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Sample records for 13c cross polarization

  1. Motion-Insensitive Localized 13C Spectroscopy Using Cyclic and Slice-Selective J Cross Polarization

    NASA Astrophysics Data System (ADS)

    Kunze, C.; Kimmich, R.

    Several new methods are proposed for the sensitive localized detection of 13C nuclei on the basis of cyclic and slice-selective J cross polarization in 13C 1H x spin systems. The 13C nuclei are detected either directly after the amplitude is enhanced by polarization transfer in the rotating frame or, preferably, indirectly by heteronuclear editing of signals of the 1H nuclei coupled to 13C. In the latter case, the sensitivity corresponds to that of 1H rather than to that of 13C resonance. Test experiments are reported. In vitro applications to a hen egg and a fresh porcine shank prove the applicability of the methods to biological objects with 13C in natural abundance. A particular advantage of the new rotating-frame methods over laboratory-frame techniques serving the same purpose is the insensitivity to motions of the object. This is demonstrated by experiments with a moving sample. Hartmann/Hahn mismatch can be compensated using the MOIST modification. The time-averaged absorbed radiofrequency power per kilogram body weight was estimated on the basis of a model for surface power absorption. The result lies well below the standard safety limits for clinical applications.

  2. 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.

  3. 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.

  4. Vibrational 13C-cross-polarization/magic angle spinning NMR spectroscopic and thermal characterization of poly(alanine-glycine) as model for silk I Bombyx mori fibroin.

    PubMed

    Monti, Patrizia; Taddei, Paola; Freddi, Giuliano; Ohgo, Kosuke; Asakura, Tetsuo

    2003-01-01

    This study focuses on the conformational characterization of poly(alanine-glycine) II (pAG II) as a model for a Bombyx mori fibroin silk I structure. Raman, IR, and 13C-cross-polarization/magic angle spinning NMR spectra of pAG II are discussed in comparison with those of the crystalline fraction of B. mori silk fibroin (chymotryptic precipitate, Cp) with a silk I (silk I-Cp) structure. The spectral data give evidence that silk I-Cp and the synthetic copolypeptide pAG II have similar conformations. Moreover, the spectral findings reveal that silk I-Cp is more crystalline than pAG II; consequently, the latter contains a larger amount of the random coil conformation. Differential scanning calorimetry measurements confirm this result. N-Deuteration experiments on pAG II allow us to attribute the Raman component at 1320 cm(-1) to the amide III mode of a beta-turn type II conformation, thus confirming the results of those who propose a repeated beta-turn type II structure for silk I. The analysis of the Raman spectra in the nuNH region confirms that the silk I structure is characterized by the presence of different types of H-bonding arrangements, in agreement with the above model.

  5. Structure of model peptides based on Nephila clavipes dragline silk spidroin (MaSp1) studied by 13C cross polarization/magic angle spinning NMR.

    PubMed

    Yang, Mingying; Nakazawa, Yasumoto; Yamauchi, Kazuo; Knight, David; Asakura, Tetsuo

    2005-01-01

    To obtain detailed structural information for spider dragline spidroin (MaSp1), we prepared three versions of the consensus peptide GGLGGQGAGAAAAAAGGAGQGGYGGLGSQGAGR labeled with 13C at six different sites. The 13C CP/MAS NMR spectra were observed after treating the peptides with different reagents known to alter silk protein conformations. The conformation-dependent 13C NMR chemical shifts and peak deconvolution were used to determine the local structure and the fractional compositions of the conformations, respectively. After trifluoroacetic acid (solvent)/diethyl ether (coagulant) treatment, the N-terminal region of poly-Ala (PLA) sequence, Ala8 and Ala10, adopted predominantly the alpha-helix with a substantial amount of beta-sheet. The central region, Ala15, Ala18, and Leu26, and C-terminal region, Ala31, of the peptide were dominated by either 3(1)-helix or alpha-helix. There was no indication of beta-sheet, although peak broadening indicates that the torsion angle distribution is relatively large. After 9 M LiBr/dialysis treatment, three kinds of conformation, beta-sheet, random coil, and 3(1)-helix, appeared, in almost equal amounts of beta-sheet and random coil conformations for Ala8 and Ala10 residues and distorted 3(1)-helix at the central region of the peptide. In contrast, after formic acid/methanol and 8 M urea/acetonitrile treatments, all of the local structure tends to beta-sheet, although small amounts of random coil are also observed. The peak pattern of the Ala Cbeta carbon after 8 M urea/acetonitrile treatment is similar to the corresponding patterns of silk fiber from Bombyx mori and Samia cynthia ricini. We also synthesized a longer 13C-labeled peptide containing two PLA blocks and three Gly-rich blocks. After 8 M urea/acetonitrile treatment, the conformation pattern was closely similar to that of the shorter peptide.

  6. - and Cross-Polarization 13C NMR Evidence of Alterations in Molecular Composition of Humic Substances Following Afforestation with Eucalypt in Distinct Brazilian Biomes

    NASA Astrophysics Data System (ADS)

    Silva, I. R.; Soares, E. M.; Schmidt-Rohr, K.; Novais, R.; Barros, N.; Fernandes, S.

    2010-12-01

    The effect of planting fast growing tree species on SOM quality in tropical regions has been overlooked. In the present study 13C-NMR approaches were used to evaluate the impact of eucalypt cultivation on humic and fulvic acids molecular composition. The results indicate that the replacement of native vegetation by eucalypt plantations increased the relative contribution of aliphatic groups in HA from soils previously under Atlantic Forest, Grassland, and the Cerrado (Curvelo site only). The same trend was observed for FA, except in the Curvelo site. A trend for degradation and smaller contribution of O-alkyl C (carbohydrates) in HA was observed in soils under eucalyptus in Atlantic Forest and Cerrado. For FA such decreases were seen in Cerrado and Grassland biomes after eucalypt planting. In the area cultivated with pasture in the Atlantic Forest biome and in the Grassland soil, the largest contributions of lignin-derived compounds were detected in HA. The HA from the Cerrado at the Curvelo site, where the woody vegetation is virtually devoid of grassy species, showed the lowest intensity of lignin signal then those from the Cerrado sensu stricto in Itacambira, where grass species are more abundant. At our study sites, charred material are most likely derived from burning of the native vegetation, as naturally occurs in the Cerrado region, or anthropogenic fires in the Grassland biome. Burning of harvest residues in eucalypt fields was also a common practice in the early rotations. The replacement of native vegetation by eucalypt plantations increases the relative contribution of nonpolar alkyl groups in HA from soils previously under Atlantic Forest, Grassland, and the Cerrado (Curvelo site only) biomes. There is evidence of substantial contribution of lignin-derived C to HA and FA, especially in sites planted with Brachiaria sp pastures. Eucalypt introduction decreases the relative contribution of carbohydrates in HA and FA. 13C DP/MAS NMR functional groups in

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

    NASA Astrophysics Data System (ADS)

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

    2007-12-01

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

  8. 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.

  9. 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

  10. 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.

  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. 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.

  13. 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.

  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. (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.

  16. 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

  17. 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

  18. 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.

  19. Reaction cross sections for. nu. sup 13 C r arrow e sup minus sup 13 N and. nu. sup 13 C r arrow. nu. prime sup 13 C sup * for low energy neutrinos

    SciTech Connect

    Fukugita, M. ); Kohyama, Y.; Kubodera, K.; Kuramoto, T. )

    1990-04-01

    Cross sections for {nu}+{sup 13}C reactions are calculated both for charged- and neutral-current reactions in order to estimate the efficiency of a {sup 13}C target as a solar neutrino detector. The relevant transition matrix elements are obtained using the semiphenomenological effective-operator approach for {ital p}-shell nuclei.

  20. 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.

  1. The complete set of spin observables for the (13)C(polarized proton, polarized neutron)(13)N and (15)N(polarized proton, polarized neutron)(15)O reactions

    NASA Astrophysics Data System (ADS)

    Du, Qun Qun

    1998-12-01

    The 13C(p,n)13N and 15N(p,n)15O reactions have been a puzzle for more than ten years. The ground state transitions are Jπ=1/2- to Jπ=1/2-. These are 'mixed' transitions because they can involve quantum number changes either (/Delta T=1,/ /Delta J=0,/ /Delta/pi=0,/ /Delta S=0), or (/Delta T=1,/ /Delta J=1,/ /Delta/pi=0,/ /Delta S=1); these quantum number changes are refered to as 'Fermi' and 'Gamow-Teller' respectively. Because the quantum number changes are the same as for Fermi and Gamow-Teller beta decay. From the systematics of (p,n) and (n,p) reactions on pure Fermi transitions (e.g. 0 + to 0+) and pure Gamow-Teller transitions (e.g. 0+ to 1+), calibrations have been established of cross section per unit B(F) or unit B(GT), where 'B' refers to doubly reduced matrix elements extracted from beta decay. However, cross sections for the 13C(p,n)13N(g.s.) and 15N(p,n)15O(g.s.) reactions are substantially larger than one would then predict from the known B(F)s and B(GT)s for these transitions. To explore this anomaly, spin observables were used to extract separately the Fermi and Gamow-Teller cross sections for these reactions. To acquire the complete sets of polarization- transfer observables, a new neutron polarimeter was designed, built, commissioned and calibrated. This polarimeter, call the '2π polarimeter' because of its complete azimuthal coverage for scattered neutrons, has very good position and timing resolution (354 ps). The complete sets of spin-transfer coefficients Dij for 13C(p,n)13N (at 0o , 5.5o , and 11o ) and 15N(p,n)15O (at 0o ) at 135 MeV were measured. Following the formalism of Ichimura and Kawahigashi, we extracted the spin-longitudinal, and spin-transverse and spin-independent responses D0,/ Dq,/ Dn and Dp from the measured Dijs. The F and GT fractions of the (p,n) cross sections are then extracted as f F=D0 and fGT=Dn+Dp+Dq=1- d0. Values of Dk for both the 13C(p,n)13N(g.s) and 15N(p,n)15O(g.s.) were extracted. From these responses, we

  2. 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

  3. Moss δ(13) C: an accurate proxy for past water environments in polar regions.

    PubMed

    Bramley-Alves, Jessica; Wanek, Wolfgang; French, Kristine; Robinson, Sharon A

    2015-06-01

    Increased aridity is of global concern. Polar regions provide an opportunity to monitor changes in bioavailable water free of local anthropogenic influences. However, sophisticated proxy measures are needed. We explored the possibility of using stable carbon isotopes in segments of moss as a fine-scale proxy for past bioavailable water. Variation in δ(13) C with water availability was measured in three species across three peninsulas in the Windmill Islands, East Antarctica and verified using controlled chamber experiments. The δ(13) C from Antarctic mosses accurately recorded long-term variations in water availability in the field, regardless of location, but significant disparities in δ(13) C between species indicated some make more sensitive proxies. δ(13) CSUGAR derived from living tissues can change significantly within the span of an Antarctic season (5 weeks) in chambers, but under field conditions, slow growth means that this technique likely represents multiple seasons. δ(13) CCELLULOSE provides a precise and direct proxy for bioavailable water, allowing reconstructions for coastal Antarctica and potentially other cold regions over past centuries.

  4. 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

  5. Actinide cross sections from the reaction of sup 13 C with sup 254 Es sup g

    SciTech Connect

    Moody, K.J.; Lougheed, R.W.; Dougan, R.J.; Hulet, E.K.; Wild, J.F.; Summerer, K.; Hahn, R.L.; Aarle, J.v.; Bethune, G.R. )

    1990-01-01

    We have measured cross sections for the formation of actinide transfer products in the reaction of 72-MeV {sup 13}C projectiles with {sup 254}Es{sup {ital g}} targets. The pattern of nuclide yields is similar to those observed in the reactions of heavier ions with {sup 254}Es{sup {ital g}}. We have constructed the primary element yields from these results and show that the total cross section for transfer reactions is 58 mb. The total reaction cross section is about 300 mb. Lawrencium isotopes are formed with larger cross sections than are consistent with the trends of the transfer-product distributions; we explain this in terms of massive transfer, and model the lawrencium yields with an evaporation code.

  6. 14N + 13C fusion cross sections and compound nucleus limitation in 27Al

    NASA Astrophysics Data System (ADS)

    Digregorio, D. E.; Gomez del Campo, J.; Chan, Y. D.; Ford, J. L. C., Jr.; Shapira, D.; Ortiz, M. E.

    1982-10-01

    Fusion cross sections for the 14N + 13C system have been measured by detecting the evaporation residues at five bombarding energies which correspond to high excitation energies in the compound nucleus: E*(27Al)=64-110 MeV. The 27Al nucleus can be populated by four different heavy-ion entrance channels-15N + 12C, 16O + 11B, 14N + 13C, and 17O + 10B-which are accessible to experimental measurements. Comparing the present data with those already existing for the above channels, it is found that for E*>60 MeV the curves E* vs Jcr for each system converge, which may be indicative of a limitation imposed by the compound nucleus. The data are discussed in terms of existing models for entrance channel and statistical yrast line limitations. The highest energy point also suggests the existence of a maximum absolute angular momentum limit of ~28ℏ. NUCLEAR REACTIONS 14N + 13C E(14N)=86.0, 103.8, 149.0, 161.3, and 180.0 MeV; measured d2σdΩdE for reaction products from Z=5 to 12. Extracted σfus, σD, σR.

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

    SciTech Connect

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

    1991-03-19

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

  8. Analyzing power measurements for the (. pi. sup + ,. pi. sup 0 ) reaction on a polarized sup 13 C target

    SciTech Connect

    Goergen, J.J.

    1991-05-01

    The analyzing powers A{sub y} differential cross sections d{sigma}/d{Omega} for the reaction {sup 13}C({pi}{sup +},{pi}{sup 0}){sup 13}N have been measured for forward scattering angles at an incident pion kinetic energy of T{sub pi}{sup +} = 163 MeV by using a transversely polarized target. Analyzing powers and reaction cross sections impose stringent constrains on nuclear reaction models and can be used to test the present understanding of nuclear structure for 1p-shell nuclei. The resulting A{sub y} are compared to the predictions of first-order Distorted Wave Impulse Approximation (DWIA) calculations, which reproduce well the differential cross sections. Although there is qualitative agreement at forward angles, the quantitative agreement is poor, especially at scattering angles larger than 50{degrees}. Since the DWIA calculations do not appear to be strongly sensitive to the assumed nuclear structure model, the discrepancy in describing the analyzing powers suggests that the reaction mechanism may not yet be well understood and higher order corrections may be important. Also measured were the analyzing powers for the elementary charge exchange reaction {pi}{sup {minus}} {bar p} {yields} {pi}{degrees}n over the same angular range and at an incident pion kinetic energy of T{sub pi}{minus} = 161 MeV. The results are compared to the most recents phase shift predictions. Within the experimental uncertainties, phase shift calculations agree with the measured A{sub y} and no changes in the {pi}N phase shifts near the P{sub 33} resonance are needed to describe the data.

  9. Spin-locking and cross-polarization under magic-angle spinning of uniformly labeled solids.

    PubMed

    Hung, Ivan; Gan, Zhehong

    2015-07-01

    Spin-locking and cross-polarization under magic-angle spinning are investigated for uniformly (13)C and (15)N labeled solids. In particular, the interferences from chemical shift anisotropy, and (1)H heteronuclear and (13)C homonuclear dipolar couplings are identified. The physical origin of these interferences provides guidelines for selecting the best (13)C and (15)N polarization transfer rf fields. Optimal settings for both the zero- and double-quantum cross-polarization transfer mechanisms are recommended.

  10. Reliable Identification of Cross-Linked Products in Protein Interaction Studies by 13C-Labeled p-Benzoylphenylalanine

    NASA Astrophysics Data System (ADS)

    Pettelkau, Jens; Ihling, Christian H.; Frohberg, Petra; van Werven, Lars; Jahn, Olaf; Sinz, Andrea

    2014-09-01

    We describe the use of the 13C-labeled artificial amino acid p-benzoyl-L-phenylalanine (Bpa) to improve the reliability of cross-linked product identification. Our strategy is exemplified for two protein-peptide complexes. These studies indicate that in many cases the identification of a cross-link without additional stable isotope labeling would result in an ambiguous assignment of cross-linked products. The use of a 13C-labeled photoreactive amino acid is considered to be preferred over the use of deuterated cross-linkers as retention time shifts in reversed phase chromatography can be ruled out. The observation of characteristic fragment ions additionally increases the reliability of cross-linked product assignment. Bpa possesses a broad reactivity towards different amino acids and the derived distance information allows mapping of spatially close amino acids and thus provides more solid structural information of proteins and protein complexes compared to the longer deuterated amine-reactive cross-linkers, which are commonly used for protein 3D-structure analysis and protein-protein interaction studies.

  11. Crossed elliptical polarization undulator

    SciTech Connect

    Sasaki, Shigemi

    1997-05-01

    The first switching of polarization direction is possible by installing two identical helical undulators in series in a same straight section in a storage ring. By setting each undulator in a circular polarization mode in opposite handedness, one can obtain linearly polarized radiation with any required polarization direction depending on the modulator setting between two undulators. This scheme can be used without any major degradation of polarization degree in any low energy low emittance storage ring.

  12. Interresidue carbonyl-carbonyl polarization transfer experiments in uniformly 13C, 15N-labeled peptides and proteins

    NASA Astrophysics Data System (ADS)

    Janik, Rafal; Ritz, Emily; Gravelle, Andrew; Shi, Lichi; Peng, Xiaohu; Ladizhansky, Vladimir

    2010-03-01

    In this work, we demonstrate that Homonuclear Rotary Resonance Recoupling (HORROR) can be used to reintroduce carbonyl-carbonyl interresidue dipolar interactions and to achieve efficient polarization transfer between carbonyl atoms in uniformly 13C, 15N-labeled peptides and proteins. We show that the HORROR condition is anisotropically broadened and overall shifted to higher radio frequency intensities because of the CSA effects. These effects are analyzed theoretically using Average Hamiltonian Theory. At spinning frequencies used in this study, 22 kHz, this broadening is experimentally found to be on the order of a kilohertz at a proton field of 600 MHz. To match HORROR condition over all powder orientations, variable amplitude radio frequency (RF) fields are required, and efficient direct transfers on the order of 20-30% can be straightforwardly established. Two- and three-dimensional chemical shift correlation experiments establishing long-range interresidue connectivities (e.g., (N[i]-CO[i - 2])) are demonstrated on the model peptide N-acetyl-valine-leucine, and on the third immunoglobulin binding domain of protein G. Possible future developments are discussed.

  13. J Cross-Polarization Methods for Localized NMR without Magnetic Field Gradients

    NASA Astrophysics Data System (ADS)

    Kostler, H.; Kimmich, R.

    1993-10-01

    This work predominantly refers to 13C in vivo spectroscopy and has two objectives. First, heteronuclear editing is considered for proton-detected NMR spectroscopy of rare nuclei. The second aspect refers to localized heteronuclear NMR spectroscopy implying the editing option. Both purposes are achieved by employing J cross polarization (or coherent rotating-frame polarization transfer). The spatial selectivity is due to different in-homogeneities of the superimposed double-resonance radiofrequency fields of the J cross-polarization experiment. A 13C surface coil, for instance, was combined with a 1H birdcage resonator, so that J cross polarization is restricted to the region where the Hartmann/Hahn condition is approached. Heteronuclear editing of NMR lines for proton-detected 13C spectroscopy was performed by the aid of a cyclic cross-polarization pathway. Test experiments demonstrating the volume selectivity of the transfer process and the editing efficiency of the cyclic cross-polarization procedure are reported.

  14. 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.

  15. 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...

  16. 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.

  17. Optically enhanced nuclear cross polarization in acridine-doped fluorene

    SciTech Connect

    Oshiro, C.M.

    1982-06-01

    The objective of this work has been to create large polarizations of the dilute /sup 13/C nuclei in the solid state. The idea was to create /sup 1/H polarizations larger than Boltzmann and to use the proton enhanced nuclear induction spectroscopy cross polarization technique to then transfer this large polarization to the /sup 13/C spin system. Optical Nuclear Polarization (ONP) of acridine-doped fluorene single crystals was studied. In addition, ONP of powdered samples of the acridine-doped fluorene was studied. In general, many compounds do not crystallize easily or do not form large crystals suitable for NMR experiments. Powdered, amorphous and randomly dispersed samples are generally far more readily available than single crystals. One objective of this work has been to (first) create large /sup 1/H polarizations. Although large optical proton polarizations in single crystals have been reported previously, optically generated polarizations in powdered samples have not been reported. For these reasons, ONP studies of powdered samples of the acridine-doped fluorene were also undertaken. Using ONP in combination with the proton enhanced nuclear induction spectroscopy experiment, large /sup 13/C polarizations have been created in fluorene single crystals. These large /sup 13/C polarizations have permitted the determination of the seven incongruent chemical shielding tensors of the fluorene molecule. Part 2 of this thesis describes the proton enhanced nuclear induction spectroscopy experiment. Part 3 describes the ONP experiment. Part 4 is a description of the experimental set-up. Part 5 describes the data analysis for the determination of the chemical shielding tensors. Part 6 presents the results of the ONP experiments performed in this work and the chemical shielding tensors determined.

  18. 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.

  19. Dual-band selective double cross polarization for heteronuclear polarization transfer between dilute spins in solid-state MAS NMR

    NASA Astrophysics Data System (ADS)

    Zhang, Zhengfeng; Miao, Yimin; Liu, Xiaoli; Yang, Jun; Li, Conggang; Deng, Feng; Fu, Riqiang

    2012-04-01

    A sinusoidal modulation scheme is described for selective heteronuclear polarization transfer between two dilute spins in double cross polarization magic-angle-spinning nuclear magnetic resonance spectroscopy. During the second N → C cross polarization, the 13C RF amplitude is modulated sinusoidally while the 15N RF amplitude is tangent. This modulation induces an effective spin-lock field in two selective frequency bands in either side of the 13C RF carrier frequency, allowing for simultaneous polarization transfers from 15N to 13C in those two selective frequency bands. It is shown by experiments and simulations that this sinusoidal modulation allows one to selectively polarize from 15N to its covalently bonded 13Cα and 13C' carbons in neighboring peptide planes simultaneously, which is useful for establishing the backbone connectivity between two sequential residues in protein structural elucidation. The selectivity and efficiency were experimentally demonstrated on a uniformly 13C,15N-labeled β1 immunoglobulin binding domain of protein G (GB1).

  20. 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.

  1. 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.

  2. Hyperpolarization of nitrogen-15 nuclei by cross polarization and dissolution dynamic nuclear polarization

    NASA Astrophysics Data System (ADS)

    Milani, Jonas; Vuichoud, Basile; Bornet, Aurélien; Melzi, Roberto; Jannin, Sami; Bodenhausen, Geoffrey

    2017-01-01

    Dynamic Nuclear Polarization (DNP) is often achieved by the direct transfer of polarization from electrons to nuclei such as 13C, induced by microwave saturation of the wings of narrow EPR lines of radicals like trityl. In the indirect approach on the other hand, DNP is used to transfer the polarization from the electrons of radicals such as nitroxides that have broad EPR lines to nuclear spins I = 1H, followed by cross-polarization (CP) from I = 1H to S = 13C or other nuclei with low gyromagnetic ratios. This approach is particularly attractive for S = 15N, since direct DNP yields modest polarizations P(15N) < 4% with build-up times that can be as long as τDNP(15N) > 2 h. In this paper, we show that CP from 1H to 15N at 1.2 K can yield P(15N) = 25% with τCP-DNP(15N) = 10-15 min. After rapid dissolution and transfer to a solution-state NMR spectrometer, a polarization P(15N) = 20% was observed at 300 K. The longitudinal relaxation times in solution can be as long as T1(15N) > 800 s in favorable cases.

  3. Polarization aberrations of crossed folding mirrors

    NASA Astrophysics Data System (ADS)

    Crandall, David G.; Chipman, Russell A.

    1995-08-01

    Polarization aberrations due to varying polarization state across the field of view (FOV) are investigated for crossed folding mirrors. We define crossed mirrors as oriented in space such that s-polarized light incident on the first mirror is p-polarized at the second mirror. This completely compensates for polarization state changes at one point in the field of view. The resulting polarization aberrations are explored across the FOV using the example of aluminum mirrors overcoated with a 12 layer, highly reflective, dielectric stack. The polarization aberration is very low along a band across the field of view. For arbitrary points in the FOV, the retardance and diattenuation are slightly elliptical.

  4. Cross polarization compatible dialysis chip.

    PubMed

    Kornreich, Micha; Heymann, Michael; Fraden, Seth; Beck, Roy

    2014-10-07

    We visualize birefringence in microliter sample volumes using a microfluidic dialysis chip optimized for cross polarization microscopy. The chip is composed of two overlapping polydimethylsiloxane (PDMS) channels separated by a commercial cellulose ester membrane. Buffer exchange in the sample chamber is achieved within minutes by dialyzing under continuous reservoir flow. Using fd virus as a birefringent model system, we monitor the fd virus isotropic to liquid crystal phase transition as a function of ionic strength. We show that the reorientation of the fd virus spans a few tens of seconds, indicative of fast ion exchange across the membrane. Complete phase separation reorganization takes minutes to hours as it involves diffusive virus mass transport within the storage chamber.

  5. (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.

  6. Elemental formula annotation of polar and lipophilic metabolites using (13) C, (15) N and (34) S isotope labelling, in combination with high-resolution mass spectrometry.

    PubMed

    Giavalisco, Patrick; Li, Yan; Matthes, Annemarie; Eckhardt, Aenne; Hubberten, Hans-Michael; Hesse, Holger; Segu, Shruthi; Hummel, Jan; Köhl, Karin; Willmitzer, Lothar

    2011-10-01

    The unbiased and comprehensive analysis of metabolites in any organism presents a major challenge if proper peak annotation and unambiguous assignment of the biological origin of the peaks are required. Here we provide a comprehensive multi-isotope labelling-based strategy using fully labelled (13) C, (15) N and (34) S plant tissues, in combination with a fractionated metabolite extraction protocol. The extraction procedure allows for the simultaneous extraction of polar, semi-polar and hydrophobic metabolites, as well as for the extraction of proteins and starch. After labelling and extraction, the metabolites and lipids were analysed using a high-resolution mass spectrometer providing accurate MS and all-ion fragmentation data, providing an unambiguous readout for every detectable isotope-labelled peak. The isotope labelling assisted peak annotation process employed can be applied in either an automated database-dependent or a database-independent analysis of the plant polar metabolome and lipidome. As a proof of concept, the developed methods and technologies were applied and validated using Arabidopsis thaliana leaf and root extracts. Along with a large repository of assigned elemental compositions, which is provided, we show, using selected examples, the accuracy and reliability of the developed workflow.

  7. Dissolution dynamic nuclear polarization of deuterated molecules enhanced by cross-polarization

    NASA Astrophysics Data System (ADS)

    Kurzbach, Dennis; Weber, Emmanuelle M. M.; Jhajharia, Aditya; Cousin, Samuel F.; Sadet, Aude; Marhabaie, Sina; Canet, Estel; Birlirakis, Nicolas; Milani, Jonas; Jannin, Sami; Eshchenko, Dmitry; Hassan, Alia; Melzi, Roberto; Luetolf, Stephan; Sacher, Marco; Rossire, Marc; Kempf, James; Lohman, Joost A. B.; Weller, Matthias; Bodenhausen, Geoffrey; Abergel, Daniel

    2016-11-01

    We present novel means to hyperpolarize deuterium nuclei in 13CD2 groups at cryogenic temperatures. The method is based on cross-polarization from 1H to 13C and does not require any radio-frequency fields applied to the deuterium nuclei. After rapid dissolution, a new class of long-lived spin states can be detected indirectly by 13C NMR in solution. These long-lived states result from a sextet-triplet imbalance (STI) that involves the two equivalent deuterons with spin I = 1. An STI has similar properties as a triplet-singlet imbalance that can occur in systems with two equivalent I = 1/2 spins. Although the lifetimes TSTI are shorter than T1(Cz), they can exceed the life-time T1(Dz) of deuterium Zeeman magnetization by a factor of more than 20.

  8. Accelerator mass spectrometry measurements of the 13C (n ,γ )14C and 14N(n ,p )14C cross sections

    NASA Astrophysics Data System (ADS)

    Wallner, A.; Bichler, M.; Buczak, K.; Dillmann, I.; Käppeler, F.; Karakas, A.; Lederer, C.; Lugaro, M.; Mair, K.; Mengoni, A.; Schätzel, G.; Steier, P.; Trautvetter, H. P.

    2016-04-01

    The technique of accelerator mass spectrometry (AMS), offering a complementary tool for sensitive studies of key reactions in nuclear astrophysics, was applied for measurements of the 13C (n ,γ )14C and the 14N(n ,p )14C cross sections, which act as a neutron poison in s -process nucleosynthesis. Solid samples were irradiated at Karlsruhe Institute of Technology with neutrons closely resembling a Maxwell-Boltzmann distribution for k T =25 keV, and also at higher energies between En=123 and 182 keV. After neutron irradiation the produced amount of 14C in the samples was measured by AMS at the Vienna Environmental Research Accelerator (VERA) facility. For both reactions the present results provide important improvements compared to previous experimental data, which were strongly discordant in the astrophysically relevant energy range and missing for the comparably strong resonances above 100 keV. For 13C (n ,γ ) we find a four times smaller cross section around k T =25 keV than a previous measurement. For 14N(n ,p ), the present data suggest two times lower cross sections between 100 and 200 keV than had been obtained in previous experiments and data evaluations. The effect of the new stellar cross sections on the s process in low-mass asymptotic giant branch stars was studied for stellar models of 2 M⊙ initial mass, and solar and 1 /10th solar metallicity.

  9. (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.

  10. SASE FEL Polarization Control Using Crossed Undulator

    SciTech Connect

    Ding, Yuantao; Huang, Zhirong; /SLAC

    2008-09-30

    There is a growing interest in producing intense, coherent x-ray radiation with an adjustable and arbitrary polarization state. In this paper, we study the crossed undulator scheme for rapid polarization control in a self-amplified spontaneous emission (SASE) free electron laser (FEL). Because a SASE source is a temporally chaotic light, we perform a statistical analysis on the state of polarization using FEL theory and simulations. We show that by adding a small phase shifter and a short (about 1.3 times the FEL power gain length), 90{sup o} rotated planar undulator after the main SASE planar undulator, one can obtain circularly polarized light--with over 80% polarization--near the FEL saturation.

  11. DWBA analysis of {sup 12}C(d,p){sup 13}C cross section data below 300 keV deuteron energy

    SciTech Connect

    Naqvi, A.A.; Ayer, Z.; Ludwig, E. ||

    1994-12-31

    {sup 12}C(d,p){sup 13}T differential cross section data at 200, 220, 250, 280 and 300 keV deuteron energies has been analyzed using finite range DWBA codes PTOLEMY and TWOFNR. It was observed that shape and magnitude of the cross section data at 300, 280 keV energies can be fitted well but the shape of 250, 220 and 200 keV data cannot be fitted. However 250, 220 and 200 keV data shape can be fitted by changing the optical model parameters at each energy. This indicates a very strong energy dependence of the optical model parameters data of the entrance channel over such a small energy range which is not observed in the presently available elastic scattering data of the entrance channel.

  12. Single Shot Polarization Characterization of XUV FEL Pulses from Crossed Polarized Undulators

    PubMed Central

    Ferrari, E.; Allaria, E.; Buck, J.; De Ninno, G.; Diviacco, B.; Gauthier, D.; Giannessi, L.; Glaser, L.; Huang, Z.; Ilchen, M.; Lambert, G.; Lutman, A. A.; Mahieu, B.; Penco, G.; Spezzani, C.; Viefhaus, J.

    2015-01-01

    Polarization control is a key feature of light generated by short-wavelength free-electron lasers. In this work, we report the first experimental characterization of the polarization properties of an extreme ultraviolet high gain free-electron laser operated with crossed polarized undulators. We investigate the average degree of polarization and the shot-to-shot stability and we analyze aspects such as existing possibilities for controlling and switching the polarization state of the emitted light. The results are in agreement with predictions based on Gaussian beams propagation. PMID:26314764

  13. Single shot polarization characterization of XUV FEL pulses from crossed polarized undulators

    DOE PAGES

    Ferrari, E.; Allaria, E.; Buck, J.; ...

    2015-08-28

    Polarization control is a key feature of light generated by short-wavelength free-electron lasers. In this work, we report the first experimental characterization of the polarization properties of an extreme ultraviolet high gain free-electron laser operated with crossed polarized undulators. We research the average degree of polarization and the shot-to-shot stability and we analyze aspects such as existing possibilities for controlling and switching the polarization state of the emitted light. The results are in agreement with predictions based on Gaussian beams propagation.

  14. Concurrent Application of ANC and THM to assess the 13C(α, n)16O Absolute Cross Section at Astrophysical Energies and Possible Consequences for Neutron Production in Low-mass AGB Stars

    NASA Astrophysics Data System (ADS)

    Trippella, O.; La Cognata, M.

    2017-03-01

    The {}13{{C}}{(α ,n)}16{{O}} reaction is considered to be the main neutron source responsible for the production of heavy nuclides (from {Sr} to {Bi}) through slow n-capture nucleosynthesis (s-process) at low temperatures during the asymptotic giant branch phase of low-mass stars (≲ 3{--}4 {M}ȯ , or LMSs). In recent years, several direct and indirect measurements have been carried out to determine the cross section at the energies of astrophysical interest (around 190+/- 40 {keV}). However, they yield inconsistent results that cause a highly uncertain reaction rate and affect the neutron release in LMSs. In this work we have combined two indirect approaches, the asymptotic normalization coefficient and the Trojan horse method, to unambiguously determine the absolute value of the {}13{{C}}{(α ,n)}16{{O}} astrophysical factor. With these, we have determined a very accurate reaction rate to be introduced into astrophysical models of s-process nucleosynthesis in LMSs. Calculations using this recommended rate have shown limited variations in the production of those neutron-rich nuclei (with 86≤slant A≤slant 209) that receive contribution only by slow neutron captures.

