procedure to improve spectral resolution in polymers microstructure studies using 13C solution NMR

    International Nuclear Information System (INIS)

    Pedroza, Oscar J.O.; Tavares, Maria I.B.

    2004-01-01

    Changes in physical properties of polymeric materials can be evaluated from their microstructures, which can be investigated using solution carbon-13 nuclear magnetic resonance (NMR). In this type of study spectral resolution is very important, which obviously depend on the sample and solvent. A pre physical treatment allows for an improvement in the spectral resolution. Consequently, more information on chain linking can be obtained, thus facilitating the determination of the stereo sequences. (author)

  18. Magnetic resonance spectroscopy and metabolism. Applications of proton and sup 13 C NMR to the study of glutamate metabolism in cultured glial cells and human brain in vivo

    Energy Technology Data Exchange (ETDEWEB)

    Portais, J.C.; Pianet, I.; Merle, M.; Raffard, G.; Biran, M.; Labouesse, J.; Canioni, P. (Bordeaux-2 Univ., 33 (FR)); Allard, M.; Kien, P.; Caille, J.M. (Centre Hospitalier Universitaire, 33 Bordeaux (FR))

    1991-01-01

    Nuclear magnetic resonance (NMR) spectroscopy was used to study the metabolism of cells from the central nervous system both in vitro on perchloric acid extracts obtained either from cultured tumoral cells (C6 rat glioma) or rat astrocytes in primary culture, and in vivo within the human brain. Analysis of carbon 13 NMR spectra of perchloric acid extracts prepared from cultured cells in the presence of NMR (1-{sup 13}C) glucose as substrate allowed determination of the glutamate and glutamine enrichments in both normal and tumoral cells. Preliminary results indicated large changes in the metabolism of these amino acids (and also of aspartate and alanine) in the C6 cell as compared to its normal counterpart. Localized proton NMR spectra of the human brain in vivo were obtained at 1.5 T, in order to evaluate the content of various metabolites, including glutamate, in peritumoral edema from a selected volume of 2 x 2 x 2 cm{sup 3}. N-acetyl aspartate, glutamate, phosphocreatine, creatine, choline and inositol derivative resonances were observed in 15 min spectra. N-acetyl-aspartate was found to be at a lower level in contrast to glutamate which was detected at a higher level in the injured area as compared to the controlateral unaffected side.

  19. Benchmarking of density functionals for a soft but accurate prediction and assignment of (1) H and (13)C NMR chemical shifts in organic and biological molecules.

    Science.gov (United States)

    Benassi, Enrico

    2017-01-15

    A number of programs and tools that simulate 1 H and 13 C nuclear magnetic resonance (NMR) chemical shifts using empirical approaches are available. These tools are user-friendly, but they provide a very rough (and sometimes misleading) estimation of the NMR properties, especially for complex systems. Rigorous and reliable ways to predict and interpret NMR properties of simple and complex systems are available in many popular computational program packages. Nevertheless, experimentalists keep relying on these "unreliable" tools in their daily work because, to have a sufficiently high accuracy, these rigorous quantum mechanical methods need high levels of theory. An alternative, efficient, semi-empirical approach has been proposed by Bally, Rablen, Tantillo, and coworkers. This idea consists of creating linear calibrations models, on the basis of the application of different combinations of functionals and basis sets. Following this approach, the predictive capability of a wider range of popular functionals was systematically investigated and tested. The NMR chemical shifts were computed in solvated phase at density functional theory level, using 30 different functionals coupled with three different triple-ζ basis sets. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

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

    KAUST Repository

    Abdul Jameel, Abdul Gani

    2016-04-22

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

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

    KAUST Repository

    Abdul Jameel, Abdul Gani; Elbaz, Ayman M.; Emwas, Abdul-Hamid M.; Roberts, William L.; Sarathy, Mani

    2016-01-01

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

  2. Introducing NMR to a General Chemistry Audience: A Structural-Based Instrumental Laboratory Relating Lewis Structures, Molecular Models, and [superscript 13]C NMR Data

    Science.gov (United States)

    Pulliam, Curtis R.; Pfeiffer, William F.; Thomas, Alyssa C.

    2015-01-01

    This paper describes a first-year general chemistry laboratory that uses NMR spectroscopy and model building to emphasize molecular shape and structure. It is appropriate for either a traditional or an atoms-first curriculum. Students learn the basis of structure and the use of NMR data through a cooperative learning hands-on laboratory…

  3. Using 1H and 13C NMR chemical shifts to determine cyclic peptide conformations: a combined molecular dynamics and quantum mechanics approach.

    Science.gov (United States)

    Nguyen, Q Nhu N; Schwochert, Joshua; Tantillo, Dean J; Lokey, R Scott

    2018-05-10

    Solving conformations of cyclic peptides can provide insight into structure-activity and structure-property relationships, which can help in the design of compounds with improved bioactivity and/or ADME characteristics. The most common approaches for determining the structures of cyclic peptides are based on NMR-derived distance restraints obtained from NOESY or ROESY cross-peak intensities, and 3J-based dihedral restraints using the Karplus relationship. Unfortunately, these observables are often too weak, sparse, or degenerate to provide unequivocal, high-confidence solution structures, prompting us to investigate an alternative approach that relies only on 1H and 13C chemical shifts as experimental observables. This method, which we call conformational analysis from NMR and density-functional prediction of low-energy ensembles (CANDLE), uses molecular dynamics (MD) simulations to generate conformer families and density functional theory (DFT) calculations to predict their 1H and 13C chemical shifts. Iterative conformer searches and DFT energy calculations on a cyclic peptide-peptoid hybrid yielded Boltzmann ensembles whose predicted chemical shifts matched the experimental values better than any single conformer. For these compounds, CANDLE outperformed the classic NOE- and 3J-coupling-based approach by disambiguating similar β-turn types and also enabled the structural elucidation of the minor conformer. Through the use of chemical shifts, in conjunction with DFT and MD calculations, CANDLE can help illuminate conformational ensembles of cyclic peptides in solution.

  4. Two dimensional solid state NMR

    International Nuclear Information System (INIS)

    Kentgens, A.P.M.

    1987-01-01

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

  5. Trace level detection of compounds related to the chemical weapons convention by 1H-detected 13C NMR spectroscopy executed with a sensitivity-enhanced, cryogenic probehead.

    Science.gov (United States)

    Cullinan, David B; Hondrogiannis, George; Henderson, Terry J

    2008-04-15

    Two-dimensional 1H-13C HSQC (heteronuclear single quantum correlation) and fast-HMQC (heteronuclear multiple quantum correlation) pulse sequences were implemented using a sensitivity-enhanced, cryogenic probehead for detecting compounds relevant to the Chemical Weapons Convention present in complex mixtures. The resulting methods demonstrated exceptional sensitivity for detecting the analytes at trace level concentrations. 1H-13C correlations of target analytes at chemical shift information could be derived quickly and simultaneously from the resulting spectra. The fast-HMQC pulse sequences generated magnitude mode spectra suitable for detailed analysis in approximately 4.5 h and can be used in experiments to efficiently screen a large number of samples. The HSQC pulse sequences, on the other hand, required roughly twice the data acquisition time to produce suitable spectra. These spectra, however, were phase-sensitive, contained considerably more resolution in both dimensions, and proved to be superior for detecting analyte 1H-13C correlations. Furthermore, a HSQC spectrum collected with a multiplicity-edited pulse sequence provided additional structural information valuable for identifying target analytes. The HSQC pulse sequences are ideal for collecting high-quality data sets with overnight acquisitions and logically follow the use of fast-HMQC pulse sequences to rapidly screen samples for potential target analytes. Use of the pulse sequences considerably improves the performance of NMR spectroscopy as a complimentary technique for the screening, identification, and validation of chemical warfare agents and other small-molecule analytes present in complex mixtures and environmental samples.

  6. NMR (1H and 13C) based signatures of abnormal choline metabolism in oral squamous cell carcinoma with no prominent Warburg effect

    International Nuclear Information System (INIS)

    Bag, Swarnendu; Banerjee, Deb Ranjan; Basak, Amit; Das, Amit Kumar; Pal, Mousumi; Banerjee, Rita; Paul, Ranjan Rashmi; Chatterjee, Jyotirmoy

    2015-01-01

    At functional levels, besides genes and proteins, changes in metabolome profiles are instructive for a biological system in health and disease including malignancy. It is understood that metabolomic alterations in association with proteomic and transcriptomic aberrations are very fundamental to unravel malignant micro-ambient criticality and oral cancer is no exception. Hence deciphering intricate dimensions of oral cancer metabolism may be contributory both for integrated appreciation of its pathogenesis and to identify any critical but yet unexplored dimension of this malignancy with high mortality rate. Although several methods do exist, NMR provides higher analytical precision in identification of cancer metabolomic signature. Present study explored abnormal signatures in choline metabolism in oral squamous cell carcinoma (OSCC) using 1 H and 13 C NMR analysis of serum. It has demonstrated down-regulation of choline with concomitant up-regulation of its break-down product in the form of trimethylamine N-oxide in OSCC compared to normal counterpart. Further, no significant change in lactate profile in OSCC possibly indicated that well-known Warburg effect was not a prominent phenomenon in such malignancy. Amongst other important metabolites, malonate has shown up-regulation but D-glucose, saturated fatty acids, acetate and threonine did not show any significant change. Analyzing these metabolomic findings present study proposed trimethyl amine N-oxide and malonate as important metabolic signature for oral cancer with no prominent Warburg effect. - Highlights: • NMR ( 1 H and 13 C) study of Oral Squamous cell Carcinoma Serum. • Abnormal Choline metabolomic signatures. • Up-regulation of Trimethylamine N-oxide. • Unchanged lactate profile indicates no prominent Warburg effect. • Proposed alternative glucose metabolism path through up-regulation of malonate

  7. NMR ({sup 1}H and {sup 13}C) based signatures of abnormal choline metabolism in oral squamous cell carcinoma with no prominent Warburg effect

    Energy Technology Data Exchange (ETDEWEB)

    Bag, Swarnendu, E-mail: Swarna.bag@gmail.com [School of Medical Science and Technology, Indian Institute of Technology-Kharagpur, 721302 West Bengal (India); Banerjee, Deb Ranjan, E-mail: debranjan2@gmail.com [Department of Chemistry, Indian Institute of Technology-Kharagpur, 721302 West Bengal (India); Basak, Amit, E-mail: absk@chem.iitkgp.ernet.in [Department of Chemistry, Indian Institute of Technology-Kharagpur, 721302 West Bengal (India); Das, Amit Kumar, E-mail: amitk@hijli.iitkgp.ernet.in [Department of Biotechnology, Indian Institute of Technology-Kharagpur, 721302 West Bengal (India); Pal, Mousumi, E-mail: drmpal62@gmail.com [Department of Oral and Maxillofacial Pathology, Guru Nanak Institute of Dental Sciences and Research, Kolkata, West Bengal (India); Banerjee, Rita, E-mail: ritabanerjee@outlook.com [Department of Science and Technology, New Mehrauli Road, New Delhi 110016 (India); Paul, Ranjan Rashmi, E-mail: dr_rsspaul@yahoo.co.in [Department of Oral and Maxillofacial Pathology, Guru Nanak Institute of Dental Sciences and Research, Kolkata, West Bengal (India); Chatterjee, Jyotirmoy, E-mail: jchatterjee.iitkgp@gmail.com [School of Medical Science and Technology, Indian Institute of Technology-Kharagpur, 721302 West Bengal (India)

    2015-04-17

    At functional levels, besides genes and proteins, changes in metabolome profiles are instructive for a biological system in health and disease including malignancy. It is understood that metabolomic alterations in association with proteomic and transcriptomic aberrations are very fundamental to unravel malignant micro-ambient criticality and oral cancer is no exception. Hence deciphering intricate dimensions of oral cancer metabolism may be contributory both for integrated appreciation of its pathogenesis and to identify any critical but yet unexplored dimension of this malignancy with high mortality rate. Although several methods do exist, NMR provides higher analytical precision in identification of cancer metabolomic signature. Present study explored abnormal signatures in choline metabolism in oral squamous cell carcinoma (OSCC) using {sup 1}H and {sup 13}C NMR analysis of serum. It has demonstrated down-regulation of choline with concomitant up-regulation of its break-down product in the form of trimethylamine N-oxide in OSCC compared to normal counterpart. Further, no significant change in lactate profile in OSCC possibly indicated that well-known Warburg effect was not a prominent phenomenon in such malignancy. Amongst other important metabolites, malonate has shown up-regulation but D-glucose, saturated fatty acids, acetate and threonine did not show any significant change. Analyzing these metabolomic findings present study proposed trimethyl amine N-oxide and malonate as important metabolic signature for oral cancer with no prominent Warburg effect. - Highlights: • NMR ({sup 1}H and {sup 13}C) study of Oral Squamous cell Carcinoma Serum. • Abnormal Choline metabolomic signatures. • Up-regulation of Trimethylamine N-oxide. • Unchanged lactate profile indicates no prominent Warburg effect. • Proposed alternative glucose metabolism path through up-regulation of malonate.

  8. Phosphorus-31, 15N, and 13C NMR of glyphosate: Comparison of pH titrations to the herbicidal dead-end complex with 5-enolpyruvoylshikimate-3-phosphate synthase

    International Nuclear Information System (INIS)

    Castellino, S.; Leo, G.C.; Sammons, R.D.; Sikorski, J.A.

    1989-01-01

    The herbicidal dead-end ternary complex (E S3P Glyph ) of glyphosate [N-(phosphonomethyl)glycine] with 5-enolpyruvoylshikimate-3-phosphate synthase (EPSPS) and the substrate shikimate 3-phosphate (S3P) has been characterized by 31 P, 15 N, and 13 C NMR. The NMR spectra of EPSPS-bound glyphosate show unique chemical shifts (δ) for each of the three nuclei. By 31 P NMR, glyphosate in the dead-end complex is a distinct species 3.5 ppm downfield from free glyphosate. The 13 C signal of glyphosate in the dead-end complex is shifted 4 ppm downfield from that of free glyphosate. The 15 N signal for glyphosate (99%) in the dead-end complex is 5 ppm further downfield than that of any free zwitterionic species and 10 ppm downfield from that of the average free species at pH 10.1. The structures of each ionic state of glyphosate are modeled with force field calculations by using MacroModel. A correlation is made for the 31 P δ and the C-P-O bond angle, and the 13 C and 15 N δ values are postulated to be related to C-C-O and C-N-C bond angles, respectively. The downfield 31 P chemical shift perturbation for S3P in the EPSPS binary complex is consistent with ionization of the 3-phosphate of S3P upon binding. Comparison with the S3P 31 P δ vs pH titration curve specifies predominantly the dianion of the 3-phosphate in the E S3P binary complex, while the E S3P Glyph complex indicates net protonation at the 3-phosphate. Chemical shift perturbations of this latter type may be explained by changes in the O-P-O bond angle

  9. Synergistic effect of the simultaneous chemometric analysis of {sup 1}H NMR spectroscopic and stable isotope (SNIF-NMR, {sup 18}O, {sup 13}C) data: Application to wine analysis

    Energy Technology Data Exchange (ETDEWEB)

    Monakhova, Yulia B., E-mail: yul-monakhova@mail.ru [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Bruker Biospin GmbH, Silberstreifen, Rheinstetten 76287 (Germany); Department of Chemistry, Saratov State University, Astrakhanskaya Street 83, Saratov 410012 (Russian Federation); Godelmann, Rolf [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Hermann, Armin [Landesuntersuchungsamt -Institut für Lebensmittelchemie und Arzneimittelprüfung, Emy-Roeder-Straße 1, Mainz 55129 (Germany); Kuballa, Thomas [Chemisches und Veterinäruntersuchungsamt (CVUA) Karlsruhe, Weissenburger Strasse 3, Karlsruhe 76187 (Germany); Cannet, Claire; Schäfer, Hartmut; Spraul, Manfred [Bruker Biospin GmbH, Silberstreifen, Rheinstetten 76287 (Germany); Rutledge, Douglas N. [AgroParisTech, UMR 1145, Ingénierie Procédés Aliments, 16 rue Claude Bernard, Paris F-75005 (France)

    2014-06-23

    Highlights: • {sup 1}H NMR profilings of 718 wines were fused with stable isotope analysis data (SNIF-NMR, {sup 18}O, {sup 13}C). • The best improvement was obtained for prediction of the geographical origin of wine. • Certain enhancement was also obtained for the year of vintage (from 88 to 97% for {sup 1}H NMR to 99% for the fused data). • Independent component analysis was used as an alternative chemometric tool for classification. - Abstract: It is known that {sup 1}H NMR spectroscopy represents a good tool for predicting the grape variety, the geographical origin, and the year of vintage of wine. In the present study we have shown that classification models can be improved when {sup 1}H NMR profiles are fused with stable isotope (SNIF-NMR, {sup 18}O, {sup 13}C) data. Variable selection based on clustering of latent variables was performed on {sup 1}H NMR data. Afterwards, the combined data of 718 wine samples from Germany were analyzed using linear discriminant analysis (LDA), partial least squares-discriminant analysis (PLS-DA), factorial discriminant analysis (FDA) and independent components analysis (ICA). Moreover, several specialized multiblock methods (common components and specific weights analysis (ComDim), consensus PCA and consensus PLS-DA) were applied to the data. The best improvement in comparison with {sup 1}H NMR data was obtained for prediction of the geographical origin (up to 100% for the fused data, whereas stable isotope data resulted only in 60–70% correct prediction and {sup 1}H NMR data alone in 82–89% respectively). Certain enhancement was obtained also for the year of vintage (from 88 to 97% for {sup 1}H NMR to 99% for the fused data), whereas in case of grape varieties improved models were not obtained. The combination of {sup 1}H NMR data with stable isotope data improves efficiency of classification models for geographical origin and vintage of wine and can be potentially used for other food products as well.

  10. Resonant states in 13C and 16,17O at high excitation energy

    International Nuclear Information System (INIS)

    Rodrigues, M R D; Borello-Lewin, T; Miyake, H; Duarte, J L M; Rodrigues, C L; Horodynski-Matsushigue, L B; Ukita, G M; Cappuzzello, F; Foti, A; Cavallaro, M; Agodi, C; Cunsolo, A; Carbone, D; Bondi, M; Napoli, M De; Roeder, B T; Linares, R; Lombardo, I

    2014-01-01

    The 9 Be( 6 Li,d) 13 C and 12,13 C( 6 Li,d) 16,17 O reactions were measured at the São Paulo Pelletron-Enge-Spectrograph facility at 25.5 MeV incident energy. The nuclear emulsion detection technique was applied. Several narrow resonances were populated up to approximately 17 MeV of excitation energy. An excellent energy resolution was obtained: 40 keV for 13 C and 15-30 keV for 16 O. The upper limit for the resonance widths were determined. Recently, d-a angular correlations were measured at θ d = 0° with incident energy of 25 MeV using the LNS Tandem-MAGNEX Spectrometer facility

  11. Resonant states in 13C and 16,17O at high excitation energy

    Science.gov (United States)

    Rodrigues, M. R. D.; Borello-Lewin, T.; Miyake, H.; Duarte, J. L. M.; Rodrigues, C. L.; Horodynski-Matsushigue, L. B.; Ukita, G. M.; Cappuzzello, F.; Cavallaro, M.; Foti, A.; Agodi, C.; Cunsolo, A.; Carbone, D.; Bondi, M.; De Napoli, M.; Roeder, B. T.; Linares, R.; Lombardo, I.

    2014-12-01

    The 9Be(6Li,d)13C and 12,13C(6Li,d)16,17O reactions were measured at the São Paulo Pelletron-Enge-Spectrograph facility at 25.5 MeV incident energy. The nuclear emulsion detection technique was applied. Several narrow resonances were populated up to approximately 17 MeV of excitation energy. An excellent energy resolution was obtained: 40 keV for 13C and 15-30 keV for 16O. The upper limit for the resonance widths were determined. Recently, d-a angular correlations were measured at θd = 0° with incident energy of 25 MeV using the LNS Tandem-MAGNEX Spectrometer facility.

  12. Determination of stability constants for thallium(III) cyanide complexes in aqueous solution by means of 13C and 205Ti NMR

    International Nuclear Information System (INIS)

    Blixt, J.; Gyori, B.; Glaser, J.

    1989-01-01

    In contrast to what is usually assumed, we have found and proved that thallium(III) forms very strong cyanide complexes in aqueous solution. The authors have investigated this system using 205 Tl, 13 C, and 14 N NMR and potentiometry and established the existence of four thallium(III)-cyanide complexes of the composition Tl(CN) n 3-n , n = 1-4. We have measured their chemical shifts and spin-spin coupling constants and determined their formation constants at 25 degree C in dilute (0.05 M) aqueous solution in the ionic medium ([Na + ] = 1 M, [Li + ] + [H + ] = 3 M, [ClO 4 - ] = 4 M). We have also determined the stability constant for HCN in the same ionic medium, log K a = 10.11 (5)

  13. Sensitivity enhanced NMR spectroscopy by quenching scalar coupling mediated relaxation: Application to the direct observation of hydrogen bonds in 13C/15N-labeled proteins

    Energy Technology Data Exchange (ETDEWEB)

    Liu Aizhuo; Hu Weidong; Qamar, Seema; Majumdar, Ananya [Memorial Sloan-Kettering Cancer Center, Cellular Biochemistry and Biophysics Program (United States)

    2000-05-15

    In this paper, we demonstrate that the sensitivity of triple-resonance NMR experiments can be enhanced significantly through quenching scalar coupling mediated relaxation by using composite-pulse decoupling (CPD) or an adiabatic decoupling sequence on aliphatic, in particular alpha-carbons in {sup 13}C/{sup 15}N-labeled proteins. The CPD-HNCO experiment renders 50% sensitivity enhancement over the conventional CT-HNCO experiment performed on a 12 kDa FK506 binding protein, when a total of 266 ms of amide nitrogen-carbonyl carbon defocusing and refocusing periods is employed. This is a typical time period for the direct detection of hydrogen bonds in proteins via trans-hydrogen bond {sup 3h}J{sub NC'} couplings. The experimental data fit theoretical analysis well. The significant enhancement in sensitivity makes the experiment more applicable to larger-sized proteins without resorting to perdeuteration.

  14. Primidone--an antiepileptic drug--characterisation by quantum chemical and spectroscopic (FTIR, FT-Raman, 1H, 13C NMR and UV-Visible) investigations.

    Science.gov (United States)

    Arjunan, V; Santhanam, R; Subramanian, S; Mohan, S

    2013-05-15

    The solid phase FTIR and FT-Raman spectra of primidone were recorded in the regions 4000-400 cm(-1) and 4000-100 cm(-1), respectively. The vibrational spectra were analysed and the observed fundamentals were assigned and analysed. The experimental wavenumbers were compared with the theoretical scaled vibrational wavenumbers determined by DFT methods. The Raman intensities were also determined with B3LYP/6-31G(d,p) method. The total electron density and molecular electrostatic potential surface of the molecule were constructed by using B3LYP/6-311++G(d,p) method to display electrostatic potential (electron+nuclei) distribution. The HOMO and LUMO energies were measured. Natural bond orbital analysis of primidone has been performed to indicate the presence of intramolecular charge transfer. The (1)H and (13)C NMR spectra were recorded and the chemical shifts of the molecule were calculated. Copyright © 2013 Elsevier B.V. All rights reserved.

  15. Structure of pyridine and quinoline vinyl ethers according to data from 1H and 13C NMR spectra and quantum-chemical calculations

    International Nuclear Information System (INIS)

    Afonin, A.V.; Voronov, V.K.; Andriankov, M.A.; Danovich, D.K.

    1987-01-01

    A systematic investigation of the structure of the vinyl ethers of heterocyclic compounds has not been undertaken. The present work was devoted to investigation of the stereochemical and electronic structure of the vinyl ethers of pyridine and quinoline. The PMR spectra of the samples were recorded for 5% solutions in deuterochloroform on a Tesla BS-497 spectrometer at 100 MHz. The 13 C NMR spectra were recorded on a Tesla BS-567A spectrometer at 25.1 MHz in deuterochloroform with the samples at concentrations of 30%. The internal standard was HMDS. The vinyl ethers of pyridine and quinoline exist preferentially in the nonplanar S-trans conformation. In the vinyl esters of pyridine and quinoline the p-π conjugation is concurrent in nature and depends on the position of the vinyloxy group in the heterocycle

  16. Unveiling the Interplay Between Diffusing CO2 and Ethanol Molecules in Champagne Wines by Classical Molecular Dynamics and (13)C NMR Spectroscopy.

    Science.gov (United States)

    Bonhommeau, David A; Perret, Alexandre; Nuzillard, Jean-Marc; Cilindre, Clara; Cours, Thibaud; Alijah, Alexander; Liger-Belair, Gérard

    2014-12-18

    The diffusion coefficients of carbon dioxide (CO2) and ethanol (EtOH) in carbonated hydroalcoholic solutions and Champagne wines are evaluated as a function of temperature by classical molecular dynamics (MD) simulations and (13)C NMR spectroscopy measurements. The excellent agreement between theoretical and experimental diffusion coefficients suggest that ethanol is the main molecule, apart from water, responsible for the value of the CO2 diffusion coefficients in typical Champagne wines, a result that could likely be extended to most sparkling wines with alike ethanol concentrations. CO2 and EtOH hydrodynamical radii deduced from viscometry measurements by applying the Stokes-Einstein relationship are found to be mostly constant and in close agreement with MD predictions. The reliability of our approach should be of interest to physical chemists aiming to model transport phenomena in supersaturated aqueous solutions or water/alcohol mixtures.

  17. Staphylococcal nuclease active-site amino acids: pH dependence of tyrosines and arginines by 13C NMR and correlation with kinetic studies

    International Nuclear Information System (INIS)

    Grissom, C.G.; Markley, J.L.

    1989-01-01

    The pH and temperature dependence of the kinetic parameters of staphylococcal nuclease have been examined with three p-nitrophenyl phosphate containing DNA analogues that vary as to 3'-substituent. With wild-type (Foggi variant) nuclease (nuclease wt) and the substrates thymidine 3'-phosphate 5'-(p-nitrophenyl phosphate) (PNPdTp), thymidine 3'-methylphosphonate 5'-(p-nitrophenyl phosphate) (PNPdTp Me), and thymidine 5'-(p-nitrophenyl phosphate) (PNPdT), k cat remains nearly constant at 13 min -1 . However, k cat /k m with nuclease wt varies considerably. The data suggests that the inflection k cat /K m with pK a at 9.67 arises from ionization of tyrosine-85, which hydrogen bonds to the divalent 3'-phosphomonester of substrates with this substituent. The enthalpy of ionization of both deprotonation steps in the k cat /K m versus pH profile is 5 kcal/mol. 13 C NMR has been used to determine the pK a values of the arginine and tyrosine residues. The results do not rule out arginine as a candidate for the acidic catalyst that protonates the 5'-ribose alkoxide prior to product release. The phenolic hydroxyl carbon of tyrosine-85 has been assigned by comparing the 13 C NMR spectrum of nuclease wt and nuclease Y85F. This correlation between pK a values along with the absence of other candidates indicates that the ionization of tyrosine-85 is the pK a seen in the k cat /K m vs pH profile for substrates with a divalent 3'-phosphomonester. This conclusion is consistent with the proposed role of tyrosine-85 as a hydrogen-bond donor to the 3'-phosphomonoester of substrates poised for exonucleolytic hydrolysis

  18. The Effect of Solvent Accessible Surface on Hammett-Type Dependencies of Infinite Dilution 29Si and 13C NMR Shifts in Ring Substituted Silylated Phenols Dissolved in Chloroform and Acetone

    Czech Academy of Sciences Publication Activity Database

    Blechta, Vratislav; Šabata, Stanislav; Sýkora, Jan; Hetflejš, Jiří; Soukupová, Ludmila; Schraml, Jan

    2012-01-01

    Roč. 50, č. 2 (2012), s. 128-134 ISSN 0749-1581 R&D Projects: GA AV ČR IAA400720706; GA ČR GA203/06/0738 Institutional research plan: CEZ:AV0Z40720504 Keywords : 1H NMR * 13C NMR * 29Si NMR Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 1.528, year: 2012

  19. Synthesis, X-ray diffraction method, spectroscopic characterization (FT-IR, 1H and 13C NMR), antimicrobial activity, Hirshfeld surface analysis and DFT computations of novel sulfonamide derivatives

    Science.gov (United States)

    Demircioğlu, Zeynep; Özdemir, Fethi Ahmet; Dayan, Osman; Şerbetçi, Zafer; Özdemir, Namık

    2018-06-01

    Synthesized compounds of N-(2-aminophenyl)benzenesulfonamide 1 and (Z)-N-(2-((2-nitrobenzylidene)amino)phenyl)benzenesulfonamide 2 were characterized by antimicrobial activity, FT-IR, 1H and 13C NMR. Two new Schiff base ligands containing aromatic sulfonamide fragment of (Z)-N-(2-((3-nitrobenzylidene)amino)phenyl)benzenesulfonamide 3 and (Z)-N-(2-((4-nitrobenzylidene)amino)phenyl)benzenesulfonamide 4 were synthesized and investigated by spectroscopic techniques including 1H and 13C NMR, FT-IR, single crystal X-ray diffraction, Hirshfeld surface, theoretical method analyses and by antimicrobial activity. The molecular geometry obtained from the X-ray structure determination was optimized Density Functional Theory (DFT/B3LYP) method with the 6-311++G(d,p) basis set in ground state. From the optimized geometry of the molecules of 3 and 4, the geometric parameters, vibrational wavenumbers and chemical shifts were computed. The optimized geometry results, which were well represented the X-ray data, were shown that the chosen of DFT/B3LYP 6-311G++(d,p) was a successful choice. After a successful optimization, frontier molecular orbitals, chemical activity, non-linear optical properties (NLO), molecular electrostatic mep (MEP), Mulliken population method, natural population analysis (NPA) and natural bond orbital analysis (NBO), which cannot be obtained experimentally, were calculated and investigated.

