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Sample records for 13c solid-state nuclear

  1. Solid-State 13C Nuclear Magnetic Resonance Characterization of Cellulose in the Cell Walls of Arabidopsis thaliana Leaves.

    PubMed Central

    Newman, R. H.; Davies, L. M.; Harris, P. J.

    1996-01-01

    Solid-state 13C nuclear magnetic resonance was used to characterize the molecular ordering of cellulose in a cell-wall preparation containing mostly primary walls obtained from the leaves of Arabidopsis thaliana. Proton and 13C spin relaxation time constants showed that the cellulose was in a crystalline rather than a paracrystalline state or amorphous state. Cellulose chains were distributed between the interiors (40%) and surfaces (60%) of crystallites, which is consistent with crystallite cross-sectional dimensions of about 3 nm. Digital resolution enhancement revealed signals indicative of triclinic and monoclinic crystalline forms of cellulose mixed in similar proportions. Of the five nuclear spin relaxation processes used, proton rotating-frame relaxation provided the clearest distinction between cellulose and other cell-wall components for purposes of editing solid-state 13C nuclear magnetic resonance spectra. PMID:12226303

  2. Chemical structural studies of natural lignin by dipolar dephasing solid-state 13C nuclear magnetic resonance

    USGS Publications Warehouse

    Hatcher, P.G.

    1987-01-01

    Two natural lignins, one from a gymnosperm wood the other from angiosperm wood, were examined by conventional solid-state and dipolar dephasing 13C nuclear magnetic resonance (NMR) techniques. The results obtained from both techniques show that the structure of natural lignins is consistent with models of softwood and hardwood lignin. The dipolar dephasing NMR data provide a measure of the degree of substitution on aromatic rings which is consistent with the models. ?? 1987.

  3. Following Suberization in Potato Wound Periderm by Histochemical and Solid-State 13C Nuclear Magnetic Resonance Methods.

    PubMed

    Stark, R. E.; Sohn, W.; Pacchiano Jr, R. A.; Al-Bashir, M.; Garbow, J. R.

    1994-02-01

    The time course of suberization in wound periderm from potato (Solanum tuberosum L.) has been monitored by histochemical and high-resolution solid-state nuclear magnetic resonance (NMR) methods. Light microscopy conducted after selective staining of the lipid and double-bonded constituents shows that suberin is deposited at the outermost intact cell-wall surface during the first 7 d of wound healing; suberization forms a barrier to tissue infiltration at later times. Cross polarization-magic angle spinning 13C NMR spectra demonstrate the deposition of a polyester containing all major suberin functional groups after just 4 d of wound healing. Initially the suberin includes a large proportion of aromatic groups and fairly short aliphatic chains, but the spectral data demonstrate the growing dominance of long-chain species during the period 7 to 14 d after wounding. The results of preliminary 13C-labeling experiments with sodium [2-13C]acetate and DL-[1-13C]phenylalanine provide an excellent prospectus for future NMR-based studies of suberin biosynthesis.

  4. Solid-state 13C nuclear magnetic resonance studies of coalified gymnosperm xylem tissue from Australian brown coals

    USGS Publications Warehouse

    Hatcher, P.G.; Lerch, H. E.; Bates, A.L.; Verheyen, T.V.

    1989-01-01

    We report here on the use of solid-state 13C nuclear magnetic resonance (NMR) spectroscopy to contrast the average chemical composition of modern degraded gymnosperm woods with fossil gymnosperm woods from Australian brown coals (Miocene). We first established the quantitative nature of the NMR techniques for these samples so that the conventional solid-state 13C NMR spectra and the dipolar dephasing NMR spectra could be used with a high degree of reliability to depict average chemical compositions. The NMR results provide some valuable insights about the early coalification of xylem tissue from gymnosperms. Though the cellulosic components of wood are degraded to varying degrees during peatification and ensuing coalification, it is unlikely that they play a major role in the formation of aromatic structures in coalified woods. The NMR data show that gynmosperm lignin, the primary aromatic contribution to the coal, is altered in part by demethylation of guaiacyl-units to catechol-like structures. The dipolar dephasing NMR data indicate that the lignin also becomes more cross-linked or condensed. ?? 1989.

  5. Advanced new relaxation filter-selective signal excitation methods for (13)C solid-state nuclear magnetic resonance.

    PubMed

    Asada, Mamiko; Nemoto, Takayuki; Mimura, Hisashi; Sako, Kazuhiro

    2014-10-21

    We have developed new relaxation filter-selective signal excitation (RFS) methods for (13)C solid-state NMR, which enable extraction of the spectrum of a target component from a mixture of several components. These methods are based on the equalization of proton relaxation time in a single domain via rapid intraproton spin diffusion and the difference in proton relaxation time of individual components in the mixture. We recently reported two types of RFS methods using proton spin-lattice relaxation time in the rotating frame ((1)H T1rho) in (13)C solid-state nuclear magnetic resonance (NMR) spectroscopy. Here, to increase the availability of RFS methods, we focus on proton spin-lattice relaxation time ((1)H T1). Introduction of simple pulse sequences to one-dimensional experiments reduced data acquisition time and increased flexibility, and led to the development of two new types of RFS methods using (1)H T1. We then demonstrated these methods by selectively exciting the (13)C signals of target components in a commercially available drug and a number of physical mixtures, and we showed them to be applicable to the quantitative analysis of individual components in these solid mixtures with an experimental duration of 1.5 to about 10 h. The practicality and versatility of these four RFS methods were increased by combining two or more of them, or by using a flip-back pulse, which is an effective means of shortening experimental duration. These RFS methods are suitable for use in a broad range of fields.

  6. Structural characterization of ion-vapor deposited hydrogenated amorphous carbon coatings by solid state {sup 13}C nuclear magnetic resonance

    SciTech Connect

    Xu, Jiao; Kato, Takahisa; Watanabe, Sadayuki; Hayashi, Hideo; Kawaguchi, Masahiro

    2014-01-07

    In the present study, unique structural heterogeneity was observed in ion-vapor deposited a-C:H coatings by performing {sup 13}C MAS and {sup 1}H-{sup 13}C CPMAS experiments on solid state nuclear magnetic resonance devices. Two distinct types of sp{sup 2} C clusters were discovered: one of them denoted as sp{sup 2} C′ in content of 3–12 at. % was non-protonated specifically localized in hydrogen-absent regions, while the other dominant one denoted as sp{sup 2} C″ was hydrogenated or at least proximate to proton spins. On basis of the notably analogous variation of sp{sup 2} C′ content and Raman parameters as function of substrate bias voltage in the whole range of 0.5 kV–3.5 kV, a model of nano-clustering configuration was proposed that the sp{sup 2} C′ clusters were embedded between sp{sup 2} C″ clusters and amorphous sp{sup 3} C matrix as trapped interfaces or boundaries where the sp{sup 2} carbon bonds were highly distorted. Continuous increase of bias voltage would promote the nano-clustering and re-ordering of dominant sp{sup 2} C″ clusters, thus results in a marked decrease of interspace and a change of the content of sp{sup 2} C′ clusters. Further investigation on the {sup 13}C magnetization recovery showed typical stretched-exponential approximation due to the prominent presence of paramagnetic centers, and the stretched power α varied within 0.6–0.9 from distinct types of sp{sup 2} C clusters. Differently, the magnetization recovery of {sup 1}H showed better bi-exponential approximation with long and short T{sub 1}(H) fluctuated within 40–60 ms and 0.1–0.3 ms approximately in content of 80% ± 5% and 20% ± 5%, respectively, varying with various bias voltages. Meanwhile, the interrupted {sup 13}C saturation recovery with an interval of short T{sub 1}(H) showed that most of quick-relaxing protons were localized in sp{sup 2} C″ clusters. Such a short T{sub 1}(H) was only possibly resulted from a relaxation mechanism

  7. Functional groups identified by solid state 13C NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Animal manure is generally high in organic matter intensity so it is well suitable for 13C nuclear magnetic resonance (NMR) analysis. Solid-state 13C NMR techniques used in characterizing organic matter and its components include, but are not limited to, cross-polarization /magic angle spinning (CP...

  8. Quantitative solid-state 13C nuclear magnetic resonance spectrometric analyses of wood xylen: effect of increasing carbohydrate content

    USGS Publications Warehouse

    Bates, A.L.; Hatcher, P.G.

    1992-01-01

    Isolated lignin with a low carbohydrate content was spiked with increasing amounts of alpha-cellulose, and then analysed by solid-state 13C nuclear magnetic resonance (NMR) using cross-polarization with magic angle spinning (CPMAS) and dipolar dephasing methods in order to assess the quantitative reliability of CPMAS measurement of carbohydrate content and to determine how increasingly intense resonances for carbohydrate carbons affect calculations of the degree of lignin's aromatic ring substitution and methoxyl carbon content. Comparisons were made of the carbohydrate content calculated by NMR with carbohydrate concentrations obtained by phenol-sulfuric acid assay and by the calculation from the known amounts of cellulose added. The NMR methods used in this study yield overestimates for carbohydrate carbons due to resonance area overlap from the aliphatic side chain carbons of lignin. When corrections are made for these overlapping resonance areas, the NMR results agree very well with results obtained by other methods. Neither the calculated methoxyl carbon content nor the degree of aromatic ring substitution in lignin, both calculated from dipolar dephasing spectra, change with cellulose content. Likewise, lignin methoxyl content does not correlate with cellulose abundance when measured by integration of CPMAS spectra. ?? 1992.

  9. Chemical structures of swine-manure chars produced under different carbonization conditions investigated by advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Two types of swine manure chars, hydrothermally-produced hydrochar and slow-pyrolysis pyrochar, and their raw swine manure solid were characterized using advanced 13C solid-state nuclear magnetic resonance (NMR) spectroscopy. Compared with the parent raw swine manure, both hydrochars and pyrochar di...

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

    USGS Publications Warehouse

    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.

  11. Solid-state /sup 13/C nuclear magnetic resonance spectroscopy of simultaneously metabolized acetate and phenol in a soil Pseudomonas sp

    SciTech Connect

    Heiman, A.S.; Copper, W.T.

    1987-01-01

    An investigation was made of the concentration-dependent primary and secondary substrate relationships in the simultaneous metabolism of the ubiquitous pollutant phenol and the naturally occurring substrate acetate by a Pseudomonas sp. soil isolate capable of utilizing either substance as a sole source of carbon and energy. In addition to conventional analytical techniques, solid-state /sup 13/C nuclear magnetic resonance spectroscopy was used to follow the cellular distribution of (1-/sup 13/C)acetate in the presence of unlabeled phenol. These results suggest that, when phenol is present as the primary substrate, acetate is preferentially shuttled into fatty acyl chain synthesis, whereas phenol carbon is funnelled into the tricarboxylic acid cycle. Thus, simultaneous use of a xenobiotic compound and a natural substrate apparently does occur, and the relative concentrations of the two substrates do influence the rate and manner in which the compounds are utilized. These results also demonstrate the unique advantage of using solid-state nuclear magnetic resonance techniques combined with /sup 13/C labeling of specific sites in substrates when doing microbial degradation studies. In this work, the entire cellular biomass was examined directly without extensive extraction, fractionation, or isolation of subcellular units; thus, there is no uncertainty about chemical alteration of substrate metabolites as a result of these often harsh treatments.

  12. Structure and dynamics of Brachypodium primary cell wall polysaccharides from two-dimensional (13)C solid-state nuclear magnetic resonance spectroscopy.

    PubMed

    Wang, Tuo; Salazar, Andre; Zabotina, Olga A; Hong, Mei

    2014-05-06

    The polysaccharide structure and dynamics in the primary cell wall of the model grass Brachypodium distachyon are investigated for the first time using solid-state nuclear magnetic resonance (NMR). While both grass and non-grass cell walls contain cellulose as the main structural scaffold, the former contains xylan with arabinose and glucuronic acid substitutions as the main hemicellulose, with a small amount of xyloglucan (XyG) and pectins, while the latter contains XyG as the main hemicellulose and significant amounts of pectins. We labeled the Brachypodium cell wall with (13)C to allow two-dimensional (2D) (13)C correlation NMR experiments under magic-angle spinning. Well-resolved 2D spectra are obtained in which the (13)C signals of cellulose, glucuronoarabinoxylan (GAX), and other matrix polysaccharides can be assigned. The assigned (13)C chemical shifts indicate that there are a large number of arabinose and xylose linkages in the wall, and GAX is significantly branched at the developmental stage of 2 weeks. 2D (13)C-(13)C correlation spectra measured with long spin diffusion mixing times indicate that the branched GAX approaches cellulose microfibrils on the nanometer scale, contrary to the conventional model in which only unbranched GAX can bind cellulose. The GAX chains are highly dynamic, with average order parameters of ~0.4. Biexponential (13)C T1 and (1)H T1ρ relaxation indicates that there are two dynamically distinct domains in GAX: the more rigid domain may be responsible for cross-linking cellulose microfibrils, while the more mobile domain may fill the interfibrillar space. This dynamic heterogeneity is more pronounced than that of the non-grass hemicellulose, XyG, suggesting that GAX adopts the mixed characteristics of XyG and pectins. Moderate differences in cellulose rigidity are observed between the Brachypodium and Arabidopsis cell walls, suggesting different effects of the matrix polysaccharides on cellulose. These data provide the first

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

    NASA Astrophysics Data System (ADS)

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

    2011-12-01

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

  14. The characterization of phospholipid functional group probe species on respirable silicon-containing dusts by solid-state 13C and 31P nuclear magnetic resonance spectroscopy.

    PubMed

    Murray, David K

    2010-03-01

    Solid-state nuclear magnetic resonance (NMR) spectroscopic studies are reported for the interactions of probe molecules with respirable silicon-containing dusts as experimental evidence complementing computational studies reported by Snyder and Madura recently in J. Phys. Chem. B 112, 7095 (2008). The selected probe molecules represent the individual functional groups of a model lung surfactant dipalmitoylphosphatidyl choline (DPPC) deposited on a respirable silica and kaolin from water solution. (13)C and (31)P solid-state NMR spectroscopies were employed to detect chemical shift, line width, and chemical shift anisotropy, providing experimental evidence of mobility and relaxation changes describing the site and orientation of surface-associated species. NMR results confirm that only the phosphate and adjacent carbons are immobilized by surface hydroxyls on kaolin, while these and the carbons of the cationic head group are likewise immobilized by surface silanols on Miu-U-Sil 5. The phosphates in phosphoryl- and phosphatidyl-cholines were the primary interaction sites, with additional weak coordination with the trimethylammonium cation species. Covalent Al-O-P formation is not likely a factor in in vivo or in vitro toxicity mechanisms of respirable silicon-containing materials, but is rather the result of dehydration or demethoxylation reactions occurring over time or during heating or reduced pressure used in preparing materials for NMR spectroscopic study. Hydration is a critical factor in the formation and preparation for spectroscopic observation of coated dusts. Care must be taken to ensure that products formed and studied correspond to species formed in vivo under suitable concentration and hydration conditions.

  15. Probing the molecular architecture of Arabidopsis thaliana secondary cell walls using two- and three-dimensional (13)C solid state nuclear magnetic resonance spectroscopy.

    PubMed

    Dupree, Ray; Simmons, Thomas J; Mortimer, Jennifer C; Patel, Dharmesh; Iuga, Dinu; Brown, Steven P; Dupree, Paul

    2015-04-14

    The plant secondary cell wall is a thickened polysaccharide and phenolic structure, providing mechanical strength to cells, particularly in woody tissues. It is the main feedstock for the developing bioenergy and green chemistry industries. Despite the role that molecular architecture (the arrangement of biopolymers relative to each other, and their conformations) plays in dictating biomass properties, such as recalcitrance to breakdown, it is poorly understood. Here, unprocessed dry (13)C-labeled stems from the model plant Arabidopsis thaliana were analyzed by a variety of (13)C solid state magic angle spinning nuclear magnetic resonance methods, such as one-dimensional cross-polarization and direct polarization, two-dimensional refocused INADEQUATE, RFDR, PDSD, and three-dimensional DARR, demonstrating their viability for the study of native polymer arrangements in intact secondary cell walls. All carbon sites of the two main glucose environments in cellulose (previously assigned to microfibril surface and interior residues) are clearly resolved, as are carbon sites of the other major components of the secondary cell wall: xylan and lignin. The xylan carbon 4 chemical shift is markedly different from that reported previously for solution or primary cell wall xylan, indicating significant changes in the helical conformation in these dried stems. Furthermore, the shift span indicates that xylan adopts a wide range of conformations in this material, with very little in the 31 conformation typical of xylan in solution. Additionally, spatial connections of noncarbohydrate species were observed with both cellulose peaks conventionally assigned as "surface" and as "interior" cellulose environments, raising questions about the origin of these two cellulose signals.

  16. Chemical structures of coal lithotypes before and after CO2 adsorption as investigated by advanced solid-state 13C nuclear magnetic resonance spectroscopy

    USGS Publications Warehouse

    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.

  17. Synthesis and solid-state NMR structural characterization of 13C-labeled graphite oxide.

    PubMed

    Cai, Weiwei; Piner, Richard D; Stadermann, Frank J; Park, Sungjin; Shaibat, Medhat A; Ishii, Yoshitaka; Yang, Dongxing; Velamakanni, Aruna; An, Sung Jin; Stoller, Meryl; An, Jinho; Chen, Dongmin; Ruoff, Rodney S

    2008-09-26

    The detailed chemical structure of graphite oxide (GO), a layered material prepared from graphite almost 150 years ago and a precursor to chemically modified graphenes, has not been previously resolved because of the pseudo-random chemical functionalization of each layer, as well as variations in exact composition. Carbon-13 (13C) solid-state nuclear magnetic resonance (SSNMR) spectra of GO for natural abundance 13C have poor signal-to-noise ratios. Approximately 100% 13C-labeled graphite was made and converted to 13C-labeled GO, and 13C SSNMR was used to reveal details of the chemical bonding network, including the chemical groups and their connections. Carbon-13-labeled graphite can be used to prepare chemically modified graphenes for 13C SSNMR analysis with enhanced sensitivity and for fundamental studies of 13C-labeled graphite and graphene.

  18. 1H–13C hetero-nuclear dipole–dipole couplings of methyl groups in stationary and magic angle spinning solid-state NMR experiments of peptides and proteins

    PubMed Central

    Wu, Chin H.; Das, Bibhuti B.; Opella, Stanley J.

    2010-01-01

    13C NMR of isotopically labeled methyl groups has the potential to combine spectroscopic simplicity with ease of labeling for protein NMR studies. However, in most high resolution separated local field experiments, such as polarization inversion spin exchange at the magic angle (PISEMA), that are used to measure 1H–13C hetero-nuclear dipolar couplings, the four-spin system of the methyl group presents complications. In this study, the properties of the 1H–13C hetero-nuclear dipolar interactions of 13C-labeled methyl groups are revealed through solid-state NMR experiments on a range of samples, including single crystals, stationary powders, and magic angle spinning of powders, of 13C3 labeled alanine alone and incorporated into a protein. The spectral simplifications resulting from proton detected local field (PDLF) experiments are shown to enhance resolution and simplify the interpretation of results on single crystals, magnetically aligned samples, and powders. The complementarity of stationary sample and magic angle spinning (MAS) measurements of dipolar couplings is demonstrated by applying polarization inversion spin exchange at the magic angle and magic angle spinning (PISEMAMAS) to unoriented samples. PMID:19896874

  19. 2H-DNP-enhanced 2H–13C solid-state NMR correlation spectroscopy

    PubMed Central

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

    2015-01-01

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

  20. 1H to 13C Energy Transfer in Solid State NMR Spectroscopy of Natural Organic Systems

    NASA Astrophysics Data System (ADS)

    Berns, Anne E.; Conte, Pellegrino

    2010-05-01

    ., van Lagen, B., Buurman, P. & de Jager, P.A., 1997. Quantitative Aspects of Solid-State 13C-NMR Spectra of Humic Substances from Soils of Volcanic Systems. Geoderma, 80, 327-338. Conte, P., Piccolo, A., van Lagen, B., Buurman, P. & Hemminga, M.A., 2002. Elemental quantitation of natural organic matter by CPMAS C-13 NMR spectroscopy. Solid State Nuclear Magnetic Resonance, 21, 158-170. Conte, P., Spaccini, R. & Piccolo, A., 2004. State of the art of CPMAS C-13-NMR spectroscopy applied to natural organic matter. Progress in Nuclear Magnetic Resonance Spectroscopy, 44, 215-223. Dria, K.J., Sachleben, J.R. & Hatcher, P.G., 2002. Solid-state carbon-13 nuclear magnetic resonance of humic acids at high magnetic field strengths. Journal of Environmental Quality, 31, 393-401. Kiem, R., Knicker, H., Korschens, M. & Kogel-Knabner, I., 2000. Refractory organic carbon in C-depleted arable soils, as studied by C-13 NMR spectroscopy and carbohydrate analysis. Organic Geochemistry, 31, 655-668. Kögel-Knabner, I., 2000. Analytical approaches for characterizing soil organic matter. Organic Geochemistry, 31, 609-625. Mao, J.D., Hu, W.G., Schmidt-Rohr, K., Davies, G., Ghabbour, E.A. & Xing, B., 2000. Quantitative characterization of humic substances by solid-state carbon-13 nuclear magnetic resonance. Soil Science Society of America Journal, 64, 873-884. Metz, G., Ziliox, M. & Smith, S.O., 1996. Towards quantitative CP-MAS NMR. Solid State Nuclear Magnetic Resonance, 7, 155-160. Preston, C.M., 2001. Carbon-13 solid-state NMR of soil organic matter - using the technique effectively. Canadian Journal of Soil Science, 81, 255-270. Smernik, R.J. & Oades, J.M., 2000a. The use of spin counting for determining quantitation in solid state C-13 NMR spectra of natural organic matter 1. Model systems and the effects of paramagnetic impurities. Geoderma, 96, 101-129. Smernik, R.J. & Oades, J.M., 2000b. The use of spin counting for determining quantitation in solid state C-13 NMR spectra of natural

  1. Solid-State Nuclear Power

    NASA Technical Reports Server (NTRS)

    George, Jeffrey A.

    2012-01-01

    A strategy for "Solid-State" Nuclear Power is proposed to guide development of technologies and systems into the second 50 years of nuclear spaceflight. The strategy emphasizes a simple and highly integrated system architecture with few moving parts or fluid loops; the leverage of modern advances in materials, manufacturing, semiconductors, microelectromechanical and nanotechnology devices; and the targeted advancement of high temperature nuclear fuels, materials and static power conversion to enable high performance from simple system topologies.

  2. Accurate measurements of 13C-13C distances in uniformly 13C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Straasø, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Khaneja, Navin; Nielsen, Niels Chr.

    2014-09-01

    Application of sets of 13C-13C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important 13C-13C distances in uniformly 13C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl (13C') and aliphatic (13Caliphatic) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasø, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly 13C,15N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of 13C'-13Caliphatic distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform 13C,15N-labeling on the FGAIL fragment.

  3. Structure of uniaxially aligned 13C labeled silk fibroin fibers with solid state 13C-NMR

    NASA Astrophysics Data System (ADS)

    Demura, Makoto; Yamazaki, Yasunobu; Asakura, Tetsuo; Ogawa, Katsuaki

    1998-01-01

    Carbon-13 isotopic labeling of B. mori silk fibroin was achieved biosynthetically with [1- 13C] glycine in order to determine the carbonyl bond orientation angle of glycine sites with the silk fibroin. Angular dependence of 13C solid state NMR spectra of uniaxially oriented silk fibroin fiber block sample due to the carbonyl 13C chemical shift anisotropy was simulated according to the chemical shift transformation with Euler angles, αF and βF, from principal axis system (PAS) to fiber axis system (FAS). The another Euler angles, αDCO and βDCO, for transformation from PAS to the molecular symmetry axis were determined from the [1- 13C] glycine sequence model compounds for the silk fibroin. By the combination of these Euler angles, the carbonyl bond orientation angle with respect to FAS of the [1- 13C] glycine sites of the silk fibroin was determined to be 90 ± 5°. This value is in agreement with the X-ray diffraction and our previous solid state NMR data of B. mori silk fibroin fiber (a typical β-pleated sheet) within experimental error.

  4. Solid state (13)C NMR analysis of human gallstones from cancer and benign gall bladder diseases.

    PubMed

    Jayalakshmi, K; Sonkar, Kanchan; Behari, Anu; Kapoor, V K; Sinha, Neeraj

    2009-09-01

    Natural abundance (13)C cross polarized (CP) magic angle spinning (MAS) nuclear magnetic resonance (NMR) analysis of human gall bladder stones collected from patients suffering from malignant and benign gall bladder disease was carried out which revealed different polymorphs of cholesterol in these stones. All gall bladder stones in present study had cholesterol as their main constituent. (13)C CP-MAS NMR analysis revealed three forms of cholesterol molecules in these stones, which are anhydrous form, monohydrate crystalline with amorphous form and monohydrate crystalline form. Our study revealed that stones collected from patients associated with chronic cholecystitis (CC) disease have mostly different polymorph of cholesterol than stones collected from patients associated with gall bladder cancer (GBC). Such study will be helpful in understanding the mechanism of formation of gallstones which are associated with different gall bladder diseases. This is the first study by solid state NMR revealing different crystal polymorphism of cholesterol in human gallstones, extending the applicability of (13)C CP-MAS NMR technique for the routine study of gallstones.

  5. Solid-state 13C NMR and molecular modeling studies of acetyl aleuritolic acid obtained from Croton cajucara Benth

    NASA Astrophysics Data System (ADS)

    da Silva San Gil, Rosane Aguiar; Albuquerque, Magaly Girão; de Alencastro, Ricardo Bicca; da Cunha Pinto, Angelo; do Espírito Santo Gomes, Fabiano; de Castro Dantas, Tereza Neuma; Maciel, Maria Aparecida Medeiros

    2008-08-01

    Solid-state 13C nuclear magnetic resonance ( 13C NMR) with magic-angle spinning (MAS) and with cross-polarization and magic-angle spinning (CP/MAS) spectra, and differential scanning calorimetry (DSC) techniques were used to obtain structural data from a sample of acetyl aleuritolic acid (AAA) extracted from the stem bark of Croton cajucara Benth. (Euphorbiaceae) and recrystallized from acetone. Since solid-state 13C NMR results suggested the presence of more than one molecule in the unitary cell for the AAA, DSC analysis and molecular modeling calculations were used to access this possibility. The absence of phase transition peaks in the DSC spectra and the dimeric models of AAA simulated using the semi-empirical PM3 method are in agreement with that proposal.

  6. Characterization of covalent protein conjugates using solid-state sup 13 C NMR spectroscopy

    SciTech Connect

    Garbow, J.R.; Fujiwara, Hideji; Sharp, C.R.; Logusch, E.W. )

    1991-07-23

    Cross-polarization magic-angle spinning (CPMAS) {sup 13}C NMR spectroscopy has been used to characterize covalent conjugates of alachlor, an {alpha}-chloroacetamide hapten, with glutathione (GSH) and bovine serum albumin (BSA). The solid-state NMR method demonstrates definitively the covalent nature of these conjugates and can also be used to characterize the sites of hapten attachment to proteins. Three different sites of alachlor binding are observed in the BSA system. Accurate quantitation of the amount of hapten covalently bound to GSH and BSA is reported. The solid-state {sup 13}C NMR technique can easily be generalized to study other small molecule/protein conjugates and can be used to assist the development and refinement of synthetic methods needed for the successful formation of such protein alkylation products.

  7. The use of 13C labeling to enhance the sensitivity of 13C solid-state CPMAS NMR to study polymorphism in low dose solid formulations.

    PubMed

    Booy, Kees-Jan; Wiegerinck, Peter; Vader, Jan; Kaspersen, Frans; Lambregts, Dorette; Vromans, Herman; Kellenbach, Edwin

    2005-02-01

    (13)C labeling was used to enhance the sensitivity of (13)C solid-state NMR to study the effect of tabletting on the polymorphism of a steroidal drug. The steroidal drug Org OD 14 was (13)C labeled and formulated into tablets containing only 0.5-2.5% active ingredient. The tablets were subsequently studied by solid-state (13)C CPMAS NMR. The crystalline form present in tablets could readily be analyzed in tablets. No change in crystalline form was observed as a result of formulation or in subsequent stability studies. Solid-state NMR in combination with (13)C labeling can, in suitable cases, be used as a strategy to study the effect of formulation on the polymorphism of low dose drugs.

  8. Quantifying the chemical composition of soil organic carbon with solid-state 13C NMR

    NASA Astrophysics Data System (ADS)

    Baldock, J. A.; Sanderman, J.

    2011-12-01

    The vulnerability of soil organic carbon (SOC) to biological decomposition and mineralisation to CO2 is defined at least partially by its chemical composition. Highly aromatic charcoal-like SOC components are more stable to biological decomposition than other forms of carbon including cellulose. Solid-state 13C NMR has gained wide acceptance as a method capable of defining SOC chemical composition and mathematical fitting processes have been developed to estimate biochemical composition. Obtaining accurate estimates depends on an ability to quantitatively detect all carbon present in a sample. Often little attention has been paid to defining the proportion of organic carbon present in a soil that is observable in solid-state 13C NMR analyses of soil samples. However, if such data is to be used to inform carbon cycling studies, it is critical that quantitative assessments of SOC observability be undertaken. For example, it is now well established that a significant discrimination exists against the detection of the low proton content polyaromatic structures typical of charcoal using cross polarisation 13C NMR analyses. Such discrimination does not exist where direct polarisation analyses are completed. In this study, the chemical composition of SOC as defined by cross polarisation and direct polarisation13C NMR analyses will be compared for Australian soils collected from under a diverse range of agricultural managements and climatic conditions. Results indicate that where significant charcoal C contents exist, it is highly under-represented in the acquired CP spectra. For some soils, a discrimination against alkyl carbon was also evident. The ability to derive correction factors to compensate for such discriminations will be assessed and presented.

  9. 13C and 15N spectral editing inside histidine imidazole ring through solid-state NMR spectroscopy.

    PubMed

    Li, Shenhui; Zhou, Lei; Su, Yongchao; Han, Bin; Deng, Feng

    2013-01-01

    Histidine usually exists in three different forms (including biprotonated species, neutral τ and π tautomers) at physiological pH in biological systems. The different protonation and tautomerization states of histidine can be characteristically determined by (13)C and (15)N chemical shifts of imidazole ring. In this work, solid-state NMR techniques were developed for spectral editing of (13)C and (15)N sites in histidine imidazole ring, which provides a benchmark to distinguish the existing forms of histidine. The selections of (13)Cγ, (13)Cδ2, (15)Nδ1, and (15)Nε2 sites were successfully achieved based on one-bond homo- and hetero-nuclear dipole interactions. Moreover, it was demonstrated that (1)H, (13)C, and (15) chemical shifts were roughly linearly correlated with the corresponding atomic charge in histidine imidazole ring by theoretical calculations. Accordingly, the (1)H, (13)C and (15)N chemical shifts variation in different protonation and tautomerization states could be ascribed to the atomic charge change due to proton transfer in biological process.

  10. Characterisation of pitch fractions by quantitative solid state {sup 13}C NMR

    SciTech Connect

    Andresen, J.M.; Dennison, P.R.; Maroto-Valer, M.M.

    1994-12-31

    Thermal and other pretreatments of pitch fractions are being widely investigated as a means to increase the extent of mesophase formation in relation to the production of high performance carbons. The structural changes that occur can be assessed using carbon skeletal parameters but, although solid state {sup 13}C NMR has been used for this purpose, the quantitative reliability of the technique has still to be established for pitch fractions. It was demonstrated previously that, as for coals, cross-polarisation (CP) can vastly underestimate quaternary aromatic carbon concentrations. A combination of a low magnetic field strength to avoid problems with spinning sidebands and the simple Bloch decay or single pulse excitation (SPE) technique is now generally recognised as offering the most satisfactory approach for obtaining quantitative {sup 13}C NMR results for coals and related materials. In this study, single pulse excitation (SPE) and associated relaxation measurements have been conducted at low field on coal-derived pitches and their toluene-insoluble (TI) fractions, together with a biomass-derived pitch and the results compared with those from CP.

  11. Multiple locations of peptides in the hydrocarbon core of gel-phase membranes revealed by peptide (13)C to lipid (2)H rotational-echo double-resonance solid-state nuclear magnetic resonance.

    PubMed

    Xie, Li; Jia, Lihui; Liang, Shuang; Weliky, David P

    2015-01-27

    Membrane locations of peptides and proteins are often critical to their functions. Solid-state rotational-echo double-resonance (REDOR) nuclear magnetic resonance is applied to probe the locations of two peptides via peptide (13)CO to lipid (2)H distance measurements. The peptides are KALP, an α-helical membrane-spanning peptide, and HFP, the β-sheet N-terminal fusion peptide of the HIV gp41 fusion protein that plays an important role in HIV-host cell membrane fusion. Both peptides are shown to have at least two distinct locations within the hydrocarbon core of gel-phase membranes. The multiple locations are attributed to snorkeling of lysine side chains for KALP and to the distribution of antiparallel β-sheet registries for HFP. The relative population of each location is also quantitated. To the best of our knowledge, this is the first clear experimental support of multiple peptide locations within the membrane hydrocarbon core. These data are for gel-phase membranes, but the approach should work for liquid-ordered membranes containing cholesterol and may be applicable to liquid-disordered membranes with appropriate additional analysis to take into account protein and lipid motion. This paper also describes the methodological development of (13)CO-(2)H REDOR using the lyophilized I4 peptide that is α-helical and (13)CO-labeled at A9 and (2)Hα-labeled at A8. The I4 spins are well-approximated as an ensemble of isolated (13)CO-(2)H spin pairs each separated by 5.0 Å with a 37 Hz dipolar coupling. A pulse sequence with rectangular 100 kHz (2)H π pulses results in rapid and extensive buildup of REDOR (ΔS/S0) with a dephasing time (τ). The buildup is well-fit by a simple exponential function with a rate of 24 Hz and an extent close to 1. These parameter values reflect nonradiative transitions between the (2)H spin states during the dephasing period. Each spin pair spends approximately two-thirds of its time in the (13)CO-(2)H (m = ±1) states and

  12. Solid-state 13C NMR studies of a large fossil gymnosperm from the Yallourn Open Cut, Latrobe Valley, Australia

    USGS Publications Warehouse

    Bates, A.L.; Hatcher, P.G.

    1989-01-01

    A series of samples taken from the cross section of a 3-m-diameter fossilized gymnospermous log (Araucariaceae) in the Yallourn Seam of the Australian brown coals was examined by solid state 13C nuclear magnetic resonance to delineate chemical changes related to the combined processes of peatification and coalification. The results show that cellulosic materials were degraded and lost on the periphery of the log, however, the degree of such degradation in the central core is substantially less. The lignin is uniformly altered by coalification reactions to a macromolecular substance displaying decreased aryl ether linkages but significantly greater amounts of carbon linkages compared to modern lignin. Changes in the methoxyl carbon contents of lignin in cross section reveal demethylation reactions, but these do not appear to be related to degree of carbon linking. Both the degredation of cellulosic materials and demethylation of lignin appear to be early diagenetic processes occurring during peatification independently of the coalification reactions. ?? 1989.

  13. Sparse (13)C labelling for solid-state NMR studies of P. pastoris expressed eukaryotic seven-transmembrane proteins.

    PubMed

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

    2016-05-01

    We demonstrate a novel sparse (13)C 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 (13)C 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.

  14. A (13)C solid-state NMR investigation of four cocrystals of caffeine and theophylline.

    PubMed

    Vigilante, Nicolas J; Mehta, Manish A

    2017-03-01

    We report an analysis of the (13)C solid-state NMR chemical shift data in a series of four cocrystals involving two active pharmaceutical ingredient (API) mimics (caffeine and theophylline) and two diacid coformers (malonic acid and glutaric acid). Within this controlled set, we make comparisons of the isotropic chemical shifts and the principal values of the chemical shift tensor. The dispersion at 14.1 T (600 MHz (1)H) shows crystallographic splittings in some of the resonances in the magic angle spinning spectra. By comparing the isotropic chemical shifts of individual C atoms across the four cocrystals, we are able to identify pronounced effects on the local electronic structure at some sites. We perform a similar analysis of the principal values of the chemical shift tensors for the anisotropic C atoms (most of the ring C atoms for the API mimics and the carbonyl C atoms of the diacid coformers) and link them to differences in the known crystal structures. We discuss the future prospects for extending this type of study to incorporate the full chemical shift tensor, including its orientation in the crystal frame of reference.

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

    PubMed

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

    2012-06-20

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

  16. Solid-state 13C NMR studies of dissolved organic matter in pore waters from different depositional environments

    USGS Publications Warehouse

    Orem, W.H.; Hatcher, P.G.

    1987-01-01

    Dissolved organic matter (DOM) in pore waters from sediments of a number of different depositional environments was isolated by ultrafiltration using membranes with a nominal molecular weight cutoff of 500. This > 500 molecular weight DOM represents 70-98% of the total DOM in these pore waters. We determined the gross chemical structure of this material using both solid-state 13C nuclear magnetic resonance spectroscopy and elemental analysis. Our results show that the DOM in these pore waters appears to exist as two major types: one type dominated by carbohydrates and paraffinic structures and the second dominated by paraffinic and aromatic structures. We suggest that the dominance of one or the other structural type of DOM in the pore water depends on the relative oxidizing/reducing nature of the sediments as well as the source of the detrital organic matter. Under dominantly anaerobic conditions carbohydrates in the sediments are degraded by bacteria and accumulate in the pore water as DOM. However, little or no degradation of lignin occurs under these conditions. In contrast, sediments thought to be predominantly aerobic in character have DOM with diminished carbohydrate and enhanced aromatic character. The aromatic structures in the DOM from these sediments are thought to arise from the degradation of lignin. The large amounts of paraffinic structures in both types of DOM may be due to the degradation of unidentified paraffinic materials in algal or bacterial remains. ?? 1987.

  17. Accurate measurements of {sup 13}C-{sup 13}C distances in uniformly {sup 13}C-labeled proteins using multi-dimensional four-oscillating field solid-state NMR spectroscopy

    SciTech Connect

    Straasø, Lasse Arnt; Nielsen, Jakob Toudahl; Bjerring, Morten; Nielsen, Niels Chr.; Khaneja, Navin

    2014-09-21

    Application of sets of {sup 13}C-{sup 13}C internuclear distance restraints constitutes a typical key element in determining the structure of peptides and proteins by magic-angle-spinning solid-state NMR spectroscopy. Accurate measurements of the structurally highly important {sup 13}C-{sup 13}C distances in uniformly {sup 13}C-labeled peptides and proteins, however, pose a big challenge due to the problem of dipolar truncation. Here, we present novel two-dimensional (2D) solid-state NMR experiments capable of extracting distances between carbonyl ({sup 13}C′) and aliphatic ({sup 13}C{sub aliphatic}) spins with high accuracy. The method is based on an improved version of the four-oscillating field (FOLD) technique [L. A. Straasø, M. Bjerring, N. Khaneja, and N. C. Nielsen, J. Chem. Phys. 130, 225103 (2009)] which circumvents the problem of dipolar truncation, thereby offering a base for accurate extraction of internuclear distances in many-spin systems. The ability to extract reliable accurate distances is demonstrated using one- and two-dimensional variants of the FOLD experiment on uniformly {sup 13}C,{sup 15}N-labeled-L-isoleucine. In a more challenging biological application, FOLD 2D experiments are used to determine a large number of {sup 13}C′-{sup 13}C{sub aliphatic} distances in amyloid fibrils formed by the SNNFGAILSS fibrillating core of the human islet amyloid polypeptide with uniform {sup 13}C,{sup 15}N-labeling on the FGAIL fragment.

  18. Characterization of pyrogenic organic matter by 2-dimenstional HETeronucleus CORelation solid-state 13C NMR (HETCOR) spectroscopy

    NASA Astrophysics Data System (ADS)

    Knicker, Heike

    2016-04-01

    During the last years, increasing evidences are provided that the common view of charcoal as a polyaromatic network is too much simplified. Experiments with model compounds indicated that it represents a heterogeneous mixture of thermally altered biomacromolecules with N, O and likely also S substitutions as common features. If produced from a N-rich feedstock, the so called black nitrogen (BN) has to be considered as an integral part of the aromatic charcoal network. In order to study this network one-dimensional (1D) solid-state nuclear magnetic resonance (NMR) spectroscopy is often applied. However, this technique suffers from broad resonance lines and low resolution. Applying 2D techniques can help but until recently, this was unfeasible for natural organic matter (NOM) due to sensitivity problems and the high complexity of the material. On the other hand, during the last decade, the development of stronger magnetic field instruments and advanced pulse sequences has put them into reach for NOM research. Although 2D NMR spectroscopy has many different applications, all pulse sequences are based on the introduction of a preparation time during which the magnetization of a spin system is adjusted into a state appropriate to whatever properties are to be detected in the indirect dimension. Then, the spins are allowed to evolve with the given conditions and after their additional manipulation during a mixing period the modulated magnetization is detected. Assembling several 1D spectra with incrementing evolution time creates a data set which is two-dimensional in time (t1, t2). Fourier transformation of both dimensions leads to a 2D contour plot correlating the interactions detected in the indirect dimension t1 with the signals detected in the direct dimension t2. The so called solid-state heteronuclear correlation (HETCOR) NMR spectroscopy represents a 2D technique allows the determination which protons are interacting with which carbons. In the present work this

  19. Variability of cork from Portuguese Quercus suber studied by solid-state (13)C-NMR and FTIR spectroscopies.

    PubMed

    Lopes, M H; Barros, A S; Pascoal Neto, C; Rutledge, D; Delgadillo, I; Gil, A M

    2001-01-01

    A new approach is presented for the study of the variability of Portuguese reproduction cork using solid-state (13)C-NMR spectroscopy and photoacoustic (PAS) FTIR (FTIR-PAS) spectroscopy combined with chemometrics. Cork samples were collected from 12 different geographical sites, and their (13)C-cross-polarization with magic angle spinning (CP/MAS) and FTIR spectra were registered. A large spectral variability among the cork samples was detected by principal component analysis and found to relate to the suberin and carbohydrate contents. This variability was independent of the sample geographical origin but significantly dependent on the cork quality, thus enabling the distinction of cork samples according to the latter property. The suberin content of the cork samples was predicted using multivariate regression models based on the (13)C-NMR and FTIR spectra of the samples as reported previously. Finally, the relationship between the variability of the (13)C-CP/MAS spectra with that of the FTIR-PAS spectra was studied by outer product analysis. This type of multivariate analysis enabled a clear correlation to be established between the peaks assigned to suberin and carbohydrate in the FTIR spectrum and those appearing in the (13)C-CP/MAS spectra.

  20. High Resolution Solid State 13C NMR Spectroscopy of Sporopollenins from Different Plant Taxa

    PubMed Central

    Guilford, William J.; Schneider, Diane M.; Labovitz, Jeffrey; Opella, Stanley J.

    1988-01-01

    The extremely chemically resistant component of the cell wall of spores, pollens, and some microorganisms, sporopollenin, is generally accepted to be derived from carotenoids or carotenoid esters. However, we report here that 13C NMR analyses of sporopollenin from several sources shows that this widely held view is incorrect, with one possible exception. Sporopollenin is not a unique substance but rather a series of related biopolymers derived from largely saturated precursors such as fatty acids. The biopolymers contain widely varying amounts of oxygen in the form of ether, hydroxyl, carboxylic acid, ester, and ketone groups. PMID:16665854

  1. Solid-State Selective 13C Excitation and Spin Diffusion NMR to Resolve Spatial Dimensions in Plant Cell Walls

    SciTech Connect

    Foston, M.; Katahira, R.; Gjersing, E.; Davis, M. F.; Ragauskas, A. J.

    2012-02-15

    The average spatial dimensions between major biopolymers within the plant cell wall can be resolved using a solid-state NMR technique referred to as a {sup 13}C cross-polarization (CP) SELDOM (selectively by destruction of magnetization) with a mixing time delay for spin diffusion. Selective excitation of specific aromatic lignin carbons indicates that lignin is in close proximity to hemicellulose followed by amorphous and finally crystalline cellulose. {sup 13}C spin diffusion time constants (T{sub SD}) were extracted using a two-site spin diffusion theory developed for {sup 13}C nuclei under magic angle spinning (MAS) conditions. These time constants were then used to calculate an average lower-limit spin diffusion length between chemical groups within the plant cell wall. The results on untreated {sup 13}C enriched corn stover stem reveal that the lignin carbons are, on average, located at distances {approx}0.7-2.0 nm from the carbons in hemicellulose and cellulose, whereas the pretreated material had larger separations.

  2. Methionine bound to Pd/γ-Al2O3 catalysts studied by solid-state (13)C NMR.

    PubMed

    Johnson, Robert L; Schwartz, Thomas J; Dumesic, James A; Schmidt-Rohr, Klaus

    2015-11-01

    The chemisorption and breakdown of methionine (Met) adsorbed on Pd/γ-Al2O3 catalysts were investigated by solid-state NMR. (13)C-enriched Met (ca. 0.4mg) impregnated onto γ-Al2O3 or Pd/γ-Al2O3 gives NMR spectra with characteristic features of binding to γ-Al2O3, to Pd nanoparticles, and oxidative or reductive breakdown of Met. The SCH3 groups of Met showed characteristic changes in chemical shift on γ-Al2O3 (13ppm) vs. Pd (19ppm), providing strong evidence for preferential binding to Pd, while the NC carbon generates a small resonance at 96ppm assigned to a distinct nonprotonated species bound to O or Pd. Additionally, NMR shows that the SCH3 groups of Met are mobile on γ-Al2O3 but immobilized by binding to Pd particles; on small Pd particles (ca. 4nm), the NCH groups undergo large-amplitude motions. In a reducing environment, Met breaks down by C-S bond cleavage followed by formation of C2-C4 organic acids. The SCH3 signal shifts to 22ppm, which is likely the signature of the principal species responsible for strong catalyst inhibition. These experiments demonstrate that solid-state magic-angle spinning NMR of (13)C-enriched Met can be a sensitive probe to investigate catalyst surfaces and characterize catalyst inhibition both before reaction and postmortem.

  3. Characterization of a Mixture of CO2 Adsorption Products in Hyperbranched Aminosilica Adsorbents by (13)C Solid-State NMR.

    PubMed

    Moore, Jeremy K; Sakwa-Novak, Miles A; Chaikittisilp, Watcharop; Mehta, Anil K; Conradi, Mark S; Jones, Christopher W; Hayes, Sophia E

    2015-11-17

    Hyperbranched amine polymers (HAS) grown from the mesoporous silica SBA-15 (hereafter "SBA-15-HAS") exhibit large capacities for CO2 adsorption. We have used static in situ and magic-angle spinning (MAS) ex situ (13)C nuclear magnetic resonance (NMR) to examine the adsorption of CO2 by SBA-15-HAS. (13)C NMR distinguishes the signal of gas-phase (13)CO2 from that of the chemisorbed species. HAS polymers possess primary, secondary, and tertiary amines, leading to multiple chemisorption reaction outcomes, including carbamate (RnNCOO(-)), carbamic acid (RnNCOOH), and bicarbonate (HCO3(-)) moieties. Carbamates and bicarbonate fall within a small (13)C chemical shift range (162-166 ppm), and a mixture was observed including carbamic acid and carbamate, the former disappearing upon evacuation of the sample. By examining the (13)C-(14)N dipolar coupling through low-field (B0 = 3 T) (13)C{(1)H} cross-polarization MAS NMR, carbamate is confirmed through splitting of the (13)C resonance. A third species that is either bicarbonate or a second carbamate is evident from bimodal T2 decay times of the ∼163 ppm peak, indicating the presence of two species comprising that single resonance. The mixture of products suggests that (1) the presence of amines and water leads to bicarbonate being present and/or (2) the multiple types of amine sites in HAS permit formation of chemically distinct carbamates.

  4. Investigation of gamma-irradiated vegetable seeds with high-resolution solid-state 13C NMR.

    PubMed

    Bardet, Michel; Maron, Sébastien; Foray, Marie Françoise; Berger, Maurice; Guillermo, Armel

    2004-04-01

    13C solid-state NMR was used to investigate the effects of gamma radiation on vegetable seeds, Pisum sativum and Latuca sativa, at absorbed doses that inhibit their germination. By combining single-pulse excitation and cross-polarization experiments under magic angle spinning, both liquid and solid domains of seeds can be characterized. We showed that the liquid domains, mostly made of triacylglycerols (TAG), of vegetable seeds are not sensitive to radiation. The main structural changes have been observed in the embryonic axes of seeds when the seeds are water-imbibed before irradiation. These results rule out a starting hypothesis concerning the potential role of TAG contained in oil bodies as a potential source of aldehydes that could further react with DNA moiety.

  5. Solid state 13C NMR and FT-IR spectroscopy of the cocoon silk of two common spiders

    NASA Astrophysics Data System (ADS)

    Bramanti, Emilia; Catalano, Donata; Forte, Claudia; Giovanneschi, Mario; Masetti, Massimo; Veracini, Carlo Alberto

    2005-11-01

    The structure of the silk from cocoons of two common spiders, Araneus diadematus (family Araneidae) and Achaearanea tepidariorum (family Theridiidae) was investigated by means of 13C solid state NMR and FT-IR spectroscopies. The combined use of these two techniques allowed us to highlight differences in the two samples. The cocoon silk of Achaearanea tepidariorum is essentially constituted by helical and β-sheet structures, whereas that of Araneus diadematus shows a more complex structure, containing also β-strands and β-turns. Moreover, the former silk is essentially crystalline while the latter contains more mobile domains. The structural differences of the two cocoon silks are ascribed to the different habitat of the two species.

  6. Identification of Li-Ion Battery SEI Compounds through (7)Li and (13)C Solid-State MAS NMR Spectroscopy and MALDI-TOF Mass Spectrometry.

    PubMed

    Huff, Laura A; Tavassol, Hadi; Esbenshade, Jennifer L; Xing, Wenting; Chiang, Yet-Ming; Gewirth, Andrew A

    2016-01-13

    Solid-state (7)Li and (13)C MAS NMR spectra of cycled graphitic Li-ion anodes demonstrate SEI compound formation upon lithiation that is followed by changes in the SEI upon delithiation. Solid-state (13)C DPMAS NMR shows changes in peaks associated with organic solvent compounds (ethylene carbonate and dimethyl carbonate, EC/DMC) upon electrochemical cycling due to the formation of and subsequent changes in the SEI compounds. Solid-state (13)C NMR spin-lattice (T1) relaxation time measurements of lithiated Li-ion anodes and reference poly(ethylene oxide) (PEO) powders, along with MALDI-TOF mass spectrometry results, indicate that large-molecular-weight polymers are formed in the SEI layers of the discharged anodes. MALDI-TOF MS and NMR spectroscopy results additionally indicate that delithiated anodes exhibit a larger number of SEI products than is found in lithiated anodes.

  7. Solid-state 13C NMR study of the mobility of polysaccharides in the cell walls of two apple cultivars of different firmness.

    PubMed

    Ng, Jovyn K T; Zujovic, Zoran D; Smith, Bronwen G; Johnston, Jason W; Schröder, Roswitha; Melton, Laurence D

    2014-03-11

    Solid-state (13)C nuclear magnetic resonance (NMR) was used to compare differences in mobility of the cell wall polysaccharides of 'Scifresh' and 'Royal Gala' apples after 20 weeks of storage. The texture of 'Scifresh' apples was markedly firmer than that of 'Royal Gala' at the end of storage. In a novel approach Two Pulse Phase Modulation (TPPM) decoupling was combined with cross polarisation (CP) and single pulse excitation (SPE) experiments. The resulting high resolution solid-state SPE spectra, unprecedented for apple cell walls, allowed a detailed insight into the physical and chemical properties of very mobile polysaccharides such as the arabinan and galactan side chains of the pectic polysaccharide rhamnogalacturonan I (RG-I). NMR showed that the cellulose rigidity was the same in the two cultivars, while arabinans were more mobile than galactans in both. Unexpectedly, arabinans in 'Scifresh' cell walls were more mobile than those in 'Royal Gala' which was unforeseen considering the greater firmness of the 'Scifresh' cultivar.

  8. /sup 13/C nuclear magnetic resonance studies of cardiac metabolism

    SciTech Connect

    Seeholzer, S.H.

    1985-01-01

    The last decade has witnessed the increasing use of Nuclear Magnetic Resonance (NMR) techniques for following the metabolic fate of compounds specifically labeled with /sup 13/C. The goals of the present study are: (1) to develop reliable quantitative procedures for measuring the /sup 13/C enrichment of specific carbon sites in compounds enriched by the metabolism of /sup 13/C-labeled substrates in rat heart, and (2) to use these quantitative measurements of fractional /sup 13/C enrichment within the context of a mathematical flux model describing the carbon flow through the TCA cycle and ancillary pathways, as a means for obtaining unknown flux parameters. Rat hearts have been perfused in vitro with various combinations of glucose, acetate, pyruvate, and propionate to achieve steady state flux conditions, followed by perfusion with the same substrates labeled with /sup 13/C in specific carbon sites. The hearts were frozen at different times after addition of /sup 13/C-labeled substrates and neutralized perchloric acid extracts were used to obtain high resolution proton-decoupled /sup 13/C NMR spectra at 90.55 MHz. The fractional /sup 13/C enrichment (F.E.) of individual carbon sites in different metabolites was calculated from the area of the resolved resonances after correction for saturation and nuclear Overhauser effects. These F.E. measurements by /sup 13/C NMR were validated by the analysis of /sup 13/C-/sup 1/H scalar coupling patterns observed in /sup 1/H NMR spectra of the extracted metabolites. The results obtained from perfusion of hearts glucose plus either (2-/sup 13/C) acetate or (3-/sup 13/C) pyruvate are similar to those obtained by previous investigators using /sup 14/C-labeled substrates.

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

    SciTech Connect

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

    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.

  10. Polydisperse methyl β-cyclodextrin–epichlorohydrin polymers: variable contact time 13C CP-MAS solid-state NMR characterization

    PubMed Central

    Mallard, Isabelle; Baudelet, Davy; Castiglione, Franca; Ferro, Monica; Panzeri, Walter; Ragg, Enzio

    2015-01-01

    Summary The polymerization of partially methylated β-cyclodextrin (CRYSMEB) with epichlorohydrin was carried out in the presence of a known amount of toluene as imprinting agent. Three different preparations (D1, D2 and D3) of imprinted polymers were obtained and characterized by solid-state 13C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials but with different absorption properties. The main purpose of the work was to find a suitable spectroscopic descriptor accounting for the different imprinting process in three homogeneous polymeric networks. The polymers were characterized by studying the kinetics of the cross-polarization process. This approach is based on variable contact time CP-MAS spectra, referred to as VCP-MAS. The analysis of the VCP-MAS spectra provided two relaxation parameters: T CH (the CP time constant) and T 1ρ (the proton spin-lattice relaxation time in the rotating frame). The results and the analysis presented in the paper pointed out that T CH is sensitive to the imprinting process, showing variations related to the toluene/cyclodextrin molar ratio used for the preparation of the materials. Conversely, the observed values of T 1ρ did not show dramatic variations with the imprinting protocol, but rather confirmed that the three polymers are morphologically similar. Thus the combined use of T CH and T 1ρ can be helpful for the characterization and fine tuning of imprinted polymeric matrices. PMID:26877800

  11. Polydisperse methyl β-cyclodextrin-epichlorohydrin polymers: variable contact time (13)C CP-MAS solid-state NMR characterization.

    PubMed

    Mallard, Isabelle; Baudelet, Davy; Castiglione, Franca; Ferro, Monica; Panzeri, Walter; Ragg, Enzio; Mele, Andrea

    2015-01-01

    The polymerization of partially methylated β-cyclodextrin (CRYSMEB) with epichlorohydrin was carried out in the presence of a known amount of toluene as imprinting agent. Three different preparations (D1, D2 and D3) of imprinted polymers were obtained and characterized by solid-state (13)C NMR spectroscopy under cross-polarization magic angle spinning (CP-MAS) conditions. The polymers were prepared by using the same synthetic conditions but with different molar ratios of imprinting agent/monomer, leading to morphologically equivalent materials but with different absorption properties. The main purpose of the work was to find a suitable spectroscopic descriptor accounting for the different imprinting process in three homogeneous polymeric networks. The polymers were characterized by studying the kinetics of the cross-polarization process. This approach is based on variable contact time CP-MAS spectra, referred to as VCP-MAS. The analysis of the VCP-MAS spectra provided two relaxation parameters: T CH (the CP time constant) and T 1ρ (the proton spin-lattice relaxation time in the rotating frame). The results and the analysis presented in the paper pointed out that T CH is sensitive to the imprinting process, showing variations related to the toluene/cyclodextrin molar ratio used for the preparation of the materials. Conversely, the observed values of T 1ρ did not show dramatic variations with the imprinting protocol, but rather confirmed that the three polymers are morphologically similar. Thus the combined use of T CH and T 1ρ can be helpful for the characterization and fine tuning of imprinted polymeric matrices.

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

    PubMed

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

    2017-03-01

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

  13. Dynamic nuclear polarization of carbonyl and methyl 13C spins in acetate using trityl OX063

    NASA Astrophysics Data System (ADS)

    Niedbalski, Peter; Parish, Christopher; Lumata, Lloyd

    2015-03-01

    Hyperpolarization via dissolution dynamic nuclear polarization (DNP) is a physics technique that amplifies the magnetic resonance signals by several thousand-fold for biomedical NMR spectroscopy and imaging (MRI). Herein we have investigated the effect of carbon-13 isotopic location on the DNP of acetate (one of the biomolecules commonly used for hyperpolarization) at 3.35 T and 1.4 K using a narrow ESR linewidth free radical trityl OX063. We have found that the carbonyl 13C spins yielded about twice the polarization produced in methyl 13C spins. Deuteration of the methyl group, beneficial in the liquid-state, did not produce an improvement in the polarization level at cryogenic conditions. Concurrently, the solid-state nuclear relaxation of these samples correlate with the polarization levels achieved. These results suggest that the location of the 13C isotopic labeling in acetate has a direct impact on the solid-state polarization achieved and is mainly governed by the nuclear relaxation leakage factor.

  14. Dynamic nuclear polarization-enhanced 13C NMR spectroscopy of static biological solids

    PubMed Central

    Potapov, Alexey; Yau, Wai-Ming; Tycko, Robert

    2013-01-01

    We explore the possibility of using dynamic nuclear polarization (DNP) to enhance signals in structural studies of biological solids by solid state NMR without sample spinning. Specifically, we use 2D 13C-13C exchange spectroscopy to probe the peptide backbone torsion angles (ϕ,ψ) in a series of selectively 13C-labeled 40-residue β-amyloid (Aβ1–40) samples, in both fibrillar and non-fibrillar states. Experiments are carried out at 9.39 T and 8 K, using a static double-resonance NMR probe and low-power microwave irradiation at 264 GHz. In frozen solutions of Aβ1–40 fibrils doped with DOTOPA-TEMPO, we observe DNP signal enhancement factors of 16–21. We show that the orientation- and frequency-dependent spin polarization exchange between sequential backbone carbonyl 13C labels can be simulated accurately using a simple expression for the exchange rate, after experimentally determined homogeneous 13C lineshapes are incorporated in the simulations. The experimental 2D 13C-13C exchange spectra place constraints on the ϕ and ψ angles between the two carbonyl labels. Although the data are not sufficient to determine ϕ and ψ uniquely, the data do provide non-trivial constraints that could be included in structure calculations. With DNP at low temperatures, 2D 13C-13C exchange spectra can be obtained from a 3.5 mg sample of Aβ1–40 fibrils in 4 hr or less, despite the broad 13C chemical shift anisotropy line shapes that are observed in static samples. PMID:23562665

  15. Optical hyperpolarization of 13C nuclear spins in nanodiamond ensembles

    NASA Astrophysics Data System (ADS)

    Chen, Q.; Schwarz, I.; Jelezko, F.; Retzker, A.; Plenio, M. B.

    2015-11-01

    Dynamical nuclear polarization holds the key for orders of magnitude enhancements of nuclear magnetic resonance signals which, in turn, would enable a wide range of novel applications in biomedical sciences. However, current implementations of DNP require cryogenic temperatures and long times for achieving high polarization. Here we propose and analyze in detail protocols that can achieve rapid hyperpolarization of 13C nuclear spins in randomly oriented ensembles of nanodiamonds at room temperature. Our protocols exploit a combination of optical polarization of electron spins in nitrogen-vacancy centers and the transfer of this polarization to 13C nuclei by means of microwave control to overcome the severe challenges that are posed by the random orientation of the nanodiamonds and their nitrogen-vacancy centers. Specifically, these random orientations result in exceedingly large energy variations of the electron spin levels that render the polarization and coherent control of the nitrogen-vacancy center electron spins as well as the control of their coherent interaction with the surrounding 13C nuclear spins highly inefficient. We address these challenges by a combination of an off-resonant microwave double resonance scheme in conjunction with a realization of the integrated solid effect which, together with adiabatic rotations of external magnetic fields or rotations of nanodiamonds, leads to a protocol that achieves high levels of hyperpolarization of the entire nuclear-spin bath in a randomly oriented ensemble of nanodiamonds even at room temperature. This hyperpolarization together with the long nuclear-spin polarization lifetimes in nanodiamonds and the relatively high density of 13C nuclei has the potential to result in a major signal enhancement in 13C nuclear magnetic resonance imaging and suggests functionalized and hyperpolarized nanodiamonds as a unique probe for molecular imaging both in vitro and in vivo.

  16. Solid state laser media driven by remote nuclear powered fluorescence

    DOEpatents

    Prelas, Mark A.

    1992-01-01

    An apparatus is provided for driving a solid state laser by a nuclear powered fluorescence source which is located remote from the fluorescence source. A nuclear reaction produced in a reaction chamber generates fluorescence or photons. The photons are collected from the chamber into a waveguide, such as a fiber optic waveguide. The waveguide transports the photons to the remote laser for exciting the laser.

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

    USGS Publications Warehouse

    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.

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

    USGS Publications Warehouse

    Benner, R.; Hatcher, P.G.; Hedges, J.I.

    1990-01-01

    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. ?? 1990.

  19. Elucidating connectivity and metal-binding structures of unlabeled paramagnetic complexes by 13C and 1H solid-state NMR under fast magic angle spinning.

    PubMed

    Wickramasinghe, Nalinda P; Shaibat, Medhat A; Ishii, Yoshitaka

    2007-08-23

    Characterizing paramagnetic complexes in solids is an essential step toward understanding their molecular functions. However, methodologies to characterize chemical and electronic structures of paramagnetic systems at the molecular level have been notably limited, particularly for noncrystalline solids. We present an approach to obtain connectivities of chemical groups and metal-binding structures for unlabeled paramagnetic complexes by 13C and 1H high-resolution solid-state NMR (SSNMR) using very fast magic angle spinning (VFMAS, spinning speed >or=20 kHz). It is experimentally shown for unlabeled Cu(II)(Ala-Thr) that 2D 13C/1H correlation SSNMR under VFMAS provides the connectivity of chemical groups and assignments for the characterization of unlabeled paramagnetic systems in solids. We demonstrate that on the basis of the assignments provided by the VFMAS approach multiple 13C-metal distances can be simultaneously elucidated by a combination of measurements of 13C anisotropic hyperfine shifts and 13C T1 relaxation due to hyperfine interactions for this peptide-Cu(II) complex. It is also shown that an analysis of 1H anisotropic hyperfine shifts allows for the determination of electron-spin states in Fe(III)-chloroprotoporphyin-IX in solid states.

  20. NMR crystallography to probe the breathing effect of the MIL-53(Al) metal-organic framework using solid-state NMR measurements of (13)C-(27)Al distances.

    PubMed

    Giovine, Raynald; Volkringer, Christophe; Trébosc, Julien; Amoureux, Jean Paul; Loiseau, Thierry; Lafon, Olivier; Pourpoint, Frédérique

    2017-03-01

    The metal-organic framework MIL-53(Al) (aluminium terephthalate) exhibits a structural transition between two porous structures with large pore (lp) or narrow pore (np) configurations. This transition, called the breathing effect, is observed upon changes in temperature or external pressure, as well as with the adsorption of guest molecules, such as H2O, within the pores. We show here how these different pore openings can be detected by observing the dephasing of (13)C magnetization under (13)C-(27)Al dipolar couplings using Rotational-Echo Saturation-Pulse Double-Resonance (RESPDOR) solid-state NMR experiments with Simultaneous Frequency and Amplitude Modulation (SFAM) recoupling. These double-resonance NMR experiments between (13)C and (27)Al nuclei, which have close Larmor frequencies, are feasible thanks to the use of a frequency splitter. The experimental SFAM-RESPDOR signal fractions agree well with those simulated from the MIL-53(Al)-lp and -np crystal structures obtained from powder X-ray diffraction analysis. Hence, these (13)C-(27)Al solid-state NMR experiments validate these structures and confirm their rigidity. A similar agreement is reported for the framework ligands in the as-synthesized (as) MIL-53(Al), in which the pores contain free ligands. Furthermore, in this case, (13)C-{(27)Al} SFAM-RESPDOR experiments allow an estimation of the average distance between the free ligands and the (27)Al nuclei of the framework.

  1. A 1H, 13C and 15N NMR study in solution and in the solid state of six N-substituted pyrazoles and indazoles.

    PubMed

    Claramunt, Rosa M; Santa María, M Dolores; Sanz, Dionisia; Alkorta, Ibon; Elguero, José

    2006-05-01

    Three N-substituted pyrazoles and three N-substituted indazoles [1-(4-nitrophenyl)-3,5-dimethylpyrazole (1), 1-(2,4-dinitrophenyl)-3,5-dimethylpyrazole (2), 1-tosyl-pyrazole (3), 1-p-chlorobenzoylindazole (4), 1-tosylinda-zole (5) and 2-(2-hydroxy-2-phenylethyl)-indazole (6)] have been studied by NMR spectroscopy in solution (1H, 13C, 15N) and in the solid state (13C, 15N). The chemical shifts have been compared with GIAO/DFT calculated absolute shieldings. Some discrepancies have been analyzed.

  2. 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

    USGS Publications Warehouse

    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.

  3. Protonation of carbon single-walled nanotubes studied using 13C and 1H-13C cross polarization nuclear magnetic resonance and Raman spectroscopies.