  15. 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

  16. 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

  17. 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.

  18. 13C NMR spectroscopy of the insoluble carbon of carbonaceous chondrites

    NASA Technical Reports Server (NTRS)

    Cronin, J. R.; Pizzarello, S.; Frye, J. S.

    1987-01-01

    13C NMR spectra have been obtained of the insoluble carbon residues resulting from HF-digestion of three carbonaceous chondrites, Orgueil (C1), Murchison (CM2), and Allende (CV3). Spectra obtained using the cross polarization magic-angle spinning technique show two major features attributable respectively to carbon in aliphatic/olefinic structures. The spectrum obtained from the Allende sample was weak, presumably as a consequence of its low hydrogen content. Single pulse excitation spectra, which do not depend on 1H-13C polarization transfer for signal enhancement were also obtained. These spectra, which may be more representative of the total carbon in the meteorite samples, indicate a greater content of carbon in aromatic/olefinic structures. These results suggest that extensive polycyclic aromatic sheets are important structural features of the insoluble carbon of all three meteorites. The Orgueil and Murchison materials contain additional hydrogenated aromatic/olefinic and aliphatic groups.

  19. Cross-polarized interferometry of a Jovian decametric radio storm

    NASA Astrophysics Data System (ADS)

    Phillips, J. A.; Carr, T. D.; Greenman, W. B.; Levy, J.

    1987-09-01

    Observations of an 18-MHz Io-A storm have been conducted using a 46 km cross-polarized interferometer at the University of Florida. The pre- and postdetection correlation properties of LH and RH elliptically polarized L bursts have been studied. Fringe visibility measurements suggest that two discrete and independent sources are sometimes simultaneously active, the polarization sense of one being LH and that of the other RH. A scintillation analysis supports the conclusion that two or more sources were active in such cases.

  20. Coherent Backscattering in the Cross-Polarized Channel

    NASA Technical Reports Server (NTRS)

    Mischenko, Michael I.; Mackowski, Daniel W.

    2011-01-01

    We analyze the asymptotic behavior of the cross-polarized enhancement factor in the framework of the standard low-packing-density theory of coherent backscattering by discrete random media composed of spherically symmetric particles. It is shown that if the particles are strongly absorbing or if the smallest optical dimension of the particulate medium (i.e., the optical thickness of a plane-parallel slab or the optical diameter of a spherically symmetric volume) approaches zero, then the cross-polarized enhancement factor tends to its upper-limit value 2. This theoretical prediction is illustrated using direct computer solutions of the Maxwell equations for spherical volumes of discrete random medium.

  1. In vivo dynamic turnover of cerebral 13C isotopomers from [U- 13C]glucose

    NASA Astrophysics Data System (ADS)

    Xu, Su; Shen, Jun

    2006-10-01

    An INEPT-based 13C MRS method and a cost-effective and widely available 11.7 Tesla 89-mm bore vertical magnet were used to detect dynamic 13C isotopomer turnover from intravenously infused [U- 13C]glucose in a 211 μL voxel located in the adult rat brain. The INEPT-based 1H → 13C polarization transfer method is mostly adiabatic and therefore minimizes signal loss due to B 1 inhomogeneity of the surface coils used. High quality and reproducible data were acquired as a result of combined use of outer volume suppression, ISIS, and the single-shot three-dimensional localization scheme built in the INEPT pulse sequence. Isotopomer patterns of both glutamate C4 at 34.00 ppm and glutamine C4 at 31.38 ppm are dominated first by a doublet originated from labeling at C4 and C5 but not at C3 (with 1JC4C5 = 51 Hz) and then by a quartet originated from labeling at C3, C4, and C5 (with 1JC3C4 = 35 Hz). A lag in the transition of glutamine C4 pattern from doublet-dominance to quartet dominance as compared to glutamate C4 was observed, which provides an independent verification of the precursor-product relationship between neuronal glutamate and glial glutamine and a significant intercompartmental cerebral glutamate-glutamine cycle between neurons and glial cells.

  2. 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.

  3. Spatio-Temporal Dynamics of Cross Polarized Wave Generation

    NASA Astrophysics Data System (ADS)

    Adams, Daniel; Squier, Jeff; Durfee, Charles

    2009-10-01

    We use time-domain Spatially and Spectrally Resolved Interferometry (SSRI) to investigate cross-polarized wave (XPW) generation in barium fluoride. We find that the XPW pulse is √3 smaller than the input in the spatiotemporal domain regardless of the input chirp. Additionally, we calculate a temporally dependent focal length resulting from the nonlinear interaction, and discuss its implications.

  4. Efficient cross-polarization using a composite 0 degrees pulse for NMR studies on static solids.

    PubMed

    Fukuchi, Masashi; Ramamoorthy, Ayyalusamy; Takegoshi, K

    2009-02-01

    In most solid-state NMR experiments, cross-polarization is an essential step to detect low-gamma nuclei such as (13)C and (15)N. In this study, we present a new cross-polarization scheme using spin-locks composed of composite 0 degrees pulses in the RF channels of high-gamma and low-gamma nuclei to establish the Hartmann-Hahn match. The composite 0 degrees pulses with no net nutation-angle{(2pi)(X)-(2pi)(-X)-(2pi)(Y)-(2pi)(-Y) -}(n) applied simultaneously to both high-gamma (I) and low-gamma (S) nuclei create an effective heteronuclear dipolar Hamiltonian H(d)((0))=d/2(2I(Z)S(Z)+I(X)S(X)+I(Y)S(Y)), which is capable of transferring the Z-component of the I spin magnetization to the Z-component of the S spin magnetization. It also retains a homonuclear dipolar coupling Hamiltonian that enables the flip-flop transfer among abundant spins. While our experimental results indicate that the new pulse sequence, called composite zero cross-polarization (COMPOZER-CP) performs well on adamantane, it is expected to be more valuable to study semi-solids like liquid crystalline materials and model lipid membranes. Theoretical analysis of COMPOZER-CP is presented along with experimental results. Our experimental results demonstrate that COMPOZER-CP overcomes the RF field inhomogeneity and Hartmann-Hahn mismatch for static solids. Experimental results comparing the performance of COMPOZER-CP with that of the traditional constant-amplitude CP and rampCP sequences are also presented in this paper.

  5. Tunable porosity and polarity of polar post-cross-linked resins and selective adsorption.

    PubMed

    Wang, Xiaomei; Zhang, Ting; Huo, Jiaqi; Huang, Jianhan; Liu, You-Nian

    2017-02-01

    Herein we synthesized three polar post-cross-linked resins by adjusting the initial cross-linking degree of the precursor copolymers, and found that the porosity and polarity of these resins could be effectively tuned. The polar post-cross-linked resin with the initial cross-linking degree of 10% (abbreviated as PVE_10%_pc) possessed a much greater BET surface area and almost all micro/mesopores, but lower content of ester groups, while that with the initial cross-linking degree of 60% (named as PVE_60%_pc) had a much less BET surface area, less micro/mesopores and considerable macropores, but higher content of ester groups. The different porosity and polarity of these resins endowed them with different selectivity for the adsorption of aromatic compounds. PVE_10%_pc owned the largest equilibrium capacity to phenol whilst PVE_40%_pc was the most efficient for adsorption of benzoic acid, and hydrogen bonding, hydrophobic interaction and π-π stacking were the main driving forces for the adsorption.

  6. Circularly Polarized Microwave Antenna Element with Very Low Off-Axis Cross-Polarization

    NASA Technical Reports Server (NTRS)

    Greem. David; DuToit, Cornelis

    2013-01-01

    The goal of this work was to improve off-axis cross-polarization performance and ease of assembly of a circularly polarized microwave antenna element. To ease assembly, the initial design requirement of Hexweb support for the internal circuit part, as well as the radiating disks, was eliminated. There is a need for different plating techniques to improve soldering. It was also desirable to change the design to eliminate soldering as well as the need to use the Hexweb support. Thus, a technique was developed to build the feed without using solder, solving the lathing and soldering issue. Internal parts were strengthened by adding curvature to eliminate Hexweb support, and in the process, the new geometries of the internal parts opened the way for improving the off-axis cross-polarization performance as well. The radiating disks curvatures were increased for increased strength, but it was found that this also improved crosspolarization. Optimization of the curvatures leads to very low off-axis cross-polarization. The feed circuit was curved into a cylinder for improved strength, eliminating Hexweb support. An aperture coupling feed mechanism eliminated the need for feed pins to the disks, which would have required soldering. The aperture coupling technique also improves cross-polarization performance by effectively exciting the radiating disks very close to the antenna s central axis of symmetry. Because of the shape of the parts, it allowed for an all-aluminum design bolted together and assembled with no solder needed. The advantage of a solderless design is that the reliability is higher, with no single-point failure (solder), and no need for special plating techniques in order to solder the unit together. The shapes (curved or round) make for a more robust build without extra support materials, as well as improved offaxis cross-polarization.

  7. 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.

  8. Polarization-assisted WMAP-NVSS Cross Correlation

    SciTech Connect

    Liu, G.-C.

    2008-10-10

    Cross-correlation of Cosmic Microwave Background (CMB) and large scale structure survey is one of the powerful tools for constraining the nature of dark energy through the so-called Integrated Sachs-Wolfe effect. However, CMB from higher redshift is the dominated noise of this effect. Here, we present the CMB polarization-assisted method to suppress this noise. We apply this method to cross-correlation of the microwave sky observed by Wilkinson Microwave Anisotropy Probe (WMAP) with the radio source catalog compiled by NRAO VLA Sky Survey (NVSS) to study the efficiency of the noise suppression. We find that the spurious correlation is reduced about 2-7%.

  9. 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.

  10. 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.

  11. 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.

  12. 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.

  13. [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.

  14. 13C-NMR spectra and contact time experiment for Skjervatjern fulvic and humic acids

    USGS Publications Warehouse

    Malcolm, R.L.

    1992-01-01

    The T(CP) and T(1p) time constants for Skjervatjern fulvic and humic acids were determined to be short with T(CP) values ranging from 0.14 ms to 0.53 ms and T(1p) values ranging from 3.3 ms to 5.9 ms. T(CP) or T(1p) time constants at a contact time of 1 ms are favorable for quantification of 13C-NMR spectra. Because of the short T(CP) values, correction factors for signal intensity for various regions of the 13C-NMR spectra would be necessary at contact times greater than 1.1 ms or less than 0.9 ms. T(CP) and T(1p) values have a limited non-homogeneity within Skjervatjern fulvic and humic acids. A pulse delay or repeat time of 700 ms is more than adequate for quantification of these 13C-NMR spectra. Paramagnetic effects in these humic substances are precluded due to low inorganic ash contents, low contents of Fe, Mn, and Co, and low organic free-radical contents. The observed T(CP) values suggest that all the carbon types in Skjervatjern fulvic and humic acids are fully cross-polarized before significant proton relaxation occurs. The 13C-NMR spectra for Skjervatjern fulvic acid is similar to most aquatic fulvic acids as it is predominantly aliphatic, low in aromaticity (fa1 = 24), low in phenolic content, high in carboxyl content, and has no resolution of a methoxyl peak. The 13C-NMR spectra for Skjervatjern humic acid is also similar to most other aquatic humic acids in that it is also predominantly aliphatic, high in aromaticity (fa1 = 38), moderate in phenolic content, moderate in carboxyl content, and has a clear resolution of a methoxyl carbon region. After the consideration of the necessary 13C-NMR experimental conditions, these spectra are considered to be quantitative. With careful consideration of the previously determined 13C-NMR experimental conditions, quantitative spectra can be obtained for humic substances in the future from the HUMEX site. Possible changes in humic substances due to acidification should be determined from 13C-NMR data.

  15. Bilayer metasurface for directional launching of cross-polarization component

    NASA Astrophysics Data System (ADS)

    Kim, Joonsoo; Lee, Yohan; Yun, Hansik; Park, Hyeonsoo; Lee, Byoungho

    2016-10-01

    In this paper, we propose a bilayer metasurface which is capable of launching helicity-inverted wave only in the forward direction. In order to obtain directional scattering characteristics of individual cells, we employed two layers of thin metasurfaces that are separated by a dielectric spacer. Multiple scattering analysis is used to derive design conditions for single metasurface reflectances for each polarization and it was shown that such target reflectances are realizable with split-ring aperture. The unit cell structure optimized for forward-only scattering of cross-polarization component is shown to have power extinction ratio as high as 32. The proposed structure can potentially form a supercell with reflective cells so that geometric phases of transmitted light and reflected light can be independently controlled. The proposed scheme is expected to pave a way to new types of metasurfaces with multiplexed optical functions.

  16. Hadronic Production of Ψ(2S) Cross section and Polarization

    SciTech Connect

    Chung, Kwangzoo

    2008-05-01

    The hadronic production cross section and the polarization of Ψ(2S) meson are measured by using the data from p$\\bar{p}$ collisions at √s = 1.96 TeV collected by the Collider Detector at Fermilab. The datasets used correspond to integrated luminosity of 1.1 fb-1 and 800 pb-1, respectively. The decay Ψ(2S) → μ+μ- is used to reconstruct Ψ(2S) mesons in the rapidity range |y(Ψ(2S))| < 0.6. The coverage of the pT range is 2.0 GeV/c ≤ pT (Ψ(2S)) < 30 GeV/c for the cross section analysis and pT ≥ 5 GeV/c for the polarization analysis. For events with pT (Ψ(2S)) > 2 GeV/c the integrated inclusive cross section multiplied by the branching ratio for dimuon decay is 3.17 ± 0.04 ± 0.28 nb . This result agrees with the CDF Run I measurement considering the increased center-of-mass energy from 1.8 TeV to 1.96 TeV. The polarization of the promptly produced Ψ(2S) mesons is found to be increasingly longitudinal as pT increases from 5 GeV/c to 30 GeV/c. The result is compared to contemporary theory models.

  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. 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.

  19. Cross-Polar Aircraft Trajectory Optimization and Potential Climate Impact

    NASA Technical Reports Server (NTRS)

    Sridhar, Banavar; Chen, Neil; Ng, Hok

    2011-01-01

    Cross-Polar routes offer new opportunities for air travel markets. Transpolar flights reduce travel times, fuel burns, and associated environmental emissions by flying direct paths between many North American and Asian cities. This study evaluates the potential benefits of flying wind-optimal polar routes and assessed their potential impact on climate change. An optimization algorithm is developed for transpolar flights to generate wind-optimal trajectories that minimize climate impact of aircraft, in terms of global warming potentials (relative to warming by one kg of CO2) of several types of emissions, while avoiding regions of airspace that facilitate persistent contrail formation. Estimations of global warming potential are incorporated into the objective function of the optimization algorithm to assess the climate impact of aircraft emissions discharged at a given location and altitude. The regions of airspace with very low ambient temperature and areas favorable to persistent contrail formation are modeled as undesirable regions that aircraft should avoid and are formulated as soft state constraints. The fuel burn and climate impact of cross-polar air traffic flying various types of trajectory including flightplan, great circle, wind-optimal, and contrail-avoidance are computed for 15 origin-destination pairs between major international airports in the U.S. and Asia. Wind-optimal routes reduce average fuel burn of flight plan routes by 4.4% on December 4, 2010 and 8.0% on August 7, 2010, respectively. The tradeoff between persistent contrail formation and additional global warming potential of aircraft emissions is investigated with and without altitude optimization. Without altitude optimization, the reduction in contrail travel times is gradual with increase in total fuel consumption. When altitude is optimized, a one percent increase in additional global warming potential, a climate impact equivalent to that of 4070kg and 4220kg CO2 emission, reduces 135

  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 (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.

  2. Cross-polarization in quasi-optical receivers: ALMA band 4 and 10

    NASA Astrophysics Data System (ADS)

    Gonzalez, A.; Uzawa, Y.

    2012-09-01

    A careful study about the influence of individual optical components on receiver cross-polarization has been performed. The basic mechanisms of generation of cross-polarization in ellipsoidal mirrors and dielectrics have been reviewed and characterized in terms of higher-order Gaussian beam modes. A simple model considering the phase differences of different Gaussian beam modes is proposed in order to calculate the final system cross-polarization pattern. This model has been successfully used to characterize the total cross-polarization in two cryogenically-cooled receivers for astronomy: ALMA band 4 and band 10.

  3. Cross polarization magic-angle spinning NMR at cryogenic temperatures

    NASA Astrophysics Data System (ADS)

    Macho, V.; Kendrick, R.; Yannoni, C. S.

    A magic angle spinning (MAS) apparatus which can be used for high resolution solid state NMR at temperatures as low as 15 K is described. To demonstrate the utility of this apparatus, 13C spectra of molecules containing methyl groups have been investigated at cryogenic temperatures. The spectra, which are described in detail, provide direct evidence for the slowdown of methyl rotation.

  4. 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.

  5. 1H to 13C Energy Transfer in Solid State NMR Spectroscopy of Natural Organic Systems

    NASA Astrophysics Data System (ADS)

    Berns, Anne E.; Conte, Pellegrino

    2010-05-01

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

  6. Carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance investigation of the interactions between maleic anhydride grafted polypropylene and wood polymers.

    PubMed

    Rude, Erica; Laborie, Marie-Pierre G

    2008-05-01

    The chemical interactions between maleic anhydride grafted polypropylene (MAPP) and wood were studied with solid-state carbon-13 cross-polarization magic-angle-spinning nuclear magnetic resonance ((13)C CPMAS NMR) spectroscopy. MAPP was synthesized with 100% (13)C enrichment at the C(1) and C(4) carbons to allow detection of the [1,4-(13)C(2)]MAPP functional groups and was melt blended with cellulose, lignin, and maple wood. In the cellulose/MAPP blend, changes in (13)C CPMAS NMR corrected signal intensities for the anhydride and dicarboxylic maleic acid functionalities suggested that esterification may have occurred predominantly from the more numerous diacid carbons. A single proton longitudinal relaxation in the rotating frame, (H)T(1rho), for the MAPP and the cellulose carbons in the blend suggested that they were spin coupled, i.e., homogeneous on a 10-200 Angstrom scale. Esterification was also suggested in the lignin/MAPP blend. Furthermore, the more significant changes in the intensities of the carbonyl signals and (H)T(1rho) values suggested that lignin may be more reactive to MAPP than cellulose. Finally, when maple was melt blended with MAPP, the same trends in the (13)C CP-MAS NMR spectra and (H)T(1rho) behavior were observed as when MAPP was blended with cellulose or lignin. This study therefore clarifies that during melt compounding of wood with MAPP, esterification occurs with wood polymers, preferentially with lignin. Understanding the interactions of MAPP with wood is of significance for the development of natural-fiber-reinforced thermoplastic composites.

  7. 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.

  8. Cross polarization optical coherence tomography for diagnosis of oral soft tissues

    NASA Astrophysics Data System (ADS)

    Gladkova, Natalia; Karabut, Maria; Kiseleva, Elena; Robakidze, Natalia; Muraev, Alexander; Fomina, Julia

    2011-03-01

    We consider the capabilities of cross-polarization OCT (CP OCT) focused on comparison of images resulting from cross-polarization and co-polarization scattering simultaneously for diagnosis of oral soft tissues. CP OCT was done for 35 patients with dental implants and 30 patients with inflammatory intestine diseases. Our study showed good diagnostic capabilities of CP OCT for detecting soft tissue pathology in the oral cavity. The cross-polarized images demonstrate the ability of tissue to depolarize. CP OCT demonstrates clinical capabilities for early diagnosis of inflammatory intestine diseases by the state of oral cavity mucosa and for early detection of gingivitis in patients above implant.

  9. 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.

  10. 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.

  11. 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.

  12. Bonding in hard and elastic amorphous carbon nitride films investigated using 15N, 13C, and 1H NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Gammon, W. J.; Hoatson, G. L.; Holloway, B. C.; Vold, R. L.; Reilly, A. C.

    2003-11-01

    The nitrogen bonding in hard and elastic amorphous carbon nitride (a-CNx) films is examined with 15N, 13C, and 1H nuclear magnetic resonance (NMR) spectroscopy. Films were deposited by dc magnetron sputtering, in a pure nitrogen discharge on Si(001) substrates at 300 °C. Nanoindentation tests revealed an elastic recovery of 80%, a hardness of 5 GPa, and an elastic modulus of 47 GPa. The NMR results show that nitrogen bonding in this material is consistent with sp2 hybridized nitrogen incorporated in an aromatic carbon environment. The data also indicate that the a-CNx prepared for this study has very low hydrogen content and is hydrophilic. Specifically, analysis of 15N and 13C cross polarization magic angle spinning and 1H NMR experiments suggests that water preferentially protonates nitrogen sites.

  13. 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.

  14. Circular polarization with crossed-planar undulators in high gain FELs.

    SciTech Connect

    Kim, K.-J.

    1999-08-31

    We propose a crossed undulator configuration for a high-gain free-electron laser to allow versatile polarization control. This configuration consists of a long (saturation length) planar undulator, a dispersive section, and a short (a few gain lengths) planar undulator oriented perpendicular to the first one. In the first undulator, a radiation component linearly polarized in the x-direction is amplified to saturation. In the second undulator, the x-polarized component propagates freely, while a new component, polarized in the y-direction, is generated and reaches saturation in a few gain lengths. By adjusting the strength of the dispersive section, the relative phase of two radiation components can be adjusted to obtain a suitable polarization for the total radiation field, including the circular polarization. The operating principle of the high-gain crossed undulator, which is quite different from that of the crossed undulator for spontaneous radiation, is illustrated in terms of 1-D FEL theory.

  15. Advantages of cross-polarization endoscopic optical coherence tomography in diagnosis of bladder neoplasia

    NASA Astrophysics Data System (ADS)

    Gladkova, N. D.; Zagaynova, E. V.; Streltsova, O. S.; Kiseleva, E. B.; Karabut, M. M.; Snopova, L. B.; Yunusova, E. E.; Tararova, E.; Gelikonov, V. M.

    2010-02-01

    We consider the cross-polarization OCT (CP OCT) that is focused on comparison of images resulting from cross-polarization and co-polarization scattering simultaneously. This technique provides information about microstructural and biochemical alterations in depolarizing tissue components (collagen). We found that mature type I collagen gives a strong signal in orthogonal polarization. CP OCT images of benign inflammatory processes always feature signal in orthogonal polarization, with layers and borders persisting to be well defined. In the presence of precancerous alterations, signal in orthogonal polarization is available in the image but it is irregular, disappearing in some areas. A CP OCT image of bladder cancer in orthogonal polarization either shows no signal at all or a weak signal.

  16. 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.

  17. 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.

  18. The effect of sample hydration on 13C CPMAS NMR spectra of fulvic acids

    USGS Publications Warehouse

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

    1991-01-01

    Three fulvic acids, two of which have been well studied by a number of other groups (Armadale and Suwannee river fulvic acids) have been examined by high resolution solid-state 13C-NMR techniques to delineate the effect of absorbed water. Two main effects of absorbed water were observed: (1) changes in spin lattice relaxation times in the rotating frame and cross polarization times and (2) total loss of signal so that some fulvic acid is effectively in solution. These results suggest that discrepancies in the literature concerning observed relative signal intensities from different structural groups are due to absorbed water and emphasize the necessity for proper precautionary drying before spectroscopic analysis. ?? 1991.

  19. 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.

  20. Polarization Analysis for Seeded FELs in a Crossed-Planar Undulator

    SciTech Connect

    Geng, Huiping; Ding, Yuantao; Huang, Zhirong; Bartolini, Riccardo; Dunning, David; Thompson, Neil; /Daresbury

    2012-06-25

    The crossed-planar undulator is a promising scheme for full polarization control in x-ray FELs. For SASE FELs, it has been shown a maximum degree of circular polarization of about 80% is achievable at fundamental wavelength just before saturation. In this paper, we study the effectiveness of a crossed undulator for a seeded x-ray FEL. The degree of circular polarization for both the fundamental and the harmonic radiation are considered. Simulations with realistic beam distributions show that a degree of circular polarization of over 90% and 80% is obtainable at the fundamental and 2nd harmonic frequencies, respectively.

  1. 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.

  2. 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

  3. Ice Shelf Modeling: A Cross-Polar Bayesian Statistical Approach

    NASA Astrophysics Data System (ADS)

    Kirchner, N.; Furrer, R.; Jakobsson, M.; Zwally, H. J.

    2010-12-01

    Ice streams interlink glacial terrestrial and marine environments: embedded in a grounded inland ice such as the Antarctic Ice Sheet or the paleo ice sheets covering extensive parts of the Eurasian and Amerasian Arctic respectively, ice streams are major drainage agents facilitating the discharge of substantial portions of continental ice into the ocean. At their seaward side, ice streams can either extend onto the ocean as floating ice tongues (such as the Drygalsky Ice Tongue/East Antarctica), or feed large ice shelves (as is the case for e.g. the Siple Coast and the Ross Ice Shelf/West Antarctica). The flow behavior of ice streams has been recognized to be intimately linked with configurational changes in their attached ice shelves; in particular, ice shelf disintegration is associated with rapid ice stream retreat and increased mass discharge from the continental ice mass, contributing eventually to sea level rise. Investigations of ice stream retreat mechanism are however incomplete if based on terrestrial records only: rather, the dynamics of ice shelves (and, eventually, the impact of the ocean on the latter) must be accounted for. However, since floating ice shelves leave hardly any traces behind when melting, uncertainty regarding the spatio-temporal distribution and evolution of ice shelves in times prior to instrumented and recorded observation is high, calling thus for a statistical modeling approach. Complementing ongoing large-scale numerical modeling efforts (Pollard & DeConto, 2009), we model the configuration of ice shelves by using a Bayesian Hiearchial Modeling (BHM) approach. We adopt a cross-polar perspective accounting for the fact that currently, ice shelves exist mainly along the coastline of Antarctica (and are virtually non-existing in the Arctic), while Arctic Ocean ice shelves repeatedly impacted the Arctic ocean basin during former glacial periods. Modeled Arctic ocean ice shelf configurations are compared with geological spatial

  4. Cross-polarization beam coupling in photorefractive GaAs crystals

    NASA Technical Reports Server (NTRS)

    Cheng, Li-Jen; Yeh, Pochi

    1988-01-01

    Theoretical and experimental investigations on the cross-polarization coupling of two contradirectional laser beams in a photorefractive GaAs crystal are reported. There is good agreement between these results.

  5. DESIGN AND PERFORMANCE OF A LOW-FREQUENCY CROSS-POLARIZED LOG-PERIODIC DIPOLE ANTENNA

    SciTech Connect

    Raja, K. Sasikumar; Kathiravan, C.; Ramesh, R.; Rajalingam, M.; Barve, Indrajit V.

    2013-07-01

    We report the design and performance of a cross-polarized log-periodic dipole (CLPD) antenna for observations of polarized radio emission from the solar corona at low frequencies. The measured isolation between the two mutually orthogonal log-periodic dipole antennas was as low as Almost-Equal-To - 43 dBm in the 65-95 MHz range. We carried out observations of the solar corona at 80 MHz with the above CLPD and successfully recorded circularly polarized emission.

  6. 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

  7. On the cross-polarization characteristics of crooked wire antennas designed by genetic-algorithms

    NASA Technical Reports Server (NTRS)

    Rengarajan, S. R.; Rahmat-Samii, Y.

    2002-01-01

    In many modern communication applications there is a need for simple circularly polarized antennas for hemispherical coverage with good axial ratio or low value of cross polarization. We revisited the crooked wire antenna because of its simplicity. This paper presents results of our investigation on the crooked wire antennas and other elements.

  8. 13C CP/MAS NMR studies of vitamin E model compounds.

    PubMed

    Witkowski, Stanislaw; Paradowska, Katarzyna; Wawer, Iwona

    2004-10-01

    13C cross-polarization magic angle spinning (CP/MAS) NMR data for 2,2,5,7,8-pentamethylchroman-6-ol (2), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (Trolox c) (3) and its acetate (4), 2-methoxy-2,2,5,7,8-pentamethylchroman-6-ol (5), 2-hydroxy-2,2,5,7,8-pentamethylchroman-6-ol (6) and 2,2,5,7,8-pentamethylchroman (7) are reported. A deshielding of 7.7 ppm for the carboxylic carbon was observed in solid Trolox due to formation of intermolecular hydrogen bonds within cyclic dimers. Such crystal packing permits effective cross-polarization and fast relaxation (short T1rho(H)). The impact of the proton concentration on the CP dynamics is reflected by the longer T(CP) and T1rhoH for Trolox-d2 (deuterated at mobile proton sites). The calculated GIAO RHF shielding constants are sensitive to intramolecular effects: rotation around the C-6-O bond (changes of sigma up to 8 ppm) and conformation at C-2.

  9. Passive millimeter-wave cross polarization imaging and phenomenology

    NASA Astrophysics Data System (ADS)

    Stein, E. Lee, Jr.; Schuetz, Christopher A.; Martin, Richard D.; Samluk, Jesse P.; Wilson, John P.; Mackrides, Daniel G.; Murakowski, Janusz A.; Murakowski, Maciej; Prather, Dennis W.

    2009-05-01

    Passive millimeter-wave (mmW) imaging has many specific defense, security and safety applications, due to the fact that all terrestrial bodies above absolute zero are emissive, and these wavelengths are not scattered by normal obscurants such as haze, fog, smoke, dust, sandstorms, clouds, or fabrics. We have previously demonstrated results from the construction of a 94 GHz passive mmW far-field imaging system utilizing optical upconversion, which imaged in only horizontal polarization. The effective radiometric temperature of an object is a combination of the object's surface and scattered radiometric temperatures. The surface radiometric temperature is a function of the object's emissivity, which is polarization dependent. Imaging with radiometric temperature data from both polarizations will allow a greater identification of the scene being imaged, and allow the recognition of subtle features which were not previously observable. This additional functionality is accomplished through the installation of added equipment and programming on our system, thus allowing the simultaneous data collection of imagery in both polarizations. Herein, we present our experimental procedures, results and passive mmW images obtained by using our far-field imaging system, a brief discussion of the phenomenology observed through the application of these techniques, as well as the preliminary details regarding our work on a 3-D passive mmW simulator capable of true physical polarization dependent effective emissivity and reflectivity rendering, based on the open-source Blender engine.

  10. 13C-NOESY-HSQC with Split Carbon Evolution for Increased Resolution with Uniformly Labeled Proteins

    NASA Astrophysics Data System (ADS)

    Baur, Matthias; Gemmecker, Gerd; Kessler, Horst

    1998-06-01

    Two new pulse sequences are presented for the recording of 2D13C-HSQC and 3D13C-NOESY-HSQC experiments, containing two consecutive carbon evolution periods. The two periods are separated by az-filter which creates a clean CxHz-quantum state for evolution in the second period. Each period is incremented (in anon-constant-time fashion) only to the extent that the defocusing of carbon inphase magnetization throughJ-coupling with neighboring carbons remains insignificant. Therefore,13C homonuclearJ-couplings are rendered ineffective, reducing the loss of signal and peak splitting commonly associated with long13C evolution times. The two periods are incremented according to a special acquisition protocol employing a13C-13C gradient echo to yield a data set analogous to one obtained by evolution over the added duration of both periods. The spectra recorded with the new technique on uniformly13C-labeled proteins at twice the evolution time of the standard13C-HSQC experiment display a nearly twofold enhancement of resolution in the carbon domain, while maintaining a good sensitivity even in the case of large proteins. Applied to the IIAManprotein ofE. coli(31 kDa), the13C-HSQC experiment recorded with a carbon evolution time of 2 × 8 ms showed a 36% decrease in linewidths compared to the standard13C-HSQC experiment, and theS/Nratio of representative cross-peaks was reduced to 40%. This reduction reflects mostly the typical loss of intensity observed when recording with an increased resolution. The13C-NOESY-HSQC experiment derived from the13C-HSQC experiment yielded additional NOE restraints between resonances which previously had been unresolved.

  11. Like and cross polarized reflections and transmission matrices for propagation across a chiral slab

    NASA Astrophysics Data System (ADS)

    Bahar, Ezekiel

    2006-10-01

    Explicit expressions are derived for the like and cross linear polarized reflection and transmission coefficients in terms of the chiral parameter. Taylor series expansions of these coefficients are derived. The diagonal like polarized reflection and transmission coefficients are insensitive to the chiral properties of the material while the off diagonal cross polarized terms are proportional to the chiral parameter to first order. Continuity relations in and perpendicular to the plane of incidence for vertically and horizontally like and cross polarized waves, energy conservation and duality relations at a free space-chiral interface are satisfied. Applications for the optimal detection and identification of chiral materials such as drugs and biological or chemical threat agents are considered.

  12. Measurements of the total cross section for the scattering of polarized neutrons from polarized {sup 3}He

    SciTech Connect

    Keith, C.D.; Gould, C.R.; Haase, D.G.; Seely, M.L.; Huffman, P.R.; Roberson, N.R.; Tornow, W.; Wilburn, W.S.

    1996-08-01

    Measurements of polarized-neutron{endash}polarized-{sup 3}He scattering are reported. The target consisted of cryogenically polarized solid {sup 3}He, with thickness 0.04 atom/b and polarization {approximately}0.4. Polarized neutrons were produced via the {sup 3}H({ital p}{searrow},{ital n}{searrow}){sup 3}He or {sup 2}H({ital d}{searrow},{ital n}{searrow}){sup 3}He polarization-transfer reactions. The longitudinal and transverse total cross-section differences {Delta}{sigma}{sub {ital L}} and {Delta}{sigma}{sub {ital T}} were measured for incident neutron energies 2{endash}8 MeV. The results are compared to phase-shift predictions based on four different analyses of {ital n}-{sup 3}He scattering. The best agreement is obtained with a recent {ital R}-matrix analysis of {ital A}=4 scattering and reaction data, lending strong support to the {sup 4}He level scheme obtained in that analysis. Discrepancies with other phase-shift parametrizations of {ital n}-{sup 3}He scattering exist, attributable in most instances to one or two particular partial waves. {copyright} {ital 1996 The American Physical Society.}

  13. 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.