  20. Solid-State NMR Study of New Copolymers as Solid Polymer Electrolytes

    Directory of Open Access Journals (Sweden)

    Jean-Christophe Daigle

    2018-01-01

    Full Text Available We report the analysis of comb-like polymers by solid-state NMR. The polymers were previously evaluated as solid-polymer-electrolytes (SPE for lithium-polymer-metal batteries that have suitable ionic conductivity at 60 °C. We propose to develop a correlation between 13C solid-state NMR measurements and phase segregation. 13C solid-state NMR is a perfect tool for differentiating polymer phases with fast or slow motions. 7Li was used to monitor the motion of lithium ions in the polymer, and activation energies were calculated.

  1. Microscopic structural analysis of fractured silk fibers from Bombyx mori and Samia cynthia ricini using 13C CP/MAS NMR with a 1 mm microcoil MAS NMR probehead

    KAUST Repository

    Yamauchi, Kazuo

    2010-07-01

    Conformational changes have been studied in silk fibers from the domestic silkworm Bombyx mori and a wild silkworm Samia cynthia ricini as a result of fractured by stretching. About 300 samples consisting of only the fractured regions of [1-13C]Ala or [1-13C]Gly labeled silk fibers were collected and observed by 13C CP/MAS NMR spectra. The total amount of these fractured fibers is only about 1 mg and therefore we used a home-built 1 mm microcoil MAS NMR probehead. A very small increase in the fraction of random coil was noted for the alanine regions of both silk fibroins and for the glycine region of B. mori silk fibroin. However, there is no difference in the spectra before and after fractured for the glycine region of S. c. ricini silk fibroin. Thus, the influence of fracture occurs exclusively at the Ala region for S. c. ricini. The relationship between sequence, fracture and structure is discussed. © 2010 Elsevier Inc. All rights reserved.

  2. Elucidation of the electronic spectrum changes of KA-Al{sup 3+} complex by potentiometric titration, FTIR, {sup 13}C NMR and quantum mechanics

    Energy Technology Data Exchange (ETDEWEB)

    Piantavini, Mário S.; Gonçalves, Alan G.; Trindade, Ângela C.L.B.; Noseda, Miguel D.; Mercê, Ana L.R.; Pontarolo, Roberto, E-mail: pontarolo@ufpr.br [Universidade Federal do Paraná (UFPR), Curitiba (Brazil); Machado, Antonio E.H. [Universidade Federal de Uberlândia (UFU), MG (Brazil)

    2017-08-15

    Kojic acid (KA) is an organic acid widely used in pharmaceutical industry, mainly as a skin lightening agent. Based on the ability of KA to form complexes with ions, we found the most possible kind of complex formed with cation aluminum. KA-Al{sup 3+} complex structures were studied using potentiometric and spectrophotometric (UV) titrations, FTIR and {sup 13}C NMR. The electronic spectroscopy showed that the KA-Al{sup 3+} complexes absorb at higher wavelengths (λ{sub max}= 305 nm) than do the non-complexed KA (λ{sub max}= 269 nm), confirming complexation. The IR spectra of KA complexed and not complexed allowed to correlate the changes in the absorption of enol and carbonyl groups in absence and presence of Al{sup 3+} in aqueous solutions. The complexation suggested by the potentiometric titration and FTIR spectroscopy are in accordance with the data obtained from NMR results. Calculations based on quantum mechanics were utilized to understand the differences found in the non complexed and complexed KAH electronic spectra. (author)

  3. Elucidation of the electronic spectrum changes of KA-Al3+ complex by potentiometric titration, FTIR, 13C NMR and quantum mechanics

    International Nuclear Information System (INIS)

    Piantavini, Mário S.; Gonçalves, Alan G.; Trindade, Ângela C.L.B.; Noseda, Miguel D.; Mercê, Ana L.R.; Pontarolo, Roberto; Machado, Antonio E.H.

    2017-01-01

    Kojic acid (KA) is an organic acid widely used in pharmaceutical industry, mainly as a skin lightening agent. Based on the ability of KA to form complexes with ions, we found the most possible kind of complex formed with cation aluminum. KA-Al 3+ complex structures were studied using potentiometric and spectrophotometric (UV) titrations, FTIR and 13 C NMR. The electronic spectroscopy showed that the KA-Al 3+ complexes absorb at higher wavelengths (λ max = 305 nm) than do the non-complexed KA (λ max = 269 nm), confirming complexation. The IR spectra of KA complexed and not complexed allowed to correlate the changes in the absorption of enol and carbonyl groups in absence and presence of Al 3+ in aqueous solutions. The complexation suggested by the potentiometric titration and FTIR spectroscopy are in accordance with the data obtained from NMR results. Calculations based on quantum mechanics were utilized to understand the differences found in the non complexed and complexed KAH electronic spectra. (author)

  4. Synthesis of biodiesel from rocket seed oil and its characterization by FT-IR, NMR (/sup 1/H and /sup 13/C) and GC-MS

    International Nuclear Information System (INIS)

    Khalid, N.

    2012-01-01

    The limited resources of fossil fuel, increasing prices of crude oils and environmental concerns have motivated the researcher for alternate fuels, such as bio diesel that is obtained from vegetable oils. Therefore, bio diesel was synthesized from Rocket seed oil by base catalyzed transesterification with methanol. The physical parameters like dynamic viscosity (3.88 cp), specific gravity (0.893 g cm/sup 3/), kinematic viscosity (5.85 mm/sup 2/s/sup 1/)), density (0.877 g cm/sup 3/), cloud point (3 deg. C), flash point (110 deg. C) and acid number (0.07 mg KOH g/sup 1/) of the synthesized rocket seed oil bio diesel (RSOB) were determined and were found to be comparable with ASTM recommended values for diesels. Chemical composition of the bio diesels formed was determined by various techniques like Fourier transform infrared (FTIR) spectroscopy, nuclear magnetic resonance (NMR) spectroscopy (/sup 1/H, 13/C) and gas chromatography-mass spectrometry (GCMS). The /sup 1/H NMR spectrum of RSOB is given. (Orig./A.B.)

  5. Solid-state NMR studies of form I of atorvastatin calcium.

    Science.gov (United States)

    Wang, Wei David; Gao, Xudong; Strohmeier, Mark; Wang, Wei; Bai, Shi; Dybowski, Cecil

    2012-03-22

    Solid-state (13)C, (19)F, and (15)N magic angle spinning NMR studies of Form I of atorvastatin calcium are reported, including chemical shift tensors of all resolvable carbon sites and fluorine sites. The complete (13)C and (19)F chemical shift assignments are given based on an extensive analysis of (13)C-(1)H HETCOR and (13)C-(19)F HETCOR results. The solid-state NMR data indicate that the asymmetric unit of this material contains two atorvastatin molecules. A possible structure of Form I of atorvastatin calcium (ATC-I), derived from solid-state NMR data and density functional theory calculations of various structures, is proposed for this important active pharmaceutical ingredient (API).

  6. 1H diffusion-weighted, 13C and 17O NMR spectroscopy: methodological developments to study brain structure and function in vivo

    International Nuclear Information System (INIS)

    Najac, Chloe

    2014-01-01

    Magnetic Resonance Spectroscopy is a unique tool that allows acquiring brain biochemical profiles and quantifying many cellular parameters in vivo. During this thesis, three different techniques have been developed: (i) 1 H diffusion-weighted, (ii) carbon-13 ( 13 C) and (iii) oxygen-17 ( 17 O) NMR spectroscopy to study brain structure and function in vivo. Brain metabolites are cell-specific endogenous tracers of the intracellular space whose translational diffusion depends on many cellular properties (e.g.: cytosol viscosity and intracellular restriction). Studying the variation of the diffusion coefficient (ADC) as a function of diffusion time (td) allows untangling and quantifying those parameters. In particular, measuring metabolites ADC at long diffusion times gives information about the metabolites compartmentation in cells. In a first study, we measured neuronal and astrocytic metabolites ADC over a large time window (from 80 ms to 1 s) in a large voxel in the macaque brain. No dependence of all metabolites ADC on td was observed suggesting that metabolites primarily diffuse in neuronal (dendrites and axons) and astrocytic processes and are not confined inside the cell body and organelles (nucleus, mitochondria). The large size of the voxel, due to low detection sensitivity, did not allow us to study metabolites compartmentation in pure white (WM) and grey matters (GM). Therefore, we performed a new study in the human brain. Results showed that in both WM and GM metabolites diffuse in fiber-like cell structure. Finally, using an even larger time window (up to 2 s) in the macaque brain and analytical models mimicking the cell structure, we estimated the length of neuronal (∼110 μm) and astrocytic (∼70 μm) processes. ATP (adenosine triphosphate), the main source of energy in the organism, is produced thanks to glucose oxidation inside the mitochondria. 13 C NMR spectroscopy is a well-known technique to study brain energy metabolism and can be used to

  7. Ab initio/GIAO-CCSD(T) study of structures, energies, and 13C NMR chemical shifts of C4H7(+) and C5H9(+) ions: relative stability and dynamic aspects of the cyclopropylcarbinyl vs bicyclobutonium ions.

    Science.gov (United States)

    Olah, George A; Surya Prakash, G K; Rasul, Golam

    2008-07-16

    The structures and energies of the carbocations C 4H 7 (+) and C 5H 9 (+) were calculated using the ab initio method. The (13)C NMR chemical shifts of the carbocations were calculated using the GIAO-CCSD(T) method. The pisigma-delocalized bisected cyclopropylcarbinyl cation, 1 and nonclassical bicyclobutonium ion, 2 were found to be the minima for C 4H 7 (+) at the MP2/cc-pVTZ level. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level the structure 2 is 0.4 kcal/mol more stable than the structure 1. The (13)C NMR chemical shifts of 1 and 2 were calculated by the GIAO-CCSD(T) method. Based on relative energies and (13)C NMR chemical shift calculations, an equilibrium involving the 1 and 2 in superacid solutions is most likely responsible for the experimentally observed (13)C NMR chemical shifts, with the latter as the predominant equilibrating species. The alpha-methylcyclopropylcarbinyl cation, 4, and nonclassical bicyclobutonium ion, 5, were found to be the minima for C 5H 9 (+) at the MP2/cc-pVTZ level. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level ion 5 is 5.9 kcal/mol more stable than the structure 4. The calculated (13)C NMR chemical shifts of 5 agree rather well with the experimental values of C 5H 9 (+).

  8. 1H and 13C NMR coordination-induced shifts in a series of tris(α-diimine)ruthenium(II) complexes containing pyridine, pyrazine, and thiazole moieties

    International Nuclear Information System (INIS)

    Orellana, G.; Ibarra, C.A.; Santoro, J.

    1988-01-01

    1 H and 13 C NMR chemical shifts of a series of ruthenium(II) tris chelates containing the heterocyclic ligands 2,2'-bipyridine, 2-(2-pyridyl)thiazole, 2-(2-pyrazyl)thiazole, and 2,2'-bithiazole are reported and compared to those of the corresponding free ligands. Calculated coordination-induced shifts (CIS, δ complexed - δ free ) range from +0.41 to -1.00 ppM for 1 H and from +5.8 to -3.7 ppM for 13 C nuclei. These values are discussed on the basis of the various effects (charge perturbation and field interactions) that arise upon chelation: electronic σ-donation to the metallic center via the nitrogen lone pair, d-π* back-donation to the ligand, van der Waals interactions, and magnetic anisotropy of the spectator ligands. Semiquantitative values of each effect at the different positions have been proposed, taking theoretical calculations of steric and anisotropic contributions as the starting point. Shielding van der Waals interaction between proximate atoms influences only the H(3') CIS of six-membered moieties, but to a very low extent (<0.15 ppM). Magnetic anisotropy of proximate ring currents practically determines the CIS of the α positions for all the complexed ligands examined (upfield shifts from -0.8 to -1.0 ppm), has a lower influence on external β positions (< 0.2 ppM), and is negligible for γ-protons. σ-donation deshields all the positions, its contribution increasing as protons separate from the coordinated nitrogen atom (up to 0.4 ppM). Π-back-bonding is a weaker effect (< 0.2 ppM upfield contribution) that operates mainly on the γ position of the pyridine and α and β positions of the pyrazine rings. 36 refs., 3 figs., 4 tabs

  9. Ab initio/GIAO-CCSD(T) (13)C NMR study of the rearrangement and dynamic aspects of rapidly equilibrating tertiary carbocations, C6H13(+) and C7H15(+).

    Science.gov (United States)

    Olah, George A; Prakash, G K Surya; Rasul, Golam

    2016-01-05

    The rearrangement pathways of the equilibrating tertiary carbocations, 2,3-dimethyl-2-butyl cation (C6H13(+), 1), 2,3,3-trimethyl-2-butyl cation (C7H15(+), 5) and 2,3-dimethyl-2-pentyl cation (C7H15(+), 8 and 9) were investigated using the ab initio/GIAO-CCSD(T) (13)C NMR method. Comparing the calculated and experimental (13)C NMR chemical shifts of a series of carbocations indicates that excellent prediction of δ(13)C could be achieved through scaling. In the case of symmetrical equilibrating cations (1 and 5) the Wagner-Meerwein 1,2-hydride and 1,2-methide shifts, respectively, produce the same structure. This indicates that the overall (13)C NMR chemical shifts are conserved and independent of temperature. However, in the case of unsymmetrical equilibrating cations (8 and 9) the Wagner-Meerwein shift produces different tertiary structures, which have slightly different thermodynamic stabilities and, thus, different spectra. At the MP4(SDTQ)/cc-pVTZ//MP2/cc-pVTZ + ZPE level structure 8 is only 90 calories/mol more stable than structure 9. Based on computed (13)C NMR chemical shift calculations, mole fractions of these isomers were determined by assuming the observed chemical shifts are due to the weighted average of the chemical shifts of the static ions. © 2015 Wiley Periodicals, Inc.

  10. [Study of hydrogen bonds in the "catalytic triad" of trypsin by NMR spectra at 1H, 13C, and 15N nuclei].

    Science.gov (United States)

    Golubeb, N S; Gindin, V A; Ligaĭ, S S; Smirnov, S N

    1994-05-01

    The 1H and 13C NMR of trypsin stabilized by chemical modification with a hydrophilic polymer have been obtained in a wide range of pH (1.0-11.0). The spectral features referred to some nuclei of the "catalytic triad" have been identified using different NMR techniques as well as chemical modification with selective reagents. It was found that the monoprotonation of this system results in a quasi-symmetrical hydrogen bond formed between the basic groups which provided explanation for the discrepancies between the experimental findings obtained by different authors concerning the protonation site in this catalytic system. Simulation of the catalytic triad by a 15N-labelled low molecular model suggests that an increase in the OH-group acidity is unaccompanied by a discrete double proton transfer; however, a smooth shift of the bridging protons from one basic atom to another occurs with quasi-symmetrical hydrogen bonds formed in intermediate cases. On the basis of experimental data a new concept has been proposed for the mechanism of acid-base catalysis performed by pains of weak basic groups, such as His-Im and Asp(Glu)-COO- (pKa = 3-7) which are not capable of proton abstraction from alcoholic or water OH-groups (pKa > 13). The catalysis may consist in changing the charge densities on the reacting groups due to strong H-bonding and, on the other hand, in facilitating the free movement of a proton in the field of several basic atoms when going along the reaction coordinate. The energy of very strong hydrogen bonds thus formed diminishes the activation energy of the reaction.

  11. NMR experiments for resonance assignments of 13C, 15N doubly-labeled flexible polypeptides: Application to the human prion protein hPrP(23-230)

    International Nuclear Information System (INIS)

    Liu Aizhuo; Riek, Roland; Wider, Gerhard; Schroetter, Christine von; Zahn, Ralph; Wuethrich, Kurt

    2000-01-01

    A combination of three heteronuclear three-dimensional NMR experiments tailored for sequential resonance assignments in uniformly 15 N, 13 C-labeled flexible polypeptide chains is described. The 3D (H)N(CO-TOCSY)NH, 3D (H)CA(CO-TOCSY)NH and 3D (H)CBCA(CO-TOCSY)NH schemes make use of the favorable 15 N chemical shift dispersion in unfolded polypeptides, exploit the slow transverse 15 N relaxation rates of unfolded polypeptides in high resolution constant-time [ 1 H, 15 N]-correlation experiments, and use carbonyl carbon homonuclear isotropic mixing to transfer magnetization sequentially along the amino acid sequence. Practical applications are demonstrated with the 100-residue flexible tail of the recombinant human prion protein, making use of spectral resolution up to 0.6 Hz in the 15 N dimension, simultaneous correlation with the two adjacent amino acid residues to overcome problems associated with spectral overlap, and the potential of the presently described experiments to establish nearest-neighbor correlations across proline residues in the amino acid sequence

  12. CORRELATION ANALYSIS OF IR, 1 H- AND 13 C-NMR SPECTRAL DATA OF N-ALKYL AND N-CYCLOALKYL CYANOACETAMIDES

    Directory of Open Access Journals (Sweden)

    Aleksandar D. Marinković

    2011-09-01

    Full Text Available Linear free energy relationships (LFER were applied to the IR, 1H- and 13C--NMR spectral data in N-alkyl and N-cycloalkyl cyanoacetamides. N-alkyl and N-cycloalkyl cyanocetamides were synthesized from corresponding amine and ethyl cyanoacetate. A number of substituents were employed for alkyl substitution, and fairly good correlations were obtained, using simple Hammett equation. In N-alkyl and N-cycloalkyl cyanoacetamides substituent cause SCS of N-H hydrogen primarily by steric interaction, polar subtituent effect influences SCS shift of C=O carbon, while steric effect of N-alkyl substituent causes IR stretching frequencies of N-H, C=O and CN group. The conformations of investigated compounds have been studied by the use of semiempirical PM6 method, and together with LFER analysis, give a better insight into the influence of such a structure on the transmission of electronic substituent effects. Negative ρ values for several correlations (reverse substituent effect were found.

  13. "1H and "1"3C NMR Data on Hydroxy/methoxy Flavonoids and the Effects of Substituents on Chemical Shifts

    International Nuclear Information System (INIS)

    Yoon, Hyuk; Eom, Sung Lock; Hyun, Ji Ye; Jo, Geun Hyeong; Hwang, Do Seok; Lee, Sun Hee; Yong, Yeon Joong; Lee, Young Han; Lim, Yoong Ho; Park, Jun Cheol

    2011-01-01

    Polyphenols have recently been examined for such applications, and they are classified based on their carbon skeletons: phenolic acids with C6-C1 skeleton, hydrocinammates with C6-C_3 skeleton, stilbenes with C6-C2-C6 skeleton, and flavonoids with C6-C_3-C6 skeleton.2 Of these compounds, flavonoids are ubiquitously found in most plants. Since flavonoids belong to polyphenols, they have many hydroxy groups. From a bioavailability point of view, hydroxy groups prevent cell membrane transport, and hydroxyflavonoids can be metabolized by O-methyltransferases. However, methoxylated flavonoids may not have these problems. Hydroxylated or methoxylated flavonoids are found from natural sources. Nuclear magnetic resonance (NMR) spectroscopy is widely used to identify different compounds including hydroxylated or methoxylated flavonoids. Because the position and the number of substituted hydroxy or/and methoxy groups will change the "1H and "1"3C chemical shifts, it is important to understand these changes so that the structures of newly isolated hydroxy/methoxy-flavonoids can be easily identified

  14. Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning 13C and 29Si NMR Enhanced by Dynamic Nuclear Polarization

    Energy Technology Data Exchange (ETDEWEB)

    Lafon, Olivier [Universite de Lille Nord de France; Thankamony, Aany S. Lilly [Universite de Lille Nord de France; Kokayashi, Takeshi [Ames Laboratory; Carnevale, Diego [Ecole Polytechnique Federale de Lausanne; Vitzthum, Veronika [Ecole Polytechnique Federale de Lausanne; Slowing, Igor I. [Ames Laboratory; Kandel, Kapil [Ames Laboratory; Vezin, Herve [Universite de Lille Nord de France; Amoureux, Jean-Paul [Universite de Lille Nord de France; Bodenhausen, Geoffrey [Ecole Polytechnique Federale de Lausanne; Pruski, Marek [Ames Laboratory

    2012-12-21

    We show that dynamic nuclear polarization (DNP) can be used to enhance NMR signals of 13C and 29Si nuclei located in mesoporous organic/inorganic hybrid materials, at several hundreds of nanometers from stable radicals (TOTAPOL) trapped in the surrounding frozen disordered water. The approach is demonstrated using mesoporous silica nanoparticles (MSN), functionalized with 3-(N-phenylureido)propyl (PUP) groups, filled with the surfactant cetyltrimethylammonium bromide (CTAB). The DNP-enhanced proton magnetization is transported into the mesopores via 1H–1H spin diffusion and transferred to rare spins by cross-polarization, yielding signal enhancements εon/off of around 8. When the CTAB molecules are extracted, so that the radicals can enter the mesopores, the enhancements increase to εon/off ≈ 30 for both nuclei. A quantitative analysis of the signal enhancements in MSN with and without surfactant is based on a one-dimensional proton spin diffusion model. The effect of solvent deuteration is also investigated.

  15. Effects of solvent concentration and composition on protein dynamics: 13C MAS NMR studies of elastin in glycerol-water mixtures.

    Science.gov (United States)

    Demuth, Dominik; Haase, Nils; Malzacher, Daniel; Vogel, Michael

    2015-08-01

    We use (13)C CP MAS NMR to investigate the dependence of elastin dynamics on the concentration and composition of the solvent at various temperatures. For elastin in pure glycerol, line-shape analysis shows that larger-scale fluctuations of the protein backbone require a minimum glycerol concentration of ~0.6 g/g at ambient temperature, while smaller-scale fluctuations are activated at lower solvation levels of ~0.2 g/g. Immersing elastin in various glycerol-water mixtures, we observe at room temperature that the protein mobility is higher for lower glycerol fractions in the solvent and, thus, lower solvent viscosity. When decreasing the temperature, the elastin spectra approach the line shape for the rigid protein at 245 K for all studied samples, indicating that the protein ceases to be mobile on the experimental time scale of ~10(-5) s. Our findings yield evidence for a strong coupling between elastin fluctuations and solvent dynamics and, hence, such interaction is not restricted to the case of protein-water mixtures. Spectral resolution of different carbon species reveals that the protein-solvent couplings can, however, be different for side chain and backbone units. We discuss these results against the background of the slaving model for protein dynamics. Copyright © 2015 Elsevier B.V. All rights reserved.

  16. Novel multi-dimensional heteronuclear NMR techniques for the study of 13C-O-acetylated oligosaccharides: Expanding the dimensions for carbohydrate structures

    Energy Technology Data Exchange (ETDEWEB)

    Jones, David N.M. [University of Colorado Health Sciences Center, Departments of Pharmacology (United States); Bendiak, Brad [University of Colorado Health Sciences Center, Departments of Cellular and Structural Biology (United States)

    1999-10-15

    Complex carbohydrates have critical roles in a wide variety of biological processes. An understanding of the molecular mechanisms that underlie these processes is essential in the development of novel oligosaccharide-based therapeutic strategies. Unfortunately, obtaining detailed structural information for larger oligosaccharides (>10 residues) can be exceedingly difficult, especially where the amount of sample available is limited. Here we demonstrate the application of {sup 13} C O-acetylation in combination with novel NMR experiments to obtain much of the information required to characterize the primary structure of oligosaccharides. (H)C{sub Me}COH-HEHAHA and H(C{sub Me})COH-HEHAHA experiments are presented that use heteronuclear Hartmann-Hahn transfer to correlate the acetyl groups with sugar ring protons in peracetylated oligosaccharides. The in-phase, pure absorption nature of the correlation peaks in these experiments allows measurement of both chemical shifts and, importantly, {sup 1}H-{sup 1}H coupling constants that are used to define the stereochemistry of the sugar ring. The (HC{sub Me})COH and (HC{sub Me})COH-RELAY experiments provide additional methods for obtaining chemical shift assignments for larger oligosaccharides to define the sites of glycosidic linkages from the patterns of acetylation.

  17. Functional Groups Determine Biochar Properties (pH and EC as Studied by Two-Dimensional (13C NMR Correlation Spectroscopy.

    Directory of Open Access Journals (Sweden)

    Xiaoming Li

    Full Text Available While the properties of biochar are closely related to its functional groups, it is unclear under what conditions biochar develops its properties. In this study, two-dimensional (2D (13C nuclear magnetic resonance (NMR correlation spectroscopy was for the first time applied to investigate the development of functional groups and establish their relationship with biochar properties. The results showed that the agricultural biomass carbonized to biochars was a dehydroxylation/dehydrogenation and aromatization process, mainly involving the cleavage of O-alkylated carbons and anomeric O-C-O carbons in addition to the production of fused-ring aromatic structures and aromatic C-O groups. With increasing charring temperature, the mass cleavage of O-alkylated groups and anomeric O-C-O carbons occurred prior to the production of fused-ring aromatic structures. The regression analysis between functional groups and biochar properties (pH and electrical conductivity further demonstrated that the pH and electrical conductivity of rice straw derived biochars were mainly determined by fused-ring aromatic structures and anomeric O-C-O carbons, but the pH of rice bran derived biochars was determined by both fused-ring aromatic structures and aliphatic O-alkylated (HCOH carbons. In summary, this work suggests a novel tool for characterising the development of functional groups in biochars.

  18. Comprehensive quantum chemical and spectroscopic (FTIR, FT-Raman, 1H, 13C NMR) investigations of O-desmethyltramadol hydrochloride an active metabolite in tramadol - An analgesic drug

    Science.gov (United States)

    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.

  19. Fractional enrichment of proteins using [2-{sup 13}C]-glycerol as the carbon source facilitates measurement of excited state {sup 13}Cα chemical shifts with improved sensitivity

    Energy Technology Data Exchange (ETDEWEB)

    Ahlner, Alexandra; Andresen, Cecilia; Khan, Shahid N. [Linköping University, Division of Chemistry, Department of Physics, Chemistry and Biology (Sweden); Kay, Lewis E. [The University of Toronto, Departments of Molecular Genetics, Biochemistry and Chemistry, One King’s College Circle (Canada); Lundström, Patrik, E-mail: patlu@ifm.liu.se [Linköping University, Division of Chemistry, Department of Physics, Chemistry and Biology (Sweden)

    2015-07-15

    A selective isotope labeling scheme based on the utilization of [2-{sup 13}C]-glycerol as the carbon source during protein overexpression has been evaluated for the measurement of excited state {sup 13}Cα chemical shifts using Carr–Purcell–Meiboom–Gill (CPMG) relaxation dispersion (RD) experiments. As expected, the fractional incorporation of label at the Cα positions is increased two-fold relative to labeling schemes based on [2-{sup 13}C]-glucose, effectively doubling the sensitivity of NMR experiments. Applications to a binding reaction involving an SH3 domain from the protein Abp1p and a peptide from the protein Ark1p establish that accurate excited state {sup 13}Cα chemical shifts can be obtained from RD experiments, with errors on the order of 0.06 ppm for exchange rates ranging from 100 to 1000 s{sup −1}, despite the small fraction of {sup 13}Cα–{sup 13}Cβ spin-pairs that are present for many residue types. The labeling approach described here should thus be attractive for studies of exchanging systems using {sup 13}Cα spin probes.

  20. 13C NMR study of effects of fasting and diabetes on the metabolism of pyruvate in the tricarboxylic acid cycle and of the utilization of pyruvate and ethanol in lipogenesis in perfused rat liver

    International Nuclear Information System (INIS)

    Cohen, S.M.