    PubMed

    Engtrakul, Chaiwat; Davis, Mark F; Gennett, Thomas; Dillon, Anne C; Jones, Kim M; Heben, Michael J

    2005-12-14

    The reversible protonation of carbon single-walled nanotubes (SWNTs) in sulfuric acid and Nafion was investigated using solid-state nuclear magnetic resonance (NMR) and Raman spectroscopies. Magic-angle spinning (MAS) was used to obtain high-resolution 13C and 1H-13C cross polarization (CP) NMR spectra. The 13C NMR chemical shifts are reported for bulk SWNTs, H2SO4-treated SWNTs, SWNT-Nafion polymer composites, SWNT-AQ55 polymer composites, and SWNTs in contact with water. Protonation occurs without irreversible oxidation of the nanotube substrate via a charge-transfer process. This is the first report of a chemically induced change in a SWNT 13C resonance brought about by a reversible interaction with an acidic proton, providing additional evidence that carbon nanotubes behave as weak bases. Cross polarization was found to be a powerful technique for providing an additional contrast mechanism for studying nanotubes in contact with other chemical species. The CP studies confirmed polarization transfer from nearby protons to nanotube carbon atoms. The CP technique was also applied to investigate water adsorbed on carbon nanotube surfaces. Finally, the degree of bundling of the SWNTs in Nafion films was probed with the 1H-13C CP-MAS technique.

  4. Probing lipid-cholesterol interactions in DOPC/eSM/Chol and DOPC/DPPC/Chol model lipid rafts with DSC and (13)C solid-state NMR.

    PubMed

    Fritzsching, Keith J; Kim, Jihyun; Holland, Gregory P

    2013-08-01

    The interaction between cholesterol (Chol) and phospholipids in bilayers was investigated for the ternary model lipid rafts, DOPC/eSM/Chol and DOPC/DPPC/Chol, with differential scanning calorimetry (DSC) and (13)C cross polarization magic angle spinning (CP-MAS) solid-state NMR. The enthalpy and transition temperature (Tm) of the Lα liquid crystalline phase transition from DSC was used to probe the thermodynamics of the different lipids in the two systems as a function of Chol content. The main chain (13)C (CH2)n resonance is resolved in the (13)C CP-MAS NMR spectra for the unsaturated (DOPC) and saturated (eSM or DPPC) chain lipid in the ternary lipid raft mixtures. The (13)C chemical shift of this resonance can be used to detect differences in chain ordering and overall interactions with Chol for the different lipid constituents in the ternary systems. The combination of DSC and (13)C CP-MAS NMR results indicate that there is a preferential interaction between SM and Chol below Tm for the DOPC/eSM/Chol system when the Chol content is ≤20mol%. In contrast, no preferential interaction between Chol and DPPC is observed in the DOPC/DPPC/Chol system above or below Tm. Finally, (13)C CP-MAS NMR resolves two Chol environments in the DOPC/eSM/Chol system below Tm at Chol contents >20mol% while, a single Chol environment is observed for DOPC/DPPC/Chol at all compositions.

  5. Dynamic pictures of membrane proteins in two-dimensional crystal, lipid bilayer and detergent as revealed by site-directed solid-state 13C NMR.

    PubMed

    Saitô, Hazime

    2004-11-01

    We have compared site-directed 13C solid-state NMR spectra of [3-13C]Ala- and/or [1-13C]Val-labeled membrane proteins, including bacteriorhodopsin (bR), pharaonis phoborhodopin (ppR), its cognate transducer (pHtrII) and Escherichia coli diacylglycerol kinase (DGK), in two-dimensional (2D) crystal, lipid bilayers, and detergent. Restricted fluctuation motions of these membrane proteins due to oligomerization of bR by specific protein-protein interactions in the 2D crystalline lattice or protein complex between ppR and pHtrII provide the most favorable environment to yield well-resolved, fully visible 13C NMR signals for [3-13C]Ala-labeled proteins. In contrast, several signals from such membrane proteins were broadened or lost owing to interference of inherent fluctuation frequencies (10(4)-10(5)Hz) with frequency of either proton decoupling or magic angle spinning, if their 13C NMR spectra were recorded as a monomer in lipid bilayers at ambient temperature. The presence of such protein dynamics is essential for the respective proteins to achieve their own biological functions. Finally, spectral broadening found for bR and DGK in detergents were discussed.

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

    NASA Astrophysics Data System (ADS)

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

    2016-04-01

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

  7. The Application of Nuclear Techniques to Solid State Devices.

    DTIC Science & Technology

    1980-12-15

    35) as the same technique showed. We then applied the method to clarify the atomic transport in bimetal layer silicide reactions. In these experiments...UNCLASSIFIED NL ’ LEVEWL L* . 4’ -.-- C7..:i I) FINAL TECHNICAL REPORT submitted to --- v OFFICE OF NAVAL RESEARCH on THE APPLICATION OF NUCLEAR TECHNIQUES TO...December 15, 1980,. , ...- 1’J I. Introduction The program "The Application of Nuclear Techniques to Solid State Devices" began on 1 January 1975. It was

  8. Solid-state and solution /sup 13/C NMR in the conformational analysis of methadone-hydrochloride and related narcotic analgesics

    SciTech Connect

    Sumner, S.C.J.

    1986-01-01

    Solid state and solution /sup 13/C NMR have been used to study the conformations of the racemic mixtures and single enantiomers of methadone hydrochloride, alpha and beta methadol hydrochloride, and alpha and beta acetylmethadol hydrochloride. The NMR spectra acquired for the compounds as solids, and in polar and nonpolar solvents are compared, in order to determine the conformation of the molecules in solution. To determine the reliability of assigning solution conformations by comparing solution and solid state chemical shift data, three bond coupling constants measured in solution are compared with those calculated from X-ray data. The conformations of the racemic mixture and plus enantiomer of methadone hydrochloride have been shown to be very similar in the solid state, where minor differences in conformation can be seen by comparing NMR spectra obtained for the solids. Also shown is that the molecules of methadone hydrochloride have conformations in polar and in nonpolar solvents which are very similar to the conformation of the molecules in the solid state.

  9. In Situ Solid-State (13)C NMR Observation of Pore Mouth Catalysis in Etherification of β-Citronellene with Ethanol on Zeolite Beta.

    PubMed

    Radhakrishnan, Sambhu; Goossens, Pieter-Jan; Magusin, Pieter C M M; Sree, Sreeprasanth Pulinthanathu; Detavernier, Christophe; Breynaert, Eric; Martineau, Charlotte; Taulelle, Francis; Martens, Johan A

    2016-03-02

    The reaction mechanism of etherification of β-citronellene with ethanol in liquid phase over acid zeolite beta is revealed by in situ solid-state (13)C NMR spectroscopy. Comparison of (13)C Hahn-echo and (1)H-(13)C cross-polarization NMR characteristics is used to discriminate between molecules freely moving in liquid phase outside the zeolite and molecules adsorbed inside zeolite pores and in pore mouths. In the absence of ethanol, β-citronellene molecules enter zeolite pores and react to isomers. In the presence of ethanol, the concentration of β-citronellene inside zeolite pores is very low because of preferential adsorption of ethanol. The etherification reaction proceeds by adsorption of β-citronellene molecule from the external liquid phase in a pore opening where it reacts with ethanol from inside the pore. By competitive adsorption, ethanol prevents the undesired side reaction of β-citronellene isomerization inside zeolite pores. β-citronellene etherification on zeolite beta is suppressed by bulky base molecules (2,4,6-collidine and 2,6-ditertiarybutylpyridine) that do not enter the zeolite pores confirming the involvement of easily accessible acid sites in pore openings. The use of in situ solid-state NMR to probe the transition from intracrystalline catalysis to pore mouth catalysis depending on reaction conditions is demonstrated for the first time. The study further highlights the potential of this NMR approach for investigations of adsorption of multicomponent mixtures in general.

  10. Modification of structure and digestibility of chestnut starch upon cooking: a solid state (13)C CP MAS NMR and enzymatic degradation study.

    PubMed

    Pizzoferrato, L; Rotilio, G; Paci, M

    1999-10-01

    The modification of starch, which is the major component of the polysaccharide fraction of chestnuts (Castanea sativa), has been studied from the point of view of structure and digestibility to understand the modifications induced by cooking and, specifically, by the Maillard reaction. The study was carried out by enzymatic degradation kinetics, monitoring the glucose released upon time, and by solid state (13)C CP MAS NMR, which has the potential of monitoring the solid state phase changes occurring upon chemical modification due to the cooking process. Results obtained reveal that large changes are induced in the macromolecular structure of starchy materials and that these changes are correlated with changes of digestibility in terms of enzymatic degradation resistance. In the system studied, the extension of the Maillard reaction is not such as to exert a significant influence on structure and/or digestibility of chestnut starch.

  11. Solid-state sup 13 C NMR of the retinal chromophore in photointermediates of bacteriorhodopsin: Characterization of two forms of M

    SciTech Connect

    Smith, S.O.; Courtin, J.; van den Berg, E.; Winkel, C.; Lugtenburg, J.; Herzfeld, J.; Griffin, R.G. )

    1989-01-10

    Solid-state {sup 13}C NMR spectra of the M photocycle intermediate of bacteriorhodopsin (bR) have been obtained from purple membrane regenerated with retinal specifically {sup 13}C labeled at positions 5, 12, 13, 14, and 15. The M intermediate was trapped at {minus}40{degree}C and pH = 9.5-10.0 in either 100 mM NaCl (M (NaCl)) or 500 mM guanidine hydrochloride (M (Gdn-HCl)). The {sup 13}C-12 chemical shift at 125.8 ppm in M (NaCl) and 128.1 ppm in M (Gdn-HCl) indicates that the C{sub 13}{double bond}C{sub 14} double bond has a cis configuration, while the {sup 13}C-13 chemical shift at 146.7 ppm in M (NaCl) and 14.57 ppm in M (Gdn-HCl) demonstrates that the Schiff base in unprotonated. The principal values of the chemical shift tensor of the {sup 13}C-5 resonance in both M (NaCl) and M (Gdn-HCl) are consistent with a 6-s-trans structure and a negative protein charge localized near C-5 as was observed in dark adapted bR. The {approximately}5 ppm upfield shift of the {sup 13}C-5 M resonance relative to {sup 13}C-5 bR{sub 568} and bR{sub 548} is attributed to an unprotonated Schiff base in the M chromophore. Of particular interest in this study were the results obtained from {sup 13}C-14 M. In M (NaCl), a dramatic upfield shift was observed for the {sup 13}C-14 resonance relative to unprotonanted Schiff base model compounds. In contrast, in M (Gdn-HCl) the {sup 13}C-14 resonance was observed at 125.7 ppm. The different {sup 13}C-14 chemical shifts in these two M preparations may be explained by different C{double prime}N configurations of the retinal-lysine Schiff base linkage, namely, syn in NaCl and anti in guanidine hydrochloride.

  12. Advances in Theory of Solid-State Nuclear Magnetic Resonance.

    PubMed

    Mananga, Eugene S; Moghaddasi, Jalil; Sana, Ajaz; Akinmoladun, Andrew; Sadoqi, Mostafa

    Recent advances in theory of solid state nuclear magnetic resonance (NMR) such as Floquet-Magnus expansion and Fer expansion, address alternative methods for solving a time-dependent linear differential equation which is a central problem in quantum physics in general and solid-state NMR in particular. The power and the salient features of these theoretical approaches that are helpful to describe the time evolution of the spin system at all times are presented. This review article presents a broad view of manipulations of spin systems in solid-state NMR, based on milestones theories including the average Hamiltonian theory and the Floquet theory, and the approaches currently developing such as the Floquet-Magnus expansion and the Fer expansion. All these approaches provide procedures to control and describe the spin dynamics in solid-state NMR. Applications of these theoretical methods to stroboscopic and synchronized manipulations, non-synchronized experiments, multiple incommensurated frequencies, magic-angle spinning samples, are illustrated. We also reviewed the propagators of these theories and discussed their convergences. Note that the FME is an extension of the popular Magnus Expansion and Average Hamiltonian Theory. It aims is to bridge the AHT to the Floquet Theorem but in a more concise and efficient formalism. Calculations can then be performed in a finite-dimensional Hilbert space instead of an infinite dimensional space within the so-called Floquet theory. We expected that the FME will provide means for more accurate and efficient spin dynamics simulation and for devising new RF pulse sequence.

  13. Advances in Theory of Solid-State Nuclear Magnetic Resonance

    PubMed Central

    Mananga, Eugene S.; Moghaddasi, Jalil; Sana, Ajaz; Akinmoladun, Andrew; Sadoqi, Mostafa

    2015-01-01

    Recent advances in theory of solid state nuclear magnetic resonance (NMR) such as Floquet-Magnus expansion and Fer expansion, address alternative methods for solving a time-dependent linear differential equation which is a central problem in quantum physics in general and solid-state NMR in particular. The power and the salient features of these theoretical approaches that are helpful to describe the time evolution of the spin system at all times are presented. This review article presents a broad view of manipulations of spin systems in solid-state NMR, based on milestones theories including the average Hamiltonian theory and the Floquet theory, and the approaches currently developing such as the Floquet-Magnus expansion and the Fer expansion. All these approaches provide procedures to control and describe the spin dynamics in solid-state NMR. Applications of these theoretical methods to stroboscopic and synchronized manipulations, non-synchronized experiments, multiple incommensurated frequencies, magic-angle spinning samples, are illustrated. We also reviewed the propagators of these theories and discussed their convergences. Note that the FME is an extension of the popular Magnus Expansion and Average Hamiltonian Theory. It aims is to bridge the AHT to the Floquet Theorem but in a more concise and efficient formalism. Calculations can then be performed in a finite-dimensional Hilbert space instead of an infinite dimensional space within the so-called Floquet theory. We expected that the FME will provide means for more accurate and efficient spin dynamics simulation and for devising new RF pulse sequence. PMID:26878063

  14. Effects of post-reactor functionalization on the phase behaviour of an ethylene-1-octene copolymer studied using solid-state high resolution 13C NMR spectroscopy.

    PubMed

    Calucci, Lucia; Cicogna, Francesca; Forte, Claudia

    2013-10-07

    The effects of post-reactor functionalization with naphthoate-TEMPO on the structure and morphology of an ethylene-1-octene copolymer were investigated by means of solid-state NMR techniques and DSC measurements. Selective (13)C MAS experiments allowed the orthorhombic and the monoclinic crystalline phases and two amorphous phases with different degree of mobility to be detected and quantified. (13)C and (1)H relaxation time measurements and spin diffusion experiments gave insight into the polymer dynamics within the different phases, the crystalline domain dimensions, and the rate of chain diffusion between amorphous and crystalline phases. Comparison of the results obtained for the pristine copolymer and the functionalized samples clearly indicated that the functionalization procedure causes redistribution within the crystalline and the amorphous phases with no relevant change in the degree of crystallinity or in the crystalline domain average size, and slows down chain diffusion.

  15. On The Potential of Dynamic Nuclear Polarization Enhanced Diamonds in Solid-State and Dissolution (13) C NMR Spectroscopy.

    PubMed

    Bretschneider, Christian O; Akbey, Ümit; Aussenac, Fabien; Olsen, Greg L; Feintuch, Akiva; Oschkinat, Hartmut; Frydman, Lucio

    2016-09-05

    Dynamic nuclear polarization (DNP) is a versatile option to improve the sensitivity of NMR and MRI. This versatility has elicited interest for overcoming potential limitations of these techniques, including the achievement of solid-state polarization enhancement at ambient conditions, and the maximization of (13) C signal lifetimes for performing in vivo MRI scans. This study explores whether diamond's (13) C behavior in nano- and micro-particles could be used to achieve these ends. The characteristics of diamond's DNP enhancement were analyzed for different magnetic fields, grain sizes, and sample environments ranging from cryogenic to ambient temperatures, in both solution and solid-state experiments. It was found that (13) C NMR signals could be boosted by orders of magnitude in either low- or room-temperature solid-state DNP experiments by utilizing naturally occurring paramagnetic P1 substitutional nitrogen defects. We attribute this behavior to the unusually long electronic/nuclear spin-lattice relaxation times characteristic of diamond, coupled with a time-independent cross-effect-like polarization transfer mechanism facilitated by a matching of the nitrogen-related hyperfine coupling and the (13) C Zeeman splitting. The efficiency of this solid-state polarization process, however, is harder to exploit in dissolution DNP-enhanced MRI contexts. The prospects for utilizing polarized diamond approaching nanoscale dimensions for both solid and solution applications are briefly discussed.

  16. Use of solid-state 13C NMR in structural studies of humic acids and humin from Holocene sediments

    USGS Publications Warehouse

    Hatcher, P.G.; VanderHart, D.L.; Earl, W.L.

    1980-01-01

    13C NMR spectra of solid humic substances in Holocene sediments have been obtained using cross polarization with magic-angle sample spinning techniques. The results demonstrate that this technique holds great promise for structural characterizations of complex macromolecular substances such as humin and humic acids. Quantifiable distinctions can be made between structural features of aquatic and terrestrial humic substances. The aliphatic carbons of the humic substances are dominant components suggestive of input from lipid-like materials. An interesting resemblance is also noted between terrestrial humic acid and humin spectra. ?? 1980.

  17. Comparison of celery (Apium graveolens L.) collenchyma and parenchyma cell wall polysaccharides enabled by solid-state (13)C NMR.

    PubMed

    Zujovic, Zoran; Chen, Da; Melton, Laurence D

    2016-02-01

    Collenchyma cells with their thickened walls are one of specific mechanical support tissues for plants, while parenchyma cells are thin walled and serve multiple functions. The parenchyma tissue is what you enjoy eating, while collenchyma, because of its fibrous nature, is not so attractive. Celery is a useful model for comparing the cell walls (CWs) of the two cell types such as collenchyma and parenchyma. However, to date, the structural characteristics of collenchyma and parenchyma cell walls from the same plant have not been compared. Monosaccharide composition suggested the collenchyma cell walls contained less pectin but more hemicellulose in comparison to parenchyma. High-resolution solid-state NMR spectra of highly mobile pectins revealed that the arabinan signals were more evident in the collenchyma spectrum, while galactan showed a much stronger resonance in the parenchyma spectrum. In addition, methyl esterified and non-esterified galacturonic acid signals were observed in parenchyma CWs, but only the latter one appeared in the collenchyma. The ratio of cellulose surface/interior obtained from CP/MAS spectra for collenchyma suggested the cellulose microfibrils were ~2.4 nm, while in the parenchyma, these were somewhat larger. X-ray diffraction indicated the size of the cellulose microfibrils were the same for both types of CWs.

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

    PubMed

    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.

  19. [Characterization of biochar by X-ray photoelectron spectroscopy and 13C nuclear magnetic resonance].

    PubMed

    Xu, Dong-yu; Jin, Jie; Yan, Yu; Han, Lan-fang; Kang, Ming-jie; Wang, Zi-ying; Zhao, Ye; Sun, Ke

    2014-12-01

    The wood (willow branch) and grass (rice straw) materials were pyrolyzed at different temperatures (300, 450 and 600 °C) to obtain the biochars used in the present study. The biochars were characterized using elementary analysis, X-ray photoelectron spectroscopy (XPS) and solid state 13C cross-polarization and magic angle spinning nuclear magnetic resonance spectroscopy (13C NMR) to illuminate the structure and composition of the biochars which were derived from the different thermal temperatures and biomass. The results showed that the H/C, O/C and (O+N)/C ratios of the biochars decreased with the increase in the pyrolysis temperatures. The surface polarity and ash content of the grass-derived biochars were higher than those of the wood-derived biochars. The minerals of the wood-derived biochars were mainly covered by the organic matter; in contrast, parts of the mineral surfaces of the grass-derived biochars were not covered by organic matter? The 13C NMR of the low temperature-derived biochars revealed a large contribution of aromatic carbon, aliphatic carbon, carboxyl and carbonyl carbon, while the high temperature-derived biochars contained a large amount of aromatic carbon. Moreover, the wood-derived biochars produced at low heat treatment temperatures contained more lignin residues than grass-derived ones, probably due to the existence of high lignin content in the feedstock soures of wood-derived biochars. The results of the study would be useful for environmental application of biochars.

  20. Impact of Ho3+-doping on 13C dynamic nuclear polarization using trityl OX063 free radical

    PubMed Central

    Kiswandhi, Andhika; Niedbalski, Peter; Parish, Christopher; Kaur, Pavanjeet; Martins, André; Fidelino, Leila; Khemtong, Chalermchai; Song, Likai; Sherry, A. Dean

    2016-01-01

    We have investigated the effects of Ho-DOTA doping on the dynamic nuclear polarization (DNP) of [1-13C] sodium acetate using trityl OX063 free radical at 3.35 T and 1.2 K. Our results indicate that addition of 2 mM Ho-DOTA on 3 M [1-13C] sodium acetate sample in 1:1 v/v glycerol:water with 15 mM trityl OX063 improves the DNP-enhanced 13C solid-state nuclear polarization by a factor of around 2.7-fold. Similar to the Gd3+ doping effect on 13C DNP, the locations of the positive and negative 13C maximum polarization peaks in the 13C microwave DNP sweep are shifted towards each other with the addition of Ho-DOTA on the DNP sample. W-band electron spin resonance (ESR) studies have revealed that while the shape and linewidth of the trityl OX063 ESR spectrum was not affected by Ho3+-doping, the electron spin-lattice relaxation time T1 of trityl OX063 was prominently reduced at cryogenic temperatures. The reduction of trityl OX063 electron T1 by Ho-doping is linked to the 13C DNP improvement in light of the thermodynamic picture of DNP. Moreover, the presence of Ho-DOTA in the dissolution liquid at room temperature has negligible reduction effect on liquid-state 13C T1, in contrast to Gd3+-doping which drastically reduces the 13C T1. The results here suggest that Ho3+-doping is advantageous over Gd3+ in terms of preservation of hyperpolarized state—an important aspect to consider for in vitro and in vivo NMR or imaging (MRI) experiments where a considerable preparation time is needed to administer the hyperpolarized 13C liquid. PMID:27424954

  1. Solid state nuclear magnetic resonance with magic-angle spinning and dynamic nuclear polarization below 25 K

    PubMed Central

    Thurber, Kent R.; Potapov, Alexey; Yau, Wai-Ming; Tycko, Robert

    2012-01-01

    We describe an apparatus for solid state nuclear magnetic resonance (NMR) with dynamic nuclear polarization (DNP) and magic-angle spinning (MAS) at 20–25 K and 9.4 Tesla. The MAS NMR probe uses helium to cool the sample space and nitrogen gas for MAS drive and bearings, as described earlier (Thurber et al., J. Magn. Reson. 2008) [1], but also includes a corrugated waveguide for transmission of microwaves from below the probe to the sample. With a 30 mW circularly polarized microwave source at 264 GHz, MAS at 6.8 kHz, and 21 K sample temperature, greater than 25-fold enhancements of cross-polarized 13C NMR signals are observed in spectra of frozen glycerol/water solutions containing the triradical dopant DOTOPA-TEMPO when microwaves are applied. As demonstrations, we present DNP-enhanced one-dimensional and two-dimensional 13C MAS NMR spectra of frozen solutions of uniformly 13C-labeled L-alanine and melittin, a 26-residue helical peptide that we have synthesized with four uniformly 13C-labeled amino acids. PMID:23238592

  2. NMR-based structural modeling of graphite oxide using multidimensional 13C solid-state NMR and ab initio chemical shift calculations.

    PubMed

    Casabianca, Leah B; Shaibat, Medhat A; Cai, Weiwei W; Park, Sungjin; Piner, Richard; Ruoff, Rodney S; Ishii, Yoshitaka

    2010-04-28

    Chemically modified graphenes and other graphite-based materials have attracted growing interest for their unique potential as lightweight electronic and structural nanomaterials. It is an important challenge to construct structural models of noncrystalline graphite-based materials on the basis of NMR or other spectroscopic data. To address this challenge, a solid-state NMR (SSNMR)-based structural modeling approach is presented on graphite oxide (GO), which is a prominent precursor and interesting benchmark system of modified graphene. An experimental 2D (13)C double-quantum/single-quantum correlation SSNMR spectrum of (13)C-labeled GO was compared with spectra simulated for different structural models using ab initio geometry optimization and chemical shift calculations. The results show that the spectral features of the GO sample are best reproduced by a geometry-optimized structural model that is based on the Lerf-Klinowski model (Lerf, A. et al. Phys. Chem. B 1998, 102, 4477); this model is composed of interconnected sp(2), 1,2-epoxide, and COH carbons. This study also convincingly excludes the possibility of other previously proposed models, including the highly oxidized structures involving 1,3-epoxide carbons (Szabo, I. et al. Chem. Mater. 2006, 18, 2740). (13)C chemical shift anisotropy (CSA) patterns measured by a 2D (13)C CSA/isotropic shift correlation SSNMR were well reproduced by the chemical shift tensor obtained by the ab initio calculation for the former model. The approach presented here is likely to be applicable to other chemically modified graphenes and graphite-based systems.

  3. Multidimensional solid-state NMR studies of the structure and dynamics of pectic polysaccharides in uniformly 13C-labeled Arabidopsis primary cell walls

    SciTech Connect

    Dick-Perez, Marilu; Wang, Tuo; Salazar, Andre; Zabotina, Olga A.; Hong, Mei

    2012-07-08

    Plant cell wall (CW) polysaccharides are responsible for the mechanical strength and growth of plant cells; however, the high-resolution structure and dynamics of the CW polysaccharides are still poorly understood because of the insoluble nature of these molecules. Here, we use 2D and 3D magic-angle-spinning (MAS) solid-state NMR (SSNMR) to investigate the structural role of pectins in the plant CW. Intact and partially depectinated primary CWs of Arabidopsis thaliana were uniformly labeled with 13C and their NMR spectra were compared. Recent 13C resonance assignment of the major polysaccharides in Arabidopsis thaliana CWs allowed us to determine the effects of depectination on the intermolecular packing and dynamics of the remaining wall polysaccharides. 2D and 3D correlation spectra show the suppression of pectin signals, confirming partial pectin removal by chelating agents and sodium carbonate. Importantly, higher cross peaks are observed in 2D and 3D 13C spectra of the depectinated CW, suggesting higher rigidity and denser packing of the remaining wall polysaccharides compared with the intact CW. 13C spin–lattice relaxation times and 1H rotating-frame spin–lattice relaxation times indicate that the polysaccharides are more rigid on both the nanosecond and microsecond timescales in the depectinated CW. Taken together, these results indicate that pectic polysaccharides are highly dynamic and endow the polysaccharide network of the primary CW with mobility and flexibility, which may be important for pectin functions. This study demonstrates the capability of multidimensional SSNMR to determine the intermolecular interactions and dynamic structures of complex plant materials under near-native conditions. Copyright © 2012 John Wiley & Sons, Ltd.

  4. Conformation and dynamics of melittin bound to magnetically oriented lipid bilayers by solid-state (31)P and (13)C NMR spectroscopy.

    PubMed Central

    Naito, A; Nagao, T; Norisada, K; Mizuno, T; Tuzi, S; Saitô, H

    2000-01-01

    The conformation and dynamics of melittin bound to the dimyristoylphosphatidylcholine (DMPC) bilayer and the magnetic orientation in the lipid bilayer systems were investigated by solid-state (31)P and (13)C NMR spectroscopy. Using (31)P NMR, it was found that melittin-lipid bilayers form magnetically oriented elongated vesicles with the long axis parallel to the magnetic field above the liquid crystalline-gel phase transition temperature (T(m) = 24 degrees C). The conformation, orientation, and dynamics of melittin bound to the membrane were further determined by using this magnetically oriented lipid bilayer system. For this purpose, the (13)C NMR spectra of site-specifically (13)C-labeled melittin bound to the membrane in the static, fast magic angle spinning (MAS) and slow MAS conditions were measured. Subsequently, we analyzed the (13)C chemical shift tensors of carbonyl carbons in the peptide backbone under the conditions where they form an alpha-helix and reorient rapidly about the average helical axis. Finally, it was found that melittin adopts a transmembrane alpha-helix whose average axis is parallel to the bilayer normal. The kink angle between the N- and C-terminal helical rods of melittin in the lipid bilayer is approximately 140 degrees or approximately 160 degrees, which is larger than the value of 120 degrees determined by x-ray diffraction studies. Pore formation was clearly observed below the T(m) in the initial stage of lysis by microscope. This is considered to be caused by the association of melittin molecules in the lipid bilayer. PMID:10777736

  5. Molecular organization in the native state of woody tissue: Studies of tertiary structure using the Raman microprobe Solid State [sup 13]C NMR and biomimetic tertiary aggregates

    SciTech Connect

    Atalla, R.H.

    1992-01-01

    A number of new approaches to the study of native wood tissue complementary to our earlier Raman spectroscopy including solid state [sup 13]C NMR and X-ray diffractometry. A wide variety of native cellulosic tissues were examined which led to the generation of biomimetic tertiary aggregates which simulate states of aggregation characteristic of cell walls. We have also explored charge transport characteristics of lignified tissue. Our Raman spectroscopic studies have advanced our understanding of key spectral features and confirmed the variability of the patterns of orientation of lignin reported earlier. A major effort was dedicated to assessing the contributions of electronic factors such as conjugation and the resonance Raman effect to enhancement of the spectra features associated with lignin. We have now established a solid foundation for spectral mapping of different regions in cell walls.

  6. Specific 13C labeling of leucine, valine and isoleucine methyl groups for unambiguous detection of long-range restraints in protein solid-state NMR studies

    NASA Astrophysics Data System (ADS)

    Fasshuber, Hannes Klaus; Demers, Jean-Philippe; Chevelkov, Veniamin; Giller, Karin; Becker, Stefan; Lange, Adam

    2015-03-01

    Here we present an isotopic labeling strategy to easily obtain unambiguous long-range distance restraints in protein solid-state NMR studies. The method is based on the inclusion of two biosynthetic precursors in the bacterial growth medium, α-ketoisovalerate and α-ketobutyrate, leading to the production of leucine, valine and isoleucine residues that are exclusively 13C labeled on methyl groups. The resulting spectral simplification facilitates the collection of distance restraints, the verification of carbon chemical shift assignments and the measurement of methyl group dynamics. This approach is demonstrated on the type-three secretion system needle of Shigella flexneri, where 49 methyl-methyl and methyl-nitrogen distance restraints including 10 unambiguous long-range distance restraints could be collected. By combining this labeling scheme with ultra-fast MAS and proton detection, the assignment of methyl proton chemical shifts was achieved.

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

    NASA Astrophysics Data System (ADS)

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

    2016-05-01

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

  8. Site-Specific Internal Motions in GB1 Protein Microcrystals Revealed by 3D 2H–13C–13C Solid-State NMR Spectroscopy

    PubMed Central

    2016-01-01

    2H quadrupolar line shapes deliver rich information about protein dynamics. A newly designed 3D 2H–13C–13C solid-state NMR magic angle spinning (MAS) experiment is presented and demonstrated on the microcrystalline β1 immunoglobulin binding domain of protein G (GB1). The implementation of 2H–13C adiabatic rotor-echo-short-pulse-irradiation cross-polarization (RESPIRATION CP) ensures the accuracy of the extracted line shapes and provides enhanced sensitivity relative to conventional CP methods. The 3D 2H–13C–13C spectrum reveals 2H line shapes for 140 resolved aliphatic deuterium sites. Motional-averaged 2H quadrupolar parameters obtained from the line-shape fitting identify side-chain motions. Restricted side-chain dynamics are observed for a number of polar residues including K13, D22, E27, K31, D36, N37, D46, D47, K50, and E56, which we attribute to the effects of salt bridges and hydrogen bonds. In contrast, we observe significantly enhanced side-chain flexibility for Q2, K4, K10, E15, E19, N35, N40, and E42, due to solvent exposure and low packing density. T11, T16, and T17 side chains exhibit motions with larger amplitudes than other Thr residues due to solvent interactions. The side chains of L5, V54, and V29 are highly rigid because they are packed in the core of the protein. High correlations were demonstrated between GB1 side-chain dynamics and its biological function. Large-amplitude side-chain motions are observed for regions contacting and interacting with immunoglobulin G (IgG). In contrast, rigid side chains are primarily found for residues in the structural core of the protein that are absent from protein binding and interactions. PMID:26849428

  9. Solid-state 13C NMR study of banana liquid crystals - 3: Alkyl-tail-group packing environments of an acute-angle bent-core molecule in the hexagonal columnar and cubic phases

    NASA Astrophysics Data System (ADS)

    Kurosu, Hiromichi; Endo, Yumi; Kimura, Saori; Hashimoto, Tomoko; Harada, Motoi; Lee, Eun-Woo; Sone, Masato; Watanabe, Junji; Kang, Sungmin

    2016-02-01

    Solid-state 13C nuclear magnetic resonance (NMR) measurements were performed on the hexagonal columnar and cubic phases of an acute-angle banana-shaped molecule, N(1,7)-S30. In the hexagonal columnar phase, three peaks appear at the NMR chemical shifts assigned to the internal methylene carbons of alkyl tails, indicating that the two alkyl tails have different packing structures, and one of the tails has two different conformations within a single molecule. Combined cross-polarization/magic-angle spinning and pulse saturation transfer/magic-angle spinning measurements show that one of the alkyl chains is located inside and the other is located outside the columnar structure. In the cubic phase, pulse saturation transfer/magic-angle spinning measurement shows that only one peak appears at the NMR chemical shifts assigned to the internal methylene carbons of alkyl tails, indicating that both of the alkyl chains are located outside the cubic structure.

  10. Solid state nuclear magnetic resonance investigations of advanced energy materials

    NASA Astrophysics Data System (ADS)

    Bennett, George D.

    In order to better understand the physical electrochemical changes that take place in lithium ion batteries and asymmetric hybrid supercapacitors solid state nuclear magnetic resonance (NMR) spectroscopy has been useful to probe and identify changes on the atomic and molecular level. NMR is used to characterize the local environment and investigate the dynamical properties of materials used in electrochemical storage devices (ESD). NMR investigations was used to better understand the chemical composition of the solid electrolyte interphase which form on the negative and positive electrodes of lithium batteries as well as identify the breakdown products that occur in the operation of the asymmetric hybrid supercapacitors. The use of nano-structured particles in the development of new materials causes changes in the electrical, structural and other material properties. NMR was used to investigate the affects of fluorinated and non fluorinated single wall nanotubes (SWNT). In this thesis three experiments were performed using solid state NMR samples to better characterize them. The electrochemical reactions of a lithium ion battery determine its operational profile. Numerous means have been employed to enhance battery cycle life and operating temperature range. One primary means is the choice and makeup of the electrolyte. This study focuses on the characteristics of the solid electrolyte interphase (SEI) that is formed on the electrodes surface during the charge discharge cycle. The electrolyte in this study was altered with several additives in order to determine the influence of the additives on SEI formation as well as the intercalation and de-intercalation of lithium ions in the electrodes. 7Li NMR studies where used to characterize the SEI and its composition. Solid state NMR studies of the carbon enriched acetonitrile electrolyte in a nonaqueous asymmetric hybrid supercapacitor were performed. Magic angle spinning (MAS) coupled with cross polarization NMR

  11. Conformational behaviour of poly(aspartic acid) and its sodium salt in the solid state as studied by high-resolution solid-state 13C-NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Wang, Pixin; Matsukawa, Shingo; Kameda, Tsunenori; Kurosu, Hiromichi; Ando, Isao

    1997-12-01

    High-resolution 13C CP/MAS NMR spectra of poly(aspartic acid) (PAA) and its sodium salt (PAANa) obtained with various neutralization numbers, n (=[COONa]/[COOH+COONa], where [ x] is the molar concentration of x), have been measured over a wide range of temperatures, in order to elucidate the conformation and its stability in the solid state. From these experimental results it was found that, at room temperature (25°C), the main chain of PAA takes a mixture of right-handed α ( αR)-helix, ω-helix and β-sheet forms and, with an increase in temperature from 25°C to 180°C, changes from αR-helix form and ω-helix form to β-sheet forms. On the other hand, the main chain of PAANa takes the right-handed αR-helix form in the temperature range from 25°C to 210°C. With a decrease in the neutralization number, PAANa changes to PAA and the NMR spectra are correspondingly changed.

  12. Insight into Understanding Dielectric Behavior of a Zn-MOF Using Variable-Temperature Crystal Structures, Electrical Conductance, and Solid-State (13)C NMR Spectra.

    PubMed

    Tong, Yuan-Bo; Liu, Shao-Xian; Zou, Yang; Xue, Chen; Duan, Hai-Bao; Liu, Jian-Lan; Ren, Xiao-Ming

    2016-11-21

    A Zn-based metal-organic framework (MOF)/porous coordination polymer (PCP), (EMIM)[Zn(SIP)] (1) (SIP(3-) = 5-sulfoisophthalate, EMIM(+) = 1-ethyl-3-methylimidazolium), was synthesized using the ionothermal reaction. The Zn(2+) ion adopts distorted square pyramid coordination geometry with five oxygen atoms from three carboxylates and one sulfo group. One of two carboxylates in SIP(3-) serves as a μ2-bridge ligand to link two Zn(2+) ions and form the dinuclear SBU, and such SBUs are connected by SIP(3-) ligands to build the three-dimensional framework with rutile (rtl) topology. The cations from the ion-liquid fill the channels. This MOF/PCP shows two-step dielectric anomalies together with two-step dielectric relaxations; the variable-temperature single-crystal structure analyses disclosed the dielectric anomaly occurring at ca. 280 K is caused by an isostructural phase transition. Another dielectric anomaly is related to the dynamic disorder of the cations in the channels. Electric modulus, conductance, and variable-temperature solid-state (13)C CP/MAS NMR spectra analyses revealed that two-step dielectric relaxations result from the dynamic motion of the cations as well as the direct-current conduction and electrode effect, respectively.

  13. Triosephosphate isomerase: 15N and 13C chemical shift assignments and conformational change upon ligand binding by magic-angle spinning solid-state NMR spectroscopy.

    PubMed

    Xu, Yimin; Lorieau, Justin; McDermott, Ann E

    2010-03-19

    Microcrystalline uniformly (13)C,(15)N-enriched yeast triosephosphate isomerase (TIM) is sequentially assigned by high-resolution solid-state NMR (SSNMR). Assignments are based on intraresidue and interresidue correlations, using dipolar polarization transfer methods, and guided by solution NMR assignments of the same protein. We obtained information on most of the active-site residues involved in chemistry, including some that were not reported in a previous solution NMR study, such as the side-chain carbons of His95. Chemical shift differences comparing the microcrystalline environment to the aqueous environment appear to be mainly due to crystal packing interactions. Site-specific perturbations of the enzyme's chemical shifts upon ligand binding are studied by SSNMR for the first time. These changes monitor proteinwide conformational adjustment upon ligand binding, including many of the sites probed by solution NMR and X-ray studies. Changes in Gln119, Ala163, and Gly210 were observed in our SSNMR studies, but were not reported in solution NMR studies (chicken or yeast). These studies identify a number of new sites with particularly clear markers for ligand binding, paving the way for future studies of triosephosphate isomerase dynamics and mechanism.

  14. Quantitative determination of site-specific conformational distributions in an unfolded protein by solid-state nuclear magnetic resonance.

    PubMed

    Hu, Kan-Nian; Havlin, Robert H; Yau, Wai-Ming; Tycko, Robert

    2009-10-02

    Solid-state nuclear magnetic resonance (NMR) techniques are used to investigate the structure of the 35-residue villin headpiece subdomain (HP35) in folded, partially denatured, and fully denatured states. Experiments are carried out in frozen glycerol/water solutions, with chemical denaturation by guanidine hydrochloride (GdnHCl). Without GdnHCl, two-dimensional solid-state (13)C NMR spectra of samples prepared with uniform (13)C labeling of selected residues show relatively sharp cross-peaks at chemical shifts that are consistent with the known three-helix bundle structure of folded HP35. At high GdnHCl concentrations, most cross-peaks broaden and shift, qualitatively indicating disruption of the folded structure and development of static conformational disorder in the frozen denatured state. Conformational distributions at one residue in each helical segment are probed quantitatively with three solid-state NMR techniques that provide independent constraints on backbone varphi and psi torsion angles in samples with sequential pairs of carbonyl (13)C labels. Without GdnHCl, the combined data are well fit by alpha-helical conformations. At [GdnHCl]=4.5 M, corresponding to the approximate denaturation midpoint, the combined data are well fit by a combination of alpha-helical and partially extended conformations at each site, but with a site-dependent population ratio. At [GdnHCl]=7.0 M, corresponding to the fully denatured state, the combined data are well fit by a combination of partially extended and polyproline II conformations, again with a site-dependent population ratio. Two entirely different models for conformational distributions lead to nearly the same best-fit distributions, demonstrating the robustness of these conclusions. This work represents the first quantitative investigation of site-specific conformational distributions in partially folded and unfolded states of a protein by solid-state NMR.

  15. The 13C nuclear magnetic resonance in graphite intercalation compounds

    NASA Technical Reports Server (NTRS)

    Tsang, T.; Resing, H. A.

    1985-01-01

    The (13)C NMR chemical shifts of graphite intercalation compounds were calculated. For acceptor types, the shifts come mainly from the paramagnetic (Ramsey) intra-atomic terms. They are related to the gross features of the two-dimensional band structures. The calculated anisotropy is about -140 ppm and is independent of the finer details such as charge transfer. For donor types, the carbon 2p pi orbitals are spin-polarized because of mixing with metal conduction electrons, thus there is an additional dipolar contribution which may be correlated with the electronic specific heat. The general agreement with experimental data is satisfactory.

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

    SciTech Connect

    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.

  17. 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.

    PubMed

    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.

  18. Characterization of the spherical intermediates and fibril formation of hCT in HEPES solution using solid-state 13C-NMR and transmission electron microscopy.

    PubMed

    Itoh-Watanabe, Hikari; Kamihira-Ishijima, Miya; Kawamura, Izuru; Kondoh, Masashi; Nakakoshi, Masamichi; Sato, Michio; Naito, Akira

    2013-10-21

    Human calcitonin (hCT) is a 32-amino acid peptide hormone that contains an intrachain disulfide bridge between Cys1 and Cys7 and a proline amide at the C-terminus. hCT tends to associate to form a fibril precipitate of the same type as amyloid fibrils, and hence has been studied as a model of amyloid fibril formation. The fibrillation process in N-(2-hydroxyethyl)piperazine-N'-2-ethanesulfonic acid (HEPES) solution was examined using transmission electron microscopy. The rate of hCT fibrillation in HEPES solution was much lower than in phosphate buffer and acetic acid solution. Spherical intermediate aggregates (nuclei) were observed during the early stage of fibril formation. Short proto-fibrils appeared on the surface of the spherical intermediates. Subsequently, the spherical intermediates transformed directly into long proto-fibrils, which then elongated into mature hCT fibrils. The fibrillation process was also examined using solid-state (13)C-NMR spectroscopy, which indicated that the fibril structure was a β-sheet in the central region and a mixture of random coils and β-sheets at the C-terminus. The kinetics of fibril formation was examined in terms of a two-step autocatalytic reaction mechanism. The first-step nucleation rate (k1) was lower in HEPES solution than in phosphate buffer and acetic acid solution because the half-life of the intermediates is significantly longer in HEPES solution. In contrast, the second-step fibril elongation rate (k2) was similar in HEPES solution and acidic solutions. Specific interaction of HEPES molecules with hCT may stabilize the spherical intermediates and consequently inhibit the fibril elongation process of hCT.

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

    PubMed

    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.

  20. Metal Carbonation of Forsterite in Supercritical CO2 and H2O Using Solid State 29Si, 13C NMR Spectroscop

    SciTech Connect

    Kwak, Ja Hun; Hu, Jian Z.; Hoyt, David W.; Sears, Jesse A.; Wang, Chong M.; Rosso, Kevin M.; Felmy, Andrew R.

    2010-03-11

    Ex situ solid state NMR was used for the first time to study fundamental mineral carbonation processes and reaction extent relevant to geologic carbon sequestration (GCS) using a model silicate mineral forsterite (Mg2SiO4)+supercriticalCO2 with and without H2O. Run conditions were 80 C and 96 atm. 29Si NMR clearly shows that in the absence of CO2, the role of H2O is to hydrolyze surface Mg-O-Si bonds to produce dissolved Mg2+, and mono- and oligomeric hydroxylated silica species. Surface hydrolysis products contain only Q0 (Si(OH)4) and Q1(Si(OH)3OSi) species. An equilibrium between Q0, Q1 and Mg2+ with a saturated concentration equivalent to less than 3.2% of the Mg2SiO4 conversion is obtained at a reaction time of up to 7 days. Using scCO2 without H2O, no reaction is observed within 7 days. Using both scCO2 and H2O, the surface reaction products for silica are mainly Q3 (SiOH(OSi)3) species accompanied by a lesser amount of Q2 (Si(OH)2(OSi)2) and Q4 (Si(OSi)4). However, no Q0 and Q1 were detected, indicating the carbonic acid formation/deprotonation and magnesite (MgCO3) precipitation reactions are faster than the forsterite hydrolysis process. Thus it can be concluded that the Mg2SiO4 hydrolysis process is the rate limiting step of the overall mineral carbonation process. 29Si NMR combined with XRD, TEM, SAED and EDX further reveal that the reaction is a surface reaction with the Mg2SiO4 crystallite in the core and with condensed Q2-Q4 species forming amorphous surface layers. 13C MAS NMR identified a possible reaction intermediate as (MgCO3)4-Mg(OH)2-5H2O. However, at long reaction times only crystallite magnesite MgCO3 products are observed.

  1. Analysis of the Aspergillus fumigatus Biofilm Extracellular Matrix by Solid-State Nuclear Magnetic Resonance Spectroscopy

    PubMed Central

    Reichhardt, Courtney; Ferreira, Jose A. G.; Joubert, Lydia-Marie; Clemons, Karl V.; Stevens, David A.

    2015-01-01

    Aspergillus fumigatus is commonly responsible for lethal fungal infections among immunosuppressed individuals. A. fumigatus forms biofilm communities that are of increasing biomedical interest due to the association of biofilms with chronic infections and their increased resistance to antifungal agents and host immune factors. Understanding the composition of microbial biofilms and the extracellular matrix is important to understanding function and, ultimately, to developing strategies to inhibit biofilm formation. We implemented a solid-state nuclear magnetic resonance (NMR) approach to define compositional parameters of the A. fumigatus extracellular matrix (ECM) when biofilms are formed in RPMI 1640 nutrient medium. Whole biofilm and isolated matrix networks were also characterized by electron microscopy, and matrix proteins were identified through protein gel analysis. The 13C NMR results defined and quantified the carbon contributions in the insoluble ECM, including carbonyls, aromatic carbons, polysaccharide carbons (anomeric and nonanomerics), aliphatics, etc. Additional 15N and 31P NMR spectra permitted more specific annotation of the carbon pools according to C-N and C-P couplings. Together these data show that the A. fumigatus ECM produced under these growth conditions contains approximately 40% protein, 43% polysaccharide, 3% aromatic-containing components, and up to 14% lipid. These fundamental chemical parameters are needed to consider the relationships between composition and function in the A. fumigatus ECM and will enable future comparisons with other organisms and with A. fumigatus grown under alternate conditions. PMID:26163318

  2. Analysis of the Aspergillus fumigatus Biofilm Extracellular Matrix by Solid-State Nuclear Magnetic Resonance Spectroscopy.

    PubMed

    Reichhardt, Courtney; Ferreira, Jose A G; Joubert, Lydia-Marie; Clemons, Karl V; Stevens, David A; Cegelski, Lynette

    2015-11-01

    Aspergillus fumigatus is commonly responsible for lethal fungal infections among immunosuppressed individuals. A. fumigatus forms biofilm communities that are of increasing biomedical interest due to the association of biofilms with chronic infections and their increased resistance to antifungal agents and host immune factors. Understanding the composition of microbial biofilms and the extracellular matrix is important to understanding function and, ultimately, to developing strategies to inhibit biofilm formation. We implemented a solid-state nuclear magnetic resonance (NMR) approach to define compositional parameters of the A. fumigatus extracellular matrix (ECM) when biofilms are formed in RPMI 1640 nutrient medium. Whole biofilm and isolated matrix networks were also characterized by electron microscopy, and matrix proteins were identified through protein gel analysis. The (13)C NMR results defined and quantified the carbon contributions in the insoluble ECM, including carbonyls, aromatic carbons, polysaccharide carbons (anomeric and nonanomerics), aliphatics, etc. Additional (15)N and (31)P NMR spectra permitted more specific annotation of the carbon pools according to C-N and C-P couplings. Together these data show that the A. fumigatus ECM produced under these growth conditions contains approximately 40% protein, 43% polysaccharide, 3% aromatic-containing components, and up to 14% lipid. These fundamental chemical parameters are needed to consider the relationships between composition and function in the A. fumigatus ECM and will enable future comparisons with other organisms and with A. fumigatus grown under alternate conditions.

  3. Characterization of sewage sludge organic matter using solid-state carbon-13 nuclear magnetic resonance spectroscopy.

    PubMed

    Smernik, Ronald J; Oliver, Ian W; Merrington, Graham

    2003-01-01

    Six sewage sludges from five sewage treatment plants in Australia were characterized using solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Spectra were acquired both before and after removal of mineral components through treatment with hydrofluoric acid (HF). Carbon mass balance indicated that little organic matter was lost on HF treatment, which significantly improved NMR sensitivity and spectral resolution, and decreased acquisition time and hence cost of NMR analysis. Two NMR techniques were used, the standard cross polarization (CP) technique and Bloch decay (BD). The BD technique had not been applied previously to the analysis of sewage sludge. For each sludge sample, both before and after HF treatment, the BD spectrum contained significantly more alkyl carbon. Spin counting, another technique applied to sewage sludge here for the first time, showed that the BD spectra of the HF-treated sludges were quantitative, while approximately 30% of the CP NMR signal went undetected. The discrepancy between CP and BD spectra was attributed to the presence of alkyl carbon with such high molecular mobility that the efficiency of cross polarization is affected. This study shows that sewage sludge organic matter is significantly different in chemistry to soil organic matter and has implications for the application of sewage sludge to agricultural land.

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

    USGS Publications Warehouse

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

    NASA Astrophysics Data System (ADS)

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

    2005-10-01

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

  6. NOTE The effect of 13C enrichment in the glassing matrix on dynamic nuclear polarization of [1-13C]pyruvate

    NASA Astrophysics Data System (ADS)

    Lumata, Lloyd; Kovacs, Zoltan; Malloy, Craig; Sherry, A. Dean; Merritt, Matthew

    2011-03-01

    Dimethyl sulfoxide (DMSO) can effectively form a glassy matrix necessary for dynamic nuclear polarization (DNP) experiments. We tested the effects of 13C enrichment in DMSO on DNP of [1-13C]pyruvate doped with trityl radical OX063Me. We found that the polarization build-up time τ of pyruvate in 13C-labeled DMSO glassing solution is twice as fast as the unenriched DMSO while the nuclear magnetic resonance enhancement was unchanged. This indicates that 13C-13C spin diffusion is a limiting factor in the kinetics of DNP in this system, but it has a minimal effect on the absolute value of polarization achievable for the target.

  7. The effect of 13C enrichment in the glassing matrix on dynamic nuclear polarization of [1-13C]pyruvate

    NASA Astrophysics Data System (ADS)

    Lumata, Lloyd; Kovacs, Zoltan; Malloy, Craig; Sherry, A. Dean; Merritt, Matthew

    2011-03-01

    Dimethyl sulfoxide (DMSO) can effectively form a glassy matrix necessary for dynamic nuclear polarization (DNP) experiments. We tested the effects of 13C enrichment in DMSO on DNP of [1-13C]pyruvate doped with trityl radical OX063Me. We found that the polarization build-up time τ of pyruvate in 13C-labeled DMSO glassing solution is twice as fast as the unenriched DMSO while the nuclear magnetic resonance enhancement was unchanged. This indicates that 13C-13C spin diffusion is a limiting factor in the kinetics of DNP in this system, but it has a minimal effect on the absolute value of polarization achievable for the target.

  8. Synthesis and evaluation of nitroxide-based oligoradicals for low-temperature dynamic nuclear polarization in solid state NMR

    PubMed Central

    Yau, Wai-Ming; Thurber, Kent R.; Tycko, Robert

    2014-01-01

    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. PMID:24887201

  9. Operational comparison of TLD albedo dosemeters and solid state nuclear tracks detectors in fuel fabrication facilities.

    PubMed

    Tsujimura, N; Takada, C; Yoshida, T; Momose, T

    2007-01-01

    The authors carried out an operational study that compared the use of TLD albedo dosemeters and solid state nuclear tracks detector in plutonium environments of Japan Nuclear Cycle Development Institute, Tokai Works. A selected group of workers engaged in the fabrication process of MOX (Plutonium-Uranium mixed oxide) fuel wore both TLD albedo dosemeters and solid state nuclear tracks detectors. The TL readings were generally proportional to the counted etch-pits, and thus the dose equivalent results obtained from TLD albedo dosemeter agreed with those from solid state nuclear tracks detector within a factor of 1.5. This result indicates that, in the workplaces of the MOX fuel plants, the neutron spectrum remained almost constant in terms of time and space, and the appropriate range of field-specific correction with spectrum variations was small in albedo dosimetry.

  10. Use of solid waste for chemical stabilization: Adsorption isotherms and {sup 13}C solid-state NMR study of hazardous organic compounds sorbed on coal fly ash

    SciTech Connect

    Netzel, D.A.; Lane, D.C.; Rovani, J.F.; Cox, J.D.; Clark, J.A.; Miknis, F.P.

    1993-09-01

    Adsorption of hazardous organic compounds on the Dave Johnston plant fly ash is described. Fly ash from Dave Johnston and Laramie River power plants were characterized using elemental, x-ray, and {sup 29}Si NMR; the Dave Johnston (DJ) fly ash had higher quartz contents, while the Laramie River fly ash had more monomeric silicate anions. Adsorption data for hydroaromatics and chlorobenzenes indicate that the adsorption capacity of DJ coal fly ash is much less than that of activated carbon by a factor of >3000; but it is needed to confirm that solid-gas and solid-liquid equilibrium isotherms can indeed be compared. However, for pyridine, pentachlorophenol, naphthalene, and 1,1,2,2-tetrachloroethane, the DJ fly ash appears to adsorb these compounds nearly as well as activated carbon. {sup 13}C NMR was used to study the adsorption of hazardous org. cpds on coal fly ash; the nuclear spin relaxation times often were very long, resulting in long experimental times to obtain a spectrum. Using a jumbo probe, low concentrations of some hazardous org. cpds could be detected; for pentachlorophenol adsorbed onto fly ash, the chemical shift of the phenolic carbon was changed. Use of NMR to study the adsorption needs further study.

  11. Strongly polarizing weakly coupled 13C nuclear spins with optically pumped nitrogen-vacancy center

    PubMed Central

    Wang, Ping; Liu, Bao; Yang, Wen

    2015-01-01

    Enhancing the polarization of nuclear spins surrounding the nitrogen-vacancy (NV) center in diamond has recently attracted widespread attention due to its various applications. Here we present an analytical formula that not only provides a clear physical picture for the recently observed polarization reversal of strongly coupled13C nuclei over a narrow range of magnetic field [H. J. Wang et al., Nat. Commun. 4, 1940 (2013)], but also demonstrates the possibility to strongly polarize weakly coupled13C nuclei. This allows sensitive magnetic field control of the 13C nuclear spin polarization for NMR applications and significant suppression of the 13C nuclear spin noise to prolong the NV spin coherence time. PMID:26521962

  12. Model-free estimation of the effective correlation time for C-H bond reorientation in amphiphilic bilayers: 1H-13C solid-state NMR and MD simulations

    NASA Astrophysics Data System (ADS)

    Ferreira, Tiago Mendes; Ollila, O. H. Samuli; Pigliapochi, Roberta; Dabkowska, Aleksandra P.; Topgaard, Daniel

    2015-01-01

    Molecular dynamics (MD) simulations give atomically detailed information on structure and dynamics in amphiphilic bilayer systems on timescales up to about 1 μs. The reorientational dynamics of the C-H bonds is conventionally verified by measurements of 13C or 2H nuclear magnetic resonance (NMR) longitudinal relaxation rates R1, which are more sensitive to motional processes with correlation times close to the inverse Larmor frequency, typically around 1-10 ns on standard NMR instrumentation, and are thus less sensitive to the 10-1000 ns timescale motion that can be observed in the MD simulations. We propose an experimental procedure for atomically resolved model-free estimation of the C-H bond effective reorientational correlation time τe, which includes contributions from the entire range of all-atom MD timescales and that can be calculated directly from the MD trajectories. The approach is based on measurements of 13C R1 and R1ρ relaxation rates, as well as 1H-13C dipolar couplings, and is applicable to anisotropic liquid crystalline lipid or surfactant systems using a conventional solid-state NMR spectrometer and samples with natural isotopic composition. The procedure is demonstrated on a fully hydrated lamellar phase of 1-palmitoyl-2-oleoyl-phosphatidylcholine, yielding values of τe from 0.1 ns for the methyl groups in the choline moiety and at the end of the acyl chains to 3 ns for the g1 methylene group of the glycerol backbone. MD simulations performed with a widely used united-atom force-field reproduce the τe-profile of the major part of the acyl chains but underestimate the dynamics of the glycerol backbone and adjacent molecular segments. The measurement of experimental τe-profiles can be used to study subtle effects on C-H bond reorientational motions in anisotropic liquid crystals, as well as to validate the C-H bond reorientation dynamics predicted in MD simulations of amphiphilic bilayers such as lipid membranes.

  13. Research program in nuclear and solid state physics

    NASA Technical Reports Server (NTRS)

    Stronach, C. E.

    1973-01-01

    The spectra of prompt gamma rays emitted following nuclear pion absorption were studied to determine the states of excited daughter nuclei, and the branching ratios for these states. Studies discussed include the negative pion absorption of C-12, S-32, and N-14; and the positive pion absorption on 0-16. Abstracts of papers submitted to the conference of the American Physical Society are included.

  14. 35Cl dynamic nuclear polarization solid-state NMR of active pharmaceutical ingredients

    DOE PAGES

    Hirsh, David A.; Rossini, Aaron J.; Emsley, Lyndon; ...

    2016-08-24

    In this paper, we show how to obtain efficient dynamic nuclear polarization (DNP) enhanced 35Cl solid-state NMR (SSNMR) spectra at 9.4 T and demonstrate how they can be used to characterize the molecular-level structure of hydrochloride salts of active pharmaceutical ingredients (APIs) in both bulk and low wt% API dosage forms. 35Cl SSNMR central-transition powder patterns of chloride ions are typically tens to hundreds of kHz in breadth, and most cannot be excited uniformly with high-power rectangular pulses or acquired under conditions of magic-angle spinning (MAS). Herein, we demonstrate the combination of DNP and 1H–35Cl broadband adiabatic inversion cross polarizationmore » (BRAIN-CP) experiments for the acquisition of high quality wideline spectra of APIs under static sample conditions, and obtain signals up to 50 times greater than in spectra acquired without the use of DNP at 100 K. We report a new protocol, called spinning-on spinning-off (SOSO) acquisition, where MAS is applied during part of the polarization delay to increase the DNP enhancements and then the MAS rotation is stopped so that a wideline 35Cl NMR powder pattern free from the effects of spinning sidebands can be acquired under static conditions. This method provides an additional two-fold signal enhancement compared to DNP-enhanced SSNMR spectra acquired under purely static conditions. DNP-enhanced 35Cl experiments are used to characterize APIs in bulk and dosage forms with Cl contents as low as 0.45 wt%. These results are compared to DNP-enhanced 1H–13C CP/MAS spectra of APIs in dosage forms, which are often hindered by interfering signals arising from the binders, fillers and other excipient materials.« less

  15. Hydrogen Bonding Interactions in Amorphous Indomethacin and Its Amorphous Solid Dispersions with Poly(vinylpyrrolidone) and Poly(vinylpyrrolidone-co-vinyl acetate) Studied Using (13)C Solid-State NMR.

    PubMed

    Yuan, Xiaoda; Xiang, Tian-Xiang; Anderson, Bradley D; Munson, Eric J

    2015-12-07

    Hydrogen bonding interactions in amorphous indomethacin and amorphous solid dispersions of indomethacin with poly(vinylpyrrolidone), or PVP, and poly(vinylpyrrolidone-co-vinyl acetate), or PVP/VA, were investigated quantitatively using solid-state NMR spectroscopy. Indomethacin that was (13)C isotopically labeled at the carboxylic acid carbon was used to selectively analyze the carbonyl region of the spectrum. Deconvolution of the carboxylic acid carbon peak revealed that 59% of amorphous indomethacin molecules were hydrogen bonded through carboxylic acid cyclic dimers, 15% were in disordered carboxylic acid chains, 19% were hydrogen bonded through carboxylic acid and amide interactions, and the remaining 7% were free of hydrogen bonds. The standard dimerization enthalpy and entropy of amorphous indomethacin were estimated to be -38 kJ/mol and -91 J/(mol · K), respectively, using polystyrene as the "solvent". Polymers such as PVP and PVP/VA disrupted indomethacin self-interactions and formed hydrogen bonds with the drug. The carboxylic acid dimers were almost completely disrupted with 50% (wt) of PVP or PVP/VA. The fraction of disordered carboxylic acid chains also decreased as the polymer content increased. The solid-state NMR results were compared with molecular dynamics (MD) simulations from the literature. The present work highlights the potential of (13)C solid-state NMR to detect and quantify various hydrogen bonded species in amorphous solid dispersions as well as to serve as an experimental validation of MD simulations.

  16. Molecular interactions between green tea catechins and cheese fat studied by solid-state nuclear magnetic resonance spectroscopy.

    PubMed

    Rashidinejad, Ali; Birch, Edward J; Hindmarsh, Jason; Everett, David W

    2017-01-15

    Molecular integrations between green tea catechins and milk fat globules in a cheese matrix were investigated using solid-state magic angle spinning nuclear magnetic resonance spectroscopy. Full-fat cheeses were manufactured containing free catechin or free green tea extract (GTE), and liposomal encapsulated catechin or liposomal encapsulated GTE. Molecular mobility of the carbon species in the cheeses was measured by a wide-line separation technique. The (1)H evolution frequency profile of the (13)C peak at 16ppm obtained for the control cheese and cheeses containing encapsulated polyphenols (catechin or GTE) were similar, however, the spectrum was narrower for cheeses containing free polyphenols. Differences in spectral width indicates changes in the molecular mobility of --CH3- or -C-C-PO4- species through hydrophobic and/or cation-π associations between green tea catechins and cheese fat components. However, the similar spectral profile suggests that encapsulation protects cheese fat from interaction with catechins.

  17. Model-free estimation of the effective correlation time for C–H bond reorientation in amphiphilic bilayers: {sup 1}H–{sup 13}C solid-state NMR and MD simulations

    SciTech Connect

    Ferreira, Tiago Mendes; Ollila, O. H. Samuli; Pigliapochi, Roberta; Dabkowska, Aleksandra P.; Topgaard, Daniel

    2015-01-28

    Molecular dynamics (MD) simulations give atomically detailed information on structure and dynamics in amphiphilic bilayer systems on timescales up to about 1 μs. The reorientational dynamics of the C–H bonds is conventionally verified by measurements of {sup 13}C or {sup 2}H nuclear magnetic resonance (NMR) longitudinal relaxation rates R{sub 1}, which are more sensitive to motional processes with correlation times close to the inverse Larmor frequency, typically around 1-10 ns on standard NMR instrumentation, and are thus less sensitive to the 10-1000 ns timescale motion that can be observed in the MD simulations. We propose an experimental procedure for atomically resolved model-free estimation of the C–H bond effective reorientational correlation time τ{sub e}, which includes contributions from the entire range of all-atom MD timescales and that can be calculated directly from the MD trajectories. The approach is based on measurements of {sup 13}C R{sub 1} and R{sub 1ρ} relaxation rates, as well as {sup 1}H−{sup 13}C dipolar couplings, and is applicable to anisotropic liquid crystalline lipid or surfactant systems using a conventional solid-state NMR spectrometer and samples with natural isotopic composition. The procedure is demonstrated on a fully hydrated lamellar phase of 1-palmitoyl-2-oleoyl-phosphatidylcholine, yielding values of τ{sub e} from 0.1 ns for the methyl groups in the choline moiety and at the end of the acyl chains to 3 ns for the g{sub 1} methylene group of the glycerol backbone. MD simulations performed with a widely used united-atom force-field reproduce the τ{sub e}-profile of the major part of the acyl chains but underestimate the dynamics of the glycerol backbone and adjacent molecular segments. The measurement of experimental τ{sub e}-profiles can be used to study subtle effects on C–H bond reorientational motions in anisotropic liquid crystals, as well as to validate the C–H bond reorientation dynamics predicted in MD

  18. A straightforward method for stereospecific assignment of val and leu prochiral methyl groups by solid-state NMR: Scrambling in the [2-13C]Glucose labeling scheme

    NASA Astrophysics Data System (ADS)

    Lv, Guohua; Faßhuber, Hannes Klaus; Loquet, Antoine; Demers, Jean-Philippe; Vijayan, Vinesh; Giller, Karin; Becker, Stefan; Lange, Adam

    2013-03-01

    The unambiguous stereospecific assignment of the prochiral methyl groups in Val and Leu plays an important role in the structural investigation of proteins by NMR. Here, we present a straightforward method for their stereospecific solid-state NMR assignment based on [2-13C]Glucose ([2-13C]Glc) as the sole carbon source during protein expression. The approach is fundamentally based on the stereo-selective biosynthetic pathway of Val and Leu, and the co-presence of [2-13C]pyruvate produced mainly by glycolysis and [3-13C]/[1,3-13C]pyruvate most probably formed through scrambling in the pentose phosphate pathway. As a consequence, the isotope spin pairs 13Cβ-13Cγ2 and 13Cα-13Cγ1 in Val, and 13Cγ-13Cδ2 and 13Cβ-13Cδ1 in Leu are obtained. The approach is successfully demonstrated with the stereospecific assignment of the methyl groups of Val and Leu of type 3 secretion system PrgI needles and microcrystalline ubiquitin.

  19. Instrumentation for solid-state dynamic nuclear polarization with magic angle spinning NMR.

    PubMed

    Rosay, Melanie; Blank, Monica; Engelke, Frank

    2016-03-01

    Advances in dynamic nuclear polarization (DNP) instrumentation and methodology have been key factors in the recent growth of solid-state DNP NMR applications. We review the current state of the art of solid-state DNP NMR instrumentation primarily based on available commercial platforms. We start with a general system overview, including options for microwave sources and DNP NMR probes, and then focus on specific developments for DNP at 100K with magic angle spinning (MAS). Gyrotron microwave sources, passive components to transmit microwaves, the DNP MAS probe, a cooling device for low-temperature MAS, and sample preparation procedures including radicals for DNP are considered.