  14. Production and NMR signal optimization of hyperpolarized 13C-labeled amino acids

    NASA Astrophysics Data System (ADS)

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

    Amino acids are targeted nutrients for consumption by cancers to sustain their rapid growth and proliferation. 13C-enriched amino acids are important metabolic tracers for cancer diagnostics using nuclear magnetic resonance (NMR) spectroscopy. Despite this diagnostic potential, 13C NMR of amino acids however is hampered by the inherently low NMR sensitivity of the 13C nuclei. In this work, we have employed a physics technique known as dynamic nuclear polarization (DNP) to enhance the NMR signals of 13C-enriched amino acids. DNP works by transferring the high polarization of electrons to the nuclear spins via microwave irradiation at low temperature and high magnetic field. Using a fast dissolution method in which the frozen polarized samples are dissolved rapidly with superheated water, injectable solutions of 13C-amino acids with highly enhanced NMR signals (by at least 5,000-fold) were produced at room temperature. Factors that affect the NMR signal enhancement levels such as the choice of free radical polarizing agents and sample preparation will be discussed along with the thermal mixing physics model of DNP. The authors would like to acknowledge the support by US Dept of Defense Award No. W81XWH-14-1-0048 and Robert A. Welch Foundation Grant No. AT-1877.

  15. Oceanic excitations on polar motion: a cross comparison among models

    NASA Astrophysics Data System (ADS)

    Zhou, Y. H.; Chen, J. L.; Liao, X. H.; Wilson, C. R.

    2005-08-01

    Recent studies based on various ocean general circulation models (OGCMs) demonstrate that the oceans are a major contributor to polar motion excitations. In this paper, we analyse and compare observed non-atmospheric polar motion excitations with oceanic angular momentum (OAM) variations determined from four OGCMs, which include the parallel ocean climate model (POCM), a barotropic ocean model (BOM), the Estimating the Circulation and Climate of the Ocean (ECCO) non-data-assimilating model (ECCO-NDA) and the ECCO data-assimilating model (ECCO-DA). The data to be analysed span a 5-yr overlapped period from 1993 to 1997. At annual timescale, considerable discrepancies exist between POCM and the other three models, which result mainly from differences in annual components of the forcing wind fields. At semi-annual timescale, however, POCM shows better phase agreement with observed non-atmospheric polar motion excitation than the other three ocean models. At intraseasonal timescales, ECCO-DA yields better agreement with observations, and reduces the variance of non-atmospheric excitations by ~60 per cent, 10-20 per cent more than those explained by the other three models. However, at the very short periods of 4-20 days, the BOM estimates could explain about half of the observed variance, twice as much as that by ECCO-NDA, and also shows considerably better correlation with observations. Due to different modelling schemes and methods, significant discrepancies could arise with respect to the quality of modelling large-scale oceanic mass redistribution and current variation. A complete understanding of global oceanic contributions to polar motion excitation still remains a challenge.

  16. Oceanic Excitations On Polar Motion: A Cross Comparison Among Models

    NASA Astrophysics Data System (ADS)

    Zhou, Y.; Chen, J.; Liao, X.; Wilson, C. R.

    2004-12-01

    Recent studies based on various oceanic general circulation models (OGCMs) demonstrated that the oceans are a major contributor to polar motion excitations. In this paper, we analyze and compare observed non-atmospheric polar motion excitations with oceanic angular momentum (OAM) variations determined from four OGCMs, which include the parallel ocean climate model (POCM), a barotropic ocean model (BOM), the Estimating the Circulation and Climate of the Ocean (ECCO) non-data-assimilating model (ECCO-NDA), and the ECCO data-assimilating model (ECCO-DA). The data to be analyzed span a 5-year¡_s overlapped period from 1993 to 1997. At annual time scale, these four OAM estimates do not agree well with each other, while POCM shows relatively larger discrepancies than other three models. At intraseasonal time scales, ECCO-DA yields the best agreement with observations, and reduces the variance of non-atmospheric excitations by about 60%, 10-20% more than those explained by other three models. However, at the very short periods of 4-20 days, the BOM estimates could explain about half of the observed variance, twice as much as that by ECCO-NDA, and also shows considerably better correlation with observations. Due to different modeling schemes and methods, significant discrepancies could arise with respect to the quantity of modeling large-scale oceanic mass redistribution and current variation. A clear understanding of global oceanic contributions to polar motion excitation still remains a challenge.

  17. Simultaneous steady-state and dynamic 13C NMR can differentiate alternative routes of pyruvate metabolism in living cancer cells.

    PubMed

    Yang, Chendong; Harrison, Crystal; Jin, Eunsook S; Chuang, David T; Sherry, A Dean; Malloy, Craig R; Merritt, Matthew E; DeBerardinis, Ralph J

    2014-02-28

    Metabolic reprogramming facilitates cancer cell growth, so quantitative metabolic flux measurements could produce useful biomarkers. However, current methods to analyze flux in vivo provide either a steady-state overview of relative activities (infusion of (13)C and analysis of extracted metabolites) or a dynamic view of a few reactions (hyperpolarized (13)C spectroscopy). Moreover, although hyperpolarization has successfully quantified pyruvate-lactate exchanges, its ability to assess mitochondrial pyruvate metabolism is unproven in cancer. Here, we combined (13)C hyperpolarization and isotopomer analysis to quantify multiple fates of pyruvate simultaneously. Two cancer cell lines with divergent pyruvate metabolism were incubated with thermally polarized [3-(13)C]pyruvate for several hours, then briefly exposed to hyperpolarized [1-(13)C]pyruvate during acquisition of NMR spectra using selective excitation to maximize detection of H[(13)C]O3(-) and [1-(13)C]lactate. Metabolites were then extracted and subjected to isotopomer analysis to determine relative rates of pathways involving [3-(13)C]pyruvate. Quantitation of hyperpolarized H[(13)C]O3(-) provided a single definitive metabolic rate, which was then used to convert relative rates derived from isotopomer analysis into quantitative fluxes. This revealed that H[(13)C]O3(-) appearance reflects activity of pyruvate dehydrogenase rather than pyruvate carboxylation followed by subsequent decarboxylation reactions. Glucose substantially altered [1-(13)C]pyruvate metabolism, enhancing exchanges with [1-(13)C]lactate and suppressing H[(13)C]O3(-) formation. Furthermore, inhibiting Akt, an oncogenic kinase that stimulates glycolysis, reversed these effects, indicating that metabolism of pyruvate by both LDH and pyruvate dehydrogenase is subject to the acute effects of oncogenic signaling on glycolysis. The data suggest that combining (13)C isotopomer analyses and dynamic hyperpolarized (13)C spectroscopy may enable

  18. PASADENA hyperpolarization of 13C biomolecules: equipment design and installation

    PubMed Central

    Hövener, Jan-Bernd; Chekmenev, Eduard Y.; Harris, Kent C.; Perman, William H.; Robertson, Larry W.; Bhattacharya, Pratip

    2009-01-01

    Object The PASADENA method has achieved hyperpolarization of 16–20% (exceeding 40,000-fold signal enhancement at 4.7 T), in liquid samples of biological molecules relevant to in vivo MRI and MRS. However, there exists no commercial apparatus to perform this experiment conveniently and reproducibly on the routine basis necessary for translation of PASADENA to questions of biomedical importance. The present paper describes equipment designed for rapid production of six to eight liquid samples per hour with high reproducibility of hyperpolarization. Materials and methods Drawing on an earlier, but unpublished, prototype, we provide diagrams of a delivery circuit, a laminar-flow reaction chamber within a low field NMR contained in a compact, movable housing. Assembly instructions are provided from which a computer driven, semiautomated PASADENA polarizer can be constructed. Results Together with an available parahydrogen generator, the polarizer, which can be operated by a single investigator, completes one cycle of hyperpolarization each 52 s. Evidence of efficacy is presented. In contrast to competing, commercially available devices for dynamic nuclear polarization which characteristically require 90 min per cycle, PASADENA provides a low-cost alternative for high throughput. Conclusions This equipment is suited to investigators who have an established small animal NMR and wish to explore the potential of heteronuclear (13C and 15N) MRI, MRS, which harnesses the enormous sensitivity gain offered by hyperpolarization. PMID:19067008

  19. 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.

  20. Calculation of total meal d13C from individual food d13C.

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Variations in the isotopic signature of carbon in biological samples can be used to distinguish dietary patterns and monitor shifts in metabolism. But for these variations to have meaning, the isotopic signature of the diet must be known. We sought to determine if knowledge of the 13C isotopic abund...

  1. Synthesis of 2H- and 13C-substituted dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2003-01-01

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithiane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  2. Synthesis Of 2h- And 13c-Substituted Dithanes

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.

    2004-05-04

    The present invention is directed to labeled compounds, [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to processes of preparing [2-.sup.13 C]dithane wherein the .sup.13 C atom is directly bonded to one or two deuterium atoms. The present invention is also directed to labeled compounds, e.g., [.sup.2 H.sub.1-2, .sup.13 C]methanol (arylthio)-, acetates wherein the .sup.13 C atom is directly bonded to exactly one or two deuterium atoms.

  3. CTS attenuation and cross polarization measurements at 11.7 GHz

    NASA Technical Reports Server (NTRS)

    Vogel, W. J.

    1979-01-01

    Attenuation and cross-polarization isolation at 11.7 GHz, measured at Austin, Texas by receiving the circularly polarized emissions from the CTS satellite are presented. A 12 month summary for Feb 78 to Jan 79 is presented. For .016 percent of the time the attenuation was greater than 10 dB, the isolation was less than 21 dB and the rainrate exceeded 55 mm/hr. Ice depolarization was observed frequently.

  4. Ray Scattering by an Arbitrarily Oriented Spheroid: 2. Transmission and Cross-polarization Effects

    NASA Technical Reports Server (NTRS)

    Lock, James A.

    1996-01-01

    Transmission of an arbitrarily polarized plane wave by an arbitrarily oriented spheroid in the short-wavelength limit is considered in the context of ray theory. The transmitted electric field is added to the diffracted plus reflected ray-theory electric field that was previously derived to obtain an approximation to the far-zone scattered intensity in the forward hemisphere. Two different types of cross-polarization effects are found. These are: (a) a rotation of the polarization state of the transmitted rays from when they are referenced with respect to their entrance into the spheroid to when they are referenced with respect to their exit from it and (b) a rotation of the polarization state of the transmitted rays when they are referenced with respect to the polarization state of the diffracted plus reflected rays.

  5. Statistical Analysis of Crossed Undulator for Polarization Control in a SASE FEL

    SciTech Connect

    Ding, Yuantao; Huang, Zhirong; /SLAC

    2008-02-01

    There is a growing interest in producing intense, coherent x-ray radiation with an adjustable and arbitrary polarization state. In this paper, we study the crossed undulator scheme (K.-J. Kim, Nucl. Instrum. Methods A 445, 329 (2000)) for rapid polarization control in a self-amplified spontaneous emission (SASE) free electron laser (FEL). Because a SASE source is a temporally chaotic light, we perform a statistical analysis on the state of polarization using FEL theory and simulations. We show that by adding a small phase shifter and a short (about 1.3 times the FEL power gain length), 90{sup o} rotated planar undulator after the main SASE planar undulator, one can obtain circularly polarized light--with over 80% polarization--near the FEL saturation.

  6. A Low Cross-Polarization Smooth-Walled Horn with Improved Bandwidth

    NASA Technical Reports Server (NTRS)

    Zeng, Lingzhen; Bennett, Charles L.; Chuss, David T.; Wollack, Edward J.

    2009-01-01

    Corrugated feed horns offer excellent beam symmetry, main beam efficiency, and cross-polar response over wide bandwidths, but can be challenging to fabricate. An easier-to-manufacture smooth-walled feed is explored that approximates these properties over a finite bandwidth. The design, optimization and measurement of a monotonically-profiled, smooth-walled scalar feedhorn with a diffraction-limited approximately 7 degrees full width at half maximum (FWHM) is presented. The feed was demonstrated to have low cross polarization (<-30 dB) across the frequency range 33-45 GHz (30% fractional bandwidth). A return loss better than -28 dB was measured across the band.

  7. A Low Cross-Polarization Smooth-Walled Horn with Improved Bandwidth

    NASA Technical Reports Server (NTRS)

    Zeng, Lingzhen; Bennette, Charles L.; Chuss, David T.; Wollack, Edward J.

    2009-01-01

    Corrugated feed horns offer excellent beam symmetry, main beam efficiency, and cross-polar response over wide bandwidths, but can be challenging to fabricate. An easier-to-manufacture smooth-walled feed is explored that approximates these properties over a finite bandwidth. The design, optimization and measurement of a monotonically-profiled, smooth-walled scalar feedhorn with a diffraction-limited approx. 14deg FWHM beam is presented. The feed was demonstrated to have low cross polarization (<-30 dB) across the frequency range 33-45 GHz (30% fractional bandwidth). A power reflection below -28 dB was measured across the band.

  8. Multiple-quantum cross-polarization in MAS NMR of quadrupolar nuclei

    NASA Astrophysics Data System (ADS)

    Ashbrook, Sharon E.; Brown, Steven P.; Wimperis, Stephen

    1998-05-01

    Using 27Al ( I=5/2) NMR of aluminium acetylacetonate, we show that it is possible to cross-polarize from a spin I=1/2 nucleus ( 1H) directly to the central triple-quantum transition of a half-integer quadrupolar nucleus ( 27Al) in a powdered sample under MAS conditions. The optimum conditions for this multiple-quantum cross-polarization (MQCP) are investigated experimentally and compared with existing theoretical results. The new technique is applied to the recently introduced two-dimensional MQMAS experiment for recording high-resolution NMR spectra of half-integer quadrupolar nuclei.

  9. Quantitative 13C traces of glucose fate in hepatitis B virus infected hepatocytes.

    PubMed

    Wan, Qianfen; Wang, Yulan; Tang, Huiru

    2017-02-21

    Quantitative characterization of 13C-labeled metabolites is an important part of the stable isotope tracing method widely used in metabolic flux analysis. Due to long relaxation time and low sensitivity of 13C nuclei, direct measurement of 13C labeled metabolites using one dimensional 13C NMR often fails to meet the demand of metabolomics studies especially with large number of samples and metabolites having low abundance. Although HSQC-based 2D NMR methods have improved sensitivity with inversion detection, they are time-consuming thus unsuitable for high-throughput absolute quantification of 13C-labeled metabolites. In this study, we developed a method for absolute quantification of 13C labeled metabolites using naturally abundant TSP as a reference with the first increment of HMQC pulse sequence, taking polarization transfer efficiencies into consideration. We validated this method using a mixture of 13C-labeled alanine, methionine, glucose and formic acid together with a mixture of alanine, lactate, glycine, uridine, cytosine, and hypoxanthine having natural 13C abundance with known concentrations. We subsequently applied this method to analyze the flux of glucose in HepG2 cells infected with hepatitis B virus (HBV). The results showed that HBV infection increased the cellular uptake of glucose, stimulated glycolysis and enhanced the pentose phosphate and hexosamine pathways for biosynthesis of RNA and DNA and nucleotide sugars to facilitate HBV replication. This method saves experimental time and provides a possibility for absolute quantitative tracking of the 13C labeled metabolites for high throughput studies.

  10. 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

  11. Imaging simulated secondary caries lesions with cross polarization OCT

    NASA Astrophysics Data System (ADS)

    Stahl, Jonathan; Kang, Hobin; Fried, Daniel

    2010-02-01

    The clinical diagnosis of secondary caries has been found to account for the replacement of the majority of intra-coronal restorations. Current methods to diagnose the presence of these lesions at early stages are considered insufficient due to their low sensitivity. Polarization-sensitive optical coherence tomography (PS-OCT) imaging studies have confirmed its effectiveness for imaging carious subsurface lesions in enamel and dentin. The objective of this study was to determine if PS-OCT can be used to nondestructively image demineralization through resin restorations on extracted teeth with both simulated and natural lesions. Simulated secondary caries lesions were created by exposing cavity preparations made in extracted human teeth to a demineralizing solution for 48 hours and subsequently restoring with resin. Negative control restorations were also prepared on each tooth. Optical changes in demineralized versus control preparations beneath restorations were measured as a function of depth using PS-OCT. PS-OCT images indicated that a significant increase in reflectivity and depth occurred in the simulated lesions compared with the control preparations. This study suggests that PS-OCT is well-suited to nondestructively detect early caries lesions in enamel beneath composite restorations.

  12. 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.

  13. Real-time cardiac metabolism assessed with hyperpolarized [1-13C]acetate in a large-animal model

    PubMed Central

    Flori, Alessandra; Liserani, Matteo; Frijia, Francesca; Giovannetti, Giulio; Lionetti, Vincenzo; Casieri, Valentina; Positano, Vincenzo; Aquaro, Giovanni Donato; Recchia, Fabio A.; Santarelli, Maria Filomena; Landini, Luigi; Ardenkjaer-Larsen, Jan Henrik; Menichetti, Luca

    2014-01-01

    Dissolution-Dynamic Nuclear Polarization (dissolution-DNP) for Magnetic Resonance (MR) Spectroscopic Imaging has recently emerged as a novel technique for non invasive studies of the metabolic fate of biomolecules in vivo. Since acetate is the most abundant extra- and intra-cellular short-chain fatty acid, we focused on [1-13C]acetate as a promising candidate for a chemical probe to study myocardial metabolism of beating heart. Dissolution-DNP procedure of Na[1-13C]acetate for in vivo cardiac applications with 3T MR scanner was optimized in pigs during bolus injection of doses up to 3 mmoles. The Na[1-13C]acetate formulation was characterized by a liquid-state polarization of 14.2% and T1Eff in vivo of 17.6 ± 1.7 s. In vivo Na[1-13C]acetate kinetic displayed a bimodal shape: [1-13C]acetyl carnitine (AcC) was detected in a slice covering the cardiac volume, and the signal of 13C-acetate and 13C-AcC was modeled using the total Area Under the Curve (AUC) for kinetic analysis. A good correlation was found between the ratio AUC(AcC)/AUC(acetate) and the apparent kinetic constant of metabolic conversion kAcC/r1 from [1-13C]acetate to [1-13C]AcC. Our study proved the feasibility and limitations of administration of large doses of hyperpolarized [1-13C]acetate with dissolution DNP to study by MR spectroscopy the myocardial conversion of [1-13C]acetate in [1-13C]acetyl-carnitine generated by acetyltransferase in healthy pigs. PMID:25201079

  14. Ultrabroadband Design for Linear Polarization Conversion and Asymmetric Transmission Crossing X- and K- Band

    NASA Astrophysics Data System (ADS)

    Zhang, Linbo; Zhou, Peiheng; Chen, Haiyan; Lu, Haipeng; Xie, Haiyan; Zhang, Li; Li, En; Xie, Jianliang; Deng, Longjiang

    2016-09-01

    In this work, a high-efficiency and broadband reflective converter using ultrathin planar metamaterial (MM) composed of single-layered SRR is firstly realized. Numerical and experimental results demonstrate that the cross-polarization conversion reflectance above 0.84 is achieved from 8.6 to 18.6 GHz for linearly polarized (LP) incident waves under normal incidence. Subsequently, a multi-layered MM based on SRR enables a dramatic improvement of the recently demonstrated asymmetric transmission (AT) effect. Theoretical and measured results present that strong one-way transmission of two orthogonally polarized waves crossing C- and K- band has been observed. These two separated AT pass-bands have a function of selective polarization filter, which can be switched on/off by changing the polarization state of incident waves. The physical mechanisms are elucidated by taking advantage of electric fields and current distributions. Considering the broad bandwidth and the dual band, we believe that these two structures will be beneficial for designing polarization-controlled and selective transmission converter.

  15. Ultrabroadband Design for Linear Polarization Conversion and Asymmetric Transmission Crossing X- and K- Band

    PubMed Central

    Zhang, Linbo; Zhou, Peiheng; Chen, Haiyan; Lu, Haipeng; Xie, Haiyan; Zhang, Li; Li, En; Xie, Jianliang; Deng, Longjiang

    2016-01-01

    In this work, a high-efficiency and broadband reflective converter using ultrathin planar metamaterial (MM) composed of single-layered SRR is firstly realized. Numerical and experimental results demonstrate that the cross-polarization conversion reflectance above 0.84 is achieved from 8.6 to 18.6 GHz for linearly polarized (LP) incident waves under normal incidence. Subsequently, a multi-layered MM based on SRR enables a dramatic improvement of the recently demonstrated asymmetric transmission (AT) effect. Theoretical and measured results present that strong one-way transmission of two orthogonally polarized waves crossing C- and K- band has been observed. These two separated AT pass-bands have a function of selective polarization filter, which can be switched on/off by changing the polarization state of incident waves. The physical mechanisms are elucidated by taking advantage of electric fields and current distributions. Considering the broad bandwidth and the dual band, we believe that these two structures will be beneficial for designing polarization-controlled and selective transmission converter. PMID:27658929

  16. 31P to 77Se cross polarization in beta-P4Se3.

    PubMed

    Pietrass, T; Seydoux, R; Roth, R E; Eckert, H; Pines, A

    1997-08-01

    Cross polarization from 31P to 77Se is demonstrated in beta-P4Se3. This material, an inorganic glass, is readily synthesized from the elements and serves as a convenient sample for setting the Hartmann-Hahn condition.

  17. A wide-band smooth-walled feedhorn with low cross polarization for millimeter astronomy

    NASA Astrophysics Data System (ADS)

    Zeng, Lingzhen; Bennett, Charles L.; Chuss, David T.; Wollack, Edward J.

    2010-07-01

    We present a smooth-walled feedhorn with cross polarization and reflected power lower than -30 dB across the entire 30% bandwidth. A prototype feedhorn has been fabricated, and the wide-band, low-cross polarization performance has been demonstrated. The feedhorn has a circular aperture and monotonically narrows towards an input waveguide interface. This allows it to be manufactured by progressively milling the profile using a set of custom tools. This is especially useful in applications where a large number of feeds are desired in a planar array format. Such applications include astronomical cameras in millimeter waveband that require large arrays of detectors for future increases in mapping speed and sensitivity. Specifically, large arrays of feedhorns are well-matched to the problem of measuring the polarization of the cosmic microwave background to search for the faint signature of inflation, as they provide good beam control, the requisite sensitivity, and compatibility with low-noise bolometric detectors.

  18. 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.

  19. Evaluation of Waveform Structure Features on Time Domain Target Recognition under Cross Polarization

    NASA Astrophysics Data System (ADS)

    Selver, M. A.; Seçmen, M.; Zoral, E. Y.

    2016-08-01

    Classification of aircraft targets from scattered electromagnetic waves is a challenging application, which suffers from aspect angle dependency. In order to eliminate the adverse effects of aspect angle, various strategies were developed including the techniques that rely on extraction of several features and design of suitable classification systems to process them. Recently, a hierarchical method, which uses features that take advantage of waveform structure of the scattered signals, is introduced and shown to have effective results. However, this approach has been applied to the special cases that consider only a single planar component of electric field that cause no-cross polarization at the observation point. In this study, two small scale aircraft models, Boeing-747 and DC-10, are selected as the targets and various polarizations are used to analyse the cross-polarization effects on system performance of the aforementioned method. The results reveal the advantages and the shortcomings of using waveform structures in time-domain target identification.

  20. Generation of spin-polarized currents via cross-relaxation with dynamically pumped paramagnetic impurities

    SciTech Connect

    Meriles, Carlos A.; Doherty, Marcus W.

    2014-07-14

    Key to future spintronics and spin-based information processing technologies is the generation, manipulation, and detection of spin polarization in a solid state platform. Here, we theoretically explore an alternative route to spin injection via the use of dynamically polarized nitrogen-vacancy (NV) centers in diamond. We focus on the geometry where carriers and NV centers are confined to proximate, parallel layers and use a “trap-and-release” model to calculate the spin cross-relaxation probabilities between the charge carriers and neighboring NV centers. We identify near-unity regimes of carrier polarization depending on the NV spin state, applied magnetic field, and carrier g-factor. In particular, we find that unlike holes, electron spins are distinctively robust against spin-lattice relaxation by other, unpolarized paramagnetic centers. Further, the polarization process is only weakly dependent on the carrier hopping dynamics, which makes this approach potentially applicable over a broad range of temperatures.

  1. Three-Dimensional Modeling of Polarization Effects on Cross-Beam Energy Transfer in OMEGA Implosions

    NASA Astrophysics Data System (ADS)

    Edgell, D. H.; Follett, R. K.; Katz, J.; Myatt, J. F.; Shaw, J.; Froula, D. H.

    2016-10-01

    Beamlet spot images are used to diagnose cross-beam energy transfer (CBET) during OMEGA direct-drive implosions. The spots are, in essence, the end point of beamlets of light originating from different regions of each beam profile and following paths determined by refraction. The intensity of each spot varies because of absorption and CBET along that path. When each beam is linearly polarized, the image is asymmetric in terms of spot intensities. A 3-D CBET postprocessor for hydrodynamics codes is used to model the intensity, wavelength, and polarization of light from each beam. Rotation of polarization caused by CBET is tracked. The model is benchmarked using a 3-D wave-based solver for simplified CBET geometries. For linearly polarized beams in OMEGA implosions, the model predicts that polarization effects will result in asymmetric polarization and unabsorbed light profiles that are different for each beam. An asymmetric beamlet spot image similar to that recorded is predicted by the CBET model for linearly polarized beams. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  2. 13C magnetic resonance spectroscopy measurements with hyperpolarized [1‐13C] pyruvate can be used to detect the expression of transgenic pyruvate decarboxylase activity in vivo

    PubMed Central

    Dzien, Piotr; Tee, Sui‐Seng; Kettunen, Mikko I.; Lyons, Scott K.; Larkin, Timothy J.; Timm, Kerstin N.; Hu, De‐En; Wright, Alan; Rodrigues, Tiago B.; Serrao, Eva M.; Marco‐Rius, Irene; Mannion, Elizabeth; D'Santos, Paula; Kennedy, Brett W. C.

    2015-01-01

    Purpose Dissolution dynamic nuclear polarization can increase the sensitivity of the 13C magnetic resonance spectroscopy experiment by at least four orders of magnitude and offers a novel approach to the development of MRI gene reporters based on enzymes that metabolize 13C‐labeled tracers. We describe here a gene reporter based on the enzyme pyruvate decarboxylase (EC 4.1.1.1), which catalyzes the decarboxylation of pyruvate to produce acetaldehyde and carbon dioxide. Methods Pyruvate decarboxylase from Zymomonas mobilis (zmPDC) and a mutant that lacked enzyme activity were expressed using an inducible promoter in human embryonic kidney (HEK293T) cells. Enzyme activity was measured in the cells and in xenografts derived from the cells using 13C MRS measurements of the conversion of hyperpolarized [1‐13C] pyruvate to H13 CO3–. Results Induction of zmPDC expression in the cells and in the xenografts derived from them resulted in an approximately two‐fold increase in the H13 CO3–/[1‐13C] pyruvate signal ratio following intravenous injection of hyperpolarized [1‐13C] pyruvate. Conclusion We have demonstrated the feasibility of using zmPDC as an in vivo reporter gene for use with hyperpolarized 13C MRS. Magn Reson Med 76:391–401, 2016. © 2015 The Authors. Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:26388418

  3. 13C-engineered carbon quantum dots for in vivo magnetic resonance and fluorescence dual-response.

    PubMed

    Xu, Yang; Li, Yu-Hao; Wang, Yue; Cui, Jian-Lin; Yin, Xue-Bo; He, Xi-Wen; Zhang, Yu-Kui

    2014-10-21

    (13)C-engineered carbon quantum dots ((13)C-QDs) were used as magnetic resonance (MR) and fluorescence dual-response probe. The enhanced (13)C-MR signal was observed at 171 ppm from carboxylic and carboxyl carbons in (13)C-QDs with 160-fold improvement on signal-to-noise ratio even when no hyperpolarization was applied, whereas the intrinsic fluorescence of C-QDs was still maintained. The stable MR and fluorescence dual-response was successfully used for long-term observation of zebrafish embryonic development. Cross-validation between MR and fluorescence confirmed the distribution of (13)C-QD in zebrafish. (13)C-MR provides specific information about the presence, magnitude, and progression of (13)C-QDs by defining MR intensity, whereas fluorescence reveals the location of (13)C-QDs with its high sensitivity. (13)C-MR and fluorescence was simultaneously observed within (13)C-QDs, and this work may expand the applications of isotope-engineered nanomaterials.

  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. 13C MAS NMR studies of the effects of hydration on the cell walls of potatoes and Chinese water chestnuts.

    PubMed

    Tang, H; Belton, P S; Ng, A; Ryden, P

    1999-02-01

    13C NMR with magic angle spinning (MAS) has been employed to investigate the cell walls of potatoes and Chinese water chestnuts over a range of hydration levels. Both single-pulse excitation (SPEMAS) and cross-polarization (CPMAS) experiments were carried out. Hydration led to a substantial increase in signal intensities of galactan and galacturonan in the SPEMAS spectra and a decrease in line width, implying mobilization in the backbone and side chains of pectin. In CPMAS spectra of both samples, noncellulose components showed signal loss as hydration increased. However, the signals of some galacturonan in the 3(1) helix configuration remained in the spectra even when the water content was as high as 110%. Cellulose was unaffected. It is concluded that the pectic polysaccharides experience a distribution of molecular conformations and mobility, whereas cellulose remained as typical rigid solid.

  6. Ultra-wideband circular-polarization converter with micro-split Jerusalem-cross metasurfaces

    NASA Astrophysics Data System (ADS)

    Gao, Xi; Yu, Xing-Yang; Cao, Wei-Ping; Jiang, Yan-Nan; Yu, Xin-Hua

    2016-12-01

    An ultrathin micro-split Jerusalem-cross metasurface is proposed in this paper, which can efficiently convert the linear polarization of electromagnetic (EM) wave into the circular polarization in ultra-wideband. By symmetrically employing two micro-splits on the horizontal arm (in the x direction) of the Jerusalem-cross structure, the bandwidth of the proposed device is significantly extended. Both simulated and experimental results show that the proposed metasurface is able to convert linearly polarized waves into circularly polarized waves in a frequency range from 12.4 GHz to 21 GHz, with an axis ratio better than 1 dB. The simulated results also show that such a broadband and high-performance are maintained over a wide range of incident angle. The presented polarization converter can be used in a number of areas, such as spectroscopy and wireless communications. Project supported by the National Natural Science Foundation of China (Grant Nos. 61461016 and 61661012), the Natural Science Foundation of Guangxi Zhuang Autonomous Region, China (Grant Nos. 2014GXNSFAA118366, 2014GXNSFAA118283, and 2015jjBB7002), and the Innovation Project of Graduate Education of Guilin University of Electronic Technology, China (Grant No. 2016YJCX82).

  7. Hyperpolarized 13C Metabolic MRI of the Human Heart

    PubMed Central

    Lau, Justin Y.C.; Chen, Albert P.; Geraghty, Benjamin J.; Perks, William J.; Roifman, Idan; Wright, Graham A.; Connelly, Kim A.

    2016-01-01

    Rationale: Altered cardiac energetics is known to play an important role in the progression toward heart failure. A noninvasive method for imaging metabolic markers that could be used in longitudinal studies would be useful for understanding therapeutic approaches that target metabolism. Objective: To demonstrate the first hyperpolarized 13C metabolic magnetic resonance imaging of the human heart. Methods and Results: Four healthy subjects underwent conventional proton cardiac magnetic resonance imaging followed by 13C imaging and spectroscopic acquisition immediately after intravenous administration of a 0.1 mmol/kg dose of hyperpolarized [1-13C]pyruvate. All subjects tolerated the procedure well with no adverse effects reported ≤1 month post procedure. The [1-13C]pyruvate signal appeared within the chambers but not within the muscle. Imaging of the downstream metabolites showed 13C-bicarbonate signal mainly confined to the left ventricular myocardium, whereas the [1-13C]lactate signal appeared both within the chambers and in the myocardium. The mean 13C image signal:noise ratio was 115 for [1-13C]pyruvate, 56 for 13C-bicarbonate, and 53 for [1-13C]lactate. Conclusions: These results represent the first 13C images of the human heart. The appearance of 13C-bicarbonate signal after administration of hyperpolarized [1-13C]pyruvate was readily detected in this healthy cohort (n=4). This shows that assessment of pyruvate metabolism in vivo in humans is feasible using current technology. Clinical Trial Registration: URL: https://www.clinicaltrials.gov. Unique identifier: NCT02648009. PMID:27635086

  8. Synthesis Of [2h, 13c]M [2h2m 13c], And [2h3,, 13c] Methyl Aryl Sulfones And Sulfoxides

    DOEpatents

    Martinez, Rodolfo A.; Alvarez, Marc A.; Silks, III, Louis A.; Unkefer, Clifford J.; Schmidt, Jurgen G.

    2004-07-20

    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 sulfones and [.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 sulfoxides, wherein the .sup.13 C methyl group attached to the sulfur of the sulfone or sulfoxide 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 methyl aryl sulfones and methyl aryl sulfoxides.

  9. CTS attenuation and cross polarization measurements at 11.7 GHz

    NASA Technical Reports Server (NTRS)

    Vogel, W. J.

    1980-01-01

    The long-term attenuation, cross-polarization, and rain-rate data monitored in Austin, Texas from the circularly polarized 11.7 GHz satellite beacon transmitter aboard the Communications Technology Satellite are analyzed. Data events are significantly more likely during April-September, than during October-March, except for ice deplorization which predominates during the winter months. A time of day dependence of the events is also noted. The 10 dB fade level is exceeded for .03% during the thunderstorm months. Isolation with the same probability is 23 dB.