    1987-01-01

    13 C NMR has been used to study the competition of pyruvate dehydrogenase with pyruvate carboxylase for entry of pyruvate into the tricarboxylic acid (TCA) cycle in perfused liver from streptozotocin-diabetic and normal donor rats. The relative proportion of pyruvate entering the TCA cycle by these two routes was estimated from the 13 C enrichments at the individual carbons of glutamate when [3- 13 C]alanine was the only exogenous substrate present. In this way, the proportion of pyruvate entering by the pyruvate dehydrogenase route relative to the pyruvate carboxylase route was determined to be 1:1.2 +/- 0.1 in liver from fed controls, 1:7.7 +/- 2 in liver from 24-fasted controls, and 1:2.6 +/- 0.3 in diabetic liver. Pursuant to this observation that conversion of pyruvate to acetyl coenzyme A (acetyl-CoA) was greatest in perfused liver from fed controls, the incorporation of 13 C label into fatty acids was monitored in this liver preparation. With the exception of the repeating methylene carbons, fatty acyl carbons labeled by [1- 13 C]acetyl-CoA (from [2- 13 C]pyruvate) gave rise to resonances distinguishable on the basis of chemical shift from those observed when label was introduced by [3- 13 C]alanine plus [2- 13 C]ethanol, which are converted to [2- 13 C]acetyl-CoA. Thus, measurement of 13 C enrichment at several specific sites in the fatty acyl chains in time-resolved spectra of perfused liver offers a novel way of monitoring the kinetics of the biosynthesis of fatty acids. In addition to obtaining the rate of lipogenesis, it was possible to distinguish the contributions of chain elongation from those of the de novo synthesis pathway and to estimate the average chain length of the 13 C-labeled fatty acids produced

  1. Heteronuclear 2D (1H-13C) MAS NMR Resolves the Electronic Structure of Coordinated Histidines in Light-Harvesting Complex II: Assessment of Charge Transfer and Electronic Delocalization Effect

    International Nuclear Information System (INIS)

    Matysik, Joerg; Boer, Ido de; Gast, Peter; Gorkom, Hans J. van; Groot, Huub J.M. de

    2004-01-01

    In a recent MAS NMR study, two types of histidine residues in the light-harvesting complex II (LH2) of Rhodopseudomonas acidophila were resolved: Type 1 (neutral) and Type 2 (positively charged) (Alia et al. J. Am. Chem. Soc.). The isotropic 13 C shifts of histidines coordinating to B850 BChl a are similar to fully positively charged histidine, while the 15 N shift anisotropy shows a predominantly neutral character. In addition the possibility that the ring currents are quenched by overlap in the superstructure of the complete ring of 18 B850 molecules in the LH2 complex could not be excluded. In the present work, by using two-dimensional heteronuclear ( 1 H- 13 C) dipolar correlation spectroscopy with phase-modulated Lee-Goldburg homonuclear 1 H decoupling applied during the t 1 period, a clear and unambiguous assignment of the protons of histidine interacting with the magnesium of a BChl a molecule is obtained and a significant ring current effect from B850 on the coordinating histidine is resolved. Using the ring current shift on 1 H, we refine the 13 C chemical shift assignment of the coordinating histidine and clearly distinguish the electronic structure of coordinating histidines from that of fully positively charged histidine. The DFT calculations corroborate that the coordinating histidines carry ∼0.2 electronic equivalent of positive charge in LH2. In addition, the data indicate that the ground state electronic structures of individual BChl a/His complexes is largely independent of supermolecular π interactions in the assembly of 18 B850 ring in LH2

  2. 1H, 13C and 31P-NMR spectroscopic study of glucose metabolism of muscle larva Trichinella spiralis (U.S.A. strain), and the effects of the end-products on the host (mouse)

    International Nuclear Information System (INIS)

    Nishina, Masami

    1988-01-01

    1 H- and 13 C-nuclear magnetic resonance (NMR) spectroscopy was used to identify and quantitate metabolites excreted by muscle larva Trichinella spiralis maintained aerobically in the presence of D- ( 13 C 6 ) glucose and (1, 1'- 13 C 2 ) succinate. End-products of glucose metabolism studied by 1 H-NMR were lactate, acetate, succinate, proionate, n-valerate and alanine, at the molar ratio of 1:2:1:0.6:0.5:0.6. 13 C-NMR measurement proved that all the products originated from the glucose in the medium via the phosphoenolpyruvate carboxykinase-succinate pathway and the tricarboxylic acid cycle. In vivo 31 P-NMR spectra were also taken by the surface coil method from the leg muscle of mice which had been infected with T. spiralis. Intracelluar pH and relative amount of ATP in the leg muscle of the infected mice were found to decrease significantly as compared with that of control mice. (author)

  3. /sup 1/H, /sup 13/C and /sup 31/P-NMR spectroscopic study of glucose metabolism of muscle larva Trichinella spiralis (U. S. A. strain), and the effects of the end-products on the host (mouse)

    Energy Technology Data Exchange (ETDEWEB)

    Nishina, Masami

    1988-11-01

    /sup 1/H- and /sup 13/C-nuclear magnetic resonance (NMR) spectroscopy was used to identify and quantitate metabolites excreted by muscle larva Trichinella spiralis maintained aerobically in the presence of D- (/sup 13/C/sub 6/) glucose and (1, 1'-/sup 13/C/sub 2/) succinate. End-products of glucose metabolism studied by /sup 1/H-NMR were lactate, acetate, succinate, proionate, n-valerate and alanine, at the molar ratio of 1:2:1:0.6:0.5:0.6. /sup 13/C-NMR measurement proved that all the products originated from the glucose in the medium via the phosphoenolpyruvate carboxykinase-succinate pathway and the tricarboxylic acid cycle. In vivo /sup 31/P-NMR spectra were also taken by the surface coil method from the leg muscle of mice which had been infected with T. spiralis. Intracelluar pH and relative amount of ATP in the leg muscle of the infected mice were found to decrease significantly as compared with that of control mice.

  4. Fast Identification of Radical Scavengers from Securigera varia by Combining 13C-NMR-Based Dereplication to Bioactivity-Guided Fractionation.

    Science.gov (United States)

    Sientzoff, Pacôme; Hubert, Jane; Janin, Coralie; Voutquenne-Nazabadioko, Laurence; Renault, Jean-Hugues; Nuzillard, Jean-Marc; Harakat, Dominique; Magid, Abdulmagid Alabdul

    2015-08-14

    Securigera varia (Fabaceae) is a common herbaceous perennial plant widely growing in Europe and Asia and purposely established for erosion control, roadside planting, and soil rehabilitation. The aim of this study was to determine the radical scavenging activity of a crude methanol extract of S. varia aerial parts by using the free radical DPPH (1,1-diphenyl-2-picrylhydrazyl) and to rapidly identify the compounds involved in this activity. The crude extract was initially separated in five fractions on Diaion HP20 resin and the most active part was fractionated by Centrifugal Partition Extraction (CPE). Known compounds were directly identified by a (13)C-NMR-based dereplication method. Semi-preparative high performance liquid chromatography purification experiments were further performed to identify unknown or minor active compounds. As a result, one new (13) and twelve known flavonoid glycosides together with three nitropropanoylglucopyranoses were isolated, including astragalin (1), kaempferol-3-O-(6-O-acetyl)-β-D-glucopyranoside (2), kaempferol-3,4'-di-O-β-D-glucopyranoside (3), trifolin (4), isoquercitrin (5), hyperoside (6), isovitexin (7), isoorientin (8), isovitexin 4'-O-β-D-glucopyranoside (9), apigenin 7-O-β-D-glucuronopyranoside (10), luteolin 7-O-β-D-glucuronopyranoside (11), apigenin 7-O-α-L-rhamnopyranosyl-(1→2)-β-D-glucuronopyranoside (12), apigenin 7-O-β-D-glucopyranosyl-(1 → 2)-β-D-glucuronopyranoside (13), 6-O-(3-nitropropanoyl)-β-D-glucopyranoside (14), coronillin (16) and coronarian (15). 120 mg of the most active compound isoorientin against the free radical DPPH was recovered by CPE with an HPLC purity of 99%.

  5. Fast Identification of Radical Scavengers from Securigera varia by Combining 13C-NMR-Based Dereplication to Bioactivity-Guided Fractionation

    Directory of Open Access Journals (Sweden)

    Pacôme Sientzoff

    2015-08-01

    Full Text Available Securigera varia (Fabaceae is a common herbaceous perennial plant widely growing in Europe and Asia and purposely established for erosion control, roadside planting, and soil rehabilitation. The aim of this study was to determine the radical scavenging activity of a crude methanol extract of S. varia aerial parts by using the free radical DPPH (1,1-diphenyl-2-picrylhydrazyl and to rapidly identify the compounds involved in this activity. The crude extract was initially separated in five fractions on Diaion HP20 resin and the most active part was fractionated by Centrifugal Partition Extraction (CPE. Known compounds were directly identified by a 13C-NMR-based dereplication method. Semi-preparative high performance liquid chromatography purification experiments were further performed to identify unknown or minor active compounds. As a result, one new (13 and twelve known flavonoid glycosides together with three nitropropanoylglucopyranoses were isolated, including astragalin (1, kaempferol-3-O-(6-O-acetyl-β-D-glucopyranoside (2, kaempferol-3,4′-di-O-β-D-glucopyranoside (3, trifolin (4, isoquercitrin (5, hyperoside (6, isovitexin (7, isoorientin (8, isovitexin 4′-O-β-D-glucopyranoside (9, apigenin 7-O-β-D-glucuronopyranoside (10, luteolin 7-O-β-D-glucuronopyranoside (11, apigenin 7-O-α-L-rhamnopyranosyl-(1→2-β-D-glucuronopyranoside (12, apigenin 7-O-β-D-glucopyranosyl-(1→2-β-D-glucuronopyranoside (13, 6-O-(3-nitropropanoyl-β-D-glucopyranoside (14, coronillin (16 and coronarian (15. 120 mg of the most active compound isoorientin against the free radical DPPH was recovered by CPE with an HPLC purity of 99%.

  6. Spin excitations in the quasi-two-dimensional charge-ordered insulator α -(BEDT-TTF ) 2I3 probed via 13C NMR

    Science.gov (United States)

    Ishikawa, Kyohei; Hirata, Michihiro; Liu, Dong; Miyagawa, Kazuya; Tamura, Masafumi; Kanoda, Kazushi

    2016-08-01

    The spin excitations from the nonmagnetic charge-ordered insulating state of α -(BEDT-TTF ) 2I3 at ambient pressure have been investigated by probing the static and low-frequency dynamic spin susceptibilities via site-selective nuclear magnetic resonance at 13C sites. The site-dependent values of the shift and the spin-lattice relaxation rate 1 /T1 below the charge-ordering transition temperature (TCO≈135 K ) demonstrate a spin density imbalance in the unit cell, in accord with the charge-density ratio reported earlier. The shift and 1 /T1 show activated temperature dependence with a static (shift) gap ΔS≈47 -52 meV and a dynamic (1 /T1 ) gap ΔR≈40 meV . The sizes of the gaps are well described in terms of a localized spin model, where spin-1/2 antiferromagnetic dimer chains are weakly coupled with each other.

  7. Heteronuclear 2D NMR studies on an engineered insulin monomer: Assignments and characterization of the receptor-binding surface by selective 2H and 13C labeling with application to protein design

    International Nuclear Information System (INIS)

    Weiss, M.A.; Hua, Qingxin; Lynch, C.S.; Shoelson, S.E.; Frank, B.H.

    1991-01-01

    Insulin provides an important model for the application of genetic engineering to rational protein design and has been well characterized in the crystal state. However, self-association of insulin in solution has precluded complementary 2D NMR study under physiological conditions. The authors demonstrate here that such limitations may be circumvented by the use of a monomeric analogue that contains three amino acid substitutions on the protein surface (HisB10 → Asp, ProB28 → Lys, and LysB29 → Pro); this analogue (designated DKP-insulin) retains native receptor-binding potency. Comparative 1 H NMR studies of native human insulin and a series of three related analogues-(i) the singly substituted analogue [HisB10→Asp], (ii) the doubly substituted analogue [ProB28→Lys; LysB29→Pro], and (iii) DKP-insulin-demonstrate progressive reduction in concentration-dependent line-broadening in accord with the results of analytical ultracentrifugation. Extensive nonlocal interactions are observed in the NOESY spectrum of DKP-insulin, indicating that this analogue adopts a compact and stably folded structure as a monomer in overall accord with crystal models. Site-specific 2 H and 13 C isotopic labels are introduced by semisynthesis as probes for the structure and dynamics of the receptor-binding surface. These studies confirm and extend under physiological conditions the results of a previous 2D NMR analysis of native insulin in 20% acetic acid. Implications for the role of protein flexibility in receptor recognition are discussed with application to the design of novel insulin analogues

  8. Blends of natural rubber and polyurethane lattices studied by solid-state NMR

    International Nuclear Information System (INIS)

    Ricardo, Nagila M.P.S.; Franca, Francisco C.F. de; Price, Colin; Heatley, Frank

    2001-01-01

    Molecular mixing in films formed from a mixture of a polyurethane and natural rubber lattices has been studied using 1 H and 13 C solid-state NMR. The techniques employed include 1 H relaxation measurements, and 13 C cross-polarisation and direct excitation methods. The spectra of the blends were essentially a weighted superposition of the spectra of the individual components, indicating that the polyurethane and rubber remained phase-separated in large domains. (author)

  9. Investigation of the role of the calvin cycle and C1 metabolism during HCHO metabolism in gaseous HCHO-treated petunia under light and dark conditions using 13C-NMR.

    Science.gov (United States)

    Sun, Huiqun; Zhang, Wei; Tang, Lijuan; Han, Shuang; Wang, Xinjia; Zhou, Shengen; Li, Kunzhi; Chen, Limei

    2015-01-01

    It has been shown that formaldehyde (HCHO) absorbed by plants can be assimilated through the Calvin cycle or C1 metabolism. Our previous study indicated that Petunia hybrida could effectively eliminate HCHO from HCHO-polluted air. To understand the roles of C1 metabolism and the Calvin cycle during HCHO metabolism and detoxification in petunia plants treated with gaseous H(13)CHO under light and dark conditions. Aseptically grown petunia plants were treated with gaseous H(13)CHO under dark and light conditions. The metabolites generated from HCHO detoxification in petunia were investigated using (13)C-NMR. [2-(13)C]glycine (Gly) was generated via C1 metabolism and [U-(13)C]glucose (Gluc) was produced through the Calvin cycle simultaneously in petunia treated with low-level gaseous H(13)CHO under light conditions. Generation of [2-(13)C]Gly decreased whereas [U-(13) C]Gluc and [U-(13)C]fructose (Fruc) production increased greatly under high-level gaseous H(13)CHO stress in the light. In contrast, [U-(13)C]Gluc and [U-(13)C] Fruc production decreased greatly and [2-(13)C]Gly generation increased significantly under low-level and high-level gaseous H(13)CHO stress in the dark. C1 metabolism and the Calvin cycle contributed differently to HCHO metabolism and detoxification in gaseous H(13CHO-treated petunia plants. As the level of gaseous HCHO increased, the role of C1 metabolism decreased and the role of the Calvin cycle increased under light conditions. However, opposite changes were observed in petunia plants under dark conditions. Copyright © 2015 John Wiley & Sons, Ltd.

  10. Detection of the sulfhydryl groups in proteins with slow hydrogen exchange rates and determination of their proton/deuteron fractionation factors using the deuterium-induced effects on the 13C(beta) NMR signals.

    Science.gov (United States)

    Takeda, Mitsuhiro; Jee, JunGoo; Terauchi, Tsutomu; Kainosho, Masatsune

    2010-05-05

    A method for identifying cysteine (Cys) residues with sulfhydryl (SH) groups exhibiting slow hydrogen exchange rates has been developed for proteins in aqueous media. The method utilizes the isotope shifts of the C(beta) chemical shifts induced by the deuteration of the SH groups. The 18.2 kDa E. coli peptidyl prolyl cis-trans isomerase b (EPPIb), which was selectively labeled with [3-(13)C;3,3-(2)H(2)]Cys, showed much narrower line widths for the (13)C(beta) NMR signals, as compared to those of the proteins labeled with either [3-(13)C]Cys or (3R)-[3-(13)C;3-(2)H]Cys. The (13)C(beta) signals of the two Cys residues of EPPIb, i.e. Cys-31 and Cys-121, labeled with [3-(13)C;3,3-(2)H(2)]Cys, split into four signals in H(2)O/D(2)O (1:1) at 40 degrees C and pH 7.5, indicating that the exchange rates of the side-chain SH's and the backbone amides are too slow to average the chemical shift differences of the (13)C(beta) signals, due to the two- and three-bond isotope shifts. By virtue of the well-separated signals, the proton/deuteron fractional factors for both the SH and amide groups of the two Cys residues in EPPIb could be directly determined, as approximately 0.4-0.5 for [SD]/[SH] and 0.9-1.0 for [ND]/[NH], by the relative intensities of the NMR signals for the isotopomers. The proton NOE's of the two slowly exchanging SH's were clearly identified in the NOESY spectra and were useful for the determining the local structure of EPPIb around the Cys residues.

  11. NMR spectroscopy of organic compounds of selenium and tellurium. Communication 9. Chemical shifts of /sup 13/C in isological series of unsaturated ethers, sulfides, selenides and tellurides

    Energy Technology Data Exchange (ETDEWEB)

    Kalabin, G.A.; Bzhezovskii, V.M.; Kushnarev, D.F.; Proidakov, A.G. (Irkutskii Gosudarstvennyj Univ. (USSR))

    1981-06-01

    The effects of heteroatoms Eh(Eh=O, S, Se, Te) on /sup 13/C chemical shifts in eleven isological series of R/sup 1/-Eh-R/sup 2/ unsaturated compounds are compared. A linear relation between /sup 13/C nuclei screening and tEh electronegativity is observed. An assumption is suggested that both likeness of the effects of 6A and 7A group elements on /sup 13/C chemical shifts of R/sup 1/ and R/sup 2/ substituents and their difference for elements of the 4A group are caused by unbonded interactions of the substituents with unshared electron pairs of heteroatoms.

  12. Measuring 13Cβ chemical shifts of invisible excited states in proteins by relaxation dispersion NMR spectroscopy

    International Nuclear Information System (INIS)

    Lundstroem, Patrik; Lin Hong; Kay, Lewis E.

    2009-01-01

    A labeling scheme is introduced that facilitates the measurement of accurate 13 C β chemical shifts of invisible, excited states of proteins by relaxation dispersion NMR spectroscopy. The approach makes use of protein over-expression in a strain of E. coli in which the TCA cycle enzyme succinate dehydrogenase is knocked out, leading to the production of samples with high levels of 13 C enrichment (30-40%) at C β side-chain carbon positions for 15 of the amino acids with little 13 C label at positions one bond removed (∼5%). A pair of samples are produced using [1- 13 C]-glucose/NaH 12 CO 3 or [2- 13 C]-glucose as carbon sources with isolated and enriched (>30%) 13 C β positions for 11 and 4 residues, respectively. The efficacy of the labeling procedure is established by NMR spectroscopy. The utility of such samples for measurement of 13 C β chemical shifts of invisible, excited states in exchange with visible, ground conformations is confirmed by relaxation dispersion studies of a protein-ligand binding exchange reaction in which the extracted chemical shift differences from dispersion profiles compare favorably with those obtained directly from measurements on ligand free and fully bound protein samples

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

    Energy Technology Data Exchange (ETDEWEB)

    Thomas, Freddy [Eurofins Scientific Analytics, BP42301, 44323 Nantes (France); Jamin, Eric [Eurofins Scientific Analytics, BP42301, 44323 Nantes (France)

    2009-09-01

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

  14. Analysis of mercerization process based on the intensity change of deconvoluted resonances of {sup 13}C CP/MAS NMR: Cellulose mercerized under cooling and non-cooling conditions

    Energy Technology Data Exchange (ETDEWEB)

    Miura, Kento [Mitsubishi Rayon Co., Ltd. Otake Research Laboratories (Japan); Nakano, Takato, E-mail: tnakano@kais.kyoto-u.ac.jp [Laboratory of Biomaterials Design, Division of Forest and Biomaterials Science, Graduate School of Agriculture, Kyoto University (Japan)

    2015-08-01

    The area intensity change of C1, C4, and C6 in spectrum obtained by {sup 13}C CP/MAS NMR and the mutual relationship between their changes were examined for cellulose samples treated with various concentrations of aqueous NaOH solutions under non-cooling and cooling conditions. The area intensity of C1-up and C6-down changed cooperatively with that of C4-down which corresponds to the crystallinity of samples: “-up” and “-down” are the up- and down- field component in a splitting peak of NMR spectrum, respectively. The intensity change of C1-up starts to decrease with decreasing in that of C4-down after that of C6-down is almost complete. These changes were more clearly observed for samples treated under cooling condition. It can be suggested that their characteristic change relates closely to the change in conformation of cellulose chains by induced decrystallization and the subsequent crystallization of cellulose II, and presumed that their changes at microscopic level relate to the macroscopic morphological changes such as contraction along the length of cellulose chains and recovery along the length. - Highlight: • Samples were mercerized at various NaOH concentrations under non-cooling and cooling. • The intensity change of C1 starts immediately after that of C6 is complete. • The creation of cell-II starts when decrystallization proceeds to a certain state. • This change relates closely to the change in conformation of cellulose chains. • The above change is more clearly found for samples treated under cooling.

  15. Solid-state NMR of inorganic semiconductors.

    Science.gov (United States)

    Yesinowski, James P

    2012-01-01

    Studies of inorganic semiconductors by solid-state NMR vary widely in terms of the nature of the samples investigated, the techniques employed to observe the NMR signal, and the types of information obtained. Compared with the NMR of diamagnetic non-semiconducting substances, important differences often result from the presence of electron or hole carriers that are the hallmark of semiconductors, and whose theoretical interpretation can be involved. This review aims to provide a broad perspective on the topic for the non-expert by providing: (1) a basic introduction to semiconductor physical concepts relevant to NMR, including common crystal structures and the various methods of making samples; (2) discussions of the NMR spin Hamiltonian, details of some of the NMR techniques and strategies used to make measurements and theoretically predict NMR parameters, and examples of how each of the terms in the Hamiltonian has provided useful information in bulk semiconductors; (3) a discussion of the additional considerations needed to interpret the NMR of nanoscale semiconductors, with selected examples. The area of semiconductor NMR is being revitalized by this interest in nanoscale semiconductors, the great improvements in NMR detection sensitivity and resolution that have occurred, and the current interest in optical pumping and spintronics-related studies. Promising directions for future research will be noted throughout.

  16. Potential energy curves and spectroscopic properties of X2Σ+ and A2Π states of 13C14N

    International Nuclear Information System (INIS)

    Liao Jian-Wen; Yang Chuan-Lu

    2014-01-01

    The potential energy curves (PECs) of X 2 Σ + and A 2 Π states of the CN molecule have been calculated with the multi-reference configuration interaction method and the aug-cc-pwCV5Z basis set. Based on the PECs, all of the vibrational and rotational levels of the 13 C 14 N molecule are obtained by solving the Schrödinger equation of the molecular nuclear motion. The spectroscopic parameters are determined by fitting the Dunham coefficients with the levels. Both the levels and the spectroscopic parameters are in good qualitative agreement with the experimental data available. The analytical potential energy functions are also deduced from the calculated PECs. The present results can provide a helpful reference for future spectroscopy experiments or dynamical calculations of the molecule. (atomic and molecular physics)

  17. Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

    Science.gov (United States)

    Cao, X.; Mastalerz, Maria; Chappell, M.A.; Miller, L.F.; Li, Y.; Mao, J.

    2011-01-01

    Four lithotypes (vitrain, bright clarain, clarain, and fusain) of a high volatile bituminous Springfield Coal from the Illinois Basin were characterized using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. The NMR techniques included quantitative direct polarization/magic angle spinning (DP/MAS), cross polarization/total sideband suppression (CP/TOSS), dipolar dephasing, CHn selection, and recoupled C-H long-range dipolar dephasing techniques. The lithotypes that experienced high-pressure CO2 adsorption isotherm analysis were also analyzed to determine possible changes in coal structure as a result of CO2 saturation at high pressure and subsequent evacuation. The main carbon functionalities present in original vitrain, bright clarain, clarain and fusain were aromatic carbons (65.9%-86.1%), nonpolar alkyl groups (9.0%-28.9%), and aromatic C-O carbons (4.1%-9.5%). Among these lithotypes, aromaticity increased in the order of clarain, bright clarain, vitrain, and fusain, whereas the fraction of alkyl carbons decreased in the same order. Fusain was distinct from other three lithotypes in respect to its highest aromatic composition (86.1%) and remarkably small fraction of alkyl carbons (11.0%). The aromatic cluster size in fusain was larger than that in bright clarain. The lithotypes studied responded differently to high pressure CO2 saturation. After exposure to high pressure CO2, vitrain and fusain showed a decrease in aromaticity but an increase in the fraction of alkyl carbons, whereas bright clarain and clarain displayed an increase in aromaticity but a decrease in the fraction of alkyl carbons. Aromatic fused-rings were larger for bright clarain but smaller for fusain in the post-CO2 adsorption samples compared to the original lithotypes. These observations suggested chemical CO2-coal interactions at high pressure and the selectivity of lithotypes in response to CO2 adsorption. ?? 2011 Elsevier B.V.

  18. The structure of poly(carbonsuboxide) on the atomic scale: a solid-state NMR study.

    Science.gov (United States)

    Schmedt auf der Günne, Jörn; Beck, Johannes; Hoffbauer, Wilfried; Krieger-Beck, Petra

    2005-07-18

    In this contribution we present a study of the structure of amorphous poly(carbonsuboxide) (C3O2)x by 13C solid-state NMR spectroscopy supported by infrared spectroscopy and chemical analysis. Poly(carbonsuboxide) was obtained by polymerization of carbonsuboxide C3O2, which in turn was synthesized from malonic acid bis(trimethylsilylester). Two different 13C labeling schemes were applied to probe inter- and intramonomeric bonds in the polymer by dipolar solid-state NMR methods and also to allow quantitative 13C MAS NMR spectra. Four types of carbon environments can be distinguished in the NMR spectra. Double-quantum and triple-quantum 2D correlation experiments were used to assign the observed peaks using the through-space and through-bond dipolar coupling. In order to obtain distance constraints for the intermonomeric bonds, double-quantum constant-time experiments were performed. In these experiments an additional filter step was applied to suppress contributions from not directly bonded 13C,13C spin pairs. The 13C NMR intensities, chemical shifts, connectivities and distances gave constraints for both the polymerization mechanism and the short-range order of the polymer. The experimental results were complemented by bond lengths predicted by density functional theory methods for several previously suggested models. Based on the presented evidence we can unambiguously exclude models based on gamma-pyronic units and support models based on alpha-pyronic units. The possibility of planar ladder- and bracelet-like alpha-pyronic structures is discussed.

  19. Uptake of 13C-glucose by cell suspensions of carrot (Daucus carota) measured by in vivo NMR: Cycling of triose, pentose- and hexose-phosphates

    NARCIS (Netherlands)

    Krook, J.; Vreugdenhil, D.; Dijkema, C.; Plas, van der L.H.W.

    2000-01-01

    After a lag phase of 2 days, batch-grown cells of carrot (Daucus carota L.) cv. Flakkese entered the exponential growth phase and started to accumulate sucrose and hexoses. Short-term feeding 13C-glucose in this period resulted in only minor labelling of sucrose or fructose. CO2 production from

  20. 13C and 17O NMR binding constant studies of uranyl carbonate complexes in near-neutral aqueous solution. Yucca Mountain Project Milestone Report 3351

    International Nuclear Information System (INIS)

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

    1995-01-01

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

  1. Computer-assisted structure elucidation from 13C-NMR-Spectra. I. The development of a three-dimensional structure code. II. The development of an isomer generating program

    International Nuclear Information System (INIS)

    Schuetz, V.