  20. Instrumentation for solid-state dynamic nuclear polarization with magic angle spinning NMR

    NASA Astrophysics Data System (ADS)

    Rosay, Melanie; Blank, Monica; Engelke, Frank

    2016-03-01

    Advances in dynamic nuclear polarization (DNP) instrumentation and methodology have been key factors in the recent growth of solid-state DNP NMR applications. We review the current state of the art of solid-state DNP NMR instrumentation primarily based on available commercial platforms. We start with a general system overview, including options for microwave sources and DNP NMR probes, and then focus on specific developments for DNP at 100 K with magic angle spinning (MAS). Gyrotron microwave sources, passive components to transmit microwaves, the DNP MAS probe, a cooling device for low-temperature MAS, and sample preparation procedures including radicals for DNP are considered.

  1. Dynamic nuclear polarization solid-state NMR in heterogeneous catalysis research

    SciTech Connect

    Kobayashi, Takeshi; Perras, Frédéric A.; Slowing, Igor I.; Sadow, Aaron D.; Pruski, Marek

    2015-10-20

    In this study, a revolution in solid-state nuclear magnetic resonance (SSNMR) spectroscopy is taking place, attributable to the rapid development of high-field dynamic nuclear polarization (DNP), a technique yielding sensitivity improvements of 2–3 orders of magnitude. This higher sensitivity in SSNMR has already impacted materials research, and the implications of new methods on catalytic sciences are expected to be profound.

  2. Dynamic nuclear polarization solid-state NMR in heterogeneous catalysis research

    DOE PAGES

    Kobayashi, Takeshi; Perras, Frédéric A.; Slowing, Igor I.; ...

    2015-10-20

    In this study, a revolution in solid-state nuclear magnetic resonance (SSNMR) spectroscopy is taking place, attributable to the rapid development of high-field dynamic nuclear polarization (DNP), a technique yielding sensitivity improvements of 2–3 orders of magnitude. This higher sensitivity in SSNMR has already impacted materials research, and the implications of new methods on catalytic sciences are expected to be profound.

  3. The use of dynamic nuclear polarization (13)C-pyruvate MRS in cancer.

    PubMed

    Gutte, Henrik; Hansen, Adam Espe; Johannesen, Helle Hjorth; Clemmensen, Andreas Ettrup; Ardenkjær-Larsen, Jan Henrik; Nielsen, Carsten Haagen; Kjær, Andreas

    2015-01-01

    In recent years there has been an immense development of new targeted anti-cancer drugs. For practicing precision medicine, a sensitive method imaging for non-invasive, assessment of early treatment response and for assisting in developing new drugs is warranted. Magnetic Resonance Spectroscopy (MRS) is a potent technique for non-invasive in vivo investigation of tissue chemistry and cellular metabolism. Hyperpolarization by Dynamic Nuclear Polarization (DNP) is capable of creating solutions of molecules with polarized nuclear spins in a range of biological molecules and has enabled the real-time investigation of in vivo metabolism. The development of this new method has been demonstrated to enhance the nuclear polarization more than 10,000-fold, thereby significantly increasing the sensitivity of the MRS with a spatial resolution to the millimeters and a temporal resolution at the subsecond range. Furthermore, the method enables measuring kinetics of conversion of substrates into cell metabolites and can be integrated with anatomical proton magnetic resonance imaging (MRI). Many nuclei and substrates have been hyperpolarized using the DNP method. Currently, the most widely used compound is (13)C-pyruvate due to favoring technicalities. Intravenous injection of the hyperpolarized (13)C-pyruvate results in appearance of (13)C-lactate, (13)C-alanine and (13)C-bicarbonate resonance peaks depending on the tissue, disease and the metabolic state probed. In cancer, the lactate level is increased due to increased glycolysis. The use of DNP enhanced (13)C-pyruvate has in preclinical studies shown to be a sensitive method for detecting cancer and for assessment of early treatment response in a variety of cancers. Recently, a first-in-man 31-patient study was conducted with the primary objective to assess the safety of hyperpolarized (13)C-pyruvate in healthy subjects and prostate cancer patients. The study showed an elevated (13)C-lactate/(13)C-pyruvate ratio in regions of

  4. The use of dynamic nuclear polarization 13C-pyruvate MRS in cancer

    PubMed Central

    Gutte, Henrik; Hansen, Adam Espe; Johannesen, Helle Hjorth; Clemmensen, Andreas Ettrup; Ardenkjær-Larsen, Jan Henrik; Nielsen, Carsten Haagen; Kjær, Andreas

    2015-01-01

    In recent years there has been an immense development of new targeted anti-cancer drugs. For practicing precision medicine, a sensitive method imaging for non-invasive, assessment of early treatment response and for assisting in developing new drugs is warranted. Magnetic Resonance Spectroscopy (MRS) is a potent technique for non-invasive in vivo investigation of tissue chemistry and cellular metabolism. Hyperpolarization by Dynamic Nuclear Polarization (DNP) is capable of creating solutions of molecules with polarized nuclear spins in a range of biological molecules and has enabled the real-time investigation of in vivo metabolism. The development of this new method has been demonstrated to enhance the nuclear polarization more than 10,000-fold, thereby significantly increasing the sensitivity of the MRS with a spatial resolution to the millimeters and a temporal resolution at the subsecond range. Furthermore, the method enables measuring kinetics of conversion of substrates into cell metabolites and can be integrated with anatomical proton magnetic resonance imaging (MRI). Many nuclei and substrates have been hyperpolarized using the DNP method. Currently, the most widely used compound is 13C-pyruvate due to favoring technicalities. Intravenous injection of the hyperpolarized 13C-pyruvate results in appearance of 13C-lactate, 13C-alanine and 13C-bicarbonate resonance peaks depending on the tissue, disease and the metabolic state probed. In cancer, the lactate level is increased due to increased glycolysis. The use of DNP enhanced 13C-pyruvate has in preclinical studies shown to be a sensitive method for detecting cancer and for assessment of early treatment response in a variety of cancers. Recently, a first-in-man 31-patient study was conducted with the primary objective to assess the safety of hyperpolarized 13C-pyruvate in healthy subjects and prostate cancer patients. The study showed an elevated 13C-lactate/13C-pyruvate ratio in regions of biopsy

  5. Elucidating the guest-host interactions and complex formation of praziquantel and cyclodextrin derivatives by (13)C and (15)N solid-state NMR spectroscopy.

    PubMed

    Arrúa, Eva C; Ferreira, M João G; Salomon, Claudio J; Nunes, Teresa G

    2015-12-30

    Praziquantel is the drug of choice to treat several parasitic infections including the neglected tropical disease schistosomiasis. Due to its low aqueous solubility, cyclodextrins have been tested as potential host candidates to prepare praziquantel inclusion complexes with improved solubility. For the first time, the interactions of praziquantel with β-cyclodextrin and β-cyclodextrin derivatives (methyl-β-cyclodextrin and hydroxypropyl-β-cyclodextrin) were investigated using high resolution solid-state NMR spectroscopy. The results of this work confirmed that solid-state NMR experiments provided structural characterization, demonstrating the formation of inclusion complexes most probably with PZQ adopting an anti conformation, also the most likely in amorphous raw PZQ. Further information on the interaction of praziquantel with methyl-β-cyclodextrin was obtained from proton rotating-frame relaxation time measurements, sensitive to kilohertz-regime motions but modulated by spin-diffusion. Evidences were presented in all cases for praziquantel complexation through the aromatic ring. In addition, 1:2 drug:carrier molar ratio appears to be the most probable and therefore suitable stoichiometry to improve pharmaceutical formulations of this antischistosomal drug.

  6. Microscopic structure of heterogeneous lipid-based formulations revealed by 13C high-resolution solid-state and 1H PFG NMR methods.

    PubMed

    Guillermo, Armel; Gerbaud, Guillaume; Bardet, Michel

    2010-03-01

    Lipid-based formulations such as lip glosses that are very alike on the base of their components may have significant differences in their expected macroscopic properties as cosmetics. To differentiate such formulations, high-resolution (13)C NMR was performed under magic angle spinning to investigate the properties at both molecular and microscopic levels. Temperature studies were carried out and no polymorphism in the solid domains could be evidenced after the thermal treatment performed for obtaining the commercial lip glosses. (13)C NMR spectra also showed that some waxes remain partially solubilized in the oils of formulations. The microscopic structure of the wax-oil liquid domains was worked out on the basis of restricted diffusion properties obtained with proton pulsed-field gradient NMR. Changing a single wax component, in two identical formulations, yields significant morphological differences. In the first one the liquid phase appears as a continuum whereas in the second one, the liquid phase is fractionated into micrometric droplets.

  7. Solid-state {sup 19}F and {sup 13}C NMR of room temperature fluorinated graphite and samples thermally treated under fluorine: Low-field and high-resolution studies

    SciTech Connect

    Giraudet, J.; Dubois, M.; Guerin, K.; Pinheiro, J.P.; Hamwi, A.; Stone, W.E.E.; Pirotte, P.; Masin, F. . E-mail: fmasin@ulb.ac.be

    2005-04-15

    Room temperature graphite fluorides consisting of raw material and samples post-treated in pure fluorine atmosphere in the temperature range 100-500 deg. C have been studied by solid-state NMR. Several NMR approaches have been used, both high and low-field {sup 19}F, {sup 19}F MAS and {sup 13}C MAS with {sup 19}F to {sup 13}C cross polarization. The modifications, in the graphitic lattice, of the catalytic iodine fluorides products have been examined. A transformation of the C-F bond character from semi-ionic to covalent has been found to occur at a post-treatment temperature close to 400 deg. C. It is shown that covalency increases with temperature.

  8. (13) C dynamic nuclear polarization using isotopically enriched 4-oxo-TEMPO free radicals.

    PubMed

    Niedbalski, Peter; Parish, Christopher; Kiswandhi, Andhika; Lumata, Lloyd

    2016-12-01

    The nitroxide-based free radical 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) is a widely used polarizing agent in NMR signal amplification via dissolution dynamic nuclear polarization (DNP). In this study, we have thoroughly investigated the effects of (15) N and/or (2) H isotopic labeling of 4-oxo-TEMPO free radical on (13) C DNP of 3 M [1-(13) C] sodium acetate samples in 1 : 1 v/v glycerol : water at 3.35 T and 1.2 K. Four variants of this free radical were used for (13) C DNP: 4-oxo-TEMPO, 4-oxo-TEMPO-(15) N, 4-oxo-TEMPO-d16 and 4-oxo-TEMPO-(15) N,d16 . Our results indicate that, despite the striking differences seen in the electron spin resonance (ESR) spectral features, the (13) C DNP efficiency of these (15) N and/or (2) H-enriched 4-oxo-TEMPO free radicals are relatively the same compared with (13) C DNP performance of the regular 4-oxo-TEMPO. Furthermore, when fully deuterated glassing solvents were used, the (13) C DNP signals of these samples all doubled in the same manner, and the (13) C polarization buildup was faster by a factor of 2 for all samples. The data here suggest that the hyperfine coupling contributions of these isotopically enriched 4-oxo-TEMPO free radicals have negligible effects on the (13) C DNP efficiency at 3.35 T and 1.2 K. These results are discussed in light of the spin temperature model of DNP. Copyright © 2016 John Wiley & Sons, Ltd.

  9. 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

    SciTech Connect

    Li, Xiaozhou; Bond, Andrew D.; Johansson, Kristoffer E.; Van de Streek, Jacco

    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.

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

    PubMed

    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.

  11. Advanced solid-state carbon-13 nuclear magnetic resonance spectroscopic studies of sewage sludge organic matter: detection of organic "domains".

    PubMed

    Smernik, Ronald J; Oliver, Ian W; Merrington, Graham

    2003-01-01

    Two novel solid-state 13C nuclear magnetic resonance (NMR) spectroscopic techniques, PSRE (proton spin relaxation editing) and RESTORE [Restoration of Spectra via T(CH) and T(1rho)H (T One Rho H) Editing], were used to provide detailed chemical characterization of the organic matter from six Australian sewage sludges. These methods were used to probe the submicrometer heterogeneity of sludge organic matter, and identify and quantify spatially distinct components. Analysis of the T1H relaxation behavior of the sludges indicated that each sludge contained two types of organic domains. Carbon-13 PSRE NMR subspectra were generated to determine the chemical nature of these domains. The rapidly relaxing component of each sludge was rich in protein and alkyl carbon, and was identified as dead bacterial material. The slowly relaxing component of each sludge was rich in carbohydrate and lignin structures, and was identified as partly degraded plant material. The bacterial domains were shown, using the RESTORE technique, to also have characteristically rapid T(1rho)H relaxation rates. This rapid T(1rho)H relaxation was identified as the main cause of underrepresentation of these domains in standard 13C cross polarization (CP) NMR spectra of sludges. The heterogeneous nature of sewage sludge organic matter has implications for land application of sewage sludge, since the two components are likely to have different capacities for sorbing organic and inorganic toxicants present in sewage sludge, and will decompose at different rates.

  12. Degradation of Wheat Straw by Fibrobacter succinogenes S85: a Liquid- and Solid-State Nuclear Magnetic Resonance Study

    PubMed Central

    Matulova, M.; Nouaille, R.; Capek, P.; Péan, M.; Forano, E.; Delort, A.-M.

    2005-01-01

    Wheat straw degradation by Fibrobacter succinogenes was monitored by nuclear magnetic resonance (NMR) spectroscopy and chemolytic methods to investigate the activity of an entire fibrolytic system on an intact complex substrate. In situ solid-state NMR with 13C cross-polarization magic angle spinning was used to monitor the modification of the composition and structure of lignocellulosic fibers (of 13C-enriched wheat straw) during the growth of bacteria on this substrate. There was no preferential degradation either of amorphous regions of cellulose versus crystalline regions or of cellulose versus hemicelluloses in wheat straw. This suggests either a simultaneous degradation of the amorphous and crystalline parts of cellulose and of cellulose and hemicelluloses by the enzymes or degradation at the surface at a molecular scale that cannot be detected by NMR. Liquid-state two-dimensional NMR experiments and chemolytic methods were used to analyze in detail the various sugars released into the culture medium. An integration of NMR signals enabled the quantification of oligosaccharides produced from wheat straw at various times of culture and showed the sequential activities of some of the fibrolytic enzymes of F. succinogenes S85 on wheat straw. In particular, acetylxylan esterase appeared to be more active than arabinofuranosidase, which was more active than α-glucuronidase. Finally, cellodextrins did not accumulate to a great extent in the culture medium. PMID:15746325

  13. Drug release from cast films of ethylene vinyl acetate (EVA) copolymer: Stability of drugs by 1H NMR and solid state 13C CP/MAS NMR.

    PubMed

    Kalachandra, S; Lin, D M; Stejskal, E O; Prakki, A; Offenbacher, S

    2005-07-01

    The study utilizes an oral biocompatible material based on ethylene vinyl acetate copolymer (EVA) designed to release drugs in vitro at therapeutic levels over several days. We examined the drug stability during film casting process using proton and solid state NMR techniques. The drug-loaded EVA films were prepared from the dry sheet obtained by solvent (dichloromethane) evaporation of polymer casting solutions. Drugs tested include chlorhexidine diacetate (CDA), doxycycline hydrochloride (DOH), tetracycline hydrochloride (TTH) and nystatin (NST). Drug release from the films was examined for at least 14 days in 10 ml ddH2O (NST in water/ethanol (4:1)) which was replaced daily. Changes in optical density were followed spectraphotometrically. Effect of temperature on rate measurements was studied and the energies of activation (E*) were calculated using Arrhenius plots. Effect of EVA copolymer composition on CDA release rate was also investigated. The enhanced rates with temperature increase may be attributed to the formation of channels with increased geometry in the polymer. The highest E* observed for CDA compared to DOH and TTH may be related to their average molecular weights. Spectral analyses for CDA and NST revealed that the chemical and physical structures of the drugs remained unaffected during the film casting process.

  14. Direct proof by 13C-nuclear magnetic resonance of semi-purified extract and isolation of ent-Catechin from leaves of Eucalyptus cinerea

    PubMed Central

    Silva, Sayonara Mendes; Abe, Simone Yae; Bueno, Fernanda Giacomini; Lopes, Norberto Peporine; de Mello, João Carlos Palazzo; Nakashima, Tomoe

    2014-01-01

    Background: Eucalyptus cinerea F. Muell. ex Benth. is native to Australia and acclimatized to Southern Brazil. Its aromatic leaves are used for ornamental purposes and have great potential for essential oil production, although reports of its use in folk medicine are few. Objective: This study evaluated the composition of E. cinerea leaves using the solid state 13C-nuclear magnetic resonance (NMR) and isolation of the compound from the semipurified extract (SE). Materials and Methods: The SE of E. cinerea leaves was evaluated in the solid state by 13C-NMR spectrum, and the SE was chromatographed on a Sephadex LH-20 column, followed by high-speed counter-current chromatography to isolate the compound. The SE was analyzed by 13C-NMR and matrix-assisted laser desorption/ionization-time-of-flight spectra. Results: Flavan-3-ol units were present, suggesting the presence of proanthocyanidins as well as a gallic acid unit. The uncommon ent-catechin was isolated. Conclusion: The presence of ent-catechin is reported for the first time in this genus and species. PMID:25210302

  15. Solid state nuclear magnetic resonance studies of prion peptides and proteins

    SciTech Connect

    Heller, Jonathan

    1997-08-01

    High-resolution structural studies using x-ray diffraction and solution nuclear magnetic resonance (NMR) are not feasible for proteins of low volubility and high tendency to aggregate. Solid state NMR (SSNMR) is in principle capable of providing structural information in such systems, however to do this efficiently and accurately, further SSNMR tools must be developed This dissertation describes the development of three new methods and their application to a biological system of interest, the priori protein (PrP).

  16. Oxygen-17 dynamic nuclear polarisation enhanced solid-state NMR spectroscopy at 18.8 T.

    PubMed

    Brownbill, Nick J; Gajan, David; Lesage, Anne; Emsley, Lyndon; Blanc, Frédéric

    2017-02-23

    We report (17)O dynamic nuclear polarisation (DNP) enhanced solid-state NMR experiments at 18.8 T. Several formulations were investigated on the Mg(OH)2 compound. A signal enhancement factor of 17 could be obtained when the solid particles were incorporated into a glassy o-terphenyl matrix doped with BDPA using the Overhauser polarisation transfer scheme whilst the cross effect mechanism enabled by TEKPol yielded a slightly lower enhancement but more time efficient data acquisition.

  17. Fermentation and Cost-Effective 13C/15N Labeling of the Nonribosomal Peptide Gramicidin S for Nuclear Magnetic Resonance Structure Analysis

    PubMed Central

    Berditsch, Marina; Afonin, Sergii; Steineker, Anna; Orel, Nataliia; Jakovkin, Igor; Weber, Christian

    2015-01-01

    Gramicidin S (GS) is a nonribosomally synthesized decapeptide from Aneurinibacillus migulanus. Its pronounced antibiotic activity is attributed to amphiphilic structure and enables GS interaction with bacterial membranes. Despite its medical use for over 70 years, the peptide-lipid interactions of GS and its molecular mechanism of action are still not fully understood. Therefore, a comprehensive structural analysis of isotope-labeled GS needs to be performed in its biologically relevant membrane-bound state, using advanced solid-state nuclear magnetic resonance (NMR) spectroscopy. Here, we describe an efficient method for producing the uniformly 13C/15N-labeled peptide in a minimal medium supplemented by selected amino acids. As GS is an intracellular product of A. migulanus, we characterized the producer strain DSM 5759 (rough-convex phenotype) and examined its biosynthetic activity in terms of absolute and biomass-dependent peptide accumulation. We found that the addition of either arginine or ornithine increases the yield only at very high supplementing concentrations (1% and 0.4%, respectively) of these expensive 13C/15N-labeled amino acids. The most cost-effective production of 13C/15N-GS, giving up to 90 mg per gram of dry cell weight, was achieved in a minimal medium containing 1% 13C-glycerol and 0.5% 15N-ammonium sulfate, supplemented with only 0.025% of 13C/15N-phenylalanine. The 100% efficiency of labeling is corroborated by mass spectrometry and preliminary solid-state NMR structure analysis of the labeled peptide in the membrane-bound state. PMID:25795666

  18. Structural analysis of geochemical samples by solid-state nuclear magnetic resonance spectrometry. Role of paramagnetic material

    USGS Publications Warehouse

    Vassallo, A.M.; Wilson, M.A.; Collin, P.J.; Oades, J.M.; Waters, A.G.; Malcolm, R.L.

    1987-01-01

    An examination of coals, coal tars, a fulvic acid, and soil fractions by solid-state 13C NMR spectrometry has demonstrated widely differing behavior regarding quantitative representation in the spectrum. Spin counting experiments on coal tars and the fulvic acid show that almost all the sample carbon is observed in both solution and solid-state NMR spectra. Similar experiments on two coals (a lignite and a bituminous coal) show that most (70-97%) of the carbon is observed; however, when the lignite is ion exchanged with 3% (w/w) Fe3+, the fraction of carbon observed drops to below 10%. In additional experiments signal intensity from soil samples is enhanced by a simple dithionite treatment. This is illustrated by 13C, 27Al, and 29Si solid-state NMR experiments on soil fractions. ?? 1987 American Chemical Society.

  19. Study of hydrogen in coals, polymers, oxides, and muscle water by nuclear magnetic resonance; extension of solid-state high-resolution techniques. [Hydrogen molybdenum bronze

    SciTech Connect

    Ryan, L.M.

    1981-10-01

    Nuclear magnetic resonance (NMR) spectroscopy has been an important analytical and physical research tool for several decades. One area of NMR which has undergone considerable development in recent years is high resolution NMR of solids. In particular, high resolution solid state /sup 13/C NMR spectra exhibiting features similar to those observed in liquids are currently achievable using sophisticated pulse techniques. The work described in this thesis develops analogous methods for high resolution /sup 1/H NMR of rigid solids. Applications include characterization of hydrogen aromaticities in fossil fuels, and studies of hydrogen in oxides and bound water in muscle.

  20. Optical Potential Parameters of Weakly Bound Nuclear System 17F+13C

    NASA Astrophysics Data System (ADS)

    An, Guang-Peng; Lin, Cheng-Jian; Zhang, Huan-Qiao; Liu, Zu-Hua; Yang, Feng; Zhang, Gao-Long; Zhang, Chun-Lei; Wu, Zhen-Dong; Jia, Fei; Jia, Hui-Ming; Xu, Xin-Xing; Bai, Chun-Lin; Yu, Ning

    2008-12-01

    Elastic scattering angular distributions of the 14N+16O system and the angular distributions of transfer reaction 16O(14N,13 C)17 F at ELab = 76.2 MeV and 57MeV have been measured and calculated by means of the exact finite-range distorted-wave Born approximation with the PTOLEMY code. The optical potential parameters for the weakly bound nuclear system 17F+13 C have been deduced and applied to analyse the elastic scattering angular distributions of the similar systems 17F+12C and 17F+14N which are taken from literature. The result shows that the transfer reaction with stable projectile and target combination can be used as an alternative method to extract the optical potential parameters for the weakly bound nuclear system.

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

    PubMed

    Li, Xiaozhou; Bond, Andrew D; Johansson, Kristoffer E; Van de Streek, Jacco

    2014-08-01

    The crystal structure of the title compound, C11H13N3O2S2, has been determined previously on the basis of refinement against laboratory powder X-ray diffraction (PXRD) data, supported by comparison of measured and calculated (13)C solid-state NMR spectra [Hangan et al. (2010). Acta Cryst. B66, 615-621]. The molecule is tautomeric, and was reported as an amine tautomer [systematic name: N-(5-ethyl-1,3,4-thiadiazol-2-yl)-p-toluenesulfonamide], rather than the correct imine tautomer. The protonation site on the molecule's 1,3,4-thiadiazole ring is indicated by the intermolecular 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 intermolecular interactions. 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 quantitative 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 (13)C SS-NMR spectrum based on the correct imine tautomer also provides considerably better agreement with the measured (13)C SS-NMR spectrum.

  2. Optimization of 13C dynamic nuclear polarization: isotopic labeling of free radicals

    NASA Astrophysics Data System (ADS)

    Niedbalski, Peter; Parish, Christopher; Kiswandi, Andhika; Lumata, Lloyd

    Dynamic nuclear polarization (DNP) is a physics technique that amplifies the nuclear magnetic resonance (NMR) signals by transferring the high polarization of the electrons to the nuclear spins. Thus, the choice of free radical is crucial in DNP as it can directly affect the NMR signal enhancement levels, typically on the order of several thousand-fold in the liquid-state. In this study, we have investigated the efficiency of four variants of the well-known 4-oxo-TEMPO radical (normal 4-oxo-TEMPO plus its 15N-enriched and/or perdeuterated variants) for use in DNP of an important metabolic tracer [1-13C]acetate. Though the variants have significant differences in electron paramagnetic resonance (EPR) spectra, we have found that changing the composition of the TEMPO radical through deuteration or 15N doping yields no significant difference in 13C DNP efficiency at 3.35 T and 1.2 K. On the other hand, deuteration of the solvent causes a significant increase of 13C polarization that is consistent over all the 4-oxo-TEMPO variants. These findings are consistent with the thermal mixing model of DNP. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and the Robert A. Welch Foundation Grant No. AT-1877.

  3. Solid State Track Recorder applications in United States nuclear reactor energy programs

    SciTech Connect

    Gold, R.; Ruddy, F.H.; Roberts, J.H.

    1980-01-01

    The domain of Solid State Track Recorder (SSTR) applications in United States nuclear reactor energy programs extends from the harsh high temperature environments found in high power reactor cores to very low flux environments arising in out-of-core locations, critical assemblies, or away from reactors (AFR) experiments. The neutron energy region arising in these applications is very broad, covering more than eight orders of magnitude from thermal up to fusion energies. The range of neutron flux/fluence intensity is even greater, extending over more than thirteen orders of magnitude. As a consequence, use of a variety of SSTR is entailed in US nuclear reactor energy programs.

  4. Solid state nuclear magnetic resonance studies of cross polarization from quadrupolar nuclei

    SciTech Connect

    De Paul, Susan M.

    1997-08-01

    The development of solid-state Nuclear Magnetic Resonance (NMR) has, to a large extent, focused on using spin-1/2 nuclei as probes to investigate molecular structure and dynamics. For such nuclei, the technique of cross polarization is well-established as a method for sensitivity enhancement. However, over two-thirds of the nuclei in the periodic table have a spin-quantum number greater than one-half and are known as quadrupolar nuclei. Such nuclei are fundamental constituents of many inorganic materials including minerals, zeolites, glasses, and gels. It is, therefore, of interest to explore the extent to which polarization can be transferred from quadrupolar nuclei. In this dissertation, solid-state NMR experiments involving cross polarization from quadrupolar nuclei to spin-1/2 nuclei under magic-angle spinning (MAS) conditions are investigated in detail.

  5. Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves.

    PubMed

    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.

  6. Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves

    PubMed Central

    Thurber, Kent R.; Tycko, Robert

    2014-01-01

    We report solid state 13C and 1H 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, 1H and cross-polarized 13C NMR signals from 15N,13C-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. PMID:24832263

  7. Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves

    SciTech Connect

    Thurber, Kent R. Tycko, Robert

    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.

  8. Conformational isomerism in solid state of AMG 853--structure studies using solid-state nuclear magnetic resonance and X-ray diffraction.

    PubMed

    Kiang, Y-H; Nagapudi, Karthik; Wu, Tian; Peterson, Matthew L; Jona, Janan; Staples, Richard J; Stephens, Peter W

    2015-07-01

    Investigation of an additional resonance peak in the (19) F solid-state nuclear magnetic resonance (NMR) spectrum of AMG 853, a dual antagonist of DP and CRTH2 previously in clinical development for asthma, has led to the identification of two conformational isomers coexisting in the crystal lattice in a continuous composition range between 89.7%:10.3% and 96.5%:3.5%. These two isomers differ in the chloro-flurorophenyl moiety orientation-the aromatic ring is flipped by 180° in these two isomers. The level of the minor isomer is directly measured through integration of the two peaks in the (19) F solid-state NMR spectrum. The values obtained from the NMR data are in excellent agreement with the degree of disorder of the fluorine atom in the crystal structure, refined using both single-crystal and high-resolution powder X-ray diffraction data.

  9. Size dependence of 13C nuclear spin-lattice relaxation in micro- and nanodiamonds

    NASA Astrophysics Data System (ADS)

    Panich, A. M.; Sergeev, N. A.; Shames, A. I.; Osipov, V. Yu; Boudou, J.-P.; Goren, S. D.

    2015-02-01

    Size dependence of physical properties of nanodiamond particles is of crucial importance for various applications in which defect density and location as well as relaxation processes play a significant role. In this work, the impact of defects induced by milling of micron-sized synthetic diamonds was studied by magnetic resonance techniques as a function of the particle size. EPR and 13C NMR studies of highly purified commercial synthetic micro- and nanodiamonds were done for various fractions separated by sizes. Noticeable acceleration of 13C nuclear spin-lattice relaxation with decreasing particle size was found. We showed that this effect is caused by the contribution to relaxation coming from the surface paramagnetic centers induced by sample milling. The developed theory of the spin-lattice relaxation for such a case shows good compliance with the experiment.

  10. Size dependence of 13C nuclear spin-lattice relaxation in micro- and nanodiamonds.

    PubMed

    Panich, A M; Sergeev, N A; Shames, A I; Osipov, V Yu; Boudou, J-P; Goren, S D

    2015-02-25

    Size dependence of physical properties of nanodiamond particles is of crucial importance for various applications in which defect density and location as well as relaxation processes play a significant role. In this work, the impact of defects induced by milling of micron-sized synthetic diamonds was studied by magnetic resonance techniques as a function of the particle size. EPR and (13)C NMR studies of highly purified commercial synthetic micro- and nanodiamonds were done for various fractions separated by sizes. Noticeable acceleration of (13)C nuclear spin-lattice relaxation with decreasing particle size was found. We showed that this effect is caused by the contribution to relaxation coming from the surface paramagnetic centers induced by sample milling. The developed theory of the spin-lattice relaxation for such a case shows good compliance with the experiment.

  11. Atomic-Level Structure Characterization of Biomass Pre- and Post-Lignin Treatment by Dynamic Nuclear Polarization-Enhanced Solid-State NMR.

    PubMed

    Perras, Frédéric A; Luo, Hao; Zhang, Ximing; Mosier, Nathan S; Pruski, Marek; Abu-Omar, Mahdi M

    2017-01-26

    Lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear (13)C-(13)C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure-function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.

  12. Introduction of the Floquet-Magnus expansion in solid-state nuclear magnetic resonance spectroscopy.

    PubMed

    Mananga, Eugène S; Charpentier, Thibault

    2011-07-28

    In this article, we present an alternative expansion scheme called Floquet-Magnus expansion (FME) used to solve a time-dependent linear differential equation which is a central problem in quantum physics in general and solid-state nuclear magnetic resonance (NMR) in particular. The commonly used methods to treat theoretical problems in solid-state NMR are the average Hamiltonian theory (AHT) and the Floquet theory (FT), which have been successful for designing sophisticated pulse sequences and understanding of different experiments. To the best of our knowledge, this is the first report of the FME scheme in the context of solid state NMR and we compare this approach with other series expansions. We present a modified FME scheme highlighting the importance of the (time-periodic) boundary conditions. This modified scheme greatly simplifies the calculation of higher order terms and shown to be equivalent to the Floquet theory (single or multimode time-dependence) but allows one to derive the effective Hamiltonian in the Hilbert space. Basic applications of the FME scheme are described and compared to previous treatments based on AHT, FT, and static perturbation theory. We discuss also the convergence aspects of the three schemes (AHT, FT, and FME) and present the relevant references.

  13. In-laboratory development of an automatic track counting system for solid state nuclear track detectors

    NASA Astrophysics Data System (ADS)

    Uzun, Sefa Kemal; Demiröz, Işık; Ulus, İzzet

    2017-01-01

    In this study, an automatic track counting system was developed for solid state nuclear track detectors (SSNTD). Firstly the specifications of required hardware components were determined, and accordingly the CCD camera, microscope and stage motor table was supplied and integrated. The system was completed by developing parametric software with VB.Net language. Finally a set of test intended for radon activity concentration measurement was applied. According to the test results, the system was enabled for routine radon measurement. Whether the parameters of system are adjusted for another SSNTD application, it could be used for other fields of SSNTD like neutron dosimetry or heavy charged particle detection.

  14. Diffraction pattern by rotated conical tracks in solid state nuclear track detectors

    NASA Astrophysics Data System (ADS)

    Stevanovic, N.; Markovic, V. M.

    2016-06-01

    The method for determination of diffraction pattern for irregular 3D objects with application on rotated conical tracks in solid state nuclear track detector (SSNTD) wasdescribed in this paper. The model can be applied for different types of the diffraction (Fresnel, Fraunhofer) and arbitrary shapes of the obstacle. By applying the developed model on conical tracks it was fond that diffraction pattern strongly depends from radius, length and rotation angle of the conical tracks. These dependences were investigated in this paper and results can be applied for determination of inner tracks structure via diffraction pattern.

  15. Chemistry and biochemistry of 13C hyperpolarized magnetic resonance using dynamic nuclear polarization

    PubMed Central

    Keshari, Kayvan R.; Wilson, David M.

    2014-01-01

    The study of transient chemical phenomena by conventional NMR has proved elusive, particularly for non-1H nuclei. For 13C, hyperpolarization using the dynamic nuclear polarization (DNP) technique has emerged as a powerful means to improve SNR. The recent development of rapid dissolution DNP methods has facilitated previously impossible in vitro and in vivo study of small molecules. This review presents the basics of the DNP technique, identification of appropriate DNP substrates, and approaches to increase hyperpolarized signal lifetimes. Also addressed are the biochemical events to which DNP-NMR has been applied, with descriptions of several probes that have met with in vivo success. PMID:24363044

  16. Theory of Stochastic Dipolar Recoupling in Solid State Nuclear Magnetic Resonance

    PubMed Central

    Tycko, Robert

    2008-01-01

    Dipolar recoupling techniques in solid state nuclear magnetic resonance (NMR) consist of radio-frequency (rf) pulse sequences applied in synchrony with magic-angle spinning (MAS) that create non-zero average magnetic dipole-dipole couplings under MAS. Stochastic dipolar recoupling (SDR) is a variant in which randomly chosen rf carrier frequency offsets are introduced to cause random phase modulations of individual pairwise couplings in the dipolar spin Hamiltonian. Several aspects of SDR are investigated through analytical theory and numerical simulations: (1) An analytical expression for the evolution of nuclear spin polarization under SDR in a two-spin system is derived and verified through simulations, which show a continuous evolution from coherent, oscillatory polarization exchange to incoherent, exponential approach to equilibrium as the range of random carrier offsets (controlled by a parameter fmax) increases; (2) In a many-spin system, polarization transfers under SDR are shown to be described accurately by a rate matrix in the limit of large fmax, with pairwise transfer rates that are proportional to the inverse sixth power of pairwise internuclear distances; (3) Quantum mechanical interferences among non-commuting pairwise dipole-dipole couplings, which are a complicating factor in solid state NMR studies of molecular structures by traditional dipolar recoupling methods, are shown to be absent from SDR data in the limit of large fmax, provided that coupled nuclei have distinct NMR chemical shifts. PMID:18085769

  17. Experimental (X-ray, (13)C CP/MAS NMR, IR, RS, INS, THz) and Solid-State DFT Study on (1:1) Co-Crystal of Bromanilic Acid and 2,6-Dimethylpyrazine.

    PubMed

    Łuczyńska, Katarzyna; Drużbicki, Kacper; Lyczko, Krzysztof; Dobrowolski, Jan Cz

    2015-06-04

    A combined structural, vibrational spectroscopy, and solid-state DFT study of the hydrogen-bonded complex of bromanilic acid with 2,6-dimethylpyrazine is reported. The crystallographic structure was determined by means of low-temperature single-crystal X-ray diffraction, which reveals the molecular units in their native protonation states, forming one-dimensional infinite nets of moderate-strength O···H-N hydrogen bonds. The nature of the crystallographic forces, stabilizing the studied structure, has been drawn by employing the noncovalent interactions analysis. It was found that, in addition to the hydrogen bonding, the intermolecular forces are dominated by stacking interactions and C-H···O contacts. The thermal and calorimetric analysis was employed to probe stability of the crystal phase. The structural analysis was further supported by a computationally assisted (13)C CP/MAS NMR study, providing a complete assignment of the recorded resonances. The vibrational dynamics was explored by combining the optical (IR, Raman, TDs-THz) and inelastic neutron scattering (INS) spectroscopy techniques with the state-of-the-art solid-state density functional theory (DFT) computations. Despite the quasi-harmonic approximation assumed throughout the study, an excellent agreement between the theoretical and experimental data was achieved over the entire spectral range, allowing for a deep and possibly thorough understanding of the vibrational characteristics of the system. Particularly, the significant influence of the long-range dipole coupling on the IR spectrum has been revealed. On the basis of a wealth of information gathered, the recent implementation of a dispersion-corrected linear-response scheme has been extensively examined.

  18. Characterization of proton exchange membrane materials for fuel cells by solid state nuclear magnetic resonance

    SciTech Connect

    Kong, Zueqian

    2010-01-01

    Solid-state nuclear magnetic resonance (NMR) has been used to explore the nanometer-scale structure of Nafion, the widely used fuel cell membrane, and its composites. We have shown that solid-state NMR can characterize chemical structure and composition, domain size and morphology, internuclear distances, molecular dynamics, etc. The newly-developed water channel model of Nafion has been confirmed, and important characteristic length-scales established. Nafion-based organic and inorganic composites with special properties have also been characterized and their structures elucidated. The morphology of Nafion varies with hydration level, and is reflected in the changes in surface-to-volume (S/V) ratio of the polymer obtained by small-angle X-ray scattering (SAXS). The S/V ratios of different Nafion models have been evaluated numerically. It has been found that only the water channel model gives the measured S/V ratios in the normal hydration range of a working fuel cell, while dispersed water molecules and polymer ribbons account for the structures at low and high hydration levels, respectively.

  19. Composite dipolar recoupling: anisotropy compensated coherence transfer in solid-state nuclear magnetic resonance.

    PubMed

    Khaneja, Navin; Kehlet, Cindie; Glaser, Steffen J; Nielsen, Niels Chr

    2006-03-21

    The efficiency of dipole-dipole coupling driven coherence transfer experiments in solid-state nuclear magnetic resonance (NMR) spectroscopy of powder samples is limited by dispersion of the orientation of the internuclear vectors relative to the external magnetic field. Here we introduce general design principles and resulting pulse sequences that approach full polarization transfer efficiency for all crystallite orientations in a powder in magic-angle-spinning experiments. The methods compensate for the defocusing of coherence due to orientation dependent dipolar coupling interactions and inhomogeneous radio-frequency fields. The compensation scheme is very simple to implement as a scaffold (comb) of compensating pulses in which the pulse sequence to be improved may be inserted. The degree of compensation can be adjusted and should be balanced as a compromise between efficiency and length of the overall pulse sequence. We show by numerical and experimental data that the presented compensation protocol significantly improves the efficiency of known dipolar recoupling solid-state NMR experiments.

  20. Effects of etching time on alpha tracks in Solid state Nuclear Track Detectors

    NASA Astrophysics Data System (ADS)

    Gillmore, Gavin; Wertheim, David; Crust, Simon

    2013-04-01

    Inhalation of radon gas is thought to be the cause of about 1100 lung cancer related deaths each year in the UK (1). Radon concentrations can be monitored using Solid State Nuclear Track Detectors (SSNTDs) as the natural decay of radon results in alpha particles which form tracks in the detectors and these tracks can be etched in order to enable microscopic analysis. We have previously shown that confocal microscopy can be used for 3D visualisation of etched SSNTDs (2, 3). The aim of the study was to examine the effect of etching time on the appearance of alpha tracks in SSNTDs. Six SSNTDs were placed in a chamber with a luminous dial watch for a fixed period. The detectors were etched for between 30 minutes and 4.5 hours using 6M NaOH at a temperature of 90oC. A 'LEXT' OLS4000 confocal laser scanning microscope (Olympus Corporation, Japan) was used to acquire 2D and 3D image datasets of CR-39 plastic SSNTDs. Confocal microscope 3D images were acquired using a x50 or x100 objective lens. Data were saved as images and also spreadsheet files with height measurements. Software was written using MATLAB (The MathWorks Inc., USA) to analyse the height data. Comparing the 30 minute and 4 hour etching time detectors, we observed that there were marked differences in track area; the lower the etching time the smaller the track area. The degree to which etching may prevent visualising adjacent tracks also requires further study as it is possible that etching could result in some tracks being subsumed in other tracks. On the other hand if there is too little etching, track sizes would be reduced and hence could be more difficult to image; thus there is a balance required to obtain suitable measurement accuracy. (1) Gray A, Read S, McGale P and Darby S. Lung cancer deaths from indoor radon and the cost effectiveness and potential of policies to reduce them. BMJ 2009; 338: a3110. (2) Wertheim D, Gillmore G, Brown L, and Petford N. A new method of imaging particle tracks in

  1. 13C Nuclear magnetic resonance studies to the binding of isocyanides to various hemoglobins and myoglobins.

    PubMed

    Dill, K; Satterlee, J D; Richards, J H

    1978-10-03

    Interactions between ethyl and isopropyl isocyanides and various hemoglobins and myoglobins have been studied by 13C nuclear magnetic resonance. The results indicate that the chemical shift of the bound isocyanide depends on the structure of the hemoglobin subunit or myoglobin. The resonances exhibited by isocyanides bound to myoglobin are sensitive to pH in contrast to the situation with rabbit and human hemoglobins. beta subunits of opossum, rabbit, and human hemoglobins show a significantly greater preferential affinity for CO relative to EIC than do alpha subunits which have allowed the assignment of resonances. Rabbit, human, and opossum hemoglobin subunits bind ethyl isocyanide without observable preferences and an excess of DPG does not appear to affect this random order of ligation. In contrast, an excess of IHP seems to cause preferential ligation of the alpha subunits in these hemoglobins. The results have been used to gain insights into the differing characteristics of the ligand binding pockets of these various hemoglobins.

  2. Theoretical aspects of dynamic nuclear polarization in the solid state - The solid effect

    NASA Astrophysics Data System (ADS)

    Hovav, Yonatan; Feintuch, Akiva; Vega, Shimon

    2010-12-01

    Dynamic nuclear polarization has gained high popularity in recent years, due to advances in the experimental aspects of this methodology for increasing the NMR and MRI signals of relevant chemical and biological compounds. The DNP mechanism relies on the microwave (MW) irradiation induced polarization transfer from unpaired electrons to the nuclei in a sample. In this publication we present nuclear polarization enhancements of model systems in the solid state at high magnetic fields. These results were obtained by numerical calculations based on the spin density operator formalism. Here we restrict ourselves to samples with low electron concentrations, where the dipolar electron-electron interactions can be ignored. Thus the DNP enhancement of the polarizations of the nuclei close to the electrons is described by the Solid Effect mechanism. Our numerical results demonstrate the dependence of the polarization enhancement on the MW irradiation power and frequency, the hyperfine and nuclear dipole-dipole spin interactions, and the relaxation parameters of the system. The largest spin system considered in this study contains one electron and eight nuclei. In particular, we discuss the influence of the nuclear concentration and relaxation on the polarization of the core nuclei, which are coupled to an electron, and are responsible for the transfer of polarization to the bulk nuclei in the sample via spin diffusion.

  3. Powder X-ray diffraction, infrared and (13)C NMR spectroscopic studies of the homologous series of some solid-state zinc(II) and sodium(I) n-alkanoates.

    PubMed

    Nelson, Peter N; Taylor, Richard A

    2015-03-05

    A comparative study of the room temperature molecular packing and lattice structures for the homologous series of zinc(II) and sodium(I) n-alkanoates adduced from Fourier transform infrared and solid-state (13)C NMR spectroscopic data in conjunction with X-ray powder diffraction measurements is carried out. For zinc carboxylates, metal-carboxyl bonding is via asymmetric bridging bidentate coordination whilst for the sodium adducts, coordination is via asymmetric chelating bidentate bonding. All compounds are packed in a monoclinic crystal system. Furthermore, the fully extended all-trans hydrocarbon chains are arranged as lamellar bilayers. For zinc compounds, there is bilayer overlap, for long chain adducts (nc>8) but not for sodium compounds where methyl groups from opposing layers in the lamellar are only closely packed. Additionally, the hydrocarbon chains are extended along the a-axis of the unit cell for zinc compounds whilst for sodium carboxylates they are extended along the c-axis. These packing differences are responsible for different levels of Van der Waals effects in the lattices of these two series of compounds, hence, observed odd-even alternation is different. The significant difference in lattice packing observed for these two series of compounds is proposed to be due to the difference in metal-carboxyl coordination mode, arising from the different electronic structure of the central metal ions.

  4. Molecular Structure of Aggregated Amyloid-β: Insights from Solid State Nuclear Magnetic Resonance

    PubMed Central

    Tycko, Robert

    2016-01-01

    Amyloid-β (Aβ) peptides aggregate to form polymorphic amyloid fibrils and a variety of intermediate assemblies, including oligomers and protofibrils, both in vitro and in human brain tissue. Since the beginning of the 21st century, considerable progress has been made on characterization of the molecular structures of Aβ aggregates. Full molecular structural models that are based primarily on data from solid state nuclear magnetic resonance measurements have been developed for several in vitro Aβ fibrils and one metastable protofibril. Partial structural characterization of other aggregation intermediates has been achieved. One full structural model for fibrils derived from brain tissue has also been reported. Future work is likely to focus on additional structures from brain tissue and on further clarification of nonfibrillar Aβ aggregates. PMID:27481836

  5. Single-sheet identification method of heavy charged particles using solid state nuclear track detectors

    NASA Astrophysics Data System (ADS)

    Zaki, M. F.; Abdel-Naby, A.; Morsy, A. Ahmed

    2007-08-01

    The theoretical and experimental investigations of the penetration of charged particles in matter played a very important role in the development of modern physics. Solid state nuclear track detectors have become one of the most important tools for many branches of science and technology. An attempt has been made to examine the suitability of the single-sheet particle identification technique in CR-39 and CN-85 polycarbonate by plotting track cone length vs. residual range for different heavy ions in these detectors. So, the maximum etchable ranges of heavy ions such as ^{93}Nb, ^{86}Kr and ^{4}He in CR-39 and ^{4}He and ^{132}Xe in CN-85 polycarbonate have been determined. The ranges of these ions in these detectors have also been computed theoretically using the Henke-Benton program. A reasonably good agreement has been observed between the experimentally and theoretically computed values.

  6. 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

    NASA Astrophysics Data System (ADS)

    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

  7. 3D visualisation and analysis of single and coalescing tracks in Solid state Nuclear Track Detectors

    NASA Astrophysics Data System (ADS)

    Wertheim, David; Gillmore, Gavin; Brown, Louise; Petford, Nick

    2010-05-01

    Exposure to radon gas (222Rn) and associated ionising decay products can cause lung cancer in humans (1). Solid state Nuclear Track Detectors (SSNTDs) can be used to monitor radon concentrations (2). Radon particles form tracks in the detectors and these tracks can be etched in order to enable 2D surface image analysis. We have previously shown that confocal microscopy can be used for 3D visualisation of etched SSNTDs (3). The aim of the study was to further investigate track angles and patterns in SSNTDs. A 'LEXT' confocal laser scanning microscope (Olympus Corporation, Japan) was used to acquire 3D image datasets of five CR-39 plastic SSNTD's. The resultant 3D visualisations were analysed by eye and inclination angles assessed on selected tracks. From visual assessment, single isolated tracks as well as coalescing tracks were observed on the etched detectors. In addition varying track inclination angles were observed. Several different patterns of track formation were seen such as single isolated and double coalescing tracks. The observed track angles of inclination may help to assess the angle at which alpha particles hit the detector. Darby, S et al. Radon in homes and risk of lung cancer : collaborative analysis of individual data from 13 European case-control studies. British Medical Journal 2005; 330, 223-226. Phillips, P.S., Denman, A.R., Crockett, R.G.M., Gillmore, G., Groves-Kirkby, C.J., Woolridge, A., Comparative Analysis of Weekly vs. Three monthly radon measurements in dwellings. DEFRA Report No., DEFRA/RAS/03.006. (2004). Wertheim D, Gillmore G, Brown L, and Petford N. A new method of imaging particle tracks in Solid State Nuclear Track Detectors. Journal of Microscopy 2010; 237: 1-6.

  8. 13 C solid-state NMR study of the 13 C-labeled peptide, (E)8 GGLGGQGAG(A)6 GGAGQGGYGG as a model for the local structure of Nephila clavipes dragline silk (MaSp1) before and after spinning.

    PubMed

    Yazawa, Koji; Yamaguchi, Erika; Knight, David; Asakura, Tetsuo

    2012-06-01

    We prepared the water soluble model peptide, (E)(8) GGLGGQGAG(A)(6) GGAGQGGYGG, to throw light on the local structure of spidroin 1 (MaSpl) protein in spider dragline silk of Nephila clavipes before and after spinning. Solution (13) C NMR showed that the conformation of the peptide in aqueous solution was essentially random coil. Solid-state NMR was used to follow conformation-dependent (13) C chemical shifts in (13) C selectively labeled versions of the peptide. The peptide lyophilized from an aqueous solution at neutral pH (hereafter referred to as "without acid treatment)"was used to mimic the state of the spidroin stored in the spider's silk gland while the peptide precipitated from the acidic solution ("with acid treatment") was used to simulate the role of acid treatment in inducing conformation change in the natural spinning process. In without acid treatment, the fraction of random coil conformation was lowest in the N-terminal region (residues 15-18) when compared with the C-terminus. The conformational change produced by the acid treatment occurred in the sequence, G(15) AG(A)(6) GGAG(27), interposed between pairs of Gly residues pairs, Gly(12,13), and Gly(29,30). The acid treated peptide showed a remarkable decrease in the fraction of random coil conformation from A(20) to A(23) in the poly-Ala region when compared with the peptide without acid treatment. These observations taken together suggest that the peptide can be used as a model for studying the localization of the conformation change in spider silk fibroin in the natural spinning and the role of acid treatment in this process.

  9. Citrate and Sugar Cofermentation in Leuconostoc oenos, a (sup13)C Nuclear Magnetic Resonance Study

    PubMed Central

    Ramos, A.; Santos, H.

    1996-01-01

    (sup13)C nuclear magnetic resonance spectroscopy was used to investigate citrate-glucose cometabolism in nongrowing cell suspensions of the wine lactic acid bacterium Leuconostoc oenos. The use of isotopically enriched substrates allowed us to identify and quantify in the end products the carbon atoms derived from each of the substrates supplied; furthermore, it was possible to differentiate between products derived from the metabolism of endogenous carbon reserves and those derived from external substrates. Citrate-sugar cometabolism was also monitored in dilute cell suspensions for comparison with the nuclear magnetic resonance results. A clear metabolic shift of the end products from glucose metabolism was observed when citrate was provided along with glucose: ethanol was replaced by acetate, and 2,3-butanediol was produced. Reciprocally, the production of lactate and 2,3-butanediol from citrate was increased in the presence of glucose. When citrate was cometabolized with glucose, a 10-fold reduction in the intracellular concentration of glucose-6-phosphate was observed, a result in line with the observed citrate-induced stimulation of glucose consumption. The presence of citrate provided additional pathways for NADP(sup+) regeneration and allowed the diversion of sugar carbon to reactions in which ATP was synthesized. The increased growth rates and maximal biomass yields of L. oenos growing on citrate-glucose mixtures resulted from increased ATP synthesis both by substrate-level phosphorylation and by a chemiosmotic mechanism. PMID:16535363

  10. Surface chemistry of group 11 atomic layer deposition precursors on silica using solid-state nuclear magnetic resonance spectroscopy.

    PubMed

    Pallister, Peter J; Barry, Seán T

    2017-02-07

    The use of chemical vapour deposition (CVD) and atomic layer deposition (ALD) as thin film deposition techniques has had a major impact on a number of fields. The deposition of pure, uniform, conformal thin films requires very specific vapour-solid reactivity that is largely unknown for the majority of ALD and CVD precursors. This work examines the initial chemisorption of several thin film vapour deposition precursors on high surface area silica (HSAS) using (13)C, (31)P, and quantitative (29)Si nuclear magnetic resonance spectroscopy (NMR). Two copper metal precursors, 1,3-diisopropyl-imidazolin-2-ylidene copper (I) hexamethyldisilazide (1) and 1,3-diethyl-imidazolin-2-ylidene copper(I) hexamethyldisilazide (2), and one gold metal precursor, trimethylphosphine gold(III) trimethyl (3), are examined. Compounds 1 and 2 were found to chemisorb at the hydroxyl surface-reactive sites to form a ||-O-Cu-NHC surface species and fully methylated silicon (||-SiMe3, due to reactivity of the hexamethyldisilazane (HMDS) ligand on the precursor) at 150 °C and 250 °C. From quantitative (29)Si solid-state NMR (SS-NMR) spectroscopy measurements, it was found that HMDS preferentially reacts at geminal disilanol surface sites while the copper surface species preferentially chemisorbed to lone silanol surface species. Additionally, the overall coverage was strongly dependent on temperature, with higher overall coverage of 1 at higher temperature but lower overall coverage of 2 at higher temperature. The chemisorption of 3 was found to produce a number of interesting surface species on HSAS. Gold(III) trimethylphosphine, reduced gold phosphine, methylated phosphoxides, and graphitic carbon were all observed as surface species. The overall coverage of 3 on HSAS was only about 10% at 100 °C and, like the copper compounds, had a preference for lone silanol surface reactive sites. The overall coverage and chemisorbed surface species have implications to the overall growth rate and

  11. Surface chemistry of group 11 atomic layer deposition precursors on silica using solid-state nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Pallister, Peter J.; Barry, Seán T.

    2017-02-01

    The use of chemical vapour deposition (CVD) and atomic layer deposition (ALD) as thin film deposition techniques has had a major impact on a number of fields. The deposition of pure, uniform, conformal thin films requires very specific vapour-solid reactivity that is largely unknown for the majority of ALD and CVD precursors. This work examines the initial chemisorption of several thin film vapour deposition precursors on high surface area silica (HSAS) using 13C, 31P, and quantitative 29Si nuclear magnetic resonance spectroscopy (NMR). Two copper metal precursors, 1,3-diisopropyl-imidazolin-2-ylidene copper (I) hexamethyldisilazide (1) and 1,3-diethyl-imidazolin-2-ylidene copper(I) hexamethyldisilazide (2), and one gold metal precursor, trimethylphosphine gold(III) trimethyl (3), are examined. Compounds 1 and 2 were found to chemisorb at the hydroxyl surface-reactive sites to form a ||-O-Cu-NHC surface species and fully methylated silicon (||-SiMe3, due to reactivity of the hexamethyldisilazane (HMDS) ligand on the precursor) at 150 °C and 250 °C. From quantitative 29Si solid-state NMR (SS-NMR) spectroscopy measurements, it was found that HMDS preferentially reacts at geminal disilanol surface sites while the copper surface species preferentially chemisorbed to lone silanol surface species. Additionally, the overall coverage was strongly dependent on temperature, with higher overall coverage of 1 at higher temperature but lower overall coverage of 2 at higher temperature. The chemisorption of 3 was found to produce a number of interesting surface species on HSAS. Gold(III) trimethylphosphine, reduced gold phosphine, methylated phosphoxides, and graphitic carbon were all observed as surface species. The overall coverage of 3 on HSAS was only about 10% at 100 °C and, like the copper compounds, had a preference for lone silanol surface reactive sites. The overall coverage and chemisorbed surface species have implications to the overall growth rate and purity of

  12. Tryptophan sidechain dynamics in hydrophobic oligopeptides determined by use of 13C nuclear magnetic resonance spectroscopy.

    PubMed

    Weaver, A J; Kemple, M D; Prendergast, F G

    1988-07-01

    Two oligopeptides, t-boc-LAWAL-OMe and t-boc-LALALW-OMe, were synthesized for the purpose of examining the sidechain dynamics of the tryptophan residue in hydrophobic environments by 13C nuclear magnetic resonance and fluorescence spectroscopy. In both peptides, the tryptophan sidechain was greater than 95% enriched with 13C at the C delta 1 position. Spin-lattice relaxation time (T1) and steady-state nuclear Overhauser effect (NOE) data were obtained at 50.3 and 75.4 MHz for both peptides in CD3OD, and at 75.4 MHz for t-boc-LALALW-OMe in lysolecithin-D2O micelles. We have adapted the model-free approach of G. Lipari and A. Szabo (1982, J. Am. Chem. Soc. 104:4546) to interpret the 13C-NMR data. Computer-generated curves based on experimental data obtained at a single frequency demonstrate relationships between an effective correlation time for tryptophan sidechain motion (tau e), a generalized order parameter (sigma) describing the extent of motional restriction, and an overall correlation time for the peptide (tau m). Assuming predominantly dipolar relaxation, least-squares fits of the dual frequency relaxation data provide values for these parameters for both peptides. The contribution of chemical shift anisotropy (CSA), however, is also explicitly assessed in the data analysis, and is shown to perturb the predicted sigma, tau e, and tau m values and to decrease chi(2) values observed in nonlinear least-squares analysis of the data. Because of uncertainty in the contribution of CSA to the relaxation of the indole ring 13C delta 1 atom, nonlinear least-squares analysis of the relaxation data were performed with and without inclusion of a CSA term in the appropriate relaxation equations. Neglecting CSA, an overall peptide correlation time of 0.69 ns is predicted for t-boc-LAWAL-OMe in CD3OD at 20 degrees C compared with 1.28 ns for t-boc-LALALW-OMe. Given these tau m values and taking into account the effect of measurement error in the T1 and NOE data, the internal

  13. Atomic-level structure characterization of biomass pre- and post-lignin treatment by dynamic nuclear polarization-enhanced solid-state NMR

    DOE PAGES

    Perras, Frederic A.; Luo, Hao; Zhang, Ximing; ...

    2016-12-27

    Here, lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear 13C–13C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure–functionmore » relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.« less

  14. Formation of carboxylic acids from alcohols and olefins in zeolite H-ZSM-5 under mild conditions via trapping of alkyl carbenium ions with carbon monoxide: An in situ {sup 13}C solid state NMR study

    SciTech Connect

    Stepanov, A.G.; Luzgin, M.V.; Romannikov, V.N.; Sidelnikov, V.N.; Zamaraev K.I.

    1996-12-01

    Using in situ {sup 13}C solid state MAS NMR (for some reagents in combination with ex situ GC-MS), it is shown that butyl alcohols and olefins (ethene, isobutene, octene-1) undergo carbonylation to form carboxylic acids (the Koch reaction) with high conversion on zeolite H-ZSM-5 at 296-373 K. The reactions proceed without application of pressurized conditions, just upon coadsorption of CO and alcohols or CO, H{sub 2}O, and olefins on zeolite. The observed Koch reaction under mild conditions provides strong evidence for the formation of alkyl carbenium ions from alcohols and olefins on the zeolites as crucial reaction intermediates. Of the family of carbenium ions, CO reacts selectively with tertiary cations to produce tertiary carboxylic acids, unless the carbonylated molecule is too large for more bulky tertiary moieties to be accommodated and carbonylated in the narrow pores of H-ZSM05. Thus, t-BuOH, i-BuOH, and isobutene produce trimethylacetic acid with high selectivity and conversion, while ethene transforms selectively into 2-methyl-2-ethyl butyric acid. Reaction of octene-1 molecules with CO and H{sub 2}O results in acids of the C{sub 8}H{sub 17}COOH and C{sub 16}H{sub 33}COOH families with predominantly linear hydrocarbon chains. The data obtained may open up new possibilities in using solid acids in organic synthesis as carbonylation catalysts under mild conditions i.e., low temperature and normal atmospheric pressure. 55 refs., 8 figs.

  15. Dynamic nuclear polarization-enhanced 1H–13C double resonance NMR in static samples below 20 K

    PubMed Central

    Potapov, Alexey; Thurber, Kent R.; Yau, Wai-Ming; Tycko, Robert

    2012-01-01

    We demonstrate the feasibility of one-dimensional and two-dimensional 1H–13C double resonance NMR experiments with dynamic nuclear polarization (DNP) at 9.4 T and temperatures below 20 K, including both 1H–13C cross-polarization and 1H decoupling, and discuss the effects of polarizing agent type, polarizing agent concentration, temperature, and solvent deuteration. We describe a two-channel low-temperature DNP/NMR probe, capable of carrying the radio-frequency power load required for 1H–13C cross-polarization and high-power proton decoupling. Experiments at 8 K and 16 K reveal a significant T2 relaxation of 13C, induced by electron spin flips. Carr–Purcell experiments and numerical simulations of Carr–Purcell dephasing curves allow us to determine the effective correlation time of electron flips under our experimental conditions. The dependence of the DNP signal enhancement on electron spin concentration shows a maximum near 80 mM. Although no significant difference in the absolute DNP enhancements for triradical (DOTOPA-TEMPO) and biradical (TOTAPOL) dopants was found, the triradical produced greater DNP build-up rates, which are advantageous for DNP experiments. Additionally the feasibility of structural measurements on 13C-labeled biomolecules was demonstrated with a two-dimensional 13C–13C exchange spectrum of selectively 13C-labeled β-amyloid fibrils. PMID:22743540

  16. 13C nuclear magnetic resonance data of lanosterol derivatives—Profiling the steric topology of the steroid skeleton via substituent effects on its 13C NMR

    NASA Astrophysics Data System (ADS)

    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.

  17. (13)C-Decoupled J-Coupling Spectroscopy Using Two-Dimensional Nuclear Magnetic Resonance at Zero-Field.

    PubMed

    Sjolander, Tobias F; Tayler, Michael C D; Kentner, Arne; Budker, Dmitry; Pines, Alexander

    2017-04-06

    We present a two-dimensional method for obtaining (13)C-decoupled, (1)H-coupled nuclear magnetic resonance (NMR) spectra in zero magnetic field using coherent spin-decoupling. The result is a spectrum determined only by the proton-proton J-coupling network. Detection of NMR signals in zero magnetic field requires at least two different nuclear spin species, but the proton J-spectrum is independent of isotopomer, thus potentially simplifying spectra and thereby improving the analytical capabilities of zero-field NMR. The protocol does not rely on a difference in Larmor frequency between the coupled nuclei, allowing for the direct determination of J-coupling constants between chemically equivalent spins. We obtain the (13)C-decoupled zero-field spectrum of [1-(13)C]-propionic acid and identify conserved quantum numbers governing the appearance of cross peaks in the two-dimensional spectrum.

  18. Solid state 13C-NMR, infrared, X-ray powder diffraction and differential thermal studies of the homologous series of some mono-valent metal (Li, Na, K, Ag) n-alkanoates: A comparative study

    NASA Astrophysics Data System (ADS)

    Nelson, Peter N.; Ellis, Henry A.; White, Nicole A. S.

    2015-06-01

    A comparative study of the molecular packing, lattice structures and phase behaviors of the homologous series of some mono-valent metal carboxylates (Li, Na, K and Ag) is carried out via solid state FT-infrared and 13C-NMR spectroscopes, X-rays powder diffraction, density measurements, differential scanning calorimetry, polarizing light microscopy and variable temperature infrared spectroscopy. It is proposed that, for lithium, sodium and potassium carboxylates, metal-carboxyl coordination is via asymmetric chelating bidentate bonding with extensive intermolecular interactions to form tetrahedral metal centers, irrespective of chain length. However, for silver n-alkanoates, carboxyl moieties are bound to silver ions via syn-syn type bridging bidentate coordination to form dimeric units held together by extensive head group inter-molecular interactions. Furthermore, the fully extended hydrocarbon chains which are crystallized in the all-trans conformation are tilted at ca. 30°, 27°, 15° and 31° with respect to a normal to the metal plane, for lithium, sodium, silver and potassium carboxylates, respectively. All compounds are packed as lamellar bilayer structures, however, lithium compounds are crystallized in a triclinic crystal system whilst silver, sodium and potassium n-alkanoates are all monoclinic with possible P1 bravais lattice. Odd-even alternation observed in various physical features is associated with different inter-planar spacing between closely packed layers in the bilayer which are not in the same plane; a phenomenon controlled by lattice packing symmetry requirements. All compounds, except silver carboxylates, show partially reversibly first order pre-melting transitions; the number of which increases with increasing chain length. These transitions are associated, for the most part, with lamellar collapse followed by increased gauche-trans isomerism in the methylene group assembly, irrespective of chain length. It is proposed that the absence of

  19. Characterization of polysulfone and polysulfone/vanillin microcapsules by 1H NMR spectroscopy, solid-state 13C CP/MAS-NMR spectroscopy, and N2 adsorption-desorption analyses.

    PubMed

    Peña, Brisa; de Ménorval, Louis-Charles; Garcia-Valls, Ricard; Gumí, Tània

    2011-11-01

    Textile detergent and softener industries have incorporated perfume microencapsulation technology to improve their products. Perfume encapsulation allows perfume protection until use and provides a long-lasting fragrance release. But, certain industrial microcapsules show low encapsulation capacity and low material stability. Polysulfone capsules have been already proposed to solve these drawbacks. Among them, PSf/Vanillin capsules were considered as a desirable system. They present both good material stability and high encapsulation capacity. However, several factors such as the final location of the perfume in the polymeric matrix, the aggregation state that it has in the capsule and its interaction with the capsule components have not been studied yet. These factors can provide vast information about the capsule performance and its improvement. With the aim to characterize these parameters, the physical and chemical properties of PSf/Vanillin capsules have been investigated by nuclear magnetic resonance (NMR) spectroscopy, scanning electron microscopy (SEM), atomic force microscopy (AFM), and N(2) adsorption-desorption measurements. AFM micrograph and N(2) isotherms confirm that the presence of vanillin modify the physical structure of PSf/Vanillin microcapsules as it is trapped in the capsule porosity. NMR results show that vanillin is present in solid state in PSf/Vanillin microcapsules.

  20. Effect of electron spin dynamics on solid-state dynamic nuclear polarization performance.

    PubMed

    Siaw, Ting Ann; Fehr, Matthias; Lund, Alicia; Latimer, Allegra; Walker, Shamon A; Edwards, Devin T; Han, Song-I

    2014-09-21

    For the broadest dissemination of solid-state dynamic nuclear polarization (ssDNP) enhanced NMR as a material characterization tool, the ability to employ generic mono-nitroxide radicals as spin probes is critical. A better understanding of the factors contributing to ssDNP efficiency is needed to rationally optimize the experimental condition for the practically accessible spin probes at hand. This study seeks to advance the mechanistic understanding of ssDNP by examining the effect of electron spin dynamics on ssDNP performance at liquid helium temperatures (4-40 K). The key observation is that bi-radicals and mono-radicals can generate comparable nuclear spin polarization at 4 K and 7 T, which is in contrast to the observation for ssDNP at liquid nitrogen temperatures (80-150 K) that finds bi-radicals to clearly outperform mono-radicals. To rationalize this observation, we analyze the change in the DNP-induced nuclear spin polarization (Pn) and the characteristic ssDNP signal buildup time as a function of electron spin relaxation rates that are modulated by the mono- and bi-radical spin concentration. Changes in Pn are consistent with a systematic variation in the product of the electron spin-lattice relaxation time and the electron spin flip-flop rate that constitutes an integral saturation factor of an inhomogeneously broadened EPR spectrum. We show that the comparable Pn achieved with both radical species can be reconciled with a comparable integral EPR saturation factor. Surprisingly, the largest Pn is observed at an intermediate spin concentration for both mono- and bi-radicals. At the highest radical concentration, the stronger inter-electron spin dipolar coupling favors ssDNP, while oversaturation diminishes Pn, as experimentally verified by the observation of a maximum Pn at an intermediate, not the maximum, microwave (μw) power. At the maximum μw power, oversaturation reduces the electron spin population differential that must be upheld between

  1. Site-specific 13C content by quantitative isotopic 13C nuclear magnetic resonance spectrometry: a pilot inter-laboratory study.