  10. Generation of four-photon polarization entangled states with cross-Kerr nonlinearity

    NASA Astrophysics Data System (ADS)

    Wang, Meiyu; Yan, Fengli

    2015-05-01

    We show how to prepare three different types of four-photon polarization entangled states among four modes. The scheme only use cross-Kerr medium, polarization beam splitters and X homodyne measurements on coherent light fields, which can be efficiently implemented in quantum optical laboratories. GHZ states and symmetric Dick states can be generated in deterministic way based on the scheme. With the possible availability of suitable strong Kerr nonlinearity, another type of entangled state called genuine four-photon entangled state can be realized as well.

  11. High-frequency microstrip cross resonators for circular polarization electron paramagnetic resonance spectroscopy.

    PubMed

    Henderson, J J; Ramsey, C M; Quddusi, H M; del Barco, E

    2008-07-01

    In this article we discuss the design and implementation of a novel microstrip resonator which allows absolute control of the microwaves polarization degree for frequencies up to 30 GHz. The sensor is composed of two half-wavelength microstrip line resonators, designed to match the 50 Omega impedance of the lines on a high dielectric constant GaAs substrate. The line resonators cross each other perpendicularly through their centers, forming a cross. Microstrip feed lines are coupled through small gaps to three arms of the cross to connect the resonator to the excitation ports. The control of the relative magnitude and phase between the two microwave stimuli at the input ports of each line allows for tuning the degree and type of polarization of the microwave excitation at the center of the cross resonator. The third (output) port is used to measure the transmitted signal, which is crucial to work at low temperatures, where reflections along lengthy coaxial lines mask the signal reflected by the resonator. Electron paramagnetic resonance spectra recorded at low temperature in an S=5/2 molecular magnet system show that 82% fidelity circular polarization of the microwaves is achieved over the central area of the resonator.

  12. Multi-year estimates of plant and ecosystem 13C discrimination at AmeriFlux sites

    NASA Astrophysics Data System (ADS)

    Dang, X.; Lai, C.; Hollinger, D. Y.; Bush, S.; Randerson, J. T.; Law, B. E.; Schauer, A. J.; Ehleringer, J.

    2011-12-01

    We estimated plant and ecosystem 13C discrimination continuously at 8 AmeriFlux sites (Howland Forest, Harvard Forest, Wind River Forest, Rannells Prairie, Freeman Ranch, Chestnut Ridge, Metolius, and Marys River fir) over 8 years (2002-2009). We used an observation-based approach from weekly measurements of eddy covariance CO2 fluxes and their 13C/12C ratios to estimate photosynthetic 13C discrimination (△A) and respiration (δ13CR) on seasonal and interannual time scales. The coordinated, systematic flask sampling across the AmeriFlux subnetwork were used for cross-site synthesis of monthly flux estimates [Dang et al. Combining tower mixing ratio and community model data to estimate regional-scale net ecosystem carbon exchange by boundary layer inversion over 4 flux towers in the U.S.A., Journal of Geophysical Research-Biogeosciences, in press]. Here, we evaluated environmental factors that also influenced temporal variability in △A and δ13CR from daily to interannual time scales, comparing atmospheric 13C/12C measurements, leaf and needle organic matter, and tree ring cellulose. Across these major biomes that dominate the continent, we show differential ecophysiological responses to environmental stresses, among which water availability appeared to be a dominant factor. Our decadal measurement period provided robust estimates of atmospheric 13C discrimination by terrestrial ecosystems, but also suggest regions where enhanced monitoring efforts are required (e.g., 13C/12C emission from fire and urban metabolism; increased temporal resolution of 13C measurements in stress-sensitive ecosystems) to make atmospheric 13C/12C measurements an effective constraint for continental-scale assessments of the terrestrial carbon cycle.

  13. Experimental and theoretical study of substituent effect on 13C NMR chemical shifts of 5-arylidene-2,4-thiazolidinediones

    NASA Astrophysics Data System (ADS)

    Rančić, Milica P.; Trišović, Nemanja P.; Milčić, Miloš K.; Ajaj, Ismail A.; Marinković, Aleksandar D.

    2013-10-01

    The electronic structure of 5-arylidene-2,4-thiazolidinediones has been studied by using experimental and theoretical methodology. The theoretical calculations of the investigated 5-arylidene-2,4-thiazolidinediones have been performed by the use of quantum chemical methods. The calculated 13C NMR chemical shifts and NBO atomic charges provide an insight into the influence of such a structure on the transmission of electronic substituent effects. Linear free energy relationships (LFERs) have been further applied to their 13C NMR chemical shifts. The correlation analyses for the substituent-induced chemical shifts (SCS) have been performed with σ using SSP (single substituent parameter), field (σF) and resonance (σR) parameters using DSP (dual substituent parameter), as well as the Yukawa-Tsuno model. The presented correlations account satisfactorily for the polar and resonance substituent effects operative at Cβ, and C7 carbons, while reverse substituent effect was found for Cα. The comparison of correlation results for the investigated molecules with those obtained for seven structurally related styrene series has indicated that specific cross-interaction of phenyl substituent and groups attached at Cβ carbon causes increased sensitivity of SCS Cβ to the resonance effect with increasing of electron-accepting capabilities of the group present at Cβ.

  14. 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.

  15. /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.

  16. Experiment to measure total cross sections, differential cross sections and polarization effects in pp elastic scattering at RHIC

    SciTech Connect

    Guryn, W.

    1998-02-01

    The authors are describing an experiment to study proton-proton (pp) elastic scattering experiment at the Relativistic Heavy Ion Collider (RHIC). Using both polarized and unpolarized beams, the experiment will study pp elastic scattering from {radical}s = 50 GeV to {radical}s = 500 GeV in two kinematical regions. In the Coulomb Nuclear Interference (CNI) region, 0.0005 < {vert_bar}t{vert_bar} < 0.12 (GeV/c){sup 2}, they will measure and study the s dependence of the total and elastic cross sections, {sigma}{sub tot} and {sigma}{sub el}; the ratio of the real to the imaginary part of the forward elastic scattering amplitude, {rho}; and the nuclear slope parameter of the pp elastic scattering, b. In the medium {vert_bar}t{vert_bar}-region, {vert_bar}t{vert_bar} < 1.5 (GeV/c){sup 2}, they plan to study the evolution of the dip structure with s, as observed at ISR in the differential elastic cross section, d{sigma}{sub el}/dt, and the s and {vert_bar}t{vert_bar} dependence of b. With the polarized beams the following can be measured: the difference in the total cross sections as function of initial transverse spin states {Delta}{sigma}{sub T}, the analyzing power, A{sub N}, and the transverse spin correlation parameter A{sub NN}. The behavior of the analyzing power A{sub N} at RHIC energies in the dip region of d{sigma}{sub el}/dt, where a pronounced structure was found at fixed-target experiments will be studied. The relation of pp elastic scattering to the beam polarization measurement at RHIC is also discussed.

  17. 13C NMR Metabolomics: Applications at Natural Abundance

    PubMed Central

    2015-01-01

    13C NMR has many advantages for a metabolomics study, including a large spectral dispersion, narrow singlets at natural abundance, and a direct measure of the backbone structures of metabolites. However, it has not had widespread use because of its relatively low sensitivity compounded by low natural abundance. Here we demonstrate the utility of high-quality 13C NMR spectra obtained using a custom 13C-optimized probe on metabolomic mixtures. A workflow was developed to use statistical correlations between replicate 1D 13C and 1H spectra, leading to composite spin systems that can be used to search publicly available databases for compound identification. This was developed using synthetic mixtures and then applied to two biological samples, Drosophila melanogaster extracts and mouse serum. Using the synthetic mixtures we were able to obtain useful 13C–13C statistical correlations from metabolites with as little as 60 nmol of material. The lower limit of 13C NMR detection under our experimental conditions is approximately 40 nmol, slightly lower than the requirement for statistical analysis. The 13C and 1H data together led to 15 matches in the database compared to just 7 using 1H alone, and the 13C correlated peak lists had far fewer false positives than the 1H generated lists. In addition, the 13C 1D data provided improved metabolite identification and separation of biologically distinct groups using multivariate statistical analysis in the D. melanogaster extracts and mouse serum. PMID:25140385

  18. Generation of four-photon polarization entangled decoherence-free states with cross-Kerr nonlinearity

    PubMed Central

    Wang, Meiyu; Yan, Fengli; Gao, Ting

    2016-01-01

    We propose a theoretical protocol for preparing four-photon polarization entangled decoherence-free states, which are immune to the collective noise. With the assistance of the cross-Kerr nonlinearities, a two-photon spatial entanglement gate, two controlled-NOT gates, a four-photon polarization entanglement gate are inserted into the circuit, where X homodyne measurements are aptly applied. Combined with some swap gates and simple linear optical elements, four-photon polarization entangled decoherence-free states which can be utilized to represent two logical qubits, |0〉L and |1〉L are achieved at the output ports of the circuit. This generation scheme may be implemented with current experimental techniques. PMID:27901116

  19. Surface configuration as an explanation for lithology-related cross-polarized radar image anomalies

    NASA Technical Reports Server (NTRS)

    Mccauley, J. R.

    1973-01-01

    One problem that has persisted since the development of multipolarized radar is the cause or causes of differential depolarization which is expressed as tonal reversals between like- and cross-polarized images of certain outcrops. Rocks producing anomalously low returns on the cross-polarized image could be classed into three general types: (1) certain geologically recent lava flows (late Pleistocene and Holocene), (2) some tertiary volcanics and (3) certain massive sandstones. Differential depolarization has been produced by volcanic rocks of various compositions including rhyolite, rhyodacite, dacite, andesite, and basalt. This has led to the conclusion that differential depolarization is not directly caused by any compositional factor. However, the study of aerial photos and subsequent field observation have led to the conclusion that the weathering and other surface characteristics of the outcrops are responsible for their appearance on multipolarized imagery.

  20. Characterization of atherosclerotic plaques by cross-polarization optical coherence tomography

    NASA Astrophysics Data System (ADS)

    Gubarkova, Ekaterina V.; Dudenkova, Varvara V.; Feldchtein, Felix I.; Timofeeva, Lidia B.; Kiseleva, Elena B.; Kuznetsov, Sergei S.; Moiseev, Alexander A.; Gelikonov, Gregory V.; Vitkin, Alex I.; Gladkova, Natalia D.

    2016-02-01

    We combined cross-polarization optical coherence tomography (CP OCT) and non-linear microscopy based on second harmonic generation (SHG) and two-photon-excited fluorescence (2PEF) to assess collagen and elastin fibers in the development of the atherosclerotic plaque (AP). The study shows potential of CP OCT for the assessment of collagen and elastin fibers condition in atherosclerotic arteries. Specifically, the additional information afforded by CP OCT, related to birefringence and cross-scattering properties of arterial tissues, may improve the robustness and accuracy of assessment about the microstructure and composition of the plaque for different stages of atherosclerosis.

  1. Cross-polarization microwave radar return at severe wind conditions: laboratory model and geophysical model function.

    NASA Astrophysics Data System (ADS)

    Troitskaya, Yuliya; Abramov, Victor; Ermoshkin, Alexey; Zuikova, Emma; Kazakov, Vassily; Sergeev, Daniil; Kandaurov, Alexandr

    2014-05-01

    Satellite remote sensing is one of the main techniques of monitoring severe weather conditions over the ocean. The principal difficulty of the existing algorithms of retrieving wind based on dependence of microwave backscattering cross-section on wind speed (Geophysical Model Function, GMF) is due to its saturation at winds exceeding 25 - 30 m/s. Recently analysis of dual- and quad-polarization C-band radar return measured from satellite Radarsat-2 suggested that the cross-polarized radar return has much higher sensitivity to the wind speed than co-polarized back scattering [1] and conserved sensitivity to wind speed at hurricane conditions [2]. Since complete collocation of these data was not possible and time difference in flight legs and SAR images acquisition was up to 3 hours, these two sets of data were compared in [2] only statistically. The main purpose of this paper is investigation of the functional dependence of cross-polarized radar cross-section on the wind speed in laboratory experiment. Since cross-polarized radar return is formed due to scattering at small-scale structures of the air-sea interface (short-crested waves, foam, sprays, etc), which are well reproduced in laboratory conditions, then the approach based on laboratory experiment on radar scattering of microwaves at the water surface under hurricane wind looks feasible. The experiments were performed in the Wind-wave flume located on top of the Large Thermostratified Tank of the Institute of Applied Physics, where the airflow was produced in the flume with the straight working part of 10 m and operating cross section 0.40?0.40 sq. m, the axis velocity can be varied from 5 to 25 m/s. Microwave measurements were carried out by a coherent Doppler X-band (3.2 cm) scatterometer with the consequent receive of linear polarizations. Experiments confirmed higher sensitivity to the wind speed of the cross-polarized radar return. Simultaneously parameters of the air flow in the turbulent boundary layer

  2. Photoionization of Synchrotron-Radiation-Excited Atoms: Separating Partial Cross Sections by Full Polarization Control

    SciTech Connect

    Aloiese, S.; Meyer, M.; Cubaynes, D.; Grum-Grzhimailo, A. N.

    2005-06-10

    Resonant atomic excitation by synchrotron radiation and subsequent ionization by a tunable dye laser is used to study the photoionization of short-lived Rydberg states in Xe. By combining circular and linear polarization of the synchrotron as well as of the laser photons the partial photoionization cross sections were separated in the region of overlapping autoionizing resonances of different symmetry and the parameters of the resonances were extracted.

  3. Large and unexpected enrichment in stratospheric 16O13C18O and its meridional variation

    PubMed Central

    Yeung, Laurence Y.; Affek, Hagit P.; Hoag, Katherine J.; Guo, Weifu; Wiegel, Aaron A.; Atlas, Elliot L.; Schauffler, Sue M.; Okumura, Mitchio; Boering, Kristie A.; Eiler, John M.

    2009-01-01

    The stratospheric CO2 oxygen isotope budget is thought to be governed primarily by the O(1D)+CO2 isotope exchange reaction. However, there is increasing evidence that other important physical processes may be occurring that standard isotopic tools have been unable to identify. Measuring the distribution of the exceedingly rare CO2 isotopologue 16O13C18O, in concert with 18O and 17O abundances, provides sensitivities to these additional processes and, thus, is a valuable test of current models. We identify a large and unexpected meridional variation in stratospheric 16O13C18O, observed as proportions in the polar vortex that are higher than in any naturally derived CO2 sample to date. We show, through photochemical experiments, that lower 16O13C18O proportions observed in the midlatitudes are determined primarily by the O(1D)+CO2 isotope exchange reaction, which promotes a stochastic isotopologue distribution. In contrast, higher 16O13C18O proportions in the polar vortex show correlations with long-lived stratospheric tracer and bulk isotope abundances opposite to those observed at midlatitudes and, thus, opposite to those easily explained by O(1D)+CO2. We believe the most plausible explanation for this meridional variation is either an unrecognized isotopic fractionation associated with the mesospheric photochemistry of CO2 or temperature-dependent isotopic exchange on polar stratospheric clouds. Unraveling the ultimate source of stratospheric 16O13C18O enrichments may impose additional isotopic constraints on biosphere–atmosphere carbon exchange, biosphere productivity, and their respective responses to climate change. PMID:19564595

  4. Hyperpolarized 13C MR Markers of Renal Tumor Aggressiveness

    DTIC Science & Technology

    2013-10-01

    reliably distinguish renal cancer aggressiveness for optimal triage of therapies . Hyperpolarized (HP) 13C magnetic resonance spectroscopic imaging (MRSI...reliably distinguish renal cancer aggressiveness for optimal triage of therapies . Hyperpolarized (HP) 13C magnetic resonance spectroscopic imaging (MRSI) is... cancer and normal tissues were obtained from nephrectomy specimens and sliced using Krumdieck slicer. With a precision gauge micrometer, the slice

  5. Hyperpolarized 13C NMR lifetimes in the liquid-state: relating structures and T1 relaxation times

    NASA Astrophysics Data System (ADS)

    Parish, Christopher; Niedbalski, Peter; Hashami, Zohreh; Fidelino, Leila; Kovacs, Zoltan; Lumata, Lloyd

    Among the various attempts to solve the insensitivity problem in nuclear magnetic resonance (NMR), the physics-based technique dissolution dynamic nuclear polarization (DNP) is probably the most successful method of hyperpolarization or amplifying NMR signals. Using this technique, liquid-state NMR signal enhancements of several thousand-fold are expected for low-gamma nuclei such as carbon-13. The lifetimes of these hyperpolarized 13C NMR signals are directly related to their 13C spin-lattice relaxation times T1. Depending upon the 13C isotopic location, the lifetimes of hyperpolarized 13C compounds can range from a few seconds to minutes. In this study, we have investigated the hyperpolarized 13C NMR lifetimes of several 13C compounds with various chemical structures from glucose, acetate, citric acid, naphthalene to tetramethylallene and their deuterated analogs at 9.4 T and 25 deg C. Our results show that the 13C T1s of these compounds can range from a few seconds to more than 60 s at this field. Correlations between the chemical structures and T1 relaxation times will be discussed and corresponding implications of these results on 13C DNP experiments will be revealed. US Dept of Defense Award No. W81XWH-14-1-0048 and Robert A. Welch Foundation Grant No. AT-1877.

  6. Linking Biogeochemistry to Microbial Diversity Using New 13C Approaches

    NASA Astrophysics Data System (ADS)

    Baggs, E. M.

    2005-12-01

    The use of 13C enables us to overcome uncertainties associated with soil C processes and to assess the links between species diversity and ecosystem function. Recent advances in stable isotope techniques enable determination of process rates, for example CH4 oxidation by direct measurement of 13C-CH4 and 13C-CO2. This overcomes uncertainties associated with reliance on changes in net CH4 emission, which may have compromised some earlier studies as both methanogenesis and CH4 oxidation may occur simultaneously in soil, providing significant advances in our understanding of the process of CH4 oxidation. These stable isotope techniques can be combined with molecular techniques (analysis of gene expression, stable isotope probing (SIP)) to relate the measured process to the microbial populations responsible. Here we will give a synthesis of results from experiments in which we applied 13C-CH4 to accurately determine CH4 oxidation rates in soils, and also present results of 13C-SIP from which we can identify the key players in the microbial population that are using the applied 13C substrate. With the 13C-CH4 technique we were able to provide direct evidence of inhibition of CH4 oxidation following fertiliser application (50-300 kg N ha-1) that was less under elevated pCO2, and evidence for anaerobic CH4 oxidation occurring in soil at 75% soil water filled pore space that would not have been apparent from changes in net CH4 emissions. 13C-SIP both through plants (using 13C-CO2) and directly into soil (using 13C-methane and -organic substrates) has revealed how key players in C utilisation vary under different soil conditions, for example, under improved and unimproved grasslands.

  7. Low-field thermal mixing in [1-(13)C] pyruvic acid for brute-force hyperpolarization.

    PubMed

    Peat, David T; Hirsch, Matthew L; Gadian, David G; Horsewill, Anthony J; Owers-Bradley, John R; Kempf, James G

    2016-07-28

    We detail the process of low-field thermal mixing (LFTM) between (1)H and (13)C nuclei in neat [1-(13)C] pyruvic acid at cryogenic temperatures (4-15 K). Using fast-field-cycling NMR, (1)H nuclei in the molecule were polarized at modest high field (2 T) and then equilibrated with (13)C nuclei by fast cycling (∼300-400 ms) to a low field (0-300 G) that activates thermal mixing. The (13)C NMR spectrum was recorded after fast cycling back to 2 T. The (13)C signal derives from (1)H polarization via LFTM, in which the polarized ('cold') proton bath contacts the unpolarised ('hot') (13)C bath at a field so low that Zeeman and dipolar interactions are similar-sized and fluctuations in the latter drive (1)H-(13)C equilibration. By varying mixing time (tmix) and field (Bmix), we determined field-dependent rates of polarization transfer (1/τ) and decay (1/T1m) during mixing. This defines conditions for effective mixing, as utilized in 'brute-force' hyperpolarization of low-γ nuclei like (13)C using Boltzmann polarization from nearby protons. For neat pyruvic acid, near-optimum mixing occurs for tmix∼ 100-300 ms and Bmix∼ 30-60 G. Three forms of frozen neat pyruvic acid were tested: two glassy samples, (one well-deoxygenated, the other O2-exposed) and one sample pre-treated by annealing (also well-deoxygenated). Both annealing and the presence of O2 are known to dramatically alter high-field longitudinal relaxation (T1) of (1)H and (13)C (up to 10(2)-10(3)-fold effects). Here, we found smaller, but still critical factors of ∼(2-5)× on both τ and T1m. Annealed, well-deoxygenated samples exhibit the longest time constants, e.g., τ∼ 30-70 ms and T1m∼ 1-20 s, each growing vs. Bmix. Mixing 'turns off' for Bmix > ∼100 G. That T1m≫τ is consistent with earlier success with polarization transfer from (1)H to (13)C by LFTM.

  8. Distinct fungal and bacterial δ13C signatures can drive the increase in soil δ13C with depth

    NASA Astrophysics Data System (ADS)

    Kohl, Lukas; Laganièrea, Jérôme; Edwards, Kate A.; Billings, Sharon A.; Morrill, Penny L.; Van Biesen, Geert; Ziegler, Susan E.

    2015-04-01

    Soil microbial biomass is a key precursor of soil organic carbon (SOC), and the enrichment in 13C during SOC diagenesis has been purported to be driven by increasing proportions of microbially derived SOC. Yet, little is known about how the δ13C of soil microbial biomass - and by extension the δ13C of microbial inputs to SOC - vary in space, time, or with the composition of the microbial community. Phospholipid fatty acids (PLFA) can be analyzed to measure the variation of the natural abundance δ13C values of both individual groups of microorganisms and the microbial community as a whole. Here, we show how variations of δ13CPLFA within the soil profile provides insight into C fluxes in undisturbed soils and demonstrate that distinct δ13C of fungal and bacterial biomass and their relative abundance can drive the increase of bulk δ13CSOC with depth. We studied the variation in natural abundance δ13C signatures of PLFA in podzolic soil profiles from mesic boreal forests in Atlantic Canada. Samples from the organic horizons (L,F,H) and the mineral (B; top 10 cm) horizons were analyzed for δ13C values of PLFA specific to fungi, G+ bacteria, or G- bacteria as proxies for the δ13C of the biomass of these groups, and for δ13C values of PLFA produced by a wide range of microorganisms (e.g. 16:0) as a proxy for the δ13C value of microbial biomass as a whole. Results were compared to fungi:bacteria ratios (F:B) and bulk δ13CSOC values. The δ13C values of group-specific PLFA were driven by differences among source organisms, with fungal PLFA consistently depleted (2.1 to 6.4‰) relative to and G+ and G- bacterial PLFA in the same sample. All group-specific PLFA, however, exhibited nearly constant δ13C values throughout the soil profile, apparently unaffected by the over 2.8‰ increase in δ13CSOC with depth from the L to B horizons. This indicates that bulk SOC poorly represents the substrates actually consumed by soil microorganisms in situ. Instead, our

  9. Analyzing Powers and Cross Sections of Inclusive Polarized Proton Scattering on LEAD-208.

    NASA Astrophysics Data System (ADS)

    Chen, Xiao-Yan

    Inclusive polarized proton-nucleus scattering at 290 and 500 MeV was performed using a ^ {208}Pb(51 mg/cm^2) target. A broad range (0-250 MeV) of excitation energy has been studied over the 4^circ -27^circ angular range. The measured analyzing power and cross section of the continuum are compared with the recent DWIA model calculations. The analyzing power and cross section of low-lying states are compared with the DWBA model calculation. The cross section in the continuum region is found to be dominated by single -step quasifree scattering. The analyzing power angular distributions of continuum peaks support RIA model predictions, and indicate the presence of relativistic medium effects.

  10. 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.

  11. 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.

  12. 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.

  13. Evaluation of cross-polarized near infrared hyperspectral imaging for early detection of dental caries

    NASA Astrophysics Data System (ADS)

    Usenik, Peter; Bürmen, Miran; Fidler, Aleš; Pernuš, Franjo; Likar, Boštjan

    2012-01-01

    Despite major improvements in dental healthcare and oral hygiene, dental caries remains one of the most prevalent oral diseases and represents the primary cause of oral pain and tooth loss. The initial stages of dental caries are characterized by demineralization of enamel crystals and are difficult to diagnose. Near infrared (NIR) hyperspectral imaging is a new promising technique for detection of early changes in the surfaces of carious teeth. This noninvasive imaging technique can characterize and differentiate between the sound tooth surface and initial or advanced tooth caries. The absorbing and scattering properties of dental tissues reflect in distinct spectral features, which can be measured, quantified and used to accurately classify and map different dental tissues. Specular reflections from the tooth surface, which appear as bright spots, mostly located around the edges and the crests of the teeth, act as a noise factor which can significantly interfere with the spectral measurements and analysis of the acquired images, degrading the accuracy of the classification and diagnosis. Employing cross-polarized imaging setup can solve this problem, however has yet to be systematically evaluated, especially in broadband hyperspectral imaging setups. In this paper, we employ cross-polarized illumination setup utilizing state-of-the-art high-contrast broadband wire-grid polarizers in the spectral range from 900 nm to 1700 nm for hyperspectral imaging of natural and artificial carious lesions of various degrees.

  14. Photoproduction of η mesons from the neutron: Cross sections and double polarization observable E

    NASA Astrophysics Data System (ADS)

    Witthauer, L.; Dieterle, M.; Afzal, F.; Anisovich, A. V.; Bantes, B.; Bayadilov, D.; Beck, R.; Bichow, M.; Brinkmann, K.-T.; Böse, S.; Challand, Th.; Crede, V.; Dutz, H.; Eberhardt, H.; Elsner, D.; Ewald, R.; Fornet-Ponse, K.; Friedrich, St.; Frommberger, F.; Funke, Ch.; Goertz, St.; Gottschall, M.; Gridnev, A.; Grüner, M.; Gutz, E.; Hammann, D.; Hammann, Ch.; Hannappel, J.; Hartmann, J.; Hillert, W.; Hoffmeister, Ph.; Honisch, Ch.; Jude, T.; Kaiser, D.; Kalinowsky, H.; Kalischewski, F.; Kammer, S.; Käser, A.; Keshelashvili, I.; Klassen, P.; Kleber, V.; Klein, F.; Koop, K.; Krusche, B.; Lang, M.; Lopatin, I.; Mahlberg, Ph.; Makonyi, K.; Metag, V.; Meyer, W.; Müller, J.; Müllers, J.; Nanova, M.; Nikonov, V.; Piontek, D.; Reicherz, G.; Rostomyan, T.; Sarantsev, A.; Schmidt, Ch.; Schmieden, H.; Seifen, T.; Sokhoyan, V.; Spieker, K.; Thiel, A.; Thoma, U.; Urban, M.; van Pee, H.; Walford, N. K.; Walther, D.; Wendel, Ch.; Werthmüller, D.; Wilson, A.; Winnebeck, A.

    2017-03-01

    Results from measurements of the photoproduction of η mesons from quasifree protons and neutrons are summarized. The experiments were performed with the CBELSA/TAPS detector at the electron accelerator ELSA in Bonn using the η→ 3π0→ 6γ decay. A liquid deuterium target was used for the measurement of total cross sections and angular distributions. The results confirm earlier measurements from Bonn and the MAMI facility in Mainz about the existence of a narrow structure in the excitation function of γ n→ nη. The current angular distributions show a forward-backward asymmetry, which was previously not seen, but was predicted by model calculations including an additional narrow P_{11} state. Furthermore, data obtained with a longitudinally polarized, deuterated butanol target and a circularly polarized photon beam were analyzed to determine the double polarization observable E. Both data sets together were also used to extract the helicity-dependent cross sections σ_{1/2} and σ_{3/2}. The narrow structure in the excitation function of γ n→ nη appears associated with the helicity-1/2 component of the reaction.

  15. Retrieval of Droplet size Density Distribution from Multiple field of view Cross polarized Lidar Signals: Theory and Experimental Validation

    DTIC Science & Technology

    2016-06-02

    is derived to facilitate use of secondary polarization. The model is supported by exper- imental MFOV lidar measurements carried out in a controlled ...Retrieval of droplet-size density distribution from multiple-field-of- view cross-polarized lidar signals: theory and experimental validation...Gilles Roy, Luc Bissonnette, Christian Bastille, and Gilles Vallee Multiple-field-of- view (MFOV) secondary-polarization lidar signals are used to

  16. Study of Urban environmental quality through Isotopes δ13C

    NASA Astrophysics Data System (ADS)

    González-Sosa, E.; Mastachi-Loza, C.; Becerril-Piña, R.; Ramos-Salinas, N. M.

    2012-04-01

    Usually, trees with similar pH values on their bark develop epiphytes of similar species, the acidity to be a factor for growth. The aim of the study was evaluate the air quality through isotope δ13C in order to define the levels of environmental quality in the city of Queretaro, Mexico. In this work were collected at least 4 epiphytes positioned in trees of the species Prosopis Laevigata at 25 sites of Queretaro City. The samples were analyzed for trace elements with an inductively coupled plasma atomic emission spectroscopy (ICP). The collecting took place during dry period, in May and early rain June 2011 period, and on four sectors to identify the spatial distribution of pollution, using isotopic analysis of concentration of δ 13C. According with the results there are significant differences among the species in each of the sampled areas. The 5 February Avenue presented greater diversity and richness of δ13C, followed by those who were surveyed in the proximity of the UAQ and finally in the middle-east area. An average value of δ13C-17.92%, followed by those surveyed in the vicinity of the UAQ that correspond to sector I and II with an concentration of δ13C-17.55% and δ13C-17.22%, and finally the samples collected in trees scattered in the East-Sector II and IV with a value of δ13C-17.02% and δ13C-15.62%, respectively. Also were observed differences between the dry and wet period. It is likely that these results of δ 13C in moist period reflect the drag of the isotopes due to rain events that could mark a trend in the dilution of this element, however there is a trend in terms of abundance and composition of finding more impact in those species sampled in dry period, in May and early June 2011.

  17. Antarctic polar plateau vertical electric field variations across heliocentric current sheet crossings

    NASA Astrophysics Data System (ADS)

    Burns, G. B.; Tinsley, B. A.; Klekociuk, A. R.; Troshichev, O. A.; Frank-Kamenetsky, A. V.; Duldig, M. L.; Bering, E. A.; Clem, J. M.

    2006-03-01

    A superposed epoch analysis of variations of the vertical electric field measured at Vostok (78.5°S, 107°E; magnetic latitude 83.6°S) during 1998 2002 heliocentric current sheet (HCS) crossings yields no significant variation other than an association imposed by polar-cap potential differences above the site. This result contradicts published reports of a reduction ˜15% in electric field 1 3 days after HCS crossings, an observation initially made ˜30 years ago. If such a reduction had been caused by reductions in stratospheric ionising radiation, the presence of polar stratospheric clouds (PSC) would seem necessary for the occurrence of this effect. PSCs would increase the resistance of the stratosphere thus making ionisation in that region significant in the context of the ionosphere ground current flow, in a manner analogous to the role of volcanic aerosols in the stratosphere in the explanation of the weakening of northern hemisphere winter cyclones associated with HCS crossings, the so-called ‘Wilcox effect’. However, separating the present data to correspond to the likely presence of PSC above Vostok also does not yield the reported reduction. Significant increases or decreases of the vertical electric field emerge from the observations when the HCS crossings are separated into sets depending on whether the solar wind magnetic field changes from ‘toward-to-away’ (increase of ˜11%) and ‘away-to-toward’ (decrease of ˜8%). Polar-cap potential changes above the site, inferred from solar wind parameters using the Weimer model, also show such step functions that reverse with the sign of HCS transition and are broadly consistent with the measured electric field increases or decreases. Remaining differences between the measurements and the model are consistent with a somewhat stronger solar wind speed and/or magnetic activity influence on polar-cap convection above Vostok than is predicted by the model. Variations in ground-level neutron counts, a

  18. Independent polarization and multi-band THz absorber base on Jerusalem cross

    NASA Astrophysics Data System (ADS)

    Arezoomand, Afsaneh Saee; Zarrabi, Ferdows B.; Heydari, Samaneh; Gandji, Navid P.

    2015-10-01

    In this paper, we present the design and simulation of a single and multi-band perfect metamaterial absorber (MA) in the THz region base on Jerusalem cross (JC) and metamaterial load in unit cells. The structures consist of dual metallic layers for allowing near-perfect absorption with absorption peak of more than 99%. In this novel design, four-different shape of Jerusalem cross is presented and by adding L, U and W shape loaded to first structure, we tried to achieve a dual-band absorber. In addition, by good implementation of these loaded, we are able to control the absorption resonance at second resonance at 0.9, 0.7 and 0.85 THz respectively. In the other hand, we achieved a semi stable designing at first resonance between 0.53 and 0.58 THz. The proposed absorber has broadband polarization angle. The surface current modeled and proved the broadband polarization angle at prototype MA. The LC resonance of the metamaterial for Jerusalem cross and modified structures are extracting from equivalent circuit. As a result, proposed MA is useful for THz medical imaging and communication systems and the dual-band absorber has applications in many scientific and technological areas.

  19. Electron-atom bremsstrahlung: Double-differential cross section and polarization correlations

    NASA Astrophysics Data System (ADS)

    Yerokhin, Vladimir A.; Surzhykov, Andrey

    2010-12-01

    The leading-order electron-atom bremsstrahlung is investigated within the rigorous relativistic approach based on the partial-wave representation of the Dirac wave functions in the external atomic field. Approximating the atomic target by an effective local potential, we calculate the double-differential cross section and the polarization correlations in a wide range of the impact energies. Connection between the bremsstrahlung at the hard-photon end point of the spectrum and the continuum-threshold limit of the radiative recombination is studied. A detailed analysis of the screening effect and the energy dependence of the polarization correlations is presented, with the main focus on the high-impact-energy region.