    1999-05-01

    The presented thesis consists of two separate programs which both aid the automated structure elucidation in the CSEARCH database system. A successful utilization of a large collection of NMR reference spectra for the prediction of chemical shift values is dependent on a strong correlation between the spectral data and the structural information via unique coding. By now, this was done using the two-dimensional HOSE code, which turned out to be insufficient whenever stereochemical effects other than cis/trans-isomerism contribute to the chemical shift values. Therefore, this new algorithm has been developed to derive the demanded three-dimensional descriptors. The calculation is performed by matching the query structures against pattern molecules taken from a carefully selected library of ring skeletons. No three-dimensional coordinates are necessary, since the algorithm elucidates the descriptors on base of two-dimensional structures having their stereocenters specified using 'up/down' bonds. The descriptors are defined as number of interactions over 3 to 5 bonds, number of cis-substituents over 1 to 2 ringbonds and markers for axial substituents. This approach of deriving descriptors for steric interactions has successfully extended the HOSE coding scheme and has been implemented into a neural network; both methods allow for high-quality prediction of 13 C-NMR chemical shift values. The second algorithm is an isomer generating program named GENERAL, which efficiently supports the structure elucidation process by calculating all mathematically possible structures to a given molecular formula. The resulting list of structures is exhaustive and free of redundancy. Besides the basic input information - like the molecular formula and the specification of structural fragments, constraints can be defined to restrict the number of resulting structures. The most valuable information is provided by state-of-the-art 2D-NMR experiments and can be easily incorporated into

  2. Solid state NMR of materials

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, Sharon A; Ferguson, David B; Haw, James F [Texas A and M Univ., College Station, TX (United States). Dept. of Chemistry

    1994-12-31

    In situ NMR experiments are studied, including probe of several structures such as the structures of the organic adsorbates, Broensted acid sites, other nuclei associated with active sites, and other framework sites. The authors report that in the absence of high concentrations of paramagnetic sites or metal particles, high resolution MAS spectra are relatively easy to obtain and interpret. It is also concluded that NMR can measure spatial distributions and rates of diffusion; and are able to characterize equilibrium structures and the frequencies and amplitudes of molecular motion

  3. Oriented solid-state NMR spectrosocpy

    DEFF Research Database (Denmark)

    Bertelsen, Kresten

    This thesis is concerned with driving forward oriented solid-state NMR spectroscopy as a viable technique for studying peptides in membrane bilayers. I will show that structural heterogeneity is an intrinsic part of the peptide/lipid system and that NMR can be used to characterize static...... and dynamic structural features of the peptides and its local surroundings. In fact one need to take into account the dynamical features of the system in order to correctly predict the structure from oriented solid-state NMR spectra.      ...

  4. Identification of solution products of lanthanoid (3) diethyldithiocarbamatohexamethyl phosphotriamide compounds from IR, electron and sup 1 H, sup 13 C, sup 31 P NMR absorption spectra. Identifikatsiya produktov rastvoreniya diehtilditiokarbamatogeksametil fosfotriamidnykh soedinenij lantanoidov (3) po IK, ehlektronnym i YaMR sup 1 H, sup 13 C, sup 31 P spektram pogloshcheniya

    Energy Technology Data Exchange (ETDEWEB)

    Skopenko, V V; Savost' yanova, A F; Trachevskij, V V; Gorbalyuk, A D; Sukhan, T A [Kievskij Gosudarstvennyj Univ., Kiev (Ukrainian SSR)

    1991-01-01

    By the methods of conductometry, IR, electron and {sup 1}H, {sup 13}C, {sup 31}P NMR spectroscopy nonaqueous solutions of the compounds (La(S{sub 2}CNEt{sub 2})Hmpa{sub 5})(BPh{sub 4}){sub 2}, Hmpa=OP(NMe{sub 2}){sub 3}; (Ln(S{sub 2}CNEt{sub 2}){sub 2}Hmpa{sub 3})BPh{sub 4}, Ln=Y, La-Lu; (Ln(S{sub 2}CNEt{sub 2}){sub 3}Hmpa{sub 2}), Ln=La-Gd, have been investigated. It is ascertained that bis-dithiocarbamate compounds are dissolved in all the studied solvents with preservation of composition and structure of lanthanide (3) inner coordination sphere. Tris-dithiocarbamates in nonaqueous solutions are subjected to reactions of ligand redistribution according to schemes depending on the solvent nature. In the process of dissolving of lanthanum monodithiocarbamate bond isomerization of dithiocarbamate groups occurs, which is pronounced in splitting of {sup 1}H and {sup 13}C NMR signals.

  5. DNP-enhanced solid-state NMR spectroscopy of active pharmaceutical ingredients.

    Science.gov (United States)

    Zhao, Li; Pinon, Arthur C; Emsley, Lyndon; Rossini, Aaron J

    2017-11-28

    Solid-state NMR spectroscopy has become a valuable tool for the characterization of both pure and formulated active pharmaceutical ingredients (APIs). However, NMR generally suffers from poor sensitivity that often restricts NMR experiments to nuclei with favorable properties, concentrated samples, and acquisition of one-dimensional (1D) NMR spectra. Here, we review how dynamic nuclear polarization (DNP) can be applied to routinely enhance the sensitivity of solid-state NMR experiments by one to two orders of magnitude for both pure and formulated APIs. Sample preparation protocols for relayed DNP experiments and experiments on directly doped APIs are detailed. Numerical spin diffusion models illustrate the dependence of relayed DNP enhancements on the relaxation properties and particle size of the solids and can be used for particle size determination when the other factors are known. We then describe the advanced solid-state NMR experiments that have been enabled by DNP and how they provide unique insight into the molecular and macroscopic structure of APIs. For example, with large sensitivity gains provided by DNP, natural isotopic abundance, 13 C- 13 C double-quantum single-quantum homonuclear correlation NMR spectra of pure APIs can be routinely acquired. DNP also enables solid-state NMR experiments with unreceptive quadrupolar nuclei such as 2 H, 14 N, and 35 Cl that are commonly found in APIs. Applications of DNP-enhanced solid-state NMR spectroscopy for the molecular level characterization of low API load formulations such as commercial tablets and amorphous solid dispersions are described. Future perspectives for DNP-enhanced solid-state NMR experiments on APIs are briefly discussed. Copyright © 2017 John Wiley & Sons, Ltd.

  6. /sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk

    Energy Technology Data Exchange (ETDEWEB)

    Bzhezovskii, V.M.; Valeev, R.B.; Kalabin, G.A.; Aliev, I.A.

    1987-06-20

    The /sup 13/C, /sup 17/O, and /sup 33/S NMR spectra of alkyl phenyl sulfones C/sub 6/H/sub 5/SO/sub 2/Alk were obtained. The changes in the screening of the /sup 13/C, /sup 17/O, and /sup 33/S nuclei in these compounds are determined by the effect of the alkyl substituents, which alternates in sign and decreases along the chain of atoms in the order: CH/sub 3/, C/sub 2/H/sub 5/, iso-C/sub 3/H/sub 7/, and tert-C/sub 4/H/sub 9/. In the alkyl phenyl sulfides C/sub 6/H/sub 5/SAlk the additional effect of disruption in the p,..pi.. interaction between the sulfur atom and the benzene ring as a result of conformational changes is superimposed on the screening of the /sup 13/C/sup ortho/ nuclei. For the changes in the screening of the /sup 13/C/sup para/ nuclei in C/sub 6/H/sub 5/SAlk the steric disruption of the p,..pi.. conjugation by the alkyl substituents is determining.

  7. A novel deconvolution method for modeling UDP-N-acetyl-D-glucosamine biosynthetic pathways based on 13C mass isotopologue profiles under non-steady-state conditions

    Directory of Open Access Journals (Sweden)

    Belshoff Alex C

    2011-05-01

    Full Text Available Abstract Background Stable isotope tracing is a powerful technique for following the fate of individual atoms through metabolic pathways. Measuring isotopic enrichment in metabolites provides quantitative insights into the biosynthetic network and enables flux analysis as a function of external perturbations. NMR and mass spectrometry are the techniques of choice for global profiling of stable isotope labeling patterns in cellular metabolites. However, meaningful biochemical interpretation of the labeling data requires both quantitative analysis and complex modeling. Here, we demonstrate a novel approach that involved acquiring and modeling the timecourses of 13C isotopologue data for UDP-N-acetyl-D-glucosamine (UDP-GlcNAc synthesized from [U-13C]-glucose in human prostate cancer LnCaP-LN3 cells. UDP-GlcNAc is an activated building block for protein glycosylation, which is an important regulatory mechanism in the development of many prominent human diseases including cancer and diabetes. Results We utilized a stable isotope resolved metabolomics (SIRM approach to determine the timecourse of 13C incorporation from [U-13C]-glucose into UDP-GlcNAc in LnCaP-LN3 cells. 13C Positional isotopomers and isotopologues of UDP-GlcNAc were determined by high resolution NMR and Fourier transform-ion cyclotron resonance-mass spectrometry. A novel simulated annealing/genetic algorithm, called 'Genetic Algorithm for Isotopologues in Metabolic Systems' (GAIMS was developed to find the optimal solutions to a set of simultaneous equations that represent the isotopologue compositions, which is a mixture of isotopomer species. The best model was selected based on information theory. The output comprises the timecourse of the individual labeled species, which was deconvoluted into labeled metabolic units, namely glucose, ribose, acetyl and uracil. The performance of the algorithm was demonstrated by validating the computed fractional 13C enrichment in these subunits

  8. Plakilactones G and H from a marine sponge. Stereochemical determination of highly flexible systems by quantitative NMR-derived interproton distances combined with quantum mechanical calculations of 13C chemical shifts

    Directory of Open Access Journals (Sweden)

    Simone Di Micco

    2013-12-01

    Full Text Available In this paper the stereostructural investigation of two new oxygenated polyketides, plakilactones G and H, isolated from the marine sponge Plakinastrella mamillaris collected at Fiji Islands, is reported. The stereostructural studies began on plakilactone H by applying an integrated approach of the NOE-based protocol and quantum mechanical calculations of 13C chemical shifts. In particular, plakilactone H was used as a template to extend the application of NMR-derived interproton distances to a highly flexible molecular system with simultaneous assignment of four non-contiguous stereocenters. Chemical derivatization and quantum mechanical calculations of 13C on plakilactone G along with a plausible biogenetic interconversion between plakilactone G and plakilactone H allowed us to determine the absolute configuration in this two new oxygenated polyketides.

  9. Creatinine and creatininium cation in water solution. Tautomerism and quantitative interpretation of the solution acidity effect on 1H, 13C and 1:4N NMR chemical shifts

    International Nuclear Information System (INIS)

    Kotsyubynskyy, D.; Molchanov, S.; Gryff-Keller, A.

    2004-01-01

    1 H, 13 C and 1 :4N NMR chemical shifts for creatinine in water solution of various acidity have been measured. Analysis of these data enabled determination of the acidity constant of creatininium cation and the chemical shifts of the neutral and protonated forms of creatinine. Molecular energies and carbon and nitrogen magnetic shielding constants for various tautomeric structures of the investigated species have been calculated using the quantum chemistry method GIAO DFT B3LYP/6-311++G(2d,p). Compilation of the available experimental and theoretical results has provided additional information on the problem of tautomerism of this important biological molecule. (author)

  10. Quantum mechanical and spectroscopic (FT-IR, 13C, 1H NMR and UV) investigations of 2-(5-(4-Chlorophenyl)-3-(pyridin-2-yl)-4,5-dihydropyrazol-1-yl)benzo[d]thiazole by DFT method

    Science.gov (United States)

    Diwaker

    2014-07-01

    The electronic, NMR, vibrational, structural properties of a new pyrazoline derivative: 2-(5-(4-Chlorophenyl)-3-(pyridine-2-yl)-4,5-dihydropyrazol-1-yl)benzo[d]thiazole has been studied using Gaussian 09 software package. Using VEDA 4 program we have reported the PED potential energy distribution of normal mode of vibrations of the title compound. We have also reported the 1H and 13C NMR chemical shifts of the title compound using B3LYP level of theory with 6-311++G(2d,2p) basis set. Using time dependent (TD-DFT) approach electronic properties such as HOMO and LUMO energies, electronic spectrum of the title compound has been studied and reported. NBO analysis and MEP surface mapping has also been calculated and reported using ab initio methods.

  11. Generation of Gaussian 09 Input Files for the Computation of 1H and 13C NMR Chemical Shifts of Structures from a Spartan’14 Conformational Search

    OpenAIRE

    sprotocols

    2014-01-01

    Authors: Spencer Reisbick & Patrick Willoughby ### Abstract This protocol describes an approach to preparing a series of Gaussian 09 computational input files for an ensemble of conformers generated in Spartan’14. The resulting input files are necessary for computing optimum geometries, relative conformer energies, and NMR shielding tensors using Gaussian. Using the conformational search feature within Spartan’14, an ensemble of conformational isomers was obtained. To convert the str...

  12. Dynamics and interactions of ibuprofen in cyclodextrin nanosponges by solid-state NMR spectroscopy

    Directory of Open Access Journals (Sweden)

    Monica Ferro

    2017-01-01

    Full Text Available Two different formulations of cyclodextrin nanosponges (CDNS, obtained by polycondensation of β-cyclodextrin with ethylenediaminetetraacetic acid dianhydride (EDTAn, were treated with aqueous solutions of ibuprofen sodium salt (IbuNa affording hydrogels that, after lyophilisation, gave two solid CDNS-drug formulations. 1H fast MAS NMR and 13C CP-MAS NMR spectra showed that IbuNa was converted in situ into its acidic and dimeric form (IbuH after freeze-drying. 13C CP-MAS NMR spectra also indicated that the structure of the nanosponge did not undergo changes upon drug loading compared to the unloaded system. However, the 13C NMR spectra collected under variable contact time cross-polarization (VCT-CP conditions showed that the polymeric scaffold CDNS changed significantly its dynamic regime on passing from the empty CDNS to the drug-loaded CDNS, thus showing that the drug encapsulation can be seen as the formation of a real supramolecular aggregate rather than a conglomerate of two solid components. Finally, the structural features obtained from the different solid-state NMR approaches reported matched the information from powder X-ray diffraction profiles.

  13. Glutamine synthetase activity in solanaceous cell suspensions accumulating alkaloids or not. {sup 13}C NMR and enzymatic assay; Activite de la glutamine synthetase dans des suspensions cellulaires de solanacees productrices ou non d'alcaloides. RMN du {sup 13}C et dosage enzymatique

    Energy Technology Data Exchange (ETDEWEB)

    Mesnard, F.; Marty, D.; Monti, J.P. [Faculte de Pharmacie, 80 - Amiens (France). Laboratoire de Biophysique, Groupe de Recherche des Biomolecules: micro-environnement et Metabolisme; Gillet-Manceau, F.; Fliniaux, M.A. [Faculte de Pharmacie, 80 - Amiens (France). Laboratoire de Phytotechnologie

    1999-09-01

    The metabolism of labelled pyruvate followed by {sup 13}C NMR and the measure of glutamine synthetase (GS) showed, according to previous results, a high activity of this enzyme in suspension cells of Nicotiana plumbaginifolia. This activity could derive glutamate from the alkaloidsynthesizing pathways. However, a recent work showed that the rate of the GS gene transcription was inversely proportional to the Gln/Glu ratio. The measures of Gln and Glu concentrations in Nicotiana plumbaginifolia cells revealed that high GS activity correlates with the weak value of Gln/Glu ratio. Therefore, the hypothesis of GS dysfunction for the non-biosynthesis of alkaloids in N. plumbaginifolia suspension cells can be discarded. This conclusion is strengthened by the results obtained when using a GS inhibitor. (author)

  14. Structural Identification of 19 Purified Isomers of the OPV Acceptor Material bisPCBM by 13C NMR and UV-Vis Absorption Spectroscopy and High-Performance Liquid Chromatography.

    Science.gov (United States)

    Liu, Tong; Abrahams, Isaac; Dennis, T John S

    2018-04-26

    The molecular structures of 19 purified isomers of bis-phenyl-C 62 -butyric acid methyl ester were identified by a combination of 13 C NMR and UV-vis absorption spectroscopies and high-performance liquid chromatography (HPLC) retention time analysis. All 19 isomers are dicyclopropafullerenes (none are homofullerenes). There were seven isomers with C 1 molecular point-group symmetry, four with C s , six with C 2 , one with C 2 v , and one with C 2 h symmetry. The C 2 h , C 2 v , and all five nonequatorial C 1 isomers were unambiguously assigned to their respective HPLC fractions. For the other 12 isomers, the 13 C NMR and UV-vis spectra placed them in six groups of two same-symmetry isomers. On the basis of the widely spaced HPLC retention times of the two isomers within each of these six groups, and the empirical inverse correlation between retention time and addend spacing, each isomer was assigned to its corresponding HPLC fraction. In addition, the missing trans-1 isomer was found, purified, and characterized.

  15. Structure and reactivity of lithium amides. /sup 6/Li, /sup 13/C, and /sup 15/N NMR spectroscopic studies and colligative measurements of lithium diphenylamide and lithium diphenylamide-lithium bromide complex solvated by tetrahydrofuran

    Energy Technology Data Exchange (ETDEWEB)

    DePue, J.S.; Collum, D.B.

    1988-08-03

    /sup 6/Li, /sup 13/C, and /sup 15/N NMR spectroscopic studies of lithium diphenylamide in THF/hydrocarbon solutions (THF = tetrahydrofuran) detected two different species. /sup 6/Li and /sup 15/N NMR spectroscopic studies of (/sup 6/Li, /sup 15/N)lithium diphenylamide showed the species observed at low THF concentrations to be a cyclic oligomer. Structural analogies provided strong support for a dimer while colligative measurements at 0/degrees/C indicated the dimer to be di- or trisolvated. On the basis of the observed mass action effects, the species appearing at intermediate THF concentrations is assigned as a contact or solvent-separated ion-paired monomer. Lithium diphenylamide forms a 1:1 adduct with lithium bromide at low THF concentrations. A combination of /sup 6/Li-/sup 15/N double labeling studies and colligative measurements supports a trisolvated cyclic mixed dimer structure. Although detailed spectroscopic studies at elevated THF concentrations were precluded by high fluctionality, the similarity of the /sup 13/C chemical shifts of lithium diphenylamide in the presence and absence of lithium bromide provide indirect evidence that the mixed dimer undergoes a THF concentration dependent dissociation to the monomeric amide and free lithium bromide. 24 references, 9 figures, 2 tables.

  16. Characterization of Two Distinct Amorphous Forms of Valsartan by Solid-State NMR.

    Science.gov (United States)

    Skotnicki, Marcin; Apperley, David C; Aguilar, Juan A; Milanowski, Bartłomiej; Pyda, Marek; Hodgkinson, Paul

    2016-01-04

    Valsartan (VAL) is an antihypertensive drug marketed in an amorphous form. Amorphous materials can have different physicochemical properties depending on preparation method, thermal history, etc., but the nature of such materials is difficult to study by diffraction techniques. This study characterizes two different amorphous forms of valsartan (AR and AM) using solid-state NMR (SSNMR) as a primary investigation tool, supported by solution-state NMR, FT-IR, TMDSC, and dissolution tests. The two forms are found to be clearly distinct, with a significantly higher level of structural arrangement in the AR form, as observed in (13)C, (15)N, and (1)H SSNMR. (13)C and (15)N NMR indicates that the fully amorphous material (AM) contains an approximately equal ratio of cis-trans conformers about the amide bond, whereas the AR form exists mainly as one conformer, with minor conformational "defects". (1)H ultrafast MAS NMR shows significant differences in the hydrogen bonding involving the tetrazole and acid hydrogens between the two materials, while (15)N NMR shows that both forms exist as a 1,2,3,4-tetrazole tautomer. NMR relaxation times show subtle differences in local and bulk molecular mobility, which can be connected with the glass transition, the stability of the glassy material, and its response to aging. Counterintuitively the fully amorphous material is found to have a significantly lower dissolution rate than the apparently more ordered AR material.

  17. New ruthenium (II) complexes derived from pyridinopyrazoline and pyridinopyrazole: /sup 1/H, /sup 13/C and /sup 99/Ru NMR study

    Energy Technology Data Exchange (ETDEWEB)

    Marzin, C.; Budde, F.; Steel, P.J.; Lerner, D.

    1987-01-01

    A series of RuL/sub 3//sup 2+/(A), Ru(bpy) L/sub 2//sup 2+/(B) and Ru(bpy)/sub 2/L/sup 2+/(C) complexes with pyridinopyrazole and pyridinopyrazoline ligands L have been prepared; their study allows the evaluation of the ligand ..pi..-acceptor ability on the complex properties; especially /sup 99/Ru and Ru/sup 2//Ru/sup 3+/ oxidation potential measurements show a good ..pi..-acceptor behavior of one of the pyridinopyrazoline ligands. All the B and C type complexes and most of the RuL/sub 3//sup 2+/ ones, emit at 77 K which is rather unusual; one of these gives rise to a double emission, possibly from two isomers. NMR studies show the presence of geometric isomers for A and B type complexes and of diastereoisomeric ones for complexes A, B and C when L includes a pyrazoline unit. 37 refs.

  18. Organometallic derivatives of furan. LII. Synthesis of carbofunctional furylsilanes and their 1H, 13C, and 29Si NMR spectroscopic and quantum-chemical investigation

    International Nuclear Information System (INIS)

    Lukevits, E.; Erchak, N.P.; Castro, I.; Popelis, Yu.Yu.; Kozyrev, A.K.; Anoshkin, V.I.; Kovalev, I.F.

    1986-01-01

    Under the standard conditions for the synthesis of furan compounds it is possible to obtain the carbofunctional derivatives of silylated furfural with retention of the trimethylsilyl group in the ring. By NMR and CNDO/2 LCAO MO methods and also as a result of the investigation of the chemical characteristics of silylated furfural and its carbofunctional derivatives it was established that the introduction of a trimethylsilyl group at position 5 of the furan ring does not change the reactivity of the carbofunctional substituents at position 2. The electronic effects of the substituents are hardly transmitted through the furan ring at all. The effect of substituents in the carbofunctional furylsilanes on the electronic structure of the ring is additive

  19. In vivo {sup 13}C MRS studies of carbohydrate metabolism

    Energy Technology Data Exchange (ETDEWEB)

    Halliday, Jane

    2003-07-01

    The work described in this thesis was performed by the author, except where indicated, within the Magnetic Resonance Centre at the University of Nottingham during the period between October 1999 and October 2002. Although much is known about the major pathways of carbohydrate metabolism, there is still much to be learnt about the exact mechanisms of many of these pathways. Of particular interest is how these pathways are modified under different physiological conditions and in diseased states. {sup 13}C NMR spectroscopy provides a non-invasive means for studying carbohydrate metabolism in vivo, and the work presented within this thesis gives two such examples of this in human subjects. Natural abundance {sup 13}C NMR spectroscopy was used to measure glycogen levels in gastrocnemius muscle. The diurnal changes in response to mixed meals were measured in both type 2 diabetic subjects and age and weight matched controls. Metabolic studies were performed to complement the NMR measurements. The data obtained in these studies show the effect of the failure of muscle glucose storage upon post-prandial hyperglycaemia despite a supra-normal increase in plasma insulin in type 2 diabetes. {sup 13}C NMR spectroscopy was also used to study cerebral metabolism. Accumulation of {sup 13}C label into glutamate and glutamine following infusion of [1{sup 13}C] glucose allows the determination of the rates of the TCA cycle (F{sub TCA}) and neurotransmitter cycling (F{sub cyc}). These rates were measured in the visual cortex under control and activated conditions. The increases seen in F{sub TCA} upon activation, together with the lack of label accumulation in lactate, suggest that cerebral glucose metabolism is oxidative, even during strong activation. No conclusion can be made as to whether or not a similar increase is seen in F{sub cyc} due to the large associated errors in these values. (author)

  20. Solid-state NMR covariance of homonuclear correlation spectra.

    Science.gov (United States)

    Hu, Bingwen; Amoureux, Jean-Paul; Trebosc, Julien; Deschamps, Michael; Tricot, Gregory

    2008-04-07

    Direct covariance NMR spectroscopy, which does not involve a Fourier transformation along the indirect dimension, is demonstrated to obtain homonuclear correlation two-dimensional (2D) spectra in the solid state. In contrast to the usual 2D Fourier transform (2D-FT) NMR, in a 2D covariance (2D-Cov) spectrum the spectral resolution in the indirect dimension is determined by the resolution along the detection dimension, thereby largely reducing the time-consuming indirect sampling requirement. The covariance method does not need any separate phase correction or apodization along the indirect dimension because it uses those applied in the detection dimension. We compare in detail the specifications obtained with 2D-FT and 2D-Cov, for narrow and broad resonances. The efficiency of the covariance data treatment is demonstrated in organic and inorganic samples that are both well crystallized and amorphous, for spin -1/2 nuclei with 13C, 29Si, and 31P through-space or through-bond homonuclear 2D correlation spectra. In all cases, the experimental time has been reduced by at least a factor of 10, without any loss of resolution and signal to noise ratio, with respect to what is necessary with the 2D-FT NMR. According to this method, we have been able to study the silicate network of glasses by 2D NMR within reasonable experimental time despite the very long relaxation time of the 29Si nucleus. The main limitation of the 2D-Cov data treatment is related to the introduction of autocorrelated peaks onto the diagonal, which does not represent any actual connectivity.

  1. Solid-State NMR and DFT Studies on the Formation of Well-Defined Silica-Supported Tantallaaziridines: From Synthesis to Catalytic Application

    KAUST Repository

    Hamzaoui, Bilel; Pelletier, Jeremie; Abou-Hamad, Edy; Chen, Yin; El Eter, Mohamad; Chermak, Edrisse; Cavallo, Luigi; Basset, Jean-Marie

    2016-01-01

    spectroscopy, elemental analysis, and 1H,13C HETCOR and DQ TQ solid-state (SS) NMR spectroscopy. The formation mechanism, by β-H abstraction, was investigated by SS NMR spectroscopy and supported by DFT calculations. The C-H activation of the dimethylamide

  2. Modification and intercalation of layered zirconium phosphates: a solid-state NMR monitoring.

    Science.gov (United States)

    Bakhmutov, Vladimir I; Kan, Yuwei; Sheikh, Javeed Ahmad; González-Villegas, Julissa; Colón, Jorge L; Clearfield, Abraham

    2017-07-01

    Several layered zirconium phosphates treated with Zr(IV) ions, modified by monomethoxy-polyethyleneglycol-monophosphate and intercalated with doxorubicin hydrochloride have been studied by solid-state MAS NMR techniques. The organic components of the phosphates have been characterized by the 13 C{ 1 H} CP MAS NMR spectra compared with those of initial compounds. The multinuclear NMR monitoring has provided to establish structure and covalent attachment of organic/inorganic moieties to the surface and interlayer spaces of the phosphates. The MAS NMR experiments including kinetics of proton-phosphorus cross polarization have resulted in an unusual structure of zirconium phosphate 6 combining decoration of the phosphate surface by polymer units and their partial intercalation into the interlayer space. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

  3. Chemical Constituents from Bombacopsis glabra (Pasq. A. Robyns: Complete 1H and 13C NMR Assignments and X Ray Structure of 5-Hydroxy-3,6,7,8,4'-pentamethoxyflavone

    Directory of Open Access Journals (Sweden)

    Paula Vanderlúcia F.

    2002-01-01

    Full Text Available The flavone 5-hydroxy-3,6,7,8,4'-pentamethoxyflavone (1 and the triterpenes lupenone, 9,19-cyclolanost-23-ene-3beta,25-diol (2, (24R-9,19-cyclolanost-25-ene-3beta,24-diol (3 and (24S-9,19-cyclolanost-25-ene-3beta,24-diol (4 were isolated from the hexane extract of the stem bark of Bombacopsis glabra (Bombacaceae. The structures were determined by 13C and ¹H NMR (1D and 2D and mass spectrometry, and by comparison with literature data for triterpenes. The structure of the flavone 1 was unambiguously confirmed by a X-ray diffraction study. The five substances were isolated for the first time from Bombacaceae species.

  4. Backbone dynamics of a model membrane protein: measurement of individual amide hydrogen-exchange rates in detergent-solubilized M13 coat protein using 13C NMR hydrogen/deuterium isotope shifts

    International Nuclear Information System (INIS)

    Henry, G.D.; Weiner, J.H.; Sykes, B.D.

    1987-01-01

    Hydrogen-exchange rates have been measured for individual assigned amide protons in M13 coat protein, a 50-residue integral membrane protein, using a 13 C nuclear magnetic resonance (NMR) equilibrium isotope shift technique. The locations of the more rapidly exchanging amides have been determined. In D 2 O solutions, a peptide carbonyl resonance undergoes a small upfield isotope shift (0.08-0.09 ppm) from its position in H 2 O solutions; in 1:1 H 2 O/D 2 O mixtures, the carbonyl line shape is determined by the exchange rate at the adjacent nitrogen atom. M13 coat protein was labeled biosynthetically with 13 C at the peptide carbonyls of alanine, glycine, phenylalanine, proline, and lysine, and the exchange rates of 12 assigned amide protons in the hydrophilic regions were measured as a function of pH by using the isotope shift method. This equilibrium technique is sensitive to the more rapidly exchanging protons which are difficult to measure by classical exchange-out experiments. In proteins, structural factors, notably H bonding, can decrease the exchange rate of an amide proton by many orders of magnitude from that observed in the freely exposed amides of model peptides such as poly(DL-alanine). With corrections for sequence-related inductive effects, the retardation of amide exchange in sodium dodecyl sulfate solubilized coat protein has been calculated with respect to poly(DL-alanine). The most rapidly exchanging protons, which are retarded very little or not at all, are shown to occur at the N- and C-termini of the molecule. A model of the detergent-solubilized coat protein is constructed from these H-exchange data which is consistent with circular dichroism and other NMR results

  5. Microscopic structural analysis of fractured silk fibers from Bombyx mori and Samia cynthia ricini using 13C CP/MAS NMR with a 1 mm microcoil MAS NMR probehead

    KAUST Repository

    Yamauchi, Kazuo; Yamasaki, Shizuo; Takahashi, Rui; Asakura, Tetsuo

    2010-01-01

    Conformational changes have been studied in silk fibers from the domestic silkworm Bombyx mori and a wild silkworm Samia cynthia ricini as a result of fractured by stretching. About 300 samples consisting of only the fractured regions of [1-13C

  6. Comparison of the Fc fragment from a human IgG1 and its CH2, pFc', and tFc' subfragments. A study using reductive methylation and 13C NMR

    International Nuclear Information System (INIS)

    Jentoft, J.E.; Rayford, R.