    PubMed

    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

    2013-07-25

    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)Ci 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)Ci 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.

  2. 35Cl dynamic nuclear polarization solid-state NMR of active pharmaceutical ingredients

    SciTech Connect

    Hirsh, David A.; Rossini, Aaron J.; Emsley, Lyndon; Schurko, Robert W.

    2016-08-24

    In this paper, we show how to obtain efficient dynamic nuclear polarization (DNP) enhanced 35Cl solid-state NMR (SSNMR) spectra at 9.4 T and demonstrate how they can be used to characterize the molecular-level structure of hydrochloride salts of active pharmaceutical ingredients (APIs) in both bulk and low wt% API dosage forms. 35Cl SSNMR central-transition powder patterns of chloride ions are typically tens to hundreds of kHz in breadth, and most cannot be excited uniformly with high-power rectangular pulses or acquired under conditions of magic-angle spinning (MAS). Herein, we demonstrate the combination of DNP and 1H–35Cl broadband adiabatic inversion cross polarization (BRAIN-CP) experiments for the acquisition of high quality wideline spectra of APIs under static sample conditions, and obtain signals up to 50 times greater than in spectra acquired without the use of DNP at 100 K. We report a new protocol, called spinning-on spinning-off (SOSO) acquisition, where MAS is applied during part of the polarization delay to increase the DNP enhancements and then the MAS rotation is stopped so that a wideline 35Cl NMR powder pattern free from the effects of spinning sidebands can be acquired under static conditions. This method provides an additional two-fold signal enhancement compared to DNP-enhanced SSNMR spectra acquired under purely static conditions. DNP-enhanced 35Cl experiments are used to characterize APIs in bulk and dosage forms with Cl contents as low as 0.45 wt%. These results are compared to DNP-enhanced 1H–13C CP/MAS spectra of APIs in dosage forms, which are often hindered by interfering signals arising from the binders, fillers and other excipient materials.

  3. Solid state 31phosphorus nuclear magnetic resonance of iron-, manganese-, and copper-containing synthetic hydroxyapatites

    NASA Technical Reports Server (NTRS)

    Sutter, B.; Taylor, R. E.; Hossner, L. R.; Ming, D. W.

    2002-01-01

    The incorporation of micronutrients into synthetic hydroxyapatite (SHA) is proposed for slow release of these nutrients to crops in the National Aeronautics and Space Administration's (NASA's) Advanced Life Support (ALS) program for Lunar or Martian outposts. Solid state 31P nuclear magnetic resonance (NMR) was utilized to examine the paramagnetic effects of Fe3+, Mn2+, and Cu2+ to determine if they were incorporated into the SHA structure. Separate Fe3+, Mn2+, and Cu2+ containing SHA materials along with a transition metal free SHA (pure-SHA) were synthesized using a precipitation method. The proximity (<1 nm) of the transition metals to the 31P nuclei of SHA were apparent when comparing the integrated 31P signal intensities of the pure-SHA (87 arbitrary units g-1) with the Fe-, Mn-, and Cu-SHA materials (37-71 arbitrary units g-1). The lower integrated 31P signal intensities of the Fe-, Mn-, and Cu-SHA materials relative to the pure-SHA suggested that Fe3+, Mn2+, and Cu2+ were incorporated in the SHA structure. Further support for Fe3+, Mn2+, and Cu2+ incorporation was demonstrated by the reduced spin-lattice relaxation constants of the Fe-, Mn-, and Cu-SHA materials (T'=0.075-0.434s) relative to pure-SHA (T1=58.4s). Inversion recovery spectra indicated that Fe3+, Mn2+, and Cu2+ were not homogeneously distributed about the 31P nuclei in the SHA structure. Extraction with diethylene-triamine-penta-acetic acid (DTPA) suggested that between 50 and 80% of the total starting metal concentrations were incorporated in the SHA structure. Iron-, Mn-, and Cu-containing SHA are potential slow release sources of Fe, Mn, and Cu in the ALS cropping system.

  4. Application of 13C Nuclear Magnetic Resonance To Elucidate the Unexpected Biosynthesis of Erythritol by Leuconostoc oenos

    PubMed Central

    Veiga-Da-Cunha, Maria; Firme, Paula; Romão, M. Vitória San; Santos, Helena

    1992-01-01

    Natural-abundance 13C nuclear magnetic resonance (13C-NMR) revealed the production of erythritol and glycerol by nongrowing cells of Leuconostoc oenos metabolizing glucose. The ratio of erythritol to glycerol was strongly influenced by the aeration conditions of the medium. The elucidation of the metabolic pathway responsible for erythritol production was achieved by 13C-NMR and 1H-NMR spectroscopy using specifically 13C-labelled d-glucose. The 1H-NMR spectrum of the cell supernatant resulting from the metabolism of [2-13C]glucose showed that only 75% of the glucose supplied was metabolized heterofermentatively and that the remaining 25% was channelled to the production of erythritol. The synthesis of this polyol resulted from the reduction of the C-4 moiety of the intermediate fructose 6-phosphate. Oxygen has an inhibitory effect on the production of erythritol by L. oenos. Preaeration of a suspension of nongrowing cells of L. oenos resulted in 30% less erythritol and in 70% more glycerol formed during the anaerobic metabolism of glucose. The anaerobic production of erythritol from glucose was also found in growing cultures of L. oenos, although to a smaller extent. PMID:16348738

  5. Characterization of oil shale, isolated kerogen, and post-pyrolysis residues using advanced 13 solid-state nuclear magnetic resonance spectroscopy

    USGS Publications Warehouse

    Cao, Xiaoyan; Birdwell, Justin E.; Chappell, Mark A.; Li, Yuan; Pignatello, Joseph J.; Mao, Jingdong

    2013-01-01

    Characterization of oil shale kerogen and organic residues remaining in postpyrolysis spent shale is critical to the understanding of the oil generation process and approaches to dealing with issues related to spent shale. The chemical structure of organic matter in raw oil shale and spent shale samples was examined in this study using advanced solid-state 13C nuclear magnetic resonance (NMR) spectroscopy. Oil shale was collected from Mahogany zone outcrops in the Piceance Basin. Five samples were analyzed: (1) raw oil shale, (2) isolated kerogen, (3) oil shale extracted with chloroform, (4) oil shale retorted in an open system at 500°C to mimic surface retorting, and (5) oil shale retorted in a closed system at 360°C to simulate in-situ retorting. The NMR methods applied included quantitative direct polarization with magic-angle spinning at 13 kHz, cross polarization with total sideband suppression, dipolar dephasing, CHn selection, 13C chemical shift anisotropy filtering, and 1H-13C long-range recoupled dipolar dephasing. The NMR results showed that, relative to the raw oil shale, (1) bitumen extraction and kerogen isolation by demineralization removed some oxygen-containing and alkyl moieties; (2) unpyrolyzed samples had low aromatic condensation; (3) oil shale pyrolysis removed aliphatic moieties, leaving behind residues enriched in aromatic carbon; and (4) oil shale retorted in an open system at 500°C contained larger aromatic clusters and more protonated aromatic moieties than oil shale retorted in a closed system at 360°C, which contained more total aromatic carbon with a wide range of cluster sizes.

  6. Cellulose-Pectin Spatial Contacts Are Inherent to Never-Dried Arabidopsis Primary Cell Walls: Evidence from Solid-State Nuclear Magnetic Resonance.

    PubMed

    Wang, Tuo; Park, Yong Bum; Cosgrove, Daniel J; Hong, Mei

    2015-07-01

    The structural role of pectins in plant primary cell walls is not yet well understood because of the complex and disordered nature of the cell wall polymers. We recently introduced multidimensional solid-state nuclear magnetic resonance spectroscopy to characterize the spatial proximities of wall polysaccharides. The data showed extensive cross peaks between pectins and cellulose in the primary wall of Arabidopsis (Arabidopsis thaliana), indicating subnanometer contacts between the two polysaccharides. This result was unexpected because stable pectin-cellulose interactions are not predicted by in vitro binding assays and prevailing cell wall models. To investigate whether the spatial contacts that give rise to the cross peaks are artifacts of sample preparation, we now compare never-dried Arabidopsis primary walls with dehydrated and rehydrated samples. One-dimensional (13)C spectra, two-dimensional (13)C-(13)C correlation spectra, water-polysaccharide correlation spectra, and dynamics data all indicate that the structure, mobility, and intermolecular contacts of the polysaccharides are indistinguishable between never-dried and rehydrated walls. Moreover, a partially depectinated cell wall in which 40% of homogalacturonan is extracted retains cellulose-pectin cross peaks, indicating that the cellulose-pectin contacts are not due to molecular crowding. The cross peaks are observed both at -20 °C and at ambient temperature, thus ruling out freezing as a cause of spatial contacts. These results indicate that rhamnogalacturonan I and a portion of homogalacturonan have significant interactions with cellulose microfibrils in the native primary wall. This pectin-cellulose association may be formed during wall biosynthesis and may involve pectin entrapment in or between cellulose microfibrils, which cannot be mimicked by in vitro binding assays.

  7. Ground-fire effects on the composition of dissolved and total organic matter in forest floor and soil solutions from Scots pine forests in Germany: new insights from solid state 13C NMR analysis

    NASA Astrophysics Data System (ADS)

    Näthe, Kerstin; Michalzik, Beate; Levia, Delphis; Steffens, Markus

    2016-04-01

    Fires represent an ecosystem disturbance and are recognized to seriously pertubate the nutrient budgets of forested ecosystems. While the effects of fires on chemical, biological, and physical soil properties have been intensively studied, especially in Mediterranean areas and North America, few investigations examined the effects of fire-induced alterations in the water-bound fluxes and the chemical composition of dissolved and particulate organic carbon and nitrogen (DOC, POC, DN, PN). The exclusion of the particulate organic matter fraction (0.45 μm < POM < 500 μm) potentially results in misleading inferences and budgeting gaps when studying the effects of fires on nutrient and energy fluxes. To our best knowledge, this is the first known study to present fire-induced changes on the composition of dissolved and total organic matter (DOM, TOM) in forest floor (FF) and soil solutions (A, B horizon) from Scots pine forests in Germany. In relation to control sites, we test the effects of low-severity fires on: (1) the composition of DOM and TOM in forest floor and soil solutions; and (2) the translocated amount of particulate in relation to DOC and DN into the subsoil. The project aims to uncover the mechanisms of water-bound organic matter transport along an ecosystem profile and its compositional changes following a fire disturbance. Forest floor and soil solutions were fortnightly sampled from March to December 2014 on fire-manipulated and control plots in a Scots pine forest in Central Germany. Shortly after the experimental duff fire in April 2014 pooled solutions samples were taken for solid-state 13C NMR spectroscopy to characterize DOM (filtered solution < 0.8μm pore size) and TOM in unfiltered solutions. Independent from fire manipulation, the composition of TOM was generally less aromatic (aromaticity index [%] according to Hatcher et al., 1981) with values between 18 (FF) - 25% (B horizon) than the DOM fraction with 23 (FF) - 27% (B horizon). For DOM

  8. Solid State Nuclear Magnetic Resonance Studies of the Murchison Organic Macromolecule

    NASA Technical Reports Server (NTRS)

    Cody, G. D., III; Alexander, C. M. OD.; Tera, F.

    2001-01-01

    We have used high speed H-1 (DEPTH) and C-13 (VACP MAS-slow spinning) solid state NMR to determine the contributions of protonated vs non-protonated carbon in the Murchison Macromolecule. Additional information is contained in the original extended abstract.

  9. Solid state nuclear magnetic resonance investigation of polymer backbone dynamics in poly(ethylene oxide) based lithium and sodium polyether-ester-sulfonate ionomers

    NASA Astrophysics Data System (ADS)

    Roach, David J.; Dou, Shichen; Colby, Ralph H.; Mueller, Karl T.

    2013-05-01

    Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (Tg) have been investigated using solid-state nuclear magnetic resonance. Experiments detecting 13C with 1H decoupling under magic angle spinning (MAS) conditions identified the different components of the polymer backbone (PEO spacer and isophthalate groups) and their relative mobilities for a suite of lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) 1H-13C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content and identity. Each of the main backbone components exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and 1H spin-lattice relaxation rate measurements. Previous 1H and 7Li spin-lattice relaxation measurements focused on both the polymer backbone and cation motion on the nanosecond timescale. The studies presented here assess the slower timescale motion of the polymer backbone allowing for a more comprehensive understanding of the polymer dynamics. The temperature dependences of 13C linewidths were used to both qualitatively and quantitatively examine the effects of cation content and identity on PEO spacer mobility. Variable contact time 1H-13C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, reported via the rate of magnetization transfer from 1H to 13C nuclei, becomes similar for T ˜x 1{.1} Tg in all ionic samples, indicating that at similar elevated reduced temperatures the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results present an improved picture, beyond those of previous findings, for the

  10. Solid State Nuclear Magnetic Resonance Investigation of Polymer Backbone Dynamics in Poly(Ethylene Oxide) Based Lithium and Sodium Polyether-ester-sulfonate Ionomers

    SciTech Connect

    Roach, David J.; Dou, Shichen; Colby, Ralph H.; Mueller, Karl T.

    2013-01-01

    Polymer backbone dynamics of single ion conducting poly(ethylene oxide) (PEO)-based ionomer samples with low glass transition temperatures (Tg) have been investigated using solid-state nuclear magnetic resonance (NMR). Experiments detecting 13C with 1H decoupling under magic angle spinning (MAS) conditions identified the different components of the polymer backbone (PEO spacer and isophthalate groups) and their relative mobilities for a suite of lithium- and sodium-containing ionomer samples with varying cation contents. Variable temperature (203-373 K) 1H-13C cross-polarization MAS (CP-MAS) experiments also provided qualitative assessment of the differences in the motions of the polymer backbone components as a function of cation content and identity. Each of the main backbone components exhibit distinct motions, following the trends expected for motional characteristics based on earlier Quasi Elastic Neutron Scattering and 1H spin-lattice relaxation rate measurements. Previous 1H and 7Li spin-lattice relaxation measurements focused on both the polymer backbone and cation motion on the nanosecond timescale. The studies presented here assess the slower timescale motion of the polymer backbone allowing for a more comprehensive understanding of the polymer dynamics. The temperature dependences of 13C linewidths were used to both qualitatively and quantitatively examine the effects of cation content and identity on PEO spacer mobility. Variable contact time 1H-13C CP-MAS experiments were used to further assess the motions of the polymer backbone on the microsecond timescale. The motion of the PEO spacer, reported via the rate of magnetization transfer from 1H to 13C nuclei, becomes similar for T ≳ 1.1 Tg in all ionic samples, indicating that at similar elevated reduced temperatures the motions of the polymer backbones on the microsecond timescale become insensitive to ion interactions. These results present an improved picture, beyond those of previous findings, for

  11. 13C and 1H Nuclear Magnetic Resonance Study of Glycogen Futile Cycling in Strains of the Genus Fibrobacter

    PubMed Central

    Matheron, Christelle; Delort, Anne-Marie; Gaudet, Geneviève; Forano, Evelyne; Liptaj, Tibor

    1998-01-01

    We investigated the carbon metabolism of three strains of Fibrobacter succinogenes and one strain of Fibrobacter intestinalis. The four strains produced the same amounts of the metabolites succinate, acetate, and formate in approximately the same ratio (3.7/1/0.3). The four strains similarly stored glycogen during all growth phases, and the glycogen-to-protein ratio was close to 0.6 during the exponential growth phase. 13C nuclear magnetic resonance (NMR) analysis of [1-13C]glucose utilization by resting cells of the four strains revealed a reversal of glycolysis at the triose phosphate level and the same metabolic pathways. Glycogen futile cycling was demonstrated by 13C NMR by following the simultaneous metabolism of labeled [13C]glycogen and exogenous unlabeled glucose. The isotopic dilutions of the CH2 of succinate and the CH3 of acetate when the resting cells were metabolizing [1-13C]glucose and unlabeled glycogen were precisely quantified by using 13C-filtered spin-echo difference 1H NMR spectroscopy. The measured isotopic dilutions were not the same for succinate and acetate; in the case of succinate, the dilutions reflected only the contribution of glycogen futile cycling, while in the case of acetate, another mechanism was also involved. Results obtained in complementary experiments are consistent with reversal of the succinate synthesis pathway. Our results indicated that for all of the strains, from 12 to 16% of the glucose entering the metabolic pathway originated from prestored glycogen. Although genetically diverse, the four Fibrobacter strains studied had very similar carbon metabolism characteristics. PMID:12033219

  12. Energy contribution of octanoate to intact rat brain metabolism measured by 13C nuclear magnetic resonance spectroscopy.

    PubMed

    Ebert, Douglas; Haller, Ronald G; Walton, Marlei E

    2003-07-02

    Glucose is the dominant oxidative fuel for brain, but studies have indicated that fatty acids are used by brain as well. We postulated that fatty acid oxidation in brain could contribute significantly to overall energy usage and account for non-glucose-derived energy production. [2,4,6,8-13C4]octanoate oxidation in intact rats was determined by nuclear magnetic resonance spectroscopy. We found that oxidation of 13C-octanoate in brain is avid and contributes approximately 20% to total brain oxidative energy production. Labeling patterns of glutamate and glutamine were distinct, and analysis of these metabolites indicated compartmentalized oxidation of octanoate in brain. Examination of liver and blood spectra revealed that label from 13C-octanoate was incorporated into glucose and ketones, which enabled calculation of its overall energy contribution to brain metabolism: glucose (predominantly unlabeled) and 13C-labeled octanoate can account for the entire oxidative metabolism of brain. Additionally, flux through anaplerotic pathways relative to tricarboxylic acid cycle flux (Y) was calculated to be 0.08 +/- 0.039 in brain, indicating that anaplerotic flux is significant and should be considered when assessing brain metabolism. Y was associated with the glutamine synthesis compartment, consistent with the view that anaplerotic flux occurs primarily in astrocytes.

  13. Effect of tacticity on the segmental dynamics of polypropylene melts investigated by 13C nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Lippow, S. M.; Qiu, XiaoHua; Ediger, M. D.

    2001-09-01

    13C nuclear magnetic resonance (NMR) T1 and nuclear Overhauser effect measurements are reported for syndiotactic and isotactic polypropylene from their melting points to 525 K. These results indicate that the segmental dynamics of syndiotactic polypropylene are 1.7 times slower than for isotactic polypropylene at 500 K. Recent molecular dynamics computer simulations [Antoniadis, Samara, and Theodorou, Macromolecules 32, 8635 (1999)] predict this trend qualitatively but predict too large a dependence of dynamics upon tacticity. The contribution of normal mode relaxation to the decay of the C-H vector autocorrelation function is significantly larger for syndiotactic polypropylene than for either isotactic or atactic polypropylene.

  14. Relativistic Force Field: Parametrization of (13)C-(1)H Nuclear Spin-Spin Coupling Constants.

    PubMed

    Kutateladze, Andrei G; Mukhina, Olga A

    2015-11-06

    Previously, we reported a reliable DU8 method for natural bond orbital (NBO)-aided parametric scaling of Fermi contacts to achieve fast and accurate prediction of proton-proton spin-spin coupling constants (SSCC) in (1)H NMR. As sophisticated NMR experiments for precise measurements of carbon-proton SSCCs are becoming more user-friendly and broadly utilized by the organic chemistry community to guide and inform the process of structure determination of complex organic compounds, we have now developed a fast and accurate method for computing (13)C-(1)H SSCCs. Fermi contacts computed with the DU8 basis set are scaled using selected NBO parameters in conjunction with empirical scaling coefficients. The method is optimized for inexpensive B3LYP/6-31G(d) geometries. The parametric scaling is based on a carefully selected training set of 274 ((3)J), 193 ((2)J), and 143 ((1)J) experimental (13)C-(1)H spin-spin coupling constants reported in the literature. The DU8 basis set, optimized for computing Fermi contacts, which by design had evolved from optimization of a collection of inexpensive 3-21G*, 4-21G, and 6-31G(d) bases, offers very short computational (wall) times even for relatively large organic molecules containing 15-20 carbon atoms. The most informative SSCCs for structure determination, i.e., (3)J, were computed with an accuracy of 0.41 Hz (rmsd). The new unified approach for computing (1)H-(1)H and (13)C-(1)H SSCCs is termed "DU8c".

  15. 250 GHz CW gyrotron oscillator for dynamic nuclear polarization in biological solid state NMR

    NASA Astrophysics Data System (ADS)

    Bajaj, Vikram S.; Hornstein, Melissa K.; Kreischer, Kenneth E.; Sirigiri, Jagadishwar R.; Woskov, Paul P.; Mak-Jurkauskas, Melody L.; Herzfeld, Judith; Temkin, Richard J.; Griffin, Robert G.

    2007-12-01

    In this paper, we describe a 250 GHz gyrotron oscillator, a critical component of an integrated system for magic angle spinning (MAS) dynamic nuclear polarization (DNP) experiments at 9 T, corresponding to 380 MHz 1H frequency. The 250 GHz gyrotron is the first gyro-device designed with the goal of seamless integration with an NMR spectrometer for routine DNP enhanced NMR spectroscopy and has operated under computer control for periods of up to 21 days with a 100% duty cycle. Following a brief historical review of the field, we present studies of the membrane protein bacteriorhodopsin (bR) using DNP enhanced multidimensional NMR. These results include assignment of active site resonances in [U- 13C, 15N]-bR and demonstrate the utility of DNP for studies of membrane proteins. Next, we review the theory of gyro-devices from quantum mechanical and classical viewpoints and discuss the unique considerations that apply to gyrotron oscillators designed for DNP experiments. We then characterize the operation of the 250 GHz gyrotron in detail, including its long-term stability and controllability. We have measured the spectral purity of the gyrotron emission using both homodyne and heterodyne techniques. Radiation intensity patterns from the corrugated waveguide that delivers power to the NMR probe were measured using two new techniques to confirm pure mode content: a thermometric approach based on the temperature-dependent color of liquid crystalline media applied to a substrate and imaging with a pyroelectric camera. We next present a detailed study of the mode excitation characteristics of the gyrotron. Exploration of the operating characteristics of several fundamental modes reveals broadband continuous frequency tuning of up to 1.8 GHz as a function of the magnetic field alone, a feature that may be exploited in future tunable gyrotron designs. Oscillation of the 250 GHz gyrotron at the second harmonic of cyclotron resonance begins at extremely low beam currents (as

  16. 250 GHz CW Gyrotron Oscillator for Dynamic Nuclear Polarization in Biological Solid State NMR

    PubMed Central

    Bajaj, Vikram S.; Hornstein, Melissa K.; Kreischer, Kenneth E.; Sirigiri, Jagadishwar R.; Woskov, Paul P.; Mak-Jurkauskas, Melody L.; Herzfeld, Judith; Temkin, Richard J.; Griffin, Robert G.

    2009-01-01

    In this paper, we describe a 250 GHz gyrotron oscillator, a critical component of an integrated system for magic angle spinning (MAS) dynamic nuclear polarization (DNP) experiments at 9T, corresponding to 380 MHz 1H frequency. The 250 GHz gyrotron is the first gyro-device designed with the goal of seamless integration with an NMR spectrometer for routine DNP-enhanced NMR spectroscopy and has operated under computer control for periods of up to 21 days with a 100% duty cycle. Following a brief historical review of the field, we present studies of the membrane protein bacteriorhodopsin (bR) using DNP-enhanced multidimensional NMR. These results include assignment of active site resonances in [U-13C,15N]-bR and demonstrate the utility of DNP for studies of membrane proteins. Next, we review the theory of gyro-devices from quantum mechanical and classical viewpoints and discuss the unique considerations that apply to gyrotron oscillators designed for DNP experiments. We then characterize the operation of the 250 GHz gyrotron in detail, including its long-term stability and controllability. We have measured the spectral purity of the gyrotron emission using both homodyne and heterodyne techniques. Radiation intensity patterns from the corrugated waveguide that delivers power to the NMR probe were measured using two new techniques to confirm pure mode content: a thermometric approach based on the temperature-dependent color of liquid crystalline media applied to a substrate and imaging with a pyroelectric camera. We next present a detailed study of the mode excitation characteristics of the gyrotron. Exploration of the operating characteristics of several fundamental modes reveals broadband continuous frequency tuning of up to 1.8 GHz as a function of the magnetic field alone, a feature that may be exploited in future tunable gyrotron designs. Oscillation of the 250 GHz gyrotron at the second harmonic of cyclotron resonance begins at extremely low beam currents (as low

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

    PubMed

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

    2015-05-18

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

  18. 13C Nuclear magnetic resonance studies of kerogen from Cretaceous black shales thermally altered by basaltic intrusions and laboratory simulations

    USGS Publications Warehouse

    Dennis, L.W.; Maciel, G.E.; Hatcher, P.G.; Simoneit, B.R.T.

    1982-01-01

    Cretaceous black shales from DSDP Leg 41, Site 368 in the Eastern Atlantic Ocean were thermally altered during the Miocene by an intrusive basalt. The sediments overlying and underlying the intrusive body were subjected to high temperatures (up to ~ 500??C) and, as a result, their kerogen was significantly altered. The extent of this alteration has been determined by examination by means of 13C nuclear magnetic resonance, using cross polarization/magic-angle spinning (CP/MAS). Results indicate that the kerogen becomes progressively more aromatic in the vicinity of the intrusive body. Laboratory heating experiments, simulating the thermal effects of the basaltic intrusion, produced similar results on unaltered shale from the drill core. The 13C CP/MAS results appear to provide a good measure of thermal alteration. ?? 1982.

  19. Infrared and 13C MAS nuclear magnetic resonance spectroscopic study of acetylation of cotton

    NASA Astrophysics Data System (ADS)

    Adebajo, Moses O.; Frost, Ray L.

    2004-01-01

    The acetylation of commercial cotton samples with acetic anhydride without solvents in the presence of about 5% 4-dimethylaminopyridine (DMAP) catalyst was followed using Fourier transform infrared (FTIR) and 13C MAS NMR spectroscopy. This preliminary investigation was conducted in an effort to develop hydrophobic, biodegradable, cellulosic materials for subsequent application in oil spill cleanup. The FTIR results provide clear evidence for successful acetylation though the NMR results indicate that the level of acetylation is low. Nevertheless, the overall results indicate that cotton fibres are potential candidates suitable for further development via acetylation into hydrophobic sorbent materials for subsequent oil spill cleanup application. The results also indicate that de-acetylation, the reverse of the equilibrium acetylation reaction, occurred when the acetylation reaction was prolonged beyond 3 h.

  20. Investigation of reflective electrochromic all-solid-state devices by Nuclear Reaction Analysis

    NASA Astrophysics Data System (ADS)

    Bange, Klaus; Ottermann, Clemens R.; Wagner, Wolfgang; Rauch, Friedrich

    1990-08-01

    Electrochromic all-solid-state devices (ASSD) produced by reactive evaporation have been investigated by iaeans of reflectance measurements in the VIS/NIR range and cyclovoltammetry. Hydrogen depth proil were then by a NRA-technique employing the resonant reaction H( N, ar) C. Two different types of designs have been characterized. The electrochromic behaviour of ASSD's can not be described by models based on H transport for devices containing only W03 layers as active materials. Using NiOXH films as electrochromic substances, the injected/ejected charge corelates with changes in the H content.

  1. Solid-State Nuclear Magnetic Resonance Investigation of the Structural Topology and Lipid Interactions of a Viral Fusion Protein Chimera Containing the Fusion Peptide and Transmembrane Domain.

    PubMed

    Yao, Hongwei; Lee, Myungwoon; Liao, Shu-Yu; Hong, Mei

    2016-12-13

    The fusion peptide (FP) and transmembrane domain (TMD) of viral fusion proteins play important roles during virus-cell membrane fusion, by inducing membrane curvature and transient dehydration. The structure of the water-soluble ectodomain of viral fusion proteins has been extensively studied crystallographically, but the structures of the FP and TMD bound to phospholipid membranes are not well understood. We recently investigated the conformations and lipid interactions of the separate FP and TMD peptides of parainfluenza virus 5 (PIV5) fusion protein F using solid-state nuclear magnetic resonance. These studies provide structural information about the two domains when they are spatially well separated in the fusion process. To investigate how these two domains are structured relative to each other in the postfusion state, when the ectodomain forms a six-helix bundle that is thought to force the FP and TMD together in the membrane, we have now expressed and purified a chimera of the FP and TMD, connected by a Gly-Lys linker, and measured the chemical shifts and interdomain contacts of the protein in several lipid membranes. The FP-TMD chimera exhibits α-helical chemical shifts in all the membranes examined and does not cause strong curvature of lamellar membranes or membranes with negative spontaneous curvature. These properties differ qualitatively from those of the separate peptides, indicating that the FP and TMD interact with each other in the lipid membrane. However, no (13)C-(13)C cross peaks are observed in two-dimensional correlation spectra, suggesting that the two helices are not tightly associated. These results suggest that the ectodomain six-helix bundle does not propagate into the membrane to the two hydrophobic termini. However, the loosely associated FP and TMD helices are found to generate significant negative Gaussian curvature to membranes that possess spontaneous positive curvature, consistent with the notion that the FP-TMD assembly may

  2. Catabolism of Glucose and Lactose in Bifidobacterium animalis subsp. lactis, Studied by 13C Nuclear Magnetic Resonance

    PubMed Central

    González-Rodríguez, Irene; Gaspar, Paula; Sánchez, Borja; Gueimonde, Miguel; Neves, Ana Rute

    2013-01-01

    Bifidobacteria are widely used as probiotics in several commercial products; however, to date there is little knowledge about their carbohydrate metabolic pathways. In this work, we studied the metabolism of glucose and lactose in the widely used probiotic strain Bifidobacterium animalis subsp. lactis BB-12 by in vivo 13C nuclear magnetic resonance (NMR) spectroscopy. The metabolism of [1-13C]glucose was characterized in cells grown in glucose as the sole carbon source. Moreover, the metabolism of lactose specifically labeled with 13C on carbon 1 of the glucose or the galactose moiety was determined in suspensions of cells grown in lactose. These experiments allowed the quantification of some intermediate and end products of the metabolic pathways, as well as determination of the consumption rate of carbon sources. Additionally, the labeling patterns in metabolites derived from the metabolism of glucose specifically labeled with 13C on carbon 1, 2, or 3 in cells grown in glucose or lactose specifically labeled in carbon 1 of the glucose moiety ([1-13Cglucose]lactose), lactose specifically labeled in carbon 1 of the galactose moiety ([1-13Cgalactose]lactose), and [1-13C]glucose in lactose-grown cells were determined in cell extracts by 13C NMR. The NMR analysis showed that the recovery of carbon was fully compatible with the fructose 6-phosphate, or bifid, shunt. The activity of lactate dehydrogenase, acetate kinase, fructose 6-phosphate phosphoketolase, and pyruvate formate lyase differed significantly between glucose and lactose cultures. The transcriptional analysis of several putative glucose and lactose transporters showed a significant induction of Balat_0475 in the presence of lactose, suggesting a role for this protein as a lactose permease. This report provides the first in vivo experimental evidence of the metabolic flux distribution in the catabolic pathway of glucose and lactose in bifidobacteria and shows that the bifid shunt is the only pathway

  3. Carbon isotopic composition (δ(13)C and (14)C activity) of plant samples in the vicinity of the Slovene nuclear power plant.

    PubMed

    Sturm, Martina; Vreča, Polona; Krajcar Bronić, Ines

    2012-08-01

    δ(13)C values of various plants (apples, wheat, and maize) collected in the vicinity of the Krško Nuclear Power Plant (Slovenia) during 2008 and 2009 were determined. By measuring dried samples and their carbonized counterparts we showed that no significant isotopic fractionation occurs during the carbonization phase of the sample preparation process in the laboratory. The measured δ(13)C values of the plants were used for δ(13)C correction of their measured (14)C activities.

  4. Preparation of Mo-Re-C samples containing Mo7Re13C with the β-Mn-type structure by solid state reaction of planetary-ball-milled powder mixtures of Mo, Re and C, and their crystal structures and superconductivity

    NASA Astrophysics Data System (ADS)

    Oh-ishi, Katsuyoshi; Nagumo, Kenta; Tateishi, Kazuya; Takafumi, Ohnishi; Yoshikane, Kenta; Sugiyama, Machiko; Oka, Kengo; Kobayashi, Ryota

    2017-01-01

    Mo-Re-C compounds containing Mo7Re13C with the β-Mn structure were synthesized with high-melting-temperature metals Mo, Re, and C powders using a conventional solid state method with a planetary ball milling machine instead of the arc melting method. Use of the ball milling machine was necessary to obtain Mo7Re13C with the β-Mn structure using the solid state method. Almost single-phase Mo7Re13C with a trace of impurity were obtained using the synthesis method. By XRF and lattice parameter measurements on the samples, Fe element existed in the compound synthesized using the planetary ball milling machine with a pot and balls made of steel, though Fe element was not detected in the compound synthesized using a pot and balls made of tungsten carbide. The former compound containg the Fe atom did not show superconductivity but the latter compound without the Fe atom showed superconductivity at 6.1 K.

  5. Comparison of structure in solid state of new 1,5- bis(4-cyano-2,6-dimethoxyphenoxy)alkanes by means of 13C CP/MAS NMR and X-ray diffraction

    NASA Astrophysics Data System (ADS)

    Żabiński, Jerzy; Wolska, Irena; Maciejewska, Dorota

    2007-05-01

    The synthesis and structural studies in solid state of new 1,5- bis(4-cyano-2,6-dimethoxyphenoxy)-3-oxapentane 1 and 1,5- bis(4-cyano-2,6-methoxyphenoxy)pentane 2 are presented. The observed complicated network of intermolecular interaction with participation of nitrile groups could play a role in their interaction with the biological target. In vitro screen against 60 human tumor cell lines revealed that compound 1 has promising growth inhibitory power GI 50 against SR (leukemia) and HOP-92 (non-small lung cancer) equal to 4.33 ×10 -6 and 1.03 ×10 -5 M, respectively.

  6. Conformation of alamethicin in oriented phospholipid bilayers determined by (15)N solid-state nuclear magnetic resonance.

    PubMed Central

    Bak, M; Bywater, R P; Hohwy, M; Thomsen, J K; Adelhorst, K; Jakobsen, H J; Sørensen, O W; Nielsen, N C

    2001-01-01

    The conformation of the 20-residue antibiotic ionophore alamethicin in macroscopically oriented phospholipid bilayers has been studied using (15)N solid-state nuclear magnetic resonance (NMR) spectroscopy in combination with molecular modeling and molecular dynamics simulations. Differently (15)N-labeled variants of alamethicin and an analog with three of the alpha-amino-isobutyric acid residues replaced by alanines have been investigated to establish experimental structural constraints and determine the orientation of alamethicin in hydrated phospholipid (dimyristoylphosphatidylcholine) bilayers and to investigate the potential for a major kink in the region of the central Pro(14) residue. From the anisotropic (15)N chemical shifts and (1)H-(15)N dipolar couplings determined for alamethicin with (15)N-labeling on the Ala(6), Val(9), and Val(15) residues and incorporated into phospholipid bilayer with a peptide:lipid molar ratio of 1:8, we deduce that alamethicin has a largely linear alpha-helical structure spanning the membrane with the molecular axis tilted by 10-20 degrees relative to the bilayer normal. In particular, we find compatibility with a straight alpha-helix tilted by 17 degrees and a slightly kinked molecular dynamics structure tilted by 11 degrees relative to the bilayer normal. In contrast, the structural constraints derived by solid-state NMR appear not to be compatible with any of several model structures crossing the membrane with vanishing tilt angle or the earlier reported x-ray diffraction structure (Fox and Richards, Nature. 300:325-330, 1982). The solid-state NMR-compatible structures may support the formation of a left-handed and parallel multimeric ion channel. PMID:11509381

  7. Chemical characterization of pigment gallstones using /sup 13/C nuclear magnetic resonance analysis

    SciTech Connect

    Woolfenden, W.R.; Grant, D.M.; Straight, R.C.; Englert, E. Jr.

    1982-07-30

    The unique ability of Carbon-13 nuclear magnetic resonance analysis with cross polarization/magic angle spinning techniques to investigate chemical structures of solids is used to probe the chemical characteristics of several gallstone types. New pulse program techniques are used to distinguish various carbon atoms in studying the polymeric nature of the black bilirubinoid pigment of pigment gallstones. Evidence for the involvement of the carboxyl group and noninvolvement of vinyl groups of bilirubinoids in the polymeric bond formation is presented. Conjugated bilirubin structures are found to be present in some solid residues from pigment stones extracted with acidic methanol/chloroform.

  8. Electron-Nuclear Spin Dynamics in a Mesoscopic Solid-State Quantum Computer

    SciTech Connect

    Berman, G.P.; Campbell, D.K.; Doolen, G.D.; Nagaev, K.E.

    1998-12-07

    We numerically simulate the process of nuclear spin measurement in Kane's quantum computer. For this purpose, we model the quantum dynamics of two coupled nuclear spins located on {sup 31}P donors implanted in Si. We estimate the minimum time of measurement necessary for the reliable transfer of quantum information from the nuclear spin subsystem to the electronic one and the probability of error for typical values of external noise.

  9. Towards the characterization of silicon surfaces: Solid state nuclear magnetic resonance studies

    NASA Astrophysics Data System (ADS)

    Caylor, Rebecca Anne

    One of the developing areas in silicon chemistry is in small silicon particles, primarily the nanoparticles regime. When on the 'nano' scale, silicon possesses very different properties and characteristics from bulk silicon. These properties include novel optical and electronic properties that are size dependent. Semiconductor nanoparticles possess a unique bright photoluminescence when in the nanoparticle regime. The photoluminescence in the nanoparticle regime answers the problem of inefficient emissions, which have previously been a problem in bulk silicon, for use in solar cells. Nanoparticle silicon (np-Si) is also biocompatible, allowing for the use in various biological applications including biological tracers, biosensors, delivery of medicine, as well as many others. Although np-Si is widely used, its surface structure still remains largely debated. The surface structure of np-Si is of critical importance as it affects the reactivity of the sample as well as the properties the samples possess. Relative to other silicon samples, np-Si lends itself to be studied by solid state NMR due to its higher surface area, although other types of silicon samples have been studied to some degree in this dissertation project. The surface structure and adjacent interior of np-Si, obtained as commercially available silicon nanopowder, were studied in this project using multinuclear, solid-state NMR spectroscopy. The results are consistent with an overall picture in which the bulk of the np-Si interior consists of highly ordered ('crystalline') silicon atoms, each bound tetrahedrally to four other silicon atoms. From a combination of 1H and 29Si magic-angle-spinning (MAS) NMR results and quantum mechanical 29Si chemical shift calculations, silicon atoms on the surface of 'as-received' np-Si were found to exist in a variety of chemical structures, including primarily structures of the types (Si-O-)n(Si-) 3-nSi-H (with n = 1--3) and (Si-O-)2Si(H)OH, where Si stands for a

  10. Partitioning of main and side-chain units between different phases: a solid-state 13C NMR inversion-recovery cross-polarization study on a homogeneous, metallocene-based, ethylene-1-octene copolymer.

    PubMed

    Litvinov, Victor M; Mathot, Vincent B F

    2002-01-01

    13C NMR inversion-recovery cross-polarization experiments are used to study the phase structure and partitioning of main and side-chain groups in a homogeneous, metallocene-based, ethylene-1-octene copolymer. The results provide strong evidence for a three-phase model, i.e. a rigid, (imperfect) crystalline phase, which is mainly composed of long sequences of methylene carbon atoms of the main chain, a semi-rigid, amorphous interphase (also denoted as 'rigid amorphous'), which is enriched by chain segments bearing methylene and methine carbon atoms of the main chain, and a soft fraction of the amorphous phase (also denoted as 'mobile amorphous'), which is largely composed of side chains and short methylene sequences of the main chain.

  11. Properties of mixtures of cholesterol with phosphatidylcholine or with phosphatidylserine studied by (13)C magic angle spinning nuclear magnetic resonance.

    PubMed Central

    Epand, Richard M; Bain, Alex D; Sayer, Brian G; Bach, Diana; Wachtel, Ellen

    2002-01-01

    The behavior of cholesterol is different in mixtures with phosphatidylcholine as compared with phosphatidylserine. In (13)C cross polarization/magic angle spinning nuclear magnetic resonance spectra, resonance peaks of the vinylic carbons of cholesterol are a doublet in samples containing 0.3 or 0.5 mol fraction cholesterol with 1-palmitoyl-2-oleoyl phosphatidylserine (POPS) or in cholesterol monohydrate crystals, but a singlet with mixtures of cholesterol and 1-palmitoyl-2-oleoyl phosphatidylcholine (POPC). At these molar fractions of cholesterol with POPS, resonances of the C-18 of cholesterol appear at the same chemical shifts as in pure cholesterol monohydrate crystals. These resonances do not appear in samples of POPS with 0.2 mol fraction cholesterol or with POPC up to 0.5 mol fraction cholesterol. In addition, there is another resonance from the cholesterol C18 that appears in all of the mixtures of phospholipid and cholesterol but not in pure cholesterol monohydrate crystals. Using direct polarization, the fraction of cholesterol present as crystallites in POPS with 0.5 mol fraction cholesterol is found to be 80%, whereas with the same mol fraction of cholesterol and POPC none of the cholesterol is crystalline. After many hours of incubation, cholesterol monohydrate crystals in POPS undergo a change that results in an increase in the intensity of certain resonances of cholesterol monohydrate in (13)C cross polarization/magic angle spinning nuclear magnetic resonance, indicating a rigidification of the C and D rings of cholesterol but not other regions of the molecule. PMID:12324423

  12. 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.

    PubMed

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

    2011-02-01

    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.

  13. Nuclear magnetic resonance studies of solid state lithium ion battery materials

    NASA Astrophysics Data System (ADS)

    Wang, Yifeng

    1999-10-01

    A variety of materials used in lithium ion battery development have been investigated by solid State 6,7Li NMR. In lithiated hard carbon, 7Li high- resolution NMR measurements reveal two distinct insertion mechanisms, one is intercalation between disordered graphene planes and the other is covalently bonded with in amorphous hydrogen-containing regions of the carbon. The irreversible portion of the Li, which constitutes the solid electrolyte interface (SEI), was detected. 7Li NMR results of lithiated natural graphite and mildly oxidized graphite show that the SEI formation is more efficient in latter, and that there is excess reversible capacity not associated with intercalated Li. With measurements of electrochemically lithiated SnO by NMR, Li 2O and LixSn phases were detected at low and intermediate Li contents, and the Lix-2Sn alloy structure is significantly different at high Li content. 6,7Li NMR spectroscopic measurements of Li1+yCoO 2 (y = 0.08, 0.35) suggest that only a small fraction (about 10% of the excess Li) may be reversible, the remainder of the excess are various impurities. For physical mixtures of LiI and nano-scale particles of Al2O 3, the high resolution (MAS) NMR method clearly resolves two or more distinct Li+ sites, one characteristic of bulk LiI and the rest associated with surface/interface regions. Composite solid electrolytes based on PEO, LiI and high surface area inorganic oxides were investigated. The MAS NMR spectrum of a sample with a PEO/Li ratio of 3/2 is consistent with at least two Li environments, one solvated by the polymer and one in small ionic clusters at room temperature. The Li environment becomes more purely ionic as the polymer-associated peak vanishes above 80°C. 6,7Li NMR results in Li-Co-Ni-O and Li- (Cr, Fe)-Mn-O sample systems are also presented.

  14. Ultrafast control of nuclear spins using only microwave pulses: Towards switchable solid-state quantum gates

    SciTech Connect

    Mitrikas, George; Sanakis, Yiannis; Papavassiliou, Georgios

    2010-02-15

    We demonstrate the control of the {alpha}-proton nuclear spin, I =1/2, coupled to the stable radical {center_dot}CH(COOH){sub 2}, S =1/2, in a {gamma}-irradiated malonic acid single crystal using only microwave pulses. We show that, depending on the state of the electron spin (m{sub S}={+-}1/2), the nuclear spin can be locked in a desired state or oscillate between m{sub I}=+1/2 and m{sub I}=-1/2 on the nanosecond time scale. This approach provides a fast way of controlling nuclear spin qubits and also enables the design of switchable spin-based quantum gates by addressing only the electron spin.

  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.

    PubMed

    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.

  16. Perturbation approach for nuclear magnetic resonance solid-state quantum computation

    DOE PAGES

    Berman, G. P.; Kamenev, D. I.; Tsifrinovich, V. I.

    2003-01-01

    A dynmore » amics of a nuclear-spin quantum computer with a large number ( L = 1000 ) of qubits is considered using a perturbation approach. Small parameters are introduced and used to compute the error in an implementation of an entanglement between remote qubits, using a sequence of radio-frequency pulses. The error is computed up to the different orders of the perturbation theory and tested using exact numerical solution.« less

  17. Solid-state dynamic nuclear polarization at 263 GHz: spectrometer design and experimental results†

    PubMed Central

    Rosay, Melanie; Tometich, Leo; Pawsey, Shane; Bader, Reto; Schauwecker, Robert; Blank, Monica; Borchard, Philipp M.; Cauffman, Stephen R.; Felch, Kevin L.; Weber, Ralph T.; Temkin, Richard J.; Griffin, Robert G.; Maas, Werner E.

    2015-01-01

    Dynamic Nuclear Polarization (DNP) experiments transfer polarization from electron spins to nuclear spins with microwave irradiation of the electron spins for enhanced sensitivity in nuclear magnetic resonance (NMR) spectroscopy. Design and testing of a spectrometer for magic angle spinning (MAS) DNP experiments at 263 GHz microwave frequency, 400 MHz 1H frequency is described. Microwaves are generated by a novel continuous-wave gyrotron, transmitted to the NMR probe via a transmission line, and irradiated on a 3.2 mm rotor for MAS DNP experiments. DNP signal enhancements of up to 80 have been measured at 95 K on urea and proline in water–glycerol with the biradical polarizing agent TOTAPOL. We characterize the experimental parameters affecting the DNP efficiency: the magnetic field dependence, temperature dependence and polarization build-up times, microwave power dependence, sample heating effects, and spinning frequency dependence of the DNP signal enhancement. Stable system operation, including DNP performance, is also demonstrated over a 36 h period. PMID:20449524

  18. 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.

    PubMed

    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.

  19. High-resolution liquid- and solid-state nuclear magnetic resonance of nanoliter sample volumes using microcoil detectors.

    PubMed

    Kentgens, A P M; Bart, J; van Bentum, P J M; Brinkmann, A; van Eck, E R H; Gardeniers, J G E; Janssen, J W G; Knijn, P; Vasa, S; Verkuijlen, M H W

    2008-02-07

    The predominant means to detect nuclear magnetic resonance (NMR) is to monitor the voltage induced in a radiofrequency coil by the precessing magnetization. To address the sensitivity of NMR for mass-limited samples it is worthwhile to miniaturize this detector coil. Although making smaller coils seems a trivial step, the challenges in the design of microcoil probeheads are to get the highest possible sensitivity while maintaining high resolution and keeping the versatility to apply all known NMR experiments. This means that the coils have to be optimized for a given sample geometry, circuit losses should be avoided, susceptibility broadening due to probe materials has to be minimized, and finally the B(1)-fields generated by the rf coils should be homogeneous over the sample volume. This contribution compares three designs that have been miniaturized for NMR detection: solenoid coils, flat helical coils, and the novel stripline and microslot designs. So far most emphasis in microcoil research was in liquid-state NMR. This contribution gives an overview of the state of the art of microcoil solid-state NMR by reviewing literature data and showing the latest results in the development of static and micro magic angle spinning (microMAS) solenoid-based probeheads. Besides their mass sensitivity, microcoils can also generate tremendously high rf fields which are very useful in various solid-state NMR experiments. The benefits of the stripline geometry for studying thin films are shown. This geometry also proves to be a superior solution for microfluidic NMR implementations in terms of sensitivity and resolution.

  20. High-resolution liquid- and solid-state nuclear magnetic resonance of nanoliter sample volumes using microcoil detectors

    NASA Astrophysics Data System (ADS)

    Kentgens, A. P. M.; Bart, J.; van Bentum, P. J. M.; Brinkmann, A.; van Eck, E. R. H.; Gardeniers, J. G. E.; Janssen, J. W. G.; Knijn, P.; Vasa, S.; Verkuijlen, M. H. W.

    2008-02-01

    The predominant means to detect nuclear magnetic resonance (NMR) is to monitor the voltage induced in a radiofrequency coil by the precessing magnetization. To address the sensitivity of NMR for mass-limited samples it is worthwhile to miniaturize this detector coil. Although making smaller coils seems a trivial step, the challenges in the design of microcoil probeheads are to get the highest possible sensitivity while maintaining high resolution and keeping the versatility to apply all known NMR experiments. This means that the coils have to be optimized for a given sample geometry, circuit losses should be avoided, susceptibility broadening due to probe materials has to be minimized, and finally the B1-fields generated by the rf coils should be homogeneous over the sample volume. This contribution compares three designs that have been miniaturized for NMR detection: solenoid coils, flat helical coils, and the novel stripline and microslot designs. So far most emphasis in microcoil research was in liquid-state NMR. This contribution gives an overview of the state of the art of microcoil solid-state NMR by reviewing literature data and showing the latest results in the development of static and micro magic angle spinning (microMAS) solenoid-based probeheads. Besides their mass sensitivity, microcoils can also generate tremendously high rf fields which are very useful in various solid-state NMR experiments. The benefits of the stripline geometry for studying thin films are shown. This geometry also proves to be a superior solution for microfluidic NMR implementations in terms of sensitivity and resolution.

  1. Investigation of {sup 6}Li + {sup 13}C scattering and observation of a nuclear quasi-rainbow

    SciTech Connect

    Dem`yanova, A.S.; Ogloblin, A.A.; Osadchii, O.Ya.

    1994-11-01

    Differential cross sections for elastic scattering of {sup 6}Li ions by {sup 13}C at E{sub c.m.s.} = 26 MeV are measured in the range of c.m.s. angles 14 - 163{degrees} at the Kurchatov Institute cyclotron in both direct and inverse kinematics by the {Delta}E-E telescope technique. A broad maximum in the angular distribution that is exhausted completely by the far component is observed at approximately 100{degrees}. The maximum is a typical manifestation of the nuclear rainbow and can be explained by the interference of waves arriving from the two branches of the deflection function (DF). However, for the potential chosen in this study, the DF has a singularity, and nuclear-rainbow scattering cannot formally take place because there is no finite scattering angle. The observed effect, which is referred to as a quasi-rainbow, demonstrates that the principal peculiarities of elastic scattering are the same in the two energy regions that are considered in a direct semiclassical approximation as corresponding to two fundamentally different phenomena: orbiting and the rainbow. 11 refs., 4 figs., 1 tab.

  2. Influence of 13C isotopic labeling location of 13C DNP of acetate using TEMPO free radical

    NASA Astrophysics Data System (ADS)

    Parish, Christopher; Niedbalski, Peter; Lumata, Lloyd

    2015-03-01

    Dynamic nuclear polarization (DNP) via the dissolution method enhances the liquid-state magnetic resonance (NMR or MRI) signals of insensitive nuclear spins by at least 10,000-fold. The basis for all these signal enhancements at room temperature is the polarization transfer from the electrons to nuclear spins at cryogenic temperature and high magnetic field. In this work, we have studied the influence of the location of 13C isotopic labeling on the DNP of sodium acetate at 3.35 T and 1.4 K using a wide ESR linewidth free radical 4-oxo-TEMPO. The carbonyl [1-13C]acetate spins produced a polarization level that is almost twice that of the methyl [2-13C]acetate spins. On the other hand, the polarization of the methyl 13C spins doubled to reach the level of [1-13C]acetate when the methyl group was deuterated. Meanwhile, the solid-state nuclear relaxation of these samples are the same and do not correlate with the polarization levels. These behavior implies that the nuclear relaxation for these samples is dominated by the contribution from the free radicals and the polarization levels can be explained by a thermodynamic picture of DNP.

  3. Solid-State Thermionic Nuclear Power for Megawatt Propulsion, Planetary Surface and Commercial Power Project

    NASA Technical Reports Server (NTRS)

    George, Jeffrey

    2014-01-01

    Thermionic (TI) power conversion is a promising technology first investigated for power conversion in the 1960's, and of renewed interest due to modern advances in nanotechnology, MEMS, materials and manufacturing. Benefits include high conversion efficiency (20%), static operation with no moving parts and potential for high reliability, greatly reduced plant complexity, and the potential for reduced development costs. Thermionic emission, credited to Edison in 1880, forms the basis of vacuum tubes and much of 20th century electronics. Heat can be converted into electricity when electrons emitted from a hot surface are collected across a small gap. For example, two "small" (6 kWe) Thermionic Space Reactors were flown by the USSR in 1987-88 for ocean radar reconnaissance. Higher powered Nuclear-Thermionic power systems driving Electric Propulsion (Q-thruster, VASIMR, etc.) may offer the breakthrough necessary for human Mars missions of < 1 yr round trip. Power generation on Earth could benefit from simpler, moe economical nuclear plants, and "topping" of more fuel and emission efficient fossil-fuel plants.

  4. Theoretical aspects of dynamic nuclear polarization in the solid state--spin temperature and thermal mixing.

    PubMed

    Hovav, Yonatan; Feintuch, Akiva; Vega, Shimon

    2013-01-07

    Dynamic nuclear polarization is a method which allows for a dramatic increase of the NMR signals due to polarization transfer between electrons and their neighboring nuclei, via microwave irradiation. These experiments have become popular in recent years due to the ability to create hyper-polarized chemically and biologically relevant molecules, in frozen glass forming mixtures containing free radicals. Three mechanisms have been proposed for the polarization transfer between electrons and their surrounding nuclei in such non-conducting samples: the solid effect and cross effect mechanisms, which are based on quantum mechanics and relaxation on small spin systems, and thermal mixing, which originates from the thermodynamic macroscopic notion of spin temperature. We have recently introduced a spin model, which is based on the density matrix formalism and includes relaxation, and applied it to study the solid effect and cross effect mechanisms on small spin systems. In this publication we use the same model to describe the thermal mixing mechanism, and the creation of spin temperature. This is obtained without relying on the spin temperature formalism. Simulations of small model systems are used on systems with homogeneously and inhomogeneously broadened EPR lines. For the case of a homogeneously broadened line we show that the nuclear enhancement results from the thermal mixing and solid effect mechanisms, and that spin temperatures are created in the system. In the inhomogeneous case the enhancements are attributed to the solid effect and cross effect mechanisms, but not thermal mixing.

  5. Crystal structure solid-state cross polarization magic angle spinning 13C NMR correlation in luminescent d10 metal-organic frameworks constructed with the 1,2-Bis(1,2,4-triazol-4-yl)ethane ligand.

    PubMed

    Habib, Hesham A; Hoffmann, Anke; Höppe, Henning A; Steinfeld, Gunther; Janiak, Christoph

    2009-03-02

    Hydrothermal reactions of 1,2-bis(1,2,4-triazol-4-yl)ethane (btre) with copper(II), zinc(II), and cadmium(II) salts have yielded the dinuclear complexes [Zn2Cl4(mu2-btre)2] (1) and [Zn2Br4(mu2-btre)2] (2), the one-dimensional coordination polymer infinity1[Zn(NCS)2(2-btre)] (3), the two-dimensional networks infinity2[Cu2(mu2-Cl)2(mu4-btre)] (4), infinity2[Cu2(mu2-Br)2(mu4-btre)] (5), and infinity2{[Cd6(mu3-OH)2(mu3-SO4)4(mu4-btre)3(H2O)6](SO4).6H2O} (6), and the three-dimensional frameworks infinity3{[Cu(mu4-btre)]ClO4.0.25H2O} (7), 3{[Zn(mu4-btre)(mu2-btre)](ClO4)2} (8), infinity3{[Cd(mu4-btre)(mu2-btre)](ClO4)2} (9), and infinity3[Cu2(mu2-CN)2(mu4-btre)] (10, 2-fold 3D interpenetrated framework). The copper-containing products 4, 5, 7, and 10 contain the metal in the +1 oxidation state, from a simultaneous redox and self-assembly reaction of the Cu(II) starting materials. The cyanide-containing framework 10 has captured the CN- ions from the oxidative btre decomposition. The perchlorate frameworks 7, 8, or 9 react in an aqueous NH4+PF6- solution with formation of the related PF6--containing frameworks. The differences in the metal-btre bridging mode (mu2-kappaN1:N1', mu2-kappaN1:N2 or mu4-kappaN1:N2:N1':N2') and the btre ligand symmetry can be correlated with different signal patterns in the 13C cross polarization magic angle spinning (CPMAS) NMR spectra. Compounds 2, 4, 5 and 7 to 10 exhibit fluorescence at 403-481 nm upon excitation at 270-373 nm which is not seen in the free btre ligand.

  6. Potential traceable markers of organic matter in organic and conventional dairy manure using ultraviolet–visible and solid-state 13C nuclear magnetic resonance spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Organic dairy (OD) production is drawing increasing attention because of public concerns about food safety, animal welfare and the potential environmental impacts of conventional dairy (CD) systems. However, very limited information is available on how organic farming practices affect the chemical ...

  7. Membranes, peptides, and disease: unraveling the mechanisms of viral proteins with solid state nuclear magnetic resonance spectroscopy.

    PubMed

    Eddy, Matthew T; Yu, Tsyr-Yan

    2014-01-01

    The interplay between peptides and lipid bilayers drives crucial biological processes. For example, a critical step in the replication cycle of enveloped viruses is the fusion of the viral membrane and host cell endosomal membrane, and these fusion events are controlled by viral fusion peptides. Thus such membrane-interacting peptides are of considerable interest as potential pharmacological targets. Deeper insight is needed into the mechanisms by which fusion peptides and other viral peptides modulate their surrounding membrane environment, and also how the particular membrane environment modulates the structure and activity of these peptides. An important step toward understanding these processes is to characterize the structure of viral peptides in environments that are as biologically relevant as possible. Solid state nuclear magnetic resonance (ssNMR) is uniquely well suited to provide atomic level information on the structure and dynamics of both membrane-associated peptides as well as the lipid bilayer itself; further ssNMR can delineate the contribution of specific membrane components, such as cholesterol, or changing cellular conditions, such as a decrease in pH on membrane-associating peptides. This paper highlights recent advances in the study of three types of membrane associated viral peptides by ssNMR to illustrate the more general power of ssNMR in addressing important biological questions involving membrane proteins.

  8. Calcium silicate hydrates investigated by solid-state high resolution {sup 1}H and {sup 29}Si nuclear magnetic resonance

    SciTech Connect

    Meducin, Fabienne . E-mail: meducin@cnrs-orleans.fr; Bresson, Bruno; Lequeux, Nicolas; Noirfontaine, Marie-Noelle de; Zanni, Helene

    2007-05-15

    This work focuses on phases formed during cement hydration under high pressure and temperature: portlandite Ca(OH){sub 2} (CH); hillebrandite Ca{sub 2}(SiO{sub 3})(OH){sub 2} ({beta}-dicalcium silicate hydrate); calcium silicate hydrate (C-S-H); jaffeite Ca{sub 6}(Si{sub 2}O{sub 7})(OH){sub 6} (tricalcium silicate hydrate); {alpha}-C{sub 2}SH Ca{sub 2}(SiO{sub 3})(OH){sub 2} ({alpha}-dicalcium silicate hydrate); xonotlite Ca{sub 6}(Si{sub 6}O{sub 17})(OH){sub 2} and kilchoanite Ca{sub 6}(SiO{sub 4})(Si{sub 3}O{sub 10}). Portlandite and hillebrandite were synthesized and characterised by high resolution solid-state {sup 1}H and {sup 29}Si Nuclear Magnetic Resonance. In addition, information from the literature concerning the last five phases was gathered. In certain cases, a schematic 3D-structure could be determined. These data allow identification of the other phases present in a mixture. Their morphology was also observed by Scanning Electron Microscopy.

  9. Calibration of solid state nuclear track detectors at high energy ion beams for cosmic radiation measurements: HAMLET results

    NASA Astrophysics Data System (ADS)

    Szabó, J.; Pálfalvi, J. K.

    2012-12-01

    The MATROSHKA experiments and the related HAMLET project funded by the European Commission aimed to study the dose burden of the crew working on the International Space Station (ISS). During these experiments a human phantom equipped with several thousands of radiation detectors was exposed to cosmic rays inside and outside the ISS. Besides the measurements realized in Earth orbit, the HAMLET project included also a ground-based program of calibration and intercomparison of the different detectors applied by the participating groups using high-energy ion beams. The Space Dosimetry Group of the Centre for Energy Research (formerly Atomic Energy Research Institute) participated in these experiments with passive solid state nuclear track detectors (SSNTDs). The paper presents the results of the calibration experiments performed in the years 2008-2011 at the Heavy Ion Medical Accelerator (HIMAC) of the National Institute of Radiological Sciences (NIRS), Chiba, Japan. The data obtained serve as update and improvement for the previous calibration curves which are necessary for the evaluation of the SSNTDs exposed in unknown space radiation fields.

  10. Structural and dynamic properties of amorphous solid dispersions: the role of solid-state nuclear magnetic resonance spectroscopy and relaxometry.

    PubMed

    Paudel, Amrit; Geppi, Marco; Van den Mooter, Guy

    2014-09-01

    Amorphous solid dispersions (ASDs) are one of the frontier strategies to improve solubility and dissolution rate of poorly soluble drugs and hence tackling the growing challenges in oral bioavailability. Pharmaceutical performance, physicochemical stability, and downstream processability of ASD largely rely on the physical structure of the product. This necessitates in-depth characterization of ASD microstructure. Solid-state nuclear magnetic resonance (SS-NMR) techniques bear the ultimate analytical capabilities to provide the molecular level information on the dynamics and phase compositions of amorphous dispersions. SS-NMR spectroscopy/relaxometry, as a single and nondestructive technique, can reveal diverse and critical structural information of complex ASD formulations that are barely amenable from any other existing technique. The purpose of the current article is to review the recent most important studies on various sophisticated and information-rich one-dimensional and two-dimensional SS-NMR spectroscopy/relaxometry for the analysis of molecular mobility, miscibility, drug-carrier interactions, crystallinity, and crystallization in ASD. Some specific examples on microstructural elucidations of challenging ASD using multidimensional and multinuclear SS-NMR are presented. Additionally, some relevant examples on the utility of solution-NMR and NMR-imaging techniques for the investigation of the dissolution behavior of ASD are gathered.

  11. Progress in spin dynamics solid-state nuclear magnetic resonance with the application of Floquet-Magnus expansion to chemical shift anisotropy.

    PubMed

    Mananga, Eugene Stephane

    2013-01-01

    The purpose of this article is to present an historical overview of theoretical approaches used for describing spin dynamics under static or rotating experiments in solid state nuclear magnetic resonance. The article gives a brief historical overview for major theories in nuclear magnetic resonance and the promising theories. We present the first application of Floquet-Magnus expansion to chemical shift anisotropy when irradiated by BABA pulse sequence.

  12. Progress in Spin Dynamics Solid-State Nuclear Magnetic Resonance with the Application of Floquet-Magnus Expansion to Chemical Shift Anisotropy

    PubMed Central

    Mananga, Eugene Stephane

    2013-01-01

    The purpose of this article is to present an historical overview of theoretical approaches used for describing spin dynamics under static or rotating experiments in solid state nuclear magnetic resonance. The article gives a brief historical overview for major theories in nuclear magnetic resonance and the promising theories. We present the first application of Floquet-Magnus expansion to chemical shift anisotropy when irradiated by BABA pulse sequence. PMID:23711337

  13. 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

    NASA Astrophysics Data System (ADS)

    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.

  14. Biosynthetic Pathway of Citrinin in the Filamentous Fungus Monascus ruber as Revealed by 13C Nuclear Magnetic Resonance

    PubMed Central

    Hajjaj, Hassan; Klaébé, Alain; Loret, Marie O.; Goma, Gérard; Blanc, Philippe J.; François, Jean

    1999-01-01

    Carbon isotope distribution of [13C]citrinin from Monascus ruber incubated with [13C]acetate revealed that the biosynthesis of the toxin originated from a tetraketide, instead of a pentaketide as has been shown for Penicillium and Aspergillus species. The production of polyketide red pigments and citrinin by M. ruber may therefore be regulated at the level of the tetraketide branch point. PMID:9872798

  15. Nuclear Magnetic Resonance Shift Reagents: Abnormal 13C Shifts Produced by Complexation of Lanthanide Chelates with Saturated Amines and n-Butyl Isocyanide

    PubMed Central

    Marzin, Claude; Leibfritz, Dieter; Hawkes, Geoffrey E.; Roberts, John D.

    1973-01-01

    Lanthanide-induced shfits of 13C nuclear magnetic resonances are reported for several amines and n-butyl isocyanide. Contact contributions to such shifts, especially of β carbons, are clearly important for the chelates of Eu+3 and Pr+3. The importance of contact terms is shown to change in a rather predictable manner with the structure of the amine. PMID:16592062

  16. A solid-state nuclear magnetic resonance study of post-plasma reactions in organosilicone microwave plasma-enhanced chemical vapor deposition (PECVD) coatings.