  20. Low-cost label-free biosensors using photonic crystals embedded between crossed polarizers.

    PubMed

    Nazirizadeh, Yousef; Bog, Uwe; Sekula, Sylwia; Mappes, Timo; Lemmer, Uli; Gerken, Martina

    2010-08-30

    There is a strong need for low-cost biosensors to enable rapid, on-site analysis of biological, biomedical, or chemical substances. We propose a platform for label-free optical biosensors based on applying the analyte onto a surface-functionalized photonic crystal slab and performing a transmission measurement with two crossed polarization filters. This dark-field approach allows for efficient background suppression as only the photonic crystal guided-mode resonances interacting with the functionalized surface experience significant polarization rotation. We present a compact biosensor demonstrator using a low-cost light emitting diode and a simple photodiode capable of detecting the binding kinetics of a 2.5 nM solution of the protein streptavidin on a biotin-functionalized photonic crystal surface.

  1. Nondestructive Monitoring of the Repair of Natural Occlusal Lesions using CrossPolarization Optical Coherence Tomography

    PubMed Central

    Kang, Hobin; Darling, Cynthia L.; Fried, Daniel

    2012-01-01

    Previous remineralization studies employing cross polarization sensitive optical coherence tomography (CP-OCT), have been limited to the repair of artificial enamel-like lesions. In this study we attempted to remineralize existing occlusal lesions on extracted teeth. Lesions were imaged before and after exposure to an acidic remineralization regimen and the integrated reflectivity and lesion depth was calculated. Automated integration routines worked well for assessing the integrated reflectivity for the lesion areas after remineralization. Polarized light microscopy was also used to examine the lesions areas after sectioning the teeth. An acidic remineralization solution was used to remineralize the lesions. The integrated reflectivity significantly increased after exposure to the remineralization solution which suggests that the acidic solution caused additional demineralization as opposed to the desired remineralization. PMID:23538837

  2. Differential diagnosis of human bladder mucosa pathologies in vivo with cross-polarization optical coherence tomography

    PubMed Central

    Kiseleva, Elena; Kirillin, Mikhail; Feldchtein, Felix; Vitkin, Alex; Sergeeva, Ekaterina; Zagaynova, Elena; Streltzova, Olga; Shakhov, Boris; Gubarkova, Ekaterina; Gladkova, Natalia

    2015-01-01

    Quantitative image analysis and parameter extraction using a specific implementation of polarization-sensitive optical coherence tomography (OCT) provides differential diagnosis of mucosal pathologies in in-vivo human bladders. We introduce a cross-polarization (CP) OCT image metric called Integral Depolarization Factor (IDF) to enable automatic diagnosis of bladder conditions (assessment the functional state of collagen fibers). IDF-based diagnostic accuracy of identification of the severe fibrosis of normal bladder mucosa is 79%; recurrence of carcinoma on the post-operative scar is 97%; and differentiation between neoplasia and acute inflammation is 75%. The promising potential of CP OCT combined with image analysis in human urology is thus demonstrated in vivo. PMID:25909028

  3. ANALYSIS OF SEEING-INDUCED POLARIZATION CROSS-TALK AND MODULATION SCHEME PERFORMANCE

    SciTech Connect

    Casini, R.; De Wijn, A. G.; Judge, P. G.

    2012-09-20

    We analyze the generation of polarization cross-talk in Stokes polarimeters by atmospheric seeing, and its effects on the noise statistics of spectropolarimetric measurements for both single-beam and dual-beam instruments. We investigate the time evolution of seeing-induced correlations between different states of one modulation cycle and compare the response to these correlations of two popular polarization modulation schemes in a dual-beam system. Extension of the formalism to encompass an arbitrary number of modulation cycles enables us to compare our results with earlier work. Even though we discuss examples pertinent to solar physics, the general treatment of the subject and its fundamental results might be useful to a wider community.

  4. Constraining 3-PG with a new δ13C submodel: a test using the δ13C of tree rings.

    PubMed

    Wei, Liang; Marshall, John D; Link, Timothy E; Kavanagh, Kathleen L; DU, Enhao; Pangle, Robert E; Gag, Peter J; Ubierna, Nerea

    2014-01-01

    A semi-mechanistic forest growth model, 3-PG (Physiological Principles Predicting Growth), was extended to calculate δ(13)C in tree rings. The δ(13)C estimates were based on the model's existing description of carbon assimilation and canopy conductance. The model was tested in two ~80-year-old natural stands of Abies grandis (grand fir) in northern Idaho. We used as many independent measurements as possible to parameterize the model. Measured parameters included quantum yield, specific leaf area, soil water content and litterfall rate. Predictions were compared with measurements of transpiration by sap flux, stem biomass, tree diameter growth, leaf area index and δ(13)C. Sensitivity analysis showed that the model's predictions of δ(13)C were sensitive to key parameters controlling carbon assimilation and canopy conductance, which would have allowed it to fail had the model been parameterized or programmed incorrectly. Instead, the simulated δ(13)C of tree rings was no different from measurements (P > 0.05). The δ(13)C submodel provides a convenient means of constraining parameter space and avoiding model artefacts. This δ(13)C test may be applied to any forest growth model that includes realistic simulations of carbon assimilation and transpiration.

  5. Detection of inflammatory cell function using 13C magnetic resonance spectroscopy of hyperpolarized [6-13C]-arginine

    PubMed Central

    Najac, Chloé; Chaumeil, Myriam M.; Kohanbash, Gary; Guglielmetti, Caroline; Gordon, Jeremy W.; Okada, Hideho; Ronen, Sabrina M.

    2016-01-01

    Myeloid-derived suppressor cells (MDSCs) are highly prevalent inflammatory cells that play a key role in tumor development and are considered therapeutic targets. MDSCs promote tumor growth by blocking T-cell-mediated anti-tumoral immune response through depletion of arginine that is essential for T-cell proliferation. To deplete arginine, MDSCs express high levels of arginase, which catalyzes the breakdown of arginine into urea and ornithine. Here, we developed a new hyperpolarized 13C probe, [6-13C]-arginine, to image arginase activity. We show that [6-13C]-arginine can be hyperpolarized, and hyperpolarized [13C]-urea production from [6-13C]-arginine is linearly correlated with arginase concentration in vitro. Furthermore we show that we can detect a statistically significant increase in hyperpolarized [13C]-urea production in MDSCs when compared to control bone marrow cells. This increase was associated with an increase in intracellular arginase concentration detected using a spectrophotometric assay. Hyperpolarized [6-13C]-arginine could therefore serve to image tumoral MDSC function and more broadly M2-like macrophages. PMID:27507680

  6. (13)C metabolic flux analysis of recombinant expression hosts.

    PubMed

    Young, Jamey D

    2014-12-01

    Identifying host cell metabolic phenotypes that promote high recombinant protein titer is a major goal of the biotech industry. (13)C metabolic flux analysis (MFA) provides a rigorous approach to quantify these metabolic phenotypes by applying isotope tracers to map the flow of carbon through intracellular metabolic pathways. Recent advances in tracer theory and measurements are enabling more information to be extracted from (13)C labeling experiments. Sustained development of publicly available software tools and standardization of experimental workflows is simultaneously encouraging increased adoption of (13)C MFA within the biotech research community. A number of recent (13)C MFA studies have identified increased citric acid cycle and pentose phosphate pathway fluxes as consistent markers of high recombinant protein expression, both in mammalian and microbial hosts. Further work is needed to determine whether redirecting flux into these pathways can effectively enhance protein titers while maintaining acceptable glycan profiles.

  7. 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.

  8. Anomalous 13C enrichment in modern marine organic carbon

    USGS Publications Warehouse

    Arthur, M.A.; Dean, W.E.; Claypool, G.E.

    1985-01-01

    Marine organic carbon is heavier isotopically (13C enriched) than most land-plant or terrestrial organic C1. Accordingly, ??13C values of organic C in modern marine sediments are routinely interpreted in terms of the relative proportions of marine and terrestrial sources of the preserved organic matter2,3. When independent geochemical techniques are used to evaluate the source of organic matter in Cretaceous or older rocks, those rocks containing mostly marine organic C are found typically to have lighter (more-negative) ??13C values than rocks containing mostly terrestrial organic C. Here we conclude that marine photosynthesis in mid-Cretaceous and earlier oceans generally resulted in a greater fractionation of C isotopes and produced organic C having lighter ??13C values. Modern marine photosynthesis may be occurring under unusual geological conditions (higher oceanic primary production rates, lower PCO2) that limit dissolved CO2 availability and minimize carbon isotope fractionation4. ?? 1985 Nature Publishing Group.

  9. An in Vivo 13C NMR Analysis of the Anaerobic Yeast Metabolism of 1-13C-Glucose

    NASA Astrophysics Data System (ADS)

    Giles, Brent J.; Matsche, Zenziwe; Egeland, Ryan D.; Reed, Ryan A.; Morioka, Scott S.; Taber, Richard L.

    1999-11-01

    A biochemistry laboratory experiment that studies the dynamics of the anaerobic yeast metabolism of 1-13C-D-glucose via NMR is described. Fleischmann's Active Dry yeast, under anaerobic conditions, produces primarily 2-13C-ethanol and some 1-13C-glycerol as end products. An experiment is described in which the yeast is subjected to osmotic shock from an increasing sodium chloride concentration. Under these conditions, the yeast increases the ratio of glycerol to ethanol. The experiment can be accomplished in a single laboratory period.

  10. Cross-polarization coupling and switching in an open nano-meta-resonator

    NASA Astrophysics Data System (ADS)

    Szabelak, W.; Nasalski, W.

    2011-11-01

    We demonstrate the reconfiguration process of optical beam fields circulating in an open nano-meta-resonator cavity. The cavity is composed of four corners or quadrants of space filled alternatively with dielectric and metamaterial media. The media are assumed to be lossless, nondispersive and of parameters precluding impedance matching at the boundaries between the subsequent corners. Beam path retracement in the cavity is obtained from a resonance condition of phase compensation along each optical ray contributed to the circulating beam. Cross-polarization coupling between TM and TE components of elegant higher-order Hermite-Gaussian beams propagating in the resonator is analysed. The existence of the phenomena of beam excitation, filtering and switching predicted on these grounds is explicitly confirmed by numerical simulations. All phenomena described depend substantially on a field cross-sectional diameter of the circulating beams.

  11. Broadband and Broad-angle Polarization-independent Metasurface for Radar Cross Section Reduction

    NASA Astrophysics Data System (ADS)

    Sun, Hengyi; Gu, Changqing; Chen, Xinlei; Li, Zhuo; Liu, Liangliang; Xu, Bingzheng; Zhou, Zicheng

    2017-01-01

    In this work, a broadband and broad-angle polarization-independent random coding metasurface structure is proposed for radar cross section (RCS) reduction. An efficient genetic algorithm is utilized to obtain the optimal layout of the unit cells of the metasurface to get a uniform backscattering under normal incidence. Excellent agreement between the simulation and experimental results show that the proposed metasurface structure can significantly reduce the radar cross section more than 10 dB from 17 GHz to 42 GHz when the angle of incident waves varies from 10° to 50°. The proposed coding metasurface provides an efficient scheme to reduce the scattering of the electromagnetic waves.

  12. Broadband and Broad-angle Polarization-independent Metasurface for Radar Cross Section Reduction

    PubMed Central

    Sun, Hengyi; Gu, Changqing; Chen, Xinlei; Li, Zhuo; Liu, Liangliang; Xu, Bingzheng; Zhou, Zicheng

    2017-01-01

    In this work, a broadband and broad-angle polarization-independent random coding metasurface structure is proposed for radar cross section (RCS) reduction. An efficient genetic algorithm is utilized to obtain the optimal layout of the unit cells of the metasurface to get a uniform backscattering under normal incidence. Excellent agreement between the simulation and experimental results show that the proposed metasurface structure can significantly reduce the radar cross section more than 10 dB from 17 GHz to 42 GHz when the angle of incident waves varies from 10° to 50°. The proposed coding metasurface provides an efficient scheme to reduce the scattering of the electromagnetic waves. PMID:28106090

  13. A complete set of spin observables for the ^13C(p,n) reaction at 135 MeV.

    NASA Astrophysics Data System (ADS)

    Du, Q.-Q.; Watson, J. W.; Anderson, B. D.; Baldwin, A. R.; Garcia, L. A. C.; Madey, R.; Manley, D. M.; Olson, M.; Prout, D. L.; Zhang, W.-M.; Cooper, D. A.; Sugarbaker, E.; Rapaport, J.; Foster, C. C.; Stephenson, E. J.

    1996-10-01

    We measured a complete set of polarization-transfer (D_ij) coefficients for the ^13C(p,n) reaction at 135 Mev for 0^circ, 5.5^circ, and 11^circ, with the ``2π'' neutron polarimeter (J. W. Watson et al.), AIP Conference Proceeding 343, 203 (1995). developed at Kent State University. Data will be presented for the transitions to the ^13N(g.s.) (J^π = (1/2)^-), and to the ^13N(3.51 MeV) (J^π = (3/2)^-) state. Previous studies(J. W. Watson et al.), Phys. Rev. Lett. 55, 1369 (1985) suggest that the mixture of ``GT'' (ΔJ = 1) and ``Fermi'' (ΔJ = 0) strength in the transition to the ^13N(g.s.) is anomalous. From our complete set of polarization-transfer data, we extract the spin-longitudinal, spin-transverse, and spin-independent responses, (M. Ichimura and K. Kawahigashi, Phys. Rev. C45), 1822 (1992). which provides a clean separation of the ``GT'' and ``Fermi'' cross sections. footnote Supported by NSF PHY 94-09265

  14. Evidence for gravitational lensing of the cosmic microwave background polarization from cross-correlation with the cosmic infrared background.

    PubMed

    Ade, P A R; Akiba, Y; Anthony, A E; Arnold, K; Atlas, M; Barron, D; Boettger, D; Borrill, J; Borys, C; Chapman, S; Chinone, Y; Dobbs, M; Elleflot, T; Errard, J; Fabbian, G; Feng, C; Flanigan, D; Gilbert, A; Grainger, W; Halverson, N W; Hasegawa, M; Hattori, K; Hazumi, M; Holzapfel, W L; Hori, Y; Howard, J; Hyland, P; Inoue, Y; Jaehnig, G C; Jaffe, A; Keating, B; Kermish, Z; Keskitalo, R; Kisner, T; Le Jeune, M; Lee, A T; Leitch, E M; Linder, E; Lungu, M; Matsuda, F; Matsumura, T; Meng, X; Miller, N J; Morii, H; Moyerman, S; Myers, M J; Navaroli, M; Nishino, H; Paar, H; Peloton, J; Poletti, D; Quealy, E; Rebeiz, G; Reichardt, C L; Richards, P L; Ross, C; Rotermund, K; Schanning, I; Schenck, D E; Sherwin, B D; Shimizu, A; Shimmin, C; Shimon, M; Siritanasak, P; Smecher, G; Spieler, H; Stebor, N; Steinbach, B; Stompor, R; Suzuki, A; Takakura, S; Tikhomirov, A; Tomaru, T; Wilson, B; Yadav, A; Zahn, O

    2014-04-04

    We reconstruct the gravitational lensing convergence signal from cosmic microwave background (CMB) polarization data taken by the Polarbear experiment and cross-correlate it with cosmic infrared background maps from the Herschel satellite. From the cross spectra, we obtain evidence for gravitational lensing of the CMB polarization at a statistical significance of 4.0σ and indication of the presence of a lensing B-mode signal at a significance of 2.3σ. We demonstrate that our results are not biased by instrumental and astrophysical systematic errors by performing null tests, checks with simulated and real data, and analytical calculations. This measurement of polarization lensing, made via the robust cross-correlation channel, not only reinforces POLARBEAR auto-correlation measurements, but also represents one of the early steps towards establishing CMB polarization lensing as a powerful new probe of cosmology and astrophysics.

  15. Hyperpolarization of Frozen Hydrocarbon Gases by Dynamic Nuclear Polarization at 1.2 K.

    PubMed

    Vuichoud, Basile; Canet, Estel; Milani, Jonas; Bornet, Aurélien; Baudouin, David; Veyre, Laurent; Gajan, David; Emsley, Lyndon; Lesage, Anne; Copéret, Christophe; Thieuleux, Chloé; Bodenhausen, Geoffrey; Koptyug, Igor; Jannin, Sami

    2016-08-18

    We report a simple and general method for the hyperpolarization of condensed gases by dynamic nuclear polarization (DNP). The gases are adsorbed in the pores of structured mesoporous silica matrices known as HYPSOs (HYper Polarizing SOlids) that have paramagnetic polarizing agents covalently bound to the surface of the mesopores. DNP is performed at low temperatures and moderate magnetic fields (T = 1.2 K and B0 = 6.7 T). Frequency-modulated microwave irradiation is applied close to the electron spin resonance frequency (f = 188.3 GHz), and the electron spin polarization of the polarizing agents of HYPSO is transferred to the nuclear spins of the frozen gas. A proton polarization as high as P((1)H) = 70% can be obtained, which can be subsequently transferred to (13)C in natural abundance by cross-polarization, yielding up to P((13)C) = 27% for ethylene.

  16. A parallel-series-fed microstrip array with high efficiency and low cross-polarization

    NASA Technical Reports Server (NTRS)

    Huang, John

    1992-01-01

    The requirements of a microstrip array with a vertically polarized fan beam are addressed that correspond to its use in C-band interferometric SAR. A combination of parallel- and series-feed techniques are utilized in an array design with a three-stage parallel-fed configuration to enhance bandwidth performance. The linearly polarized traveling-wave microstrip array antenna is fed by microstrip transmission lines in two rows of 36 elements that resonate at 5.30 GHz. The transmission lines are impedance-matched at every junction for all the waves that travel toward the two ends of the array. The two measured principal-plane patterns are shown, and the measured narrow-beam pattern is found to agree with the calculated values. The VSWR bandwidths and narrow and broad beamwidths of the antenna are found to permit efficient performance. The efficiency is attributed to the parallel and series-feed configuration which allows proper impedance matching, and low cross-polarization is a result of the antiphase feed technique employed in the configuration.

  17. Monitoring tooth demineralization using a cross polarization optical coherence tomographic system with an integrated MEMS scanner

    NASA Astrophysics Data System (ADS)

    Fried, Daniel; Staninec, Michal; Darling, Cynthia; Kang, Hobin; Chan, Kenneth

    2012-01-01

    New methods are needed for the nondestructive measurement of tooth demineralization and remineralization to monitor the progression of incipient caries lesions (tooth decay) for effective nonsurgical intervention and to evaluate the performance of anti-caries treatments such as chemical treatments or laser irradiation. Studies have shown that optical coherence tomography (OCT) has great potential to fulfill this role since it can be used to measure the depth and severity of early lesions with an axial resolution exceeding 10-μm, it is easy to apply in vivo and it can be used to image the convoluted topography of tooth occlusal surfaces. In this paper we present early results using a new cross-polarization OCT system introduced by Santec. This system utilizes a swept laser source and a MEMS scanner for rapid acquisition of cross polarization images. Preliminary studies show that this system is useful for measurement of the severity of demineralization on tooth surfaces and for showing the spread of occlusal lesions under the dentinal-enamel junction.

  18. Multiscale and cross entropy analysis of auroral and polar cap indices during geomagnetic storms

    NASA Astrophysics Data System (ADS)

    Gopinath, Sumesh; Prince, P. R.

    2016-01-01

    In order to improve general monoscale information entropy methods like permutation and sample entropy in characterizing the irregularity of complex magnetospheric system, it is necessary to extend these entropy metrics to a multiscale paradigm. We propose novel multiscale and cross entropy method for the analysis of magnetospheric proxies such as auroral and polar cap indices during geomagnetic disturbance times. Such modified entropy metrics are certainly advantageous in classifying subsystems such as individual contributions of auroral electrojets and field aligned currents to high latitude magnetic perturbations during magnetic storm and polar substorm periods. We show that the multiscale entropy/cross entropy of geomagnetic indices vary with scale factor. These variations can be attributed to changes in multiscale dynamical complexity of non-equilibrium states present in the magnetospheric system. These types of features arise due to imbalance in injection and dissipation rates of energy with variations in magnetospheric response to solar wind. We also show that the multiscale entropy values of time series decrease during geomagnetic storm times which reveals an increase in temporal correlations as the system gradually shifts to a more orderly state. Such variations in entropy values can be interpreted as the signature of dynamical phase transitions which arise at the periods of geomagnetic storms and substorms that confirms several previously found results regarding emergence of cooperative dynamics, self-organization and non-Markovian nature of magnetosphere during disturbed periods.

  19. Adiabatic sweep cross-polarization magic-angle-spinning NMR of half-integer quadrupolar spins

    NASA Astrophysics Data System (ADS)

    Wi, Sungsool; Kim, Chul; Schurko, Robert; Frydman, Lucio

    2017-04-01

    The use of frequency-swept radiofrequency (rf) pulses for enhancing signals in the magic-angle spinning (MAS) spectra of half-integer quadrupolar nuclides was explored. The broadband adiabatic inversion cross-polarization magic-angle spinning (BRAIN-CPMAS) method, involving an adiabatic inversion pulse on the S-channel and a simultaneous rectangular spin-lock pulse on the I-channel (1H), was applied to I(1/2) → S(3/2) systems. Optimal BRAIN-CPMAS matching conditions were found to involve low rf pulse strengths for both the I- and S-spin channels. At these low and easily attainable rf field strengths, level-crossing events among the energy levels | 3 / 2 >, | 1 / 2 >, | - 1 / 2 >, | - 3 / 2 > that are known to complicate the CPMAS of quadrupolar nuclei, are mostly avoided. Zero- and double-quantum polarization transfer modes, akin to those we have observed for I(1/2) → S(1/2) polarization transfers, were evidenced by these analyses even in the presence of the quadrupolar interaction. 1H-23Na and 1H-11B BRAIN-CPMAS conditions were experimentally explored on model compounds by optimizing the width of the adiabatic sweep, as well as the rf pulse powers of the 1H and 23Na/11B channels, for different MAS rates. The experimental data obtained on model compounds containing spin-3/2 nuclides, matched well predictions from numerical simulations and from an average Hamiltonian theory model. Extensions to half-integer spin nuclides with higher spins and potential applications of this BRAIN-CPMAS approach are discussed.

  20. A cross-polarized freeform illumination design for glare reduction in fruit quality inspection

    NASA Astrophysics Data System (ADS)

    Keresztes, Janos C.; Koshel, R. John; Chipman, Russel; Stover, John C.; Saeys, Wouter

    2015-09-01

    Common illumination systems in short wave infrared (SWIR) hyperspectral imaging (HSI) include direct or indirect tungsten halogen lights. While direct lights provide more radiation onto the samples than dome setups, thus being more energy efficient, the acquired images often suffer from specular reflections and gloss. Glare artifacts in images increase variability in the data limiting the accuracy of machine vision algorithms for defect detection and quality inspection, or even providing false positives. Although domes are known to provide a near Lambertian illumination and glare free images, glossy regions and heterogeneities may remain in the data in practice. More particularly, in the field of fruit and vegetable quality inspection, due to their waxy surface, it remains challenging to design an efficient realistic lighting system. This paper suggests a new approach to optimize the illumination of fruit and vegetables based on measurements of the bidirectional reflectance distribution function (BRDF), shape and Stokes parameters. From these measured values, a BRDF model is loaded into ray-tracing software for realistic illumination engineering in order to determine the most suitable illumination scheme. This concept is applied to apples and a cross polarizer (CP) with freeform optics (FO) optical configuration is proposed, which allows the FO to be optimized to maximize uniformity in the field of view of the imager and removes the parallel polarized gloss on the apples. The performance of this CP illumination system was determined experimentally for a set of apples. This cross polarized (CP) illumination system provided a uniformity (U) of 92% and an efficiency (ν) of 90%, while U = 87% and ν = 14% for an ideal dome configuration when illuminating a rectangular target. The simulated imaged apples with assigned optical properties performed better with CP (U=80%) than when using a dome (U=73%) by 7%. Finally, the sensitivity of the design for the light

  1. Cross-Polar Aircraft Trajectory Optimization and the Potential Climate Impact

    NASA Technical Reports Server (NTRS)

    Ng, Hok K.; Sridhar, Banavar; Grabbe, Shon; Chen, Neil

    2011-01-01

    Cross-Polar routes offer new opportunities for air travel markets. Transpolar flights reduce travel times, fuel burns, and associated environmental emissions by flying direct paths between many North American and Asian cities. This study evaluates the potential benefits of flying wind-optimal polar routes and assessed their potential impact on climate change. An optimization algorithm is developed for transpolar flights to generate wind-optimal trajectories that minimize climate impact of aircraft, in terms of global warming potentials (relative to warming by one kg of CO2) of several types of emissions, while avoiding regions of airspace that facilitate persistent contrail formation. Estimations of global warming potential are incorporated into the objective function of the optimization algorithm to assess the climate impact of aircraft emissions discharged at a given location and altitude. The regions of airspace with very low ambient temperature and areas favorable to persistent contrail formation are modeled as undesirable regions that aircraft should avoid and are formulated as soft state constraints. The fuel burn and climate impact of cross-polar air traffic flying various types of trajectory including flight plan, great circle, wind-optimal, and contrail-avoidance are computed for 15 origin-destination pairs between major international airports in the U.S. and Asia. Wind-optimal routes reduce average fuel burn of flight plan routes by 4.4% on December 4, 2010 and 8.0% on August 7, 2010, respectively. The tradeoff between persistent contrail formation and additional global warming potential of aircraft emissions is investigated with and without altitude optimization. Without altitude optimization, the reduction in contrail travel times is gradual with increase in total fuel consumption. When altitude is optimized, a one percent increase in additional global warming potential, a climate impact equivalent to that of 4070kg and 4220kg CO2 emission, reduces 135

  2. Measurement of Ultra Wideband Radar Cross Sections of an Automobile at Ka Band Using Circular Polarizations

    NASA Astrophysics Data System (ADS)

    Osaki, Hideyuki; Nishide, Takehiko; Kobayashi, Takehiko

    Ultra wideband (UWB) radar cross sections (RCSs) of several targets have been measured using various combinations of transmitting and receiving linear polarizations (V-V, H-H, and +45°--45°) with a view to obtaining information on the design of vehicular short-range radars. This paper reports the UWB RCSs (σLR and σLL) of a typical passenger automobile using two circular polarization combinations (L and R denote left and right circular polarizations). The wideband measurements were carried out with use of a vector network analyzer by sweeping the frequency from 24.5 to 28.8GHz in a radio anechoic chamber. The UWB RCSs were derived by integrating the received power in the frequency domain. Similar to the linear polarization results, fluctuations of the RCSs were smaller in the UWB than in narrowband for both L-R and L-L, because the ultra-wide bandwidth cancels out RCS plunges caused by narrowband interference among reflected waves from various facets of the target. The median of (σLR-σLL) was 2dB, while the median of (σHH-σ+45°--45°) or (σVV-σ+45°--45°) was 6dB. This is because the body of the automobile comprises a number of smaller scattering objects yielding σLL, either similar to the corner reflectors or asymmetrical to the radar boresight. Frequency-domain responses showed a number of notches caused by the interference between numerous reflecting waves having power levels of a similar order and different round-trip path lengths. Some representative reflective parts of the automobile were identified through analyses of time-domain responses.

  3. 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

  4. Singlet order conversion and parahydrogen-induced hyperpolarization of 13C nuclei in near-equivalent spin systems

    NASA Astrophysics Data System (ADS)

    Eills, James; Stevanato, Gabriele; Bengs, Christian; Glöggler, Stefan; Elliott, Stuart J.; Alonso-Valdesueiro, Javier; Pileio, Giuseppe; Levitt, Malcolm H.

    2017-01-01

    We have demonstrated two radiofrequency pulse methods which convert the nuclear singlet order of proton spin pairs into the magnetisation of nearby 13C nuclei. These irradiation schemes work well in the near-equivalence regime of the three-spin system, which applies when the difference in the two 1H-13C couplings is much smaller than the 1H-1H coupling. We use pulse sequences to generate thermally polarized singlet states in a reproducible manner, and study the singlet-to-magnetisation transfer step. Preliminary results demonstrate a parahydrogen-enhanced 13C polarization level of at least 9%, providing a signal enhancement factor of more than 9000, using 50% enriched parahydrogen.

  5. Single shot three‐dimensional pulse sequence for hyperpolarized 13C MRI

    PubMed Central

    Wang, Jiazheng; Wright, Alan J.; Hu, De‐en; Hesketh, Richard

    2016-01-01

    Purpose Metabolic imaging with hyperpolarized 13C‐labeled cell substrates is a promising technique for imaging tissue metabolism in vivo. However, the transient nature of the hyperpolarization, and its depletion following excitation, limits the imaging time and the number of excitation pulses that can be used. We describe here a single‐shot three‐dimensional (3D) imaging sequence and demonstrate its capability to generate 13C MR images in tumor‐bearing mice injected with hyperpolarized [1‐13C]pyruvate. Methods The pulse sequence acquires a stack‐of‐spirals at two spin echoes after a single excitation pulse and encodes the kz‐dimension in an interleaved manner to enhance robustness to B0 inhomogeneity. Spectral‐spatial pulses are used to acquire dynamic 3D images from selected hyperpolarized 13C‐labeled metabolites. Results A nominal spatial/temporal resolution of 1.25 × 1.25 × 2.5 mm3 × 2 s was achieved in tumor images of hyperpolarized [1‐13C]pyruvate and [1‐13C]lactate acquired in vivo. Higher resolution in the z‐direction, with a different k‐space trajectory, was demonstrated in measurements on a thermally polarized [1‐13C]lactate phantom. Conclusion The pulse sequence is capable of imaging hyperpolarized 13C‐labeled substrates at relatively high spatial and temporal resolutions and is robust to moderate system imperfections. Magn Reson Med 77:740–752, 2017. © 2016 The Authors Magnetic Resonance in Medicine published by Wiley Periodicals, Inc. on behalf of International Society for Magnetic Resonance in Medicine. This is an open access article under the terms of the Creative Commons Attribution License, which permits use, distribution and reproduction in any medium, provided the original work is properly cited. PMID:26916384

  6. 13C-based metabolic flux analysis: fundamentals and practice.

    PubMed

    Yang, Tae Hoon

    2013-01-01

    Isotope-based metabolic flux analysis is one of the emerging technologies applied to system level metabolic phenotype characterization in metabolic engineering. Among the developed approaches, (13)C-based metabolic flux analysis has been established as a standard tool and has been widely applied to quantitative pathway characterization of diverse biological systems. To implement (13)C-based metabolic flux analysis in practice, comprehending the underlying mathematical and computational modeling fundamentals is of importance along with carefully conducted experiments and analytical measurements. Such knowledge is also crucial when designing (13)C-labeling experiments and properly acquiring key data sets essential for in vivo flux analysis implementation. In this regard, the modeling fundamentals of (13)C-labeling systems and analytical data processing are the main topics we will deal with in this chapter. Along with this, the relevant numerical optimization techniques are addressed to help implementation of the entire computational procedures aiming at (13)C-based metabolic flux analysis in vivo.

  7. A scientific workflow framework for (13)C metabolic flux analysis.

    PubMed

    Dalman, Tolga; Wiechert, Wolfgang; Nöh, Katharina

    2016-08-20

    Metabolic flux analysis (MFA) with (13)C labeling data is a high-precision technique to quantify intracellular reaction rates (fluxes). One of the major challenges of (13)C MFA is the interactivity of the computational workflow according to which the fluxes are determined from the input data (metabolic network model, labeling data, and physiological rates). Here, the workflow assembly is inevitably determined by the scientist who has to consider interacting biological, experimental, and computational aspects. Decision-making is context dependent and requires expertise, rendering an automated evaluation process hardly possible. Here, we present a scientific workflow framework (SWF) for creating, executing, and controlling on demand (13)C MFA workflows. (13)C MFA-specific tools and libraries, such as the high-performance simulation toolbox 13CFLUX2, are wrapped as web services and thereby integrated into a service-oriented architecture. Besides workflow steering, the SWF features transparent provenance collection and enables full flexibility for ad hoc scripting solutions. To handle compute-intensive tasks, cloud computing is supported. We demonstrate how the challenges posed by (13)C MFA workflows can be solved with our approach on the basis of two proof-of-concept use cases.

  8. Synthesis and applications of {sup 13}C glycerol

    SciTech Connect

    Stocking, E.; Khalsa, O.; Martinez, R.A.; Silks, L.A. III

    1994-12-01

    Due in part to the use of labeled glycerol for the {sup 13}C enrichment of biomolecules, we are currently developing new synthetic routes to various isotopomers of glycerol. Judging from our experience, traditional methods of glycerol synthesis are not easily adapted for isotopic enrichment and/or have poor overall yields (12 to 15%). Furthermore, the use of glycerol for enrichment can be prohibitively expensive and its availability is limited by the level of demand. We are presently developing a short de novo synthesis of glycerol from carbon dioxide ({approximately}53% overall yield for four steps) and are examining the feasibility of synthesizing site-specific {sup 13}C-labeled glycerol and dihydroxyacetone (DHA) from labeled methanol and carbon dioxide. One application of {sup 13}C glycerol we have examined is enzymatic conversion of glycerol to glyceraldehyde-3-monophosphate or dihydroxyacetone monophosphate (DHAP) with yields ranging from 25 to 50% (as determined by NMR spectroscopy). We are also pursuing the chemical conversion of {sup 13}C-labeled DHA to DHAP. We are especially interested in {sup 13}C-labeled DHAP because we are investigating its use as a chemo-enzymatic precursor for both labeled 2-deoxyribose and 2-deoxyribonucleic acids.

  9. 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.

  10. Feasibility study of the 13C(α, n)16O reaction at LUNA

    NASA Astrophysics Data System (ADS)

    Kochanek, I.; Boeltzig, A.; Ciani, G. F.