    1989-01-01

    The Fc fragment of a human monoclonal IgG1 was compared with subfragments containing (a) the intact CH2 domain (CH2 fragment) or (b) the intact CH3 domain (pFc' and tFc' fragments). All fragments were reductively 13 C-methylated and their resulting dimethyllysyl resonances characterized in 0.1 M KCl as a function of pH by 13 C NMR spectroscopy. Seven resonances were characterized for the 18 lysine residues of the Fc fragment, eight for the 12 lysines of the CH2 fragment, and five each for the 9 lysines of the pFc' and the 6 lysines of the tFc' fragments, respectively. The multiplicity of resonances indicates that the lysine residues in each fragment exist in a variety of microenvironments and that the fragments are all highly structured. The correspondence between 6 of the 12 or 13 perturbed lysine residues in the Fc fragment and the smaller subfragments indicates that the conformation of the CH2 and CH3 domains is largely unchanged in the smaller fragments. However, in addition to three lysines at the CH2-CH3 domain interface, whose environments were known to be disrupted in the smaller fragments, three or four lysine residues have somewhat different properties in the Fc fragment and in the subfragments, indicating that some local perturbations are included in the domain structure in the subfragments

  7. Yeast-expressed human membrane protein aquaporin-1 yields excellent resolution of solid-state MAS NMR spectra

    International Nuclear Information System (INIS)

    Emami, Sanaz; Fan Ying; Munro, Rachel; Ladizhansky, Vladimir; Brown, Leonid S.

    2013-01-01

    One of the biggest challenges in solid-state NMR studies of membrane proteins is to obtain a homogeneous natively folded sample giving high spectral resolution sufficient for structural studies. Eukaryotic membrane proteins are especially difficult and expensive targets in this respect. Methylotrophic yeast Pichia pastoris is a reliable producer of eukaryotic membrane proteins for crystallography and a promising economical source of isotopically labeled proteins for NMR. We show that eukaryotic membrane protein human aquaporin 1 can be doubly ( 13 C/ 15 N) isotopically labeled in this system and functionally reconstituted into phospholipids, giving excellent resolution of solid-state magic angle spinning NMR spectra.

  8. Synthesis of [21-13C]-cholesterol

    International Nuclear Information System (INIS)

    Caballero, G.M.; Gros, E.G.

    1994-01-01

    The synthesis of [21- 13 C]-cholesterol from 3β-O-(t-butyldimethylsilyl)-17β-cyano-androst-5-ene is described. Labelled carbon-atom was introduced by Grignard reaction of nitrile derivative with [ 13 C]-methylmagnesium iodide. Location of label was confirmed by 13 C-NMR spectroscopy. (author)

  9. Synthesis, single crystal X-ray, spectroscopic (FT-IR, UV-vis, fluorescence, 1H &13C NMR), computational (DFT/B3LYP) studies of some imidazole based picrates

    Science.gov (United States)

    Arockia doss, M.; Rajarajan, G.; Thanikachalam, V.; Selvanayagam, S.; Sridhar, B.

    2018-04-01

    2,4,5-triphenyl-1H-imidazol-3-ium picrate (1), 2-(4-fluorophenyl)-4,5-diphenyl-1H-imidazol-3-ium picrate (2), 2-(4-methylphenyl)-4,5-diphenyl-1H-imidazol-3-ium picrate (3) were synthesised. These compounds 1-3 were characterized by elemental, FT-IR, 1H NMR and 13C NMR analyses. The structure of compound 3 was further confirmed by single crystal X-ray diffraction. The studies reveal that the molecule is associated with weak Nsbnd H⋯O and Csbnd H⋯N and van der Waals interactions which are responsible for the formation and strengthening of supramolecular assembly. The nature of the interactions and their importance are explored using the Hirshfeld surface method. The physicochemical properties of the compounds 1-3 were evaluated by UV-vis spectroscopy, fluorescence spectroscopy, and thermogravimetric analysis. According to thermal data the salts possess excellent thermal stabilities with decomposition temperatures ranging from 220 to 280 °C. Second-harmonic generation (SHG) results exposed that the picrates 1-3 were about 1.13-1.50 times greater than potassium dihydrogen phosphate (KDP). Here we also used Density functional theory (DFT) calculations in order to investigate the opto-electronic properties. The obtained theoretical results validate with available experimental data.

  10. 43Ca NMR in solid state

    Science.gov (United States)

    Bellot, P.-V.; Trokiner, A.; Zhdanov, Yu.; Yakubovskii, A.

    1998-02-01

    In this paper we show that 43Ca is a suitable NMR probe to study the properties of high-Tc superconducting oxides. In the normal state, we report the temperature and doping dependencies of the spin susceptibility measured by 43Ca NMR. In the superconducting state and more exactly in the mixed state, by analysing 43Ca NMR linewidth, we have studied the magnetic induction distribution due to the presence of vortices and deduced λ, the penetration depth. Dans cet article, on montre que l'isotope 43 du calcium est une bonne sonde RMN pour l'étude des propriétés des oxydes supraconducteurs à haute température. Dans l'état normal, par la détermination du déplacement de la raie, en fonction de la température, on accède à la variation thermique de la susceptibilité de spin. Dans l'état supraconducteur et plus particulièrement dans l'état mixte, la largeur de raie RMN permet d'étudier la distribution d'induction magnétique due à la présence des vortex et de déterminer λ, la longueur de pénétration.

  11. In vivo 13C MRS studies of carbohydrate metabolism

    International Nuclear Information System (INIS)

    Halliday, Jane

    2003-01-01

    The work described in this thesis was performed by the author, except where indicated, within the Magnetic Resonance Centre at the University of Nottingham during the period between October 1999 and October 2002. Although much is known about the major pathways of carbohydrate metabolism, there is still much to be learnt about the exact mechanisms of many of these pathways. Of particular interest is how these pathways are modified under different physiological conditions and in diseased states. 13 C NMR spectroscopy provides a non-invasive means for studying carbohydrate metabolism in vivo, and the work presented within this thesis gives two such examples of this in human subjects. Natural abundance 13 C NMR spectroscopy was used to measure glycogen levels in gastrocnemius muscle. The diurnal changes in response to mixed meals were measured in both type 2 diabetic subjects and age and weight matched controls. Metabolic studies were performed to complement the NMR measurements. The data obtained in these studies show the effect of the failure of muscle glucose storage upon post-prandial hyperglycaemia despite a supra-normal increase in plasma insulin in type 2 diabetes. 13 C NMR spectroscopy was also used to study cerebral metabolism. Accumulation of 13 C label into glutamate and glutamine following infusion of [1 1 3 C] glucose allows the determination of the rates of the TCA cycle (F TCA ) and neurotransmitter cycling (F cyc ). These rates were measured in the visual cortex under control and activated conditions. The increases seen in F TCA upon activation, together with the lack of label accumulation in lactate, suggest that cerebral glucose metabolism is oxidative, even during strong activation. No conclusion can be made as to whether or not a similar increase is seen in F cyc due to the large associated errors in these values. (author)

  12. Measurement of the signs of methyl {sup 13}C chemical shift differences between interconverting ground and excited protein states by R{sub 1{rho}}: an application to {alpha}B-crystallin

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, Andrew J.; Kay, Lewis E., E-mail: kay@pound.med.utoronto.ca [University of Toronto, Departments of Molecular Genetics, Biochemistry and Chemistry (Canada)

    2012-05-15

    Carr-Purcell-Meiboom-Gill relaxation dispersion (CPMG RD) NMR spectroscopy has emerged as a powerful tool for quantifying the kinetics and thermodynamics of millisecond time-scale exchange processes involving the interconversion between a visible ground state and one or more minor, sparsely populated invisible 'excited' conformational states. Recently it has also become possible to determine atomic resolution structural models of excited states using a wide array of CPMG RD approaches. Analysis of CPMG RD datasets provides the magnitudes of the chemical shift differences between the ground and excited states, {Delta}{omega}, but not the sign. In order to obtain detailed structural insights from, for example, excited state chemical shifts and residual dipolar coupling measurements, these signs are required. Here we present an NMR experiment for obtaining signs of {sup 13}C chemical shift differences of {sup 13}CH{sub 3} methyl groups using weak field off-resonance R{sub 1{rho}} relaxation measurements. The accuracy of the method is established by using an exchanging system where the invisible, excited state can be converted to the visible, ground state by altering sample conditions so that the signs of {Delta}{omega} values obtained from the spin-lock approach can be validated against those measured directly. Further, the spin-lock experiments are compared with the established H(S/M)QC approach for measuring signs of chemical shift differences and the relative strengths of each method are discussed. In the case of the 650 kDa human {alpha}B-crystallin complex where there are large transverse relaxation differences between ground and excited state spins the R{sub 1{rho}} method is shown to be superior to more 'traditional' experiments for sign determination.

  13. Solid-state NMR spectroscopy on complex biomolecules

    NARCIS (Netherlands)

    Renault, M.A.M.; Cukkemane, A.A.; Baldus, M.

    2010-01-01

    Biomolecular applications of NMR spectroscopy are often merely associated with soluble molecules or magnetic resonance imaging. However, since the late 1970s, solid-state NMR (ssNMR) spectroscopy has demonstrated its ability to provide atomic-level insight into complex biomolecular systems ranging

  14. Solid-state NMR basic principles and practice

    CERN Document Server

    Apperley, David C; Hodgkinson, Paul

    2014-01-01

    Nuclear Magnetic Resonance (NMR) has proved to be a uniquely powerful and versatile tool for analyzing and characterizing chemicals and materials of all kinds. This book focuses on the latest developments and applications for "solid-state" NMR, which has found new uses from archaeology to crystallography to biomaterials and pharmaceutical science research. The book will provide materials engineers, analytical chemists, and physicists, in and out of lab, a survey of the techniques and the essential tools of solid-state NMR, together with a practical guide on applications. In this concise introduction to the growing field of solid-state nuclear magnetic resonance spectroscopy The reader will find: * Basic NMR concepts for solids, including guidance on the spin-1/2 nuclei concept * Coverage of the quantum mechanics aspects of solid state NMR and an introduction to the concept of quadrupolar nuclei * An understanding relaxation, exchange and quantitation in NMR * An analysis and interpretation of NMR data, with e...

  15. Spectroscopic (FT-IR, FT-Raman, 1H- and 13C-NMR, Theoretical and Microbiological Study of trans o-Coumaric Acid and Alkali Metal o-Coumarates

    Directory of Open Access Journals (Sweden)

    Małgorzata Kowczyk-Sadowy

    2015-02-01

    Full Text Available This work is a continuation of research on a correlation between the molecular structure and electronic charge distribution of phenolic compounds and their biological activity. The influence of lithium, sodium, potassium, rubidium and cesium cations on the electronic system of trans o-coumaric (2-hydroxy-cinnamic acid was studied. We investigated the relationship between the molecular structure of the tested compounds and their antimicrobial activity. Complementary molecular spectroscopic techniques such as infrared (FT-IR, Raman (FT-Raman, ultraviolet-visible (UV-VIS and nuclear magnetic resonance (1H- and 13C-NMR were applied. Structures of the molecules were optimized and their structural characteristics were calculated by the density functional theory (DFT using the B3LYP method with 6-311++G** as a basis set. Geometric and magnetic aromaticity indices, atomic charges, dipole moments and energies were also calculated. Theoretical parameters were compared to the experimental characteristics of investigated compounds. Correlations between certain vibrational bands and some metal parameters, such as electronegativity, ionization energy, atomic and ionic radius, were found. The microbial activity of studied compounds was tested against Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, Staphylococcus aureus, Proteus vulgaris and Candida albicans.

  16. Structure-based predictions of 13C-NMR chemical shifts for a series of 2-functionalized 5-(methylsulfonyl)-1-phenyl-1H-indoles derivatives using GA-based MLR method

    Science.gov (United States)

    Ghavami, Raouf; Sadeghi, Faridoon; Rasouli, Zolikha; Djannati, Farhad

    2012-12-01

    Experimental values for the 13C NMR chemical shifts (ppm, TMS = 0) at 300 K ranging from 96.28 ppm (C4' of indole derivative 17) to 159.93 ppm (C4' of indole derivative 23) relative to deuteride chloroform (CDCl3, 77.0 ppm) or dimethylsulfoxide (DMSO, 39.50 ppm) as internal reference in CDCl3 or DMSO-d6 solutions have been collected from literature for thirty 2-functionalized 5-(methylsulfonyl)-1-phenyl-1H-indole derivatives containing different substituted groups. An effective quantitative structure-property relationship (QSPR) models were built using hybrid method combining genetic algorithm (GA) based on stepwise selection multiple linear regression (SWS-MLR) as feature-selection tools and correlation models between each carbon atom of indole derivative and calculated descriptors. Each compound was depicted by molecular structural descriptors that encode constitutional, topological, geometrical, electrostatic, and quantum chemical features. The accuracy of all developed models were confirmed using different types of internal and external procedures and various statistical tests. Furthermore, the domain of applicability for each model which indicates the area of reliable predictions was defined.

  17. Comprehensive quantum chemical and spectroscopic (FTIR, FT-Raman, 1H, 13C NMR) investigations of O-desmethyltramadol hydrochloride an active metabolite in tramadol--an analgesic drug.

    Science.gov (United States)

    Arjunan, V; Santhanam, R; Marchewka, M K; Mohan, S

    2014-03-25

    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 (1)H and (13)C NMR chemical shifts of the molecule have been anlysed. Copyright © 2013 Elsevier B.V. All rights reserved.

  18. Comprehensive quantum chemical and spectroscopic (FTIR, FT-Raman, (1)H, (13)C NMR) investigations of (1,2-epoxyethyl)benzene and (1,2-epoxy-2-phenyl)propane.

    Science.gov (United States)

    Arjunan, V; Anitha, R; Devi, L; Mohan, S; Yang, Haifeng

    2015-01-25

    Aromatic epoxides are causative factors for mutagenic and carcinogenic activity of polycyclic arenes. The 1,2- or 2,3-epoxy compounds are widely used to a considerable extent in the textile, plastics, pharmaceutical, cosmetics, detergent and photochemical industries. The FTIR and FT-Raman spectra of (1,2-epoxyethyl)benzene and (1,2-epoxy-2-phenyl)propane are recorded in the regions 4000-400 cm(-1) and 4000-100 cm(-1), respectively. The observed fundamentals are assigned to different normal modes of vibration. The structure of the compound has been optimised with B3LYP method using 6-311++G(**) and cc-pVTZ basis sets. The IR and Raman intensities are determined. The total electron density and molecular electrostatic potential surfaces of the molecule are constructed by using B3LYP/6-311++G(d,p) method to display electrostatic potential (electron+nuclei) distribution. The electronic properties HOMO and LUMO energies were measured. Natural bond orbital analysis of the compounds has been performed to indicate the presence of intramolecular charge transfer. The (1)H and (13)C NMR chemical shifts of the molecules have been analysed. Copyright © 2014 Elsevier B.V. All rights reserved.

  19. Solution and solid state NMR studies of the structure and dynamics of C60 and C70

    International Nuclear Information System (INIS)

    Johnson, R.D.; Yannoni, C.S.; Salem, J.; Meijer, G.; Bethune, D.S.

    1991-01-01

    This paper investigates the structure and dynamics of C 60 and C 70 with 13 C NMR spectroscopy. In solution, high-resolution spectra reveal that C 60 has a single resonance at 143 ppm, indicating a strained, aromatic system with high symmetry. This is strong evidence for a C 60 soccer ball geometry. A 2D NMR INADEQUATE experiment on 13 C-enriched C 70 reveals the bonding connectivity to be a linear string, in firm support of the proposed rugby ball structure with D 5h symmetry, and furnishes resonance assignments. Solid state NMR spectra of C 60 at ambient temperatures yield a narrow resonance, indicative of rapid molecular reorientation. Variable temperature T 1 measurements show that the rotational correlation time is ∼ 10 - 9 s at 230 K. At 77 K, this time increases to more than 1 ms, and the 13 C NMR spectrum of C 60 is a powder pattern due to chemical shift anisotropy (tensor components 220, 186, 40 ppm). At intermediate temperatures a narrow peak is superimposed on the powder pattern, suggesting a distribution of barriers to molecular motion in the sample, or the presence of an additional phase in the solid state. A Carr-Purcell dipolar experiment on C 60 in the solid state allows the first precise determination of the C 60 bond lengths: 1.45 and 1.40 Angstrom

  20. 1H, 15N and 13C assignments of domain 5 of Dictyostelium discoideum gelation factor (ABP-120) in its native and 8M urea-denatured states.

    Science.gov (United States)

    Hsu, Shang-Te Danny; Cabrita, Lisa D; Christodoulou, John; Dobson, Christopher M

    2009-06-01

    The gelation factor from Dictyostelium discoideum (ABP-120) is an actin binding protein consisting of six immunoglobulin (Ig) domains in the C-terminal rod domain. We have recently used the pair of domains 5 and 6 of ABP-120 as a model system for studying multi-domain nascent chain folding on the ribosome. Here we present the NMR assignments of domain 5 in its native and 8M urea-denatured states.

  1. Solvent effect in implicit/explicit model on FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra, linear, second- and third-nonlinear optical parameters of 2-(trifluoromethyl)benzoic acid: Experimental and computational study

    Science.gov (United States)

    Avcı, Davut; Altürk, Sümeyye; Tamer, Ömer; Kuşbazoğlu, Mustafa; Atalay, Yusuf

    2017-09-01

    FT-IR, 1H, 13C and 19F NMR, UV-vis and fluorescence spectra for 2-(trifluoromethyl)benzoic acid (2-TFMBA) were recorded. DFT//B3LYP/6-31++G(d,p) calculations were used to determine the optimized molecular geometry, vibrational frequencies, 1H, 13C and 19F GIAO-NMR chemical shifts of 2-TFMBA. The detailed assignments of vibrational frequencies were carried out on the basis of potential energy distribution (PED) by using VEDA program. TD-DFT/B3LYP/6-31++G(d,p) calculations with the PCM (polarizable continuum model) in ethanol and DMSO solvents based on implicit/explicit model and gas phase in the excited state were employed to investigate UV-vis absorption and fluorescence emission wavelengths. The UV-vis and emission spectra were given in ethanol and DMSO solvents, and the major contributions to the electronic transitions were obtained. In addition, the NLO parameters (β, γ and χ(3)) and frontier molecular orbital energies of 2-TFMBA were calculated by using B3LYP/6-31++G(d,p) level. The NLO parameters of 2-TFMBA were compared with that of para-Nitroaniline (pNA) and urea which are the typical NLO materials. The refractive index (n) is calculated by using the Lorentz-Lorenz equation to observe polarization behavior of 2-TFMBA in DMSO and ethanol solvents. In order to investigate intramolecular and hydrogen bonding interactions, NBO calculations were also performed by the same level. To sum up, considering the well-known biological role, photochemical properties of 2-TFMBA were discussed.

  2. Synthesis and characterization of "1"3C_3-tristearin

    International Nuclear Information System (INIS)

    Wu Hangyu; Lin Lin; Li Lei; Chen Dazhou

    2011-01-01

    A highly efficient synthesis of "1"3C_3 labeled triglycerides of stearic acids from "1"3C_3-glycerol and stearic acids, by immobilized lipase-catalyzed in solvent-free medium was described. The structure of the product were characterized by fourier transform infrared spectrum (FT-IR), nuclear magnetic resonance (NMR), mass spectra (MS). The results showed that triglycerides of stearic acids contained three "1"3C atoms. The isotope abundance of "1"3C_3-tristearin was more than 99% and the yield was 80% of "1"3C_3-tristearin through calculation. Chemical purity (> 98%) was obtained by differential scanning calorimetry (DSC). (authors)

  3. Isotopic variations ({delta}{sup 13} C and {delta}{sup 18} O) in Siderastrea stellata (Cnidaria-Anthozoa), Itamaraca island, State of Pernambuco, Northeastern Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Valderez P.; Sial, Alcides N. [Pernambuco Univ., Recife, PE (Brazil). Dept. de Geologia. Lab. de Isotopos Estaveis; Mayeal, Elga M.; Exner, Marco Antonio [Pernambuco Univ., Recife, PE (Brazil). Dept. de Zoologia. Lab. de Macro e Megabentos

    1998-12-01

    Isotopic determinations for O and C were performed in coral skeletons collected in beach rocks from two localities (Orange and Catuama), Itamaraca Island, north littoral of the State of pernambuco, northeastern Brazil. Large variations of {delta}{sup 18} O and {delta}{sup 13} C in corals from both localities are found, the largest ones being observed at the Orange locality {delta}{sup 13} C in this locality varies from -0.8 to +1.8% PDB and {delta}{sup 1.8} O from -5.3 to -1.8% PDB, while at the Catuama locality, they vary from -1.8 to 0.1% PDB and -3.8 to -2.7% PDB, respectively. Large variations in {delta}{sup 18} O (up to 2.5%) coupled with weakly defined positive correlation between {delta}{sup 18} O and {delta}{sup 13} C, can be attributed to temperature variations as consequence of climatic perturbations. Temperature estimates, calculated from {delta}{sup 18} O values, assuming isotopic equilibrium with seawater, yield values between 24.9 deg C and 43.1 deg C at Orange, and from 28.4 deg C to 35 deg C at Catuama, all of them (expect one growth band from one sample) are high enough for the full development of the coral colony. Temperature average is 31.4 deg C at Orange, which is a little bit higher than that at Catuama, but both of them indicate thermal stress conditions. In all analyzed specimens, expect for one, at Orange, T increases was accompanied by decreasing in the organic activity, as suggested by corresponding negative {delta}{sup 13} C anomaly. Therefore, the observed bleaching is possibly related to thermal stress and the high T may be related to the El Nino-Southern Oscillation (ENSO) warning event. On the other hand, anthropogenic action at Orange, local of intense tourism throughout the year, coupled with high rate of sedimentation in the region, may contribute to the observed coral bleaching. (author)

  4. Determination of the pKa value of the hydroxyl group in the alpha-hydroxycarboxylates citrate, malate and lactate by 13C NMR: implications for metal coordination in biological systems.

    Science.gov (United States)

    Silva, Andre M N; Kong, XiaoLe; Hider, Robert C

    2009-10-01

    Citric acid is an important metal chelator of biological relevance. Citric acid helps solubilizing metals, increasing their bioavailability for plants and microbes and it is also thought to be a constituent of both the extracellular and cytoplasmic low molecular iron pools occurring in plants and vertebrates. Metal coordination by citric acid involves coordination both by the carboxylate and hydroxyl groups, of particular interest is its alpha-hydroxycarboxylate function. This structural feature is highly conserved in siderophores produced by evolutionarily distant species and seems to confer specificity toward Fe(III) binding. In order to understand the mechanism of metal coordination by alpha-hydroxycarboxylates and correctly evaluate the respective complex stability constants, it is essential to improve the knowledge about the ionisation of the alcohol group in these compounds. We have evaluated the hydroxyl pKa value of citric, malic and lactic acids with the objective of understanding the influence of alpha-carbon substitution. Studies at high pH values, utilizing (13)C NMR, permitted estimation of the pKa values for the three acids. The pKa (alcohol) values (14.4 for citric acid, 14.5 for malic acid, and 15.1 for lactic acid) are considerably higher than the previously reported value for citric acid (11.6) but still lower than the value of 15.5 for methanol. A comparative analysis of the three compounds indicates that different substitutions on the alpha-carbon introduce changes to the inductive effect experienced by the hydroxyl group thereby modulating its ionisation behaviour. Comparison with the siderophore rhizoferrin, which pKa (alcohol) values were confirmed to be 10 and 11.3, suggests that intra-molecular hydrogen bonding may also aid in the hydroxyl ionisation by stabilizing the resulting anion. Studies of metal coordination by alpha-hydroxycarboxylates should take these factors into account.

  5. Natural abundant solid state NMR studies in designed tripeptides for differentiation of multiple conformers.

    Science.gov (United States)

    Jayanthi, S; Chatterjee, Bhaswati; Raghothama, S

    2009-10-01

    Solid state NMR (SSNMR) experiments on heteronuclei in natural abundance are described for three synthetically designed tripeptides Piv-(L)Pro-(L)Pro-(L)Phe-OMe (1), Piv-(D)Pro-(L)Pro-(L)Phe-OMe (2), and Piv-(D)Pro-(L)Pro-(L)Phe-NHMe (3). These peptides exist in different conformation as shown by solution state NMR and single crystal X-ray analysis (Chatterjee et al., Chem Eur J 2008, 14, 6192). In this study, SSNMR has been used to probe the conformations of these peptides in their powder form. The (13)C spectrum of peptide (1) showed doubling of resonances corresponding to cis/cis form, unlike in solution where the similar doubling is attributed to cis/trans form. This has been confirmed by the chemical shift differences of C(beta) and C(gamma) carbon of Proline in peptide (1) both in solution and SSNMR. Peptide (2) and (3) provided single set of resonances which represented all trans form across the di-Proline segment. The results are in agreement with the X-ray analysis. Solid state (15)N resonances, especially from Proline residues provided additional information, which is normally not observable in solution state NMR. (1)H chemical shifts are also obtained from a two-dimensional heteronuclear correlation experiment between (1)H--(13)C. The results confirm the utility of NMR as a useful tool for identifying different conformers in peptides in the solid state. (c) 2009 Wiley Periodicals, Inc. Biopolymers 91: 851-860, 2009.

  6. Carbon-13 NMR spectroscopy of biological systems

    CERN Document Server

    Beckmann, Nicolau

    1995-01-01

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

  7. Synthesis and applications of 13C glycerol

    International Nuclear Information System (INIS)

    Stocking, E.; Khalsa, O.; Martinez, R.A.; Silks, L.A. III

    1994-01-01

    Due in part to the use of labeled glycerol for the 13 C enrichment of biomolecules, we are currently developing new synthetic routes to various isotopomers of glycerol. Judging from our experience, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment and/or have poor overall yields (12 to 15%). Furthermore, the use of glycerol for enrichment can be prohibitively expensive and its availability is limited by the level of demand. We are presently developing a short de novo synthesis of glycerol from carbon dioxide (∼53% overall yield for four steps) and are examining the feasibility of synthesizing site-specific 13 C-labeled glycerol and dihydroxyacetone (DHA) from labeled methanol and carbon dioxide. One application of 13 C glycerol we have examined is enzymatic conversion of glycerol to glyceraldehyde-3-monophosphate or dihydroxyacetone monophosphate (DHAP) with yields ranging from 25 to 50% (as determined by NMR spectroscopy). We are also pursuing the chemical conversion of 13 C-labeled DHA to DHAP. We are especially interested in 13 C-labeled DHAP because we are investigating its use as a chemo-enzymatic precursor for both labeled 2-deoxyribose and 2-deoxyribonucleic acids

  8. Synthesis and applications of 13C glycerol

    International Nuclear Information System (INIS)

    Stocking, E.; Khalsa, O.; Martinez, R.; Silks, L.A. III

    1994-01-01

    The authors are currently developing new synthetic routes to the various isotopomers of glycerol. Labeled glycerol is useful for 13 C enrichment of biomolecules. However, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment or have poor overall yields (12-15%). In addition, the use of glycerol for enrichment can be prohibitively expensive and its availability depends on the level of demand. The authors have developed a short de novo synthesis of [U- 13 C]glycerol from carbon dioxide (∼53% overall yield for four steps) and are currently examining the feasibility of synthesizing site-specific 13 C labeled glycerol and dihydroxyacetone (DHA) from methanol and carbon dioxide. The authors have examined the enzymatic conversion of [U- 13 C]glycerol to glyceraldehyde-3-monophosphate or dihydroxyacetone monophosphate (DHAP) with yields ranging from 25-50% (as determined by NMR spectroscopy). The authors are also pursuing the chemical conversion of 13 C labeled DHA to DHAP and the results are presented. Labeled DHAP is a possible enzymatic precursor for both labeled 2-deoxyribose and 2-deoxyribonucleic acids

  9. Soil fertility, humic fractions and natural abundance of "1"3C and "1"5N in soil under different land use in Parana State, Southern Brazil

    International Nuclear Information System (INIS)

    Loss, Arcangelo; Pereia, Marcos Gervasio; Costa, Elias Mendes; Beutler, Sidinei Julio; Piccolo, Marisa de Cassia

    2016-01-01

    Humic fractions of soil organic matter (SOM) and measurements of "1"3C and "1"5N isotope can be used to highlight differences between management systems with different intensities of land use. This study characterized soil fertility, quantified carbon levels in the humic fractions and evaluated the natural abundance of "1"3C and "1"5N in systems cultivated under no-tillage system (NTS) and conventional tillage system (CTS) or used with secondary forest or perennial pasture in Marmeleiro, Parana State, Southern Brazil. NTS was more efficient than the conventional tillage system (CTS) in increasing pH (0.0-0.10 m layer), Ca (0.0-0.05 m layer), P (except 0.05-0.10 m layer) and N (0.0-0.10 m) levels, total organic carbon (TOC) stocks (0.0-0.20 and 0.0-0.40 m layers); carbon of the humin fraction (C-HUM) in 0.0-0.40 m; the fulvic acid fraction (C-FAF) and humic acid (C-HAF) in 0.0-0.05 m. The use of grasses, in NTS and pasture, increased TOC stocks compared to the other soil use or management systems evaluated in the 0.0-0.40 m layer. In the topsoil layer, the anthropogenic influence of plowing and harrowing in CTS promoted greater loss of carbon in C-HUM, C-FAF and C-HAF than NTS, forest and pasture. In CTS, growing corn for 42 years after the removal of forest cover did not alter the "1"3C at 0.0-0.40 m. In pasture, the absence of legumes, constant deposition of cattle manure and a more stable organic matter favored high "1"5N levels (except at 0.0-0.05 m in CTS). The decrease in "1"5N values from the 0.0-0.10 to 0.10-0.20 m layer in CTS indicates that soil turnover (by plowing and harrowing) has the potential to disturb the depth-related variation in soil "1"5N, accelerating decomposition and compromising N transformations. Among the variables analyzed, the determination of carbon in humic fractions and "1"5N values were efficient in identifying soil changes produced by land use or management systems

  10. Solid state NMR studies for a new carbonization process with high temperature preheating

    Science.gov (United States)

    Saito, Koji; Hatakeyama, Moriaki; Komaki, Ikuo; Katoh, Kenji

    2002-01-01

    A new carbonization process with rapid preheating and coke discharging at medium temperature has been developed in Japan. The result of this process shows that even when no or slightly coking coal is by 50 wt% the coking property is improved and a coking coke with cold strength usable at blast furnace can be manufactured with the new carbonization process. The mechanism of the coking property improvement was examined by coal properties using mainly solid state NMR ( 1H CRAMPS and 13C SPE/MAS, CP/MAS) and NMR imaging (single point imaging, in-situ imaging). It has been clarified that the molecular structure of coal is relaxed by the rapid heating treatment and, in addition, there is a close relation between hydrogen bonding and relaxation of the molecular structure of coal.