    PubMed

    Hall, Colin J; Ponnusamy, Thirunavukkarasu; Murphy, Peter J; Lindberg, Mats; Antzutkin, Oleg N; Griesser, Hans J

    2014-06-11

    Plasma-polymerized organosilicone coatings can be used to impart abrasion resistance and barrier properties to plastic substrates such as polycarbonate. Coating rates suitable for industrial-scale deposition, up to 100 nm/s, can be achieved through the use of microwave plasma-enhanced chemical vapor deposition (PECVD), with optimal process vapors such as tetramethyldisiloxane (TMDSO) and oxygen. However, it has been found that under certain deposition conditions, such coatings are subject to post-plasma changes; crazing or cracking can occur anytime from days to months after deposition. To understand the cause of the crazing and its dependence on processing plasma parameters, the effects of post-plasma reactions on the chemical bonding structure of coatings deposited with varying TMDSO-to-O2 ratios was studied with (29)Si and (13)C solid-state magic angle spinning nuclear magnetic resonance (MAS NMR) using both single-pulse and cross-polarization techniques. The coatings showed complex chemical compositions significantly altered from the parent monomer. (29)Si MAS NMR spectra revealed four main groups of resonance lines, which correspond to four siloxane moieties (i.e., mono (M), di (D), tri (T), and quaternary (Q)) and how they are bound to oxygen. Quantitative measurements showed that the ratio of TMDSO to oxygen could shift the chemical structure of the coating from 39% to 55% in Q-type bonds and from 28% to 16% for D-type bonds. Post-plasma reactions were found to produce changes in relative intensities of (29)Si resonance lines. The NMR data were complemented by Fourier transform infrared (FTIR) spectroscopy. Together, these techniques have shown that the bonding environment of Si is drastically altered by varying the TMDSO-to-O2 ratio during PECVD, and that post-plasma reactions increase the cross-link density of the silicon-oxygen network. It appears that Si-H and Si-OH chemical groups are the most susceptible to post-plasma reactions. Coatings produced at a

  17. Characterization of fungal-degraded lime wood by X-ray diffraction and cross-polarization magic-angle-spinning 13C-nuclear magnetic resonance spectroscopy.

    PubMed

    Popescu, Carmen-Mihaela; Larsson, Per Tomas; Tibirna, Carmen Mihaela; Vasile, Cornelia

    2010-09-01

    X-ray diffraction, scanning electron microscopy (SEM), and solid-state cross-polarization magic-angle-spinning (CP/MAS) (13)C-NMR spectroscopy were applied to determine changes over time in the morphology and crystallinity of lime wood (Tilia cordata Miller) generated by the soft-rot fungi. Wood samples were inoculated with Trichoderma viride Pers for various durations up to 84 days. Structural and morphological modifications were assessed by comparing the structural features of decayed lime wood samples with references. Significant morphology changes such as defibration or small cavities were clearly observed on the SEM micrographs of lime wood samples exposed to fungi. Following the deconvolution process of the diffraction patterns, the degree of crystallinity, apparent lateral crystallite size, the proportion of crystallite interior chains, and the cellulose fraction have been determined. It was found that all crystallographic data vary with the duration of exposure to fungi. The degree of crystallinity and cellulose fraction tend to decrease, whereas the apparent lateral crystallite size and the proportion of crystallite interior chains increase with prolonged biodegradation processes. The most relevant signals in CP/MAS (13)C-NMR spectra were assigned according to literature data. The differences observed were discussed in terms of lignin and cellulose composition: by fixing the lignin reference signal intensity, the cellulose and hemicelluloses moieties showed a relative decrease compared to the lignin signals in decayed wood.

  18. Prospects for sub-micron solid state nuclear magnetic resonance imaging with low-temperature dynamic nuclear polarization.

    PubMed

    Thurber, Kent R; Tycko, Robert

    2010-06-14

    We evaluate the feasibility of (1)H nuclear magnetic resonance (NMR) imaging with sub-micron voxel dimensions using a combination of low temperatures and dynamic nuclear polarization (DNP). Experiments are performed on nitroxide-doped glycerol-water at 9.4 T and temperatures below 40 K, using a 30 mW tunable microwave source for DNP. With DNP at 7 K, a 0.5 microL sample yields a (1)H NMR signal-to-noise ratio of 770 in two scans with pulsed spin-lock detection and after 80 db signal attenuation. With reasonable extrapolations, we infer that (1)H NMR signals from 1 microm(3) voxel volumes should be readily detectable, and voxels as small as 0.03 microm(3) may eventually be detectable. Through homonuclear decoupling with a frequency-switched Lee-Goldburg spin echo technique, we obtain 830 Hz (1)H NMR linewidths at low temperatures, implying that pulsed field gradients equal to 0.4 G/d or less would be required during spatial encoding dimensions of an imaging sequence, where d is the resolution in each dimension.

  19. Quantitation of a spin polarization-induced nuclear Overhauser effect (SPINOE) between a hyperpolarized (13) C-labeled cell metabolite and water protons.

    PubMed

    Marco-Rius, Irene; Bohndiek, Sarah E; Kettunen, Mikko I; Larkin, Timothy J; Basharat, Meer; Seeley, Colm; Brindle, Kevin M

    2014-01-01

    The spin polarization-induced nuclear Overhauser effect (SPINOE) describes the enhancement of spin polarization of solvent nuclei by the hyperpolarized spins of a solute. In this communication we demonstrate that SPINOEs can be observed between [1,4-(13) C2 ]fumarate, hyperpolarized using the dissolution dynamic nuclear polarization technique, and solvent water protons. We derive a theoretical expression for the expected enhancement and demonstrate that this fits well with experimental measurements. Although the magnitude of the effect is relatively small (around 2% measured here), the SPINOE increases at lower field strengths, so that at clinically relevant magnetic fields (1.5-3 T) it may be possible to track the passage through the circulation of a bolus containing a hyperpolarized (13) C-labeled substrate through the increase in solvent water (1) H signal.

  20. Solid-state Marx based two-switch voltage modulator for the On-Line Isotope Mass Separator accelerator at the European Organization for Nuclear Research

    SciTech Connect

    Redondo, L. M.; Canacsinh, H.; Ferrao, N.; Mendes, C.; Silva, J. Fernando; Soares, R.; Schipper, J.; Fowler, A.

    2010-07-15

    A new circuit topology is proposed to replace the actual pulse transformer and thyratron based resonant modulator that supplies the 60 kV target potential for the ion acceleration of the On-Line Isotope Mass Separator accelerator, the stability of which is critical for the mass resolution downstream separator, at the European Organization for Nuclear Research. The improved modulator uses two solid-state switches working together, each one based on the Marx generator concept, operating as series and parallel switches, reducing the stress on the series stacked semiconductors, and also as auxiliary pulse generator in order to fulfill the target requirements. Preliminary results of a 10 kV prototype, using 1200 V insulated gate bipolar transistors and capacitors in the solid-state Marx circuits, ten stages each, with an electrical equivalent circuit of the target, are presented, demonstrating both the improved voltage stability and pulse flexibility potential wanted for this new modulator.

  1. Mechanism of Solid-State Thermolysis of Ammonia Boraine: 15N NMR Study Using Fast Magic-Angle Spinning and Dynamic Nuclear Polarization

    SciTech Connect

    Kobayashi, Takeshi; Gupta, Shalabh; Caporini, Marc A; Pecharsky, Vitalij K; Pruski, Marek

    2014-08-28

    The solid-state thermolysis of ammonia borane (NH3BH3, AB) was explored using state-of-the-art 15N solid-state NMR spectroscopy, including 2D indirectly detected 1H{15N} heteronuclear correlation and dynamic nuclear polarization (DNP)-enhanced 15N{1H} cross-polarization experiments as well as 11B NMR. The complementary use of 15N and 11B NMR experiments, supported by density functional theory calculations of the chemical shift tensors, provided insights into the dehydrogenation mechanism of AB—insights that have not been available by 11B NMR alone. Specifically, highly branched polyaminoborane derivatives were shown to form from AB via oligomerization in the “head-to-tail” manner, which then transform directly into hexagonal boron nitride analog through the dehydrocyclization reaction, bypassing the formation of polyiminoborane.

  2. Enhanced forensic discrimination of pollutants by position-specific isotope analysis using isotope ratio monitoring by (13)C nuclear magnetic resonance spectrometry.

    PubMed

    Julien, Maxime; Nun, Pierrick; Höhener, Patrick; Parinet, Julien; Robins, Richard J; Remaud, Gérald S

    2016-01-15

    In forensic environmental investigations the main issue concerns the inference of the original source of the pollutant for determining the liable party. Isotope measurements in geochemistry, combined with complimentary techniques for contaminant identification, have contributed significantly to source determination at polluted sites. In this work we have determined the intramolecular (13)C profiles of several molecules well-known as pollutants. By giving additional analytical parameters, position-specific isotope analysis performed by isotope ratio monitoring by (13)C nuclear magnetic resonance (irm-(13)C NMR) spectrometry gives new information to help in answering the major question: what is the origin of the detected contaminant? We have shown that isotope profiling of the core of a molecule reveals both the raw materials and the process used in its manufacture. It also can reveal processes occurring between the contamination site 'source' and the sampling site. Thus, irm-(13)C NMR is shown to be a very good complement to compound-specific isotope analysis currently performed by mass spectrometry for assessing polluted sites involving substantial spills of pollutant.

  3. Solid state amorphization kinetic of alpha lactose upon mechanical milling.

    PubMed

    Caron, Vincent; Willart, Jean-François; Lefort, Ronan; Derollez, Patrick; Danède, Florence; Descamps, Marc

    2011-11-29

    It has been previously reported that α-lactose could be totally amorphized by ball milling. In this paper we report a detailed investigation of the structural and microstructural changes by which this solid state amorphization takes place. The investigations have been performed by Powder X-ray Diffraction, Solid State Nuclear Magnetic Resonance ((13)C CP-MAS) and Differential Scanning Calorimetry. The results reveal the structural complexity of the material in the course of its amorphization so that it cannot be considered as a simple mixture made of a decreasing crystalline fraction and an increasing amorphous fraction. Heating this complexity can give rise to a fully nano-crystalline material. The results also show that chemical degradations upon heating are strongly connected to the melting process.

  4. Construction and 13C NMR signal-amplification efficiency of a dynamic nuclear polarizer at 6.4 T and 1.4 K

    NASA Astrophysics Data System (ADS)

    Kiswandhi, Andhika; Niedbalski, Peter; Parish, Christopher; Ferguson, Sarah; Taylor, David; McDonald, George; Lumata, Lloyd

    Dissolution dynamic nuclear polarization (DNP) is a rapidly emerging technique in biomedical and metabolic imaging since it amplifies the liquid-state nuclear magnetic resonance (NMR) and imaging (MRI) signals by >10,000-fold. Originally used in nuclear scattering experiments, DNP works by creating a non-Boltzmann nuclear spin distribution by transferring the high electron (γ = 28,000 MHz/T) thermal polarization to the nuclear spins via microwave irradiation of the sample at high magnetic field and low temperature. A dissolution device is used to rapidly dissolve the frozen sample and consequently produces an injectable ``hyperpolarized'' liquid at physiologically-tolerable temperature. Here we report the construction and performance evaluation of a dissolution DNP hyperpolarizer at 6.4 T and 1.4 K using a continuous-flow cryostat. The solid and liquid-state 13C NMR signal enhancement levels of 13C acetate samples doped with trityl OX063 and 4-oxo-TEMPO free radicals will be discussed and compared with the results from the 3.35 T commercial hyperpolarizer. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and Robert A. Welch Foundation Grant No. AT-1877.

  5. Quantification of the d-Ala-d-Lac-Terminated Peptidoglycan Structure in Vancomycin-Resistant Enterococcus faecalis Using a Combined Solid-State Nuclear Magnetic Resonance and Mass Spectrometry Analysis.

    PubMed

    Chang, James D; Foster, Erin E; Yang, Hao; Kim, Sung Joon

    2017-01-31

    Induction of vancomycin resistance in vancomycin-resistant enterococci (VRE) involves replacement of the d-Ala-d-Ala terminus of peptidoglycan (PG) stems with d-Ala-d-Lac, dramatically reducing the binding affinity of vancomycin for lipid II. Effects from vancomycin resistance induction in Enterococcus faecalis (ATCC 51299) were characterized using a combined solid-state nuclear magnetic resonance (NMR) and liquid chromatography-mass spectrometry (LC-MS) analysis. Solid-state NMR directly measured the total amounts of d-Lac and l,d-Ala metabolized from [2-(13)C]pyruvate, accumulated Park's nucleotide, and changes to the PG bridge-linking density during the early exponential growth phase (OD660 = 0.4) in intact whole cells of VRE. A high level of accumulation of depsipeptide-substituted Park's nucleotide consistent with the inhibition of the transglycosylation step of PG biosynthesis during the initial phase of vancomycin resistance was observed, while no changes to the PG bridge-linking density following the induction of vancomycin resistance were detected. This indicated that the attachment of the PG bridge to lipid II by the peptidyl transferases was not inhibited by the d-Ala-d-Lac-substituted PG stem structure in VRE. Compositions of mutanolysin-digested isolated cell walls of VRE grown with and without vancomycin resistance induction were determined by LC-MS. Muropeptides with PG stems terminating in d-Ala-d-Lac were found only in VRE grown in the presence of vancomycin. Percentages of muropeptides with a pentapeptide stem terminating in d-Ala-d-Lac for VRE grown in the presence of vancomycin were 26% for the midexponential phase (OD660 = 0.6) and 57% for the stationary growth phase (OD660 = 1.0). These high percentages indicate that d-Ala-d-Lac-substituted lipid II was efficiently utilized for PG biosynthesis in VRE.

  6. Fragment-based {sup 13}C nuclear magnetic resonance chemical shift predictions in molecular crystals: An alternative to planewave methods

    SciTech Connect

    Hartman, Joshua D.; Beran, Gregory J. O.; Monaco, Stephen; Schatschneider, Bohdan

    2015-09-14

    We assess the quality of fragment-based ab initio isotropic {sup 13}C chemical shift predictions for a collection of 25 molecular crystals with eight different density functionals. We explore the relative performance of cluster, two-body fragment, combined cluster/fragment, and the planewave gauge-including projector augmented wave (GIPAW) models relative to experiment. When electrostatic embedding is employed to capture many-body polarization effects, the simple and computationally inexpensive two-body fragment model predicts both isotropic {sup 13}C chemical shifts and the chemical shielding tensors as well as both cluster models and the GIPAW approach. Unlike the GIPAW approach, hybrid density functionals can be used readily in a fragment model, and all four hybrid functionals tested here (PBE0, B3LYP, B3PW91, and B97-2) predict chemical shifts in noticeably better agreement with experiment than the four generalized gradient approximation (GGA) functionals considered (PBE, OPBE, BLYP, and BP86). A set of recommended linear regression parameters for mapping between calculated chemical shieldings and observed chemical shifts are provided based on these benchmark calculations. Statistical cross-validation procedures are used to demonstrate the robustness of these fits.

  7. Towards a beyond 1 GHz solid-state nuclear magnetic resonance: External lock operation in an external current mode for a 500 MHz nuclear magnetic resonance

    NASA Astrophysics Data System (ADS)

    Takahashi, Masato; Ebisawa, Yusuke; Tennmei, Konosuke; Yanagisawa, Yoshinori; Hosono, Masami; Takasugi, Kenji; Hase, Takashi; Miyazaki, Takayoshi; Fujito, Teruaki; Nakagome, Hideki; Kiyoshi, Tsukasa; Yamazaki, Toshio; Maeda, Hideaki

    2012-10-01

    Achieving a higher magnetic field is important for solid-state nuclear magnetic resonance (NMR). But a conventional low temperature superconducting (LTS) magnet cannot exceed 1 GHz (23.5 T) due to the critical magnetic field. Thus, we started a project to replace the Nb3Sn innermost coil of an existing 920 MHz NMR (21.6 T) with a Bi-2223 high temperature superconducting (HTS) innermost coil. Unfortunately, the HTS magnet cannot be operated in persistent current mode; an external dc power supply is required to operate the NMR magnet, causing magnetic field fluctuations. These fluctuations can be stabilized by a field-frequency lock system based on an external NMR detection coil. We demonstrate here such a field-frequency lock system in a 500 MHz LTS NMR magnet operated in an external current mode. The system uses a 7Li sample in a microcoil as external NMR detection system. The required field compensation is calculated from the frequency of the FID as measured with a frequency counter. The system detects the FID signal, determining the FID frequency, and calculates the required compensation coil current to stabilize the sample magnetic field. The magnetic field was stabilized at 0.05 ppm/3 h for magnetic field fluctuations of around 10 ppm. This method is especially effective for a magnet with large magnetic field fluctuations. The magnetic field of the compensation coil is relatively inhomogeneous in these cases and the inhomogeneity of the compensation coil can be taken into account.

  8. Modeling of hydrogen/deuterium dynamics and heat generation on palladium nanoparticles for hydrogen storage and solid-state nuclear fusion.

    PubMed

    Tanabe, Katsuaki

    2016-01-01

    We modeled the dynamics of hydrogen and deuterium adsorbed on palladium nanoparticles including the heat generation induced by the chemical adsorption and desorption, as well as palladium-catalyzed reactions. Our calculations based on the proposed model reproduce the experimental time-evolution of pressure and temperature with a single set of fitting parameters for hydrogen and deuterium injection. The model we generated with a highly generalized set of formulations can be applied for any combination of a gas species and a catalytic adsorbent/absorbent. Our model can be used as a basis for future research into hydrogen storage and solid-state nuclear fusion technologies.

  9. Monolayer to interdigitated partial bilayer smectic C transition in thiophene-based spacer mesogens: X-ray diffraction and (13)C nuclear magnetic resonance studies.

    PubMed

    Kesava Reddy, M; Varathan, E; Lobo, Nitin P; Roy, Arun; Narasimhaswamy, T; Ramanathan, K V

    2015-10-06

    Mesophase organization of molecules built with thiophene at the center and linked via flexible spacers to rigid side arm core units and terminal alkoxy chains has been investigated. Thirty homologues realized by varying the span of the spacers as well as the length of the terminal chains have been studied. In addition to the enantiotropic nematic phase observed for all the mesogens, the increase of the spacer as well as the terminal chain lengths resulted in the smectic C phase. The molecular organization in the smectic phase as investigated by temperature dependent X-ray diffraction measurements revealed an interesting behavior that depended on the length of the spacer vis-a-vis the length of the terminal chain. Thus, a tilted interdigitated partial bilayer organization was observed for molecules with a shorter spacer length, while a tilted monolayer arrangement was observed for those with a longer spacer length. High-resolution solid state (13)C NMR studies carried out for representative mesogens indicated a U-shape for all the molecules, indicating that intermolecular interactions and molecular dynamics rather than molecular shape are responsible for the observed behavior. Models for the mesophase organization have been considered and the results understood in terms of segregation of incompatible parts of the mesogens combined with steric frustration leading to the observed lamellar order.

  10. High-resolution {sup 13}C nuclear magnetic resonance evidence of phase transition of Rb,Cs-intercalated single-walled nanotubes

    SciTech Connect

    Bouhrara, M.; Saih, Y.; Waagberg, T.; Goze-Bac, C.; Abou-Hamad, E.

    2011-09-01

    We present 13 C high-resolution magic-angle-turning (MAT) and magic angle spinning nuclear magnetic resonance data of Cs and Rb intercalated single walled carbon nanotubes. We find two distinct phases at different intercalation levels. A simple charge transfer is applicable at low intercalation level. The new phase at high intercalation level is accompanied by a hybridization of alkali (s) orbitals with the carbon (sp2) orbitals of the single walled nanotubes, which indicate bundle surface sites is the most probable alkali site.

  11. Atomic and nuclear polarization of /sup 12/C, /sup 13/C, and /sup 15/N by beam-foil interaction at 300--400 keV

    SciTech Connect

    Lu, F.Q.; Tang, J.Y.; Deutch, B.I.

    1982-03-01

    Induced nuclear spin polarization P by hyperfine interaction following passage of 0.5 ..mu..A 300--keV beams of /sup 12/C/sup +/, /sup 13/C/sup +/, and /sup 15/N/sup +/ through single tilted carbon foils yields Vertical BarPVertical Bar = (0.4 +- 0.8)%, (3.2 +- 0.6)%, and (5.7 +- 0.9)%, respectively. The nuclear polarizations were enhanced by passage through two tilted foils, and the sign of the polarization flipped by a simple flip of the foil direction with respect to the beam direction. From quantum-beat measurements with circularly polarized light, experimental quantum beat frequencies ..omega.. = 6790 +- 570 and 747 +- 62 MHz for the unresolved 6578--6583 A doublet in CII, and ..omega..(5667 A) = 2860 +- 240, ..omega..(5680 A) = 4810 +- 40 MHz in NII are determined.

  12. Characterization of the phosphatic mineral of the barnacle Ibla cumingi at atomic level by solid-state nuclear magnetic resonance: comparison with other phosphatic biominerals

    PubMed Central

    Reid, David G.; Mason, Matthew J.; Chan, Benny K. K.; Duer, Melinda J.

    2012-01-01

    Ibliform barnacles are among the few invertebrate animals harnessing calcium phosphate to construct hard tissue. The 31P solid-state NMR (SSNMR) signal from the shell plates of Ibla cumingi (Iblidae) is broader than that of bone, and shifted by ca 1 ppm to low frequency. 1H–31P heteronuclear correlation (HETCOR) experiments show a continuum of different phosphorus/phosphate atomic environments, close to hydrogen populations with resonance frequencies between ca 10 and 20 ppm. Associated 1H and 31P chemical shifts argue the coexistence of weakly (high 31P frequency, low 1H frequency) to more strongly (lower 31P frequency, higher 1H frequency) hydrogen-bonded hydrogen phosphate-like molecular/ionic species. There is no resolved signal from discrete OH− ions. 13C SSNMR shows chitin, protein and other organic biomolecules but, unlike bone, there are no significant atomic scale organic matrix–mineral contacts. The poorly ordered hydrogen phosphate-like iblid mineral is strikingly different, structurally and compositionally, from both vertebrate bone mineral and the more crystalline fluoroapatite of the linguliform brachiopods. It probably represents a previously poorly characterized calcium phosphate biomineral, the evolution of which may have reflected either the chemical conditions of ancestral seas or the mechanical advantages of phosphatic biomineralization over a calcium carbonate equivalent. PMID:22298816

  13. Effect of pressure on the carbon speciation in silicate glasses and melts: Insights from multi-nuclear solid-state NMR

    NASA Astrophysics Data System (ADS)

    Kim, E. J.; Fei, Y.; Lee, S. K.

    2015-12-01

    The pressure-induced structural changes in carbon-bearing silicate glasses and melts is essential to understand the changes in melt properties in the Earth interior and yield atomistic insights into the deep carbon cycle. Despite the extensive pioneering studies on carbon-bearing silicate glasses, spectroscopic and scattering studies at high pressure above ~4 GPa is limited due to the lack of suitable experimental probes. Here, we report the pressure-induced structural changes around C, Si and Al in albite and Na-trisilicate (Na2O:SiO2=1:3, NS3) glasses with varying pressure up to 8 GPa, using 27Al, 29Si and 13C solid-state high-resolution NMR. 27Al 3QMAS NMR spectra for carbon-bearing albite glasses quenched from melts at high pressure up to 6 GPa show only [4]Al environments. The FWHM of [4]Al in albite glasses increases with increasing pressure, indicating that the overall densification of albite glasses at high pressure is accompanied by an increase in the topological disorder around Al. 29Si MAS NMR spectra for NS3 glasses at high pressure up to 8 GPa show the presence of highly coordinated Si, [5,6]Si, which contributes to an increases in the total configurational disorder in the NS3 glasses with pressure. 13C MAS NMR spectra for carbon-bearing albite glasses show the presence of dominant fraction of CO2, and minor amounts of CO32-, and CO. At least three distinct carbonate species, such as [4]Si(CO3)[4]Si, [4]Si(CO3)[4]Al, and CO32- were observed. Among those species, the increase in the fraction of [4]Si(CO3)[4]Al species is most prevalent. 13C MAS NMR spectra for NS3 glasses show the presence of carbonate species. The peaks position of the carbonate species shifts to lower frequency upon compression, suggesting the pressure-induced structural distortion of CO32- in the glasses above 6 GPa. Spin-lattice (T1) relaxation time for molecular CO2 in carbon-bearing albite glasses increases with increasing pressure. T1 relaxation time for CO2 species at 6 GPa is 3

  14. Correlation between structure and fluidity of coal tar pitch fractions studied by ambient {sup 13}C and high temperature in-situ {sup 1}H nuclear magnetic resonance

    SciTech Connect

    Andresen, J.M.; Schober, H.H.; Rusinko, F.J. Jr.

    1999-07-01

    The unique properties of coal tar pitches have resulted in numerous applications for carbon products, such as binders for carbon artifacts. However, as the number of by-product coke ovens is diminishing, the design of superior binders from alternative materials or processes is sought by the carbon industry. Accordingly, structural characterization of coal tar pitches and their solvent fractions, using quantitative analytical techniques is required to successfully obtain this goal. Quantitative solid state {sup 13}C NMR has previously been shown to be a powerful technique to study the overall aromatic ring-size for coal tar pitches and their toluene insoluble (TI) fractions. The TI fraction can further be separated into its quinoline soluble part (beta-resin) and insoluble fraction (QI). Both these fractions affect the overall coking yield and especially the fluidity of the pitches. The assessment of fluidity interactions between coal tar pitch solvent fractions during heating is therefore important for the future design of pitches from untraditional sources or processes. High temperature {sup 1}H NMR is a useful technique to investigate the fluid and rigid components of pitches, especially with its interaction with coal and to quantify mesophase. However, very little work has been performed to correlate the overall fluidity behavior of pitch with the mobility of its different solubility fractions and their structure. Accordingly, this paper addresses the fluidity interactions between different pitch solvent fractions (TS, beta-resin and QI) by high temperature {sup 1}H NMR. Particularly, the fluidity studies on the beta-resin alone can verify whether this fraction becomes plastic during heating.

  15. Multinuclear solid state nuclear magnetic resonance investigation of water penetration in proton exchange membrane Nafion-117 by mechanical spinning.

    PubMed

    Sabarinathan, Venkatachalam; Wu, Zhen; Cheng, Ren-Hao; Ding, Shangwu

    2013-05-30

    (1)H, (17)O, and (19)F solid state NMR spectroscopies have been used to investigate water penetration in Nafion-117 under mechanical spinning. It is found that both (1)H and (17)O spectra depend on the orientation of the membrane with respect to the magnetic field. The intensities of the side chain (19)F spectra depend slightly on the orientation of membrane with respect to the magnetic field, but the backbone (19)F spectra do not exhibit orientation dependence. By analyzing the orientation dependent (1)H and (17)O spectra and time-resolved (1)H spectra, we show that the water loaded in Nafion-117, under high spinning speed, may penetrate into regions that are normally inaccessible by water. Water penetration is enhanced as the spinning speed is increased or the spinning time is increased. In the meantime, mechanical spinning accelerates water exchange. It is also found that water penetration by mechanical spinning is persistent; i.e., after spinning, water remains in those newly found regions. While water penetration changes the pores and channels in Nafion, (19)F spectra indicate that the chemical environments of the polymer backbone do not show change. These results provide new insights about the structure and dynamics of Nafion-117 and related materials. They are relevant to proton exchange membrane aging and offer enlightening points of view on antiaging and modification of this material for better proton conductivity. It is also interesting to view this phenomenon in the perspective of forced nanofiltration.

  16. Microstructural and nuclear magnetic resonance studies of solid-state amorphization in Al-Ti-Si composites prepared by mechanical alloying

    SciTech Connect

    Manna, I.; Nandi, P.; Bandyopadhyay, B.; Ghoshray, K.; Ghoshray, A

    2004-08-16

    Three Al{sub 30}Ti{sub 70-x} Si{sub x} (x=10, 20, 30), along with an Al-rich (Al{sub 50}Ti{sub 40}Si{sub 10}) and an Al-lean (Al{sub 10}Ti{sub 60}Si{sub 30}) elemental powder blends were subjected to mechanical alloying by high-energy planetary ball milling to yield a composite microstructure with varying proportions of amorphous and nanocrystalline intermetallic phases. Microstructural characterization at different stages of milling was carried out by X-ray diffraction, high-resolution transmission electron microscopy and energy dispersive X-ray spectroscopy. Furthermore, {sup 27}Al nuclear magnetic resonance (NMR) studies were undertaken to probe the mechanism of solid-state amorphization. Ball milling leads to alloying, nanocrystallization and partial solid-state amorphization followed/accompanied by strain-induced nucleation of nanocrystalline intermetallic phases from an amorphous solid solution. Both these amorphous and nano-intermetallic phases are associated with characteristic NMR peaks at lower frequencies (than that of pure Al). Thus, mechanical alloying of Al-Ti-Si appears a suitable technique for developing nanocrystalline intermetallic phase/compound dispersed amorphous matrix composites.

  17. Level crossing analysis of chemically induced dynamic nuclear polarization: Towards a common description of liquid-state and solid-state cases.

    PubMed

    Sosnovsky, Denis V; Jeschke, Gunnar; Matysik, Jörg; Vieth, Hans-Martin; Ivanov, Konstantin L

    2016-04-14

    Chemically Induced Dynamic Nuclear Polarization (CIDNP) is an efficient method of creating non-equilibrium polarization of nuclear spins by using chemical reactions, which have radical pairs as intermediates. The CIDNP effect originates from (i) electron spin-selective recombination of radical pairs and (ii) the dependence of the inter-system crossing rate in radical pairs on the state of magnetic nuclei. The CIDNP effect can be investigated by using Nuclear Magnetic Resonance (NMR) methods. The gain from CIDNP is then two-fold: it allows one to obtain considerable amplification of NMR signals; in addition, it provides a very useful tool for investigating elusive radicals and radical pairs. While the mechanisms of the CIDNP effect in liquids are well established and understood, detailed analysis of solid-state CIDNP mechanisms still remains challenging; likewise a common theoretical frame for the description of CIDNP in both solids and liquids is missing. Difficulties in understanding the spin dynamics that lead to the CIDNP effect in the solid-state case are caused by the anisotropy of spin interactions, which increase the complexity of spin evolution. In this work, we propose to analyze CIDNP in terms of level crossing phenomena, namely, to attribute features in the CIDNP magnetic field dependence to Level Crossings (LCs) and Level Anti-Crossings (LACs) in a radical pair. This approach allows one to describe liquid-state CIDNP; the same holds for the solid-state case where anisotropic interactions play a significant role in CIDNP formation. In solids, features arise predominantly from LACs, since in most cases anisotropic couplings result in perturbations, which turn LCs into LACs. We have interpreted the CIDNP mechanisms in terms of the LC/LAC concept. This consideration allows one to find analytical expressions for a wide magnetic field range, where several different mechanisms are operative; furthermore, the LAC description gives a way to determine CIDNP sign

  18. Solid-state configurations

    NASA Technical Reports Server (NTRS)

    Schroeder, K. G.

    1980-01-01

    Two prototype solid-state phased array systems concepts developed for the solar power satellite (SPS) are described. In both concepts, the beam was centered on the rectenna by means of phase conjugation of a pilot signal emanating from the ground. Also discussed are results of solid state studies.

  19. Solid State Division

    SciTech Connect

    Green, P.H.; Watson, D.M.

    1989-08-01

    This report contains brief discussions on work done in the Solid State Division of Oak Ridge National Laboratory. The topics covered are: Theoretical Solid State Physics; Neutron scattering; Physical properties of materials; The synthesis and characterization of materials; Ion beam and laser processing; and Structure of solids and surfaces. (LSP)

  20. Atomic-level structure characterization of biomass pre- and post-lignin treatment by dynamic nuclear polarization-enhanced solid-state NMR

    SciTech Connect

    Perras, Frederic A.; Luo, Hao; Zhang, Ximing; Mosier, Nathan S.; Pruski, Marek; Abu-Omar, Mahdi M.

    2016-12-27

    Here, lignocellulosic biomass is a promising sustainable feedstock for the production of biofuels, biomaterials, and biospecialty chemicals. However, efficient utilization of biomass has been limited by our poor understanding of its molecular structure. Here, we report a dynamic nuclear polarization (DNP)-enhanced solid-state (SS)NMR study of the molecular structure of biomass, both pre- and postcatalytic treatment. This technique enables the measurement of 2D homonuclear 13C–13C correlation SSNMR spectra under natural abundance, yielding, for the first time, an atomic-level picture of the structure of raw and catalytically treated biomass samples. We foresee that further such experiments could be used to determine structure–function relationships and facilitate the development of more efficient, and chemically targeted, biomass-conversion technologies.

  1. Crystal structures of tiotropium bromide and its monohydrate in view of combined solid-state nuclear magnetic resonance and gauge-including projector-augmented wave studies.

    PubMed

    Pindelska, Edyta; Szeleszczuk, Lukasz; Pisklak, Dariusz Maciej; Majka, Zbigniew; Kolodziejski, Waclaw

    2015-07-01

    Tiotropium bromide is an anticholinergic bronchodilator used in the management of chronic obstructive pulmonary disease. The crystal structures of this compound and its monohydrate have been previously solved and published. However, in this paper, we showed that those structures contain some major errors. Our methodology based on combination of the solid-state nuclear magnetic resonance (NMR) spectroscopy and quantum mechanical gauge-including projector-augmented wave (GIPAW) calculations of NMR shielding constants enabled us to correct those errors and obtain reliable structures of the studied compounds. It has been proved that such approach can be used not only to perform the structural analysis of a drug substance and to identify its polymorphs, but also to verify and optimize already existing crystal structures.

  2. Estimates of Oil and Gas Potential of Source Rock by 13C Nuclear Magnetic Resonance (NMR) Spectroscopy

    NASA Astrophysics Data System (ADS)

    Longbottom, T. L.; Hockaday, W. C.; Boling, K. S.; Dworkin, S. I.

    2014-12-01

    Kerogen is defined as the insoluble fraction of organic matter preserved in sediments. Due to its structural complexity, kerogen is poorly understood, yet it holds vast economic importance as petroleum source rock, and represents the largest organic carbon pool on earth. Kerogen originates from a mixture of organic biomolecules and tends to be dominated by the polymeric components of cell walls and cellular membranes, which undergo interactions with sedimentary minerals at elevated temperature and pressure upon burial. Due to the importance of burial diagenesis to petroleum formation, much of our knowledge of chemical properties of kerogens is related to diagenetic and catagenetic effects. The more common geochemical evaluations of the oil and gas potentials of source rock are based upon proximate analyses such as hydrogen and oxygen indices and thermal stability indices, such as those provided by Fisher assay and Rock Eval®. However, proximate analyses provide limited information regarding the chemical structure of kerogens, and therefore provide little insight to the processes of kerogen formation. NMR spectra of kerogen have been previously shown to be useful in estimating oil and gas potential, and the proposed study seeks to refine nuclear magnetic resonance spectroscopy as a tool in kerogen characterization, specifically for the purpose of oil and gas potential calculations.

  3. Determination of size and sign of hetero-nuclear coupling constants from 2D 19F-13C correlation spectra

    NASA Astrophysics Data System (ADS)

    Ampt, Kirsten A. M.; Aspers, Ruud L. E. G.; Dvortsak, Peter; van der Werf, Ramon M.; Wijmenga, Sybren S.; Jaeger, Martin

    2012-02-01

    Fluorinated organic compounds have become increasingly important within the polymer and the pharmaceutical industry as well as for clinical applications. For the structural elucidation of such compounds, NMR experiments with fluorine detection are of great value due to the favorable NMR properties of the fluorine nucleus. For the investigation of three fluorinated compounds, triple resonance 2D HSQC and HMBC experiments were adopted to fluorine detection with carbon and/or proton decoupling to yield F-C, F-C{H}, F-C{Cacq} and F-C{H,Cacq} variants. Analysis of E.COSY type cross-peak patterns in the F-C correlation spectra led, apart from the chemical shift assignments, to determination of size and signs of the JCH, JCF, and JHF coupling constants. In addition, the fully coupled F-C HMQC spectrum of steroid 1 was interpreted in terms of E.COSY type patterns. This example shows how coupling constants due to different nuclei can be determined together with their relative signs from a single spectrum. The analysis of cross-peak patterns, as presented here, not only provides relatively straightforward routes to the determination of size and sign of hetero-nuclear J-couplings in fluorinated compounds, it also provides new and easy ways for the determination of residual dipolar couplings and thus for structure elucidation. The examples and results presented in this study may contribute to a better interpretation and understanding of various F-C correlation experiments and thereby stimulate their utilization.

  4. Investigation of gamma radiation effect on the anion exchange resin Amberlite IRA-400 in hydroxide form by Fourier transformed infrared and 13C nuclear magnetic resonance spectroscopies.

    PubMed

    Traboulsi, A; Dupuy, N; Rebufa, C; Sergent, M; Labed, V

    2012-03-02

    Radiation-induced decomposition of the anion exchange resin Amberlite IRA-400 in hydroxide form by gamma radiolysis has been studied under different irradiation doses and irradiation atmospheres. In this work, we focused on the degradation of the solid part of the resin by Fourier transformed infrared (FTIR) and (13)C nuclear magnetic resonance (NMR) spectroscopies associated with chemometric treatments. FTIR and (13)C NMR techniques showed that only -CH(2)N(+)(CH(3))(3) groups were detached from the resin whereas the polystyrene divinylbenzene backbone remains intact. The quaternary ammonium groups were replaced by amine or carbonyl groups according to the irradiation atmosphere (with or without water or oxygen). Principal components analysis (PCA) was used to classify the degraded resins according to their irradiation conditions by separating the effect of the dose or the environment. The PCA loadings have shown spectral regions which discriminate the irradiated resins whereas SIMPLe-to-use Interactive Self-modeling Mixture Analysis (SIMPLISMA) allows to identify families of component characterizing the chemical structure of resins and estimate their relative contributions according to the irradiation atmospheres.

  5. 13C Nuclear Magnetic Resonance and Electron Paramagnetic Spectroscopic Comparison of Hydrophobic Acid, Transphilic Acid, and Reverse Osmosis May 2012 Isolates of Organic Matter from the Suwannee River

    PubMed Central

    Nwosu, Ugwumsinachi G.; Cook, Robert L.

    2015-01-01

    Abstract Dissolved organic matter (DOM) is found in most natural waters at concentrations low enough to make DOM isolation methodologies critical to full analytical characterization and preservation. During the last few decades, two major protocols have been developed for the extraction of DOM isolates from natural waters. These methods utilize XAD resins and reverse osmosis (RO). In this work, the hydrophobic acid (May 2012 HPOA) and transphilic acid (May 2012 TPIA) isolates from XAD-8 and XAD-4 resins, respectively, were compared with the RO (May 2012 RO) natural organic matter isolate of the Suwannee River water using 13C nuclear magnetic resonance (NMR) and electron paramagnetic resonance (EPR) spectroscopies. 13C NMR analysis showed that the May 2012 RO isolate could be viewed as a hybrid of the more hydrophobic May 2012 HPOA isolate and more hydrophilic May 2012 TPIA isolate. The May 2012 HPOA isolate is shown to be higher in alkyl and aromatic moieties, while the May 2012 TPIA isolate is higher in O-alkyl moieties. EPR analysis revealed that the May 2012 TPIA and, in particular, May 2012 HPOA isolates had higher radical concentrations than the May 2012 RO isolate. It is postulated that some of the radical concentrations came from the use of base during the isolation procedures, especially in the XAD method. PMID:25565761

  6. 13C-nuclear magnetic resonance spectroscopy studies of hepatic glucose metabolism in normal subjects and subjects with insulin-dependent diabetes mellitus.

    PubMed Central

    Cline, G W; Rothman, D L; Magnusson, I; Katz, L D; Shulman, G I

    1994-01-01

    To determine the effect of insulin-dependent diabetes mellitus (IDDM) on rates and pathways of hepatic glycogen synthesis, as well as flux through hepatic pyruvate dehydrogenase, we used 13C-nuclear magnetic resonance spectroscopy to monitor the peak intensity of the C1 resonance of the glucosyl units of hepatic glycogen, in combination with acetaminophen to sample the hepatic UDP-glucose pool and phenylacetate to sample the hepatic glutamine pool, during a hyperglycemic-hyperinsulinemic clamp using [1-13C]-glucose. Five subjects with poorly controlled IDDM and six age-weight-matched control subjects were clamped at a mean plasma glucose concentration of approximately 9 mM and mean plasma insulin concentrations approximately 400 pM for 5 h. Rates of hepatic glycogen synthesis were similar in both groups (approximately 0.43 +/- 0.09 mumol/ml liver min). However, flux through the indirect pathway of glycogen synthesis (3 carbon units-->-->glycogen) was increased by approximately 50% (P < 0.05), whereas the relative contribution of pyruvate oxidation to TCA cycle flux was decreased by approximately 30% (P < 0.05) in the IDDM subjects compared to the control subjects. These studies demonstrate that patients with poorly controlled insulin-dependent diabetes mellitus have augmented hepatic gluconeogenesis and relative decreased rates of hepatic pyruvate oxidation. These abnormalities are not immediately reversed by normalizing intraportal concentrations of glucose, insulin, and glucagon and may contribute to postprandial hyperglycemia. PMID:7989593

  7. (13)C-labeled biochemical probes for the study of cancer metabolism with dynamic nuclear polarization-enhanced magnetic resonance imaging.

    PubMed

    Salamanca-Cardona, Lucia; Keshari, Kayvan R

    2015-01-01

    In recent years, advances in metabolic imaging have become dependable tools for the diagnosis and treatment assessment in cancer. Dynamic nuclear polarization (DNP) has recently emerged as a promising technology in hyperpolarized (HP) magnetic resonance imaging (MRI) and has reached clinical relevance with the successful visualization of [1-(13)C] pyruvate as a molecular imaging probe in human prostate cancer. This review focuses on introducing representative compounds relevant to metabolism that are characteristic of cancer tissue: aerobic glycolysis and pyruvate metabolism, glutamine addiction and glutamine/glutamate metabolism, and the redox state and ascorbate/dehydroascorbate metabolism. In addition, a brief introduction of probes that can be used to trace necrosis, pH changes, and other pathways relevant to cancer is presented to demonstrate the potential that HP MRI has to revolutionize the use of molecular imaging for diagnosis and assessment of treatments in cancer.

  8. Detection of poly(ethylene glycol) residues from nonionic surfactants in surface water by1h and13c nuclear magnetic resonance spectrometry

    USGS Publications Warehouse

    Leenheer, J.A.; Wershaw, R. L.; Brown, P.A.; Noyes, T.I.

    1991-01-01

    ??? Poly(ethylene glycol) (PEG) residues were detected in organic solute isolates from surface water by 1H nuclear magnetic resonance spectrometry (NMR), 13C NMR spectrometry, and colorimetric assay. PEG residues were separated from natural organic solutes in Clear Creek, CO, by a combination of methylation and chromatographic procedures. The isolated PEG residues, characterized by NMR spectrometry, were found to consist of neutral and acidic residues that also contained poly(propylene glycol) moieties. The 1H NMR and the colorimetric assays for poly(ethylene glycol) residues were done on samples collected in the lower Mississippi River and tributaries between St. Louis, MO, and New Orleans, LA, in July-August and November-December 1987. Aqueous concentrations for poly(ethylene glycol) residues based on colorimetric assay ranged from undetectable to ???28 ??g/L. Concentrations based on 1H NMR spectrometry ranged from undetectable to 145 ??g/L.

  9. Gas-phase detection of solid-state fission product complexes for post-detonation nuclear forensic analysis.

    PubMed

    Stratz, S Adam; Jones, Steven A; Oldham, Colton J; Mullen, Austin D; Jones, Ashlyn V; Auxier, John D; Hall, Howard L

    2016-01-01

    This study presents the first known detection of fission products commonly found in post-detonation nuclear debris samples using solid sample introduction and a uniquely coupled gas chromatography inductively-coupled plasma time-of-flight mass spectrometer. Rare earth oxides were chemically altered to incorporate a ligand that enhances the volatility of the samples. These samples were injected (as solids) into the aforementioned instrument and detected for the first time. Repeatable results indicate the validity of the methodology, and this capability, when refined, will prove to be a valuable asset for rapid post-detonation nuclear forensic analysis.

  10. Magnetic susceptibility effects on 13C MAS NMR spectra of carbon materials and graphite.

    PubMed

    Freita, J C; Emmerich, F G; Cernicchiaro, G R; Sampaio, L C; Bonagamba, T J

    2001-01-01

    13C high-resolution solid-state nuclear magnetic resonance (NMR) was employed to study carbon materials prepared through the thermal decomposition of four different organic precursors (rice hulls, endocarp of babassu coconut, peat, and PVC). For heat treatment temperatures (HTTs) above about 600 C, all materials presented 13C NMR spectra composed of a unique resonance line associated with carbon atoms in aromatic planes. With increasing HTT a continuous broadening of this resonance and a diamagnetic shift in its central frequency were verified for all samples. The evolution of the magnitude and anisotropy of the magnetic susceptibility of the heat-treated carbon samples with HTT explains well these findings. It is shown that these results are better understood when a comparison is made with the features of the 13C NMR spectrum of polycrystalline graphite, for which the magnetic susceptibility effect is also present and is much more pronounced.

  11. Solid-state C-13 and H-1 NMR imaging stdies of the accelerated-sulfur cured high vinyl polybutadiene. [NMR (nuclear magnetic resonance)

    SciTech Connect

    Rana, M.A.

    1993-01-01

    Solid-state [sup 13]C NMR and [sup 1]H Imaging methods have been used to follow the progress of accelerated-sulfur vulcanization of unfilled high vinyl polybutadiene. Different NMR pulse sequences have been used to characterize the micro-network structures present in the bulk of the finally cured rubber samples. These studies were made as a function of formulation and processing variables. The time-resolved, integrated rubber network. Mono-sulfidic as well as the residual accelerator fragments were differentiated from the polysulfidic crosslinks in a finally cured material. Dynamic studies of these network structures were made using spin-spin relaxation (T[sub 2c]) measurements. The activation energies calculated based on T[sub 2] were used to verify different carbons, directly attached to the sulfur atoms. A swelling method based on Flory-Rehner's equation was also used to determine the crosslink densities and the number-average molecular weight between the nodal junctions in different formulations. Different spatially resolved structural features have been detected in the swollen samples using NMR imaging method. The voids, no-voids and other impurities were differentiated on the basis of magnetic susceptibility differences. Cyclohexane was used as a swelling solvent to probe the morphological defects in these materials. The T[sub 2]-weighted images were used to evaluate the crosslink densities in different samples. The quantitative estimations based on histogram was also employed to determine the average volume per crosslink region. The contrast based on H-1 spin-density or mobility was highlighted in T[sub 2]-weighted images. The variations were found to be closely related to variation in both concentration and mobility of the network.

  12. The Organic Solid State.

    ERIC Educational Resources Information Center

    Cowan, Dwaine O.; Wlygul, Frank M.

    1986-01-01

    Reviews interesting and useful electrical, magnetic, and optical properties of the organic solid state. Offers speculation as to areas of fruitful research. Discusses organic superconductors, conducting organic polymers, organic metals, and traces recent history of creation of organic metals. (JM)

  13. Solid state switch

    DOEpatents

    Merritt, Bernard T.; Dreifuerst, Gary R.

    1994-01-01

    A solid state switch, with reverse conducting thyristors, is designed to operate at 20 kV hold-off voltage, 1500 A peak, 1.0 .mu.s pulsewidth, and 4500 pps, to replace thyratrons. The solid state switch is more reliable, more economical, and more easily repaired. The switch includes a stack of circuit card assemblies, a magnetic assist and a trigger chassis. Each circuit card assembly contains a reverse conducting thyristor, a resistor capacitor network, and triggering circuitry.

  14. Solid state 31P cross-polarization/magic angle sample spinning nuclear magnetic resonance studies of crystalline glycogen phosphorylase b

    PubMed Central

    Taguchi, Jocelyn E.; Heyes, Stephen J.; Barford, David; Johnson, Louise N.; Dobson, Christopher M.

    1993-01-01

    31P cross-polarization/magic angle sample spinning nuclear magnetic resonance spectra have been obtained for pyridoxal 5′-phosphate (PLP) bound to glycogen phosphorylase b (GPb) in two different crystalline forms, monoclinic and tetragonal. Analysis of the intensities of the spinning sidebands in the nuclear magnetic resonance spectra has enabled estimates of the principal values of the 31P chemical shift tensors to be obtained. Differences between the two sets of values suggest differences in the environment of the phosphate moiety of the pyridoxal phosphate in the two crystalline forms. The tensor for the tetragonal crystalline form, T state GPb, is fully consistent with those found for dianionic phosphate groups in model compounds. The spectrum for the monoclinic crystalline form, R state GPb, although closer to that of dianionic than monoanionic model phosphate compounds, deviates significantly from that expected for a simple dianion or monoanion. This is likely to result from specific interactions between the PLP phosphate group and residues in its binding site in the protein. A possible explanation for the spectrum of the monoclinic crystals is that the shift tensor is averaged by a proton exchange process between different ionization states of the PLP associated with the presence of a sulfate ion bound in the vicinity of the PLP. PMID:8457673

  15. Thorium-229 solid-state nuclear clock prospects in MgF2 and LiSAF

    NASA Astrophysics Data System (ADS)

    Meyer, Edmund; Barker, Beau; Collins, Lee

    2016-05-01

    The 229 Th isomer is thought to be a good candidate for a nuclear clock based on its relatively low-energy isomer excitation of ~ 7 . 8 eV. We report on the study of Th atoms embedded in two crystals, MgF2 and LiSAF (LiSrAlF6). For MgF2 we perform an oxidation study to find the preferred ionization state of the Th atom in the crystal; Thn+, where n = 2 - 4 . We find that the preferred state is n = 4 which requires two interstitial Fluorine atoms to charge compensate. Using the results of MgF2 we then search within LiSAF for suitable dopant sites (the Sr, Al, or Li can all serve). Employing a standard density functional package using a plane-wave basis and psuedopotentials, we optimize a doped cell of increasing particle number sizes and use this to estimate the dilute doped-limit band-gap of LiSAF. Placement of the dopant on the Sr and Al sites with accompanying double and single F interstitial atom placements is also studied to determine the ground state, and comparisons are made with previous calculations. In both crystal ground states, we find that the band gap is large enough for the observation of the 229 Th nuclear isomer transition; > 9 eV.

  16. Determination of the 1,3- and 2-positional distribution of fatty acids in olive oil triacylglycerols by 13C nuclear magnetic resonance spectroscopy.

    PubMed

    Vlahov, Giovanna

    2006-01-01

    Linear models were selected from a large data set acquired for Italian olive oil samples by quantitative 13C nuclear magnetic resonance (NMR) spectroscopy with distortionless enhancement by polarization transfer (DEPT). The models were used to determine the composition of the 2 fatty acid pools esterifying the 1,3- and 2-positions of triacylglycerols. The linear models selected proved that the 1,3- and 2-distribution of saturated, oleate, and linoleate chains in olive oil triacylglycerols deviated from the random distribution pattern to an extent that depended on the concentration of the fatty acid in the whole triacylglycerol. To calculate the fatty acid composition of the 1,3- and 2-positions of olive oil triacylglycerols, the equations of the selected linear models were applied to the fatty acid percentages determined by gas chromatography. These data were compared with the values predicted by the computer method (used to determine the theoretical amounts of triacylglycerols), which is based on the 1,3-random-2-random theory of the fatty acid distribution in triacylglycerols. The biggest differences were found in the linoleate chain, which is the chain that deviated the most from a random distribution pattern. The results confirmed that the 1,3-random-2-random distribution theory provides an approximate method for determining the structure of triacylglycerols; however, the linear models calculated by the direct method that applies 13C NMR spectroscopy represent a more precise measurement of the composition of the 2 fatty acid pools esterifying the 1,3- and 2-positions of triacylglycerols.

  17. Wide-angle x-ray scattering and solid-state nuclear magnetic resonance data combined to test models for cellulose microfibrils in mung bean cell walls.

    PubMed

    Newman, Roger H; Hill, Stefan J; Harris, Philip J

    2013-12-01

    A synchrotron wide-angle x-ray scattering study of mung bean (Vigna radiata) primary cell walls was combined with published solid-state nuclear magnetic resonance data to test models for packing of (1→4)-β-glucan chains in cellulose microfibrils. Computer-simulated peak shapes, calculated for 36-chain microfibrils with perfect order or uncorrelated disorder, were sharper than those in the experimental diffractogram. Introducing correlated disorder into the models broaden the simulated peaks but only when the disorder was increased to unrealistic magnitudes. Computer-simulated diffractograms, calculated for 24- and 18-chain models, showed good fits to experimental data. Particularly good fits to both x-ray and nuclear magnetic resonance data were obtained for collections of 18-chain models with mixed cross-sectional shapes and occasional twinning. Synthesis of 18-chain microfibrils is consistent with a model for cellulose-synthesizing complexes in which three cellulose synthase polypeptides form a particle and six particles form a rosette.

  18. Note: Real time optical sensing of alpha-radiation emitting radioactive aerosols based on solid state nuclear track detector

    NASA Astrophysics Data System (ADS)

    Kulkarni, A.; Ha, S.; Joshirao, P.; Manchanda, V.; Bak, M. S.; Kim, T.

    2015-06-01

    A sensitive radioactive aerosols sensor has been designed and developed. Its design guidance is based on the need for a low operational cost and reliable measurements to provide daily aerosol monitoring. The exposure of diethylene-glycol bis (allylcarbonate) to radiation causes modification of its physico-chemical properties like surface roughness and reflectance. In the present study, optical sensor based on the reflectance measurement has been developed with an aim to monitor real time presence of alpha radioactive aerosols emitted from thorium nitrate hydrate. The results shows that the fabricated sensor can detect 0.0157 kBq to 0.1572 kBq of radio activity by radioactive aerosols generated from (Th(NO3)4 ṡ 5H2O) at 0.1 ml/min flow rate. The proposed instrument will be helpful to monitor radioactive aerosols in/around a nuclear facility, building construction sites, mines, and granite polishing factories.

  19. Note: Real time optical sensing of alpha-radiation emitting radioactive aerosols based on solid state nuclear track detector.

    PubMed

    Kulkarni, A; Ha, S; Joshirao, P; Manchanda, V; Bak, M S; Kim, T

    2015-06-01

    A sensitive radioactive aerosols sensor has been designed and developed. Its design guidance is based on the need for a low operational cost and reliable measurements to provide daily aerosol monitoring. The exposure of diethylene-glycol bis (allylcarbonate) to radiation causes modification of its physico-chemical properties like surface roughness and reflectance. In the present study, optical sensor based on the reflectance measurement has been developed with an aim to monitor real time presence of alpha radioactive aerosols emitted from thorium nitrate hydrate. The results shows that the fabricated sensor can detect 0.0157 kBq to 0.1572 kBq of radio activity by radioactive aerosols generated from (Th(NO3)4 ⋅ 5H2O) at 0.1 ml/min flow rate. The proposed instrument will be helpful to monitor radioactive aerosols in/around a nuclear facility, building construction sites, mines, and granite polishing factories.

  20. Note: Real time optical sensing of alpha-radiation emitting radioactive aerosols based on solid state nuclear track detector

    SciTech Connect

    Kulkarni, A.; Bak, M. S. E-mail: moonsoo@skku.edu; Ha, S.; Joshirao, P.; Manchanda, V.; Kim, T. E-mail: moonsoo@skku.edu

    2015-06-15

    A sensitive radioactive aerosols sensor has been designed and developed. Its design guidance is based on the need for a low operational cost and reliable measurements to provide daily aerosol monitoring. The exposure of diethylene-glycol bis (allylcarbonate) to radiation causes modification of its physico-chemical properties like surface roughness and reflectance. In the present study, optical sensor based on the reflectance measurement has been developed with an aim to monitor real time presence of alpha radioactive aerosols emitted from thorium nitrate hydrate. The results shows that the fabricated sensor can detect 0.0157 kBq to 0.1572 kBq of radio activity by radioactive aerosols generated from (Th(NO{sub 3}){sub 4} ⋅ 5H{sub 2}O) at 0.1 ml/min flow rate. The proposed instrument will be helpful to monitor radioactive aerosols in/around a nuclear facility, building construction sites, mines, and granite polishing factories.

  1. Local structures of mesoporous bioactive glasses and their surface alterations in vitro: inferences from solid-state nuclear magnetic resonance

    PubMed Central

    Gunawidjaja, Philips N.; Mathew, Renny; Lo, Andy Y. H.; Izquierdo-Barba, Isabel; García, Ana; Arcos, Daniel; Mattias Edén, María Vallet-Regí

    2012-01-01

    We review the benefits of using 29Si and 1H magic angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy for probing the local structures of both bulk and surface portions of mesoporous bioactive glasses (MBGs) of the CaO–SiO2−(P2O5) system. These mesoporous materials exhibit an ordered pore arrangement, and are promising candidates for improved bone and tooth implants. We discuss experimental MAS NMR results from three MBGs displaying different Ca, Si and P contents: the 29Si NMR spectra were recorded either directly by employing radio-frequency pulses to 29Si, or by magnetization transfers from neighbouring protons using cross polarization, thereby providing quantitative information about the silicate speciation present in the pore wall and at the MBG surface, respectively. The surface modifications were monitored for the three MBGs during their immersion in a simulated body fluid (SBF) for intervals between 30 min and one week. The results were formulated as a reaction sequence describing the interconversions between the distinct silicate species. We generally observed a depletion of Ca2+ ions at the MBG surface, and a minor condensation of the silicate-surface network over one week of SBF soaking. PMID:22349247

  2. Analytical continuous slowing down model for nuclear reaction cross-section measurements by exploitation of stopping for projectile energy scanning and results for 13C(3He,α)12C and 13C(3He,p)15N

    NASA Astrophysics Data System (ADS)

    Möller, S.

    2017-03-01

    Ion beam analysis is a set of precise, calibration free and non-destructive methods for determining surface-near concentrations of potentially all elements and isotopes in a single measurement. For determination of concentrations the reaction cross-section of the projectile with the targets has to be known, in general at the primary beam energy and all energies below. To reduce the experimental effort of cross-section measurements a new method is presented here. The method is based on the projectile energy reduction when passing matter of thick targets. The continuous slowing down approximation is used to determine cross-sections from a thick target at projectile energies below the primary energy by backward calculation of the measured product spectra. Results for 12C(3He,p)14N below 4.5 MeV are in rough agreement with literature data and reproduce the measured spectra. New data for reactions of 3He with 13C are acquired using the new technique. The applied approximations and further applications are discussed.

  3. /sup 13/C nuclear magnetic resonance studies of the biosynthesis by Microbacterium ammoniaphilum of L-glutamate selectively enriched with carbon-13

    SciTech Connect

    Walker, T.E.; Han, C.H.; Kollman, V.H.; London, R.E.; Matwiyoff, N.A.

    1982-02-10

    /sup 13/C NMR of isotopically enriched metabolites has been used to study the metabolism of Microbacterium ammoniaphilum, a bacterium which excretes large quantities of L-glutamic acid into the medium. Biosynthesis from 90% (1-/sup 13/C) glucose results in relatively high specificity of the label, with (2,4-/sup 13/C/sub 2/) glutamate as the major product. The predominant biosynthetic pathway for synthesis of glutamate from glucose was determined to be the Embden Meyerhof glycolytic pathway followed by P-enolpyruvate carboxylase and the first third of the Krebs cycle. Different metabolic pathways are associated with different correlations in the enrichment of the carbons, reflected in the spectrum as different /sup 13/C-/sup 13/C scalar multiplet intensities. Hence, intensity and /sup 13/C-/sup 13/C multiplet analysis allows quantitation of the pathways involved. Although blockage of the Krebs cycle at the ..cap alpha..-ketoglutarate dehydrogenase step is the basis for the accumulation of glutamate, significant Krebs cycle activity was found in glucose grown cells, and extensive Krebs cycle activity in cells metabolizing (1-/sup 13/C) acetate. In addition to the observation of the expected metabolites, the disaccharide ..cap alpha..,..cap alpha..-trehalose and ..cap alpha..,..beta..-glucosylamine were identified from the /sup 13/C NMR spectra.

  4. Soil gas radon-thoron monitoring in Dharamsala area of north-west Himalayas, India using solid state nuclear track detectors

    NASA Astrophysics Data System (ADS)

    Kumar, Gulshan; Kumar, Arvind; Walia, Vivek; Kumar, Jitender; Gupta, Vikash; Yang, Tsanyao Frank; Singh, Surinder; Bajwa, Bikramjit Singh

    2013-10-01

    The study described here is based on the measurements of soil gas radon-thoron concentrations performed at Dharamsala region of north-west (NW) Himalayas, India. The study area is tectonically and environmentally significant and shows the features of ductile shear zone due to the presence of distinct thrust planes. Solid state nuclear track detectors (LR-115 films) have been used for the soil gas radon-thoron monitoring. Twenty five radon-thoron discriminators with LR-115 films were installed in the borehole of about 50 cm in the study areas. The recorded radon concentration varies from 1593 to 13570 Bq/m3 with an average value of 5292 Bq/m3. The recorded thoron concentration varies from 223 to 2920 Bq/m3 with an average value of 901 Bq/m3. The anomalous value of radon-thoron has been observed near to the faults like main boundary thrust (MBT and MBT2) as well as neotectonic lineaments in the region.

  5. A Solid-State Study of a Novel 31P Spin Pair Using Magic-Angle-Spinning Nuclear Magnetic Resonance Spectroscopy

    NASA Astrophysics Data System (ADS)

    Challoner, R.; Mcdowell, C. A.; Yoshifuji, M.; Toyota, K.; Tossell, J. A.

    The present investigation concerns the solid-state nuclear magnetic resonance spectroscopy of the 31P spin pair in the novel three-membered heterocyclic compound 3-(dichloromethylene)- trans-1,2-bis( 2,4,6-tri- tert-butylphenyl)- 1,2-diphosphirane using the magic-angle-spinning (MAS) technique. The homogeneous 31P lineshapes are analyzed to extract the principal components of the shielding tensors using the Maricq and Waugh description of homonuclear spin-pair systems by average-Hamiltonian theory, modified to encompass the n = 0 rotational resonance situation. The experimental values of the shielding-tensor components are compared with those obtained from ab initio calculations performed on the model molecule P 2C 2H 4 to aid further the interpretation of the 31P MAS NMR spectrum of the chloromethylene-diphosphirane. The magnitudes and orientations of calculated shielding-tensor components of the model compound methylene-diphosphirane P 2C 2H 4 are compared with those for the phosphorus spin pair in the molecular environments of P 2, P 2H 2, and P 2H 4. The electronic structures and bonding in all of those molecular species are discussed.

  6. Characterization of solid state nuclear track detectors of the polyallyl-diglycol-carbonate (CR-39/PM-355) type for light charged particle spectroscopy

    SciTech Connect

    Malinowska, A. Jaskóła, M.; Korman, A.; Kuk, M.; Szydłowski, A.

    2014-12-15

    This paper presents a method which uses the characteristics of the etch pits induced in a polyallyl-diglycol-carbonate (PADC) detector of the CR-39/PM-355 type to estimate particle energy. This method is based on the data provided by a semiautomatic system that selects tracks according to two parameters, crater diameters, and mean gray level values. In this paper we used the results of the calibration measurements that were obtained in our laboratory in the period 2000–2014. Combining the information on the two parameters it is possible to determine unambiguously the incident projectile energy values. The paper presents the results of an attempt to estimate the energy resolution of the method when analyzing the tracks produced in the CR-39/PM-355 detector by energetic ions such as alpha particles, protons, and deuterons. We discuss the energy resolution of the measurement of light charged particle energy which is based on the parameters (crater diameter and mean gray level value) of tracks induced in solid state nuclear track detectors of the PADC type.

  7. Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning 13C and 29Si NMR Enhanced by Dynamic Nuclear Polarization

    SciTech Connect

    Lafon, Olivier; Thankamony, Aany S. Lilly; Kokayashi, Takeshi; Carnevale, Diego; Vitzthum, Veronika; Slowing, Igor I.; Kandel, Kapil; Vezin, Herve; Amoureux, Jean-Paul; Bodenhausen, Geoffrey; Pruski, Marek

    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.

  8. (1)H and (13)C dynamic nuclear polarization in aqueous solution with a two-field (0.35 T/14 T) shuttle DNP spectrometer.

    PubMed

    Reese, Marcel; Türke, Maria-Teresa; Tkach, Igor; Parigi, Giacomo; Luchinat, Claudio; Marquardsen, Thorsten; Tavernier, Andreas; Höfer, Peter; Engelke, Frank; Griesinger, Christian; Bennati, Marina

    2009-10-28

    Dynamic nuclear polarization (DNP) permits increasing the NMR signal of nuclei by pumping the electronic spin transitions of paramagnetic centers nearby. This method is emerging as a powerful tool to increase the inherent sensitivity of NMR in structural biology aiming at detection of macromolecules. In aqueous solution, additional technical issues associated with the penetration of microwaves in water and heating effects aggravate the performance of the experiment. To examine the feasibility of low-field (9.7 GHz/0.35 T) DNP in high resolution NMR, we have constructed the prototype of a two-field shuttle DNP spectrometer that polarizes nuclei at 9.7 GHz/0.35 T and detects the NMR spectrum at 14 T. We report our first (1)H and (13)C DNP enhancements with this spectrometer. Effective enhancements up to 15 were observed for small molecules at (1)H 600 MHz/14 T as compared to the Boltzmann signal. The results provide a proof of principle for the feasibility of a shuttle DNP experiment and open up perspectives for the application potential of this method in solution NMR.

  9. Solid state switch

    DOEpatents

    Merritt, B.T.; Dreifuerst, G.R.

    1994-07-19

    A solid state switch, with reverse conducting thyristors, is designed to operate at 20 kV hold-off voltage, 1,500 A peak, 1.0 [mu]s pulsewidth, and 4,500 pps, to replace thyratrons. The solid state switch is more reliable, more economical, and more easily repaired. The switch includes a stack of circuit card assemblies, a magnetic assist and a trigger chassis. Each circuit card assembly contains a reverse conducting thyristor, a resistor capacitor network, and triggering circuitry. 6 figs.

  10. The solid state

    SciTech Connect

    Guinier, A.; Remi, J.

    1989-01-01

    This book is an introduction to the solid state for students and non-specialists. Authors aim to relate the macroscopic properties of solids (usually crystalline) to models of their atomic structure. Thermal expansion, the electronic conductivity of metals, ferromagnetism, plastic deformation and diffusion in real systems are among specific topics addressed. Advanced mathematical explanations are set off from the rest of the text in boxed sections for readers wishing a more indepth treatment of topics. Abbreviated bibliography included. For academic collections in solid state physics.

  11. /sup 18/O isotope effect in /sup 13/C nuclear magnetic resonance spectroscopy. Part 9. Hydrolysis of benzyl phosphate by phosphatase enzymes and in acidic aqueous solutions

    SciTech Connect

    Parente, J.E.; Risley, J.M.; Van Etten, R.L.