    2017-03-01

    The 13C(α, n)16O reaction determines the dominant neutron source of the sprocess in thermally pulsing, low-mass, asymptotic giant branch (TP-AGB) stars. The temperature during the s-process in the 13C pocket of 90×106 K corresponds to a Gamow window of 140-230 keV. Since this energy is far below the Coulomb barrier, the cross section of this reaction is extremely small and its rate can only be extrapolated from the measurements at higher energies. At present, the cross section at Gamow peak is uncertain by almost one order of magnitude. An experimental campaign aimed at measuring low energy cross section in 13C(α n)16O is scheduled at the underground LUNA-400 accelerator in Gran Sasso Laboratory, Italy. The unique underground location of this facility offers significant improvement in sensitivity compared with previous investigations. It will allow to establish the interference pattern of the resonances and the absolute scale of this reaction.

  11. /sup 1/H and /sup 13/C spin-lattice relaxation in gaseous benzene

    SciTech Connect

    Folkendt, M.M.; Weiss-Lopez, B.E.; True, N.S.

    1988-08-25

    The nuclear spin-lattice relaxation time, T/sub 1/, measured for benzene protons at densities between 0.81 and 54.4 mol/m/sup 3/ (15 and 980 Torr) at 381 K exhibits a characteristic nonlinear density dependence. Analysis of the density-dependent T/sub 1/ data yields a spin-rotation coupling constant, C/sub eff/, of /vert bar/182.6 (0.4)/vert bar/ Hz and an angular momentum reorientation cross section, sigma, of 131 (1) /Angstrom//sup 2/. The /sup 13/C spin-lattice relaxation time of singly labeled /sup 13/C benzene is a linear function of density over the density range 1.07-75.12 mol/m/sup 3/ (20-1330 Torr). /sup 13/C T/sub 1/ values are shorter than /sup 1/H T/sub 1/ values by a factor of ca. 100 at comparable densities. The nuclear Overhauser enhancement factor, /eta/, is 0.0 /plus minus/ 0.02 at densities between 11 and 85.3 mol/m/sup 3/ (200 and 1500 Torr), demonstrating that dipole-dipole relaxation is relatively inefficient in this region. The spin-rotation coupling constant, C/sub eff/, for /sup 13/C nuclei in benzene is estimated to be /vert bar/1602 (68)/vert bar/ Hz.

  12. δ(13)C values of some succulent plants from Madagascar.

    PubMed

    Winter, Klaus

    1979-01-01

    δ(13)C values were determined in 20 succulents from Madagascar. The values were indicative of Crassulacean Acid Metabolism in 10 species of the Didiereaceae, 4 species of the Euphorbiaceae, 2 species of the Crassulaceae and 1 species of the Cucurbitaceae. The Didiereaceae and Euphorbiaceae studied are major components of a high biomass xerophytic flora in the semi-arid southwest and south of Madagascar. Three species of the Euphorbiaceae with succulent stems and non-succulent leaves, which were cultivated outdoors in the Tananarive Botanic Garden, showed C3 like δ(13)C values for both leaves and stems. δ(13)C values of leaf and stem material from a similar species, collected in the south of Madagascar, indicated Crassulacean Acid Metabolism.

  13. {sup 13}C relaxation in an RNA hairpin

    SciTech Connect

    King, G.C. |; Akratos, C.; Xi, Z.; Michnica, M.J.

    1994-12-01

    This initial survey of {sup 13}C relaxation in the {triangle}TAR RNA element has generated a number of interesting results that should prove generally useful for future studies. The most readily comparable study in the literature monitored {sup 13}C relaxation of the methyl groups from unusual bases in tRNA{sup Phe}. The study, which used T{sub 1} and NOE data only, reported order parameters for the methyl group axis that ranged between 0.51 and 0.97-a range similar to that observed here. However, they reported a breakdown of the standard order parameter analysis at higher (118-MHz {sup 13}C) frequencies, which should serve to emphasize the need for a thorough exploration of suitable motional models.

  14. Cross-reactivity of stimulants found in sports drug testing by two fluorescence polarization immunoassays.

    PubMed

    de la Torre, R; Badia, R; Gonzàlez, G; García, M; Pretel, M J; Farré, M; Segura, J

    1996-01-01

    We investigated the usefulness of immunological methods for presumptive detection of stimulants found in sports drug testing. The ingestion of substances that show no cross-reactivity in tests commercially available for the detection of amphetamines can produce positive results in the urine. Human metabolism contributes to the positive results of some urine samples when the parent compound does not cross-react with the antibodies of the assay. Urine samples from healthy volunteers given stimulants were tested by chromatographic methods and by two different fluorescence polarization immunoassays (FPIA) from Abbott Laboratories for the analysis of amphetamines. According to the results obtained, we classified stimulants into four groups: detectable stimulants that gave rise to amphetamine by human metabolism (group 1); detectable ephedrines and related compounds, appearing in the urine either as parent compounds or originated by metabolism (group 2); detectable stimulants that displayed actual cross-reactivity with amphetamine tests (group 3); and stimulants not detected by FPIA (group 4). Most of the true doping cases due to the ingestion of stimulants may be detected by FPIA. The specificity of the results may be increased by combining immunological assays with different antibodies.

  15. Phase dynamics in vertical-cavity surface-emitting lasers with delayed optical feedback and cross-polarized reinjection

    NASA Astrophysics Data System (ADS)

    Javaloyes, J.; Marconi, M.; Giudici, M.

    2014-08-01

    We study theoretically the nonlinear polarization dynamics of vertical-cavity surface-emitting lasers in the presence of an external cavity providing delayed optical feedback and cross-polarized reinjection. We show that, far from the laser threshold, the dynamics remains confined close to the equatorial plane of a Poincaré sphere with a fixed radius. It entails that the evolution of the system is described by two phase variables: the orientation phase of the quasilinear polarization and the optical phase of the field. We explore the complex modal structure given by the double reinjection configuration and how it evolves between the cases of single cross-polarized reinjection and single optical feedback, hence disclosing the relationship with the Lang-Kobayashi model. We also reinterpret the square-wave switching observed by J. Mulet et al. [Phys. Rev. A 76, 043801 (2007), 10.1103/PhysRevA.76.043801] in terms of phase kinks.

  16. 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.

  17. Hyperpolarized 13C allows a direct measure of flux through a single enzyme-catalyzed step by NMR

    PubMed Central

    Merritt, Matthew E.; Harrison, Crystal; Storey, Charles; Jeffrey, F. Mark; Sherry, A. Dean; Malloy, Craig R.

    2007-01-01

    13C NMR is a powerful tool for monitoring metabolic fluxes in vivo. The recent availability of automated dynamic nuclear polarization equipment for hyperpolarizing 13C nuclei now offers the potential to measure metabolic fluxes through select enzyme-catalyzed steps with substantially improved sensitivity. Here, we investigated the metabolism of hyperpolarized [1-13C1]pyruvate in a widely used model for physiology and pharmacology, the perfused rat heart. Dissolved 13CO2, the immediate product of the first step of the reaction catalyzed by pyruvate dehydrogenase, was observed with a temporal resolution of ≈1 s along with H13CO3−, the hydrated form of 13CO2 generated catalytically by carbonic anhydrase. In hearts presented with the medium-chain fatty acid octanoate in addition to hyperpolarized [1-13C1]pyruvate, production of 13CO2 and H13CO3− was suppressed by ≈90%, whereas the signal from [1-13C1]lactate was enhanced. In separate experiments, it was shown that O2 consumption and tricarboxylic acid (TCA) cycle flux were unchanged in the presence of added octanoate. Thus, the rate of appearance of 13CO2 and H13CO3− from [1-13C1]pyruvate does not reflect production of CO2 in the TCA cycle but rather reflects flux through pyruvate dehydrogenase exclusively. PMID:18056642

  18. The magnetic field dependence of cross-effect dynamic nuclear polarization under magic angle spinning

    SciTech Connect

    Mance, Deni; Baldus, Marc; Gast, Peter; Huber, Martina; Ivanov, Konstantin L.

    2015-06-21

    We develop a theoretical description of Dynamic Nuclear Polarization (DNP) in solids under Magic Angle Spinning (MAS) to describe the magnetic field dependence of the DNP effect. The treatment is based on an efficient scheme for numerical solution of the Liouville-von Neumann equation, which explicitly takes into account the variation of magnetic interactions during the sample spinning. The dependence of the cross-effect MAS-DNP on various parameters, such as the hyperfine interaction, electron-electron dipolar interaction, microwave field strength, and electron spin relaxation rates, is analyzed. Electron spin relaxation rates are determined by electron paramagnetic resonance measurements, and calculations are compared to experimental data. Our results suggest that the observed nuclear magnetic resonance signal enhancements provided by MAS-DNP can be explained by discriminating between “bulk” and “core” nuclei and by taking into account the slow DNP build-up rate for the bulk nuclei.

  19. 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

  20. 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.

  1. Observational Evidence that Magnetosheath Plasma Parameters are Prominent in Determining Cross Polar Cap Potential Saturation

    NASA Astrophysics Data System (ADS)

    Clauer, Robert; Xu, Zhonghua; Hartinger, Michael; Ruohoniemi, Michael; Scales, Wayne; Maimaiti, Maimaitirebike; Nicolls, Michael; Wilder, Rick; Lopez, Ramon

    2016-04-01

    A variety of statistical studies have shown that the ionospheric polar potential produced by solar wind - magnetosphere - ionosphere coupling is linear for weak to moderate solar wind driving, but becomes non-linear during periods of very strong driving. It has been shown that this applies to the two-cell convection potential that develops during southward interplanetary magnetic field (IMF) and also to the reverse convection cells that develop during northward IMF. This has been described as polar potential saturation and it appears to begin when the driving solar wind electric field becomes greater than 3 mV/m. It has also been shown that the summer ionospheric electric field saturates at about the same value (20 mV/m) for both northward or southward IMF. Recent measurements of the high latitude convection on September 12 - 13, 2014 using the Resolute Incoherent Scatter Radar during periods of large northward IMF show ionospheric electric fields varying between 56 mV/m and 156 mV/m within the dayside reverse convection cells. There is no indication of saturation during these periods of very strong driving. We believe that the extremely rare conditions in the solar wind that produce extreme driving while also producing a high plasma beta in the magnetosheath provide the best explanation for the lack of potential saturation of the reverse convection cells. That is to say, the conditions in the magnetosheath that contribute to enhancing or limiting reconnection are most important in determining cross polar cap potential saturation. This research was supported at Virginia Tech by National Science Foundation Grant AGS-1216373.

  2. A new formulation for the ionospheric cross polar cap potential including saturation effects

    NASA Astrophysics Data System (ADS)

    Ridley, A. J.

    2005-12-01

    It is known that the ionospheric cross polar cap potential (CPCP) saturates when the interplanetary magnetic field (IMF) Bz becomes very large. Few studies have offered physical explanations as to why the polar cap potential saturates. We present 13 events in which the reconnection electric field (REF) goes above 12mV/m at some time. When these events are examined as typically done in previous studies, all of them show some signs of saturation (i.e., over-prediction of the CPCP based on a linear relationship between the IMF and the CPCP). We show that by taking into account the size of the magnetosphere and the fact that the post-shock magnetic field strength is strongly dependent upon the solar wind Mach number, we can better specify the ionospheric CPCP. The CPCP (Φ) can be expressed as Φ=(10-4v2+11.7B(1-e-Ma/3)sin3(θ/2)) {rms/9 (where v is the solar wind velocity, B is the combined Y and Z components of the interplanetary magnetic field, Ma is the solar wind Mach number, θ=acos(Bz/B), and rms is the stand-off distance to the magnetopause, assuming pressure-balance between the solar wind and the magnetosphere). This is a simple modification of the original Boyle et al. (1997) formulation.

  3. Parallel and series FED microstrip array with high efficiency and low cross polarization

    NASA Technical Reports Server (NTRS)

    Huang, John (Inventor)

    1995-01-01

    A microstrip array antenna for vertically polarized fan beam (approximately 2 deg x 50 deg) for C-band SAR applications with a physical area of 1.7 m by 0.17 m comprises two rows of patch elements and employs a parallel feed to left- and right-half sections of the rows. Each section is divided into two segments that are fed in parallel with the elements in each segment fed in series through matched transmission lines for high efficiency. The inboard section has half the number of patch elements of the outboard section, and the outboard sections, which have tapered distribution with identical transmission line sections, terminated with half wavelength long open-circuit stubs so that the remaining energy is reflected and radiated in phase. The elements of the two inboard segments of the two left- and right-half sections are provided with tapered transmission lines from element to element for uniform power distribution over the central third of the entire array antenna. The two rows of array elements are excited at opposite patch feed locations with opposite (180 deg difference) phases for reduced cross-polarization.

  4. Differential cross sections and recoil polarizations for the reaction γp→K+Σ0

    DOE PAGES

    Dey, B.; Meyer, C. A.; Bellis, M.; ...

    2010-08-06

    Here, high-statistics measurements of differential cross sections and recoil polarizations for the reactionmore » $$\\gamma p \\rightarrow K^+ \\Sigma^0$$ have been obtained using the CLAS detector at Jefferson Lab. We cover center-of-mass energies ($$\\sqrt{s}$$) from 1.69 to 2.84 GeV, with an extensive coverage in the $K^+$ production angle. Independent measurements were made using the $$K^{+}p\\pi^{-}$$($$\\gamma$$) and $$K^{+}p$$($$\\pi^-,\\gamma$$) final-state topologies, and were found to exhibit good agreement. Our differential cross sections show good agreement with earlier CLAS, SAPHIR and LEPS results, while offering better statistical precision and a 300-MeV increase in $$\\sqrt{s}$$ coverage. Above $$\\sqrt{s} \\approx 2.5$$ GeV, $t$- and $u$-channel Regge scaling behavior can be seen at forward- and backward-angles, respectively. Our recoil polarization ($$P_\\Sigma$$) measurements represent a substantial increase in kinematic coverage and enhanced precision over previous world data. At forward angles we find that $$P_\\Sigma$$ is of the same magnitude but opposite sign as $$P_\\Lambda$$, in agreement with the static SU(6) quark model prediction of $$P_\\Sigma \\approx -P_\\Lambda$$. This expectation is violated in some mid- and backward-angle kinematic regimes, where $$P_\\Sigma$$ and $$P_\\Lambda$$ are of similar magnitudes but also have the same signs. In conjunction with several other meson photoproduction results recently published by CLAS, the present data will help constrain the partial wave analyses being performed to search for missing baryon resonances.« less

  5. 1H-2H cross-polarization NMR in fast spinning solids by adiabatic sweeps

    NASA Astrophysics Data System (ADS)

    Wi, Sungsool; Schurko, Robert; Frydman, Lucio

    2017-03-01

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

  6. Metabolic flux analysis using 13C peptide label measurements

    Technology Transfer Automated Retrieval System (TEKTRAN)

    13C metabolic flux analysis (MFA) has become the experimental method of choice to investigate cellular metabolism. MFA has established flux maps of central metabolism for dozens of microbes, cell cultures, and plant seeds. Steady-state MFA utilizes isotopic labeling measurements of amino acids obtai...

  7. Quantitative 13C NMR characterization of fast pyrolysis oils

    DOE PAGES

    Happs, Renee M.; Lisa, Kristina; Ferrell, III, Jack R.

    2016-10-20

    Quantitative 13C NMR analysis of model catalytic fast pyrolysis (CFP) oils following literature procedures showed poor agreement for aromatic hydrocarbons between NMR measured concentrations and actual composition. Furthermore, modifying integration regions based on DEPT analysis for aromatic carbons resulted in better agreement. Solvent effects were also investigated for hydrotreated CFP oil.

  8. Modeling of the 2007 JET ^13C migration experiments

    NASA Astrophysics Data System (ADS)

    Strachan, J. D.; Likonen, J.; Hakola, A.; Coad, J. P.; Widdowson, A.; Koivuranta, S.; Hole, D. E.; Rubel, M.

    2010-11-01

    Using the last run day of the 2007 JET experimental campaign, ^13CH4 was introduced repeatedly from the vessel top into a single plasma type (H-mode, Ip= 1.6 MA, Bt= 1.6 T). Similar experiments were performed in 2001 (vessel top into L-Mode) and 2004 (outer divertor into H-Mode). Divertor and wall tiles were removed and been analysed using secondary ion mass spectrometry (SIMS) and Rutherford backscattering (RBS) to determine the ^13C migration. ^13C was observed to migrate both to the inner (largest deposit), outer divertor (less) , and the floor tiles (least). This paper reports the EDGE2D/NIMBUS based modelling of the carbon migration. The emphasis is on the comparison of the 2007 results with the 2001 results where both injections were from the machine top but ELMs were present in 2007 but not present in 2001. The ELMs seemed to cause more ^13C re-erosion near the inner strike point. Also of interest is the difference in the Private Flux Region deposits where the changes in divertor geometry between 2004 and 2007 caused differences in the deposits. In 2007, the tilting of the load bearing tile caused regions of the PFR to be shadowed from the inner strike point which were not shadowed in 2004, indicating ^13C neutrals originated from the OSP.

  9. Complete 1H and 13C spectral assignment of floridoside.

    PubMed

    Simon-Colin, Christelle; Kervarec, Nelly; Pichon, Roger; Deslandes, Eric

    2002-02-11

    Floridoside (2-O-alpha-D-galactopyranosylglycerol) was extracted from the red marine alga Rhodymenia palmata, and purified by ion-exchange chromatography: 1D and 2D NMR spectroscopy experiments were used to unambiguously assign the complete 1H and 13C spectra.

  10. Does the Shuram δ13C excursion record Ediacaran oxygenation?

    NASA Astrophysics Data System (ADS)

    Husson, J. M.; Maloof, A. C.; Schoene, B.; Higgins, J. A.

    2013-12-01

    The most negative carbon isotope excursion in Earth history is found in carbonate rocks of the Ediacaran Period (635-542 Ma). Known colloquially as the the 'Shuram' excursion, workers have long noted its tantalizing, broad concordance with the rise of abundant macro-scale fossils in the rock record, variously interpreted as animals, giant protists, macro-algae and lichen, and known as the 'Ediacaran Biota.' Thus, the Shuram excursion has been interpreted by many in the context of a dramatically changing redox state of the Ediacaran oceans - e.g., a result of methane cycling in a low O2 atmosphere, the final destruction of a large pool of recalcitrant dissolved organic carbon (DOC), and the step-wise oxidation of the Ediacaran oceans. More recently, diagenetic interpretations of the Shuram excursion - e.g. sedimentary in-growth of very δ13C depleted authigenic carbonates, meteoric alteration of Ediacaran carbonates, late-stage burial diagenesis - have challenged the various Ediacaran redox models. A rigorous geologic context is required to discriminate between these explanatory models, and determine whether the Shuram excursion can be used to evaluate terminal Neoproterozoic oxygenation. Here, we present chemo-stratigraphic data (δ13C, δ18O, δ44/42Ca and redox sensitive trace element abundances) from 12 measured sections of the Ediacaran-aged Wonoka Formation (Fm.) of South Australia that require a syn-depositional age for the extraordinary range of δ13C values (-12 to +4‰) observed in the formation. In some locations, the Wonoka Fm. is ~700 meters (m) of mixed shelf limestones and siliclastics that record the full 16 ‰ δ13C excursion in a remarkably consistent fashion across 100s of square kilometers of basin area. Fabric-altering diagenesis, where present, occurs at the sub-meter vertical scale, only results in sub-permil offsets in δ13C and cannot be used to explain the full δ13C excursion. In other places, the Wonoka Fm. is host to deep (1 km

  11. Control of Mercury Accumulation And Mobility in a Forest Soil as Indicated by δ13C

    NASA Astrophysics Data System (ADS)

    Bajracharya, U.; Jackson, B.; Feng, X.

    2015-12-01

    Mobility and cycling of mercury (Hg) in soils is important. Hg leaching results in its transport to wetlands, where Hg methylates and bioaccumulates through aquatic food webs. It has been shown that Hg cycle in soil is controlled by organic matter (OM) quantity as well as quality. The latter is indicated by increase of Hg/C ratio as C/N decreases by decomposition. Here we investigate the Hg-C relationship in a temperate forest soil in Hanover, NH, with a focus of examining the control of OM quality on soil Hg accumulation and mobility. We use δ13C as an indicator of carbon quality. The soil samples from A, B and C horizons were separated into six particle size fractionations from <25 µm to 1 mm. Both the bulk soil and particle size separates were analyzed for Hg concentrations, carbon content (C%), δ13C, and Hg partition coefficient (Kd =mg gSoil-1/mg Lsolution-1). We found that the bulk Hg concentration decreases significantly with increasing δ13C (R2=0.90, p <0.0001), but Hg/C increases with δ13C (R2=0.59, p =0.009). Both Hg/C and δ13C increase with soil depth, and at a given horizon, they both increase with decreasing particle size. These results indicate that high Hg/C ratios are associated with aged, decomposed, and low quality OM. Mostly likely, this accumulation of Hg in older OM is a result of retention of Hg upon carbon loss during soil respiration. However, the relationship between particle size and Hg/C is significantly different among different horizons; the most prominent relationship occurs at the deepest C horizon. This cross effect of horizon and particle size cannot be explained by normal aging of the OM through decomposition, pointing to mechanisms of changing in Hg bonding characteristics with OM aging or particle aggregation. The measured Kd value decreased with increasing δ13C (R2=0.43, p =0.0031), indicating that Hg associated with older OM is more subject to leaching compared to younger, fresher OM. This association can also be

  12. A Low Energy Measurement of the 13C(α,n) Reaction

    NASA Astrophysics Data System (ADS)

    Toomey, Rebecca; Febbraro, Michael; Pain, Steven; Cizewski, Jolie

    2016-09-01

    The slow neutron capture process (s process) is a key mechanism in heavy-element synthesis, reaching up to 209Bi. The s process creates elements along the line of beta-stability via neutron capture and beta decay in a low neutron flux environment in AGB stars. The dominant source of neutrons for the s process is the 13C(α,n) reaction. At the low energies occurring in these stellar conditions, this reaction cross section is very low, making direct measurement of the reaction rate difficult. Currently the state-of-the-art measurements using high-efficiency moderated neutron counter detectors have constrained this cross section down to approximately 300 keV - still well above stellar conditions, therefore requiring extrapolation of the S factor into the Gamow window ( 140-230 keV). This talk will focus on the motivation and preparation for low-energy measurements of the 13C(α,n) reaction using a neutron spectroscopic technique with the aim of reducing uncertainties in current measurements, and also attempt measurements at lower energies. Background measurements and the characterisation of the experimental set up from the measurement of 13C(α,n) at higher energies at the University of Notre Dame will be presented. This work is supported in part by the U.S. Department of Energy and National Science Foundation.

  13. Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

    DOEpatents

    Martinez, Rodolfo A. , Unkefer; Clifford J. , Alvarez; Marc, A [Santa Fe, NM

    2012-06-12

    The present invention is directed to the labeled compounds, ##STR00001## wherein C* is each either .sup.13C and .sup.12C where at least one C* is .sup.13C, each hydrogen of the methylene group is hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is sulfide, sulfinyl, or sulfone, Z is an aryl group such as 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, or a phenyl group ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently either hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group such as NH.sub.2, NHR and NRR' where R and R' are each independently either a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms. The present invention is also directed to the labeled compounds ##STR00003##

  14. Synthesis of [1-.sup.13C]pyruvic acid], [2-.sup.13C]pyruvic acid], [3-.sup.13C]pyruvic acid] and combinations thereof

    DOEpatents

    Martinez, Rodolfo A.; Unkefer, Clifford J.; Alvarez, Marc A.

    2009-09-01

    The present invention is directed to labeled compounds, of the formulae ##STR00001## wherein C* is each independently selected from the group consisting of .sup.13C and .sup.12C with the proviso that at least one C* is .sup.13C, each hydrogen of the methylene group can independently be either hydrogen or deuterium, the methyl group includes either zero or three deuterium atoms, Q is from the group of sulfide, sulfinyl, and sulfone, Z is an aryl group from the group of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently from the group of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group from the group of NH.sub.2, NHR and NRR' where R and R' are each independently from the group of a C.sub.1-C.sub.4 lower alkyl, a phenyl, and an alkoxy group, and the methyl group can include either zero or three deuterium atoms.

  15. Quantification of 13C pyruvate and 13C lactate in dog blood by reversed-phase liquid chromatography-electrospray ionization mass spectrometry after derivatization with 3-nitrophenylhydrazine.

    PubMed

    Uran, Steinar; Landmark, Kristin Eitrem; Hjellum, Gro; Skotland, Tore

    2007-08-15

    Injection of hyperpolarized (13)C-labelled pyruvate ((13)C pyruvate) is under evaluation as an agent for medical metabolic imaging by measuring formation of (13)C lactate using magnetic resonance spectroscopy of the (13)C nuclei. A quantitative method for analysis of these (13)C-labelled substances in dog blood was needed as part of the development of this agent and we here describe a liquid chromatography-mass spectrometry method for that purpose. Immediately after blood collection, the blood proteins were precipitated using methanol added internal standard ([U-(13)C]pyruvate and [U-(13)C]lactate). Prior to analysis, the compounds were derivatized using 3-nitrophenylhydrazine. Following separation on a Supelco Discovery HS C18 column, (13)C pyruvate and (13)C lactate were detected using negative electrospray ionization mass spectrometry. Calibration standards (4.5-4500 microM (13)C pyruvate and 9-9000 microM (13)C lactate) and added internal standard were used to make the calibration curves, which were fitted to a non-linear equation y=a+bx+cx(2) and weighted with a weighting factor of 1/y(2). The analytical lower limit of quantification of (13)C pyruvate and (13)C lactate was 4.5 and 9 microM, respectively. The total precision of the method was below 9.2% for (13)C pyruvate and below 5.8% for (13)C lactate. The accuracy of the method showed a relative error less than 2.4% for (13)C pyruvate and less than 6.3% for (13)C lactate. The recoveries were in the range 93-115% for (13)C pyruvate and 70-111% for (13)C lactate. Both substances were stable in protein-free supernatant when stored for up to 3 weeks in a -20 degrees C freezer, during three freeze/thaw cycles, and when stored in an autosampler for at least 30 h.

  16. 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.

  17. A comparison of quantitative methods for clinical imaging with hyperpolarized (13)C-pyruvate.

    PubMed

    Daniels, Charlie J; McLean, Mary A; Schulte, Rolf F; Robb, Fraser J; Gill, Andrew B; McGlashan, Nicholas; Graves, Martin J; Schwaiger, Markus; Lomas, David J; Brindle, Kevin M; Gallagher, Ferdia A

    2016-04-01

    Dissolution dynamic nuclear polarization (DNP) enables the metabolism of hyperpolarized (13)C-labelled molecules, such as the conversion of [1-(13)C]pyruvate to [1-(13)C]lactate, to be dynamically and non-invasively imaged in tissue. Imaging of this exchange reaction in animal models has been shown to detect early treatment response and correlate with tumour grade. The first human DNP study has recently been completed, and, for widespread clinical translation, simple and reliable methods are necessary to accurately probe the reaction in patients. However, there is currently no consensus on the most appropriate method to quantify this exchange reaction. In this study, an in vitro system was used to compare several kinetic models, as well as simple model-free methods. Experiments were performed using a clinical hyperpolarizer, a human 3 T MR system, and spectroscopic imaging sequences. The quantitative methods were compared in vivo by using subcutaneous breast tumours in rats to examine the effect of pyruvate inflow. The two-way kinetic model was the most accurate method for characterizing the exchange reaction in vitro, and the incorporation of a Heaviside step inflow profile was best able to describe the in vivo data. The lactate time-to-peak and the lactate-to-pyruvate area under the curve ratio were simple model-free approaches that accurately represented the full reaction, with the time-to-peak method performing indistinguishably from the best kinetic model. Finally, extracting data from a single pixel was a robust and reliable surrogate of the whole region of interest. This work has identified appropriate quantitative methods for future work in the analysis of human hyperpolarized (13)C data.

  18. Dual resonant birdcage coils for 1H detected 13C microscopic imaging at 11.7 T.

    PubMed

    Hudson, A M; Köckenberger, W; Bowtell, R W

    2000-06-01

    Liquid state, rotating frame cross polarisation experiments are very sensitive to RF field inhomogeneity. In this work, we present an easily fabricated, co-resident high- and low-pass linear birdcage resonator, optimised to perform liquid state rotating frame polarisation transfer at 1H and 13C frequencies. Both the RF fields have been experimentally mapped, and used to validate the spatial signal dependence of a proton detected, 13C image. The predicted performance was then confirmed using PRAWN-based, cyclic J-cross polarisation (CYCLCROP) imaging. A novel variant of a B(1)-field mapping approach is also presented, using the signal enhancement of the CYCLCROP sequence to generate proton detected, 13C field maps.

  19. 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.

  20. 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.

  1. Two models of cross polar cap potential saturation compared: Siscoe-Hill model versus Kivelson-Ridley model

    NASA Astrophysics Data System (ADS)

    Gao, Ye; Kivelson, Margaret G.; Walker, Raymond J.

    2013-02-01

    The cross polar cap potential is considered an instantaneous monitor of the rate at which magnetic flux couples the solar wind to the Earth's magnetosphere-ionosphere system. Studies have shown that the cross polar cap potential responds linearly to the solar wind electric field under nominal solar wind conditions but asymptotes to the order of 200 kV for large electric field. Saturation of the cross polar cap potential is also found to occur in MHD simulations. Several mechanisms have been proposed to explain this phenomenon. Two well-developed models are those of Siscoe et al. (2002), herein referred to as the Siscoe-Hill model, and of Kivelson and Ridley (2008), herein referred to as the Kivelson-Ridley model. In this study, we compare the mathematical formulas as well as the predictions of the two models with data. We find that the two models predict similar saturation limits. Their difference can be expressed in terms of a factor, which is close to unity during a saturation interval. A survey of the differences in the model predictions show that, on average, the potential of the Kivelson-Ridley model is smaller than that of the Siscoe-Hill model by 10 kV. Measurements of AMIE, DMSP, PC index, and SuperDARN are used to differentiate between the two models. However, given the uncertainties of the measurements, it is impossible to conclude that one model does a better job than the other of predicting the observed cross polar cap potentials.

  2. Impact of Recent Laboratory Measurements of the ClOOCl Cross Section On Our Understanding of Polar Ozone Chemistry

    NASA Astrophysics Data System (ADS)

    Canty, T.; Salawitch, R. J.; Stimpfle, R. M.; Wilmouth, D. M.; Anderson, J. G.; von Hobe, M.; Stroh, F.; Rex, M.; Schofield, R.; Kurylo, M.; Sinnhuber, B.; Kinnison, D.

    2008-12-01

    The photolysis of ClOOCl is crucial in determining the rate of polar ozone loss due to the ClO+ClO cycle. Laboratory measurements of the ClOOCl cross section published in 2007 suggest that its photolysis rate is about a factor of six slower than the value used in most computer models. We show that the incorporation of these new cross sections into a photochemical model leads to poor agreement with values of ClO and ClOOCl measured during previous aircraft campaigns. The model under-estimates measured ClO and over- estimates measured ClOOCl by amounts much larger than the measurement uncertainties. These comparisons indicate that a model using the new cross section, and no other changes, provides a poor description of the chlorine photochemistry in the activated polar vortex. Such a simulation also results in much slower ozone loss rates than observed. Interestingly, a 3-D chemical transport model, WACCM, constrained to the slower photolysis rate produces chemical ozone loss rates greater than expected. We will present a summary of our understanding of polar ozone chemistry that builds on a workshop for the SPARC Initiative on the Role of Halogen Chemistry in Polar Stratospheric Ozone Depletion held during summer 2008 in Cambridge, England. We will also describe a new website that is designed to interface future laboratory determinations of the ClOOCl cross section with existing atmospheric measurements of ClO and ClOOCl.

  3. SMMR data set development for GARP. [impact of cross polarization and Faraday rotation on SMMR derived brightness temperatures

    NASA Technical Reports Server (NTRS)

    Kogut, J.

    1981-01-01

    The NIMBUS 7 Scanning Multichannel Microwave Radiometer (SMMR) data are analyzed. The impact of cross polarization and Faraday rotation on SMMR derived brightness temperatures is evaluated. The algorithms used to retrieve the geophysical parameters are tested, refined, and compared with values derived by other techniques. The technical approach taken is described and the results presented.

  4. Spectral density mapping at multiple magnetic fields suitable for 13C NMR relaxation studies

    NASA Astrophysics Data System (ADS)

    Kadeřávek, Pavel; Zapletal, Vojtěch; Fiala, Radovan; Srb, Pavel; Padrta, Petr; Přecechtělová, Jana Pavlíková; Šoltésová, Mária; Kowalewski, Jozef; Widmalm, Göran; Chmelík, Josef; Sklenář, Vladimír; Žídek, Lukáš

    2016-05-01

    Standard spectral density mapping protocols, well suited for the analysis of 15N relaxation rates, introduce significant systematic errors when applied to 13C relaxation data, especially if the dynamics is dominated by motions with short correlation times (small molecules, dynamic residues of macromolecules). A possibility to improve the accuracy by employing cross-correlated relaxation rates and on measurements taken at several magnetic fields has been examined. A suite of protocols for analyzing such data has been developed and their performance tested. Applicability of the proposed protocols is documented in two case studies, spectral density mapping of a uniformly labeled RNA hairpin and of a selectively labeled disaccharide exhibiting highly anisotropic tumbling. Combination of auto- and cross-correlated relaxation data acquired at three magnetic fields was applied in the former case in order to separate effects of fast motions and conformational or chemical exchange. An approach using auto-correlated relaxation rates acquired at five magnetic fields, applicable to anisotropically moving molecules, was used in the latter case. The results were compared with a more advanced analysis of data obtained by interpolation of auto-correlated relaxation rates measured at seven magnetic fields, and with the spectral density mapping of cross-correlated relaxation rates. The results showed that sufficiently accurate values of auto- and cross-correlated spectral density functions at zero and 13C frequencies can be obtained from data acquired at three magnetic fields for uniformly 13C -labeled molecules with a moderate anisotropy of the rotational diffusion tensor. Analysis of auto-correlated relaxation rates at five magnetic fields represents an alternative for molecules undergoing highly anisotropic motions.