  11. Insulin induces a positive relationship between the rates of ATP and glycogen changes in isolated rat liver in presence of glucose; a 31P and 13C NMR study

    Directory of Open Access Journals (Sweden)

    Gin Henri

    2005-11-01

    Full Text Available Abstract Background There is an emerging theory suggesting that insulin, which is known to be the predominant postprandial anabolic hormone, is also a major regulator of mitochondrial oxidative phosphorylation in human skeletal muscle. However, little is known about its effects in the liver. Since there is a theoretical relationship between glycogen metabolism and energy status, a simultaneous and continuous investigation of hepatic ATP and glycogen content was performed in intact and isolated perfused liver by 31P and 13C nuclear magnetic resonance (NMR The hepatic rates of ATP and glycogen changes were evaluated with different concentrations of insulin and glucose during continuous and short-term supply. Results Liver from rats fed ad libitum were perfused with Krebs-Henseleit Buffer (KHB(controls or KHB containing 6 mM glucose, 30 mM glucose, insulin alone, insulin + 6 mM glucose, insulin + 30 mM glucose. In the control, glycogenolysis occurred at a rate of -0.53 ± 0.021 %·min-1 and ATP content decreased at a rate of -0.28 ± 0.029 %·min-1. In the absence of insulin, there was a close proportional relationship between the glycogen flux and the glucose concentration, whereas ATP rates never varied. With insulin + glucose, both glycogen and ATP rates were strongly related to the glucose concentration; the magnitude of net glycogen flux was linearly correlated to the magnitude of net ATP flux: fluxglycogen = 72.543(fluxATP + 172.08, R2 = 0.98. Conclusion Only the co-infusion of 30 mM glucose and insulin led to (i a net glycogen synthesis, (ii the maintenance of the hepatic ATP content, and a strong positive correlation between their net fluxes. This has never previously been reported. The specific effect of insulin on ATP change is likely related to a rapid stimulation of the hepatic mitochondrial oxidative phosphorylation. We propose that variations in the correlation between rates of ATP and glycogen changes could be a probe for insulin

  12. Combination of {sup 13}C/{sup 113}Cd NMR, potentiometry, and voltammetry in characterizing the interactions between Cd and two models of the main components of soil organic matter

    Energy Technology Data Exchange (ETDEWEB)

    Lenoble, V. [IFRE PMSE 112, CEREGE (UMR 6635 CNRS/Universite Paul Cezanne), Aix-en-Provence (France); Universite du Sud Toulon Var, Laboratoire PROTEE, La Garde Cedex (France); Garnier, C. [Universite du Sud Toulon Var, Laboratoire PROTEE, La Garde Cedex (France); Universite Bordeaux I, ISM-LPTC (UMR CNRS 5255), Talence (France); Masion, A.; Garnier, J.M. [IFRE PMSE 112, CEREGE (UMR 6635 CNRS/Universite Paul Cezanne), Aix-en-Provence (France); Ziarelli, F. [CNRS, Federation des Sciences Chimiques de Marseille, Spectropole, Marseille cedex 20 (France)

    2008-01-15

    This work allowed the characterization of the Cd-binding sites of two compounds taken as models for exudates, the main components of soil organic matter (SOM). The studied compounds were exopolysaccharides (EPS), specifically exudates of roots (polygalacturonic acid) and of soil bacteria (Phytagel). Potentiometric acid-base titrations were performed and fitting of the obtained results indicated the presence of two main classes of acidic sites, defined by their pK{sub a} values, for both EPS but of a different nature when comparing the two compounds. The two studied exopolysaccharides presented different acidic/basic site ratios: 0.15 for Phytagel and 0.76 for polygalacturonic acid. Spectroscopic techniques ({sup 13}C/{sup 113}Cd NMR, FTIR) distinguished different Cd surroundings for each of the studied EPS, which is in agreement with the titration results. Furthermore, these analyses indicated the presence of -COOH and -OH groups in various proportions for each exopolysaccharide, which should be linked to their reactivity towards cadmium. Cadmium titrations (voltammetric measurements) also differentiated different binding sites for each compound and allowed the determination of the strength of the Cd-binding site of the EPS. Fitting of the results of such voltammetric measurements was performed using PROSECE (Programme d'Optimisation et de Speciation Chimique dans l'Environnement), a software coupling chemical speciation calculation and binding parameter optimization. The fitting, taking into account the Cd{sup 2+}/H{sup +} competition towards exopolysaccharides, confirmed the acid-base titrations and spectroscopic analyses by revealing two classes of binding sites: (i) one defined as a strong complexant regarding its Cd{sup 2+}-EPS association (logK = 9-10.4) and with basic functionality regarding H{sup +}-EPS association (pK{sub a} = 11.3-11.7), and (ii) one defined as a weak complexant (logK = 7.1-8.2) and with acidic functionality (pK{sub a} = 3

  13. Insulin induces a positive relationship between the rates of ATP and glycogen changes in isolated rat liver in presence of glucose; a 31P and 13C NMR study.

    Science.gov (United States)

    Baillet-Blanco, Laurence; Beauvieux, Marie-Christine; Gin, Henri; Rigalleau, Vincent; Gallis, Jean-Louis

    2005-11-21

    There is an emerging theory suggesting that insulin, which is known to be the predominant postprandial anabolic hormone, is also a major regulator of mitochondrial oxidative phosphorylation in human skeletal muscle. However, little is known about its effects in the liver. Since there is a theoretical relationship between glycogen metabolism and energy status, a simultaneous and continuous investigation of hepatic ATP and glycogen content was performed in intact and isolated perfused liver by 31P and 13C nuclear magnetic resonance (NMR) The hepatic rates of ATP and glycogen changes were evaluated with different concentrations of insulin and glucose during continuous and short-term supply. Liver from rats fed ad libitum were perfused with Krebs-Henseleit Buffer (KHB)(controls) or KHB containing 6 mM glucose, 30 mM glucose, insulin alone, insulin + 6 mM glucose, insulin + 30 mM glucose. In the control, glycogenolysis occurred at a rate of -0.53 +/- 0.021 % x min(-1) and ATP content decreased at a rate of -0.28 +/- 0.029 % x min(-1). In the absence of insulin, there was a close proportional relationship between the glycogen flux and the glucose concentration, whereas ATP rates never varied. With insulin + glucose, both glycogen and ATP rates were strongly related to the glucose concentration; the magnitude of net glycogen flux was linearly correlated to the magnitude of net ATP flux: flux(glycogen) = 72.543(fluxATP) + 172.08, R2 = 0.98. Only the co-infusion of 30 mM glucose and insulin led to (i) a net glycogen synthesis, (ii) the maintenance of the hepatic ATP content, and a strong positive correlation between their net fluxes. This has never previously been reported. The specific effect of insulin on ATP change is likely related to a rapid stimulation of the hepatic mitochondrial oxidative phosphorylation. We propose that variations in the correlation between rates of ATP and glycogen changes could be a probe for insulin resistance due to the action of substrates

  14. Spin-echo based diagonal peak suppression in solid-state MAS NMR homonuclear chemical shift correlation spectra

    Science.gov (United States)

    Wang, Kaiyu; Zhang, Zhiyong; Ding, Xiaoyan; Tian, Fang; Huang, Yuqing; Chen, Zhong; Fu, Riqiang

    2018-02-01

    The feasibility of using the spin-echo based diagonal peak suppression method in solid-state MAS NMR homonuclear chemical shift correlation experiments is demonstrated. A complete phase cycling is designed in such a way that in the indirect dimension only the spin diffused signals are evolved, while all signals not involved in polarization transfer are refocused for cancellation. A data processing procedure is further introduced to reconstruct this acquired spectrum into a conventional two-dimensional homonuclear chemical shift correlation spectrum. A uniformly 13C, 15N labeled Fmoc-valine sample and the transmembrane domain of a human protein, LR11 (sorLA), in native Escherichia coli membranes have been used to illustrate the capability of the proposed method in comparison with standard 13C-13C chemical shift correlation experiments.

  15. The phenomenology of optically pumped 13C NMR in diamond at 7.05 T: Room temperature polarization, orientation dependence, and the effect of defect concentration on polarization dynamics

    Science.gov (United States)

    Scott, Eric; Drake, Melanie; Reimer, Jeffrey A.

    2016-03-01

    Room temperature optical illumination of NV- imbibed single crystal diamonds with a 532 nm laser produces 13C polarization enhancements up to 200 times greater than that of the thermal equilibrium value at 7.05 T. We report high field NV- mediated 13C polarization as a function of the number and type (NV- and P1) of defects in commercially available diamonds. Surprisingly, both positive and negative 13C polarizations are observed depending on the orientation of the crystal with respect to the external magnetic field and the electric field vector of the optical illumination. The data reported herein cannot be explained by a previously proposed mechanism.

  16. In situ solid-state NMR spectroscopy of electrochemical cells: batteries, supercapacitors, and fuel cells.

    Science.gov (United States)

    Blanc, Frédéric; Leskes, Michal; Grey, Clare P

    2013-09-17

    prevent dendrite formation. The in situ method was also applied to monitor (by (11)B NMR) electrochemical double-layer formation in supercapacitors in real time. Though this method is useful, it comes with challenges. The separation of the contributions from the different cell components in the NMR spectra is not trivial because of overlapping resonances. In addition, orientation-dependent NMR interactions, including the spatial- and orientation-dependent bulk magnetic susceptibility (BMS) effects, can lead to resonance broadening. Efforts to understand and mitigate these BMS effects are discussed in this Account. The in situ NMR investigation of fuel cells initially focused on the surface electrochemistry at the electrodes and the electrochemical oxidation of methanol and CO to CO2 on the Pt cathode. On the basis of the (13)C and (195)Pt NMR spectra of the adsorbates and electrodes, CO adsorbed on Pt and other reaction intermediates and complete oxidation products were detected and their mode of binding to the electrodes investigated. Appropriate design and engineering of the NMR hardware has allowed researchers to integrate intact direct methanol fuel cells into NMR probes. Chemical transformations of the circulating methanol could be followed and reaction intermediates could be detected in real time by either (2)H or (13)C NMR spectroscopy. By use of the in situ NMR approach, factors that control fuel cell performance, such as methanol cross over and catalyst performance, were identified.

  17. Combined solid state and solution NMR studies of α,ε-15N labeled bovine rhodopsin

    International Nuclear Information System (INIS)

    Werner, Karla; Lehner, Ines; Dhiman, Harpreet Kaur; Richter, Christian; Glaubitz, Clemens; Schwalbe, Harald; Klein-Seetharaman, Judith; Khorana, H. Gobind

    2007-01-01

    Rhodopsin is the visual pigment of the vertebrate rod photoreceptor cell and is the only member of the G protein coupled receptor family for which a crystal structure is available. Towards the study of dynamics in rhodopsin, we report NMR-spectroscopic investigations of α,ε- 15 N-tryptophan labeled rhodopsin in detergent micelles and reconstituted in phospholipids. Using a combination of solid state 13 C, 15 N-REDOR and HETCOR experiments of all possible 13 C' i-1 carbonyl/ 15 N i -tryptophan isotope labeled amide pairs, and H/D exchange 1 H, 15 N-HSQC experiments conducted in solution, we assigned chemical shifts to all five rhodopsin tryptophan backbone 15 N nuclei and partially to their bound protons. 1 H, 15 N chemical shift assignment was achieved for indole side chains of Trp35 1.30 and Trp175 4.65 . 15 N chemical shifts were found to be similar when comparing those obtained in the native like reconstituted lipid environment and those obtained in detergent micelles for all tryptophans except Trp175 4.65 at the membrane interface. The results suggest that the integrated solution and solid state NMR approach presented provides highly complementary information in the study of structure and dynamics of large membrane proteins like rhodopsin

  18. Estimates of methyl 13C and 1H CSA values (Δσ) in proteins from cross-correlated spin relaxation

    International Nuclear Information System (INIS)

    Tugarinov, Vitali; Scheurer, Christoph; Brueschweiler, Rafael; Kay, Lewis E.

    2004-01-01

    Simple pulse schemes are presented for the measurement of methyl 13 C and 1 H CSA values from 1 H- 13 C dipole/ 13 C CSA and 1 H- 13 C dipole/ 1 H CSA cross-correlated relaxation. The methodology is applied to protein L and malate synthase G. Average 13 C CSA values are considerably smaller for Ile than Leu/Val (17 vs 25 ppm) and are in good agreement with previous solid state NMR studies of powders of amino acids and dipeptides and in reasonable agreement with quantum-chemical DFT calculations of methyl carbon CSA values in peptide fragments. Small averaged 1 H CSA values on the order of 1 ppm are measured, consistent with a solid state NMR determination of the methyl group 1 H CSA in dimethylmalonic acid

  19. Parallel β-Sheet Structure of Alanine Tetrapeptide in the Solid State As Studied by Solid-State NMR Spectroscopy.

    Science.gov (United States)

    Asakura, Tetsuo; Horiguchi, Kumiko; Aoki, Akihiro; Tasei, Yugo; Naito, Akira

    2016-09-01

    The structural analysis of alanine oligopeptides is important for understanding the crystalline region in silks from spiders and wild silkworms and also the mechanism of cellular toxicity of human diseases arising from expansion in polyalanine sequences. The atomic-level structures of alanine tripeptide and tetrapeptide with antiparallel β-sheet structures (AP-Ala3 and AP-Ala4, respectively) together with alanine tripeptide with parallel β-sheet structures (P-Ala3) have been determined, but alanine tetrapeptide with a parallel β-sheet structure (P-Ala4) has not been reported yet. In this article, first, we established the preparation protocol of P-Ala4 from more stable AP-Ala4. Second, complete assignments of the (13)C, (15)N, and (1)H solid-state NMR spectra were performed with (13)C- and (15)N-labeled Ala4 samples using several solid-state NMR techniques. Then, the structural constraints were obtained, for example, the amide proton peaks of P-Ala4 in the (1)H double-quantum magic-angle spinning NMR spectrum were heavily overlapped and observed at about 7.4 ppm, which was a much higher field than that of 8.7-9.1 ppm observed for AP-Ala4, indicating that the intermolecular hydrogen-bond lengths across strands (N-H···O═C) were considerably longer for P-Ala4, that is, 2.21-2.34 Å, than those reported for AP-Ala4, that is, 1.8-1.9 Å. The structural model was proposed for P-Ala4 by NMR results and MD calculations.

  20. An unprecedented up-field shift in the 13C NMR spectrum of the carboxyl carbons of the lantern-type dinuclear complex TBA[Ru2(O2CCH3)4Cl2] (TBA+ = tetra(n-butyl)ammonium cation).

    Science.gov (United States)

    Hiraoka, Yuya; Ikeue, Takahisa; Sakiyama, Hiroshi; Guégan, Frédéric; Luneau, Dominique; Gillon, Béatrice; Hiromitsu, Ichiro; Yoshioka, Daisuke; Mikuriya, Masahiro; Kataoka, Yusuke; Handa, Makoto

    2015-08-14

    A large up-field shift (-763 ppm) has been observed for the carboxyl carbons of the dichlorido complex TBA[Ru(2)(O(2)CCH(3))(4)Cl(2)] (TBA(+) = tetra(n-butyl)ammonium cation) in the (13)C NMR spectrum (CD(2)Cl(2) at 25 °C). The DFT calculations showed spin delocalization from the paramagnetic Ru(2)(5+) core to the ligands, in agreement with the large up-field shift.

  1. Fast mapping of global protein folding states by multivariate NMR:

    DEFF Research Database (Denmark)

    Malmendal, Anders; Underhaug, Jarl; Otzen, Daniel

    2010-01-01

    To obtain insight into the functions of proteins and their specific roles, it is important to establish efficient procedures for exploring the states that encapsulate their conformational space. Global Protein folding State mapping by multivariate NMR (GPS NMR) is a powerful high-throughput method......-lactalbumin in the presence of the anionic surfactant sodium dodecyl sulfate, SDS, and compare these with other surfactants, acid, denaturants and heat....

  2. Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR

    Science.gov (United States)

    Yau, Wai-Ming; Thurber, Kent R.; Tycko, Robert

    2014-07-01

    We describe the synthesis of new nitroxide-based biradical, triradical, and tetraradical compounds and the evaluation of their performance as paramagnetic dopants in dynamic nuclear polarization (DNP) experiments in solid state nuclear magnetic resonance (NMR) spectroscopy with magic-angle spinning (MAS). Under our experimental conditions, which include temperatures in the 25-30 K range, a 9.4 T magnetic field, MAS frequencies of 6.2-6.8 kHz, and microwave irradiation at 264.0 GHz from a 800 mW extended interaction oscillator source, the most effective compounds are triradicals that are related to the previously-described compound DOTOPA-TEMPO (see Thurber et al., 2010), but have improved solubility in glycerol/water solvent near neutral pH. Using these compounds at 30 mM total nitroxide concentration, we observe DNP enhancement factors of 92-128 for cross-polarized 13C NMR signals from 15N,13C-labeled melittin in partially protonated glycerol/water, and build-up times of 2.6-3.8 s for 1H spin polarizations. Net sensitivity enhancements with biradical and tetraradical dopants, taking into account absolute 13C NMR signal amplitudes and build-up times, are approximately 2-4 times lower than with the best triradicals.

  3. Sensitivity and Resolution Enhanced Solid-State NMR for Paramagnetic Systems and Biomolecules under Very Fast Magic Angle Spinning

    KAUST Repository

    Parthasarathy, Sudhakar

    2013-09-17

    Recent research in fast magic angle spinning (MAS) methods has drastically improved the resolution and sensitivity of NMR spectroscopy of biomolecules and materials in solids. In this Account, we summarize recent and ongoing developments in this area by presenting (13)C and (1)H solid-state NMR (SSNMR) studies on paramagnetic systems and biomolecules under fast MAS from our laboratories. First, we describe how very fast MAS (VFMAS) at the spinning speed of at least 20 kHz allows us to overcome major difficulties in (1)H and (13)C high-resolution SSNMR of paramagnetic systems. As a result, we can enhance both sensitivity and resolution by up to a few orders of magnitude. Using fast recycling (∼ms/scan) with short (1)H T1 values, we can perform (1)H SSNMR microanalysis of paramagnetic systems on the microgram scale with greatly improved sensitivity over that observed for diamagnetic systems. Second, we discuss how VFMAS at a spinning speed greater than ∼40 kHz can enhance the sensitivity and resolution of (13)C biomolecular SSNMR measurements. Low-power (1)H decoupling schemes under VFMAS offer excellent spectral resolution for (13)C SSNMR by nominal (1)H RF irradiation at ∼10 kHz. By combining the VFMAS approach with enhanced (1)H T1 relaxation by paramagnetic doping, we can achieve extremely fast recycling in modern biomolecular SSNMR experiments. Experiments with (13)C-labeled ubiquitin doped with 10 mM Cu-EDTA demonstrate how effectively this new approach, called paramagnetic assisted condensed data collection (PACC), enhances the sensitivity. Lastly, we examine (13)C SSNMR measurements for biomolecules under faster MAS at a higher field. Our preliminary (13)C SSNMR data of Aβ amyloid fibrils and GB1 microcrystals acquired at (1)H NMR frequencies of 750-800 MHz suggest that the combined use of the PACC approach and ultrahigh fields could allow for routine multidimensional SSNMR analyses of proteins at the 50-200 nmol level. Also, we briefly discuss the

  4. Location of radiation-induced grafted chains in polymers studied by solid-state NMR

    International Nuclear Information System (INIS)

    Whittacker, A.; Liu, H.

    1998-01-01

    In this study styrene and N-phenyl maleimide monomers were grafted onto poly(ethylene) (PE) chains using gamma radiation. Of main interest is the distribution of grafted chains within the polymer matrix, as this will determine the efficacy of mixing with the glassy polymers. It is expected that grafting will occur within the amorphous regions, and especially near the interface of the crystalline and amorphous regions. A suitable method for characterising the location of the grafted chains is solid-state 13 C NMR spectroscopy. The 13 C CPMAS spectrum of the blend of PE and N-phenyl maleimide mixed in the melt at 150 deg C , prior to reaction, is shown above. The spectrum shows the typical peaks for poly(ethylene) due to the amorphous and crystalline phase at 30.5 and 32.5 ppm, respectively. Peaks are also seen in the aromatic and carbonyl region due to the maleimide (not plotted). Experiments will be described where the NMR magnetisation is prepared in either the crystalline and amorphous regions of the poly(ethylene) prior to spin diffusion to the maleimide and styrene fractions. The location of the grafted monomers can then be determined by monitoring the changes in signal of polymer and graft with time

  5. Host-guest interaction of styrene and ethylbenzene in MIL-53 studied by solid-state NMR.

    Science.gov (United States)

    Li, Shenhui; Li, Jing; Tang, Jing; Deng, Feng

    Solid-state NMR was utilized to explore the host-guest interaction between adsorbate and adsorbent at atomic level to understand the separation mechanism of styrene (St) and ethylbenzene (EB) in MIL-53(Al). 13 C- 27 Al double-resonance NMR experiments revealed that the host-guest interaction between St and MIL-53 was much stronger than that of EB adsorption. In addition, 13 C DIPSHIFT experiments suggested that the adsorbed St was less mobile than EB confined inside the MIL-53 pore. Furthermore, the host-guest interaction model between St, EB and MIL-53 was established on the basis of the spatial proximities information extracted from 2D 1 H- 1 H homo-nuclear correlation NMR experiments. According to the experimental observation from solid-state NMR, it was found that the presence of π-π interaction between St and MIL-53 resulted in the stronger host-guest interaction and less mobility of St. This work provides direct experimental evidence for understanding the separation mechanism of St and EB using MIL-53 as an adsorbent. Copyright © 2017 Elsevier Inc. All rights reserved.

  6. Determination of the conformation of 2-hydroxy- and 2-aminobenzoic acid dimers using 13C NMR and density functional theory/natural bond order analysis: the central importance of the carboxylic acid carbon.

    Science.gov (United States)

    Burnette, Ronald R; Weinhold, Frank

    2006-07-20

    The 13C chemical shift for the carboxylic acid carbon provides a powerful diagnostic probe to determine the preferred isomeric dimer structures of benzoic acid derivatives undergoing intra- and intermolecular H-bonding in the gas, solution and crystalline phases. We have employed hybrid density functional calculations and natural bond orbital analysis to elucidate the electronic origins of the observed 13C shieldings and their relationship to isomeric stability. We find that delocalizing interactions from the carbonyl oxygen lone pairs (nO) into vicinal carbon-oxygen and carbon-carbon antibonds (sigmaCO*,sigmaCC*) make critical contributions to the 13C shieldings, and these nO --> sigmaCO*, nO --> sigmaCC* interactions are in turn sensitive to the intramolecular interactions that dictate dimer structure and stability. The carboxyl carbon atom can thus serve as a useful detector of subtle structural and conformational features in this pharmacologically important class of carboxylic acid interactions.

  7. Acceleration of natural-abundance solid-state MAS NMR measurements on bone by paramagnetic relaxation from gadolinium-DTPA

    Science.gov (United States)

    Mroue, Kamal H.; Zhang, Rongchun; Zhu, Peizhi; McNerny, Erin; Kohn, David H.; Morris, Michael D.; Ramamoorthy, Ayyalusamy

    2014-07-01

    Reducing the data collection time without affecting the signal intensity and spectral resolution is one of the major challenges for the widespread application of multidimensional nuclear magnetic resonance (NMR) spectroscopy, especially in experiments conducted on complex heterogeneous biological systems such as bone. In most of these experiments, the NMR data collection time is ultimately governed by the proton spin-lattice relaxation times (T1). For over two decades, gadolinium(III)-DTPA (Gd-DTPA, DTPA = Diethylene triamine pentaacetic acid) has been one of the most widely used contrast-enhancement agents in magnetic resonance imaging (MRI). In this study, we demonstrate that Gd-DTPA can also be effectively used to enhance the longitudinal relaxation rates of protons in solid-state NMR experiments conducted on bone without significant line-broadening and chemical-shift-perturbation side effects. Using bovine cortical bone samples incubated in different concentrations of Gd-DTPA complex, the 1H T1 values were calculated from data collected by 1H spin-inversion recovery method detected in natural-abundance 13C cross-polarization magic angle spinning (CPMAS) NMR experiments. Our results reveal that the 1H T1 values can be successfully reduced by a factor of 3.5 using as low as 10 mM Gd-DTPA without reducing the spectral resolution and thus enabling faster data acquisition of the 13C CPMAS spectra. These results obtained from 13C-detected CPMAS experiments were further confirmed using 1H-detected ultrafast MAS experiments on Gd-DTPA doped bone samples. This approach considerably improves the signal-to-noise ratio per unit time of NMR experiments applied to bone samples by reducing the experimental time required to acquire the same number of scans.

  8. Electric dipole moment of 13C

    Science.gov (United States)

    Yamanaka, Nodoka; Yamada, Taiichi; Hiyama, Emiko; Funaki, Yasuro

    2017-06-01

    We calculate for the first time the electric dipole moment (EDM) of 13C generated by the isovector charge conjugation-parity (CP)-odd pion exchange nuclear force in the α -cluster model, which describes well the structures of low-lying states of the 13C nucleus. The linear dependence of the EDM of 13C on the neutron EDM and the isovector CP-odd nuclear coupling is found to be d13C=-0.33 dn-0.0020 G¯π(1 ) . The linear enhancement factor of the CP-odd nuclear coupling is smaller than that of the deuteron, due to the difference of the structure between the 1 /21- state and the opposite-parity (1 /2+ ) states. We clarify the role of the structure played in the enhancement of the EDM. This result provides good guiding principles to search for other nuclei with large enhancement factor. We also mention the role of the EDM of 13C in determining the new physics beyond the standard model.

  9. Solid-state NMR studies of nucleic acid components

    Czech Academy of Sciences Publication Activity Database

    Dračínský, Martin; Hodgkinson, P.