    1984-12-26

    The /sup 18/O isotope-induced shifts in /sup 13/C and /sup 31/P nuclear magnetic resonance (NMR) spectroscopy were used to establish the position of bond cleavage in the phosphatase-catalyzed and acid-catalyzed hydrolysis reactions of benzyl phosphate. The application of the /sup 18/O-isotope effect in NMR spectroscopy affords a continuous, nondestructive assay method for following the kinetics and position of bond cleavage in the hydrolytic process. The technique provides advantages over most discontinuous methods in which the reaction components must be isolated and converted to volatile derivatives prior to analysis. In the present study, (..cap alpha..-/sup 13/C,ester-/sup 18/O)benzyl phosphate and (ester-/sup 18/O)benzyl phosphate were synthesized for use in enzymatic and nonenzymatic studies. Hydrolysis reactions catalyzed by the alkaline phosphatase from E. coli and by the acid phosphatases isolated from human prostate and human liver were all accompanied by cleavage of the substrate phosphorus-oxygen bond consistent with previously postulated mechanisms involving covalent phosphoenzyme intermediates. An extensive study of the acid-catalyzed hydrolysis of benzyl phosphate at 75/sup 0/C revealed that the site of bond cleavage is dependent on pH. At pH less than or equal to 1.3, the hydrolysis proceeds with C-O bond cleavage; at 1.3 < pH < 2.0, there is a mixture of C-O and P-O bond scission, the latter progressively predominating as the pH is raised; at pH greater than or equal to 2.0, the hydrolysis proceeds with exclusive P-O bond scission. (S)-(+)-(..cap alpha..-/sup 2/H)Benzyl phosphate was also synthesized. Hydrolysis of this chiral benzyl derivative demonstrated that the acid-catalyzed C-O bond scission of benzyl phosphate proceeds by an A-1 (S/sub N/1) mechanism with 70% racemization and 30% inversion at carbon. 37 references, 4 figures, 2 tables.

  12. Solid-State Devices.

    ERIC Educational Resources Information Center

    Sutliff, Ronald D.; And Others

    This self-study course is designed to familiarize Marine Corps enlisted personnel with the principles of solid-state devices and their functions. The course contains four study units. Each study unit begins with a general objective, which is a statement of what the student should learn from the unit. The study units are divided into numbered work…

  13. Solid State Lighting

    SciTech Connect

    Hastbacka, Mildred; Dieckmann, John; Bouza, Antonio

    2013-03-30

    The article discusses solid state lighting technologies. This topic was covered in two previous ASHRAE Journal columns (2010). This article covers advancements in technologies and the associated efficacies. The life-cycle, energy savings and market potential of these technologies are addressed as well.

  14. 13C metabolic flux analysis.

    PubMed

    Wiechert, W

    2001-07-01

    Metabolic flux analysis using 13C-labeled substrates has become an important tool in metabolic engineering. It allows the detailed quantification of all intracellular fluxes in the central metabolism of a microorganism. The method has strongly evolved in recent years by the introduction of new experimental procedures, measurement techniques, and mathematical data evaluation methods. Many of these improvements require advanced skills in the application of nuclear magnetic resonance and mass spectrometry techniques on the one hand and computational and statistical experience on the other hand. This minireview summarizes these recent developments and sketches the major practical problems. An outlook to possible future developments concludes the text.

  15. How High Concentrations of Proteins Stabilize the Amorphous State of Calcium Orthophosphate: A Solid-State Nuclear Magnetic Resonance (NMR) Study of the Casein Case.

    PubMed

    De Sa Peixoto, Paulo; Silva, Juliana V C; Laurent, Guillaume; Schmutz, Marc; Thomas, Daniel; Bouchoux, Antoine; Gésan-Guiziou, Geneviève

    2017-02-07

    Understanding how proteins stabilize amorphous calcium ortho-phosphate (ACP) phases is of great importance in biology and for pharmaceutical or food applications. Until now, most of the former investigations about ACP-protein stability and equilibrium were performed under conditions where ACP colloidal nanoclusters are surrounded by low to moderate concentrations of peptides or proteins (15-30 g L(-1)). As a result, the question of ACP-protein interactions in highly concentrated protein systems has clearly been overlooked, whereas it corresponds to actual industrial conditions such as drying or membrane filtration in the dairy industry for instance. In this study, the structure of an ACP phase is monitored in association with one model phosphorylated protein (casein) using solid-state nuclear magnetic resonance (ssNMR) under two conditions of high protein concentration (300 and 400 g L(-1)). At both concentrations and at 25 °C, it is found that the caseins maintain the mineral phase in an amorphous form with no detectable influence on its structure or size. Interestingly, and in both cases, a significant amount of the nonphosphorylated side chains interacts with ACP through hydrogen bonds. The number of these interacting side chains is found to be higher at the highest casein concentration. At 45 °C, which is a destabilizing temperature of ACP under protein-free conditions, the amorphous structure of the mineral phase is partially transformed at a casein concentration of 300 g L(-1), while it remains almost intact at a casein concentration of 400 g L(-1). Therefore, these results clearly indicate that increasing the concentration of proteins favors ACP-protein interactions and stabilizes the ACP clusters more efficiently.

  16. Structure, Topology and Tilt of Cell-Signaling Peptides Containing Nuclear Localization Sequences in Membrane Bilayers Determined by Solid-State NMR and Molecular Dynamics Simulation Studies

    PubMed Central

    Ramamoorthy, Ayyalusamy; Kandasamy, Senthil K.; Lee, Dong-Kuk; Kidambi, Srikanth; Larson, Ronald G.

    2008-01-01

    Cell-signaling peptides have been extensively used to transport functional molecules across the plasma membrane into living cells. These peptides consist of a hydrophobic sequence and a cationic nuclear localization sequence (NLS). It has been assumed that the hydrophobic region penetrates through the hydrophobic lipid bilayer and delivers the NLS inside the cell. To better understand the transport mechanism of these peptides, in this study, we investigated the structure, orientation, tilt of the peptide relative to the bilayer normal, and the membraneinteraction of two cell-signaling peptides, SA and SKP. Results from CD and solid-state NMR experiments combined with molecular dynamics simulations suggest that the hydrophobic region is helical and has a transmembrane orientation with the helical axis tilted away from the bilayer normal. The influence of the hydrophobic mismatch, between the hydrophobic length of the peptide and the hydrophobic thickness of the bilayer, on the tilt angle of the peptides was investigated using thicker POPC and thinner DMPC bilayers. NMR experiments showed that the hydrophobic domain of each peptide has a tilt angle of 15±3° in POPC, while in DMPC 25±3° and 30±3° tilts were observed for SA and SKP peptides respectively. These results are in good agreement with molecular dynamics simulations, which predicts a tilt angle of 13.3° (SA in POPC), 16.4° (SKP in POPC), 22.3° (SA in DMPC) and 31.7° (SKP in POPC). These results and simulations on the hydrophobic fragment of SA or SKP suggest that the tilt of helices increases with a decrease in the bilayer thickness without changing the phase, order, and structure of the lipid bilayers. PMID:17240980

  17. Rapid and accurate determination of the lignin content of lignocellulosic biomass by solid-state NMR.

    PubMed

    Fu, Li; McCallum, Scott A; Miao, Jianjun; Hart, Courtney; Tudryn, Gregory J; Zhang, Fuming; Linhardt, Robert J

    2015-02-01

    Biofuels and biomaterials, produced from lignocellulosic feedstock, require facile access to cellulose and hemicellulose to be competitive with petroleum processing and sugar-based fermentation. Physical-chemical barriers resulting from lignin complicates the hydrolysis biomass into fermentable sugars. Thus, the amount of lignin within a substrate is critical in determining biomass processing. The application of (13)C cross-polarization, magic-angle spinning, and solid-state nuclear magnetic resonance for the direct quantification of lignin content in biomass is examined. Using a standard curve constructed from pristine lignin and cellulose, the lignin content of a biomass sample is accurately determined through direct measurement without chemical or enzymatic pre-treatment.

  18. Solid State Laser

    NASA Technical Reports Server (NTRS)

    1990-01-01

    The Titan-CW Ti:sapphire (titanium-doped sapphire) tunable laser is an innovation in solid-state laser technology jointly developed by the Research and Solid State Laser Divisions of Schwartz Electro-optics, Inc. (SEO). SEO is producing the laser for the commercial market, an outgrowth of a program sponsored by Langley Research Center to develop Ti:sapphire technology for space use. SEO's Titan-CW series of Ti:sapphire tunable lasers have applicability in analytical equipment designed for qualitative analysis of carbohydrates and proteins, structural analysis of water, starch/sugar analyses, and measurements of salt in meat. Further applications are expected in semiconductor manufacture, in medicine for diagnosis and therapy, and in biochemistry.

  19. Solid State Research

    NASA Technical Reports Server (NTRS)

    Shaver, David C.

    1995-01-01

    This report covers in detail the research work of the Solid State Division at Lincoln Laboratory for the period 1 May-31 July 1995. The topics covered are: Electrooptical Devices, Quantum Electronics, Materials Research, Submicrometer Technology, High Speed Electronics, Microelectronics, and analog device technology. Funding is provided primarily by the Air Force, with additional Support provided by the Army, ARPA, Navy, BMDO, NASA and NIST.

  20. Solid State Research

    NASA Technical Reports Server (NTRS)

    Shaver, David C.

    1996-01-01

    This report covers in detail the research work of the Solid State Division at Lincoln Laboratory for the period 1 May - 31 July 1996. The topics covered are Electrooptical Devices, Quantum Electronics, Materials Research, Submicrometer Technology, High Speed Electronics, Microelectronics, and Analog Device Technology. Funding is provided primarily by the Air Force, with additional Support provided by the Army, DARPA, Navy, BMDO, NASA, and NIST.

  1. Solid State Research.

    DTIC Science & Technology

    2007-11-02

    Technology, High Speed Electronics, Microelectronics, Analog Device Technology, and Advanced Silicon Technology. Funding is provided primarily by the...Illustrations vii Table ix Introduction xi Reports on Solid State Research xiii Organization xxiii 1. QUANTUM ELECTRONICS 1 1.1 High -Power Passively...Microchemical Etching of Silicon 13 3.2 Calorimetric Measurements of Optical Materials for 193-nm Lithography 17 4. HIGH SPEED ELECTRONICS 21 4.1

  2. Tunable solid state lasers

    SciTech Connect

    Hammerling, R.; Budgor, A.B.; Pinto, A.

    1985-01-01

    This book presents the papers given at a conference on solid state lasers. Topics considered at the conference included transition-metal-doped lasers, line-narrowed alexandrite lasers, NASA specification, meteorological lidars, laser materials spectroscopy, laser pumped single pass gain, vibronic laser materials growth, crystal growth methods, vibronic laser theory, cross-fertilization through interdisciplinary fields, and laser action of color centers in diamonds.

  3. Solid State Research

    DTIC Science & Technology

    1986-11-15

    Uttaro, R.S. Vera , A. Wilde, R.E. Young, E.M. * Research Assistant T Staff Associate t Part Time XXVI 1.1 1. SOLID STATE DEVICE RESEARCH A...substrate temperature of 850° C, as shown in Figure 3-7(b). Figure 3-8 shows the low-temperature PL spectra of an Alo 2gGao 72AS layer excited by an Ar-ion

  4. Solid-state dynamics of uranyl polyoxometalates.

    PubMed

    Alam, Todd M; Liao, Zuolei; Zakharov, Lev N; Nyman, May

    2014-07-01

    Understanding fundamental uranyl polyoxometalate (POM) chemistry in solution and the solid state is the first step to defining its future role in the development of new actinide materials and separation processes that are vital to every step of the nuclear fuel cycle. Many solid-state geometries of uranyl POMs have been described, but we are only beginning to understand their chemical behavior, which thus far includes the role of templates in their self-assembly, and the dynamics of encapsulated species in solution. This study provides unprecedented detail into the exchange dynamics of the encapsulated species in the solid state through Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectroscopy. Although it was previously recognized that capsule-like molybdate and uranyl POMs exchange encapsulated species when dissolved in water, analogous exchange in the solid state has not been documented, or even considered. Here, we observe the extremely high rate of transport of Li(+) and aqua species across the uranyl shell in the solid state, a process that is affected by both temperature and pore blocking by larger species. These results highlight the untapped potential of emergent f-block element materials and vesicle-like POMs.

  5. Solid State Research.

    DTIC Science & Technology

    2007-11-02

    Functionality Process Accuracy CCD MDAC 25,000 Multiply/add 2-Poly-Si, 2-metal 1.2 /zm Analog x 8 b Digital CMOS [1] 2,300 Multiply/add 2-Poly...additional support provided by the Army, ARPA, Navy, BMDO, NASA, and NIST. in TABLE OF CONTENTS Abstract üi List of Illustrations yii List of Tables x ...Introduction x * Reports on Solid State Research xiii Organization xxm 1. ELECTROOPTICAL DEVICES 1 1.1 1.3-jUm Strained-Layer InGaAsP/InP Quantum

  6. Solid state optical microscope

    SciTech Connect

    Young, Ian T.

    1983-01-01

    A solid state optical microscope wherein wide-field and high-resolution images of an object are produced at a rapid rate by utilizing conventional optics with a charge-coupled photodiode array. A galvanometer scanning mirror, for scanning in one of two orthogonal directions is provided, while the charge-coupled photodiode array scans in the other orthogonal direction. Illumination light from the object is incident upon the photodiodes, creating packets of electrons (signals) which are representative of the illuminated object. The signals are then processed, stored in a memory, and finally displayed as a video signal.

  7. Solid state optical microscope

    DOEpatents

    Young, I.T.

    1983-08-09

    A solid state optical microscope wherein wide-field and high-resolution images of an object are produced at a rapid rate by utilizing conventional optics with a charge-coupled photodiode array. A galvanometer scanning mirror, for scanning in one of two orthogonal directions is provided, while the charge-coupled photodiode array scans in the other orthogonal direction. Illumination light from the object is incident upon the photodiodes, creating packets of electrons (signals) which are representative of the illuminated object. The signals are then processed, stored in a memory, and finally displayed as a video signal. 2 figs.

  8. Solid State Research

    DTIC Science & Technology

    1990-11-15

    Alo .3Gao.7As confining layers. 38 IX Figure No. Page 3-2 Schematic structure and energy diagram of AlInGaAs/AlGaAs SCH SQW diode laser. 39 3-3...Lithography Photooxidation of a-Conjugated Si-Si Network Polymers High-Power Solid-State Laser Radar Technology Heat Driven Cryocoolers for...M.J. Nichols, K.B. Parker, CD. Rabe, S. Rathman, D.D. Smith, F.W., III Vera , A. xxvn ELECTROOPTICAL DEVICES ANALOG DEVICE TECHNOLOGY R.C

  9. Solid state oxygen sensor

    DOEpatents

    Garzon, F.H.; Chung, B.W.; Raistrick, I.D.; Brosha, E.L.

    1996-08-06

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer. 4 figs.

  10. Solid state oxygen sensor

    DOEpatents

    Garzon, Fernando H.; Chung, Brandon W.; Raistrick, Ian D.; Brosha, Eric L.

    1996-01-01

    Solid state oxygen sensors are provided with a yttria-doped zirconia as an electrolyte and use the electrochemical oxygen pumping of the zirconia electrolyte. A linear relationship between oxygen concentration and the voltage arising at a current plateau occurs when oxygen accessing the electrolyte is limited by a diffusion barrier. A diffusion barrier is formed herein with a mixed electronic and oxygen ion-conducting membrane of lanthanum-containing perovskite or zirconia-containing fluorite. A heater may be used to maintain an adequate oxygen diffusion coefficient in the mixed conducting layer.

  11. Structure and Dynamics of Brachypodium Primary Cell Wall Polysaccharides from Two-Dimensional 13C Solid-State Nuclear Magnetic Resonance Spectroscopy

    SciTech Connect

    Wang, Tuo; Salazar, Andre; Zabotina, Olga A.; Hong, Mei

    2014-04-10

    The polysaccharide structure and dynamics in the primary cell wall of the model grass Brachypodium distachyon are investigated for the first time using solid-state nuclear magnetic resonance (NMR). While both grass and non-grass cell walls contain cellulose as the main structural scaffold, the former contains xylan with arabinose and glucuronic acid substitutions as the main hemicellulose, with a small amount of xyloglucan (XyG) and pectins, while the latter contains XyG as the main hemicellulose and significant amounts of pectins. We labeled the Brachypodium cell wall with 13C to allow two-dimensional (2D) 13C correlation NMR experiments under magic-angle spinning. Well-resolved 2D spectra are obtained in which the 13C signals of cellulose, glucuronoarabinoxylan (GAX), and other matrix polysaccharides can be assigned. The assigned 13C chemical shifts indicate that there are a large number of arabinose and xylose linkages in the wall, and GAX is significantly branched at the developmental stage of 2 weeks. 2D 13C–13C correlation spectra measured with long spin diffusion mixing times indicate that the branched GAX approaches cellulose microfibrils on the nanometer scale, contrary to the conventional model in which only unbranched GAX can bind cellulose. The GAX chains are highly dynamic, with average order parameters of 0.4. Biexponential 13C T1 and 1H T relaxation indicates that there are two dynamically distinct domains in GAX: the more rigid domain may be responsible for cross-linking cellulose microfibrils, while the more mobile domain may fill the interfibrillar space. This dynamic heterogeneity is more pronounced than that of the non-grass hemicellulose, XyG, suggesting that GAX adopts the mixed characteristics of XyG and pectins. Moderate differences in cellulose rigidity are observed between the Brachypodium and Arabidopsis cell walls

  12. Solid State Humidity Sensors

    NASA Astrophysics Data System (ADS)

    Chang, Song-Lin

    There are only a few solid state humidity sensors available today. Most of those sensors use a porous oxide material as a principal part of the device. The devices work on the basis of a change in resistance as the moisture in the air varies. In this experiment, two solid state humidity sensors have been developed for use under practical conditions. One is a Polymer Oxide Semiconductor device with a POLYOX film that absorbs the moisture from the air. The amount of water dipoles absorbed by the polymer is a function of relative humidity. This sensor can measure relative humidity from 20% to 90%. The other is a Dew Point sensor. The sensor is in contact with the upper surface of a miniature Peltier cooler. Water molecules deposited on the sensor surface cause the electrical current through the sensor to increase. The operator adjusts the temperature of the Peltier cooler until a saturated current through the sensor is reached. About one min. is required to measure low relative humidities. The Dew Point sensor can measure a range of relative humidities of 30% to 80%.

  13. Packaging of solid state devices

    DOEpatents

    Glidden, Steven C.; Sanders, Howard D.

    2006-01-03

    A package for one or more solid state devices in a single module that allows for operation at high voltage, high current, or both high voltage and high current. Low thermal resistance between the solid state devices and an exterior of the package and matched coefficient of thermal expansion between the solid state devices and the materials used in packaging enables high power operation. The solid state devices are soldered between two layers of ceramic with metal traces that interconnect the devices and external contacts. This approach provides a simple method for assembling and encapsulating high power solid state devices.

  14. DFT calculations of quadrupolar solid-state NMR properties: Some examples in solid-state inorganic chemistry.

    PubMed

    Cuny, Jerome; Messaoudi, Sabri; Alonzo, Veronique; Furet, Eric; Halet, Jean-François; Le Fur, Eric; Ashbrook, Sharon E; Pickard, Chris J; Gautier, Regis; Le Polles, Laurent

    2008-10-01

    This article presents results of first-principles calculations of quadrupolar parameters measured by solid-state nuclear magnetic measurement (NMR) spectroscopy. Different computational methods based on density functional theory were used to calculate the quadrupolar parameters. Through a series of illustrations from different areas of solid state inorganic chemistry, it is shown how quadrupolar solid-state NMR properties can be tackled by a theoretical approach and can yield structural information.

  15. Solid state rapid thermocycling

    DOEpatents

    Beer, Neil Reginald; Spadaccini, Christopher

    2014-05-13

    The rapid thermal cycling of a material is targeted. A solid state heat exchanger with a first well and second well is coupled to a power module. A thermoelectric element is coupled to the first well, the second well, and the power module, is configured to transfer thermal energy from the first well to the second well when current from the power module flows through the thermoelectric element in a first direction, and is configured to transfer thermal energy from the second well to the first well when current from the power module flows through the thermoelectric element in a second direction. A controller may be coupled to the thermoelectric elements, and may switch the direction of current flowing through the thermoelectric element in response to a determination by sensors coupled to the wells that the amount of thermal energy in the wells falls below or exceeds a pre-determined threshold.

  16. Solid state power controllers

    NASA Technical Reports Server (NTRS)

    Gibbs, R. S.

    1973-01-01

    The rationale, analysis, design, breadboarding and testing of the incremental functional requirements are reported that led to the development of prototype 1 and 5 Amp dc and 1 Amp ac solid state power controllers (SSPC's). The SSPC's are to be considered for use as a replacement of electro-mechanical relays and circuit breakers in future spacecraft and aircraft. They satisfy the combined function of both the relay and circuit breaker and can be remotely controlled by small signals, typically 10 mA, 5 to 28 Vdc. They have the advantage over conventional relay/circuit breaker systems in that they can be located near utilization equipment and the primary ac or dc bus. The low level control, trip indication and status signals can be circuited by small guage wire for control, computer interface, logic, electrical multiplexing, unboard testing, and power management and distribution purposes. This results in increased system versatility at appreciable weight saving and increased reliability.

  17. Application of Metabolic 13C Labeling in Conjunction with High-Field Nuclear Magnetic Resonance Spectroscopy for Comparative Conformational Analysis of High Mannose-Type Oligosaccharides

    PubMed Central

    Kamiya, Yukiko; Yanagi, Kotaro; Kitajima, Toshihiko; Yamaguchi, Takumi; Chiba, Yasunori; Kato, Koichi

    2013-01-01

    High mannose-type oligosaccharides are enzymatically trimmed in the endoplasmic reticulum, resulting in various processing intermediates with exposed glycotopes that are recognized by a series of lectins involved in glycoprotein fate determination in cells. Although recent crystallographic data have provided the structural basis for the carbohydrate recognition of intracellular lectins, atomic information of dynamic oligosaccharide conformations is essential for a quantitative understanding of the energetics of carbohydrate–lectin interactions. Carbohydrate NMR spectroscopy is useful for characterizing such conformational dynamics, but often hampered by poor spectral resolution and lack of recombinant techniques required to produce homogeneous glycoforms. To overcome these difficulties, we have recently developed a methodology for the preparation of a homogeneous high mannose-type oligosaccharide with 13C labeling using a genetically engineered yeast strain. We herein successfully extended this method to result in the overexpression of 13C-labeled Man9GlcNAc2 (M9) with a newly engineered yeast strain with the deletion of four genes involved in N-glycan processing. This enabled high-field NMR analyses of 13C-labeled M9 in comparison with its processing product lacking the terminal mannose residue ManD2. Long-range NOE data indicated that the outer branches interact with the core in both glycoforms, and such foldback conformations are enhanced upon the removal of ManD2. The observed conformational variabilities might be significantly associated with lectins and glycan-trimming enzymes. PMID:24970159

  18. Significance of symmetry in the nuclear spin Hamiltonian for efficient heteronuclear dipolar decoupling in solid-state NMR: A Floquet description of supercycled rCW schemes

    NASA Astrophysics Data System (ADS)

    Equbal, Asif; Shankar, Ravi; Leskes, Michal; Vega, Shimon; Nielsen, Niels Chr.; Madhu, P. K.

    2017-03-01

    Symmetry plays an important role in the retention or annihilation of a desired interaction Hamiltonian in NMR experiments. Here, we explore the role of symmetry in the radio-frequency interaction frame Hamiltonian of the refocused-continuous-wave (rCW) pulse scheme that leads to efficient 1H heteronuclear decoupling in solid-state NMR. It is demonstrated that anti-periodic symmetry of single-spin operators (Ix, Iy, Iz) in the interaction frame can lead to complete annihilation of the 1H-1H homonuclear dipolar coupling effects that induce line broadening in solid-state NMR experiments. This symmetry also plays a critical role in cancelling or minimizing the effect of 1H chemical-shift anisotropy in the effective Hamiltonian. An analytical description based on Floquet theory is presented here along with experimental evidences to understand the decoupling efficiency of supercycled (concatenated) rCW scheme.

  19. Significance of symmetry in the nuclear spin Hamiltonian for efficient heteronuclear dipolar decoupling in solid-state NMR: A Floquet description of supercycled rCW schemes.

    PubMed

    Equbal, Asif; Shankar, Ravi; Leskes, Michal; Vega, Shimon; Nielsen, Niels Chr; Madhu, P K

    2017-03-14

    Symmetry plays an important role in the retention or annihilation of a desired interaction Hamiltonian in NMR experiments. Here, we explore the role of symmetry in the radio-frequency interaction frame Hamiltonian of the refocused-continuous-wave (rCW) pulse scheme that leads to efficient (1)H heteronuclear decoupling in solid-state NMR. It is demonstrated that anti-periodic symmetry of single-spin operators (Ix, Iy, Iz) in the interaction frame can lead to complete annihilation of the (1)H-(1)H homonuclear dipolar coupling effects that induce line broadening in solid-state NMR experiments. This symmetry also plays a critical role in cancelling or minimizing the effect of (1)H chemical-shift anisotropy in the effective Hamiltonian. An analytical description based on Floquet theory is presented here along with experimental evidences to understand the decoupling efficiency of supercycled (concatenated) rCW scheme.

  20. Towards hyperpolarized 13C-succinate imaging of brain cancer

    NASA Astrophysics Data System (ADS)

    Bhattacharya, Pratip; Chekmenev, Eduard Y.; Perman, William H.; Harris, Kent C.; Lin, Alexander P.; Norton, Valerie A.; Tan, Chou T.; Ross, Brian D.; Weitekamp, Daniel P.

    2007-05-01

    We describe a novel 13C enriched precursor molecule, sodium 1- 13C acetylenedicarboxylate, which after hydrogenation by PASADENA (Parahydrogen and Synthesis Allows Dramatically Enhanced Nuclear Alignment) under controlled experimental conditions, becomes hyperpolarized 13C sodium succinate. Fast in vivo 3D FIESTA MR imaging demonstrated that, following carotid arterial injection, the hyperpolarized 13C-succinate appeared in the head and cerebral circulation of normal and tumor-bearing rats. At this time, no in vivo hyperpolarized signal has been localized to normal brain or brain tumor. On the other hand, ex vivo samples of brain harvested from rats bearing a 9L brain tumor, 1 h or more following in vivo carotid injection of hyperpolarized 13C sodium succinate, contained significant concentrations of the injected substrate, 13C sodium succinate, together with 13C maleate and succinate metabolites 1- 13C-glutamate, 5- 13C-glutamate, 1- 13C-glutamine and 5- 13C-glutamine. The 13C substrates and products were below the limits of NMR detection in ex vivo samples of normal brain consistent with an intact blood-brain barrier. These ex vivo results indicate that hyperpolarized 13C sodium succinate may become a useful tool for rapid in vivo identification of brain tumors, providing novel biomarkers in 13C MR spectral-spatial images.

  1. Application and Reliability of Solid-State NMR in Environmental Sciences

    NASA Astrophysics Data System (ADS)

    Knicker, Heike

    2010-05-01

    For the characterization of soil organic matter, a suite of analytical approaches are available. Chemical degradative methods involve an extraction scheme with which the soluble part of the mixture is isolated and analyzed by colorimetrical or chromatographic means. Macromolecular structures can be subjected to thermolytic or combined thermochemolytic degradation. Because secondary reactions (rearrangement, cracking, hydrogenation and polymerization) in a heterogeneous mixture cannot be excluded, it is obvious that conclusions regarding the original structure in the macromolecular phase have to be drawn with caution. A powerful alternative represents solid-state nuclear magnetic resonance (NMR) spectroscopy, allowing the examination of the bulk sample without major pre-treatment In environmental sciences, this technique mostly involves the isotope 13C to study the chemical composition of organic matter in soils, sediments or compost to study the temporal development of humic material or chemical alterations due to variation in environmental parameters. Due to its low sensibility solid-state 15N NMR studies on such samples are only found occasionally. The emphasis of solid-state NMR spectroscopy is not only to determine the gross chemical composition of the material under study via a chemical shift assignment but also a quantitative correlation between the different signal intensities and the relative contribution of the respective C or N types to the total organic C or N content. However, despite increasing popularity, this approach is still viewed as mysterious techniques, in particular with respect to quantification. Accordingly, the purpose of this review is to give a short overview on the possibilities and limitations of this technique in environmental science and in particular for the study of soil organic matter. In general, solid-state 13C NMR spectra of soil organic matter are obtained with the cross polarization magic angle spinning (CPMAS) technique. This

  2. Polarized Solid State Target

    NASA Astrophysics Data System (ADS)

    Dutz, Hartmut; Goertz, Stefan; Meyer, Werner

    2017-01-01

    The polarized solid state target is an indispensable experimental tool to study single and double polarization observables at low intensity particle beams like tagged photons. It was one of the major components of the Crystal-Barrel experiment at ELSA. Besides the operation of the 'CB frozen spin target' within the experimental program of the Crystal-Barrel collaboration both collaborative groups of the D1 project, the polarized target group of the Ruhr Universität Bochum and the Bonn polarized target group, have made significant developments in the field of polarized targets within the CRC16. The Bonn polarized target group has focused its work on the development of technically challenging polarized solid target systems towards the so called '4π continuous mode polarized target' to operate them in combination with 4π-particle detection systems. In parallel, the Bochum group has developed various highly polarized deuterated target materials and high precision NMR-systems, in the meantime used for polarization experiments at CERN, JLAB and MAMI, too.

  3. Solid state laser

    NASA Technical Reports Server (NTRS)

    Rines, Glen A. (Inventor); Moulton, Peter F. (Inventor); Harrison, James (Inventor)

    1993-01-01

    A wavelength-tunable, injection-seeded, dispersion-compensated, dispersively-pumped solid state laser includes a lasing medium; a highly reflective mirror; an output coupler; at least one isosceles Brewster prism oriented to the minimum deviation angle between the medium and the mirror for directing light of different wavelengths along different paths; means for varying the angle of the highly reflective mirror relative to the light from at least one Brewster angle for selecting a predetermined laser operating wavelength; a dispersion compensation apparatus associated with the lasing medium; a laser injection seeding port disposed between the dispersion compensation apparatus and one of the mirror and coupler and including a reflective surface at an acute non-Brewster angle to the laser beam for introducing a seed input; a dispersion compensation apparatus associated with the laser medium including opposite chirality optical elements; the lasing medium including a pump surface disposed at an acute angle to the laser beam to define a discrete path for the pumping laser beam separate from the pumped laser beam.

  4. sup 13 C and sup 15 N nuclear magnetic resonance evidence of the ionization state of substrates bound to bovine dihydrofolate reductase

    SciTech Connect

    Selinsky, B.S.; Perlman, M.E.; London, R.E. ); Unkefer, C.J. ); Mitchell, J. ); Blakley, R.L. Univ. of Tennessee, Memphis )

    1990-02-06

    The state of protonation of substrates bound to mammalian dihydrofolate reductase (DHFR) has significance for the mechanism of catalysis. To investigate this, dihydrofolate and dihydropteroylpentaglutamate have been synthesized with {sup 15}N enrichment at N-5. {sup 15}N NMR studies have been performed on the binary complexes formed by bovine DHFR with these compounds and with (5-{sup 15}N)dihydrobiopterin. The results indicate that there is no protonation at N-5 in the binary complexes, and this was confirmed by {sup 13}C NMR studies with folate and dihydrofolate synthesized with {sup 13}C enrichment at C-6. The chemical shift displacements produced by complex formation are in the same direction as those which result from deprotonation of the N-3/C-4-O amide group and are consistent with at least partial loss of the proton from N-3. This would be possible if, as crystallographic data indicate, there is interaction of N-3 and the 2-amino group of the bound ligands with the carboxylate of the active site glutamate residue (Glu{sup 30}).

  5. Orphan spin operators enable the acquisition of multiple 2D and 3D magic angle spinning solid-state NMR spectra

    NASA Astrophysics Data System (ADS)

    Gopinath, T.; Veglia, Gianluigi

    2013-05-01

    We propose a general method that enables the acquisition of multiple 2D and 3D solid-state NMR spectra for U-13C, 15N-labeled proteins. This method, called MEIOSIS (Multiple ExperIments via Orphan SpIn operatorS), makes it possible to detect four coherence transfer pathways simultaneously, utilizing orphan (i.e., neglected) spin operators of nuclear spin polarization generated during 15N-13C cross polarization (CP). In the MEIOSIS experiments, two phase-encoded free-induction decays are decoded into independent nuclear polarization pathways using Hadamard transformations. As a proof of principle, we show the acquisition of multiple 2D and 3D spectra of U-13C, 15N-labeled microcrystalline ubiquitin. Hadamard decoding of CP coherences into multiple independent spin operators is a new concept in solid-state NMR and is extendable to many other multidimensional experiments. The MEIOSIS method will increase the throughput of solid-state NMR techniques for microcrystalline proteins, membrane proteins, and protein fibrils.

  6. Detection of high-pressure silica polymorphs in whole-rock samples from a meteor crater, Arizona, impact sample using solid-state silicon-29 nuclear magnetic resonance spectroscopy

    NASA Astrophysics Data System (ADS)

    Yang, W.-H.; Kirkpatrick, R. J.; Vergo, N.; McHone, J.; Emilsson, T. I.; Oldfield, E.

    1986-03-01

    High-resolution solid-state silicon-29 nuclear magnetic resonance spectroscopy using "magic-angle" sample-spinning can readily detect the presence of the high pressure silica polymorphs coesite and stishovite in whole-rock samples from a Meteor Crater Arizona, impact sample, and yields accurate coesite/stishovite ratios. Such determinations are being carried out by partially suppressing (saturating) intense quartz signals (which have long spinlattice relaxation times) by means of short experimental recycle-times. This method enhances the signal-to-noise ratios of coesite and stishovite (which have relatively short spin-lattice relaxation times). For the sample examined, the coesite/stishovite ratio is about 27.

  7. Protein structure determination with paramagnetic solid-state NMR spectroscopy.

    PubMed

    Sengupta, Ishita; Nadaud, Philippe S; Jaroniec, Christopher P

    2013-09-17

    Many structures of the proteins and protein assemblies that play central roles in fundamental biological processes and disease pathogenesis are not readily accessible via the conventional techniques of single-crystal X-ray diffraction and solution-state nuclear magnetic resonance (NMR). On the other hand, many of these challenging biological systems are suitable targets for atomic-level structural and dynamic analysis by magic-angle spinning (MAS) solid-state NMR spectroscopy, a technique that has far less stringent limitations on the molecular size and crystalline state. Over the past decade, major advances in instrumentation and methodology have prompted rapid growth in the field of biological solid-state NMR. However, despite this progress, one challenge for the elucidation of three-dimensional (3D) protein structures via conventional MAS NMR methods is the relative lack of long-distance data. Specifically, extracting unambiguous interatomic distance restraints larger than ∼5 Å from through-space magnetic dipole-dipole couplings among the protein (1)H, (13)C, and (15)N nuclei has proven to be a considerable challenge for researchers. It is possible to circumvent this problem by extending the structural studies to include several analogs of the protein of interest, intentionally modified to contain covalently attached paramagnetic tags at selected sites. In these paramagnetic proteins, the hyperfine couplings between the nuclei and unpaired electrons can manifest themselves in NMR spectra in the form of relaxation enhancements of the nuclear spins that depend on the electron-nucleus distance. These effects can be significant for nuclei located up to ∼20 Å away from the paramagnetic center. In this Account, we discuss MAS NMR structural studies of nitroxide and EDTA-Cu(2+) labeled variants of a model 56 amino acid globular protein, B1 immunoglobulin-binding domain of protein G (GB1), in the microcrystalline solid phase. We used a set of six EDTA-Cu(2

  8. A chelate-stabilized ruthenium(sigma-pyrrolato) complex: resolving ambiguities in nuclearity and coordination geometry through 1H PGSE and 31P solid-state NMR studies.

    PubMed

    Foucault, Heather M; Bryce, David L; Fogg, Deryn E

    2006-12-11

    Reaction of RuCl2(PPh3)3 with LiNN' (NN' = 2-[(2,6-diisopropylphenyl)imino]pyrrolide) affords a single product, with the empirical formula RuCl[(2,6-iPr2C6H3)N=CHC4H3N](PPh3)2. We identify this species as a sigma-pyrrolato complex, [Ru(NN')(PPh3)2]2(mu-Cl)2 (3b), rather than mononuclear RuCl(NN')(PPh3)2 (3a), on the basis of detailed 1D and 2D NMR characterization in solution and in the solid state. Retention of the chelating, sigma-bound iminopyrrolato unit within 3b, despite the presence of labile (dative) chloride and PPh3 donors, indicates that the chelate effect is sufficient to inhibit sigma --> pi isomerization of 3b to a piano-stool, pi-pyrrolato structure. 2D COSY, SECSY, and J-resolved solid-state 31P NMR experiments confirm that the PPh3 ligands on each metal center are magnetically and crystallographically inequivalent, and 31P CP/MAS NMR experiments reveal the largest 99Ru-31P spin-spin coupling constant (1J(99Ru,31P) = 244 +/- 20 Hz) yet measured. Finally, 31P dipolar-chemical shift spectroscopy is applied to determine benchmark phosphorus chemical shift tensors for phosphine ligands in hexacoordinate ruthenium complexes.

  9. Solid-state NMR for bacterial biofilms

    NASA Astrophysics Data System (ADS)

    Reichhardt, Courtney; Cegelski, Lynette

    2014-04-01

    Bacteria associate with surfaces and one another by elaborating an extracellular matrix to encapsulate cells, creating communities termed biofilms. Biofilms are beneficial in some ecological niches, but also contribute to the pathogenesis of serious and chronic infectious diseases. New approaches and quantitative measurements are needed to define the composition and architecture of bacterial biofilms to help drive the development of strategies to interfere with biofilm assembly. Solid-state nuclear magnetic resonance (NMR) is uniquely suited to the examination of insoluble and complex macromolecular and whole-cell systems. This article highlights three examples that implement solid-state NMR to deliver insights into bacterial biofilm composition and changes in cell-wall composition as cells transition to the biofilm lifestyle. Most recently, solid-state NMR measurements provided a total accounting of the protein and polysaccharide components in the extracellular matrix of an Escherichia coli biofilm and transformed our qualitative descriptions of matrix composition into chemical parameters that permit quantitative comparisons among samples. We present additional data for whole biofilm samples (cells plus the extracellular matrix) that complement matrix-only analyses. The study of bacterial biofilms by solid-state NMR is an exciting avenue ripe with many opportunities and we close the article by articulating some outstanding questions and future directions in this area.

  10. Design and test of a double-nuclear RF coil for (1)H MRI and (13)C MRSI at 7T.

    PubMed

    Rutledge, Omar; Kwak, Tiffany; Cao, Peng; Zhang, Xiaoliang

    2016-06-01

    RF coil operation at the ultrahigh field of 7T is fraught with technical challenges that limit the advancement of novel human in vivo applications at 7T. In this work, a hybrid technique combining a microstrip transmission line and a lumped-element L-C loop coil to form a double-nuclear RF coil for proton magnetic resonance imaging and carbon magnetic resonance spectroscopy at 7T was proposed and investigated. Network analysis revealed a high Q-factor and excellent decoupling between the coils. Proton images and localized carbon spectra were acquired with high sensitivity. The successful testing of this novel double-nuclear coil demonstrates the feasibility of this hybrid design for double-nuclear MR imaging and spectroscopy studies at the ultrahigh field of 7T.

  11. Design and test of a double-nuclear RF coil for 1H MRI and 13C MRSI at 7 T

    NASA Astrophysics Data System (ADS)

    Rutledge, Omar; Kwak, Tiffany; Cao, Peng; Zhang, Xiaoliang

    2016-06-01

    RF coil operation at the ultrahigh field of 7 T is fraught with technical challenges that limit the advancement of novel human in vivo applications at 7 T. In this work, a hybrid technique combining a microstrip transmission line and a lumped-element L-C loop coil to form a double-nuclear RF coil for proton magnetic resonance imaging and carbon magnetic resonance spectroscopy at 7 T was proposed and investigated. Network analysis revealed a high Q-factor and excellent decoupling between the coils. Proton images and localized carbon spectra were acquired with high sensitivity. The successful testing of this novel double-nuclear coil demonstrates the feasibility of this hybrid design for double-nuclear MR imaging and spectroscopy studies at the ultrahigh field of 7 T.

  12. High power solid state lasers

    SciTech Connect

    Weber, H.

    1988-01-01

    These proceedings discuss the following subjects: trends in materials processing with laser radiation; slabs and high power systems; glasses and new crystals; solid state lasers at HOYA Corp.; lamps, resonators and transmission; glasses as active materials for high average power solid state lasers; flashlamp pumped GGG-crystals; alexandrite lasers; designing telescope resonators; mode operation of neodymium: YAG lasers; intracavity frequency doubling with KTP crystal and thermal effects in cylinder lasers.

  13. Solid State Photovoltaic Research Branch

    SciTech Connect

    Not Available

    1990-09-01

    This report summarizes the progress of the Solid State Photovoltaic Research Branch of the Solar Energy Research Institute (SERI) from October 1, 1988, through September 30,l 1989. Six technical sections of the report cover these main areas of SERIs in-house research: Semiconductor Crystal Growth, Amorphous Silicon Research, Polycrystalline Thin Films, III-V High-Efficiency Photovoltaic Cells, Solid-State Theory, and Laser Raman and Luminescence Spectroscopy. Sections have been indexed separately for inclusion on the data base.

  14. Spatially resolved solid-state MAS-NMR-spectroscopy.

    PubMed

    Scheler, U; Schauss, G; Blümich, B; Spiess, H W

    1996-07-01

    A comprehensive account of spatially resolved solid-state MAS NMR of 13C is given. A device generating field gradients rotating synchronously with the magic angle spinner is described. Spatial resolution and sensitivity are compared for phase and frequency encoding of spatial information. The suppression of spinning sidebands is demonstrated for both cases. Prior knowledge about the involved materials can be used for the reduction of data from spatially resolved spectra to map chemical structure. Indirect detection via 13C NMR gives access to the information about mobility from proton-wideline spectra. Two-dimensional solid-state spectroscopy with spatial resolution is demonstrated for a rotor synchronized MAS experiment which resolves molecular order as a function of space. By comparison of different experiments the factors affecting the spatial resolution are investigated.

  15. Solid-state NMR studies of form I of atorvastatin calcium.

    PubMed

    Wang, Wei David; Gao, Xudong; Strohmeier, Mark; Wang, Wei; Bai, Shi; Dybowski, Cecil

    2012-03-22

    Solid-state (13)C, (19)F, and (15)N magic angle spinning NMR studies of Form I of atorvastatin calcium are reported, including chemical shift tensors of all resolvable carbon sites and fluorine sites. The complete (13)C and (19)F chemical shift assignments are given based on an extensive analysis of (13)C-(1)H HETCOR and (13)C-(19)F HETCOR results. The solid-state NMR data indicate that the asymmetric unit of this material contains two atorvastatin molecules. A possible structure of Form I of atorvastatin calcium (ATC-I), derived from solid-state NMR data and density functional theory calculations of various structures, is proposed for this important active pharmaceutical ingredient (API).

  16. Solid-state 17O nuclear magnetic resonance spectroscopy without isotopic enrichment: direct detection of bridging oxygen in radiation damaged zircon.

    PubMed

    Ashbrook, Sharon E; Farnan, IanIan

    2004-09-01

    Protocols are presented for obtaining natural abundance (17)O magic angle spinning and static NMR spectra in the solid state. Rotor-assisted population transfer (RAPT), Carr-Purcell-Meiboom-Gill (CPMG) echo trains and cross-polarisation (CP) are all used to obtain spectra of sites with large as well as small electric field gradients in proton and non-proton containing inorganic materials. Spectra are of sufficient quality to obtain the typical NMR parameters by standard fitting of the spectra. The protocol is then applied to identifying the changes that accompany radioactive decay in zircon (ZrSiO(4)) where enrichment is impossible. The (17)O NMR spectra of a partially metamict zircon sample clearly show evidence of bridging oxygens being produced as a consequence of radiation damage. The spectra have been acquired at moderate magnetic fields over periods typically of 60 h (1 weekend) and it is concluded that a 'routine' overnight (17)O experiment of 15 h at high field (e.g. 21 T) may well be possible.

  17. Solid-State NMR Studies of Amyloid Fibril Structure

    NASA Astrophysics Data System (ADS)

    Tycko, Robert

    2011-05-01

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

  18. Testing the limits of sensitivity in a solid-state structural investigation by combined X-ray powder diffraction, solid-state NMR, and molecular modelling.

    PubMed

    Filip, Xenia; Borodi, Gheorghe; Filip, Claudiu

    2011-10-28

    A solid state structural investigation of ethoxzolamide is performed on microcrystalline powder by using a multi-technique approach that combines X-ray powder diffraction (XRPD) data analysis based on direct space methods with information from (13)C((15)N) solid-state Nuclear Magnetic Resonance (SS-NMR) and molecular modeling. Quantum chemical computations of the crystal were employed for geometry optimization and chemical shift calculations based on the Gauge Including Projector Augmented-Wave (GIPAW) method, whereas a systematic search in the conformational space was performed on the isolated molecule using a molecular mechanics (MM) approach. The applied methodology proved useful for: (i) removing ambiguities in the XRPD crystal structure determination process and further refining the derived structure solutions, and (ii) getting important insights into the relationship between the complex network of non-covalent interactions and the induced supra-molecular architectures/crystal packing patterns. It was found that ethoxzolamide provides an ideal case study for testing the accuracy with which this methodology allows to distinguish between various structural features emerging from the analysis of the powder diffraction data.

  19. Modern solid state laser materials

    SciTech Connect

    Krupke, W.F.

    1984-06-20

    This document contains visual aids used in an invited talk entitled Modern Solid State Laser Materials, presented at the Conference on Lasers and Electro-Optics (CLEO) held in Anaheim, California, on June 20, 1984. Interest at LLNL in solid state lasers focuses on evaluating the potential of solid state laser media for high average power applications, including inertial fusion power production. This talk identifies the relevant bulk material parameters characterizing average power capacity and uses chromium and neodymium co-doped gadolinium scandium gallium garnet (Nd:Cr:GSGG) as an example of a laser material with improved laser properties relative to Nd:YAG (plausible large-scale growth, more efficient spectral coupling to xenon flashlamp radiation, reduced stimulated emission cross section, adequate thermal shock and optical damage threshold parameters, etc.). Recently measured spectroscopic, kinetic, and thermo-mechanical properties of Nd:Cr:GSGG are given.

  20. Rapid and accurate determination of the lignin content of lignocellulosic biomass by solid-state NMR

    PubMed Central

    Fu, Li; McCallum, Scott A.; Miao, Jianjun; Hart, Courtney; Tudryn, Gregory J.; Zhang, Fuming; Linhardt, Robert J.

    2014-01-01

    Biofuels and biomaterials, produced from lignocellulosic feedstock, require facile access to cellulose and hemicellulose to be competitive with petroleum processing and sugar-based fermentation. Physical-chemical barriers resulting from lignin complicates the hydrolysis biomass into fermentable sugars. Thus, the amount of lignin within a substrate is critical in determining biomass processing. The application of 13C cross-polarization, magic-angle spinning, and solid-state nuclear magnetic resonance for the direct quantification of lignin content in biomass is examined. Using a standard curve constructed from pristine lignin and cellulose, the lignin content of a biomass sample is accurately determined through direct measurement without chemical or enzymatic pre-treatment. PMID:25404762

  1. Folding of xylan onto cellulose fibrils in plant cell walls revealed by solid-state NMR

    NASA Astrophysics Data System (ADS)

    Simmons, Thomas J.; Mortimer, Jenny C.; Bernardinelli, Oigres D.; Pöppler, Ann-Christin; Brown, Steven P.; Deazevedo, Eduardo R.; Dupree, Ray; Dupree, Paul

    2016-12-01

    Exploitation of plant lignocellulosic biomass is hampered by our ignorance of the molecular basis for its properties such as strength and digestibility. Xylan, the most prevalent non-cellulosic polysaccharide, binds to cellulose microfibrils. The nature of this interaction remains unclear, despite its importance. Here we show that the majority of xylan, which forms a threefold helical screw in solution, flattens into a twofold helical screw ribbon to bind intimately to cellulose microfibrils in the cell wall. 13C solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, supported by in silico predictions of chemical shifts, shows both two- and threefold screw xylan conformations are present in fresh Arabidopsis stems. The twofold screw xylan is spatially close to cellulose, and has similar rigidity to the cellulose microfibrils, but reverts to the threefold screw conformation in the cellulose-deficient irx3 mutant. The discovery that induced polysaccharide conformation underlies cell wall assembly provides new principles to understand biomass properties.

  2. Solid-state lithium battery

    SciTech Connect

    Ihlefeld, Jon; Clem, Paul G; Edney, Cynthia; Ingersoll, David; Nagasubramanian, Ganesan; Fenton, Kyle Ross

    2014-11-04

    The present invention is directed to a higher power, thin film lithium-ion electrolyte on a metallic substrate, enabling mass-produced solid-state lithium batteries. High-temperature thermodynamic equilibrium processing enables co-firing of oxides and base metals, providing a means to integrate the crystalline, lithium-stable, fast lithium-ion conductor lanthanum lithium tantalate (La.sub.1/3-xLi.sub.3xTaO.sub.3) directly with a thin metal foil current collector appropriate for a lithium-free solid-state battery.

  3. 15N and 13C NMR Determination of Allantoin Metabolism in Developing Soybean Cotyledons 1

    PubMed Central

    Coker, George T.; Schaefer, Jacob

    1985-01-01

    The metabolism of allantoin by immature cotyledons of soybean (Glycine max L. cv Elf) grown in culture was investigated using solid state 13C and 15N nuclear magnetic resonance. All of the nitrogens of allantoin were incorporated into protein in a manner similar to that of each other and to the amide nitrogen of glutamine. The C-2 of allantoin was not incorporated into cellular material; presumably it was lost as CO2. About 50% of the C-5 of allantoin was incorporated into cellular material as a methylene carbon; the other 50% was presumably also lost as CO2. The 13C-15N bonds of [5-13C;1-15N] and [2-13C;1,3-15N]allantoin were broken prior to the incorporation of the nitrogens into protein. These data are consistent with allantoin's degradation to two molecules of urea and one two-carbon fragment. Cotyledons grown on allantoin as a source of nitrogen accumulated 21% of the nitrogen of cotyledons grown on glutamine. Only 50% of the nitrogen of the degraded allantoin was incorporated into the cotyledon as organic nitrogen; the other 50% was recovered as NH4+ in the media in which the cotyledons had been grown. The latter results suggests that the lower accumulation of nitrogen by cotyledons grown on allantoin was in part due to failure to assimilate NH4+ produced from allantoin. The seed coats had a higher activity of glutamine synthetase and a higher rate of allantoin degradation than cotyledons indicating that seed coats play an important role in the assimilation and degradation of allantoin. PMID:16663995

  4. Solid State Reactor Final Report

    SciTech Connect

    Mays, G.T.

    2004-03-10

    The Solid State Reactor (SSR) is an advanced reactor concept designed to take advantage of Oak Ridge National Laboratory's (ORNL's) recently developed graphite foam that has enhanced heat transfer characteristics and excellent high-temperature mechanical properties, to provide an inherently safe, self-regulated, source of heat for power and other potential applications. This work was funded by the U.S. Department of Energy's Nuclear Energy Research Initiative (NERI) program (Project No. 99-064) from August 1999 through September 30, 2002. The initial concept of utilizing the graphite foam as a basis for developing an advanced reactor concept envisioned that a suite of reactor configurations and power levels could be developed for several different applications. The initial focus was looking at the reactor as a heat source that was scalable, independent of any heat removal/power conversion process. These applications might include conventional power generation, isotope production and destruction (actinides), and hydrogen production. Having conducted the initial research on the graphite foam and having performed the scoping parametric analyses from neutronics and thermal-hydraulic perspectives, it was necessary to focus on a particular application that would (1) demonstrate the viability of the overall concept and (2) require a reasonably structured design analysis process that would synthesize those important parameters that influence the concept the most as part of a feasible, working reactor system. Thus, the application targeted for this concept was supplying power for remote/harsh environments and a design that was easily deployable, simplistic from an operational standpoint, and utilized the new graphite foam. Specifically, a 500-kW(t) reactor concept was pursued that is naturally load following, inherently safe, optimized via neutronic studies to achieve near-zero reactivity change with burnup, and proliferation resistant. These four major areas of research

  5. Interaction between the marine sponge cyclic peptide theonellamide A and sterols in lipid bilayers as viewed by surface plasmon resonance and solid-state (2)H nuclear magnetic resonance.

    PubMed

    Espiritu, Rafael Atillo; Matsumori, Nobuaki; Murata, Michio; Nishimura, Shinichi; Kakeya, Hideaki; Matsunaga, Shigeki; Yoshida, Minoru

    2013-04-09

    Theonellamides (TNMs) are members of a distinctive family of antifungal and cytotoxic bicyclic dodecapeptides isolated from the marine sponge Theonella sp. Recently, it has been shown that TNMs recognize 3β-hydroxysterol-containing membranes, induce glucan overproduction, and damage cellular membranes. However, to date, the detailed mode of sterol binding at a molecular level has not been determined. In this study, to gain insight into the mechanism of sterol recognition of TNM in lipid bilayers, surface plasmon resonance (SPR) experiments and solid-state deuterium nuclear magnetic resonance ((2)H NMR) measurements were performed on theonellamide A (TNM-A). SPR results revealed that the incorporation of 10 mol % cholesterol or ergosterol into 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) membranes significantly enhances the affinity of the peptide for the membrane, particularly in the initial binding to the membrane surface. These findings, together with the fact that binding of TNM-A to epicholesterol (3α-cholesterol)-containing liposomes and pure POPC liposomes was comparably weak, confirmed the preference of the peptide for the 3β-hydroxysterol-containing membranes. To further establish the formation of the complex of TNM-A with 3β-hydroxysterols in lipid bilayers, solid-state (2)H NMR measurements were conducted using deuterium-labeled cholesterol, ergosterol, or epicholesterol. The (2)H NMR spectra showed that TNM-A significantly inhibits the fast rotational motion of cholesterol and ergosterol, but not epicholesterol, therefore verifying the direct complexation between TNM-A and 3β-hydroxysterols in lipid bilayers. This study demonstrates that TNM-A directly recognizes the 3β-OH moiety of sterols, which greatly facilitates its binding to bilayer membranes.

  6. Final Report for "Boron and Tin in Nuclear Medicien: The Development of Reactive Solid-State Reagents for PET and SPECT

    SciTech Connect

    George W. Kabalka

    2006-01-13

    The research program was directed at the use of functionalized organometallic reagents that would rapidly react with radiolabeled agents generated by a medical cyclotron or reactor. The radioisotopes included fluorine-18, oxgygen-15, nitrogen-13, carbon-11 and iodine-123; all short lived nuclides of importantce in nuclear medicine imaging studies utilizing emission tomography techniques. The early studies led to the development of extensive new isotope incorporation chemistry. These studies validated the feasibility of using reactive intermediates, such as the organoboranes, and acted as a catalyst for others to investigate organometallic agents based on mercury, tin, and silicon. A large number of radiolabeling techniques and radiopharmaceuticals were developed. These included agents for use in oncology, neurology, and metabolism. The research resulted in the generation of one hundred and one journal articles, eighty seven refereed published abstracts and forty one invited lectures. Thirteen postdoctoral students, fourteen graduate students, and twenty eight undergraduate students were trained in the scientific aspects of nuclear medicine imaging under the asupices of this grant.

  7. Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations.

    PubMed

    Wang, Tuo; Yang, Hui; Kubicki, James D; Hong, Mei

    2016-06-13

    The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D (13)C-(13)C correlation spectra of uniformly (13)C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose (13)C chemical shifts differ significantly from the (13)C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing, and hydrogen bonding from celluloses of other organisms. 2D (13)C-(13)C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Celluloses f and g are well mixed chains on the microfibril surface, celluloses a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of

  8. Cellulose Structural Polymorphism in Plant Primary Cell Walls Investigated by High-Field 2D Solid-State NMR Spectroscopy and Density Functional Theory Calculations

    PubMed Central

    Wang, Tuo; Yang, Hui; Kubicki, James D.; Hong, Mei

    2017-01-01

    The native cellulose of bacterial, algal, and animal origins has been well studied structurally using X-ray and neutron diffraction and solid-state NMR spectroscopy, and is known to consist of varying proportions of two allomorphs, Iα and Iβ, which differ in hydrogen bonding, chain packing, and local conformation. In comparison, cellulose structure in plant primary cell walls is much less understood because plant cellulose has lower crystallinity and extensive interactions with matrix polysaccharides. Here we have combined two-dimensional magic-angle-spinning (MAS) solid-state nuclear magnetic resonance (solid-state NMR) spectroscopy at high magnetic fields with density functional theory (DFT) calculations to obtain detailed information about the structural polymorphism and spatial distributions of plant primary-wall cellulose. 2D 13C-13C correlation spectra of uniformly 13C-labeled cell walls of several model plants resolved seven sets of cellulose chemical shifts. Among these, five sets (denoted a-e) belong to cellulose in the interior of the microfibril while two sets (f and g) can be assigned to surface cellulose. Importantly, most of the interior cellulose 13C chemical shifts differ significantly from the 13C chemical shifts of the Iα and Iβ allomorphs, indicating that plant primary-wall cellulose has different conformations, packing and hydrogen bonding from celluloses of other organisms. 2D 13C-13C correlation experiments with long mixing times and with water polarization transfer revealed the spatial distributions and matrix-polysaccharide interactions of these cellulose structures. Cellulose f and g are well mixed chains on the microfibril surface, cellulose a and b are interior chains that are in molecular contact with the surface chains, while cellulose c resides in the core of the microfibril, outside spin diffusion contact with the surface. Interestingly, cellulose d, whose chemical shifts differ most significantly from those of bacterial, algal

  9. Differential effects of safflower oil versus fish oil feeding on insulin-stimulated glycogen synthesis, glycolysis, and pyruvate dehydrogenase flux in skeletal muscle: a 13C nuclear magnetic resonance study.

    PubMed

    Jucker, B M; Cline, G W; Barucci, N; Shulman, G I

    1999-01-01

    To examine the effects of safflower oil versus fish oil feeding on in vivo intramuscular glucose metabolism and relative pyruvate dehydrogenase (PDH) versus tricarboxylic acid (TCA) cycle flux, rats were pair-fed on diets consisting of 1) 59% safflower oil, 2) 59% menhaden fish oil, or 3) 59% carbohydrate (control) in calories. Rates of glycolysis and glycogen synthesis were assessed by monitoring [1-(13)C]glucose label incorporation into [1-(13)C]glycogen, [3-(13)C]lactate, and [3-(13)C]alanine in the hindlimb of awake rats via 13C nuclear magnetic resonance (NMR) spectroscopy during a euglycemic (approximately 6 mmol/l) hyperinsulinemic (approximately 180 microU/ml) clamp. A steady-state isotopic analysis of lactate, alanine, and glutamate was used to determine the relative PDH versus TCA cycle flux present in muscle under these conditions. The safflower oil-fed rats were insulin resistant compared with control and fish oil-fed rats, as reflected by a markedly reduced glucose infusion rate (Ginf) during the clamp (21.4 +/- 2.3 vs. 31.6 +/- 2.8 and 31.7 +/- 1.9 mg x kg(-1) x min(-1) in safflower oil versus control and fish oil groups, respectively, P < 0.006). This decrease in insulin-stimulated glucose disposal in the safflower oil group was associated with a lower rate of glycolysis (21.7 +/- 2.2 nmol x g(-1) x min(-1)) versus control (62.1 +/- 10.3 nmol x g(-1) x min(-1), P < 0.001) and versus fish oil (45.7 +/- 6.7 nmol x g(-1) x min(-1), P < 0.04), as no change in glycogen synthesis (103 +/- 15, 133 +/- 19, and 125 +/- 14 nmol x g(-1) x min(-1) in safflower oil, fish oil, and control, respectively) was detected. The intramuscular triglyceride (TG) content was increased in the safflower oil group (7.3 +/- 0.8 micromol/g) compared with the control group (5.2 +/- 0.8 micromol/g, P < 0.05) and the fish oil group (3.6 +/- 1.1 micromol/g, P < 0.01). Conversely, the percent PDH versus TCA cycle flux was decreased in the safflower oil (43 +/- 8%) versus the control

  10. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks Using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A.; Rosay, Melanie; Johnson, Duane D.; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt²⁺ and Cu²⁺) and a zirconium metal–organic framework (UiO-66-NH₂) was explored using dynamic nuclear polarization-enhanced ¹⁵N{¹H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt²⁺ coordinates with two NH₂ groups from the MOF and two Cl⁻ from the metal precursor, whereas Cu²⁺ do not form chemical bonds with the NH₂ groups of the MOF framework. Density functional calculations reveal that Pt²⁺ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  11. Selective Host-Guest Interaction between Metal Ions and Metal-Organic Frameworks using Dynamic Nuclear Polarization Enhanced Solid-State NMR Spectroscopy

    SciTech Connect

    Guo, Zhiyong; Kobayashi, Takeshi; Wang, Lin-Lin; Goh, Tian Wei; Xiao, Chaoxian; Caporini, Marc A; Rosay, Melanie; Johnson, Duane D; Pruski, Marek; Huang, Wenyu

    2014-10-08

    The host–guest interaction between metal ions (Pt2+ and Cu2+) and a zirconium metal–organic framework (UiO-66-NH2) was explored using dynamic nuclear polarization-enhanced 15N{1H} CPMAS NMR spectroscopy supported by X-ray absorption spectroscopy and density functional calculations. The combined experimental results conclude that each Pt2+ coordinates with two NH2 groups from the MOF and two Cl- from the metal precursor, whereas Cu2+ do not form chemical bonds with the NH2 groups of the MOF framework. Density functional calculations reveal that Pt2+ prefers a square-planar structure with the four ligands and resides in the octahedral cage of the MOF in either cis or trans configurations.

  12. Solid-State Dynamic Nuclear Polarization at 9.4 and 18.8 T from 100 K to Room Temperature

    PubMed Central

    2015-01-01

    Efficient dynamic nuclear polarization (DNP) in solids, which enables very high sensitivity NMR experiments, is currently limited to temperatures of around 100 K and below. Here we show how by choosing an adequate solvent, 1H cross effect DNP enhancements of over 80 can be obtained at 240 K. To achieve this we use the biradical TEKPol dissolved in a glassy phase of ortho-terphenyl (OTP). We study the solvent DNP enhancement of both TEKPol and BDPA in OTP in the range from 100 to 300 K at 9.4 and 18.8 T. Surprisingly, we find that the DNP enhancement decreases only relatively slowly for temperatures below the glass transition of OTP (Tg = 243 K), and 1H enhancements around 15–20 at ambient temperature can be observed. We use this to monitor molecular dynamic transitions in the pharmaceutically relevant solids Ambroxol and Ibuprofen. PMID:26555676

  13. The solid-state signaling pathway from extracellular matrix to nuclear matrix: The critical role of three-dimensional architecture for functional differentiation

    SciTech Connect

    Lelievre, S.; Bissell, M.J.

    1997-02-01

    Breast cells are useful experimental subjects for cell biologists because the mammary gland is one of the few tissues that undergoes dramatic changes in form and function after adulthood. Recently, the study in our laboratory of a human breast tumor progression series has allowed for the analysis of changes in cellular architecture (including nuclear architecture) when phenotypically normal cells become tumorigenic. This research aims to participate in the battle against breast cancer by helping to understand tumor progression and to identify new therapeutic markers for cancer treatment. This article explores the advantages and challenges of using high resolution X-ray computed microtomography for the study of 3-dimensional organization of breast tissue architecture.

  14. Detection of kestoses and kestose-related oligosaccharides in extracts of Festuca arundinacea, Dactylis glomerate L. , and Asparagus officinalis L. root cultures and invertase by sup 13 C and sup 1 H nuclear magnetic resonance spectroscopy

    SciTech Connect

    Forsythe, K.L.; Feather, M.S.; Gracz, H.; Wong, T.C. )

    1990-04-01

    Previous studies show that {sup 13}C nuclear magnetic resonance spectroscopy can be used to detect and identify mixtures of 1-kestose and neokestose after conversion to the acetate derivatives. In this study, unequivocal assignments are made for the anomeric carbon and proton signals for the above two trisaccharide acetates as well as for 6-kestose hendecaacetate and for nystose tetradecaacetate (a 1-kestose-derived tetrasaccharide). A number of oligosaccharide fractions were isolated from several plant species, converted to the acetates, and nuclear magnetic resonance spectra obtained. Using the above reference data, the following information was obtained. The trisaccharide fraction from Dactylis gomerata L. stem tissue and Asparagus officinalis L. roots contain both 1-kestose and neokestose, and the tetrasaccharide fractions contain three components, one of which is nystose. Penta- and hexasaccharide acetates were also isolated from A. officinalis L. roots and were found to contain, respectively, four and at least five components. All components of both of the above species appear to contain a kestose residue and to be produced by the sequential addition of fructofuranosyl units to these. The trisaccharide fraction from Festuca arundinacea is complex, and contains at least five different components, two of which appear to be 1-kestose and neokestose.

  15. Effective Hamiltonians by optimal control: solid-state NMR double-quantum planar and isotropic dipolar recoupling.

    PubMed

    Tosner, Zdenek; Glaser, Steffen J; Khaneja, Navin; Nielsen, Niels Chr

    2006-11-14

    We report the use of optimal control algorithms for tailoring the effective Hamiltonians in nuclear magnetic resonance (NMR) spectroscopy through sophisticated radio-frequency (rf) pulse irradiation. Specifically, we address dipolar recoupling in solid-state NMR of powder samples for which case pulse sequences offering evolution under planar double-quantum and isotropic mixing dipolar coupling Hamiltonians are designed. The pulse sequences are constructed numerically to cope with a range of experimental conditions such as inhomogeneous rf fields, spread of chemical shifts, the intrinsic orientation dependencies of powder samples, and sample spinning. While the vast majority of previous dipolar recoupling sequences are operating through planar double-or zero-quantum effective Hamiltonians, we present here not only improved variants of such experiments but also for the first time homonuclear isotropic mixing sequences which transfers all I(x), I(y), and I(z) polarizations from one spin to the same operators on another spin simultaneously and with equal efficiency. This property may be exploited to increase the signal-to-noise ratio of two-dimensional experiments by a factor of square root 2 compared to conventional solid-state methods otherwise showing the same efficiency. The sequences are tested numerically and experimentally for a powder of (13)C(alpha),(13)C(beta)-L-alanine and demonstrate substantial sensitivity gains over previous dipolar recoupling experiments.