  5. Investigating {sup 13}C+{sup 12}C reaction by the activation method. Sensitivity tests

    SciTech Connect

    Chesneanu, Daniela Trache, L.; Margineanu, R.; Pantelica, A.; Ghita, D.; Straticiuc, M.; Burducea, I.; Blebea-Apostu, A. M.; Gomoiu, C. M.; Tang, X.

    2015-02-24

    We have performed experiments to check the limits of sensitivity of the activation method using the new 3 MV Tandetron accelerator and the low and ultra-low background laboratories of the “Horia Hulubei” National Institute of Physics and Nuclear Engineering (IFIN-HH). We have used the {sup 12}C+{sup 13}C reaction at beam energies E{sub lab}= 6, 7 and 8 MeV. The knowledge of this fusion cross section at deep sub-barrier energies is of interest for astrophysical applications, as it provides an upper limit for the fusion cross section of {sup 12}C+{sup 12}C over a wide energy range. A {sup 13}C beam with intensities 0.5–2 particleμA was provided by the accelerator and used to bombard graphite targets, resulting in activation with {sup 24}Na from the {sup 12}C({sup 13}C,p) reaction. The 1369 and 2754 keV gamma-rays from {sup 24}Na de-activation were clearly observed in the spectra obtained in two different laboratories used for measurements at low and ultralow background: one at the surface and one located underground in the Unirea salt mine from Slanic Prahova, Romania. In the underground laboratory, for E{sub lab} = 6 MeV we have measured an activity of 0.085 ± 0.011 Bq, corresponding to cross sections of 1–3 nb. This demonstrates that it is possible to measure {sup 12}C targets irradiated at lower energies for at least 10 times lower cross sections than before β–γ coincidences will lead us another factor of 10 lower, proving that this installations can be successfully used for nuclear astrophysics measurements.

  6. 13C Tracer Studies of Metabolism in Mouse Tumor Xenografts

    PubMed Central

    Lane, Andrew N.; Yan, Jun; Fan, Teresa W-M.

    2015-01-01

    Mice are widely used for human tumor xenograft studies of cancer development and drug efficacy and toxicity. Stable isotope tracing coupled with metabolomic analysis is an emerging approach for assaying metabolic network activity. In mouse models there are several routes of tracer introduction, which have particular advantages and disadvantages that depend on the model and the questions addressed. This protocol describes the bolus i.v. route via repeated tail vein injections of solutions of stable isotope enriched tracers including 13C6-glucose and 13C5,15N2-glutamine. Repeated injections give higher enrichments and over longer labeling periods than a single bolus. Multiple injections of glutamine are necessary to achieve adequate enrichment in engrafted tumors. PMID:26693168

  7. Late pleistocene-recent atmospheric [delta][sup 13]C record in C[sub 4] grasses

    SciTech Connect

    Toolin, L.J. . NSF Accelerator Facility for Radioisotope Analysis); Eastoe, C. . Dept. of Geosciences)

    1993-01-01

    Samples of Setaria species from packrat middens, herbarium specimens and modern plants preserve a record of [delta][sup 13]C of atmospheric CO[sub 2] from 12,600 Bp to the present. No secular trend is detected between 12,600 and 1,800 Bp, when the mean value of [delta][sup 13]C during that period was [minus]6.5 [plus minus] 0.1[per thousand] (the error is the standard deviation of the mean). The value agrees with [delta][sup 13]C averages of pre-industrial CO[sub 2] from polar ice cores, and differs significantly from modern regional ([minus]8.2 [plus minus] 0.1[per thousand]) and global ([minus]7.7[per thousand]) values, which are higher because of fossil fuel burning.

  8. Theory of solid effect and cross effect dynamic nuclear polarization with half-integer high-spin metal polarizing agents in rotating solids.

    PubMed

    Corzilius, Björn

    2016-10-21

    Dynamic nuclear polarization (DNP) is a powerful method to enhance sensitivity especially of solid-state magic-angle spinning (MAS) NMR by up to several orders of magnitude. The increased interest both from a practical as well as theoretical viewpoint has spawned several fields of active research such as the development of new polarizing agents with improved or unique properties and description of the underlying DNP mechanisms such as solid effect (SE) and cross effect (CE). Even though a novel class of unique polarizing agents based on high-spin metal ions such as Gd(iii) and Mn(ii) has already been utilized for MAS DNP a theoretical description of the involved DNP mechanism is still incomplete. Here, we review several aspects of DNP-relevant electron-paramagnetic resonance (EPR) properties of the general class of these half-integer high-spin metal ions with isotropic Zeeman interaction but significant zero-field splitting (ZFS). While the SE can be relatively easily described similar to that of a S = 1/2 system and is assumed to be effective only for polarizing agents featuring a narrow central EPR transitions (i.e., mS = -1/2 → +1/2) with respect to the nuclear Larmor frequency, the CE between two high-spin ions requires a more detailed theoretical investigation due to a multitude of possible transitions and matching conditions. This is especially interesting in light of recent understanding of CE being induced by MAS-driven level anti-crossings (LACs) between dipolar-coupled electron spins. We discuss the requirements of such CE-enabling LACs to occur due to anisotropy of ZFS, the expected adiabaticity, and the resulting possibilities of high-spin metal ion pairs to act as polarizing agents for DNP. This theoretical description serves as a framework for a detailed experimental study published directly following this work.

  9. Use of hyperpolarized [1-13C]pyruvate and [2-13C]pyruvate to probe the effects of the anticancer agent dichloroacetate on mitochondrial metabolism in vivo in the normal rat.

    PubMed

    Hu, Simon; Yoshihara, Hikari A I; Bok, Robert; Zhou, Jenny; Zhu, Minhua; Kurhanewicz, John; Vigneron, Daniel B

    2012-12-01

    Development of hyperpolarized technology utilizing dynamic nuclear polarization has enabled the measurement of (13)C metabolism in vivo at very high signal-to-noise ratio (SNR). In vivo mitochondrial metabolism can, in principle, be monitored with pyruvate, which is catalyzed to acetyl-CoA via pyruvate dehydrogenase (PDH). The purpose of this work was to determine whether the compound sodium dichloroacetate (DCA) could aid the study of mitochondrial metabolism with hyperpolarized pyruvate. DCA stimulates PDH by inhibiting its inhibitor, pyruvate dehydrogenase kinase. In this work, hyperpolarized [1-(13)C]pyruvate and [2-(13)C]pyruvate were used to probe mitochondrial metabolism in normal rats. Increased conversion to bicarbonate (+181±69%, P=.025) was measured when [1-(13)C]pyruvate was injected after DCA administration, and increased glutamate (+74±23%, P=.004), acetoacetate (+504±281%, P=.009) and acetylcarnitine (+377±157%, P=.003) were detected when [2-(13)C]pyruvate was used.

  10. Galactose oxidation using (13)C in healthy and galactosemic children.

    PubMed

    Resende-Campanholi, D R; Porta, G; Ferrioli, E; Pfrimer, K; Ciampo, L A Del; Junior, J S Camelo

    2015-03-01

    Galactosemia is an inborn error of galactose metabolism that occurs mainly as the outcome of galactose-1-phosphate uridyltransferase (GALT) deficiency. The ability to assess galactose oxidation following administration of a galactose-labeled isotope (1-(13)C-galactose) allows the determination of galactose metabolism in a practical manner. We aimed to assess the level of galactose oxidation in both healthy and galactosemic Brazilian children. Twenty-one healthy children and seven children with galactosemia ranging from 1 to 7 years of age were studied. A breath test was used to quantitate (13)CO2 enrichment in exhaled air before and at 30, 60, and 120 min after the oral administration of 7 mg/kg of an aqueous solution of 1-(13)C-galactose to all children. The molar ratios of (13)CO2 and (12)CO2 were quantified by the mass/charge ratio (m/z) of stable isotopes in each air sample by gas-isotope-ratio mass spectrometry. In sick children, the cumulative percentage of (13)C from labeled galactose (CUMPCD) in the exhaled air ranged from 0.03% at 30 min to 1.67% at 120 min. In contrast, healthy subjects showed a much broader range in CUMPCD, with values from 0.4% at 30 min to 5.58% at 120 min. The study found a significant difference in galactose oxidation between children with and without galactosemia, demonstrating that the breath test is useful in discriminating children with GALT deficiencies.

  11. 13C NMR of Nephila clavipes major ampullate silk gland.

    PubMed

    Hijirida, D H; Do, K G; Michal, C; Wong, S; Zax, D; Jelinski, L W

    1996-12-01

    The major ampullate glands of the spider Nephila clavipes contain approximately 0.2 microliter each of a highly concentrated (approximately 50%) solution of silk fibroin. Therefore, the reservoir of silk in these glands presents an ideal opportunity to observe prefolded conformations of a protein in its native state. To this end, the structure and conformation of major ampullate gland silk fibroin within the glands of the spider N. clavipes were examined by 13C NMR spectroscopy. These results were compared to those from silk protein first drawn from the spinneret and then denatured. The 13C NMR chemical shifts, along with infrared and circular dichroism data, suggest that the silk fibroin in the glands exists in dynamically averaged helical conformations. Furthermore, there is no evidence of proline residues in U-(13)C-D-glucose-labeled silk. This transient prefolded "molten fibril" state may correspond to the silk I form found in Bombyx mori silk. There is no evidence of the final beta-sheet structure in the ampullate gland silk fibroin before final silk processing. However, the conformation of silk in the glands appears to be in a highly metastable state, as plasticization with water produces the beta-sheet structure. Therefore, the ducts connecting the ampullate glands to the spinnerets play a larger role in silk processing than previously thought.

  12. Polarization rotation of light propagating through a medium with efficient four-wave mixing and cross-phase modulation

    NASA Astrophysics Data System (ADS)

    Sahoo, Sushree S.; Bhowmick, Arup; Mohapatra, Ashok K.

    2017-03-01

    We have studied the rotation of an elliptically polarized light propagating through thermal rubidium vapor with efficient four-wave mixing (FWM) and cross-phase modulation (XPM). These nonlinear processes are enhanced by Zeeman coherence within the degenerate sub-levels of the two-level atomic system. The elliptically polarized light with small ellipticity is considered as the superposition of a strong-linearly-polarized pump beam and a weak-orthogonal-polarized probe beam. The interference of the probe and the newly generated light field due to degenerate FWM and their gain in the medium due to a large XPM induced by the pump beam leads to the rotation of the elliptical polarized light. A theoretical analysis of the probe propagation through the nonlinear medium was used to explain the experimental observation and the fitting of the experimental data gives the estimates of the third-order non-linear susceptibilities associated with FWM and XPM. Our study can provide useful parameters for the generation of efficient squeezed vacuum states and squeezed polarization states of light. Furthermore our study finds application in controlling the diffraction of a linearly-polarized light beam traversing the medium.

  13. Micron-scale intra-ring analyses of δ13C in early Eocene Arctic wood from Ellesmere Island

    NASA Astrophysics Data System (ADS)

    Schubert, B.; Jahren, H.; Eberle, J.; Sternberg, L.

    2009-12-01

    Early Eocene (ca. 53 Ma) fossil assemblages on Ellesmere Island (75 oN paleolatitude), provide rich information about the plant and animal life of the lush polar ecosystems of the time. Fossil wood recovered from Ellesmere Island is abundant and not permineralized; however, morphological features such as growth rings and resin canals have been obliterated by compression. We report on exceptionally high-resolution intra-ring analyses of δ13C within fossil wood, sampled at ~30 micron intervals across several centimeters of wood sample. Clear patterns in systematic seasonal increases and decreases in wood δ13C allowed us to identify at least 5 annual cycles in the wood. The patterns of increase and decrease in δ13C were consistent with patterns observed for evergreen wood, and distinct from the deciduous patterns we have observed for Metasequoia fossil wood from the middle Eocene (ca. 45 Ma) Arctic site on Axel Heiberg Island. We believe that the high point in the δ13C value of wood seen in each cycle corresponds to the highest environmental temperatures during the annual cycle, as has been seen for modern evergreens (e.g., Barbour et al., 2002). Modern studies have also noted that high temperature periods are correlated with the highest vapor-pressure and soil-water deficits of the annual cycle; these environmental factors would cause the plant to change its discrimination during photosynthesis. We will discuss the relatively low amplitude of δ13C fluctuations (0.5-1.0 ‰) clearly defined by Ellesmere fossil wood, in comparison to observations on modern common evergreens (2.0-4.0 ‰), and speculate that this difference implies greatly dampened seasonal temperature fluctuations in Eocene polar environments, relative to today. Barbour M.M., Walcroft A.S., Farquhar G.D., 2002, Seasonal variation in δ13C and δ18O of cellulose from growth rings of Pinus radiata. Plant, Cell and Environment: v. 25, p. 1483-1499.

  14. Millimeter and submillimeter wave spectra of 13C methylamine

    NASA Astrophysics Data System (ADS)

    Motiyenko, R. A.; Margulès, L.; Ilyushin, V. V.; Smirnov, I. A.; Alekseev, E. A.; Halfen, D. T.; Ziurys, L. M.

    2016-03-01

    Context. Methylamine (CH3NH2) is a light molecule of astrophysical interest, which has an intensive rotational spectrum that extends in the submillimeter wave range and far beyond, even at temperatures characteristic for the interstellar medium. It is likely for 13C isotopologue of methylamine to be identified in astronomical surveys, but there is no information available for the 13CH3NH2 millimeter and submillimeter wave spectra. Aims: In this context, to provide reliable predictions of 13CH3NH2 spectrum in millimeter and submillimeter wave ranges, we have studied rotational spectra of the 13C methylamine isotopologue in the frequency range from 48 to 945 GHz. Methods: The spectrum of 13C methylamine was recorded using conventional absorption spectrometers. The analysis of the rotational spectrum of 13C methylamine in the ground vibrational state was performed on the basis of the group-theoretical high-barrier tunneling Hamiltonian that was developed for methylamine. The available multiple observations of the parent methylamine species toward Sgr B2(N) at 1, 2, and 3 mm using the Submillimeter Telescope and the 12 m antenna of the Arizona Radio Observatory were used to make a search for interstellar 13CH3NH2. Results: In the recorded spectra, we have assigned 2721 rotational transitions that belong to the ground vibrational state of the 13CH3NH2. These measurements were fitted to the Hamiltonian model that uses 75 parameters to achieve an overall weighted rms deviation of 0.73. On the basis of these spectroscopic results, predictions of transition frequencies in the frequency range up to 950 GHz with J ≤ 50 and Ka ≤ 20 are presented. The search for interstellar 13C methylamine in available observational data was not successful and therefore only an upper limit of 6.5 × 1014 cm-2 can be derived for the column density of 13CH3NH2 toward Sgr B2(N), assuming the same source size, temperature, linewidth, and systemic velocity as for parent methylamine isotopic

  15. Optimisation of polarization controlled colour tuning using nanoscale cross-shaped apertures in silver films

    NASA Astrophysics Data System (ADS)

    Balaur, Eugeniu; Sadatnajafi, Catherine; Langley, Daniel; Abbey, Brian

    2016-12-01

    Nanofabrication of metamaterials based on thin metallic films have resulted in a host of different designs that support Extraordinary Optical Transmission (EOT). In contrast to the more widely studied circular-shaped apertures, cross-shaped apertures have characteristics which can be modified in response to linearly polarized light, opening up new pathways for light manipulation at the nanoscale. Here we present a systematic study of the influence of device geometry and composition on the functional characteristics of polarisation controlled optical plasmonic devices. We also discuss some issues that arise using the focused ion beam (FIB) milling technique to fabricate optical metamaterials. In particular, we show that producing high-quality patterns lead to a significant over-deposition of the substrate material. This effect significantly alters the metal surface chemistry, which poses a considerable obstacle for applications involving molecular and bio sensing. This work lays the foundation for the optimisation of the properties of optical plasmonic devices for a wide-range of applications including colour filtering and bio-sensing.

  16. Wavelength Detuning Cross-Beam Energy Transfer Mitigation for Polar Direct Drive and Symmetric Direct Drive

    NASA Astrophysics Data System (ADS)

    Marozas, J. A.; Collins, T. J. B.; McKenty, P. W.; Radha, P. B.; Hohenberger, M.; Rosenberg, M. J.

    2016-10-01

    Cross-beam energy transfer (CBET) results from two-beam energy exchange via stimulated Brillouin scattering, which reduces absorbed light and implosion velocity, alters time-resolved scattered-light spectra, and redistributes absorbed and scattered light. These effects reduce target performance in polar direct drive (PDD) and symmetric direct drive (SDD) at the National Ignition Facility (NIF) and on the OMEGA Laser System. The CBET package (Adaawam) incorporated into the 2-D hydrodynamics code DRACO is an integral part of the 3-D ray-trace package (Mazinisin). Detuning the initial laser wavelength (dλ0) reduces the CBET interaction volume, which can be combined with other mitigation domains (e.g., spatial and temporal). Recent PDD experiments on the NIF explored this option using a cone-swapping technique with dλ0 = +/- 2.34 Å UV, which are compared with DRACO simulations. DRACO simulations of wavelength detuning in SDD on OMEGA predict the expected mitigation using OMEGA's three main amplifier chains in both near-term dλ0 = { - 3 , 0 , + 3 } -Å and long-term dλ0 = { - 6 , 0 , + 6 } -Å UV configurations. The detuning simulations predict improved performance and changes in 2-D and 3-D morphology in both PDD and SDD. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  17. Chemical shift anisotropy and offset effects in cross polarization solid-state NMR spectroscopy.

    PubMed

    Shekar, Srinivasan C; Lee, Dong-Kuk; Ramamoorthy, A

    2002-08-01

    The effect of an offset term in the cross-polarization (CP) Hamiltonian of a heteronuclear spin-12 pair due to off-resonant radio frequency (rf) irradiation and/or chemical shift anisotropy on one of the rf channels is investigated. Analytical solutions, simulations, and experimental results are presented. Formulating the CP spin dynamics in terms of an explicit unitary evolution operator enables the CP period to be inserted as a module in a given pulse scheme regardless of the initial density matrix present. The outcome of post-CP manipulation via pulses can be calculated on the resulting density matrix as the phases and amplitudes of all coherence modes are available. Using these tools it is shown that the offset can be used to reduce the rf power on that channel and the performance is further improved by a post-CP pulse whose flip angle matches and compensates the tilt of the effective field on the offset channel. Experimental investigations on single crystalline and polycrystalline samples of peptides confirm the oscillatory nature of CP dynamics and prove the slowing down of the dynamics under offset and/or mismatch conditions.

  18. Clinical cross-polarization optical coherence tomography assessment of subsurface enamel below dental resin composite restorations

    PubMed Central

    Lenton, Patricia; Rudney, Joel; Fok, Alex; Jones, Robert S.

    2014-01-01

    Abstract. A newly designed intraoral swept source cross-polarization optical coherence tomography (CP-OCT) imaging system was used to examine the integrity of the subsurface enamel below resin composite restorations placed in primary teeth. CP-OCT analysis was performed using images obtained from resin composite restoration in 62 (n=62) pediatric subjects. Clinical examination was performed by a single examiner prior to CP-OCT imaging and analysis. CP-OCT images are presented using a unique combined intensity image, where a false color scale is overlaid on the grayscale intensity image. There was a clear difference in the distribution of the mean-backscattered intensity (mR) between restorations recently placed and those possessing frank cavitation (Student’s t-test, P<0.0001). For mR above 15.49 dB, the sensitivity was 80% and specificity 86%. The Youden index J was 0.8 above 12.3 dB where sensitivity was 100% and specificity was 80%. CP-OCT imaging may be used to confirm the subsurface marginal integrity below resin composite restorations but with careful consideration of limitations of the imaging modality. CP-OCT imaging may be a useful adjunct to clinical visual investigation to confirm that a composite margin has a sound and well-adapted interface. PMID:26158031

  19. Cross-polarization confocal imaging of subsurface flaws in silicon nitride.

    SciTech Connect

    Liu, Z.; Sun, J. G.; Pei, Z.

    2011-03-01

    A cross-polarization confocal microscopy (CPCM) method was developed to image subsurface flaws in optically translucent silicon nitride (Si{sub 3}N{sub 4}) ceramics. Unlike conventional confocal microscopy, which measures reflected light so is applicable only to transparent and semi-transparent materials, CPCM detects scattered light from subsurface while filtering out the reflected light from ceramic surface. For subsurface imaging, the refractive-index mismatch between imaging (air) and imaged (ceramic) medium may cause image distortion and reduce resolution in the depth direction. This effect, characterized by an axial scaling factor (ASF), was analyzed and experimentally determined for glass and Si{sub 3}N{sub 4} materials. The experimental CPCM system was used to image Hertzian C-cracks generated by various indentation loads in the subsurface of a Si{sub 3}N{sub 4} specimen. It was demonstrated that CPCM may provide detailed information of subsurface cracks, such as crack angle and path, and subsurface microstructural variations.

  20. Adsorption of Rhodamine B on two novel polar-modified post-cross-linked resins: Equilibrium and kinetics.

    PubMed

    Jiang, Xiangfu; Huang, Jianhan

    2016-04-01

    We employed two polar monomers, triallyl isocyanurate (TAIC) and butyl acrylate (BA), to copolymerize with divinylbenzene (DVB), and synthesized two starting copolymers labeled PDT and PDB. Then, the Friedel-Crafts alkylation reaction was performed for the two starting copolymers, and the residual pendent vinyl groups were consumed, and hence we obtained two novel polar-modified post-cross-linked resins PDTpc and PDBpc. The surface polarity greatly improved due to introduction of the polar monomers, and the Brunauer-Emmett-Teller (BET) surface area and pore volume significantly increased after the Friedel-Crafts alkylation reaction. Compared with the starting copolymers, the non-polar post-cross-linked resin PDVBpc and some other adsorbents in the references, PDTpc and PDBpc possessed a much enhanced adsorption to Rhodamine B, and the equilibrium capacity reached 578.2mg/g and 328.7mg/g, respectively, at an equilibrium concentration of 100mg/L, and the Freundlich model characterized the equilibrium data very well. The adsorption was a fast process and the kinetic data obeyed the micropore diffusion model. These results confirmed that PDTpc and PDBpc had the potential superiority in adsorptive removal of Rhodamine B from aqueous solution.

  1. Wave-mixing interference in three-photon resonant atomic excitation with cross-polarized angled beams

    SciTech Connect

    Peet, V.

    2006-09-15

    Three-photon excitation and associated wave mixing near the 6s and 6s{sup '} resonances of xenon have been studied utilizing resonance-enhanced multiphoton ionization in angled beams with different polarizations. It has been shown that a complete cancellation of three-photon resonant atomic excitation caused by the well-known destructive wave-mixing interference occurs in s and p polarization of angled beams but distinct resonance ionization enhancement is observed when pump beams have orthogonal polarization planes. Pressure-induced evolution of the resonance ionization peak in cross-polarized beams is identical to that observed with counterpropagating beams. The reason for such resonance ionization enhancement is unknown and cannot be explained within the frame work of existing theory. The effect may result from some peculiarities of wave-mixing interference in a multilevel atomic system, where different degenerate magnetic sublevels of the upper atomic state and multiple interfering excitation processes are involved. Another possibility is that the resonance ionization enhancement results from a process where weak counterpropagating light is generated within the excitation region of cross-polarized angled beams.

  2. In vivo investigation of cardiac metabolism in the rat using MRS of hyperpolarized [1-13C] and [2-13C]pyruvate.

    PubMed

    Josan, Sonal; Park, Jae Mo; Hurd, Ralph; Yen, Yi-Fen; Pfefferbaum, Adolf; Spielman, Daniel; Mayer, Dirk

    2013-12-01

    Hyperpolarized (13)C MRS allows the in vivo assessment of pyruvate dehydrogenase complex (PDC) flux, which converts pyruvate to acetyl-coenzyme A (acetyl-CoA). [1-(13)C]pyruvate has been used to measure changes in cardiac PDC flux, with demonstrated increase in (13)C-bicarbonate production after dichloroacetate (DCA) administration. With [1-(13)C]pyruvate, the (13)C label is released as (13 CO2 /(13)C-bicarbonate, and, hence, does not allow us to follow the fate of acetyl-CoA. Pyruvate labeled in the C2 position has been used to track the (13)C label into the TCA (tricarboxylic acid) cycle and measure [5-(13)C]glutamate as well as study changes in [1-(13)C]acetylcarnitine with DCA and dobutamine. This work investigates changes in the metabolic fate of acetyl-CoA in response to metabolic interventions of DCA-induced increased PDC flux in the fed and fasted state, and increased cardiac workload with dobutamine in vivo in rat heart at two different pyruvate doses. DCA led to a modest increase in the (13)C labeling of [5-(13)C]glutamate, and a considerable increase in [1-(13)C]acetylcarnitine and [1,3-(13)C]acetoacetate peaks. Dobutamine resulted in an increased labeling of [2-(13)C]lactate, [2-(13)C]alanine and [5-(13)C]glutamate. The change in glutamate with dobutamine was observed using a high pyruvate dose but not with a low dose. The relative changes in the different metabolic products provide information about the relationship between PDC-mediated oxidation of pyruvate and its subsequent incorporation into the TCA cycle compared with other metabolic pathways. Using a high dose of pyruvate may provide an improved ability to observe changes in glutamate.

  3. Cross-splicing method for compensating fiber birefringence in polarization-maintaining fiber ring laser mode locked by nonlinear polarization evolution.

    PubMed

    Wang, Yunzheng; Zhang, Liqiang; Zhuo, Zhuang; Guo, Songzhen

    2016-07-20

    We propose a cross-splicing method, for the first time to our knowledge, to compensate the effect of fiber birefringence in a polarization-maintaining fiber ring laser mode locked by nonlinear polarization evolution. This method has been investigated numerically and experimentally. The results indicate that stable mode-locking pulses can be obtained in the cavity with this method; otherwise, no mode-locking states are achieved. The design processes of the laser cavity are presented. Pulses with single pulse energy of 2.1 nJ are generated at pump power of 460 mW. The spectral bandwidth and pulse duration are 17.5 nm and 11.7 ps, respectively. The tunability of the laser is also studied. The central wavelength can be tuned from 1023.2 to 1045.9 nm.

  4. The 13C(α,n) reaction and its role as a neutron source for the s process

    NASA Astrophysics Data System (ADS)

    Heil, M.; Detwiler, R.; Azuma, R. E.; Couture, A.; Daly, J.; Görres, J.; Käppeler, F.; Reifarth, R.; Tischhauser, P.; Ugalde, C.; Wiescher, M.

    2008-08-01

    The 13C(α,n)16O reaction constitutes the dominant neutron source for the main s process, which operates at a thermal energy of kT=8 keV. Since the cross section at stellar energies is very small, the reaction rate cannot be directly determined and has to be extrapolated from cross section results obtained at higher energies. To remove various discrepancies in the normalization of previous data sets and to subsequently improve the reliability of the extrapolation, we performed measurements of the 13C(α,n)16O reaction in the energy range Ec.m.=320-700 keV. In addition, the double differential scattering cross section 13C(α,α)13C was measured in the energy range Elab=2.6-6.2 MeV for 28 angles. These data were used to constrain possible contributions from background resonances for a reliable extrapolation with the multichannel R-matrix code SAMMY. As a result, the uncertainties were significantly reduced, and a reaction rate of (4.6±1.0)×10-14 cm3/moles at kT=8 keV (T=0.1×109 K) was determined.

  5. 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.

  6. Reconstructing past climate using a multi-specific 13C-approach

    NASA Astrophysics Data System (ADS)

    Ferrio, Juan Pedro; Aguilera, Mónica; Voltas, Jordi

    2010-05-01

    Carbon isotope composition (δ13C) in tree-rings has become routinely used in palaeoclimatic research for the assessment of changes in water availability in seasonally dry climates. Long tree-ring chronologies, however, are relatively scarce, whereas the original climate signal of wood δ13C is usually well preserved in fossil charcoal [1, 4] Accordingly, charcoal δ13C records are an alternative to classic dendroclimatology to characterize past changes in water availability (e.g. precipitation). In this work, we explore the potential for palaeoenvironmental research of two co-occuring Mediterranean species with contrasting strategies to cope with drought [2]: Aleppo pine (Pinus halepensis Mill.) and holm oak (Quercus ilex L.). We hypothesize that the differential sensitivity of pine and oak to climate variables can be exploited to refine palaeoclimate reconstructions based on δ13C in wood or charcoal. For this purpose, we put together published tree-core-δ13C data from 40 sites across Spain [2, 3] and new δ13C data from 15 sites where both species co-existed in mixed stands. The sites were selected to represent the range of variation in thermal and precipitation regimes for these species, while avoiding any correlation between precipitation and temperature across sites. Five dominant or codominant trees were selected per site, and microcores including the most recently formed tree rings were obtained with a Trephor tool [5]. Fragments were oven-dried at 60 ° C for 48 h and milled separately to a fine powder using a ball mill (Retsch MM301, Haan, Germany) for δ13C analysis. Current meteorological data (monthly estimates of air mean temperature (minimum, mean and maximum), precipitation and solar radiation) was obtained from the Digital Climatic Atlas of the Iberian Peninsula (http://opengis.uab.es/wms/iberia/index.htm) (spatial resolution of 200 m). A family of models (either linear or exponential) best predicting monthly and annual precipitation from δ13C

  7. (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.

  8. 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

  9. 13C metabolic flux analysis in complex systems.

    PubMed

    Zamboni, Nicola

    2011-02-01

    Experimental determination of in vivo metabolic rates by methods of (13)C metabolic flux analysis is a pivotal approach to unravel structure and regulation of metabolic networks, in particular with microorganisms grown in minimal media. However, the study of real-life and eukaryotic systems calls for the quantification of fluxes also in cellular compartments, rich media, cell-wide metabolic networks, dynamic systems or single cells. These scenarios drastically increase the complexity of the task, which is only partly dealt by existing approaches that rely on rigorous simulations of label propagation through metabolic networks and require multiple labeling experiments or a priori information on pathway inactivity to simplify the problem. Albeit qualitative and largely driven by human interpretation, statistical analysis of measured (13)C-patterns remains the exclusive alternative to comprehensively handle such complex systems. In the future, this practice will be complemented by novel modeling frameworks to assay particular fluxes within a network by stable isotopic tracer for targeted validation of well-defined hypotheses.

  10. Glucogenesis in an insect, Manduca sexta L., estimated from the 13C isotopomer distribution in trehalose synthesized from [1,3-13C2]glycerol.

    PubMed

    Thompson, S N

    1997-07-19

    Glucogenesis from [3-13C]alanine and [1,3-13C2]glycerol was demonstrated in the insect Manduca sexta by examining the 13C enrichment of trehalose, a non-reducing disaccharide of glucose synthesized in the insect fat body and released into the blood or hemolymph. In insects maintained on a low carbohydrate diet, trehalose synthesized from [3-13C]alanine was selectively enriched at C1 and C6, and C2 and C5. The 13C-labelling pattern indicated the carboxylation of [3-13C]pyruvate, formed by transamination of the [3-13C]alanine followed by randomization of the label at the fumarate step of the tricarboxylic acid cycle and glucose synthesis via the gluconeogenic pathway. 13C enrichment of trehalose was absent in similarly maintained insect larvae administered 3-mercaptopicolinic acid, an inhibitor of hepatic phosphoenolpyruvate carboxykinase. Insects on the low carbohydrate diet also synthesized trehalose from [1,3-13C2]glycerol. 13C multiplets were observed in trehalose C3 and C4 demonstrating the synthesis of three 13C enriched glucose isotopomers from the 13C-labelled glycerol. The relative contributions of 13C-labelled glycerol and unlabelled 3 carbon substrates to the synthesis of the 13C enriched trehalose isotopomers were determined from the multiplet structure at C3, and calculation of minimal rates of glucogenesis were based on the 13C enrichment of C4. The C4/C3 13C enrichment ratio in trehalose synthesized from [1,3-13C2]glycerol was close to unity, and total glucogenesis was calculated after estimation of the expected contribution of unlabelled trehalose synthesis from 3 carbon substrates by comparison of the ratio of unlabelled and labelled contributions to the 13C enriched trehalose isotopomers with the 13C enrichment of [1,3-13C2]glycerol-3-phosphate. The estimated total rates of glucogenesis varied from 0.33 to 2.80 micromol glucose/g fresh weight/h. The blood sugar level of M. sexta was also highly variable. Although the potential importance of

  11. Heteronuclear cross-polarization in multinuclear multidimensional NMR: Prospects for triple-resonance CP

    SciTech Connect

    Majumdar, A.; Zuiderweg, E.R.P.

    1994-12-01

    Heteronuclear multiple-pulse-based Cross Polarization (HECP) between scalar coupled spins is gaining an important role in high-resolution multidimensional NMR of isotopically labeled biomolecules, especially in experiments involving net magnetization transfer. It has generally been observed that in these situations, the performance of HECP is superior to that of INEPT-based sequences. In particular, HECP-based three-dimensional HCCH spectroscopy is more efficient than the INEPT version of the same experiment. Differences in sensitivity have been intuitively attributed to relaxation effects and technical factors such as radiofrequency (rf) inhomogeneity We present theoretical analyses and computer simulations to probe the effects of these factors. Relaxation effects were treated phenomenologically; we found that relaxation differences are relatively small (up to 25%) between pulsed-free-precession (INEPT) and HECP-although always in favor of HECP. We explored the rf effects by employing a Gaussian distribution of rf amplitude over sample volume. We found that inhomogeneity effects significantly favor HECP over INEPT, especially under conditions of {open_quotes}matched {close_quotes} inhomogeneity in the two rf coils. The differences in favor of HECP indicate that an extension of HECP to triple resonance experiments (TRCP) in I -> S -> Q net transfers might yield better results relative to analogous INEPT-based net transfers. We theoretically analyze the possibilities of TRCP and find that transfer functions are critically dependent on the ratio J{sub IS}/J{sub SQ}. When J{sub IS} equals J{sub SQ}, we find that 100% transfer is possible for truly simultaneous TRCP and this transfer is obtained in a time 1.41 /J. The TRCP time requirement compares favorably with optimally concatenated INEPT-transfers, where net transfer I -> S -> Q is complete at 1.5 /J.