    2015-01-01

    Roč. 5, č. 16 (2015), s. 12300-12310 ISSN 2046-2069 R&D Projects: GA ČR GA13-24880S Institutional support: RVO:61388963 Keywords : NMR spectroscopy * nucleic acid s * solid-state NMR Subject RIV: CB - Analytical Chemistry, Separation Impact factor: 3.289, year: 2015 http://pubs.rsc.org/en/content/articlepdf/2015/ra/c4ra14404j

  10. NMR backbone resonance assignments of the prodomain variants of BDNF in the urea denatured state.

    Science.gov (United States)

    Wang, Jing; Bains, Henrietta; Anastasia, Agustin; Bracken, Clay

    2018-04-01

    Brain derived neurotrophic factor (BDNF) is a member of the neurotrophin family of proteins which plays a central role in neuronal survival, growth, plasticity and memory. A single Val66Met variant has been identified in the prodomain of human BDNF that is associated with anxiety, depression and memory disorders. The structural differences within the full-length prodomain Val66 and Met66 isoforms could shed light on the mechanism of action of the Met66 and its impact on the development of neuropsychiatric-associated disorders. In the present study, we report the backbone 1 H, 13 C, and 15 N NMR assignments of both full-length Val66 and Met66 prodomains in the presence of 2 M urea. These conditions were utilized to suppress residual structure and aid subsequent native state structural investigations aimed at mapping and identifying variant-dependent conformational differences under native-state conditions.

  11. Synthesis of [5,6-13C2, 1-14C]olivetolic acid, methyl [1'-13C]olivetolate and [5,6-13C2, 1-14C]cannabigerolic acid

    International Nuclear Information System (INIS)

    Porwoll, J.P.; Leete, E.

    1985-01-01

    Potential advanced intermediates in the biosynthesis of delta 9 -tetrahydrocannabinol, the major psychoactive principle of marijuana, have been synthesized labeled with two contiguous 13 C atoms and 14 C. Methyl [5,6- 13 C 2 , 1- 14 C]olivetolate was prepared from lithium [ 13 C 2 ]acetylide and dimethyl [2- 14 C]malonate. Reaction with geranyl bromide afforded methyl [5,6- 13 C 2 , 1- 14 C]cannabigerolate, and hydrolysis of these methyl esters with lithium propyl mercaptide yielded the corresponding labeled acids. The 13 C- 13 C couplings observable in the 13 C NMR spectra of these 13 C-enriched compounds and their synthetic precursors are recorded. Methyl [1'- 14 C]olivetolate was prepared from 13 CO 2 to confirm assignments of the 13 C chemical shifts in the pentyl side chain of these compounds. (author)

  12. Structural analysis of alanine tripeptide with antiparallel and parallel beta-sheet structures in relation to the analysis of mixed beta-sheet structures in Samia cynthia ricini silk protein fiber using solid-state NMR spectroscopy.

    Science.gov (United States)

    Asakura, Tetsuo; Okonogi, Michi; Nakazawa, Yasumoto; Yamauchi, Kazuo

    2006-05-10

    The structural analysis of natural protein fibers with mixed parallel and antiparallel beta-sheet structures by solid-state NMR is reported. To obtain NMR parameters that can characterize these beta-sheet structures, (13)C solid-state NMR experiments were performed on two alanine tripeptide samples: one with 100% parallel beta-sheet structure and the other with 100% antiparallel beta-sheet structure. All (13)C resonances of the tripeptides could be assigned by a comparison of the methyl (13)C resonances of Ala(3) with different [3-(13)C]Ala labeling schemes and also by a series of RFDR (radio frequency driven recoupling) spectra observed by changing mixing times. Two (13)C resonances observed for each Ala residue could be assigned to two nonequivalent molecules per unit cell. Differences in the (13)C chemical shifts and (13)C spin-lattice relaxation times (T(1)) were observed between the two beta-sheet structures. Especially, about 3 times longer T(1) values were obtained for parallel beta-sheet structure as compared to those of antiparallel beta-sheet structure, which could be explicable by the difference in the hydrogen-bond networks of both structures. This very large difference in T(1) becomes a good measure to differentiate between parallel or antiparallel beta-sheet structures. These differences in the NMR parameters found for the tripeptides may be applied to assign the parallel and antiparallel beta-sheet (13)C resonances in the asymmetric and broad methyl spectra of [3-(13)C]Ala silk protein fiber of a wild silkworm, Samia cynthia ricini.

  13. NMR

    International Nuclear Information System (INIS)

    Kneeland, J.B.; Lee, B.C.P.; Whalen, J.P.; Knowles, R.J.R.; Cahill, P.T.

    1984-01-01

    Although still quite new, NMR imaging has already emerged as a safe, noninvasive, painless, and effective diagnostic modality requiring no ionizing radiation. Also, NMR appears already to have established itself as the method of choice for the examination of the brain spinal cord (excluding herniated disks). Another area in which NMR excels is in the examination of the pelvis. The use of surface coils offers the promise of visualizing structures with resolution unobtainable by any other means. In addition, NMR, with its superb visualization of vascular structures and potential ability to measure flow, may soon revolutionize the diagnosis of cardiovascular disease. Finally, NMR, through biochemically and physiologically based T/sub 1/ and T/sub 2/ indices or through spectroscopy, may provide a means of monitoring therapeutic response so as to permit tailoring of treatment to the individual patient. In short, NMR is today probably at the same stage as the x-ray was in Roentgen's day

  14. Computer Code for Interpreting 13C NMR Relaxation Measurements with Specific Models of Molecular Motion: The Rigid Isotropic and Symmetric Top Rotor Models and the Flexible Symmetric Top Rotor Model

    Science.gov (United States)

    2017-01-01

    top rotor superimposes an effective correlation time, τe, onto a symmetric top rotor to account for internal motion. 2. THEORY The purpose...specifically describe how simple 13C relaxation theory is used to describe quantitatively simple molecular 3 motions. More-detailed accounts ...of nuclear magnetic relaxation can be found in a number of basic textbooks (i.e., Farrar and Becker, 1971; Fukushima and Roeder, 1981; Harris, 1986

  15. 13C and 15N CP/MAS, 1H-15N SCT CP/MAS and FTIR spectroscopy as tools for qualitative detection of the presence of zwitterionic and non-ionic forms of ansa-macrolide 3-formylrifamycin SV and its derivatives in solid state.

    Science.gov (United States)

    Przybylski, Piotr; Pyta, Krystian; Klich, Katarzyna; Schilf, Wojciech; Kamieński, Bohdan

    2014-01-01

    (13)C, (15)N CP/MAS, including (1)H-(13)C and (1)H-(15)N short contact time CP/MAS experiments, and FTIR methods were applied for detailed structural characterization of ansa-macrolides as 3-formylrifamycin SV (1) and its derivatives (2-6) in crystal and in powder forms. Although HPLC chromatograms for 2/CH3 OH and 2/CH3 CCl3 were the same for rifampicin crystals dissolved in respective solvents, the UV-vis data recorded for them were different in 300-375 nm region. Detailed solid state (13)C and (15)N CP/MAS NMR and FTIR studies revealed that rifampicin (2), in contrast to 3-formylrifamycin SV (1) and its amino derivatives (3-6), can occur in pure non-ionic or zwitterionic forms in crystal and in pure these forms or a mixture of them in a powder. Multinuclear CP/MAS and FTIR studies demonstrated also that 3-6 derivatives were present exclusively in pure zwitterionic forms, both in powder and in crystal. On the basis of the solid state NMR and FTIR studies, two conformers of 3-formylrifamycin SV were detected in powder form due to the different orientations of carbonyl group of amide moiety. The PM6 molecular modeling at the semi-empirical level of theory, allowed visualization the most energetically favorable non-ionic and zwitterionic forms of 1-6 antibiotics, strongly stabilized via intramolecular H-bonds. FTIR studies indicated that the originally adopted forms of these type antibiotics in crystal or in powder are stable in standard laboratory conditions in time. The results presented point to the fact that because of a possible presence of two forms of rifampicin (compound 2), quantification of the content of this antibiotic in relevant pharmaceuticals needs caution. Copyright © 2013 John Wiley & Sons, Ltd.

  16. Solid state NMR of spin-1/2 nuclei

    International Nuclear Information System (INIS)

    Wind, R.A.

    1991-01-01

    The detection of nuclear magnetic resonance by Bloch et al. and Purcell and co-workers in 1946 has led to the development of one of the most powerful spectroscopic techniques known today. The reason is that, besides the applied external magnetic field, a nuclear spin also experiences extra local magnetic fields, which are due to surrounding electron clouds (the chemical shift) and other spins. These local fields differ for nuclei located at chemically different positions in a molecule. The result is that an NMR spectrum often consists of several lines, which can be considered to be a fingerprint of the material under investigation an can assist the clarifying its molecular structure. NMR has been especially successful in liquids and liquid like materials, where fast molecular tumblings average out the anisotropies in the local fields, resulting in well-resolved NMR spectra. This paper reports that initially the development of solid-state NMR was less dramatic. Originally, for reasons of sensitivity, attention was focused mainly on 1 H NMR. The result is that the NMR spectrum usually consists of single, broad, featureless line, which, except for special cases such as more or less isolated spin pairs or methyl groups, does not provide much information

  17. Experimental solid state NMR of gas hydrates : problems and solutions

    Energy Technology Data Exchange (ETDEWEB)

    Moudrakovski, I.; Lu, H.; Ripmeester, J. [National Research Council of Canada, Ottawa, ON (Canada). Steacie Inst. for Molecular Sciences; Kumar, R.; Susilo, R. [British Columbia Univ., Vancouver, BC (Canada). Dept. of Chemical and Biological Engineering; Luzi, M. [GeoForschungsZentrum Potsdam, Potsdam (Germany)

    2008-07-01

    Solid State NMR is a suitable spectroscopic technique for hydrate research for several reasons, including its capability to distinguish between different structural types of hydrates, its quantitative nature and potential for both in-situ and time resolved experiments. This study illustrated the applications of solid state NMR for compositional and structural studies of clathrate hydrates, with particular emphasis on experimental techniques and potential ways to overcome technical difficulties. In order to use the method to its full capacity, some instrumental developments are needed to adapt it to the specific experimental requirements of hydrate studies, such as very low temperatures and high pressures. This presentation discussed the quantification of the Carbon-13 spectra with examples from natural and synthetic hydrates prepared from multi-component mixtures of hydrocarbons. The main approach used for the first two examples was Carbon-13 NMR with Magic Angle Spinning (MAS) at -100 degrees C. The detailed characterization of mixed hydrogen hydrates required low temperature hydrogen MAS. The quantification problems encountered during these experiments were also discussed. The purpose of these recent experimental developments was to prompt wider application of Solid State NMR in hydrate research. NMR proved to be a viable method for analyzing the composition and structure of multi-component mixed gas hydrates; characterizing natural gas hydrates; and, evaluating the formation conditions and properties of mixed hydrogen hydrates. The limitations of the method were highlighted and sensible choices of experimental conditions and techniques that ensure accurate results were discussed. 34 refs., 10 figs.

  18. Flavonoids from Lonchocarpus araripensis (Leguminoseae): isolation, unequivocal assignment of NMR signals {sup 1}H and {sup 13}C and conformational analysis; Flavonoides de Lonchocarpus araripensis (Leguminoseae): isolamento, atribuicao inequivoca dos sinais de RMN {sup 1}H e {sup 13}C e analise conformacional

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Almi F.; Ferreira, Daniele A.; Monte, Francisco Jose Q., E-mail: fmonte@dqoi.ufc.br [Universidade Federal do Ceara (UFC), Fortaleza, CE (Brazil). Centro de Ciencias. Departamento de Quimica Organica e Inorganica; Braz-Filho, Raimundo [Universidade Estadual do Norte Fluminense (UENF), Campo dos Goytacazes, RJ (Brazil). Centro de Ciencias Tecnologicas. Laboratorio de Ciencias Quimicas

    2014-07-01

    In a continuing investigation for potentially bioactive natural products, flavonoids were isolated from Lonchocarpus araripensis (Leguminoseae) and identified as 3-methoxy-6-O-prenyl-6'',6''-dimethylchromene-[7,8,2'',3'']-flavone (1), 3,6-dimethoxy-6'',6''-dimethylchromene-[7,8,2'',3'']-flavone (2) and 3,5,8-trimethoxy-[6,7,2{sup ,}3{sup ]}-furanoflavone (3). This is the first time compound 3 has been described. Compound 2 has been previously isolated from roots while this is the first time 1 is reported in this species. Complete NMR assignments are given for 1 ,2 and 3 together with the determination of conformation for 1. (author)

  19. Structural characterization of alkyl-benzene fractions by carbon-13, hydrogen-1, NMR; Caracterizacao estrutural de fracoes de alquilbenzenos por RMN de {sup 13} C e de {sup 1} H

    Energy Technology Data Exchange (ETDEWEB)

    Queiroz, Jorge F. de; San Gil, Rosane A.S. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica; Marques, Rosana G.G. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

    1994-12-31

    This work presents studies concerning the utilization of carbon-13, hydrogen-1, NMR as chemical analytical technique to evaluate molecular characteristics of alkyl-benzene fractions. The methodology is described, including standards solutions and their preparations, as well as the experimental techniques used. The results are presented and discussed 2 refs., 4 tabs.

  20. Solid-State NMR Spectroscopy Proves the Presence of Penta-coordinated Sc Sites in MIL-100(Sc).

    Science.gov (United States)

    Giovine, Raynald; Volkringer, Christophe; Ashbrook, Sharon E; Trébosc, Julien; McKay, David; Loiseau, Thierry; Amoureux, Jean-Paul; Lafon, Olivier; Pourpoint, Frédérique

    2017-07-18

    Advanced solid-state NMR methods and first-principles calculations demonstrate for the first time the formation of penta-coordinated scandium sites. These coordinatively unsaturated sites were shown during the thermal activation of scandium-based metal-organic frameworks (MOFs). A 45 Sc NMR experiment allows their specific observation in activated Sc 3 BTB 2 (H 3 BTB=1,3,5-tris(4-carboxyphenyl)benzene) and MIL-100(Sc) MOFs. The assignment of the ScO 5 groups is supported by the DFT calculations of NMR parameters. The presence of ScO 5 Lewis acid sites in MIL-100(Sc) explains furthermore its catalytic activity. The first NMR experiment to probe 13 C- 45 Sc distances is also introduced. This advanced solid-state NMR pulse sequence allows the demonstration of the shrinkage of the MIL-100(Sc) network when the activation temperature is raised. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

  1. Advances in solid-state NMR of cellulose.

    Science.gov (United States)

    Foston, Marcus

    2014-06-01

    Nuclear magnetic resonance (NMR) spectroscopy is a well-established analytical and enabling technology in biofuel research. Over the past few decades, lignocellulosic biomass and its conversion to supplement or displace non-renewable feedstocks has attracted increasing interest. The application of solid-state NMR spectroscopy has long been seen as an important tool in the study of cellulose and lignocellulose structure, biosynthesis, and deconstruction, especially considering the limited number of effective solvent systems and the significance of plant cell wall three-dimensional microstructure and component interaction to conversion yield and rate profiles. This article reviews common and recent applications of solid-state NMR spectroscopy methods that provide insight into the structural and dynamic processes of cellulose that control bulk properties and biofuel conversion. Copyright © 2014 Elsevier Ltd. All rights reserved.

  2. Measurement of conformational constraints in an elastin-mimetic protein by residue-pair selected solid-state NMR

    Energy Technology Data Exchange (ETDEWEB)

    Hong, Mei [Iowa State University, Department of Chemistry (United States)], E-mail: mhong@iastate.edu; McMillan, R. Andrew; Conticello, Vincent P. [Emory University, Department of Chemistry (United States)

    2002-02-15

    We introduce a solid-state NMR technique for selective detection of a residue pair in multiply labeled proteins to obtain site-specific structural constraints. The method exploits the frequency-offset dependence of cross polarization to achieve {sup 13}CO{sub i} {sup {yields}} {sup 15}N{sub i} {sup {yields}} {sup 13}C{alpha}{sub i} transfer between two residues. A {sup 13}C, {sup 15}N-labeled elastin mimetic protein (VPGVG){sub n} is used to demonstrate the method. The technique selected the Gly3 C{alpha} signal while suppressing the Gly5 C{alpha} signal, and allowed the measurement of the Gly3 C{alpha} chemical shift anisotropy to derive information on the protein conformation. This residue-pair selection technique should simplify the study of protein structure at specific residues.

  3. Calculating the Response of NMR Shielding Tensor .sigma.(31P) and 2J(31P,13C) Coupling Constants in Nucleic Acid Phosphate to Coordination of the Mg2+Cation

    Czech Academy of Sciences Publication Activity Database

    Benda, Ladislav; Schneider, Bohdan; Sychrovský, Vladimír

    2011-01-01

    Roč. 115, č. 11 (2011), s. 2385-2395 ISSN 1089-5639 R&D Projects: GA AV ČR IAA400550701; GA ČR GAP205/10/0228 Institutional research plan: CEZ:AV0Z40550506; CEZ:AV0Z50520701 Keywords : nucleic acids * phosphate * NMR Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 2.946, year: 2011

  4. Nano-mole scale sequential signal assignment by 1 H-detected protein solid-state NMR

    KAUST Repository

    Wang, Songlin; Parthasarathy, Sudhakar; Xiao, Yiling; Nishiyama, Yusuke; Long, Fei; Matsuda, Isamu; Endo, Yuki; Nemoto, Takahiro; Yamauchi, Kazuo; Asakura, Tetsuo; Takeda, Mitsuhiro; Terauchi, Tsutomu; Kainosho, Masatsune; Ishii, Yoshitaka

    2015-01-01

    We present a 3D 1H-detected solid-state NMR (SSNMR) approach for main-chain signal assignments of 10-100 nmol of fully protonated proteins using ultra-fast magic-angle spinning (MAS) at ∼80 kHz by a novel spectral-editing method, which permits drastic spectral simplification. The approach offers ∼110 fold time saving over a traditional 3D 13C-detected SSNMR approach. This journal is © The Royal Society of Chemistry 2015.

  5. On the structure of amorphous calcium carbonate--a detailed study by solid-state NMR spectroscopy.

    Science.gov (United States)

    Nebel, Holger; Neumann, Markus; Mayer, Christian; Epple, Matthias

    2008-09-01

    The calcium carbonate phases calcite, aragonite, vaterite, monohydrocalcite (calcium carbonate monohydrate), and ikaite (calcium carbonate hexahydrate) were studied by solid-state NMR spectroscopy ( (1)H and (13)C). Further model compounds were sodium hydrogencarbonate, potassium hydrogencarbonate, and calcium hydroxide. With the help of these data, the structure of synthetically prepared additive-free amorphous calcium carbonate (ACC) was analyzed. ACC contains molecular water (as H 2O), a small amount of mobile hydroxide, and no hydrogencarbonate. This supports the concept of ACC as a transient precursor in the formation of calcium carbonate biominerals.

  6. Tannin Fingerprinting in Vegetable Tanned Leather by Solid State NMR Spectroscopy and Comparison with Leathers Tanned by Other Processes

    OpenAIRE

    Jan H. van der Westhuizen; David G. Reid; Melinda J. Duer; Susan L. Bonnet; Frederik H. Romer; Andrew P. Underwood; Nadine D. Senekal

    2011-01-01

    Solid state 13C-NMR spectra of pure tannin powders from four different sources – mimosa, quebracho, chestnut and tara – are readily distinguishable from each other, both in pure commercial powder form, and in leather which they have been used to tan.  Groups of signals indicative of the source, and type (condensed vs. hydrolyzable) of tannin used in the manufacture are well resolved in the spectra of the finished leathers.  These fingerprints are compared with those arising from leathers tann...

  7. Solid-State NMR Spectroscopy for the Physical Chemistry Laboratory

    Science.gov (United States)

    Kinnun, Jacob J.; Leftin, Avigdor; Brown, Michael F.

    2013-01-01

    Solid-state nuclear magnetic resonance (NMR) spectroscopy finds growing application to inorganic and organic materials, biological samples, polymers, proteins, and cellular membranes. However, this technique is often neither included in laboratory curricula nor typically covered in undergraduate courses. On the other hand, spectroscopy and…

  8. Study of the diurnal time variability of δ15 N and δ13 C in domestic sewage of Piracicaba city (Sao Paulo State, Brazil)

    International Nuclear Information System (INIS)

    Evangelista, Ricardo A.O.; Bortoletto Junior, Milton J.; Mortatti, Jefferson

    2002-01-01

    Diurnal variability concentrations and δ 13 C of DOC (dissolved organic carbon), DTC (dissolved total carbon) and POC (particulate organic carbon) as well as concentrations and δ 13 N of NH 4 + and PON (particulate organic nitrogen) have been measured using a ANCA-SL mass spectrometry in three points of raw sewage inputs within Piracicaba river. The results shows an important variability in the isotopic signatures and concentrations of the nitrogen and carbon forms during the diurnal period that can be successfully used to characterize and to distinguish three types of investigated effluents. (author)

  9. A solid state NMR study of layered double hydroxides intercalated with para-amino salicylate, a tuberculosis drug

    DEFF Research Database (Denmark)

    Jensen, Nicholai Daugaard; Bjerring, Morten; Nielsen, Ulla Gro

    2016-01-01

    Para-amino salicylate (PAS), a tubercolosis drug, was intercalated in three different layered double hydroxides (MgAl, ZnAl, and CaAl-LDH) and the samples were studied by multi-nuclear (1H, 13C, and 27Al) solid state NMR (SSNMR) spectroscopy in combination with powder X-ray diffraction (PXRD....... Moreover, 13C MAS NMR and infra-red spectroscopy show that PAS did not decompose during synthesis. Large amounts (20-41%) of amorphous aluminum impurities were detected in the structure using 27Al single pulse and 3QMAS NMR spectra, which in combination with 1H single and double quantum experiments also...... showed that the M(II):Al ratio was higher than predicted from the bulk metal composition of MgAl-PAS and ZnAl-PAS. Moreover, the first high-resolution 1H SSNMR spectra of a CaAl LDH is reported and assigned using 1H single and double quantum experiments in combination with 27Al{1H} HETCOR....

  10. Out-and-back {sup 13}C-{sup 13}C scalar transfers in protein resonance assignment by proton-detected solid-state NMR under ultra-fast MAS

    Energy Technology Data Exchange (ETDEWEB)

    Barbet-Massin, Emeline; Pell, Andrew J. [University of Lyon, CNRS/ENS Lyon/UCB Lyon 1, Centre de RMN a Tres Hauts Champs (France); Jaudzems, Kristaps [Latvian Institute of Organic Synthesis (Latvia); Franks, W. Trent; Retel, Joren S. [Leibniz-Institut fuer Molekulare Pharmakologie (Germany); Kotelovica, Svetlana; Akopjana, Inara; Tars, Kaspars [Biomedical Research and Study Center (Latvia); Emsley, Lyndon [University of Lyon, CNRS/ENS Lyon/UCB Lyon 1, Centre de RMN a Tres Hauts Champs (France); Oschkinat, Hartmut [Leibniz-Institut fuer Molekulare Pharmakologie (Germany); Lesage, Anne; Pintacuda, Guido, E-mail: guido.pintacuda@ens-lyon.fr [University of Lyon, CNRS/ENS Lyon/UCB Lyon 1, Centre de RMN a Tres Hauts Champs (France)

    2013-08-15

    We present here {sup 1}H-detected triple-resonance H/N/C experiments that incorporate CO-CA and CA-CB out-and-back scalar-transfer blocks optimized for robust resonance assignment in biosolids under ultra-fast magic-angle spinning (MAS). The first experiment, (H)(CO)CA(CO)NH, yields {sup 1}H-detected inter-residue correlations, in which we record the chemical shifts of the CA spins in the first indirect dimension while during the scalar-transfer delays the coherences are present only on the longer-lived CO spins. The second experiment, (H)(CA)CB(CA)NH, correlates the side-chain CB chemical shifts with the NH of the same residue. These high sensitivity experiments are demonstrated on both fully-protonated and 100 %-H{sup N} back-protonated perdeuterated microcrystalline samples of Acinetobacter phage 205 (AP205) capsids at 60 kHz MAS.

  11. Structural diversity of solid dispersions of acetylsalicylic acid as seen by solid-state NMR.

    Science.gov (United States)

    Policianova, Olivia; Brus, Jiri; Hruby, Martin; Urbanova, Martina; Zhigunov, Alexander; Kredatusova, Jana; Kobera, Libor

    2014-02-03

    Solid dispersions of active pharmaceutical ingredients are of increasing interest due to their versatile use. In the present study polyvinylpyrrolidone (PVP), poly[N-(2-hydroxypropyl)-metacrylamide] (pHPMA), poly(2-ethyl-2-oxazoline) (PEOx), and polyethylene glycol (PEG), each in three Mw, were used to demonstrate structural diversity of solid dispersions. Acetylsalicylic acid (ASA) was used as a model drug. Four distinct types of the solid dispersions of ASA were created using a freeze-drying method: (i) crystalline solid dispersions containing nanocrystalline ASA in a crystalline PEG matrix; (ii) amorphous glass suspensions with large ASA crystallites embedded in amorphous pHPMA; (iii) solid solutions with molecularly dispersed ASA in rigid amorphous PVP; and (iv) nanoheterogeneous solid solutions/suspensions containing nanosized ASA clusters dispersed in a semiflexible matrix of PEOx. The obtained structural data confirmed that the type of solid dispersion can be primarily controlled by the chemical constitutions of the applied polymers, while the molecular weight of the polymers had no detectable impact. The molecular structure of the prepared dispersions was characterized using solid-state NMR, wide-angle X-ray scattering (WAXS), and differential scanning calorimetry (DSC). By applying various (1)H-(13)C and (1)H-(1)H correlation experiments combined with T1((1)H) and T1ρ((1)H) relaxation data, the extent of the molecular mixing was determined over a wide range of distances, from intimate intermolecular contacts (0.1-0.5 nm) up to the phase-separated nanodomains reaching ca. 500 nm. Hydrogen-bond interactions between ASA and polymers were probed by the analysis of (13)C and (15)N CP/MAS NMR spectra combined with the measurements of (1)H-(15)N dipolar profiles. Overall potentialities and limitations of individual experimental techniques were thoroughly evaluated.

  12. Spectroscopic (FT-IR, FT-Raman, UV, 1H and 13C NMR insights, electronic profiling and DFT computations on ({(E-[3-(1H-imidazol-1-yl-1-phenylpropylidene] amino}oxy(4-nitrophenylmethanone, an imidazole-bearing anti-Candida agent

    Directory of Open Access Journals (Sweden)

    Al-Wahaibi Lamya H.

    2018-02-01

    Full Text Available The anti-Candida agent, ({(E-[3-(1H-imidazol-1-yl-1-phenylpropylidene]amnio}oxy(4-nitropheny methanone (IPAONM, was subjected to comprehensive spectroscopic (FT-IR, FT-Raman, UV–Vis 1H and 13C NMR characterization as well as Hartree Fock and density functional theory computation studies. The selected optimized geometric bond lengths and bond angles of the IPAONM molecule were compared with the experimental values. The calculated wavenumbers have been scaled and compared with the experimental spectra. Mulliken charges and natural bond orbital analysis of the title molecule were calculated and interpreted. The energy and oscillator strengths of the IPAONM molecule were calculated by time-dependent density functional theory (TD-DFT. In addition, frontier molecular orbitals and molecular electrostatic potential diagram of the title compound were computed and analyzed. A study on the electronic properties, such as HOMO, HOMO-1, LUMO and LUMO+1 energies was carried out using TD-DFT approach. The 1H and 13C NMR chemical shift values of the title compound were calculated by the gauge independent atomic orbital method and compared with the experimental results.

  13. Site-selective 13C labeling of proteins using erythrose

    International Nuclear Information System (INIS)

    Weininger, Ulrich

    2017-01-01

    NMR-spectroscopy enables unique experimental studies on protein dynamics at atomic resolution. In order to obtain a full atom view on protein dynamics, and to study specific local processes like ring-flips, proton-transfer, or tautomerization, one has to perform studies on amino-acid side chains. A key requirement for these studies is site-selective labeling with 13 C and/or 1 H, which is achieved in the most general way by using site-selectively 13 C-enriched glucose (1- and 2- 13 C) as the carbon source in bacterial expression systems. Using this strategy, multiple sites in side chains, including aromatics, become site-selectively labeled and suitable for relaxation studies. Here we systematically investigate the use of site-selectively 13 C-enriched erythrose (1-, 2-, 3- and 4- 13 C) as a suitable precursor for 13 C labeled aromatic side chains. We quantify 13 C incorporation in nearly all sites in all 20 amino acids and compare the results to glucose based labeling. In general the erythrose approach results in more selective labeling. While there is only a minor gain for phenylalanine and tyrosine side-chains, the 13 C incorporation level for tryptophan is at least doubled. Additionally, the Phe ζ and Trp η2 positions become labeled. In the aliphatic side chains, labeling using erythrose yields isolated 13 C labels for certain positions, like Ile β and His β, making these sites suitable for dynamics studies. Using erythrose instead of glucose as a source for site-selective 13 C labeling enables unique or superior labeling for certain positions and is thereby expanding the toolbox for customized isotope labeling of amino-acid side-chains.

  14. High resolution solid-state NMR spectroscopy of the Yersinia pestis outer membrane protein Ail in lipid membranes

    International Nuclear Information System (INIS)

    Yao, Yong; Dutta, Samit Kumar; Park, Sang Ho; Rai, Ratan; Fujimoto, L. Miya; Bobkov, Andrey A.; Opella, Stanley J.; Marassi, Francesca M.