  16. Stacking structure of confined 1-butanol in SBA-15 investigated by solid-state NMR spectroscopy.

    PubMed

    Lin, Yun-Chih; Chou, Hung-Lung; Sarma, Loka Subramanyam; Hwang, Bing-Joe

    2009-10-12

    Understanding the complex thermodynamic behavior of confined amphiphilic molecules in biological or mesoporous hosts requires detailed knowledge of the stacking structures. Here, we present detailed solid-state NMR spectroscopic investigations on 1-butanol molecules confined in the hydrophilic mesoporous SBA-15 host. A range of NMR spectroscopic measurements comprising of (1)H spin-lattice (T(1)), spin-spin (T(2)) relaxation, (13)C cross-polarization (CP), and (1)H,(1)H two-dimensional nuclear Overhauser enhancement spectroscopy ((1)H,(1)H 2D NOESY) with the magic angle spinning (MAS) technique as well as static wide-line (2)H NMR spectra have been used to investigate the dynamics and to observe the stacking structure of confined 1-butanol in SBA-15. The results suggest that not only the molecular reorientation but also the exchange motions of confined molecules of 1-butanol are extremely restricted in the confined space of the SBA-15 pores. The dynamics of the confined molecules of 1-butanol imply that the (1)H,(1)H 2D NOESY should be an appropriate technique to observe the stacking structure of confined amphiphilc molecules. This study is the first to observe that a significant part of confined 1-butanol molecules are orientated as tilted bilayered structures on the surface of the host SBA-15 pores in a time-average state by solid-state NMR spectroscopy with the (1)H,(1)H 2D NOESY technique.

  17. Solid-state evaluation and polymorphic quantification of venlafaxine hydrochloride raw materials using the Rietveld method.

    PubMed

    Bernardi, Larissa S; Ferreira, Fábio F; Cuffini, Silvia L; Campos, Carlos E M; Monti, Gustavo A; Kuminek, Gislaine; Oliveira, Paulo R; Cardoso, Simone G

    2013-12-15

    Venlafaxine hydrochloride (VEN) is an antidepressant drug widely used for the treatment of depression. The purpose of this study was to carry out the preparation and solid state characterization of the pure polymorphs (Forms 1 and 2) and the polymorphic identification and quantification of four commercially-available VEN raw materials. These two polymorphic forms were obtained from different crystallization methods and characterized by X-ray Powder Diffraction (XRPD), Diffuse Reflectance Infrared Fourier Transform (DRIFT), Raman Spectroscopy (RS), liquid and solid state Nuclear Magnetic Resonance (NMR and ssNMR) spectroscopies, Differential Scanning Calorimetry (DSC), and Scanning Electron Microscopy (SEM) techniques. The main differences were observed by DSC and XRPD and the latter was chosen as the standard technique for the identification and quantification studies in combination with the Rietveld method for the commercial raw materials (VEN1-VEN4) acquired from different manufacturers. Additionally Form 1 and Form 2 can be clearly distinguished from their (13)C ssNMR spectra. Through the analysis, it was possible to conclude that VEN1 and VEN2 were composed only of Form 1, while VEN3 and VEN4 were a mixture of Forms 1 and 2. Additionally, the Rietveld refinement was successfully applied to quantify the polymorphic ratio for VEN3 and VEN4.

  18. Modern solid state laser materials

    NASA Astrophysics Data System (ADS)

    Krupke, W. F.

    1984-06-01

    Visual aids used in an invited talk entitled Modern Solid State Laser Materials are presented. Interest at LLNL in solid state lasers focuses on evaluating the potential inertial fusion power production. The relevant bulk material parameters characterizing average power capacity are identified and chromium and neodymium co-doped gadolinium scandium gallium garnet (Nd:Cr:GSGG) are used as an example of a laser material with improved laser properties relative to Nd:YAG (plausible large scale growth, more efficient spectral coupling to xenon flashlamp radiation, reduced stimulated emission cross section, adequate thermal shock and optical damage threshold parameters, etc.). Recently measured spectroscopic, kinetic, and thermomechanical properties of Nd:Cr:GSGG are given.

  19. Solid-state membrane module

    DOEpatents

    Gordon, John Howard; Taylor, Dale M.

    2011-06-07

    Solid-state membrane modules comprising at least one membrane unit, where the membrane unit has a dense mixed conducting oxide layer, and at least one conduit or manifold wherein the conduit or manifold comprises a dense layer and at least one of a porous layer and a slotted layer contiguous with the dense layer. The solid-state membrane modules may be used to carry out a variety of processes including the separating of any ionizable component from a feedstream wherein such ionizable component is capable of being transported through a dense mixed conducting oxide layer of the membrane units making up the membrane modules. For ease of construction, the membrane units may be planar.

  20. Solid state cell with anolyte

    SciTech Connect

    Barnette, L. H.; Liang, C. C.

    1985-06-25

    A solid state cell having a solid cathode, a solid electrolyte, and a solid anolyte comprised of at least 50% by volume of ionically conductive materials such as the electrolye and 50% or less by volume of an active metal. The anolyte is either the cell anode or alternatively the anolyte is an additional structural member within said cell positioned between an anode, comprised of the same active metal, and the solid electrolyte.

  1. Radiation sensitive solid state switch

    NASA Technical Reports Server (NTRS)

    Hutto, R. J. (Inventor)

    1973-01-01

    A mechanically operable solid state switch suited for use in achieving a variable circuit-switching function is described. This switch is characterized by an annular array of photoresponsive switching devices, disposed in communication with an included source of radiation, and a plurality of interchangeable, mechanically operable interrupter disks. Each disk has a predetermined pattern of transparent and opaque portions. Operative displacement of each disk serves to make and break selected electrical circuits through the photo responsive devices of said array.

  2. Solid state electrochemical current source

    DOEpatents

    Potanin, Alexander Arkadyevich; Vedeneev, Nikolai Ivanovich

    2002-04-30

    A cathode and a solid state electrochemical cell comprising said cathode, a solid anode and solid fluoride ion conducting electrolyte. The cathode comprises a metal oxide and a compound fluoride containing at least two metals with different valences. Representative compound fluorides include solid solutions of bismuth fluoride and potassium fluoride; and lead fluoride and potassium fluoride. Representative metal oxides include copper oxide, lead oxide, manganese oxide, vanadium oxide and silver oxide.

  3. Solid-state membrane module

    DOEpatents

    Hinklin, Thomas Ray; Lewinsohn, Charles Arthur

    2015-06-30

    A module for separating oxygen from an oxygen-containing gaseous mixture comprising planar solid-state membrane units, each membrane unit comprising planar dense mixed conducting oxides layers, planar channel-free porous support layers, and one or more planar intermediate support layers comprising at least one channeled porous support layer. The porosity of the planar channeled porous support layers is less than the porosity of the planar channel-free porous support layers.

  4. Structure and dynamics of retinal in rhodopsin elucidated by deuterium solid state NMR

    NASA Astrophysics Data System (ADS)

    Salgado, Gilmar Fernandes De Jesus

    Rhodopsin is a seven transmembrane helix GPCR found which mediates dim light vision, in which the binding pocket is occupied by the ligand 11- cis-retinal. A site-directed 2H-labeling approach utilizing solid-state 2H NMR spectroscopy was used to investigate the structure and dynamics of retinal within its binding pocket in the dark state of rhodopsin, and as well the MetaI and MetaII. 11-cis-[5-C 2H3]-, 11-cis-[9-C 2H3]-, and 11-cis-[13-C2H 3]-retinal were used to regenerate bleached rhodopsin. Recombinant membranes comprising purified rhodopsin and 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine (POPC) were prepared (1:50 molar ratio). Solid-state 2H NMR spectra were obtained for the aligned rhodopsin/POPC recombinant membranes at temperatures below the order-disorder phase transition temperature of POPC. The solid-state NMR studies of aligned samples, give the orientations of the 2H nuclear coupling tensor relative to the membrane frame, which involve both the conformation and orientation of the bound retinal chromophore. Theoretical simulations of the experimental 2H NMR spectra employed a new lineshape treatment for a semi-random distribution due to static uniaxial disorder. The analysis gives the orientation of the 2H-labeled C-C2H3 methyl bond axes relative to the membrane plane as well as the extent of three-dimensional alignment disorder (mosaic spread). These results clearly demonstrate the applicability of site-directed 2H NMR methods for investigating conformational changes and dynamics of ligands bound to rhodopsin and other GPCRs in relation to their characteristic mechanisms of action.

  5. Comparison of X-ray powder diffraction and solid-state nuclear magnetic resonance in estimating crystalline fraction of tacrolimus in sustained-release amorphous solid dispersion and development of discriminating dissolution method.

    PubMed

    Rahman, Ziyaur; Bykadi, Srikant; Siddiqui, Akhtar; Khan, Mansoor A

    2015-05-01

    The focus of present investigation was to explore X-ray powder diffraction (XRPD) and solid-state nuclear magnetic resonance (ssNMR) techniques for amorphous and crystalline tacrolimus quantification in the sustained-release amorphous solid dispersion (ASD), and to propose discriminating dissolution method that can detect crystalline drug. The ASD and crystalline physical mixture was mixed in various proportions to make sample matrices containing 0%-100% crystalline-amorphous tacrolimus. Partial-least-square regression and principle component regression were applied to the spectral data. Dissolution of the ASD in the US FDA recommended dissolution medium with and without surfactant was performed. R(2) > 0.99 and slope was close to one for all the models. Root-mean-square of prediction, standard error of prediction, and bias were higher in ssNMR-based models when compared with XRPD data models. Dissolution of the ASD decreased with an increase in the crystalline tacrolimus in the formulations. Furthermore, detection of crystalline tacrolimus in the ASD was progressively masked with an increase in the surfactant level in the dissolution medium. XRPD and ssNMR can be used equally to quantitate the crystalline and amorphous fraction of tacrolimus in the ASD with good accuracy; however, ssNMR data collection time is excessively long, and minimum surfactant level in the dissolution medium maximizes detection of crystalline reversion in the formulation.

  6. Comparative Dynamics of Leucine Methyl Groups in FMOC-Leucine and in a Protein Hydrophobic Core Probed by Solid-State Deuteron Nuclear Magnetic Resonance over 7-324 K Temperature Range

    SciTech Connect

    Vugmeyster, Liliya; Ostrovsky, Dmitry; Moses, Mark; Ford, Joseph J.; Lipton, Andrew S.; Hoatson, Gina; Vold, Robert L.

    2010-12-09

    Quantitative dynamics of methyl groups in 9-fluorenylmethyloxycarbonyl-leucine (FMOC-leu) have been analyzed and compared with earlier studies of methyl dynamics in chicken villin headpiece subdomain protein (HP36) labeled at L69, a key hydrophobic core position. A combination of deuteron solid-state nuclear magnetic resonance experiments over the temperature range of 7-324 K and computational modeling indicated that while the two compounds show the same modes of motions, there are marked differences in the best-fit parameters of these motions. One of the main results is that the crossover observed in the dynamics of the methyl groups in the HP36 sample at 170 K is absent in FMOC-leu. A second crossover at around 95-88 K is present in both samples. The differences in the behavior of the two compounds suggest that some of the features of methyl dynamics reflect the complexity of the protein hydrophobic core and are not determined solely by local interactions.

  7. 13C MAS NMR studies of crystalline cholesterol and lipid mixtures modeling atherosclerotic plaques.

    PubMed Central

    Guo, W; Hamilton, J A

    1996-01-01

    Cholesterol and cholesteryl esters are the predominant lipids of atherosclerotic plaques. To provide fundamental data for the quantitative study of plaque lipids in situ, crystalline cholesterol (CHOL) and CHOL/cholesteryl ester (CE) mixtures with other lipids were studied by solid-state nuclear magnetic resonance with magic-angle-sample spinning. Highly distinctive spectra for three different crystalline structures of CHOL were obtained. When CHOL crystals were mixed with isotropic CE oil, solubilized CHOL (approximately 13 mol % CHOL) was detected by characteristic resonances such as C5, C6, and C3; the excess crystalline CHOL (either anhydrous or monohydrate) remained in its original crystalline structure, without being affected by the coexisting CE. By use of 13C-enriched CHOL, the solubility of CHOL in the CE liquid-crystalline phase (approximately 8 mol %) was measured. When phosphatidylcholine was hydrated in presence of CHOL and CE, magic-angle-sampling nuclear magnetic resonance revealed liquid-crystalline CHOL/phosphatidylcholine multilayers with approximately an equal molar ratio of CHOL/phosphatidylcholine. Excess CHOL existed in the monohydrate crystalline form, and CE in separate oil or crystalline phases, depending on the temperature. The magic-angle-sampling nuclear magnetic resonance protocol for identifying different lipid phases was applied to intact (ex vivo) atherosclerotic plaques of cholesterol-fed rabbits. Liquid, liquid-crystalline, and solid phases of CE were characterized. Images FIGURE 2 PMID:8913623

  8. Furthering the understanding of silicate-substitution in α-tricalcium phosphate: an X-ray diffraction, X-ray fluorescence and solid-state nuclear magnetic resonance study.

    PubMed

    Duncan, J; Hayakawa, S; Osaka, A; MacDonald, J F; Hanna, J V; Skakle, J M S; Gibson, I R

    2014-03-01

    High-purity (SupT) and reagent-grade (ST), stoichiometric and silicate-containing α-tricalcium phosphate (α-TCP: ST0/SupT0 and Si-TCP x=0.10: ST10/SupT10) were prepared by solid-state reaction based on the substitution mechanism Ca3(PO4)(2-x)(SiO4)x. Samples were determined to be phase pure by X-ray diffraction (XRD), and Rietveld analysis performed on the XRD data confirmed inclusion of Si in the α-TCP structure as determined by increases in unit cell parameters; particularly marked increases in the b-axis and β-angle were observed. X-ray fluorescence (XRF) confirmed the presence of expected levels of Si in Si-TCP compositions as well as significant levels of impurities (Mg, Al and Fe) present in all ST samples; SupT samples showed both expected levels of Si and a high degree of purity. Phosphorus ((31)P) magic-angle-spinning solid-state nuclear magnetic resonance (MAS NMR) measurements revealed that the high-purity reagents used in the synthesis of SupT0 can resolve the 12 expected peaks in the (31)P spectrum of α-TCP compared to the low-purity ST0 that showed significant spectral line broadening; line broadening was also observed with the inclusion of Si which is indicative of induced structural disorder. Silicon ((29)Si) MAS NMR was also performed on both Si-TCP samples which revealed Q(0) species of Si with additional Si Q(1)/Q(2) species that may indicate a potential charge-balancing mechanism involving the inclusion of disilicate groups; additional Q(4) Si species were also observed, but only for ST10. Heating and cooling rates were briefly investigated by (31)P MAS NMR which showed no significant line broadening other than that associated with the emergence of β-TCP which was only realised with the reagent-grade sample ST0. This study provides an insight into the structural effects of Si-substitution in α-TCP and could provide a basis for understanding how substitution affects the physicochemical properties of the material.

  9. Solid-state and unilateral NMR study of deterioration of a Dead Sea Scroll fragment.

    PubMed

    Masic, A; Chierotti, M R; Gobetto, R; Martra, G; Rabin, I; Coluccia, S

    2012-02-01

    Unilateral and solid-state nuclear magnetic resonance (NMR) analyses were performed on a parchment fragment of the Dead Sea Scroll (DSS). The analyzed sample belongs to the collection of non-inscribed and nontreated fragments of known archaeological provenance from the John Rylands University Library in Manchester. Therefore, it can be considered as original DSS material free from any contamination related to the post-discovery period. Considering the paramount significance of the DSS, noninvasive approaches and portable in situ nondestructive methods are of fundamental importance for the determination of composition, structure, and chemical-physical properties of the materials under study. NMR studies reveal low amounts of water content associated with very short proton relaxation times, T(1), indicating a high level of deterioration of collagen molecules within scroll fragments. In addition, (13)C cross-polarization magic-angle-spinning (CPMAS) NMR spectroscopy shows characteristic peaks of lipids whose presence we attribute to the production technology that did not involve liming. Extraction with chloroform led to the reduction of both lipid and protein signals in the (13)C CPMAS spectrum indicating probable involvement of lipids in parchment degradation processes. NMR absorption and relaxation measurements provide nondestructive, discriminative, and sensitive tools for studying the deterioration effects on the organization and properties of water and collagen within ancient manuscripts.

  10. Solid state electrochromic light modulator

    DOEpatents

    Cogan, Stuart F.; Rauh, R. David

    1993-01-01

    An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

  11. Solid-state optical microscope

    DOEpatents

    Young, I.T.

    1981-01-07

    A solid state optical microscope is described wherein wide-field and high-resolution images of an object are produced at a rapid rate by utilizing conventional optics with a charge-coupled photodiode array. Means for scanning in one of two orthogonal directions are provided, while the charge-coupled photodiode array scans in the other orthogonal direction. Illumination light from the object is incident upon the photodiodes, creating packets of electrons (signals) which are representative of the illuminated object. The signals are then processed, stored in a memory, and finally displayed as a video signal.

  12. Solid-State Personal Dosimetry

    NASA Technical Reports Server (NTRS)

    Wrbanek, John D.; Fralick, Gustave C.; Wrbanek, Susan Y.

    2005-01-01

    This document is a web site page, and a data sheet about Personal protection (i.e., space suits) presented to the Radiation and Micrometeoroid Mitigation Technology Focus Group meeting. The website describes the work of the PI to improve solid state personal radiation dosimetry. The data sheet presents work on the active personal radiation detection system that is to provide real-time local radiation exposure information during EVA. Should undue exposure occur, knowledge of the dynamic intensity conditions during the exposure will allow more precise diagnostic assessment of the potential health risk to the exposed individual.

  13. Solid state electrochromic light modulator

    DOEpatents

    Cogan, Stuart F.; Rauh, R. David

    1993-12-07

    An all solid-state variable transmission electrochromic device has a source of charge compensating ions. An inorganic oxide counterelectrode film which on reduction with the accompanying insertion of the charge compensating ions increases its transmission of light of predetermined wavelength is separated from a primary electrochromic film which on reduction with the accompanying insertion of the charge compensating ions decreases its transmission of light of predetermined wavelength by an insulating electrolyte film that transports the charge compensating ions. First and second electrodes are contiguous with the inorganic oxide counter electrode film and the primary electrochromic film, respectively, and separated by the three films.

  14. Study and validity of 13C stable carbon isotopic ratio analysis by mass spectrometry and 2H site-specific natural isotopic fractionation by nuclear magnetic resonance isotopic measurements to characterize and control the authenticity of honey.

    PubMed

    Cotte, J F; Casabianca, H; Lhéritier, J; Perrucchietti, C; Sanglar, C; Waton, H; Grenier-Loustalot, M F

    2007-01-16

    Honey samples were analyzed by stable carbon isotopic ratio analysis by mass spectrometry (SCIRA-MS) and site-specific natural isotopic fractionation measured by nuclear magnetic resonance (SNIF-NMR) to first determine their potentials for characterizing the substance and then to combat adulteration. Honey samples from several geographic and botanical origins were analyzed. The delta(13)C parameter was not significant for characterizing an origin, while the (D/H)(I) ratio could be used to differentiate certain single-flower varieties. Application of the official control method of adding a C(4) syrup (AOAC official method 998.12) to our authentic samples revealed anomalies resulting from SCIRA indices that were more negative than -1 per thousand (permil). A filtration step was added to the experimental procedure and provided results that were compliant with the natural origin of our honey samples. In addition, spiking with a C(4) syrup could be detected starting at 9-10%. The use of SNIF-NMR is limited by the detection of a syrup spike starting only at 20%, which is far from satisfying.

  15. Solid-State NMR Spectroscopy for the Physical Chemistry Laboratory

    ERIC Educational Resources Information Center

    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…

  16. Contamination and solid state welds.

    SciTech Connect

    Mills, Bernice E.

    2007-05-01

    Since sensitivity to contamination is one of the verities of solid state joining, there is a need for assessing contamination of the part(s) to be joined, preferably nondestructively while it can be remedied. As the surfaces that are joined in pinch welds are inaccessible and thus provide a greater challenge, most of the discussion is of the search for the origin and effect of contamination on pinch welding and ways to detect and mitigate it. An example of contamination and the investigation and remediation of such a system is presented. Suggestions are made for techniques for nondestructive evaluation of contamination of surfaces for other solid state welds as well as for pinch welds. Surfaces that have good visual access are amenable to inspection by diffuse reflection infrared Fourier transform (DRIFT) spectroscopy. Although other techniques are useful for specific classes of contaminants (such as hydrocarbons), DRIFT can be used most classes of contaminants. Surfaces such as the interior of open tubes or stems that are to be pinch welded can be inspected using infrared reflection spectroscopy. It must be demonstrated whether or not this tool can detect graphite based contamination, which has been seen in stems. For tubes with one closed end, the technique that should be investigated is emission infrared spectroscopy.

  17. Solid-state proton conductors

    NASA Astrophysics Data System (ADS)

    Jewulski, J. R.; Osif, T. L.; Remick, R. J.

    1990-12-01

    The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling, and optimization studies. Correlation and optimization studies are described which include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells are presented which include the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms.

  18. Solid-state proton conductors

    SciTech Connect

    Jewulski, J.R.; Osif, T.L.; Remick, R.J.

    1990-12-01

    The purpose of this program was to survey the field of solid-state proton conductors (SSPC), identify conductors that could be used to develop solid-state fuel cells suitable for use with coal derived fuel gases, and begin the experimental research required for the development of these fuel cells. This document covers the following topics: the history of developments and current status of the SSPC, including a review of proton conducting electrolyte structures, the current status of the medium temperature SSPC development, electrodes for moderate temperature (SSPC) fuel cell, basic material and measurement techniques applicable for SSPC development, modeling and optimization studies. Correlation and optimization studies, to include correlation studies on proton conduction and oxide cathode optimization for the SSPC fuel cell. Experiments with the SSPC fuel cells including the fabrication of the electrolyte disks, apparatus for conducting measurements, the strontium-cerium based electrolyte, the barium-cerium based electrolyte with solid foil electrodes, the barium-cerium based electrolyte with porous electrodes, and conduction mechanisms. 164 refs., 27 figs., 13 tabs.

  19. Sensitivity-enhanced solid-state NMR detection of expansin’s target in plant cell walls

    PubMed Central

    Wang, Tuo; Park, Yong Bum; Caporini, Marc A.; Rosay, Melanie; Zhong, Linghao; Cosgrove, Daniel J.; Hong, Mei

    2013-01-01

    Structure determination of protein binding to noncrystalline macromolecular assemblies such as plant cell walls (CWs) poses a significant structural biology challenge. CWs are loosened during growth by expansin proteins, which weaken the noncovalent network formed by cellulose, hemicellulose, and pectins, but the CW target of expansins has remained elusive because of the minute amount of the protein required for activity and the complex nature of the CW. Using solid-state NMR spectroscopy, combined with sensitivity-enhancing dynamic nuclear polarization (DNP) and differential isotopic labeling of expansin and polysaccharides, we have now determined the functional binding target of expansin in the Arabidopsis thaliana CW. By transferring the electron polarization of a biradical dopant to the nuclei, DNP allowed selective detection of 13C spin diffusion from trace concentrations of 13C, 15N-labeled expansin in the CW to nearby polysaccharides. From the spin diffusion data of wild-type and mutant expansins, we conclude that to loosen the CW, expansin binds highly specific cellulose domains enriched in xyloglucan, whereas more abundant binding to pectins is unrelated to activity. Molecular dynamics simulations indicate short 13C-13C distances of 4–6 Å between a hydrophobic surface of the cellulose microfibril and an aromatic motif on the expansin surface, consistent with the observed NMR signals. DNP-enhanced 2D 13C correlation spectra further reveal that the expansin-bound cellulose has altered conformation and is enriched in xyloglucan, thus providing unique insight into the mechanism of CW loosening. DNP-enhanced NMR provides a powerful, generalizable approach for investigating protein binding to complex macromolecular targets. PMID:24065828

  20. Solid State Lighting Program (Falcon)

    SciTech Connect

    Meeks, Steven

    2012-06-30

    Over the past two years, KLA-Tencor and partners successfully developed and deployed software and hardware tools that increase product yield for High Brightness LED (HBLED) manufacturing and reduce product development and factory ramp times. This report summarizes our development effort and details of how the results of the Solid State Light Program (Falcon) have started to help HBLED manufacturers optimize process control by enabling them to flag and correct identified killer defect conditions at any point of origin in the process manufacturing flow. This constitutes a quantum leap in yield management over current practice. Current practice consists of die dispositioning which is just rejection of bad die at end of process based upon probe tests, loosely assisted by optical in-line monitoring for gross process deficiencies. For the first time, and as a result of our Solid State Lighting Program, our LED manufacturing partners have obtained the software and hardware tools that optimize individual process steps to control killer defects at the point in the processes where they originate. Products developed during our two year program enable optimized inspection strategies for many product lines to minimize cost and maximize yield. The Solid State Lighting Program was structured in three phases: i) the development of advanced imaging modes that achieve clear separation between LED defect types, improves signal to noise and scan rates, and minimizes nuisance defects for both front end and back end inspection tools, ii) the creation of defect source analysis (DSA) software that connect the defect maps from back-end and front-end HBLED manufacturing tools to permit the automatic overlay and traceability of defects between tools and process steps, suppress nuisance defects, and identify the origin of killer defects with process step and conditions, and iii) working with partners (Philips Lumileds) on product wafers, obtain a detailed statistical correlation of automated

  1. A solid state NMR study of layered double hydroxides intercalated with para-amino salicylate, a tuberculosis drug.

    PubMed

    Jensen, Nicholai Daugaard; Bjerring, Morten; Nielsen, Ulla Gro

    2016-09-01

    Para-amino salicylate (PAS), a tuberculosis drug, was intercalated in three different layered double hydroxides (MgAl, ZnAl, and CaAl-LDH) and the samples were studied by multi-nuclear ((1)H, (13)C, and (27)Al) solid state NMR (SSNMR) spectroscopy in combination with powder X-ray diffraction (PXRD), elemental analysis and IR-spectroscopy to gain insight into the bulk and atomic level structure of these LDHs especially with a view to the purity of the LDH-PAS materials and the concentration of impurities. The intercalations of PAS in MgAl-, ZnAl-, and CaAl-LDH's were confirmed by (13)C SSNMR and PXRD. Moreover, (13)C MAS NMR and infrared spectroscopy show that PAS did not decompose during synthesis. Large amounts (20-41%) of amorphous aluminum impurities were detected in the structure using (27)Al single pulse and 3QMAS NMR spectra, which in combination with (1)H 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 (1)H SSNMR spectra of a CaAl LDH is reported and assigned using (1)H single and double quantum experiments in combination with (27)Al{(1)H} HETCOR.

  2. Coherent manipulation of single quantum systems in the solid state

    NASA Astrophysics Data System (ADS)

    Childress, Lilian Isabel

    2007-12-01

    The controlled, coherent manipulation of quantum-mechanical systems is an important challenge in modern science and engineering, with significant applications in quantum information science. Solid-state quantum systems such as electronic spins, nuclear spins, and superconducting islands are among the most promising candidates for realization of quantum bits (qubits). However, in contrast to isolated atomic systems, these solid-state qubits couple to a complex environment which often results in rapid loss of coherence, and, in general, is difficult to understand. Additionally, the strong interactions which make solid-state quantum systems attractive can typically only occur between neighboring systems, leading to difficulties in coupling arbitrary pairs of quantum bits. This thesis presents experimental progress in understanding and controlling the complex environment of a solid-state quantum bit, and theoretical techniques for extending the distance over which certain quantum bits can interact coherently. Coherent manipulation of an individual electron spin associated with a nitrogen-vacancy center in diamond is used to gain insight into its mesoscopic environment. Furthermore, techniques for exploiting coherent interactions between the electron spin and a subset of the environment are developed and demonstrated, leading to controlled interactions with single isolated nuclear spins. The quantum register thus formed by a coupled electron and nuclear spin provides the basis for a theoretical proposal for fault-tolerant long-distance quantum communication with minimal physical resource requirements. Finally, we consider a mechanism for long-distance coupling between quantum dots based on chip-scale cavity quantum electrodynamics.

  3. Synthesis of exemestane labelled with (13)C.

    PubMed

    Fontana, Erminia; Pignatti, Alberto; Giribone, Danilo; Di Salle, Enrico

    2008-08-01

    The synthesis of exemestane Aromasin, an irreversible steroidal aromatase inhibitor, specifically labelled with (13)C is reported. The preparation of [(13)C(3)]exemestane was achieved according to an eight-step procedure starting from the commercially available testosterone.

  4. Synthesis of Site-Specifically (13)C Labeled Linoleic Acids.

    PubMed

    Offenbacher, Adam R; Zhu, Hui; Klinman, Judith P

    2016-10-12

    Soybean lipoxygenase-1 (SLO-1) catalyzes the C-H abstraction from the reactive carbon (C-11) in linoleic acid as the first and rate-determining step in the formation of alkylhydroperoxides. While previous labeling strategies have focused on deuterium labeling to ascertain the primary and secondary kinetic isotope effects for this reaction, there is an emerging interest and need for selectively enriched (13)C isotopologues. In this report, we present synthetic strategies for site-specific (13)C labeled linoleic acid substrates. We take advantage of a Corey-Fuchs formyl to terminal (13)C-labeled alkyne conversion, using (13)CBr4 as the labeling source, to reduce the number of steps from a previous fatty acid (13)C synthetic labeling approach. The labeled linoleic acid substrates are useful as nuclear tunneling markers and for extracting active site geometries of the enzyme-substrate complex in lipoxygenase.

  5. 6-Aminopenicillanic acid revisited: A combined solid state NMR and in silico refinement

    NASA Astrophysics Data System (ADS)

    Aguiar, Daniel Lima Marques de; San Gil, Rosane Aguiar da Silva; Alencastro, Ricardo Bicca de; Souza, Eugenio Furtado de; Borré, Leandro Bandeira; Vaiss, Viviane da Silva; Leitão, Alexandre Amaral

    2016-09-01

    13C/15N (experimental and ab initio) solid-state NMR was used to achieve an affordable way to improve hydrogen refinement of 6-aminopenicillanic acid (6-APA) structure. The lattice effect on the isotropic chemical shifts was probed by using two different magnetic shielding calculations: isolated molecules and periodic crystal structure. The electron density difference maps of optimized and non-optimized structures were calculated in order to investigate the interactions inside the 6-APA unit cell. The 13C and 15N chemical shifts assignments were unambiguously stablished. In addition, some of the literature 13C resonances ambiguities could be properly solved.

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

    PubMed

    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.

  7. Whole-core analysis by sup 13 C NMR

    SciTech Connect

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

    1991-06-01

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

  8. Solid-State Electronic Spin Coherence Time Approaching One Second

    DTIC Science & Technology

    2013-04-23

    Methods) allows for common-mode rejection of noise, but does not remove the effect of pulse errors. We noticed a modest reduction in signal contrast and...for natural abundance diamond (1.1% 13C), as the dynamical decoupling sequences we employ are also effective in suppressing dephasing caused by the...since for ensembles of NVs in the presence of 13C nuclear spins, additional decoherence is caused by variations in the effective Larmor frequency of

  9. 15N chemical shift referencing in solid state NMR.

    PubMed

    Bertani, Philippe; Raya, Jésus; Bechinger, Burkhard

    2014-01-01

    Solid-state NMR spectroscopy has much advanced during the last decade and provides a multitude of data that can be used for high-resolution structure determination of biomolecules, polymers, inorganic compounds or macromolecules. In some cases the chemical shift referencing has become a limiting factor to the precision of the structure calculations and we have therefore evaluated a number of methods used in proton-decoupled (15)N solid-state NMR spectroscopy. For (13)C solid-state NMR spectroscopy adamantane is generally accepted as an external standard, but to calibrate the (15)N chemical shift scale several standards are in use. As a consequence the published chemical shift values exhibit considerable differences (up to 22 ppm). In this paper we report the (15)N chemical shift of several commonly used references compounds in order to allow for comparison and recalibration of published data and future work. We show that (15)NH4Cl in its powdered form (at 39.3 ppm with respect to liquid NH3) is a suitable external reference as it produces narrow lines when compared to other reference compounds and at the same time allows for the set-up of cross-polarization NMR experiments. The compound is suitable to calibrate magic angle spinning and static NMR experiments. Finally the temperature variation of (15)NH4Cl chemical shift is reported.

  10. Solid-state rechargeable magnesium battery

    DOEpatents

    Shao, Yuyan; Liu, Jun; Liu, Tianbiao; Li, Guosheng

    2016-09-06

    Embodiments of a solid-state electrolyte comprising magnesium borohydride, polyethylene oxide, and optionally a Group IIA or transition metal oxide are disclosed. The solid-state electrolyte may be a thin film comprising a dispersion of magnesium borohydride and magnesium oxide nanoparticles in polyethylene oxide. Rechargeable magnesium batteries including the disclosed solid-state electrolyte may have a coulombic efficiency .gtoreq.95% and exhibit cycling stability for at least 50 cycles.

  11. Solid state radiative heat pump

    DOEpatents

    Berdahl, Paul H.

    1986-01-01

    A solid state radiative heat pump (10, 50, 70) operable at room temperature (300.degree. K.) utilizes a semiconductor having a gap energy in the range of 0.03-0.25 eV and operated reversibly to produce an excess or deficit of charge carriers as compared to thermal equilibrium. In one form of the invention (10, 70) an infrared semiconductor photodiode (21, 71) is used, with forward or reverse bias, to emit an excess or deficit of infrared radiation. In another form of the invention (50), a homogeneous semiconductor (51) is subjected to orthogonal magnetic and electric fields to emit an excess or deficit of infrared radiation. Three methods of enhancing transmission of radiation through the active surface of the semiconductor are disclosed. In one method, an anti-reflection layer (19) is coated into the active surface (13) of the semiconductor (11), the anti-reflection layer (19) having an index of refraction equal to the square root of that of the semiconductor (11). In the second method, a passive layer (75) is spaced from the active surface (73) of the semiconductor (71) by a submicron vacuum gap, the passive layer having an index of refractive equal to that of the semiconductor. In the third method, a coupler (91) with a paraboloid reflecting surface (92) is in contact with the active surface (13, 53) of the semiconductor (11, 51), the coupler having an index of refraction about the same as that of the semiconductor.

  12. Solid state radiative heat pump

    DOEpatents

    Berdahl, P.H.

    1984-09-28

    A solid state radiative heat pump operable at room temperature (300 K) utilizes a semiconductor having a gap energy in the range of 0.03-0.25 eV and operated reversibly to produce an excess or deficit of change carriers as compared equilibrium. In one form of the invention an infrared semiconductor photodiode is used, with forward or reverse bias, to emit an excess or deficit of infrared radiation. In another form of the invention, a homogenous semiconductor is subjected to orthogonal magnetic and electric fields to emit an excess or deficit of infrared radiation. Three methods of enhancing transmission of radiation the active surface of the semiconductor are disclosed. In one method, an anti-refection layer is coated into the active surface of the semiconductor, the anti-reflection layer having an index of refraction equal to the square root of that of the semiconductor. In the second method, a passive layer is speaced trom the active surface of the semiconductor by a submicron vacuum gap, the passive layer having an index of refractive equal to that of the semiconductor. In the third method, a coupler with a paraboloid reflecting surface surface is in contact with the active surface of the semiconductor, the coupler having an index of refraction about the same as that of the semiconductor.

  13. Solid state safety jumper cables

    DOEpatents

    Kronberg, J.W.

    1993-02-23

    Solid state jumper cables for connecting two batteries in parallel, having two bridge rectifiers for developing a reference voltage, a four-input decoder for determining which terminals are to be connected based on a comparison of the voltage at each of the four terminals to the reference voltage, and a pair of relays for effecting the correct connection depending on the determination of the decoder. No connection will be made unless only one terminal of each battery has a higher voltage than the reference voltage, indicating positive'' terminals, and one has a lower voltage than the reference voltage, indicating negative'' terminals, and that, therefore, the two high voltage terminals may be connected and the two lower voltage terminals may be connected. Current flows once the appropriate relay device is closed. The relay device is preferably a MOSFET (metal oxide semiconductor field effect transistor) combined with a series array of photodiodes that develop MOSFET gate-closing potential when the decoder output causes an LED to light.

  14. Solid state safety jumper cables

    DOEpatents

    Kronberg, James W.

    1993-01-01

    Solid state jumper cables for connecting two batteries in parallel, having two bridge rectifiers for developing a reference voltage, a four-input decoder for determining which terminals are to be connected based on a comparison of the voltage at each of the four terminals to the reference voltage, and a pair of relays for effecting the correct connection depending on the determination of the decoder. No connection will be made unless only one terminal of each battery has a higher voltage than the reference voltage, indicating "positive" terminals, and one has a lower voltage than the reference voltage, indicating "negative" terminals, and that, therefore, the two high voltage terminals may be connected and the two lower voltage terminals may be connected. Current flows once the appropriate relay device is closed. The relay device is preferably a MOSFET (metal oxide semiconductor field effect transistor) combined with a series array of photodiodes that develop MOSFET gate-closing potential when the decoder output causes an LED to light.

  15. Structure and backbone dynamics of a microcrystalline metalloprotein by solid-state NMR

    PubMed Central

    Knight, Michael J.; Pell, Andrew J.; Bertini, Ivano; Felli, Isabella C.; Gonnelli, Leonardo; Pierattelli, Roberta; Herrmann, Torsten; Emsley, Lyndon; Pintacuda, Guido

    2012-01-01

    We introduce a new approach to improve structural and dynamical determination of large metalloproteins using solid-state nuclear magnetic resonance (NMR) with 1H detection under ultrafast magic angle spinning (MAS). The approach is based on the rapid and sensitive acquisition of an extensive set of 15N and 13C nuclear relaxation rates. The system on which we demonstrate these methods is the enzyme Cu, Zn superoxide dismutase (SOD), which coordinates a Cu ion available either in Cu+ (diamagnetic) or Cu2+ (paramagnetic) form. Paramagnetic relaxation enhancements are obtained from the difference in rates measured in the two forms and are employed as structural constraints for the determination of the protein structure. When added to 1H-1H distance restraints, they are shown to yield a twofold improvement of the precision of the structure. Site-specific order parameters and timescales of motion are obtained by a Gaussian axial fluctuation (GAF) analysis of the relaxation rates of the diamagnetic molecule, and interpreted in relation to backbone structure and metal binding. Timescales for motion are found to be in the range of the overall correlation time in solution, where internal motions characterized here would not be observable. PMID:22723345

  16. The determination of enantiomeric excess of valine by ODESSA solid-state NMR experiment.

    PubMed

    Tadeusiak, Elzbieta J; Ciesielski, Włodzimierz; Olejniczak, Sebastian

    2006-10-01

    The enantiomeric excess (ee) can be determined by many methods; one among them is nuclear magnetic resonance in solid-state (SS NMR). In this study we used the SS NMR ODESSA experiment for determination of the ee of valine.

  17. (13)C NMR Metabolomics: INADEQUATE Network Analysis.

    PubMed

    Clendinen, Chaevien S; Pasquel, Christian; Ajredini, Ramadan; Edison, Arthur S

    2015-06-02

    The many advantages of (13)C NMR are often overshadowed by its intrinsically low sensitivity. Given that carbon makes up the backbone of most biologically relevant molecules, (13)C NMR offers a straightforward measurement of these compounds. Two-dimensional (13)C-(13)C correlation experiments like INADEQUATE (incredible natural abundance double quantum transfer experiment) are ideal for the structural elucidation of natural products and have great but untapped potential for metabolomics analysis. We demonstrate a new and semiautomated approach called INETA (INADEQUATE network analysis) for the untargeted analysis of INADEQUATE data sets using an in silico INADEQUATE database. We demonstrate this approach using isotopically labeled Caenorhabditis elegans mixtures.

  18. Spinning sidebands from chemical shift anisotropy in 13C MAS imaging.

    PubMed

    Scheler, U; Blümich, B; Spiess, H W

    1993-07-01

    Solid state imaging by 13C MAS imaging is described. The spinning sidebands occurring at moderate spinning speeds, which disturb the images, can be suppressed by TOSS. For rigid solids the spatial resolution that can be achieved in this way is better than that of 1H images at the same spinning speed. Spatially resolved spectra with or without spinning sidebands can likewise be recorded providing information about the isotropic and the anisotropic chemical shifts which can be exploited for the study of structure, order and dynamics. The techniques are demonstrated on a phantom made with 13C-labelled glycine.

  19. Synthesis and NMR studies of (13)C-labeled vitamin D metabolites.

    PubMed

    Okamura, William H; Zhu, Gui-Dong; Hill, David K; Thomas, Richard J; Ringe, Kerstin; Borchardt, Daniel B; Norman, Anthony W; Mueller, Leonard J

    2002-03-08

    Isotope-labeled drug molecules may be useful for probing by NMR spectroscopy the conformation of ligand associated with biological hosts such as membranes and proteins. Triple-labeled [7,9,19-(13)C(3)]-vitamin D(3) (56), its 25-hydroxylated and 1 alpha,25-dihydroxylated metabolites (58 and 68, respectively), and other labeled materials have been synthesized via coupling of [9-(13)C]-Grundmann's ketone 39 or its protected 25-hydroxy derivative 43 with labeled A ring enyne fragments 25 or 26. The labeled CD-ring fragment 39 was prepared by a sequence involving Grignard addition of [(13)C]-methylmagnesium iodide to Grundmann's enone 28, oxidative cleavage, functional group modifications leading to seco-iodide 38, and finally a kinetic enolate S(N)2 cycloalkylation. The C-7,19 double labeling of the A-ring enyne was achieved by the Corey-Fuchs/Wittig processes on keto aldehyde 11. By employing these labeled fragments in the Wilson-Mazur route, the C-7,9,19 triple-(13)C-labeled metabolites 56, 58, and 68 as well as other (13)C-labeled metabolites have been prepared. In an initial NMR investigation of one of the labeled metabolites prepared in this study, namely [7,9,19-(13)C(3)]-25-hydroxyvitamin D(3) (58), the three (13)C-labeled carbons of the otherwise water insoluble steroid could be clearly detected by (13)C NMR analysis at 0.1 mM in a mixture of CD(3)OD/D(2)O (60/40) or in aqueous dimethylcyclodextrin solution and at 2 mM in 20 mM sodium dodecyl sulfate (SDS) aqueous micellar solution. In the SDS micellar solution, a double half-filter NOESY experiment revealed that the distance between the H(19Z) and H(7) protons is significantly shorter than that of the corresponding distance calculated from the solid state (X-ray) structure of the free ligand. The NMR data in micelles reveals that 58 exists essentially completely in the alpha-conformer with the 3 beta-hydroxyl equatorially oriented, just as in the solid state. The shortened distance (H(19Z))-H(7)) in micellar

  20. New guidelines for δ13C measurements

    USGS Publications Warehouse

    Coplen, Tyler B.; Brand, Willi A.; Gehre, Matthias; Groning, Manfred; Meijer, Harro A. J.; Toman, Blaza; Verkouteren, R. Michael

    2006-01-01

    Consistency of δ13C measurements can be improved 39−47% by anchoring the δ13C scale with two isotopic reference materials differing substantially in 13C/12C. It is recommended thatδ13C values of both organic and inorganic materials be measured and expressed relative to VPDB (Vienna Peedee belemnite) on a scale normalized by assigning consensus values of −46.6‰ to L-SVEC lithium carbonate and +1.95‰ to NBS 19 calcium carbonate. Uncertainties of other reference material values on this scale are improved by factors up to two or more, and the values of some have been notably shifted:  the δ13C of NBS 22 oil is −30.03%.

  1. Solid State Li-ion Batteries

    DTIC Science & Technology

    2013-10-23

    demonstrated that the vapor deposition of thin lithium films onto Li2S-P2S5 glass-ceramic solid -state electrolyte (SSE) pellets can improve...and S.-H. Lee, “Glass–ceramic Li2S–P2S5 electrolytes prepared by a single step ball billing process and their application for all- solid -state lithium ...Kitaura, A. Hayashi, T. Ohtomo, S. Hama and M. Tatsumisago, “Fabrication of electrode– electrolyte interfaces in all- solid -state rechargeable lithium

  2. Nuclear magnetic resonance studies on covalent modification of amino acids thiol and amino residues by monofunctional aryl 13C-isocyanates, models of skin and respiratory sensitizers: transformation of thiocarbamates into urea adducts.

    PubMed

    Fleischel, Olivier; Giménez-Arnau, Elena; Lepoittevin, Jean-Pierre

    2009-06-01

    Exposure to aryl isocyanates, intermediates in the manufacture of polyurethanes, provokes lung sensitization and asthma but also occupational allergic contact dermatitis, sensitization occurring from a single accidental exposure. The initial step in the sensitization process is believed to be the covalent binding of the -N triple bond C triple bond O group with nucleophilic residues on proteins. While a wide knowledge exists on the reactivity of skin sensitizers toward amino acids, little is known about respiratory sensitizers such as aryl isocyanates. (13)C-Labeled monofunctional aryl isocyanates were synthesized, and their reactivities toward nucleophilic amino acids, GSH, and a model peptide were studied by (13)C and [(1)H-(13)C] NMR spectroscopy. An acetonitrile/buffer solution was used as a solvent to avoid the hampering of the follow up of the reactivity by the isocyanate hydrolysis competing reaction. The compounds reacted with thiol groups, through the formation of thiocarbamate bonds and with amino groups to form urea derivatives. The reactivity was confirmed with GSH, containing both free amino and thiol groups, and with a model peptide, particularly in the case of the reaction with lysine. The use of (13)C NMR to follow the aryl isocyanates reversible conjugation with thiol groups is also reported. Particularly, it is shown that thiocarbamate adducts can be converted into adducts of the urea kind by reaction with amino groups. These results confirmed the hypothesis by which thiol-containing peptides/proteins may act as carriers of isocyanates for possible reaction at a later time and/or place with other nucleophiles and confirmed the role of lysine as a good competing nucleophilic amino acid. The reactivity of aryl isocyanates with thiol and amino groups needs thus to be considered in their assigned sensitization processes.

  3. Exploration of structure and function in biomolecules through solid-state NMR and computational methods

    NASA Astrophysics Data System (ADS)

    Heider, Elizabeth M.

    Solid-State Nuclear Magnetic Resonance (SSNMR) spectroscopy and quantum mechanical calculations are powerful analysis tools. Leveraged independently, each method yields important nuclear and molecular information. Used in concert, SSNMR and computational techniques provide complementary data about the structure of solids. These methods are particularly useful in characterizing the structures of microcrystalline organic compounds and revealing mechanisms of biological activity. Such applications may possess special relevance in analysis of pharmaceutical products; 90% of all pharmaceuticals are marketed as solids and bioactivity is strongly linked with molecular conformation. Accordingly, this dissertation employs both SSNMR and quantum mechanical computation to study three bioactive molecules: citrinin, two forms of Atrasentan (Abt-627), and paclitaxel (Taxol RTM). First, a computational study is utilized to determine the mechanism for unusual antioxidant activity in citrinin. Here, molecular geometries and bond dissociation enthalpies (BDE) of the citrinin O--H groups are calculated from first principles (ab initio). The total molecular Hamiltonian is determined by approximating the individual contributors to energy including electronic energy and contributions from modes of molecular vibration. This study of citrinin clearly identifies specific reaction sites in the active form, establishing the central role of intramolecular hydrogen bonding in this activity. Notably, it is discovered that citrinin itself is not the active species. Instead, a pair of hydrated Michael addition products of citrinin act as radical scavengers via O--H bond dissociation. Next, two separate compounds of the anticancer drug Abt-627 (form I and form II) are examined via SSNMR. The three principal values of the 13C diagonalized chemical shift tensor are acquired through the high resolution 2D experiment, FIREMAT. Isotropic chemical shift assignments are made utilizing both dipolar

  4. Solid state laser technology - A NASA perspective

    NASA Technical Reports Server (NTRS)

    Allario, F.

    1985-01-01

    NASA's program for developing solid-state laser technology and applying it to the Space Shuttle and Space Platform is discussed. Solid-state lasers are required to fulfill the Earth Observation System's requirements. The role of the Office of Aeronautics and Space Technology in developing a NASA tunable solid-state laser program is described. The major goals of the program involve developing a solid-state pump laser in the green, using AlGaAs array technology, pumping a Nd:YAG/SLAB crystal or glass, and fabricating a lidar system, with either a CO2 laser at 10.6 microns or a Nd:YAG laser at 1.06 microns, to measure tropospheric winds to an accuracy of + or - 1 m/s and a vertical resolution of 1 km. The procedures to be followed in order to visualize this technology plan include: (1) material development and characterization, (2) laser development, and (3) implementation of the lasers.

  5. Standards Development for Solid-State Lighting

    SciTech Connect

    2011-12-16

    To accelerate the development and implementation of needed standards for solid-state lighting products, DOE works closely with a network of standards-setting organizations and offers technical assistance and support

  6. Solid-state light sources getting smart.

    PubMed

    Schubert, E Fred; Kim, Jong Kyu

    2005-05-27

    More than a century after the introduction of incandescent lighting and half a century after the introduction of fluorescent lighting, solid-state light sources are revolutionizing an increasing number of applications. Whereas the efficiency of conventional incandescent and fluorescent lights is limited by fundamental factors that cannot be overcome, the efficiency of solid-state sources is limited only by human creativity and imagination. The high efficiency of solid-state sources already provides energy savings and environmental benefits in a number of applications. However, solid-state sources also offer controllability of their spectral power distribution, spatial distribution, color temperature, temporal modulation, and polarization properties. Such "smart" light sources can adjust to specific environments and requirements, a property that could result in tremendous benefits in lighting, automobiles, transportation, communication, imaging, agriculture, and medicine.

  7. Structural biology applications of solid state MAS DNP NMR.

    PubMed

    Akbey, Ümit; Oschkinat, Hartmut

    2016-08-01

    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  8. Structural biology applications of solid state MAS DNP NMR

    NASA Astrophysics Data System (ADS)

    Akbey, Ümit; Oschkinat, Hartmut

    2016-08-01

    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  9. Folding of xylan onto cellulose fibrils in plant cell walls revealed by solid-state NMR

    PubMed Central

    Simmons, Thomas J.; Mortimer, Jenny C.; Bernardinelli, Oigres D.; Pöppler, Ann-Christin; Brown, Steven P.; deAzevedo, Eduardo R.; Dupree, Ray; Dupree, Paul

    2016-01-01

    Exploitation of plant lignocellulosic biomass is hampered by our ignorance of the molecular basis for its properties such as strength and digestibility. Xylan, the most prevalent non-cellulosic polysaccharide, binds to cellulose microfibrils. The nature of this interaction remains unclear, despite its importance. Here we show that the majority of xylan, which forms a threefold helical screw in solution, flattens into a twofold helical screw ribbon to bind intimately to cellulose microfibrils in the cell wall. 13C solid-state magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy, supported by in silico predictions of chemical shifts, shows both two- and threefold screw xylan conformations are present in fresh Arabidopsis stems. The twofold screw xylan is spatially close to cellulose, and has similar rigidity to the cellulose microfibrils, but reverts to the threefold screw conformation in the cellulose-deficient irx3 mutant. The discovery that induced polysaccharide conformation underlies cell wall assembly provides new principles to understand biomass properties. PMID:28000667

  10. Detection of chiral defects in crystalline organic solids using solid-state NMR spectroscopy.

    PubMed

    Berendt, Robert T; Munson, Eric J

    2011-05-01

    The marketing of enantiopure pharmaceuticals has become more common due to regulatory and safety concerns surrounding the potential differences in biological activity of opposite enantiomers. However, achieving the desired enantiopurity can be a challenge, and low levels of the undesired enantiomer (chiral impurity) may be present in the final product. The location and nature of this impurity can potentially alter pharmaceutically relevant properties. In this article, we show that it is possible to identify and quantitate the crystallographic locations of small amounts of one enantiomer (l) in the presence of predominantly the opposite D-enantiomer using solid-state nuclear magnetic resonance (NMR) spectroscopy. Proline was used as a model compound, and crystalline samples containing both D- and L-proline were prepared by solvent evaporation, lyophilization, spray drying, and cryogrinding. Isotopic labeling, (13)C cross polarization-magic angle spinning NMR spectral subtractions, and (1)H T(1) spin-lattice relaxation measurements allowed selective observation and characterization of the crystal environments into which the L-proline impurity was incorporated upon concurrent crystallization with D-proline. Results show that L-proline was incorporated in up to four different crystalline forms, including L-proline as a kinetically trapped substitutional chiral defect in the D-proline host crystal lattice.

  11. Origin of the different emission wavelengths in Alq 3 analyzed by solid-state NMR

    NASA Astrophysics Data System (ADS)

    Kaji, Hironori; Fukushima, Tatsuya; Takami, Kousuke; Kusaka, Yasunari

    2007-09-01

    Tris(8-hydroxyquinoline) aluminum(III) (Alq 3) is one of the most widely used materials in organic light-emitting diodes (OLEDs), and the relationship between the structures and the luminescent wavelengths is of recent interest; yellowish-green emissions are observed for the α- and amorphous Alq 3, whereas blue emissions are found for the γ- and δ-Alq 3. In order to clarify the relationship between the structures and the emission wavelengths, we carried out solid-state nuclear magnetic resonance (NMR) experiments on the different polymorphs of Alq 3 and the amorphous state. Based on 27Al and 13C magic angle spinning (MAS) NMR experiments, it is found that the isomeric state of the amorphous Alq 3 is the same as that of α-Alq 3 and is different from those of γ- and δ-Alq 3. Not only for the amorphous, but also for α-Alq 3, the local structures are found to be disordered. We also obtained clear evidence that γ-Alq 3 is in the facial isomeric state. It is suggested that δ-Alq 3 is also facial. The difference between γ- and δ-Alq 3 is the intermolecular packing; the effect of intermolecular packing is found only for δ-Alq 3. A further confirmation of the isomeric states of these Alq 3 samples is obtained from temperature-dependent X-ray diffraction experiments.

  12. Grating enhanced solid-state laser amplifiers

    DOEpatents

    Erlandson, Alvin C.; Britten, Jerald A.

    2010-11-09

    A novel method and apparatus for suppressing ASE and parasitic oscillation modes in a high average power laser is introduced. Such an invention, as disclosed herein, uses diffraction gratings to increase gain, stored energy density, and pumping efficiency of solid-state laser gain media, such as, but not limited to rods, disks and slabs. By coupling predetermined gratings to solid-state gain media, such as crystal or ceramic laser gain media, ASE and parasitic oscillation modes can be effectively suppressed.

  13. Realistic Theory of Solid-State Qubits

    DTIC Science & Technology

    2006-03-20

    limited by decoherence due to the many extra degrees of freedom of a solid state system. We investigate a system of two solid state qubits that are...of systems with finite degrees of freedom whose dynamics are Lie-algebraically closed. vi) Transfer of knowledge to quantum dot charge qubis We studied...the stationary current depending on the internal degrees of freedom . In particular, it turns out that at fixed transport voltage, the current through

  14. Solid state neutron detector array

    SciTech Connect

    Seidel, J.G.; Ruddy, F.H.; Brandt, C.D.; Dulloo, A.R.; Lott, R.G.; Sirianni, E.; Wilson, R.O.

    1999-08-17

    A neutron detector array is capable of measuring a wide range of neutron fluxes. The array includes multiple semiconductor neutron detectors. Each detector has a semiconductor active region that is resistant to radiation damage. In one embodiment, the array preferably has a relatively small size, making it possible to place the array in confined locations. The ability of the array to detect a wide range of neutron fluxes is highly advantageous for many applications such as detecting neutron flux during start up, ramp up and full power of nuclear reactors. 7 figs.

  15. Advances in solid-state NMR of cellulose.

    PubMed

    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.

  16. Detection of pulsed neutrons with solid-state electronics

    NASA Astrophysics Data System (ADS)

    Chatzakis, J.; Rigakis, I.; Hassan, S. M.; Clark, E. L.; Lee, P.

    2016-09-01

    Measurements of the spatial and time-resolved characteristics of pulsed neutron sources require large area detection materials and fast circuitry that can process the electronic pulses readout from the active region of the detector. In this paper, we present a solid-state detector based on the nuclear activation of materials by neutrons, and the detection of the secondary particle emission of the generated radionuclides’ decay. The detector utilizes a microcontroller that communicates using a modified SPI protocol. A solid-state, pulse shaping filter follows a charge amplifier, and it is designed as an inexpensive, low-noise solution for measuring pulses measured by a digital counter. An imaging detector can also be made by using an array of these detectors. The system can communicate with an interface unit and pass an image to a personal computer.

  17. 13C NMR of tunnelling methyl groups

    NASA Astrophysics Data System (ADS)

    Detken, A.

    The dipolar interactions between the protons and the central 13C nucleus of a 13CH3 group are used to study rotational tunnelling and incoherent dynamics of such groups in molecular solids. Single-crystal 13C NMR spectra are derived for arbitrary values of the tunnel frequency upsilon t. Similarities to ESR and 2H NMR are pointed out. The method is applied to three different materials. In the hydroquinone/acetonitrile clathrate, the unique features in the 13C NMR spectra which arise from tunnelling with a tunnel frequency that is much larger than the dipolar coupling between the methyl protons and the 13C nucleus are demonstrated, and the effects of incoherent dynamics are studied. The broadening of the 13C resonances is related to the width of the quasi-elastic line in neutron scattering. Selective magnetization transfer experiments for studying slow incoherent dynamics are proposed. For the strongly hindered methyl groups of L-alanine, an upper limit for upsilon is derived from the 13C NMR spectrum. In aspirinTM (acetylsalicylic acid), incoherent reorientations dominate the spectra down to the lowest temperatures studied; their rate apparently increases with decreasing temperature below 25K.

  18. Chemical structure and heterogeneity differences of two lignins from loblolly pine as investigated by advanced solid-state NMR spectroscopy

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Advanced solid-state NMR was employed to investigate differences in chemical structure and heterogeneity between milled wood lignin (MWL) and residual enzyme lignin (REL). Wiley and conventional milled woods were also studied. The advanced NMR techniques included 13C quantitative direct polarization...

  19. Chemical shift tensor determination using magnetically oriented microcrystal array (MOMA): 13C solid-state CP NMR without MAS

    NASA Astrophysics Data System (ADS)

    Kusumi, R.; Kimura, F.; Song, G.; Kimura, T.

    2012-10-01

    Chemical shift tensors for the carboxyl and methyl carbons of L-alanine crystals were determined using a magnetically oriented microcrystal array (MOMA) prepared from a microcrystalline powder sample of L-alanine. A MOMA is a single-crystal-like composite in which microcrystals are aligned three-dimensionally in a matrix resin. The single-crystal rotation method was applied to the MOMA to determine the principal values and axes of the chemical shift tensors. The result showed good agreement with the literature data for the single crystal of L-alanine. This demonstrates that the present technique is a powerful tool for determining the chemical shift tensor of a crystal from a microcrystal powder sample.

  20. Monolithic solid-state lasers for spaceflight

    NASA Astrophysics Data System (ADS)

    Krainak, Michael A.; Yu, Anthony W.; Stephen, Mark A.; Merritt, Scott; Glebov, Leonid; Glebova, Larissa; Ryasnyanskiy, Aleksandr; Smirnov, Vadim; Mu, Xiaodong; Meissner, Stephanie; Meissner, Helmuth

    2015-02-01

    A new solution for building high power, solid state lasers for space flight is to fabricate the whole laser resonator in a single (monolithic) structure or alternatively to build a contiguous diffusion bonded or welded structure. Monolithic lasers provide numerous advantages for space flight solid-state lasers by minimizing misalignment concerns. The closed cavity is immune to contamination. The number of components is minimized thus increasing reliability. Bragg mirrors serve as the high reflector and output coupler thus minimizing optical coatings and coating damage. The Bragg mirrors also provide spectral and spatial mode selection for high fidelity. The monolithic structure allows short cavities resulting in short pulses. Passive saturable absorber Q-switches provide a soft aperture for spatial mode filtering and improved pointing stability. We will review our recent commercial and in-house developments toward fully monolithic solid-state lasers.

  1. Driver circuit for solid state light sources

    DOEpatents

    Palmer, Fred; Denvir, Kerry; Allen, Steven

    2016-02-16

    A driver circuit for a light source including one or more solid state light sources, a luminaire including the same, and a method of so driving the solid state light sources are provided. The driver circuit includes a rectifier circuit that receives an alternating current (AC) input voltage and provides a rectified AC voltage. The driver circuit also includes a switching converter circuit coupled to the light source. The switching converter circuit provides a direct current (DC) output to the light source in response to the rectified AC voltage. The driver circuit also includes a mixing circuit, coupled to the light source, to switch current through at least one solid state light source of the light source in response to each of a plurality of consecutive half-waves of the rectified AC voltage.

  2. Solid state recording current meter conversion

    USGS Publications Warehouse

    Cheng, Ralph T.; Wang, Lichen

    1985-01-01

    The authors describe the conversion of an Endeco-174 current meter to a solid-state recording current meter. A removable solid-state module was designed to fit in the space originally occupied by an 8-track tape cartridge. The module contains a CPU and 128 kilobytes of nonvolatile CMOS memory. The solid-state module communicates with any terminal or computer using an RS-232C interface at 4800 baud rate. A primary consideration for conversion was to keep modifications of the current meter to a minimum. The communication protocol was designed to emulate the Endeco tape translation unit, thus the need for a translation unit was eliminated and the original data reduction programs can be used without any modification. After conversion, the data recording section of the current meter contains no moving parts; the storage capacity of the module is equivalent to that of the original tape cartridge.

  3. Lithium Based Anodes for Solid State Batteries

    DTIC Science & Technology

    1981-06-30

    AFOSR- 77- 3460 LITHIUM BASED ANODES FOR SOLID STATE BATTERIES R.A.H. Edwards, J.R. Owen and B.C.H. Steele I!Tolfson Unit for Solid State Ionics, D...use in secondary lithium batteries . Three main problems associated with the use of pure lithium as the negative plate are as follows: (a) Formation of...Proceedings of the Workshop on Lithium Non aque ous Battery Electrochemistry. Case Western Reserve Univ. June 4-6 1980, pp.130-142, The Electrochemical Soc

  4. Scalar operators in solid-state NMR

    SciTech Connect

    Sun, Boqin

    1991-11-01

    Selectivity and resolution of solid-state NMR spectra are determined by dispersion of local magnetic fields originating from relaxation effects and orientation-dependent resonant frequencies of spin nuclei. Theoretically, the orientation-dependent resonant frequencies can be represented by a set of irreducible tensors. Among these tensors, only zero rank tensors (scalar operators) are capable of providing high resolution NMR spectra. This thesis presents a series of new developments in high resolution solid-state NMR concerning the reconstruction of various scalar operators motion in solid C{sub 60} is analyzed.

  5. Solid State Lasers from an Efficiency Perspective

    NASA Technical Reports Server (NTRS)

    Barnes, Norman P.

    2007-01-01

    Solid state lasers have remained a vibrant area of research because several major innovations expanded their capability. Major innovations are presented with emphasis focused on the laser efficiency. A product of efficiencies approach is developed and applied to describe laser performance. Efficiency factors are presented in closed form where practical and energy transfer effects are included where needed. In turn, efficiency factors are used to estimate threshold and slope efficiency, allowing a facile estimate of performance. Spectroscopic, thermal, and mechanical data are provided for common solid state laser materials.

  6. Millimeter and submillimeter wave spectra of 13C-glycolaldehydes

    NASA Astrophysics Data System (ADS)

    Haykal, I.; Motiyenko, R. A.; Margulès, L.; Huet, T. R.

    2013-01-01

    Context. Glycolaldehyde (CH2OHCHO) is the simplest sugar and an important intermediate in the path toward forming more complex biologically relevant molecules. Astronomical surveys of interstellar molecules, such as those available with the very sensitive ALMA telescope, require preliminary laboratory investigations of the microwave and submillimeter-wave spectra of molecular species including new isotopologs - to identify these in the interstellar media. Aims: To achieve the detection of the 13C isotopologs of glycolaldehyde in the interstellar medium, their rotational spectra in the millimeter and submillimeter-wave regions were studied. Methods: The spectra of 13CH2OHCHO and CH2OH13CHO were recorded in the 150-945 GHz spectral range in the laboratory using a solid-state submillimeter-wave spectrometer in Lille. The observed line frequencies were measured with an accuracy of 30 kHz up to 700 GHz and of 50 kHz above 700 GHz. We analyzed the spectra with a standard Watson Hamiltonian. Results: About 10 000 new lines were identified for each isotopolog. The spectroscopic parameters were determined for the ground- and the three lowest vibrational states up to 945 and 630 GHz. Previous microwave assignments of 13CH2OHCHO were not confirmed. Conclusions: The provided line-lists and sets of molecular parameters meet the needs for a first astrophysical search of 13C-glycolaldehydes. Full Tables 3 and 4 are only available at the CDS via anonymous ftp to cdsarc.u-strasbg.fr (130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/549/A96

  7. Efficient theory of dipolar recoupling in solid-state nuclear magnetic resonance of rotating solids using Floquet-Magnus expansion: application on BABA and C7 radiofrequency pulse sequences.

    PubMed

    Mananga, Eugene S; Reid, Alicia E; Charpentier, Thibault

    2012-02-01

    This article describes the use of an alternative expansion scheme called Floquet-Magnus expansion (FME) to study the dynamics of spin system in solid-state NMR. The main tool used to describe the effect of time-dependent interactions in NMR is the average Hamiltonian theory (AHT). However, some NMR experiments, such as sample rotation and pulse crafting, seem to be more conveniently described using the Floquet theory (FT). Here, we present the first report highlighting the basics of the Floquet-Magnus expansion (FME) scheme and hint at its application on recoupling sequences that excite more efficiently double-quantum coherences, namely BABA and C7 radiofrequency pulse sequences. The use of Λ(n)(t) functions available only in the FME scheme, allows the comparison of the efficiency of BABA and C7 sequences.

  8. Solvent suppression in DNP enhanced solid state NMR

    NASA Astrophysics Data System (ADS)

    Yarava, Jayasubba Reddy; Chaudhari, Sachin Rama; Rossini, Aaron J.; Lesage, Anne; Emsley, Lyndon

    2017-04-01

    We show how DNP enhanced solid-state NMR spectra can be dramatically simplified by suppression of solvent signals. This is achieved by (i) exploiting the paramagnetic relaxation enhancement of solvent signals relative to materials substrates, or (ii) by using short cross-polarization contact times to transfer hyperpolarization to only directly bonded carbon-13 nuclei in frozen solutions. The methods are evaluated for organic microcrystals, surfaces and frozen solutions. We show how this allows for the acquisition of high-resolution DNP enhanced proton-proton correlation experiments to measure inter-nuclear proximities in an organic solid.

  9. Spectroscopy of composite solid-state spin environments in diamond

    NASA Astrophysics Data System (ADS)

    Bar-Gill, Nir; Linh Pham, My; Belthangady, Chinmay; Le Sage, David; Lukin, Mikhail; Yacoby, Amir; Cappellaro, Paola; Walsworth, Ronald

    2012-06-01

    We apply dynamical decoupling pulse sequences to nitrogen-vacancy centers in diamond in order to spectrally decompose the dynamics of their spin environment, which consists of nuclear and electronic spin impurities. We study a variety of diamond samples to identify the dynamics of the different spin baths and the interplay between them. These results are useful for the basic understanding of spin dynamics in solid-state systems and the central spin problem and could inform efforts in engineering optimized samples for collective quantum information processing and quantum metrology.

  10. Vanadium bisimide bonding investigated by X-ray crystallography, 51V and 13C nuclear magnetic resonance spectroscopy, and V L(3,2)-edge X-ray absorption near-edge structure spectroscopy.

    PubMed

    La Pierre, Henry S; Minasian, Stefan G; Abubekerov, Mark; Kozimor, Stosh A; Shuh, David K; Tyliszczak, Tolek; Arnold, John; Bergman, Robert G; Toste, F Dean

    2013-10-07

    Syntheses of neutral halide and aryl vanadium bisimides are described. Treatment of VCl2(NtBu)[NTMS(N(t)Bu)], 2, with PMe3, PEt3, PMe2Ph, or pyridine gave vanadium bisimides via TMSCl elimination in good yield: VCl(PMe3)2(N(t)Bu)2 3, VCl(PEt3)2(N(t)Bu)2 4, VCl(PMe2Ph)2(N(t)Bu)2 5, and VCl(Py)2(N(t)Bu)2 6. The halide series (Cl-I) was synthesized by use of TMSBr and TMSI to give VBr(PMe3)2(N(t)Bu)2 7 and VI(PMe3)2(N(t)Bu)2 8. The phenyl derivative was obtained by reaction of 3 with MgPh2 to give VPh(PMe3)2(N(t)Bu)2 9. These neutral complexes are compared to the previously reported cationic bisimides [V(PMe3)3(N(t)Bu)2][Al(PFTB)4] 10, [V(PEt3)2(N(t)Bu)2][Al(PFTB)4] 11, and [V(DMAP)(PEt3)2(N(t)Bu)2][Al(PFTB)4] 12 (DMAP = dimethylaminopyridine, PFTB = perfluoro-tert-butoxide). Characterization of the complexes by X-ray diffraction, (13)C NMR, (51)V NMR, and V L(3,2)-edge X-ray absorption near-edge structure (XANES) spectroscopy provides a description of the electronic structure in comparison to group 6 bisimides and the bent metallocene analogues. The electronic structure is dominated by π bonding to the imides, and localization of electron density at the nitrogen atoms of the imides is dictated by the cone angle and donating ability of the axial neutral supporting ligands. This phenomenon is clearly seen in the sensitivity of (51)V NMR shift, (13)C NMR Δδ(αβ), and L3-edge energy to the nature of the supporting phosphine ligand, which defines the parameters for designing cationic group 5 bisimides that would be capable of breaking stronger σ bonds. Conversely, all three methods show little dependence on the variable equatorial halide ligand. Furthermore, this analysis allows for quantification of the electronic differences between vanadium bisimides and the structurally analogous mixed Cp/imide system CpV(N(t)Bu)X2 (Cp = C5H5(1-)).

  11. The Pythagorean Theorem and the Solid State

    ERIC Educational Resources Information Center

    Kelly, Brenda S.; Splittgerber, Allan G.

    2005-01-01

    Packing efficiency and crystal density can be calculated from basic geometric principles employing the Pythagorean theorem, if the unit-cell structure is known. The procedures illustrated have applicability in courses such as general chemistry, intermediate and advanced inorganic, materials science, and solid-state physics.

  12. Density functional theory in the solid state.

    PubMed

    Hasnip, Philip J; Refson, Keith; Probert, Matt I J; Yates, Jonathan R; Clark, Stewart J; Pickard, Chris J

    2014-03-13

    Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure-property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program.

  13. Intracavity solid state Raman marine transmitters

    NASA Astrophysics Data System (ADS)

    Murray, James T.; Austin, William L.; Calmes, Lonnie K.; Powell, Richard C.; McLean, John W.; Bryan, Elisabeth L.

    1997-07-01

    The design and performance of a short-pulse (1.5 ns), high- energy (90 mJ/pulse) nonlinear cavity-dumped, frequency- doubled, solid-state intracavity Raman laser is presented. The laser described is utilized as the transmitter in a high- resolution surf-zone marine imaging lidar system.

  14. Density functional theory in the solid state

    PubMed Central

    Hasnip, Philip J.; Refson, Keith; Probert, Matt I. J.; Yates, Jonathan R.; Clark, Stewart J.; Pickard, Chris J.

    2014-01-01

    Density functional theory (DFT) has been used in many fields of the physical sciences, but none so successfully as in the solid state. From its origins in condensed matter physics, it has expanded into materials science, high-pressure physics and mineralogy, solid-state chemistry and more, powering entire computational subdisciplines. Modern DFT simulation codes can calculate a vast range of structural, chemical, optical, spectroscopic, elastic, vibrational and thermodynamic phenomena. The ability to predict structure–property relationships has revolutionized experimental fields, such as vibrational and solid-state NMR spectroscopy, where it is the primary method to analyse and interpret experimental spectra. In semiconductor physics, great progress has been made in the electronic structure of bulk and defect states despite the severe challenges presented by the description of excited states. Studies are no longer restricted to known crystallographic structures. DFT is increasingly used as an exploratory tool for materials discovery and computational experiments, culminating in ex nihilo crystal structure prediction, which addresses the long-standing difficult problem of how to predict crystal structure polymorphs from nothing but a specified chemical composition. We present an overview of the capabilities of solid-state DFT simulations in all of these topics, illustrated with recent examples using the CASTEP computer program. PMID:24516184

  15. SPS solid state antenna power combiner

    NASA Technical Reports Server (NTRS)

    Fitzsimmons, G. W.

    1980-01-01

    Solid state dc-rf converters offer potential improvements in reliability, mass and low voltage operation, provided that anticipated efficiencies in excess of 80 percent can be realized. Field effect transistors offer the greatest potential in the SPS frequency band at 2.45 GHz. To implement this approach it is essential that means be found to sum the power of many relatively low power solid state sources in a low-loss manner, and that means be provided to properly control the phase of the outputs of the large number of solid state sources required. To avoid the power combining losses associated with circuit hybrids it was proposed that the power from multiple solid state amplifiers be combined by direct coupling of each amplifier's output to the radiating antenna structure. The selected power-combining antenna consists of a unique printed (metalized) microstrip circuit on a ceramic type dielectric substrate which is backed by a shallow lightweight aluminum cavity which sums the power of four microwave sources. The antenna behaves like two one-half wavelength slot-line antennas coupled together via their common cavity structure.

  16. Friction Stir & Ultrasonic Solid State Joining Magnesium

    SciTech Connect

    Grant, Glenn J.; Hovanski, Yuri; Santella, M. L.

    2009-12-30

    Solid state joining between automotive sheet steel and magnesium alloys was investigated. Both friction stir welding and ultrasonic welding were utilized to study the potential for creating structural bonds between these dissimilar materials. A detailed investigation into the joint characteristics was undertaken including an evaluation of joint strength, microstructure, chemical structures, and alloy formation.

  17. Solar-pumped solid state Nd lasers

    NASA Technical Reports Server (NTRS)

    Williams, M. D.; Zapata, L.

    1985-01-01

    Solid state neodymium lasers are considered candidates for space-based polar-pumped laser for continuous power transmission. Laser performance for three different slab laser configurations has been computed to show the excellent power capability of such systems if heat problems can be solved. Ideas involving geometries and materials are offered as potential solutions to the heat problem.

  18. High power diode and solid state lasers

    NASA Astrophysics Data System (ADS)

    Eichler, H. J.; Fritsche, H.; Lux, O.; Strohmaier, S. G.

    2017-01-01

    Diode lasers are now basic pump sources of crystal, glass fiber and other solid state lasers. Progress in the performance of all these lasers is related. Examples of recently developed diode pumped lasers and Raman frequency converters are described for applications in materials processing, Lidar and medical surgery.

  19. Solid state, S-band, power amplifier

    NASA Technical Reports Server (NTRS)

    Digrindakis, M.

    1973-01-01

    The final design and specifications for a solid state, S-band, power amplifier is reported. Modifications from a previously proposed design were incorporated to improve efficiency and meet input overdrive and noise floor requirements. Reports on the system design, driver amplifier, power amplifier, and voltage and current limiter are included along with a discussion of the testing program.

  20. Nanoscale solid-state cooling: a review

    NASA Astrophysics Data System (ADS)

    Ziabari, Amirkoushyar; Zebarjadi, Mona; Vashaee, Daryoosh; Shakouri, Ali

    2016-09-01

    The recent developments in nanoscale solid-state cooling are reviewed. This includes both theoretical and experimental studies of different physical concepts, as well as nanostructured material design and device configurations. We primarily focus on thermoelectric, thermionic and thermo-magnetic coolers. Particular emphasis is given to the concepts based on metal-semiconductor superlattices, graded materials, non-equilibrium thermoelectric devices, Thomson coolers, and photon assisted Peltier coolers as promising methods for efficient solid-state cooling. Thermomagnetic effects such as magneto-Peltier and Nernst-Ettingshausen cooling are briefly described and recent advances and future trends in these areas are reviewed. The ongoing progress in solid-state cooling concepts such as spin-calorimetrics, electrocalorics, non-equilibrium/nonlinear Peltier devices, superconducting junctions and two-dimensional materials are also elucidated and practical achievements are reviewed. We explain the thermoreflectance thermal imaging microscopy and the transient Harman method as two unique techniques developed for characterization of thermoelectric microrefrigerators. The future prospects for solid-state cooling are briefly summarized.

  1. Coordinated garbage collection for raid array of solid state disks

    DOEpatents

    Dillow, David A; Ki, Youngjae; Oral, Hakki S; Shipman, Galen M; Wang, Feiyi

    2014-04-29

    An optimized redundant array of solid state devices may include an array of one or more optimized solid-state devices and a controller coupled to the solid-state devices for managing the solid-state devices. The controller may be configured to globally coordinate the garbage collection activities of each of said optimized solid-state devices, for instance, to minimize the degraded performance time and increase the optimal performance time of the entire array of devices.

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

    PubMed

    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.

  3. Comparative absorption of [13C]glucose and [13C]lactose by premature infants.

    PubMed

    Murray, R D; Boutton, T W; Klein, P D; Gilbert, M; Paule, C L; MacLean, W C

    1990-01-01

    Oxidation of orally administered [13C]glucose and [13C]lactose and fecal recovery of malabsorbed substrates were determined in two groups of premature infants. Eighteen studies were performed with six infants at Johns Hopkins Hospital (JHH); 24 studies were performed with nine infants at Columbus Children's Hospital (CCH). The two groups differed in that JHH infants had shorter gestations but were older when studied. Fecal 13C loss after [13C]glucose administration did not differ between the two groups. Compared with glucose, the metabolism of lactose appeared to involve more malabsorption and colonic fermentation in JHH infants than in CCH infants and resulted in higher fecal losses of substrate carbon. Maturation appeared to involve increased proximal intestinal absorption and greater retention of absorbed carbohydrate. Simultaneous absorption of substrate from the small and large intestine may limit the usefulness of breath tests for 13C in the premature infant.

  4. Synthesis Of [2h, 13c] And [2h3, 13c]Methyl Aryl Sulfides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-03-30

    The present invention is directed to labeled compounds, [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2, .sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms and the aryl group is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR1## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4, and R.sub.5 are each independently, hydrogen, a C.sub.1 -C.sub.4 lower alkyl, a halogen, an amino group from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each a C.sub.1 -C.sub.4 lower alkyl, a phenyl, or an alkoxy group. The present invention is also directed to processes of preparing [.sup.2 H.sub.1, .sup.13 C], [.sup.2 H.sub.2,.sup.13 C] and [.sup.2 H.sub.3, .sup.13 C]methyl aryl sulfides wherein the .sup.13 C methyl group attached to the sulfur of the sulfide includes exactly one, two or three deuterium atoms. The present invention is also directed to the labeled compounds of [.sup.2 H.sub.1, .sup.13 C]methyl iodide and [.sup.2 H.sub.2, .sup.13 C]methyl iodide.

  5. Imaging pH with hyperpolarized 13C.

    PubMed

    Gallagher, Ferdia A; Kettunen, Mikko I; Brindle, Kevin M

    2011-10-01

    pH is a fundamental physiological parameter that is tightly controlled by endogenous buffers. The acid-base balance is altered in many disease states, such as inflammation, ischemia and cancer. Despite the importance of pH, there are currently no routine methods for imaging the spatial distribution of pH in humans. The enormous gain in sensitivity afforded by dynamic nuclear polarization (DNP) has provided a novel way in which to image tissue pH using MR, which has the potential to be translated into the clinic. This review explores the advantages and disadvantages of current pH imaging techniques and how they compare with DNP-based approaches for the measurement and imaging of pH with hyperpolarized (13)C. Intravenous injection of hyperpolarized (13)C-labeled bicarbonate results in the rapid production of hyperpolarized (13)CO(2) in the reaction catalyzed by carbonic anhydrase. As this reaction is close to equilibrium in the body and is pH dependent, the ratio of the (13)C signal intensities from H(13)CO(3)(-) and (13)CO(2), measured using MRS, can be used to calculate pH in vivo. The application of this technique to a murine tumor model demonstrated that it measured predominantly extracellular pH and could be mapped in the animal using spectroscopic imaging techniques. A second approach has been to use the production of hyperpolarized (13)CO(2) from hyperpolarized [1-(13)C]pyruvate to measure predominantly intracellular pH. In tissues with a high aerobic capacity, such as the heart, the hyperpolarized [1-(13)C]pyruvate undergoes rapid oxidative decarboxylation, catalyzed by intramitochondrial pyruvate dehydrogenase. Provided that there is sufficient carbonic anhydrase present to catalyze the rapid equilibration of the hyperpolarized (13)C label between CO(2) and bicarbonate, the ratio of their resonance intensities may again be used to estimate pH, which, in this case, is predominantly intracellular. As both pyruvate and bicarbonate are endogenous molecules they

  6. Characterization of the International Humic Substances Society standard and reference fulvic and humic acids by solution state carbon-13 (13C) and hydrogen-1 (1H) nuclear magnetic resonance spectrometry

    USGS Publications Warehouse

    Thorn, Kevin A.; Folan, Daniel W.; MacCarthy, Patrick

    1989-01-01

    Standard and reference samples of the International Humic Substances Society have been characterized by solution state carbon-13 and hydrogen-1 nuclear magnetic resonance (NMR) spectrometry. Samples included the Suwannee River, soil, and peat standard fulvic and humic acids, the Leonardite standard humic acid, the Nordic aquatic reference fulvic and humic acids, and the Summit Hill soil reference humic acid. Aqueous-solution carbon-13 NMR analyses included the measurement of spin-lattice relaxation times, measurement of nuclear Overhauser enhancement factors, measurement of quantitative carbon distributions, recording of attached proton test spectra, and recording of spectra under nonquantitative conditions. Distortionless enhancement by polarization transfer carbon-13 NMR spectra also were recorded on the Suwannee River fulvic acid in deuterated dimethyl sulfoxide. Hydrogen-1 NMR spectra were recorded on sodium salts of the samples in deuterium oxide. The carbon aromaticities of the samples ranged from 0.24 for the Suwannee River fulvic acid to 0.58 for the Leonardite humic acid.

  7. One Kilowatt UHF Solid State Power Amplifier.

    DTIC Science & Technology

    1982-02-01

    den:fiy t, . .mber) One-Killowat t Satellite Communications UHF Hopping Filter Solid State Amplifier 20. ABSTRACT (Continue on reverse aide It neceeary...in this report are power input versus power output, intermodulation products measurement, thermal, and satellite tests.FORM13 DD , JAN73 1 3 EDITION OF...DESCRIPTIONS OF TESTS 18 1. Laboratory and Flight Preliminary Tests 18 2. Power Input vs Power Output Tests 27 3. Satellite Tests 30 4

  8. Rechargeable Sodium All-Solid-State Battery.

    PubMed

    Zhou, Weidong; Li, Yutao; Xin, Sen; Goodenough, John B

    2017-01-25

    A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. All-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C.

  9. High energy efficient solid state laser sources

    NASA Technical Reports Server (NTRS)

    Byer, Robert L.

    1987-01-01

    Diode-laser-pumped solid-state laser oscillators and nonlinear processes were investigated. A new generation on nonplanar oscillator was fabricated, and it is anticipated that passive linewidths will be pushed to the kilohertz regime. A number of diode-pumped laser transitions were demonstrated in the rod configuration. Second-harmonic conversion efficiencies as high as 15% are routinely obtained in a servo-locked external resonant doubling crystal at 15 mW cw input power levels at 1064 nm.

  10. Pulsed solid state lasers for medicine

    NASA Astrophysics Data System (ADS)

    Kertesz, Ivan; Danileiko, A. Y.; Denker, Boris I.; Kroo, Norbert; Osiko, Vyacheslav V.; Prokhorov, Alexander M.

    1994-02-01

    The effect on living tissues of different pulsed solid state lasers: Nd:YAG ((lambda) equals 1.06 micrometers ) Er:glass (1.54 micrometers ), Ho:YAG (2.1 micrometers ) and Er:YAG (2.94 micrometers ) is compared with the continuous wave Nd:YAG- and CO2-lasers used in operating theaters. Portable Er:glass- and Er:YAG-lasers are developed for surgery/cosmetics and HIV-safe blood testing.

  11. Solid-state-laser-rod holder

    DOEpatents

    Gettemy, D.J.; Barnes, N.P.; Griggs, J.E.

    1981-08-11

    The disclosure relates to a solid state laser rod holder comprising Invar, copper tubing, and epoxy joints. Materials and coefficients of expansion of the components of the holder combine with the rod to produce a joint which will give before the rod itself will. The rod may be lased at about 70 to 80/sup 0/K and returned from such a temperature to room temperature repeatedly without its or the holder's destruction.

  12. High energy efficient solid state laser sources

    NASA Technical Reports Server (NTRS)

    Byer, Robert L.

    1987-01-01

    Investigations continue of diode-laser-pumped solid-state laser oscillators and nonlinear processes using them as sources. Diode laser array pumped Nd:YAG and Nd:glass lasers have been demonstrated. Theoretical studies of non-planar oscillators have been advanced, producing new designs which should be more resistant to feedback and offer better frequency stability. A monolithic, singly resonant Optical Parametric Oscillator in MgO:LiNbO3 has been operated.

  13. Solid state synthesis of poly(dichlorophosphazene)

    DOEpatents

    Allen, Christopher W.; Hneihen, Azzam S.; Peterson, Eric S.

    2001-01-01

    A method for making poly(dichlorophosphazene) using solid state reactants is disclosed and described. The present invention improves upon previous methods by removing the need for chlorinated hydrocarbon solvents, eliminating complicated equipment and simplifying the overall process by providing a "single pot" two step reaction sequence. This may be accomplished by the condensation reaction of raw materials in the melt phase of the reactants and in the absence of an environmentally damaging solvent.

  14. Solid-state NMR characterization of Mowry Formation shales

    SciTech Connect

    Miknis, F.P.

    1992-04-01

    Solid-state {sup 13}C and {sup 29}Si NMR measurements were carried out on a series of petroleum source rocks from the Mowry Formation of the Powder River Basin in Wyoming. The objectives of this study wereto use CP/MAS {sup 13}C NMR measurements to monitor changes in the carbon structure of the kerogen that result from depth of burial, and to examine the feasibility of {sup 29}Si NMR for studying the thermal alteration of clay minerals during diagenesis. Carbon and silicon NMR measurements were made on a suite of samples covering a present-day depth interval of 3,000 to 11,500 ft.In general, the NMR results endorsed other geochemical analyses that were performed on the source rocks as part of another study to examine pressure compartmentalization in the Mowry Formation. The carbon aromaticity of the kerogen increased with depth of burial, and at depths greater that approximately 10,000 ft the kerogen showed little capacity to generate additional oil because of the small fraction of residual aliphatic carbon. By combining NMR and Rock-Eval measurements, an estimate of the hydrogen budget was obtained. The calculations indicated that approximately 20% of the kerogen was converted to hydrocarbons, and that sufficient hydrogen was liberated from aromatization and condensation reactions to stabilize the generated products. The {sup 29}Si NMR spectra were characterized by a relatively sharp quartz resonance and a broad resonance from the clay minerals. With increasing depth of burial, the clay resonance became broader and shifted slightly downfield. These changes qualitatively support X-ray analysis that shows progressive alteration of illite to smectite with depth of burial.

  15. Solid-state NMR characterization of Mowry Formation shales

    SciTech Connect

    Miknis, F.P.

    1992-04-01

    Solid-state [sup 13]C and [sup 29]Si NMR measurements were carried out on a series of petroleum source rocks from the Mowry Formation of the Powder River Basin in Wyoming. The objectives of this study wereto use CP/MAS [sup 13]C NMR measurements to monitor changes in the carbon structure of the kerogen that result from depth of burial, and to examine the feasibility of [sup 29]Si NMR for studying the thermal alteration of clay minerals during diagenesis. Carbon and silicon NMR measurements were made on a suite of samples covering a present-day depth interval of 3,000 to 11,500 ft.In general, the NMR results endorsed other geochemical analyses that were performed on the source rocks as part of another study to examine pressure compartmentalization in the Mowry Formation. The carbon aromaticity of the kerogen increased with depth of burial, and at depths greater that approximately 10,000 ft the kerogen showed little capacity to generate additional oil because of the small fraction of residual aliphatic carbon. By combining NMR and Rock-Eval measurements, an estimate of the hydrogen budget was obtained. The calculations indicated that approximately 20% of the kerogen was converted to hydrocarbons, and that sufficient hydrogen was liberated from aromatization and condensation reactions to stabilize the generated products. The [sup 29]Si NMR spectra were characterized by a relatively sharp quartz resonance and a broad resonance from the clay minerals. With increasing depth of burial, the clay resonance became broader and shifted slightly downfield. These changes qualitatively support X-ray analysis that shows progressive alteration of illite to smectite with depth of burial.

  16. SPS solid state antenna power combiner

    NASA Technical Reports Server (NTRS)

    Fitzsimmons, G. W.

    1980-01-01

    A concept for a solar power satellite antenna power combiner which utilizes solid state dc-rf converters is described. To avoid the power combining losses associated with circuit hybrids it is proposed that the power from multiple solid state amplifiers be combined by direct coupling of each amplifier's output to the radiating antenna structure. The selected power-combining antenna consists of a printed (metalized) microstrip circuit on a ceramic type dielectric substrate which is backed by a shallow lightweight aluminum cavity which sums the power of four microwave sources. The antenna behaves like two one-half wavelength slot-line antennas coupled together via their common cavity structure. A significant feature of the antenna configuration selected is that the radiated energy is summed to yield a single radiated output phase which represents the average insertion phase of the four power amplifiers. This energy may be sampled and, by comparison with the input signal, one can phase error correct to maintain the insertion phase of all solid state power combining modules at exactly the same value. This insures that the insertion phase of each SPS power combining antenna module is identical. An experiment verification program is described.

  17. Accurate determinations of one-bond 13C-13C couplings in 13C-labeled carbohydrates

    NASA Astrophysics Data System (ADS)

    Azurmendi, Hugo F.; Freedberg, Darón I.

    2013-03-01

    Carbon plays a central role in the molecular architecture of carbohydrates, yet the availability of accurate methods for 1DCC determination has not been sufficiently explored, despite the importance that such data could play in structural studies of oligo- and polysaccharides. Existing methods require fitting intensity ratios of cross- to diagonal-peaks as a function of the constant-time (CT) in CT-COSY experiments, while other methods utilize measurement of peak separation. The former strategies suffer from complications due to peak overlap, primarily in regions close to the diagonal, while the latter strategies are negatively impacted by the common occurrence of strong coupling in sugars, which requires a reliable assessment of their influence in the context of RDC determination. We detail a 13C-13C CT-COSY method that combines a variation in the CT processed with diagonal filtering to yield 1JCC and RDCs. The strategy, which relies solely on cross-peak intensity modulation, is inspired in the cross-peak nulling method used for JHH determinations, but adapted and extended to applications where, like in sugars, large one-bond 13C-13C couplings coexist with relatively small long-range couplings. Because diagonal peaks are not utilized, overlap problems are greatly alleviated. Thus, one-bond couplings can be determined from different cross-peaks as either active or passive coupling. This results in increased accuracy when more than one determination is available, and in more opportunities to measure a specific coupling in the presence of severe overlap. In addition, we evaluate the influence of strong couplings on the determination of RDCs by computer simulations. We show that individual scalar couplings are notably affected by the presence of strong couplings but, at least for the simple cases studied, the obtained RDC values for use in structural calculations were not, because the errors introduced by strong couplings for the isotropic and oriented phases are very

  18. Accurate determinations of one-bond 13C-13C couplings in 13C-labeled carbohydrates.

    PubMed

    Azurmendi, Hugo F; Freedberg, Darón I

    2013-03-01

    Carbon plays a central role in the molecular architecture of carbohydrates, yet the availability of accurate methods for (1)D(CC) determination has not been sufficiently explored, despite the importance that such data could play in structural studies of oligo- and polysaccharides. Existing methods require fitting intensity ratios of cross- to diagonal-peaks as a function of the constant-time (CT) in CT-COSY experiments, while other methods utilize measurement of peak separation. The former strategies suffer from complications due to peak overlap, primarily in regions close to the diagonal, while the latter strategies are negatively impacted by the common occurrence of strong coupling in sugars, which requires a reliable assessment of their influence in the context of RDC determination. We detail a (13)C-(13)C CT-COSY method that combines a variation in the CT processed with diagonal filtering to yield (1)J(CC) and RDCs. The strategy, which relies solely on cross-peak intensity modulation, is inspired in the cross-peak nulling method used for J(HH) determinations, but adapted and extended to applications where, like in sugars, large one-bond (13)C-(13)C couplings coexist with relatively small long-range couplings. Because diagonal peaks are not utilized, overlap problems are greatly alleviated. Thus, one-bond couplings can be determined from different cross-peaks as either active or passive coupling. This results in increased accuracy when more than one determination is available, and in more opportunities to measure a specific coupling in the presence of severe overlap. In addition, we evaluate the influence of strong couplings on the determination of RDCs by computer simulations. We show that individual scalar couplings are notably affected by the presence of strong couplings but, at least for the simple cases studied, the obtained RDC values for use in structural calculations were not, because the errors introduced by strong couplings for the isotropic and

  19. 13C MRS of Human Brain at 7 Tesla Using [2-13C]Glucose Infusion and Low Power Broadband Stochastic Proton Decoupling

    PubMed Central

    Li, Shizhe; An, Li; Yu, Shao; Araneta, Maria Ferraris; Johnson, Christopher S.; Wang, Shumin; Shen, Jun

    2015-01-01

    Purpose 13C magnetic resonance spectroscopy (MRS) of human brain at 7 Tesla (T) may pose patient safety issues due to high RF power deposition for proton decoupling. The purpose of present work is to study the feasibility of in vivo 13C MRS of human brain at 7 T using broadband low RF power proton decoupling. Methods Carboxylic/amide 13C MRS of human brain by broadband stochastic proton decoupling was demonstrated on a 7 T scanner. RF safety was evaluated using the finite-difference time-domain method. 13C signal enhancement by nuclear Overhauser effect (NOE) and proton decoupling was evaluated in both phantoms and in vivo. Results At 7 T, the peak amplitude of carboxylic/amide 13C signals was increased by a factor of greater than 4 due to the combined effects of NOE and proton decoupling. The 7 T 13C MRS technique used decoupling power and average transmit power of less than 35 W and 3.6 W, respectively. Conclusion In vivo 13C MRS studies of human brain can be performed at 7 T well below the RF safety threshold by detecting carboxylic/amide carbons with broadband stochastic proton decoupling. PMID:25917936

  20. Probing Silica-Biomolecule Interactions by Solid-State NMR and Molecular Dynamics Simulations.

    PubMed

    Brückner, Stephan Ingmar; Donets, Sergii; Dianat, Arezoo; Bobeth, Manfred; Gutiérrez, Rafael; Cuniberti, Gianaurelio; Brunner, Eike

    2016-11-08

    Understanding the molecular interactions between inorganic phases such as silica and organic material is fundamental for chromatographic applications, for tailoring silica-enzyme interactions, and for elucidating the mechanisms of biomineralization. The formation, structure, and properties of the organic/inorganic interface is crucial in this context. Here, we investigate the interaction of selectively (13)C-labeled choline with (29)Si-labeled monosilicic acid/silica at the molecular level. Silica/choline nanocomposites were analyzed by solid-state NMR spectroscopy in combination with extended molecular dynamics (MD) simulations to understand the silica/organic interface. Cross-polarization magic angle spinning (CP MAS)-based NMR experiments like (1)H-(13)C CP-REDOR (rotational-echo double resonance), (1)H-(13)C HETCOR (heteronuclear correlation), and (1)H-(29)Si-(1)H double CP are employed to determine spatial parameters. The measurement of (29)Si-(13)C internuclear distances for selectively (13)C-labeled choline provides an experimental parameter that allows the direct verification of MD simulations. Atomistic modeling using classical MD methodologies is performed using the INTERFACE force field. The modeling results are in excellent agreement with the experimental data and reveal the relevant molecular conformations as well as the nature and interplay of the interactions between the choline cation and the silica surface. Electrostatic interactions and hydrogen bonding are both important and depend strongly on the hydration level as well as the charge state of the silica surface.

  1. The Target of β-Expansin EXPB1 in Maize Cell Walls from Binding and Solid-State NMR Studies.

    PubMed

    Wang, Tuo; Chen, Yuning; Tabuchi, Akira; Cosgrove, Daniel J; Hong, Mei

    2016-12-01

    The wall-loosening actions of β-expansins are known primarily from studies of EXPB1 extracted from maize (Zea mays) pollen. EXPB1 selectively loosens cell walls (CWs) of grasses, but its specific binding target is unknown. We characterized EXPB1 binding to sequentially extracted maize CWs, finding that the protein primarily binds glucuronoarabinoxylan (GAX), the major matrix polysaccharide in grass CWs. This binding is strongly reduced by salts, indicating that it is predominantly electrostatic in nature. For direct molecular evidence of EXPB1 binding, we conducted solid-state nuclear magnetic resonance experiments using paramagnetic relaxation enhancement (PRE), which is sensitive to distances between unpaired electrons and nuclei. By mixing (13)C-enriched maize CWs with EXPB1 functionalized with a Mn(2+) tag, we measured Mn(2+)-induced PRE Strong (1)H and (13)C PREs were observed for the carboxyls of GAX, followed by more moderate PREs for carboxyl groups in homogalacturonan and rhamnogalacturonan-I, indicating that EXPB1 preferentially binds GAX In contrast, no PRE was observed for cellulose, indicating very weak interaction of EXPB1 with cellulose. Dynamics experiments show that EXPB1 changes GAX mobility in a complex manner: the rigid fraction of GAX became more rigid upon EXPB1 binding while the dynamic fraction became more mobile. Combining these data with previous results, we propose that EXPB1 loosens grass CWs by disrupting noncovalent junctions between highly substituted GAX and GAX of low substitution, which binds cellulose. This study provides molecular evidence of β-expansin's target in grass CWs and demonstrates a new strategy for investigating ligand binding for proteins that are difficult to express heterologously.

  2. Revisiting spin-lattice relaxation time measurements for dilute spins in high-resolution solid-state NMR spectroscopy.

    PubMed

    Fu, Riqiang; Li, Jun; Cui, Jingyu; Peng, Xinhua

    2016-07-01

    Numerous nuclear magnetic resonance (NMR) measurements of spin-lattice relaxation times (T1S) for dilute spins such as (13)C have led to investigations of the motional dynamics of individual functional groups in solid materials. In this work, we revisit the Solomon equations and analyze how the heteronuclear cross relaxation between the dilute S (e.g. (13)C) and abundant I (e.g. (1)H) spins affects the measured T1S values in solid-state NMR in the absence of (1)H saturation during the recovery time. It is found theoretically that at the beginning of the S spin magnetization recovery, the existence of non-equilibrium I magnetization introduces the heteronuclear cross relaxation effect onto the recovery of the S spin magnetization and confirmed experimentally that such a heteronuclear cross relaxation effect results in the recovery overshoot phenomena for the dilute spins when T1S is on the same order of T1H, leading to inaccurate measurements of the T1S values. Even when T1S is ten times larger than T1H, the heteronuclear cross relaxation effect on the measured T1S values is still noticeable. Furthermore, this cross relaxation effect on recovery trajectory of the S spins can be manipulated and even suppressed by preparing the initial I and S magnetization, so as to obtain the accurate T1S values. A sample of natural abundance l-isoleucine powder has been used to demonstrate the T1S measurements and their corresponding measured T1C values under various experimental conditions.

  3. Optoacoustic 13C-breath test analyzer

    NASA Astrophysics Data System (ADS)

    Harde, Hermann; Helmrich, Günther; Wolff, Marcus

    2010-02-01

    The composition and concentration of exhaled volatile gases reflects the physical ability of a patient. Therefore, a breath analysis allows to recognize an infectious disease in an organ or even to identify a tumor. One of the most prominent breath tests is the 13C-urea-breath test, applied to ascertain the presence of the bacterium helicobacter pylori in the stomach wall as an indication of a gastric ulcer. In this contribution we present a new optical analyzer that employs a compact and simple set-up based on photoacoustic spectroscopy. It consists of two identical photoacoustic cells containing two breath samples, one taken before and one after capturing an isotope-marked substrate, where the most common isotope 12C is replaced to a large extent by 13C. The analyzer measures simultaneously the relative CO2 isotopologue concentrations in both samples by exciting the molecules on specially selected absorption lines with a semiconductor laser operating at a wavelength of 2.744 μm. For a reliable diagnosis changes of the 13CO2 concentration of 1% in the exhaled breath have to be detected at a concentration level of this isotope in the breath of about 500 ppm.

  4. BOOK REVIEW: Solid State Physics: An Introduction

    NASA Astrophysics Data System (ADS)

    Jakoby, Bernhard

    2009-07-01

    There's a wealth of excellent textbooks on solid state physics. The author of the present book is well aware of this fact and does not attempt to write just another one. Rather, he has provided a very compact introduction to solid state physics for third-year students. As we are faced with the continuous appearance interdisciplinary fields and associated study curricula in natural and engineering sciences (biophysics, mechatronics, etc), a compact text in solid state physics would be appreciated by students of these disciplines as well. The book features 11 chapters where each is provided with supplementary discussion questions and problems. The first chapters deal with a review of chemical bonding mechanisms, crystal structures and mechanical properties of solids, which are brief but by no means superficial. The following, somewhat more detailed chapter on thermal properties of lattices includes a nice introduction to phonons. The foundations of solid state electronics are treated in the next three chapters. Here the author first discusses the classical treatment of electronic behaviour in metals (Drude model) and continues with a quantum-theoretical approach starting with the free-electron model and leading to the band structures in conductive solids. The next chapter is devoted to semiconductors and ends with a brief but, with respect to the topical scope, adequate discussion of semiconductor devices. The classical topics of magnetic and dielectric behaviour are treated in the sequel. The book closes with a chapter on superconductivity and a brief chapter covering the modern topics of quantum confinement and aspects of nanoscale physics. In my opinion, the author has succeeded in creating a very concise yet not superficial textbook. The account presented often probes subjects deep enough to lay the basis for a thorough understanding, preparing the reader for more specialized textbooks. For instance, I think that this book may serve as an excellent first

  5. Refined Analysis of Brain Energy Metabolism Using In Vivo Dynamic Enrichment of 13C Multiplets

    PubMed Central

    Dehghani M., Masoumeh; Duarte, João M. N.; Kunz, Nicolas; Gruetter, Rolf

    2016-01-01

    Carbon-13 nuclear magnetic resonance spectroscopy in combination with the infusion of 13C-labeled precursors is a unique approach to study in vivo brain energy metabolism. Incorporating the maximum information available from in vivo localized 13C spectra is of importance to get broader knowledge on cerebral metabolic pathways. Metabolic rates can be quantitatively determined from the rate of 13C incorporation into amino acid neurotransmitters such as glutamate and glutamine using suitable mathematical models. The time course of multiplets arising from 13C-13C coupling between adjacent carbon atoms was expected to provide additional information for metabolic modeling leading to potential improvements in the estimation of metabolic parameters. The aim of the present study was to extend two-compartment neuronal/glial modeling to include dynamics of 13C isotopomers available from fine structure multiplets in 13C spectra of glutamate and glutamine measured in vivo in rats brain at 14.1 T, termed bonded cumomer approach. Incorporating the labeling time courses of 13C multiplets of glutamate and glutamine resulted in elevated precision of the estimated fluxes in rat brain as well as reduced correlations between them. PMID:26969691

  6. Room-temperature solid-state maser.

    PubMed

    Oxborrow, Mark; Breeze, Jonathan D; Alford, Neil M

    2012-08-16

    The invention of the laser has resulted in many innovations, and the device has become ubiquitous. However, the maser, which amplifies microwave radiation rather than visible light, has not had as large an impact, despite being instrumental in the laser's birth. The maser's relative obscurity has mainly been due to the inconvenience of the operating conditions needed for its various realizations: atomic and free-electron masers require vacuum chambers and pumping; and solid-state masers, although they excel as low-noise amplifiers and are occasionally incorporated in ultrastable oscillators, typically require cryogenic refrigeration. Most realizations of masers also require strong magnets, magnetic shielding or both. Overcoming these various obstacles would pave the way for improvements such as more-sensitive chemical assays, more-precise determinations of biomolecular structure and function, and more-accurate medical diagnostics (including tomography) based on enhanced magnetic resonance spectrometers incorporating maser amplifiers and oscillators. Here we report the experimental demonstration of a solid-state maser operating at room temperature in pulsed mode. It works on a laboratory bench, in air, in the terrestrial magnetic field and amplifies at around 1.45 gigahertz. In contrast to the cryogenic ruby maser, in our maser the gain medium is an organic mixed molecular crystal, p-terphenyl doped with pentacene, the latter being photo-excited by yellow light. The maser's pumping mechanism exploits spin-selective molecular intersystem crossing into pentacene's triplet ground state. When configured as an oscillator, the solid-state maser's measured output power of around -10 decibel milliwatts is approximately 100 million times greater than that of an atomic hydrogen maser, which oscillates at a similar frequency (about 1.42 gigahertz). By exploiting the high levels of spin polarization readily generated by intersystem crossing in photo-excited pentacene and other

  7. Solid-state NMR and EPR analysis of carbon-doped titanium dioxide photocatalysts (TiO(2-)(x)C(x)).

    PubMed

    Reyes-Garcia, Enrique A; Sun, Yanping; Reyes-Gil, Karla R; Raftery, Daniel

    2009-04-01

    Carbon-doped TiO(2) have received attention recently because of their potential for environmental photocatalysis and solar hydrogen conversion applications. Three different carbon-doped TiO(2) nanoparticle materials were synthesized via sol-gel and hydrothermal procedures, and analyzed by (13)C solid-state nuclear magnetic resonance (SSNMR) and other methods to characterize the environment of the doping species. UV/vis spectra and powder X-ray diffraction (XRD) patterns showed that the synthesized materials absorbed visible light and their crystal structures corresponded to anatase. (13)C SSNMR analyses of TiO(2-)(x)C(x) displayed signals corresponding to carbonate-type or sp(2)-type carbon species. Variable contact CP-MAS and dipolar dephasing analyses gave evidence for the presence and proximity of H atoms near these carbonate species. Electron paramagnetic resonance (EPR) spectroscopy showed that the thermally oxidized TiO(2-)(x)C(x) displayed a complex mixture of point defects, electron and hole trapping centers, all attributable to the incorporation of carbon, while the XPS data ruled out the presence of carbide species.

  8. Long-observation-window band-selective homonuclear decoupling: Increased sensitivity and resolution in solid-state NMR spectroscopy of proteins

    NASA Astrophysics Data System (ADS)

    Struppe, Jochem O.; Yang, Chen; Wang, Yachong; Hernandez, Roy V.; Shamansky, Lisa M.; Mueller, Leonard J.

    2013-11-01

    Sensitivity and resolution are the two fundamental obstacles to extending solid-state nuclear magnetic resonance to even larger protein systems. Here, a novel long-observation-window band-selective homonuclear decoupling (LOW BASHD) scheme is introduced that increases resolution up to a factor of 3 and sensitivity up to 1.8 by decoupling backbone alpha-carbon (Cα) and carbonyl (C‧) nuclei in U-13C-labeled proteins during direct 13C acquisition. This approach introduces short (<200 μs) pulse breaks into much longer (˜8 ms) sampling windows to efficiently refocus the J-coupling interaction during detection while avoiding the deleterious effects on sensitivity inherent in rapid stroboscopic band-selective homonuclear decoupling techniques. A significant advantage of LOW-BASHD detection is that it can be directly incorporated into existing correlation methods, as illustrated here for 2D CACO, NCO, and NCA correlation spectroscopy applied to the β1 immunoglobulin binding domain of protein G and 3D CBCACO correlation spectroscopy applied to the α-subunit of tryptophan synthase.

  9. Understanding API-polymer proximities in amorphous stabilized composite drug products using fluorine-carbon 2D HETCOR solid-state NMR.

    PubMed

    Abraham, Anuji; Crull, George

    2014-10-06

    A simple and robust method for obtaining fluorine-carbon proximities was established using a (19)F-(13)C heteronuclear correlation (HETCOR) two-dimensional (2D) solid-state nuclear magnetic resonance (ssNMR) experiment under magic-angle spinning (MAS). The method was applied to study a crystalline active pharmaceutical ingredient (API), avagacestat, containing two types of fluorine atoms and its API-polymer composite drug product. These results provide insight into the molecular structure, aid with assigning the carbon resonances, and probe API-polymer proximities in amorphous spray dried dispersions (SDD). This method has an advantage over the commonly used (1)H-(13)C HETCOR because of the large chemical shift dispersion in the fluorine dimension. In the present study, fluorine-carbon distances up to 8 Å were probed, giving insight into the API structure, crystal packing, and assignments. Most importantly, the study demonstrates a method for probing an intimate molecular level contact between an amorphous API and a polymer in an SDD, giving insights into molecular association and understanding of the role of the polymer in API stability (such as recrystallization, degradation, etc.) in such novel composite drug products.

  10. Using solid-state NMR to monitor the molecular consequences of Cryptococcus neoformans melanization with different catecholamine precursors.

    PubMed

    Chatterjee, Subhasish; Prados-Rosales, Rafael; Frases, Susana; Itin, Boris; Casadevall, Arturo; Stark, Ruth E

    2012-08-07

    Melanins are a class of natural pigments associated with a wide range of biological functions, including microbial virulence, energy transduction, and protection against solar radiation. Because of their insolubility and structural heterogeneity, solid-state nuclear magnetic resonance (NMR) spectroscopy provides an unprecedented means to define the molecular architecture of these enigmatic pigments. The requirement of obligatory catecholamines for melanization of the pathogenic fungus Cryptococcus neoformans also offers unique opportunities for investigating melanin development. In the current study, pigments produced with L-dopa, methyl-L-dopa, epinephrine, and norepinephrine precursors are compared structurally using (13)C and (1)H magic-angle spinning (MAS) NMR. Striking structural differences were observed for both aromatic and aliphatic molecular constituents of the mature fungal pigment assemblies, thus making it possible to redefine the molecular prerequisites for formation of the aromatic domains of insoluble indole-based biopolymers, to rationalize their distinctive physical characteristics, and to delineate the role of cellular constituents in assembly of the melanized macromolecules with polysaccharides and fatty acyl chain-containing moieties. By achieving an augmented understanding of the mechanisms of C. neoformans melanin biosynthesis and cellular assembly, such studies can guide future drug discovery efforts related to melanin-associated virulence, resistance to tumor therapy, and production of melanin mimetics under cell-free conditions.

  11. Synthesis and solid-state NMR characterization of cubic mesoporous silica SBA-1 functionalized with sulfonic acid groups.

    PubMed

    Tsai, Hui-Hsu Gavin; Chiu, Po-Jui; Jheng, Guang-Liang; Ting, Chun-Chiang; Pan, Yu-Chi; Kao, Hsien-Ming

    2011-07-01

    Well-ordered cubic mesoporous silicas SBA-1 functionalized with sulfonic acid groups have been synthesized through in situ oxidation of mercaptopropyl groups with H(2)O(2) via co-condensation of tetraethoxysilane (TEOS) and 3-mercaptopropyltrimethoxysilane (MPTMS) templated by cetyltriethylammonium bromide (CTEABr) under strong acidic conditions. Various synthesis parameters such as the amounts of H(2)O(2) and MPTMS on the structural ordering of the resultant materials were systematically investigated. The materials thus obtained were characterized by a variety of techniques including powder X-ray diffraction (XRD), multinuclear solid-state Nuclear Magnetic Resonance (NMR) spectroscopy, (29)Si{(1)H} 2D HETCOR (heteronuclear correlation) NMR spectroscopy, thermogravimetric analysis (TGA), and nitrogen sorption measurements. By using (13)C CPMAS NMR technique, the status of the incorporated thiol groups and their transformation to sulfonic acid groups can be monitored and, as an extension, to define the optimum conditions to be used for the oxidation reaction to be quantitative. In particular, (29)Si{(1)H} 2D HETCOR NMR revealed that the protons in sulfonic acid groups are in close proximity to the silanol Q(3) species, but not close enough to form a hydrogen bond.

  12. Fast-neutron solid-state dosimeter

    DOEpatents

    Kecker, K.H.; Haywood, F.F.; Perdue, P.T.; Thorngate, J.H.

    1975-07-22

    This patent relates to an improved fast-neutron solid-state dosimeter that does not require separation of materials before it can be read out, that utilizes materials that do not melt or otherwise degrade at about 300$sup 0$C readout temperature, that provides a more efficient dosimeter, and that can be reused. The dosimeters are fabricated by intimately mixing a TL material, such as CaSO$sub 4$:Dy, with a powdered polyphenyl, such as p-sexiphenyl, and hot- pressing the mixture to form pellets, followed by out-gassing in a vacuum furnace at 150$sup 0$C prior to first use dosimeters. (auth)

  13. Passivation-free solid state battery

    DOEpatents

    Abraham, K.M.; Peramunage, D.

    1998-06-16

    This invention pertains to passivation-free solid-state rechargeable batteries composed of Li{sub 4}Ti{sub 5}O{sub 12} anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn{sub 2}O{sub 4}, LiCoO{sub 2}, LiNiO{sub 2} and LiV{sub 2}O{sub 5} and their derivatives. 5 figs.

  14. The Galileo Solid-State Imaging experiment

    NASA Technical Reports Server (NTRS)

    Belton, Michael J. S.; Klaasen, Kenneth P.; Clary, Maurice C.; Anderson, James L.; Anger, Clifford D.; Carr, Michael H.; Chapman, Clark R.; Davies, Merton E.; Greeley, Ronald; Anderson, Donald

    1992-01-01

    The Galileo Orbiter's Solid-State Imaging (SSI) experiment uses a 1.5-m focal length TV camera with 800 x 800 pixel, virtual-phase CCD detector in order to obtain images of Jupiter and its satellites which possess a combination of sensitivity levels, spatial resolutions, geometric fidelity, and spectral range that are unmatched by earlier imaging data. After describing the performance of this equipment on the basis of ground calibrations, attention is given to the SSI experiment's Jupiter system observation objectives; these encompass atmospheric science, satellite surfaces, ring structure, and 'darkside' experiments.

  15. High Speed Solid State Circuit Breaker

    NASA Technical Reports Server (NTRS)

    Podlesak, Thomas F.

    1993-01-01

    The U.S. Army Research Laboratory, Fort Monmouth, NJ, has developed and is installing two 3.3 MW high speed solid state circuit breakers at the Army's Pulse Power Center. These circuit breakers will interrupt 4160V three phase power mains in no more than 300 microseconds, two orders of magnitude faster than conventional mechanical contact type circuit breakers. These circuit breakers utilize Gate Turnoff Thyristors (GTO's) and are currently utility type devices using air cooling in an air conditioned enclosure. Future refinements include liquid cooling, either water or two phase organic coolant, and more advanced semiconductors. Each of these refinements promises a more compact, more reliable unit.

  16. Proteins as solid-state electronic conductors.

    PubMed

    Ron, Izhar; Pecht, Israel; Sheves, Mordechai; Cahen, David

    2010-07-20

    Protein structures can facilitate long-range electron transfer in solution. But a fundamental question remains: can these structures also serve as solid-state electronic conductors? Answering this question requires methods for studying conductivity of the "dry" protein (which only contains tightly bound structured water molecules) sandwiched between two electronic conductors in a solid-state type configuration. If successful, such systems could serve as the basis for future, bioinspired electronic device technology. In this Account, we survey, analyze, and compare macroscopic and nanoscopic (scanning probe) solid-state conductivities of proteins, noting the inherent constraints of each of these, and provide the first status report on this research area. This analysis shows convincing evidence that "dry" proteins pass orders of magnitude higher currents than saturated molecules with comparable thickness and that proteins with known electrical activity show electronic conductivity, nearly comparable to that of conjugated molecules ("wires"). These findings suggest that the structural features of proteins must have elements that facilitate electronic conductivity, even if they do not have a known electron transfer function. As a result, proteins could serve not only as sensing, polar,or photoactive elements in devices (such as field-effect transistor configurations) but also as electronic conductors. Current knowledge of peptide synthesis and protein modification paves the way toward a greater understanding of how changes in a protein's structure affect its conductivity. Such an approach could minimize the need for biochemical cascades in systems such as enzyme-based circuits, which transduce the protein's response to electronic current. In addition, as precision and sensitivity of solid-state measurements increase, and as knowledge of the structure and function of "dry" proteins grows, electronic conductivity may become an additional approach to study electron

  17. Entanglement and Squeezing in Solid State Circuits

    SciTech Connect

    Wen Yihuo; Gui Lulong

    2008-11-07

    We investigate the dynamics of a system consisting of a Cooper-pair box and two superconducting transmission line resonators. There exist both linear and nonlinear interactions in such a system. We show that single-photon entanglement state can be generated in a simple way in the linear interaction regime. In nonlinear interaction regime, we derive the Hamiltonian of degenerate three-wave mixing and propose a scheme for generating squeezed state of microwave using the three-wave mixing in solid state circuits. In the following, we design a system for generating squeezed states of nanamechanical resonator.

  18. Solid State Marx Modulators for Emerging Applications

    SciTech Connect

    Kemp, M.A.; /SLAC

    2012-09-14

    Emerging linear accelerator applications increasingly push the boundaries of RF system performance and economics. The power modulator is an integral part of RF systems whose characteristics play a key role in the determining parameters such as efficiency, footprint, cost, stability, and availability. Particularly within the past decade, solid-state switch based modulators have become the standard in high-performance, high power modulators. One topology, the Marx modulator, has characteristics which make it particularly attractive for several emerging applications. This paper is an overview of the Marx topology, some recent developments, and a case study of how this architecture can be applied to a few proposed linear accelerators.

  19. Passivation-free solid state battery

    DOEpatents

    Abraham, Kuzhikalail M.; Peramunage, Dharmasena

    1998-01-01

    This invention pertains to passivation-free solid-state rechargeable batteries composed of Li.sub.4 Ti.sub.5 O.sub.12 anode, a solid polymer electrolyte and a high voltage cathode. The solid polymer electrolyte comprises a polymer host, such as polyacrylonitrile, poly(vinyl chloride), poly(vinyl sulfone), and poly(vinylidene fluoride), plasticized by a solution of a Li salt in an organic solvent. The high voltage cathode includes LiMn.sub.2 O.sub.4, LiCoO.sub.2, LiNiO.sub.2 and LiV.sub.2 O.sub.5 and their derivatives.

  20. Rechargeable Sodium All-Solid-State Battery

    PubMed Central

    2017-01-01

    A reversible plating/stripping of a dendrite-free metallic-sodium anode with a reduced anode/ceramic interfacial resistance is created by a thin interfacial interlayer formed in situ or by the introduction of a dry polymer film. Wetting of the sodium on the interfacial interlayer suppresses dendrite formation and growth at different discharge/charge C-rates. All-solid-state batteries were obtained with a high cycling stability and Coulombic efficiency at 65 °C. PMID:28149953

  1. Solid state nanopores for gene expression profiling

    NASA Astrophysics Data System (ADS)

    Mussi, V.; Fanzio, P.; Repetto, L.; Firpo, G.; Valbusa, U.; Scaruffi, P.; Stigliani, S.; Tonini, G. P.

    2009-07-01

    Recently, nanopore technology has been introduced for genome analysis. Here we show results related to the possibility of preparing "engineered solid state nanopores". The nanopores were fabricated on a suspended Si 3N 4 membrane by Focused Ion Beam (FIB) drilling and chemically functionalized in order to covalently bind oligonucleotides (probes) on their surface. Our data show the stable effect of DNA attachment on the ionic current measured through the nanopore, making it possible to conceive and develop a selective biosensor for gene expression profiling.

  2. Solid-state-based analog of optomechanics

    DOE PAGES

    Naumann, Nicolas L.; Droenner, Leon; Carmele, Alexander; ...

    2016-09-01

    In this study, we investigate a semiconductor quantum dot as a microscopic analog of a basic optomechanical setup. We show that optomechanical features can be reproduced by the solid-state platform, arising from parallels of the underlying interaction processes, which in the optomechanical case is the radiation pressure coupling and in the semiconductor case the electron–phonon coupling. We discuss bistabilities, lasing, and phonon damping, and recover the same qualitative behaviors for the semiconductor and the optomechanical cases expected for low driving strengths. However, in contrast to the optomechanical case, distinct signatures of higher order processes arise in the semiconductor model.

  3. Nanoengineering for solid-state lighting.

    SciTech Connect

    Schubert, E. Fred; Koleske, Daniel David; Wetzel, Christian; Lee, Stephen Roger; Missert, Nancy A.; Lin, Shawn-Yu; Crawford, Mary Hagerott; Fischer, Arthur Joseph

    2009-09-01

    This report summarizes results from a 3-year Laboratory Directed Research and Development project performed in collaboration with researchers at Rensselaer Polytechnic Institute. Our collaborative effort was supported by Sandia's National Institute for Nanoengineering and focused on the study and application of nanoscience and nanoengineering concepts to improve the efficiency of semiconductor light-emitting diodes for solid-state lighting applications. The project explored LED efficiency advances with two primary thrusts: (1) the study of nanoscale InGaN materials properties, particularly nanoscale crystalline defects, and their impact on internal quantum efficiency, and (2) nanoscale engineering of dielectric and metal materials and integration with LED heterostructures for enhanced light extraction efficiency.

  4. Solid state opening switches of new type

    NASA Astrophysics Data System (ADS)

    Kudasov, Yu. B.; Makarov, I. V.; Pavlov, V. N.

    2001-04-01

    We discuss two new types of high-current solid-state opening switches based on nonlinear diffusion of a strong magnetic field into a substance. In the first case, a magnetic field penetrates into solid solution (V 1- xCr x) 2O 3, which undergoes a metal-insulator phase transition of the first order under Joule heating. In the second case, a switching of current occurs due to the Hall diffusion of magnetic field into n-InAs. Results of numerical analysis are presented.

  5. The 60 GHz solid state power amplifier

    NASA Technical Reports Server (NTRS)

    Mcclymonds, J.

    1991-01-01

    A new amplifier architecture was developed during this contract that is superior to any other solid state approach. The amplifier produced 6 watts with 4 percent efficiency over a 2 GHz band at 61.5 GHz. The unit was 7 x 9 x 3 inches in size, 5.5 pounds in weight, and the conduction cooling through the baseplate is suitable for use in space. The amplifier used high efficiency GaAs IMPATT diodes which were mounted in 1-diode circuits, called modules. Eighteen modules were used in the design, and power combining was accomplished with a proprietary passive component called a combiner plate.

  6. Solid state transport-based thermoelectric converter

    DOEpatents

    Hu, Zhiyu

    2010-04-13

    A solid state thermoelectric converter includes a thermally insulating separator layer, a semiconducting collector and an electron emitter. The electron emitter comprises a metal nanoparticle layer or plurality of metal nanocatalyst particles disposed on one side of said separator layer. A first electrically conductive lead is electrically coupled to the electron emitter. The collector layer is disposed on the other side of the separator layer, wherein the thickness of the separator layer is less than 1 .mu.m. A second conductive lead is electrically coupled to the collector layer.

  7. Pulsed Power for Solid-State Lasers

    SciTech Connect

    Gagnon, W; Albrecht, G; Trenholme, J; Newton, M

    2007-04-19

    Beginning in the early 1970s, a number of research and development efforts were undertaken at U.S. National Laboratories with a goal of developing high power lasers whose characteristics were suitable for investigating the feasibility of laser-driven fusion. A number of different laser systems were developed and tested at ever larger scale in pursuit of the optimum driver for laser fusion experiments. Each of these systems had associated with it a unique pulsed power option. A considerable amount of original and innovative engineering was carried out in support of these options. Ultimately, the Solid-state Laser approach was selected as the optimum driver for the application. Following this, the Laser Program at the Lawrence Livermore National Laboratory and the University of Rochester undertook aggressive efforts directed at developing the technology. In particular, at Lawrence Livermore National Laboratory, a series of laser systems beginning with the Cyclops laser and culminating in the present with the National Ignition Facility were developed and tested. As a result, a large amount of design information for solid-state laser pulsed power systems has been documented. Some of it is in the form of published papers, but most of it is buried in internal memoranda, engineering reports and LLNL annual reports. One of the goals of this book is to gather this information into a single useable format, such that it is easily accessed and understood by other engineers and physicists for use with future designs. It can also serve as a primer, which when seriously studied, makes the subsequent reading of original work and follow-up references considerably easier. While this book deals only with the solid-state laser pulsed power systems, in the bibliography we have included a representative cross section of papers and references from much of the very fine work carried out at other institutions in support of different laser approaches. Finally, in recent years, there has

  8. Detection of human muscle glycogen by natural abundance /sup 13/C NMR

    SciTech Connect

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

    1988-03-01

    Natural abundance /sup 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 /sup 1/H decoupling was used to obtain decoupled natural abundance /sup 13/C NMR spectra of the C-1 position of muscle glycogen.

  9. A theoretical perspective on the accuracy of rotational resonance (R 2)-based distance measurements in solid-state NMR

    NASA Astrophysics Data System (ADS)

    Pandey, Manoj Kumar; Ramachandran, Ramesh

    2010-03-01

    The application of solid-state NMR methodology for bio-molecular structure determination requires the measurement of constraints in the form of 13C-13C and 13C-15N distances, torsion angles and, in some cases, correlation of the anisotropic interactions. Since the availability of structurally important constraints in the solid state is limited due to lack of sufficient spectral resolution, the accuracy of the measured constraints become vital in studies relating the three-dimensional structure of proteins to its biological functions. Consequently, the theoretical methods employed to quantify the experimental data become important. To accentuate this aspect, we re-examine analytical two-spin models currently employed in the estimation of 13C-13C distances based on the rotational resonance (R 2) phenomenon. Although the error bars for the estimated distances tend to be in the range 0.5-1.0 Å, R 2 experiments are routinely employed in a variety of systems ranging from simple peptides to more complex amyloidogenic proteins. In this article we address this aspect by highlighting the systematic errors introduced by analytical models employing phenomenological damping terms to describe multi-spin effects. Specifically, the spin dynamics in R 2 experiments is described using Floquet theory employing two different operator formalisms. The systematic errors introduced by the phenomenological damping terms and their limitations are elucidated in two analytical models and analysed by comparing the results with rigorous numerical simulations.

  10. Use of microcoil probehead for determination of the structure of oriented silk fibers by solid-state NMR.

    PubMed

    Yamauchi, K; Imada, T; Asakura, T

    2005-09-22

    A microcoil probehead for solid-state NMR was developed with a two-channel radio-frequency circuit, and 13C observation with a proton-decoupling probehead was performed to obtain information on the distribution of the orientation of silk fibroin molecules in the fiber. The coil (1 mm (diameter) x 5 mm (length)) of the probehead was placed at the angles 90 degrees and 30 degrees , relative to the static magnetic field. Only 70 mug of [1-13C]Gly silk fibroin fiber was used in a magnet of 9.4 T (400 MHz for proton channel).

  11. Activities of the Solid State Division

    NASA Astrophysics Data System (ADS)

    Green, P. H.; Hinton, L. W.

    1994-08-01

    This report covers research progress in the Solid State Division from April 1, 1992, to September 30, 1993. During this period, the division conducted a broad, interdisciplinary materials research program with emphasis on theoretical solid state physics, neutron scattering, synthesis and characterization of materials, ion beam and laser processing, and the structure of solids and surfaces. This research effort was enhanced by new capabilities in atomic-scale materials characterization, new emphasis on the synthesis and processing of materials, and increased partnering with industry and universities. The theoretical effort included a broad range of analytical studies, as well as a new emphasis on numerical simulation stimulated by advances in high-performance computing and by strong interest in related division experimental programs. Superconductivity research continued to advance on a broad front from fundamental mechanisms of high-temperature superconductivity to the development of new materials and processing techniques. The Neutron Scattering Program was characterized by a strong scientific user program and growing diversity represented by new initiatives in complex fluids and residual stress. The national emphasis on materials synthesis and processing was mirrored in division research programs in thin-film processing, surface modification, and crystal growth. Research on advanced processing techniques such as laser ablation, ion implantation, and plasma processing was complemented by strong programs in the characterization of materials and surfaces including ultrahigh resolution scanning transmission electron microscopy, atomic-resolution chemical analysis, synchrotron x-ray research, and scanning tunneling microscopy.

  12. The Pythagorean Theorem and the Solid State

    NASA Astrophysics Data System (ADS)

    Kelly, Brenda S.; Splittgerber, Allen G.

    2005-05-01

    Solid-state parameters such as radius ratios, packing efficiencies, and crystal densities may be calculated for various crystal structures from basic Euclidean geometry relating to the Pythagorean theorem of right triangles. Because simpler cases are often discussed in the standard inorganic chemistry texts, this article only presents calculations for closest-packed A-type lattices (one type of particle) and several compound AB lattices (A and B particles) including sodium chloride, cesium chloride, zinc blende (sphalerite), wurtzite, and fluorite. For A-type metallic crystals, the use of recommended values of atomic radii results in calculated densities within 1% of observed values. For AB lattices, assuming ionic crystals, the use of recommended values of ionic radii results in density determinations that are usually but not always close to observed values. When there is covalent character to the bonding, the use of covalent radii results in calculated densities that correlate well with observed values. If interionic or interatomic spacings are used, the calculated densities are always close to the observed values. As indicated by a survey of the standard inorganic texts, these calculations are generally not presented. However, as an illustration of the application of simple mathematical principles to the study of chemistry, discussion of the methods presented in this manuscript may be of value in classroom presentations pertaining to the solid state.

  13. Nanocrystal-enabled solid state bonding.

    SciTech Connect

    San Diego State University, San Diego, CA; Puskar, Joseph David; Tikare, Veena; Garcia Cardona, Cristina; Reece, Mark; Brewer, Luke N.; Holm, Elizabeth Ann

    2010-10-01

    In this project, we performed a preliminary set of sintering experiments to examine nanocrystal-enabled diffusion bonding (NEDB) in Ag-on-Ag and Cu-on-Cu using Ag nanoparticles. The experimental test matrix included the effects of material system, temperature, pressure, and particle size. The nanoparticle compacts were bonded between plates using a customized hot press, tested in shear, and examined post mortem using microscopy techniques. NEDB was found to be a feasible mechanism for low-temperature, low-pressure, solid-state bonding of like materials, creating bonded interfaces that were able to support substantial loads. The maximum supported shear strength varied substantially within sample cohorts due to variation in bonded area; however, systematic variation with fabrication conditions was also observed. Mesoscale sintering simulations were performed in order to understand whether sintering models can aid in understanding the NEDB process. A pressure-assisted sintering model was incorporated into the SPPARKS kinetic Monte Carlo sintering code. Results reproduce most of the qualitative behavior observed in experiments, indicating that simulation can augment experiments during the development of the NEDB process. Because NEDB offers a promising route to low-temperature, low-pressure, solid-state bonding, we recommend further research and development with a goal of devising new NEDB bonding processes to support Sandia's customers.

  14. Dissipative entanglement of solid-state spins in diamond

    NASA Astrophysics Data System (ADS)

    Rao, D. D. Bhaktavatsala; Yang, Sen; Wrachtrup, Jörg

    2017-02-01

    Generating robust entanglement among solid-state spins is key for applications in quantum information processing and precision sensing. Here we show a dissipative approach to generate such entanglement among the hyperfine coupled electron nuclear spins using the rapid optical decay of electronic excited states. The combined dark state interference effects of the optical and microwave driving fields in the presence of spontaneous emission from the short-lived excited state leads to a dissipative formation of an entangled steady state. We show that the dissipative entanglement is generated for any initial state conditions of the spins and is resilient to external field fluctuations. We analyze the scheme for both continuous and pulsed driving fields in the presence of realistic noise sources.

  15. Solid State Division progress report, September 30, 1981

    SciTech Connect

    Not Available

    1982-04-01

    Progress made during the 19 months from March 1, 1980, through September 30, 1981, is reported in the following areas: theoretical solid state physics (surfaces, electronic and magnetic properties, particle-solid interactions, and laser annealing); surface and near-surface properties of solids (plasma materials interactions, ion-solid interactions, pulsed laser annealing, and semiconductor physics and photovoltaic conversion); defects in solids (radiation effects, fracture, and defects and impurities in insulating crystals); transport properties of solids (fast-ion conductors, superconductivity, and physical properties of insulating materials); neutron scattering (small-angle scattering, lattice dynamics, and magnetic properties); crystal growth and characterization (nuclear waste forms, ferroelectric mateirals, high-temperature materials, and special materials); and isotope research materials. Publications and papers are listed. (WHK)

  16. Structural studies of methyl brevifolincarboxylate in solid state by means of NMR spectroscopy and DFT calculations

    NASA Astrophysics Data System (ADS)

    Wolniak, Michał; Tomczyk, Michał; Gudej, Jan; Wawer, Iwona

    2006-12-01

    Methyl brevifolincarboxylate isolated from the herb of Potentilla argentea L. (Rosaceae) is a representative of the naturally occurring polyphenols. The compound is of pharmaceutical interest mainly because of its antiviral and antioxidant properties. 13C NMR spectra were recorded for solution and solid phase. 13C CPMAS spectra were assigned by comparison with solution data, dipolar dephasing and short contact time experiments. The correctness of assignments was verified by GIAO DFT calculations of shielding constants. The differences between the solution and solid state chemical shift values were explained in terms of orientation of OH groups and intramolecular hydrogen bonds. The splitting of the C1 dbnd O resonance shows that there exists a polymorphism in the solid phase, whic