    2017-01-01

    The outer membrane protein Ail (Adhesion invasion locus) is one of the most abundant proteins on the cell surface of Yersinia pestis during human infection. Its functions are expressed through interactions with a variety of human host proteins, and are essential for microbial virulence. Structures of Ail have been determined by X-ray diffraction and solution NMR spectroscopy, but those samples contained detergents that interfere with functionality, thus, precluding analysis of the structural basis for Ail’s biological activity. Here, we demonstrate that high-resolution solid-state NMR spectra can be obtained from samples of Ail in detergent-free phospholipid liposomes, prepared with a lipid to protein molar ratio of 100. The spectra, obtained with 13 C or 1 H detection, have very narrow line widths (0.40–0.60 ppm for 13 C, 0.11–0.15 ppm for 1 H, and 0.46–0.64 ppm for 15 N) that are consistent with a high level of sample homogeneity. The spectra enable resonance assignments to be obtained for N, CO, CA and CB atomic sites from 75 out of 156 residues in the sequence of Ail, including 80% of the transmembrane region. The 1 H-detected solid-state NMR 1 H/ 15 N correlation spectra obtained for Ail in liposomes compare very favorably with the solution NMR 1 H/ 15 N TROSY spectra obtained for Ail in nanodiscs prepared with a similar lipid to protein molar ratio. These results set the stage for studies of the molecular basis of the functional interactions of Ail with its protein partners from human host cells, as well as the development of drugs targeting Ail.

  15. High resolution solid-state NMR spectroscopy of the Yersinia pestis outer membrane protein Ail in lipid membranes

    Energy Technology Data Exchange (ETDEWEB)

    Yao, Yong; Dutta, Samit Kumar [Sanford Burnham Prebys Medical Discovery Institute (United States); Park, Sang Ho; Rai, Ratan [University of California San Diego, Department of Chemistry and Biochemistry (United States); Fujimoto, L. Miya; Bobkov, Andrey A. [Sanford Burnham Prebys Medical Discovery Institute (United States); Opella, Stanley J. [University of California San Diego, Department of Chemistry and Biochemistry (United States); Marassi, Francesca M., E-mail: fmarassi@sbp.edu [Sanford Burnham Prebys Medical Discovery Institute (United States)

    2017-03-15

    The outer membrane protein Ail (Adhesion invasion locus) is one of the most abundant proteins on the cell surface of Yersinia pestis during human infection. Its functions are expressed through interactions with a variety of human host proteins, and are essential for microbial virulence. Structures of Ail have been determined by X-ray diffraction and solution NMR spectroscopy, but those samples contained detergents that interfere with functionality, thus, precluding analysis of the structural basis for Ail’s biological activity. Here, we demonstrate that high-resolution solid-state NMR spectra can be obtained from samples of Ail in detergent-free phospholipid liposomes, prepared with a lipid to protein molar ratio of 100. The spectra, obtained with {sup 13}C or {sup 1}H detection, have very narrow line widths (0.40–0.60 ppm for {sup 13}C, 0.11–0.15 ppm for {sup 1}H, and 0.46–0.64 ppm for {sup 15}N) that are consistent with a high level of sample homogeneity. The spectra enable resonance assignments to be obtained for N, CO, CA and CB atomic sites from 75 out of 156 residues in the sequence of Ail, including 80% of the transmembrane region. The {sup 1}H-detected solid-state NMR {sup 1}H/{sup 15}N correlation spectra obtained for Ail in liposomes compare very favorably with the solution NMR {sup 1}H/{sup 15}N TROSY spectra obtained for Ail in nanodiscs prepared with a similar lipid to protein molar ratio. These results set the stage for studies of the molecular basis of the functional interactions of Ail with its protein partners from human host cells, as well as the development of drugs targeting Ail.

  16. Tannin Fingerprinting in Vegetable Tanned Leather by Solid State NMR Spectroscopy and Comparison with Leathers Tanned by Other Processes

    Directory of Open Access Journals (Sweden)

    Jan H. van der Westhuizen

    2011-01-01

    Full Text Available Solid state 13C-NMR spectra of pure tannin powders from four different sources – mimosa, quebracho, chestnut and tara – are readily distinguishable from each other, both in pure commercial powder form, and in leather which they have been used to tan.  Groups of signals indicative of the source, and type (condensed vs. hydrolyzable of tannin used in the manufacture are well resolved in the spectra of the finished leathers.  These fingerprints are compared with those arising from leathers tanned with other common tanning agents.  Paramagnetic chromium (III tanning causes widespread but selective disappearance of signals from the spectrum of leather collagen, including resonances from acidic aspartyl and glutamyl residues, likely bound to Cr (III structures. Aluminium (III and glutaraldehyde tanning both cause considerable leather collagen signal sharpening suggesting some increase in molecular structural ordering. The 27Al-NMR signal from the former material is consistent with an octahedral coordination by oxygen ligands. Solid state NMR thus provides easily recognisable reagent specific spectral fingerprints of the products of vegetable and some other common tanning processes. Because spectra are related to molecular properties, NMR is potentially a powerful tool in leather process enhancement and quality or provenance assurance.

  17. Atomic substitutions in synthetic apatite; Insights from solid-state NMR spectroscopy

    Science.gov (United States)

    Vaughn, John S.

    that fluorine occupies a complex distribution of atomic positions, which give rise to complex 19F peak shapes owing to varied F-Ca distance. 13C NMR analysis of carbonate-hydroxylapatite indicates that AB-type carbonate hydroxylapatite can be prepared without the presence of sodium or heat treatment. Isotopic 17O enrichment of hydroxylapatite and 17O NMR analysis reveals distinct signals corresponding to phosphate and hydroxyl oxygens, and heat treatment under vacuum results in loss of hydroxyl signal due to decomposition to tricalcium phosphate, which was observed by powder X-Ray diffraction (PXRD).

  18. A facile synthesis of δ-aminolevulinic acid (ALA) regio-selectively labeled with 13C and direct observation of enzymatic transformation from ALA to porphobilinogen (PBG)

    International Nuclear Information System (INIS)

    Kurumaya, Katsuyuki; Okazaki, Takeo; Seido, Nobuo; Akasaka, Yuzuru; Kawajiri, Yoshiki; Kajiwara, Masahiro; Kondo, Masao

    1989-01-01

    δ-Aminolevulinic acid (ALA), labeled with 13 C at position 1, 2, 3, 4, or 5, was synthesized from 13 C-labeled glycine, Meldrum's acid, or bromoacetate. The latter compounds were prepared from 13 C-sodium acetate or 13 C-acetic acid. Enzymatic transformation from ALA to porphobilinogen (PBG) was directly observed by 13 C-NMR. (author)

  19. Peakr: simulating solid-state NMR spectra of proteins

    International Nuclear Information System (INIS)

    Schneider, Robert; Odronitz, Florian; Hammesfahr, Bjorn; Hellkamp, Marcel; Kollmar, Martin

    2013-01-01

    When analyzing solid-state nuclear magnetic resonance (NMR) spectra of proteins, assignment of resonances to nuclei and derivation of restraints for 3D structure calculations are challenging and time-consuming processes. Simulated spectra that have been calculated based on, for example, chemical shift predictions and structural models can be of considerable help. Existing solutions are typically limited in the type of experiment they can consider and difficult to adapt to different settings. Here, we present Peakr, a software to simulate solid-state NMR spectra of proteins. It can generate simulated spectra based on numerous common types of internuclear correlations relevant for assignment and structure elucidation, can compare simulated and experimental spectra and produces lists and visualizations useful for analyzing measured spectra. Compared with other solutions, it is fast, versatile and user friendly. (authors)

  20. Combined solid state and solution NMR studies of {alpha},{epsilon}-{sup 15}N labeled bovine rhodopsin

    Energy Technology Data Exchange (ETDEWEB)

    Werner, Karla; Lehner, Ines [Johann Wolfgang Goethe-Universitaet Frankfurt, Center for Biomolecular Magnetic Resonance (Germany); Dhiman, Harpreet Kaur [University of Pittsburgh School of Medicine, Department of Structural Biology (United States); Richter, Christian; Glaubitz, Clemens; Schwalbe, Harald, E-mail: schwalbe@nmr.uni-frankfurt.de; Klein-Seetharaman, Judith [Johann Wolfgang Goethe-Universitaet Frankfurt, Center for Biomolecular Magnetic Resonance (Germany); Khorana, H. Gobind [Massachusetts Institute of Technology, Departments of Biology and Chemistry (United States)], E-mail: khorana@mit.edu

    2007-04-15

    Rhodopsin is the visual pigment of the vertebrate rod photoreceptor cell and is the only member of the G protein coupled receptor family for which a crystal structure is available. Towards the study of dynamics in rhodopsin, we report NMR-spectroscopic investigations of {alpha},{epsilon}-{sup 15}N-tryptophan labeled rhodopsin in detergent micelles and reconstituted in phospholipids. Using a combination of solid state {sup 13}C,{sup 15}N-REDOR and HETCOR experiments of all possible {sup 13}C'{sub i-1} carbonyl/{sup 15}N{sub i}-tryptophan isotope labeled amide pairs, and H/D exchange {sup 1}H,{sup 15}N-HSQC experiments conducted in solution, we assigned chemical shifts to all five rhodopsin tryptophan backbone {sup 15}N nuclei and partially to their bound protons. {sup 1}H,{sup 15}N chemical shift assignment was achieved for indole side chains of Trp35{sup 1.30} and Trp175{sup 4.65}. {sup 15}N chemical shifts were found to be similar when comparing those obtained in the native like reconstituted lipid environment and those obtained in detergent micelles for all tryptophans except Trp175{sup 4.65} at the membrane interface. The results suggest that the integrated solution and solid state NMR approach presented provides highly complementary information in the study of structure and dynamics of large membrane proteins like rhodopsin.

  1. State of Motor-Evacuation Function of the Stomach According to 13C-Octanoate Breath Test in Patients with Gastroesophageal Reflux Disease

    Directory of Open Access Journals (Sweden)

    V.G. Mishchuk

    2014-09-01

    Full Text Available We examined 58 patients with erosive form of gastroesophageal reflux disease and 10 healthy volunteers. All patients underwent fibrogastroduodenoscopy, 24 hour pH monitoring in the lower third of esophagus, 13C-octanoate breath test, identified concentration of cholecystokinin-pankreozymin in blood serum. It is found that 44.83 % of patients with gastroesophageal reflux disease have delayed, 36.21 % — rapid and 18.97 % — normal motor-e­vacuation function of the stomach. In patients with delayed gastric motility we observed prevalence of bile reflux with pH over 6 in the lower third of the esophagus, amounting to 42 % (p = 0.044, and increased concentration in the blood of cholecystokinin-pankreozymin up to (7.12 ± 0.21 ng/ml (p < 0.05, in healthy subjects — (5.91 ± 0.34 ng/ml. In patients with accelerated motility number of refluxes under 4 was 45 %, and cholecystokinin-pankreozymin le­vel — (4.4 ± 1.2 ng/ml. These data support the view of other authors that causes of heartburn as a leading symptom of gastroesophageal reflux disease can be duodenogastric reflux and visceral hyperalgesia.

  2. Solid state NMR sequential resonance assignments and conformational analysis of the 2x10.4 kDa dimeric form of the Bacillus subtilis protein Crh

    Energy Technology Data Exchange (ETDEWEB)

    Boeckmann, Anja [Institut de Biologie et Chimie des Proteines, C.N.R.S UMR 5086 (France)], E-mail: a.bockmann@ibcp.fr; Lange, Adam [Max-Planck-Institute for Biophysical Chemistry, Solid-state NMR (Germany); Galinier, Anne [Institut de Biologie Structurale et Microbiologie, C.N.R.S UPR 9043 (France); Luca, Sorin [Max-Planck-Institute for Biophysical Chemistry, Solid-state NMR (Germany); Giraud, Nicolas; Juy, Michel [Institut de Biologie et Chimie des Proteines, C.N.R.S UMR 5086 (France); Heise, Henrike [Max-Planck-Institute for Biophysical Chemistry, Solid-state NMR (Germany); Montserret, Roland; Penin, Francois [Institut de Biologie et Chimie des Proteines, C.N.R.S UMR 5086 (France); Baldus, Marc [Max-Planck-Institute for Biophysical Chemistry, Solid-state NMR (Germany)], E-mail: maba@mpibpc.mpg.de

    2003-12-15

    Solid state NMR sample preparation and resonance assignments of the U-[{sup 13}C,{sup 15}N] 2x10.4 kDa dimeric form of the regulatory protein Crh in microcrystalline, PEG precipitated form are presented. Intra- and interresidue correlations using dipolar polarization transfer methods led to nearly complete sequential assignments of the protein, and to 88% of all {sup 15}N, {sup 13}C chemical shifts. For several residues, the resonance assignments differ significantly from those reported for the monomeric form analyzed by solution state NMR. Dihedral angles obtained from a TALOS-based statistical analysis suggest that the microcrystalline arrangement of Crh must be similar to the domain-swapped dimeric structure of a single crystal form recently solved using X-ray crystallography. For a limited number of protein residues, a remarkable doubling of the observed NMR resonances is observed indicative of local static or dynamic conformational disorder. Our study reports resonance assignments for the largest protein investigated by solid state NMR so far and describes the conformational dimeric variant of Crh with previously unknown chemical shifts.

  3. Site-specific 13C content by quantitative isotopic 13C Nuclear Magnetic Resonance spectrometry: A pilot inter-laboratory study

    International Nuclear Information System (INIS)

    Chaintreau, Alain; Fieber, Wolfgang; Sommer, Horst; Gilbert, Alexis; Yamada, Keita; Yoshida, Naohiro; Pagelot, Alain; Moskau, Detlef; Moreno, Aitor; Schleucher, Jürgen; Reniero, Fabiano; Holland, Margaret; Guillou, Claude; Silvestre, Virginie; Akoka, Serge; Remaud, Gérald S.

    2013-01-01

    Graphical abstract: -- Highlights: •First ring test on isotopic 13 C NMR spectrometry. •Evaluation of the intra- and inter-variability of the NMR spectrometers used. •Definition of a protocol for qualification of the performance of the spectrometer. -- Abstract: Isotopic 13 C NMR spectrometry, which is able to measure intra-molecular 13 C composition, is of emerging demand because of the new information provided by the 13 C site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic 13 C NMR as a routine tool. This paper describes the first collaborative study of intra-molecular 13 C composition by NMR. The main goals of the ring test were to establish intra- and inter-variability of the spectrometer response. Eight instruments with different configuration were retained for the exercise on the basis of a qualification test. Reproducibility at the natural abundance of isotopic 13 C NMR was then assessed on vanillin from three different origins associated with specific δ 13 C i profiles. The standard deviation was, on average, between 0.9 and 1.2‰ for intra-variability. The highest standard deviation for inter-variability was 2.1‰. This is significantly higher than the internal precision but could be considered good in respect of a first ring test on a new analytical method. The standard deviation of δ 13 C i in vanillin was not homogeneous over the eight carbons, with no trend either for the carbon position or for the configuration of the spectrometer. However, since the repeatability for each instrument was satisfactory, correction factors for each carbon in vanillin could be calculated to harmonize the results

  4. Site-specific {sup 13}C content by quantitative isotopic {sup 13}C Nuclear Magnetic Resonance spectrometry: A pilot inter-laboratory study

    Energy Technology Data Exchange (ETDEWEB)

    Chaintreau, Alain; Fieber, Wolfgang; Sommer, Horst [Firmenich SA, Corporate R and D Division, P.O. Box 239, 1211 Geneva 8 (Switzerland); Gilbert, Alexis; Yamada, Keita [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503 (Japan); Yoshida, Naohiro [Department of Environmental Chemistry and Engineering, Tokyo Institute of Technology, 4259 Nagatsuta-cho, Midori-ku, Yokohama, Kanagawa 226-8503 (Japan); Earth-Life Science Institute, Tokyo Institute of Technology, Meguro, Tokyo 152-8551 (Japan); Pagelot, Alain [Bruker Biospin SAS, 34 rue de l‘Industrie, 67166 Wissembourg Cedex (France); Moskau, Detlef; Moreno, Aitor [Bruker Biospin AG, Industriestrasse 26, 8117 Fällanden (Switzerland); Schleucher, Jürgen [Department of Medical Biochemistry and Biophysics, Umeå University, S-90187 Umeå (Sweden); Reniero, Fabiano; Holland, Margaret; Guillou, Claude [European Commission, Joint Research Centre – Institute for Health and Consumer Protection, via E. Fermi 2749, I-21027 Ispra (Italy); Silvestre, Virginie; Akoka, Serge [EBSI team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 rue de la Houssinière, BP 92208, F-44322 Nantes cedex 3 (France); Remaud, Gérald S., E-mail: gerald.remaud@univ-nantes.fr [EBSI team, Interdisciplinary Chemistry: Synthesis, Analysis, Modelling (CEISAM), University of Nantes-CNRS UMR 6230, 2 rue de la Houssinière, BP 92208, F-44322 Nantes cedex 3 (France)

    2013-07-25

    Graphical abstract: -- Highlights: •First ring test on isotopic {sup 13}C NMR spectrometry. •Evaluation of the intra- and inter-variability of the NMR spectrometers used. •Definition of a protocol for qualification of the performance of the spectrometer. -- Abstract: Isotopic {sup 13}C NMR spectrometry, which is able to measure intra-molecular {sup 13}C composition, is of emerging demand because of the new information provided by the {sup 13}C site-specific content of a given molecule. A systematic evaluation of instrumental behaviour is of importance to envisage isotopic {sup 13}C NMR as a routine tool. This paper describes the first collaborative study of intra-molecular {sup 13}C composition by NMR. The main goals of the ring test were to establish intra- and inter-variability of the spectrometer response. Eight instruments with different configuration were retained for the exercise on the basis of a qualification test. Reproducibility at the natural abundance of isotopic {sup 13}C NMR was then assessed on vanillin from three different origins associated with specific δ{sup 13}C{sub i} profiles. The standard deviation was, on average, between 0.9 and 1.2‰ for intra-variability. The highest standard deviation for inter-variability was 2.1‰. This is significantly higher than the internal precision but could be considered good in respect of a first ring test on a new analytical method. The standard deviation of δ{sup 13}C{sub i} in vanillin was not homogeneous over the eight carbons, with no trend either for the carbon position or for the configuration of the spectrometer. However, since the repeatability for each instrument was satisfactory, correction factors for each carbon in vanillin could be calculated to harmonize the results.

  5. Solid-state NMR on complex biomolecules: novel methods and applications

    NARCIS (Netherlands)

    Nand, D.

    2011-01-01

    Solid-state NMR (ssNMR) represents a versatile technique in providing atomic-resolution information without the need for crystals or fast molecular motion required for X-ray crystallography and solution-state NMR, respectively. Recent past has witnessed the ability of this technique in providing

  6. Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves

    International Nuclear Information System (INIS)

    Thurber, Kent R.; Tycko, Robert

    2014-01-01

    We report solid state 13 C and 1 H nuclear magnetic resonance (NMR) experiments with magic-angle spinning (MAS) on frozen solutions containing nitroxide-based paramagnetic dopants that indicate significant perturbations of nuclear spin polarizations without microwave irradiation. At temperatures near 25 K, 1 H and cross-polarized 13 C NMR signals from 15 N, 13 C-labeled L-alanine in trinitroxide-doped glycerol/water are reduced by factors as large as six compared to signals from samples without nitroxide doping. Without MAS or at temperatures near 100 K, differences between signals with and without nitroxide doping are much smaller. We attribute most of the reduction of NMR signals under MAS near 25 K to nuclear spin depolarization through the cross-effect dynamic nuclear polarization mechanism, in which three-spin flips drive nuclear polarizations toward equilibrium with spin polarization differences between electron pairs. When T 1e is sufficiently long relative to the MAS rotation period, the distribution of electron spin polarization across the nitroxide electron paramagnetic resonance lineshape can be very different from the corresponding distribution in a static sample at thermal equilibrium, leading to the observed effects. We describe three-spin and 3000-spin calculations that qualitatively reproduce the experimental observations

  7. Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves.

    Science.gov (United States)

    Thurber, Kent R; Tycko, Robert

    2014-05-14

    We report solid state (13)C and (1)H nuclear magnetic resonance (NMR) experiments with magic-angle spinning (MAS) on frozen solutions containing nitroxide-based paramagnetic dopants that indicate significant perturbations of nuclear spin polarizations without microwave irradiation. At temperatures near 25 K, (1)H and cross-polarized (13)C NMR signals from (15)N,(13)C-labeled L-alanine in trinitroxide-doped glycerol/water are reduced by factors as large as six compared to signals from samples without nitroxide doping. Without MAS or at temperatures near 100 K, differences between signals with and without nitroxide doping are much smaller. We attribute most of the reduction of NMR signals under MAS near 25 K to nuclear spin depolarization through the cross-effect dynamic nuclear polarization mechanism, in which three-spin flips drive nuclear polarizations toward equilibrium with spin polarization differences between electron pairs. When T1e is sufficiently long relative to the MAS rotation period, the distribution of electron spin polarization across the nitroxide electron paramagnetic resonance lineshape can be very different from the corresponding distribution in a static sample at thermal equilibrium, leading to the observed effects. We describe three-spin and 3000-spin calculations that qualitatively reproduce the experimental observations.

  8. Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves

    Energy Technology Data Exchange (ETDEWEB)

    Thurber, Kent R., E-mail: thurberk@niddk.nih.gov; Tycko, Robert [Laboratory of Chemical Physics, National Institute of Diabetes and Digestive and Kidney Diseases, National Institutes of Health, Bethesda, Maryland 20892-0520 (United States)

    2014-05-14

    We report solid state {sup 13}C and {sup 1}H nuclear magnetic resonance (NMR) experiments with magic-angle spinning (MAS) on frozen solutions containing nitroxide-based paramagnetic dopants that indicate significant perturbations of nuclear spin polarizations without microwave irradiation. At temperatures near 25 K, {sup 1}H and cross-polarized {sup 13}C NMR signals from {sup 15}N,{sup 13}C-labeled L-alanine in trinitroxide-doped glycerol/water are reduced by factors as large as six compared to signals from samples without nitroxide doping. Without MAS or at temperatures near 100 K, differences between signals with and without nitroxide doping are much smaller. We attribute most of the reduction of NMR signals under MAS near 25 K to nuclear spin depolarization through the cross-effect dynamic nuclear polarization mechanism, in which three-spin flips drive nuclear polarizations toward equilibrium with spin polarization differences between electron pairs. When T{sub 1e} is sufficiently long relative to the MAS rotation period, the distribution of electron spin polarization across the nitroxide electron paramagnetic resonance lineshape can be very different from the corresponding distribution in a static sample at thermal equilibrium, leading to the observed effects. We describe three-spin and 3000-spin calculations that qualitatively reproduce the experimental observations.

  9. Genotype evaluation of cowpea seeds (Vigna unguiculata) using 1H qNMR combined with exploratory tools and solid-state NMR.

    Science.gov (United States)

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

    2017-01-01

    The ultimate aim of this study was to apply a non-targeted chemometric analysis (principal component analysis and hierarchical clustering analysis using the heat map approach) of NMR data to investigate the variability of organic compounds in nine genotype cowpea seeds, without any complex pre-treatment. In general, both exploratory tools show that Tvu 233, CE-584, and Setentão genotypes presented higher amount mainly of raffinose and Tvu 382 presented the highest content of choline and least content of raffinose. The evaluation of the aromatic region showed the Setentão genotype with highest content of niacin/vitamin B3 whereas Tvu 382 with lowest amount. To investigate rigid and mobile components in the seeds cotyledon, 13 C CP and SP/MAS solid-state NMR experiments were performed. The cotyledon of the cowpea comprised a rigid part consisting of starch as well as a soft portion made of starch, fatty acids, and protein. The variable contact time experiment suggests the presence of lipid-amylose complexes. Copyright © 2016 Elsevier Ltd. All rights reserved.

  10. Uniform isotope labeling of a eukaryotic seven-transmembrane helical protein in yeast enables high-resolution solid-state NMR studies in the lipid environment

    International Nuclear Information System (INIS)

    Fan Ying; Shi Lichi; Ladizhansky, Vladimir; Brown, Leonid S.

    2011-01-01

    Overexpression of isotope-labeled multi-spanning eukaryotic membrane proteins for structural NMR studies is often challenging. On the one hand, difficulties with achieving proper folding, membrane insertion, and native-like post-translational modifications frequently disqualify bacterial expression systems. On the other hand, eukaryotic cell cultures can be prohibitively expensive. One of the viable alternatives, successfully used for producing proteins for solution NMR studies, is yeast expression systems, particularly Pichia pastoris. We report on successful implementation and optimization of isotope labeling protocols, previously used for soluble secreted proteins, to produce homogeneous samples of a eukaryotic seven-transmembrane helical protein, rhodopsin from Leptosphaeria maculans. Even in shake-flask cultures, yields exceeded 5 mg of purified uniformly 13 C, 15 N-labeled protein per liter of culture. The protein was stable (at least several weeks at 5°C) and functionally active upon reconstitution into lipid membranes at high protein-to-lipid ratio required for solid-state NMR. The samples gave high-resolution 13 C and 15 N solid-state magic angle spinning NMR spectra, amenable to a detailed structural analysis. We believe that similar protocols can be adopted for challenging mammalian targets, which often resist characterization by other structural methods.

  11. High resolution NMR spectroscopy of synthetic polymers in bulk

    International Nuclear Information System (INIS)

    Komorski, R.A.

    1986-01-01

    The contents of this book are: Overview of high-resolution NMR of solid polymers; High-resolution NMR of glassy amorphous polymers; Carbon-13 solid-state NMR of semicrystalline polymers; Conformational analysis of polymers of solid-state NMR; High-resolution NMR studies of oriented polymers; High-resolution solid-state NMR of protons in polymers; and Deuterium NMR of solid polymers. This work brings together the various approaches for high-resolution NMR studies of bulk polymers into one volume. Heavy emphasis is, of course, given to 13C NMR studies both above and below Tg. Standard high-power pulse and wide-line techniques are not covered

  12. Non-stationary (13)C-metabolic flux ratio analysis.

    Science.gov (United States)

    Hörl, Manuel; Schnidder, Julian; Sauer, Uwe; Zamboni, Nicola

    2013-12-01

    (13)C-metabolic flux analysis ((13)C-MFA) has become a key method for metabolic engineering and systems biology. In the most common methodology, fluxes are calculated by global isotopomer balancing and iterative fitting to stationary (13)C-labeling data. This approach requires a closed carbon balance, long-lasting metabolic steady state, and the detection of (13)C-patterns in a large number of metabolites. These restrictions mostly reduced the application of (13)C-MFA to the central carbon metabolism of well-studied model organisms grown in minimal media with a single carbon source. Here we introduce non-stationary (13)C-metabolic flux ratio analysis as a novel method for (13)C-MFA to allow estimating local, relative fluxes from ultra-short (13)C-labeling experiments and without the need for global isotopomer balancing. The approach relies on the acquisition of non-stationary (13)C-labeling data exclusively for metabolites in the proximity of a node of converging fluxes and a local parameter estimation with a system of ordinary differential equations. We developed a generalized workflow that takes into account reaction types and the availability of mass spectrometric data on molecular ions or fragments for data processing, modeling, parameter and error estimation. We demonstrated the approach by analyzing three key nodes of converging fluxes in central metabolism of Bacillus subtilis. We obtained flux estimates that are in agreement with published results obtained from steady state experiments, but reduced the duration of the necessary (13)C-labeling experiment to less than a minute. These results show that our strategy enables to formally estimate relative pathway fluxes on extremely short time scale, neglecting cellular carbon balancing. Hence this approach paves the road to targeted (13)C-MFA in dynamic systems with multiple carbon sources and towards rich media. © 2013 Wiley Periodicals, Inc.

  13. Hydration properties and phosphorous speciation in native, gelatinized and enzymatically modified potato starch analyzed by solid-state MAS NMR

    DEFF Research Database (Denmark)

    Larsen, Flemming H.; Kasprzak, Miroslaw Marek; Lærke, Helle Nygaard

    2013-01-01

    Hydration of granular, gelatinized and molecularly modified states of potato starch in terms of molecular mobility were analyzed by 13C and 31P solid-state MAS NMR. Gelatinization (GEL) tremendously reduced the immobile fraction compared to native (NA) starch granules. This effect was enhanced...... by enzyme-assisted catalytic branching with branching enzyme (BE) or combined BE and β-amylase (BB) catalyzed exo-hydrolysis. Carbons of the glycosidic α-1,6 linkages required high hydration rates before adopting uniform chemical shifts indicating solid-state disorder and poor water accessibility...... regions was only observed in NA starch. Moreover phosphorous was observed in a minor pH-insensitive form and as major phosphate in hydrated GEL and BE starches....