  12. Preparation of four-photon polarization-entangled decoherence-free states employing weak cross-Kerr nonlinearities

    NASA Astrophysics Data System (ADS)

    Xiu, Xiao-Ming; Li, Qing-Yang; Lin, Yan-Fang; Dong, Hai-Kuan; Dong, Li; Gao, Ya-Jun

    2016-10-01

    With the assistance of weak cross-Kerr nonlinearities, we present a preparation scheme of four-photon polarization-entangled decoherence-free states, which can be used to construct the minimal optical decoherence-free subspaces where a logical qubit is fully protected against collective decoherence. To complete the preparation task, one spatial entanglement process, two polarization entanglement processes, and one detecting process are applied. The fulfillments of the above processes are contributed by a cross-Kerr nonlinear interaction between the signal photons and a coherent state via Kerr media. Exploiting the available single-photon resource and simple linear optics elements, this scheme is feasible and desirable to be extended to the construction of multiphoton decoherence-free states against the collective decoherence.

  13. Measuring changes in substrate utilization in the myocardium in response to fasting using hyperpolarized [1-13C]butyrate and [1-13C]pyruvate

    PubMed Central

    Bastiaansen, Jessica A. M.; Merritt, Matthew E.; Comment, Arnaud

    2016-01-01

    Cardiac dysfunction is often associated with a shift in substrate preference for ATP production. Hyperpolarized (HP) 13C magnetic resonance spectroscopy (MRS) has the unique ability to detect real-time metabolic changes in vivo due to its high sensitivity and specificity. Here a protocol using HP [1-13C]pyruvate and [1-13C]butyrate is used to measure carbohydrate versus fatty acid metabolism in vivo. Metabolic changes in fed and fasted Sprague Dawley rats (n = 36) were studied at 9.4 T after tail vein injections. Pyruvate and butyrate competed for acetyl-CoA production, as evidenced by significant changes in [13C]bicarbonate (−48%), [1-13C]acetylcarnitine (+113%), and [5-13C]glutamate (−63%), following fasting. Butyrate uptake was unaffected by fasting, as indicated by [1-13C]butyrylcarnitine. Mitochondrial pseudoketogenesis facilitated the labeling of the ketone bodies [1-13C]acetoacetate and [1-13C]β-hydroxybutyryate, without evidence of true ketogenesis. HP [1-13C]acetoacetate was increased in fasting (250%) but decreased during pyruvate co-injection (−82%). Combining HP 13C technology and co-administration of separate imaging agents enables noninvasive and simultaneous monitoring of both fatty acid and carbohydrate oxidation. This protocol illustrates a novel method for assessing metabolic flux through different enzymatic pathways simultaneously and enables mechanistic studies of the changing myocardial energetics often associated with disease. PMID:27150735

  14. Influence of collision energy and reagent rotation on the cross sections and product polarizations of the reaction F+ HCl

    NASA Astrophysics Data System (ADS)

    Duan, Zhi Xin; Li, Wen Liang; Qiu, Ming Hui

    2012-04-01

    Quasiclassical trajectory calculations have been carried out for the F+HCl reaction in three dimensions on a recent DHSN PES of the ground 12A' electronic state [M. P. Deskevich, M. Y. Hayes, K. Takahashi, R. T. Skodje, and D. J. Nesbitt, J. Chem. Phys. 124, 224303 (2006)]. The effects of the collision energy and the reagent initial rotational excitation on the cross sections and product polarization are studied for the v = 0 and j ⩽ 10 states of HCl over a wide collision energy range. It has been found that either the collision energy or the HCl rotational excitation increase remarkably reaction cross sections. The QCT-calculated integral cross sections are in good agreement with previous QM results. A detailed study on product polarization for the title reaction is also performed. The calculated results show that the product rotational angular momentum j' is not only aligned, but also oriented along the direction perpendicular to the scattering plane. The orientation of the HF product rotational angular momentum vector j' depends very sensitively on the collision energy and also affected by the reagent rotation. The theoretical findings and especially the roles of the collision energy and initial rotational momentum on the product polarization are discussed and reasonably explained by the HLH mass combination, the property of the PES, as well as the reactive mechanism.

  15. Influence of collision energy and reagent rotation on the cross sections and product polarizations of the reaction F + HCl.

    PubMed

    Duan, Zhi Xin; Li, Wen Liang; Qiu, Ming Hui

    2012-04-14

    Quasiclassical trajectory calculations have been carried out for the F+HCl reaction in three dimensions on a recent DHSN PES of the ground 1(2)A' electronic state [M. P. Deskevich, M. Y. Hayes, K. Takahashi, R. T. Skodje, and D. J. Nesbitt, J. Chem. Phys. 124, 224303 (2006)]. The effects of the collision energy and the reagent initial rotational excitation on the cross sections and product polarization are studied for the v = 0 and j ≤ 10 states of HCl over a wide collision energy range. It has been found that either the collision energy or the HCl rotational excitation increase remarkably reaction cross sections. The QCT-calculated integral cross sections are in good agreement with previous QM results. A detailed study on product polarization for the title reaction is also performed. The calculated results show that the product rotational angular momentum j' is not only aligned, but also oriented along the direction perpendicular to the scattering plane. The orientation of the HF product rotational angular momentum vector j' depends very sensitively on the collision energy and also affected by the reagent rotation. The theoretical findings and especially the roles of the collision energy and initial rotational momentum on the product polarization are discussed and reasonably explained by the HLH mass combination, the property of the PES, as well as the reactive mechanism.

  16. Luminescence dynamics and {sup 13}C NMR characteristics of dinuclear complexes exhibiting coupled lanthanide(III) cation pairs

    SciTech Connect

    Matthews, K.D.; Bailey-Folkes, S.A.; Kahwa, I.A.

    1992-08-20

    Luminescence and cross-polarization magic angle spinning (CP-MAS) {sup 13}C NMR properties of lanthanide dinuclear macrocyclic complexes of a compartmental Schiff base chelate (1) derived from the condensation of 2,6-diformyl-p-cresol and 3,6-dioxa-1,8-octanediamine are reported. The Schiff base chromophore in 1 is a strong light absorber and an efficient sensitizer for intense Tb{sup 3+}({sup 5}D{sub 4}) and Eu{sup 3+}({sup 5}D{sub 0})(T < 110 K ) emission which does not exhibit self-quenching effects. Emission from Tb{sup 3+} is sensitized by the ligand singlet state; in striking contrast, Eu{sup 3+} emission is sensitized by the triplet state and reveals an unusual nonradiative quenching process at T > 110 K with a thermal barrier of {approx} 2300 cm{sup {minus}1}. Weak emission is observed from Dy{sup 3+}({sup 4}F{sub 9/2}), Sm{sup 3+}({sup 4}G{sub 5/2}), and Pr{sup 3+}({sup 1}D{sub 2}) diluted in Gd{sup 3+} (i.e., from Gd{sup 3+}-Ln{sup 3+} heteropairs, Ln = Pr, Sm, Dy). Intramolecular metal-metal (Ln-Ln = 4 {Angstrom}) interactions account for the greatly quenched emission from Sm{sup 3+}-Sm{sup 3+} and Dy{sup 3+}-Dy{sup 3+} homopairs compared to Gd{sup 3+}-Ln heteropairs (Ln = Sm, Dy). Gd{sup 3+}-Ln{sup 3+} emission lifetimes at 77 K are 1610 (Tb{sup 3+}), 890 (Eu{sup 3+}), 14 (Dy{sup 3+}) and {approx} 13 {mu}s (Sm{sup 3+}). Nonradiative relaxation processes at 77 K in dilute Ln{sup 3+}:Gd{sub 2}1(NO{sub 3}){sub 4}{center_dot}H{sub 2}O, being temperature independent for Sm{sup 3+} and Eu{sup 3+} but temperature dependent for Tb{sup 3+}, follow the energy gap law with {alpha} {approx} - 10{sup {minus}3} cm and B {approx} 2 x 10{sup 8} s{sup {minus}1}. CP-MAS data show paramagnetic broadening of {sup 13}C resonances which increases with the magnetic moment of Ln{sup 3+}. Surprisingly, no significant shifts in resonance positions corresponding to the changing nature of paramagnetic Ln{sup 3+} ions are observed. 43 refs., 8 figs., 2 tabs.

  17. Improved ground state and ν12 = 1 state rovibrational constants for ethylene-13C2 (13C2H4)

    NASA Astrophysics Data System (ADS)

    Gabona, M. G.; Tan, T. L.

    2014-05-01

    The Fourier transform infrared (FTIR) absorption spectrum of the ν12 fundamental band of ethylene-13C2 (13C2H4) was recorded in the frequency range of 1350-1550 cm-1 with unapodized resolution of 0.0063 cm-1. Improved upper state (ν12 = 1) rovibrational constants consisting of three rotational, five quartic and five sextic constants were derived by assigning and fitting 1731 infrared transitions using Watson's A-reduced Hamiltonian in the Ir representation. The root-mean-square deviation of the fit was 0.00030 cm-1. More higher-order upper state (ν12 = 1) constant were derived in the present analysis than previously reported. Improved ground state rovibrational constants were also determined from the fit of 1104 ground state combination differences (GSCD) with a root-mean-square deviation of 0.00029 cm-1. The A-type ν12 band centered at 1436.65409 ± 0.00002 cm-1 has a calculated inertial defect Δ12 is 0.242896 ± 0.000007 μÅ2. No indications of perturbation were found in the analysis of the band.

  18. High-throughput hyperpolarized 13C metabolic investigations using a multi-channel acquisition system

    NASA Astrophysics Data System (ADS)

    Lee, Jaehyuk; Ramirez, Marc S.; Walker, Christopher M.; Chen, Yunyun; Yi, Stacey; Sandulache, Vlad C.; Lai, Stephen Y.; Bankson, James A.

    2015-11-01

    Magnetic resonance imaging and spectroscopy of hyperpolarized (HP) compounds such as [1-13C]-pyruvate have shown tremendous potential for offering new insight into disease and response to therapy. New applications of this technology in clinical research and care will require extensive validation in cells and animal models, a process that may be limited by the high cost and modest throughput associated with dynamic nuclear polarization. Relatively wide spectral separation between [1-13C]-pyruvate and its chemical endpoints in vivo are conducive to simultaneous multi-sample measurements, even in the presence of a suboptimal global shim. Multi-channel acquisitions could conserve costs and accelerate experiments by allowing acquisition from multiple independent samples following a single dissolution. Unfortunately, many existing preclinical MRI systems are equipped with only a single channel for broadband acquisitions. In this work, we examine the feasibility of this concept using a broadband multi-channel digital receiver extension and detector arrays that allow concurrent measurement of dynamic spectroscopic data from ex vivo enzyme phantoms, in vitro anaplastic thyroid carcinoma cells, and in vivo in tumor-bearing mice. Throughput and the cost of consumables were improved by up to a factor of four. These preliminary results demonstrate the potential for efficient multi-sample studies employing hyperpolarized agents.

  19. Impact of Gd3+ doping and glassing solvent deuteration on 13C DNP at 5 Tesla

    NASA Astrophysics Data System (ADS)

    Kiswandhi, Andhika; Lama, Bimala; Niedbalski, Peter; Goderya, Mudrekh; Long, Joanna; Lumata, Lloyd

    Dynamic nuclear polarization (DNP) is a technique which can be used to amplify signals in nuclear magnetic resonance (NMR) and magnetic resonance imaging (MRI) by several thousand-fold. The most commonly available DNP system typically operates at the W-band field or 3.35 T, at which it has been shown that 13C NMR signal can be enhanced by deuteration and Gd3+ doping. In this work, we have investigated the applicability of these procedures at 5 T. Our results indicate that the deuteration of the glassing matrix still yields an enhancement of 13C DNP when 4-oxo-TEMPO free radical is used. The effect is attributed to the lower heat load of the deuterons compared to protons. An addition of a trace amount of Gd3+ gives a modest enhancement of the signal when trityl OX063 is used, albeit with a less pronounced relative enhancement compared to the results obtained at 3.35 T. The results suggest that the enhancement obtained via Gd3+ doping may become saturated at higher field. These results will be discussed using a thermodynamic model of DNP. This work is supported by US Dept of Defense Award No. W81XWH-14-1-0048 and Robert A. Welch Foundation Grant No. AT-1877.

  20. 13C Metabolomics: NMR and IROA for Unknown Identification

    PubMed Central

    Clendinen, Chaevien S.; Stupp, Gregory S.; Wang, Bing; Garrett, Timothy J.; Edison, Arthur S.

    2016-01-01

    Abstract: Background Isotopic Ratio Outlier Analysis (IROA) is an untargeted metabolomics method that uses stable isotopic labeling and LC-HRMS for identification and relative quantification of metabolites in a biological sample under varying experimental conditions. Objective We demonstrate a method using high-sensitivity 13C NMR to identify an unknown metabolite isolated from fractionated material from an IROA LC-HRMS experiment. Methods IROA samples from the nematode Caenorhabditis elegans were fractionated using LC-HRMS using 5 repeated injections and collecting 30 sec fractions. These were concentrated and analyzed by 13C NMR. Results We isotopically labeled samples of C. elegans and collected 2 adjacent LC fractions. By HRMS, one contained at least 2 known metabolites, phenylalanine and inosine, and the other contained tryptophan and an unknown feature with a monoisotopic mass of m/z 380.0742 [M+H]+. With NMR, we were able to easily verify the known compounds, and we then identified the spin system networks responsible for the unknown resonances. After searching the BMRB database and comparing the molecular formula from LC-HRMS, we determined that the fragments were a modified anthranilate and a glucose modified by a phosphate. We then performed quantum chemical NMR chemical shift calculations to determine the most likely isomer, which was 3’-O-phospho-β-D-glucopyranosyl-anthranilate. This compound had previously been found in the same organism, validating our approach. Conclusion We were able to dereplicate previously known metabolites and identify a metabolite that was not in databases by matching resonances to NMR databases and using chemical shift calculations to determine the correct isomer. This approach is efficient and can be used to identify unknown compounds of interest using the same material used for IROA. PMID:28090435

  1. 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

  2. 1H, 13C and 15N NMR assignments of phenazopyridine derivatives.

    PubMed

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

    2005-03-01

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

  3. The First in Vivo Observation of 13C- 15N Coupling in Mammalian Brain

    NASA Astrophysics Data System (ADS)

    Kanamori, Keiko; Ross, Brian D.

    2001-12-01

    [5-13C,15N]Glutamine, with 1J(13C-15N) of 16 Hz, was observed in vivo in the brain of spontaneously breathing rats by 13C MRS at 4.7 T. The brain [5-13C]glutamine peak consisted of the doublet from [5-13C,15N]glutamine and the center [5-13C,14N]glutamine peak, resulting in an apparent triplet with a separation of 8 Hz. The time course of formation of brain [5-13C,15N]glutamine was monitored in vivo with a time resolution of 20-35 min. This [5-13C,15N]glutamine was formed by glial uptake of released neurotransmitter [5-13C]glutamate and its reaction with 15NH3 catalyzed by the glia-specific glutamine synthetase. The neurotransmitter glutamate C5 was selectively13C-enriched by intravenous [2,5-13C]glucose infusion to 13C-label whole-brain glutamate C5, followed by [12C]glucose infusion to chase 13C from the small and rapidly turning-over glial glutamate pool, leaving 13C mainly in the neurotransmitter [5-13C]glutamate pool, which is sequestered in vesicles until release. Hence, the observed [5-13C,15N]glutamine arises from a coupling between 13C of neuronal origin and 15N of glial origin. Measurement of the rate of brain [5-13C,15N]glutamine formation provides a novel noninvasive method of studying the kinetics of neurotransmitter uptake into glia in vivo, a process that is crucial for protecting the brain from glutamate excitotoxicity.

  4. Application of (13)C ramp CPMAS NMR with phase-adjusted spinning sidebands (PASS) for the quantitative estimation of carbon functional groups in natural organic matter.

    PubMed

    Ikeya, Kosuke; Watanabe, Akira

    2016-01-01

    The composition of carbon (C) functional groups in natural organic matter (NOM), such as dissolved organic matter, soil organic matter, and humic substances, is frequently estimated using solid-state (13)C NMR techniques. A problem associated with quantitative analysis using general cross polarization/magic angle spinning (CPMAS) spectra is the appearance of spinning side bands (SSBs) split from the original center peaks of sp (2) hybridized C species (i.e., aromatic and carbonyl C). Ramp CP/phase-adjusted side band suppressing (PASS) is a pulse sequence that integrates SSBs separately and quantitatively recovers them into their inherent center peaks. In the present study, the applicability of ramp CP/PASS to NOM analysis was compared with direct polarization (DPMAS), another quantitative method but one that requires a long operation time, and/or a ramp CP/total suppression side band (ramp CP/TOSS) technique, a popular but non-quantitative method for deleting SSBs. The test materials were six soil humic acid samples with various known degrees of aromaticity and two fulvic acids. There were no significant differences in the relative abundance of alkyl C, O-alkyl C, and aromatic C between the ramp CP/PASS and DPMAS methods, while the signal intensities corresponding to aromatic C in the ramp CP/TOSS spectra were consistently less than the values obtained in the ramp CP/PASS spectra. These results indicate that ramp CP/PASS can be used to accurately estimate the C composition of NOM samples.

  5. Measurement of local, internal magnetic fluctuations via cross-polarization scattering in the DIII-D tokamak (invited).

    PubMed

    Barada, K; Rhodes, T L; Crocker, N A; Peebles, W A

    2016-11-01

    We present new measurements of internal magnetic fluctuations obtained with a novel eight channel cross polarization scattering (CPS) system installed on the DIII-D tokamak. Measurements of internal, localized magnetic fluctuations provide a window on an important physics quantity that we heretofore have had little information on. Importantly, these measurements provide a new ability to challenge and test linear and nonlinear simulations and basic theory. The CPS method, based upon the scattering of an incident microwave beam into the opposite polarization by magnetic fluctuations, has been significantly extended and improved over the method as originally developed on the Tore Supra tokamak. A new scattering geometry, provided by a unique probe beam, is utilized to improve the spatial localization and wavenumber range. Remotely controllable polarizer and mirror angles allow polarization matching and wavenumber selection for a range of plasma conditions. The quasi-optical system design, its advantages and challenges, as well as important physics validation tests are presented and discussed. Effect of plasma beta (ratio of kinetic to magnetic pressure) on both density and magnetic fluctuations is studied and it is observed that internal magnetic fluctuations increase with beta. During certain quiescent high confinement operational regimes, coherent low frequency modes not detected by magnetic probes are detected locally by CPS diagnostics.

  6. Measurement of local, internal magnetic fluctuations via cross-polarization scattering in the DIII-D tokamak (invited)

    NASA Astrophysics Data System (ADS)

    Barada, K.; Rhodes, T. L.; Crocker, N. A.; Peebles, W. A.

    2016-11-01

    We present new measurements of internal magnetic fluctuations obtained with a novel eight channel cross polarization scattering (CPS) system installed on the DIII-D tokamak. Measurements of internal, localized magnetic fluctuations provide a window on an important physics quantity that we heretofore have had little information on. Importantly, these measurements provide a new ability to challenge and test linear and nonlinear simulations and basic theory. The CPS method, based upon the scattering of an incident microwave beam into the opposite polarization by magnetic fluctuations, has been significantly extended and improved over the method as originally developed on the Tore Supra tokamak. A new scattering geometry, provided by a unique probe beam, is utilized to improve the spatial localization and wavenumber range. Remotely controllable polarizer and mirror angles allow polarization matching and wavenumber selection for a range of plasma conditions. The quasi-optical system design, its advantages and challenges, as well as important physics validation tests are presented and discussed. Effect of plasma beta (ratio of kinetic to magnetic pressure) on both density and magnetic fluctuations is studied and it is observed that internal magnetic fluctuations increase with beta. During certain quiescent high confinement operational regimes, coherent low frequency modes not detected by magnetic probes are detected locally by CPS diagnostics.

  7. 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.

  8. Thermal Degradation studies of nitroplasticized estane 5703 utilizing [sup 13] C enriched model polymers.

    SciTech Connect

    Wrobleski, Debra A.; Langlois, D. A.; Orler, E. B.; Schoonover, J. R.; Osborn, J. C.; Small, J. H.

    2002-01-01

    Predicting the lifetime of PBX 9501 is critical to assurance of the reliability of the nuclear weapons stockpile. Ln support of the Lifetime Prediction Model, we have been investigating the physical and chemical aging processes that can potentially affect the lifetime of PBX 9501. Surveillance data of stockpile PBX 9501 binder have shown a decrease in Estane molecular weight as a fiinction of age. Estane is a poly(ester urethane) consisting of poly(buly1ene adipate) as the flexible soft segment and 4,4{prime}-methylenediphenyl-1,1{prime}-diisocyanate (MDI) chain extended with 1,4-butanediol (BDO) as the rigid hard segment efforts have focused on chemical reactions that may cause chain scission of Estane through hydrolytic degradation of the polyester soft segments. Thermal aging of Estane in the absence of water shows no signs of hydrolytic degradation, whereas, appearance of high molecular weight species has been observed for Estane aged at elevated temperatures in the presence of nitroplasticizer. These high molecular weight species are most likely due to branching reactions that eventually leads to formation of an insoluble, cross-linked gel. While the mechanisms of hydrolytic degradation of polyesters has been addressed, the degradations reactions of poly(ester urethane) (PESU) in the presence of NP are not well understood. We have prepared a series of isotopically enriched PESU model compounds chemically similar to Estane for aging experiments in order to understand possible cross-linking mechanisms. Changes in physical properties are observed with less than 1% chemical cross-linking. Isotopic enrichment of 13C from 1.1 % natural abundance to 100% improves the sensitivity of spectroscopic techniques so that small quantities of degradation products can be observed. Because degradation reaction mechanisms of importance may occur at the hard segment portion of the polymer, we have prepared 13C PESU with 13C labeled at the methylene carbon. These model polymers

  9. New optical analyzer for 13C-breath test

    NASA Astrophysics Data System (ADS)

    Harde, Hermann; Dressler, Matthias; Helmrich, Günther; Wolff, Marcus; Groninga, Hinrich

    2008-04-01

    Medical breath tests are well established diagnostic tools, predominantly for gastroenterological inspections, but also for many other examinations. Since the composition and concentration of exhaled volatile gases reflect the physical condition of a patient, a breath analysis allows one 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 is based on photoacoustic spectroscopy and uses a DFB diode laser at 2.744 μm. The concentration ratio of the CO II isotopologues is determined by measuring the absorption on a 13CO II line in comparison to a 12CO II line. In the specially selected spectral range the lines have similar strengths, although the concentrations differ by a factor of 90. Therefore, the signals are well comparable. Due to an excellent signal-noise-ratio isotope variations of less than 1% can be resolved as required for the breath test.

  10. How to measure a complete set of polarization-dependent differential cross sections in a scattering experiment with aligned reagents?

    PubMed

    Wang, Fengyan; Lin, Jui-San; Liu, Kopin

    2014-02-28

    Polarization-dependent differential cross section (PDDCS) is one of the three-vector correlations (k, k('), j) in molecular collisions, which provides the most detailed insights into the steric requirements of chemical reactions, i.e., how the reactivity depends on the polarization of reagents. Only quite recently has such quantity been fully realized experimentally in the study of the reaction of the aligned CHD3(v1 = 1, |jK⟩ = |10⟩) molecules with Cl((2)P3/2) atoms. Theoretically, PDDCS is a relatively new concept; experimental realization of the theoretical construct requires some careful considerations that are not readily available in the literature. Here, we present the "know-how" behind the full PDDCS measurements to fill the gaps and to provide a clear roadmap for future applications. To make the connection apparent between the methodology presented here and the stereodynamics revealed in previous reports, the same Cl + aligned CHD3 reaction is used for illustration.

  11. Chemical shift powder spectra enhanced by multiple-contact cross-polarization under slow magic-angle spinning.

    PubMed

    Raya, Jésus; Perrone, Barbara; Hirschinger, Jérôme

    2013-02-01

    A simple multiple-contact cross-polarization (CP) scheme is applied to a powder sample of ferrocene and β-calcium formate under static and magic-angle spinning (MAS) conditions. The method is described analytically through the density matrix formalism. We show that multiple equilibrations-re-equilibrations with the proton spin bath improves the polarization transfer efficiency at short contact times and provides higher signal enhancements than state-of-the art techniques such as adiabatic passage through the Hartmann-Hahn condition CP (APHH-CP) when MAS is applied. The resulting chemical shift powder spectra then are identical to the ones obtained by using ROtor-Directed Exchange of Orientations CP (APHH-RODEO-CP) with intensity gains of a factor 1.1-1.3.

  12. Chemical shift powder spectra enhanced by multiple-contact cross-polarization under slow magic-angle spinning

    NASA Astrophysics Data System (ADS)

    Raya, Jésus; Perrone, Barbara; Hirschinger, Jérôme

    2013-02-01

    A simple multiple-contact cross-polarization (CP) scheme is applied to a powder sample of ferrocene and β-calcium formate under static and magic-angle spinning (MAS) conditions. The method is described analytically through the density matrix formalism. We show that multiple equilibrations-re-equilibrations with the proton spin bath improves the polarization transfer efficiency at short contact times and provides higher signal enhancements than state-of-the art techniques such as adiabatic passage through the Hartmann-Hahn condition CP (APHH-CP) when MAS is applied. The resulting chemical shift powder spectra then are identical to the ones obtained by using ROtor-Directed Exchange of Orientations CP (APHH-RODEO-CP) with intensity gains of a factor 1.1-1.3.

  13. HYPERPOLARIZED 13C MAGNETIC RESONANCE AND ITS USE IN METABOLIC ASSESSMENT OF CULTURED CELLS AND PERFUSED ORGANS

    PubMed Central

    Lumata, Lloyd; Yang, Chendong; Ragavan, Mukundan; Carpenter, Nicholas; DeBerardinis, Ralph J.; Merritt, Matthew E.

    2016-01-01

    Diseased tissue is often characterized by abnormalities in intermediary metabolism. Observing these alterations in situ may lead to an improved understanding of pathological processes and novel ways to monitor these processes non-invasively in human patients. Although 13C is a stable isotope safe for use in animal models of disease as well as human subjects, its utility as a metabolic tracer has largely been limited to ex vivo analyses employing analytical techniques like mass spectrometry or nuclear magnetic resonance spectroscopy. Neither of these techniques is suitable for non-invasive metabolic monitoring, and the low abundance and poor gyromagnetic ratio of conventional 13C make it a poor nucleus for imaging. However, the recent advent of hyperpolarization methods, particularly dynamic nuclear polarization (DNP), make it possible to enhance the spin polarization state of 13C by many orders of magnitude, resulting in a temporary amplification of the signal sufficient for monitoring kinetics of enzyme-catalyzed reactions in living tissue through magnetic resonance spectroscopy or magnetic resonance imaging. Here we review DNP techniques to monitor metabolism in cultured cells, perfused hearts, and perfused livers, focusing on our experiences with hyperpolarized [1-13C]pyruvate. We present detailed approaches to optimize the DNP procedure, streamline biological sample preparation, and maximize detection of specific metabolic activities. We also discuss practical aspects in the choice of metabolic substrates for hyperpolarization studies, and outline some of the current technical and conceptual challenges in the field, including efforts to use hyperpolarization to quantify metabolic rates in vivo. PMID:26358902

  14. 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.

  15. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2014 CFR

    2014-07-01

    ... 40 Protection of Environment 31 2014-07-01 2014-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  16. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2010 CFR

    2010-07-01

    ... 40 Protection of Environment 30 2010-07-01 2010-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  17. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2012 CFR

    2012-07-01

    ... 40 Protection of Environment 32 2012-07-01 2012-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  18. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2011 CFR

    2011-07-01

    ... 40 Protection of Environment 31 2011-07-01 2011-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  19. 40 CFR 721.6505 - Polymers of C13C15 oxoalcohol ethoxolates.

    Code of Federal Regulations, 2013 CFR

    2013-07-01

    ... 40 Protection of Environment 32 2013-07-01 2013-07-01 false Polymers of C13C15 oxoalcohol... Specific Chemical Substances § 721.6505 Polymers of C13C15 oxoalcohol ethoxolates. (a) Chemical substance... polymers of C13C15 oxoalcohol ethoxolates (PMNs P-96-950/951) are subject to reporting under this...

  20. Area per lipid and cholesterol interactions in membranes from separated local-field (13)C NMR spectroscopy.

    PubMed

    Leftin, Avigdor; Molugu, Trivikram R; Job, Constantin; Beyer, Klaus; Brown, Michael F

    2014-11-18

    Investigations of lipid membranes using NMR spectroscopy generally require isotopic labeling, often precluding structural studies of complex lipid systems. Solid-state (13)C magic-angle spinning NMR spectroscopy at natural isotopic abundance gives site-specific structural information that can aid in the characterization of complex biomembranes. Using the separated local-field experiment DROSS, we resolved (13)C-(1)H residual dipolar couplings that were interpreted with a statistical mean-torque model. Liquid-disordered and liquid-ordered phases were characterized according to membrane thickness and average cross-sectional area per lipid. Knowledge of such structural parameters is vital for molecular dynamics simulations, and provides information about the balance of forces in membrane lipid bilayers. Experiments were conducted with both phosphatidylcholine (dimyristoylphosphatidylcholine (DMPC) and palmitoyloleoylphosphatidylcholine (POPC)) and egg-yolk sphingomyelin (EYSM) lipids, and allowed us to extract segmental order parameters from the (13)C-(1)H residual dipolar couplings. Order parameters were used to calculate membrane structural quantities, including the area per lipid and bilayer thickness. Relative to POPC, EYSM is more ordered in the ld phase and experiences less structural perturbation upon adding 50% cholesterol to form the lo phase. The loss of configurational entropy is smaller for EYSM than for POPC, thus favoring its interaction with cholesterol in raftlike lipid systems. Our studies show that solid-state (13)C NMR spectroscopy is applicable to investigations of complex lipids and makes it possible to obtain structural parameters for biomembrane systems where isotope labeling may be prohibitive.

  1. Longitudinal double-spin asymmetry and cross section for inclusive jet production in polarized proton collisions at square root of s = 200 GeV.

    PubMed

    Abelev, B I; Aggarwal, M M; Ahammed, Z; Amonett, J; Anderson, B D; Anderson, M; Arkhipkin, D; Averichev, G S; Bai, Y; Balewski, J; Barannikova, O; Barnby, L S; Baudot, J; Bekele, S; Belaga, V V; Bellingeri-Laurikainen, A; Bellwied, R; Benedosso, F; Bhardwaj, S; Bhasin, A; Bhati, A K; Bichsel, H; Bielcik, J; Bielcikova, J; Bland, L C; Blyth, S-L; Bonner, B E; Botje, M; Bouchet, J; Brandin, A V; Bravar, A; Burton, T P; Bystersky, M; Cadman, R V; Cai, X Z; Caines, H; Sánchez, M Calderón de la Barca; Castillo, J; Catu, O; Cebra, D; Chajecki, Z; Chaloupka, P; Chattopadhyay, S; Chen, H F; Chen, J H; Cheng, J; Cherney, M; Chikanian, A; Christie, W; Coffin, J P; Cormier, T M; Cosentino, M R; Cramer, J G; Crawford, H J; Das, D; Das, S; Dash, S; Daugherity, M; de Moura, M M; Dedovich, T G; Dephillips, M; Derevschikov, A A; Didenko, L; Dietel, T; Djawotho, P; Dogra, S M; Dong, W J; Dong, X; Draper, J E; Du, F; Dunin, V B; Dunlop, J C; Mazumdar, M R Dutta; Eckardt, V; Edwards, W R; Efimov, L G; Emelianov, V; Engelage, J; Eppley, G; Erazmus, B; Estienne, M; Fachini, P; Fatemi, R; Fedorisin, J; Filip, P; Finch, E; Fine, V; Fisyak, Y; Fu, J; Gagliardi, C A; Gaillard, L; Ganti, M S; Ghazikhanian, V; Ghosh, P; Gonzalez, J E; Gorbunov, Y G; Gos, H; Grebenyuk, O; Grosnick, D; Guertin, S M; Guimaraes, K S F F; Gupta, N; Gutierrez, T D; Haag, B; Hallman, T J; Hamed, A; Harris, J W; He, W; Heinz, M; Henry, T W; Hepplemann, S; Hippolyte, B; Hirsch, A; Hjort, E; Hoffman, A M; Hoffmann, G W; Horner, M J; Huang, H Z; Huang, S L; Hughes, E W; Humanic, T J; Igo, G; Jacobs, P; Jacobs, W W; Jakl, P; Jia, F; Jiang, H; Jones, P G; Judd, E G; Kabana, S; Kang, K; Kapitan, J; Kaplan, M; Keane, D; Kechechyan, A; Khodyrev, V Yu; Kim, B C; Kiryluk, J; Kisiel, A; Kislov, E M; Klein, S R; Kocoloski, A; Koetke, D D; Kollegger, T; Kopytine, M; Kotchenda, L; Kouchpil, V; Kowalik, K L; Kramer, M; Kravtsov, P; Kravtsov, V I; Krueger, K; Kuhn, C; Kulikov, A I; Kumar, A; Kuznetsov, A A; Lamont, M A C; Landgraf, J M; Lange, S; LaPointe, S; Laue, F; Lauret, J; Lebedev, A; Lednicky, R; Lee, C-H; Lehocka, S; LeVine, M J; Li, C; Li, Q; Li, Y; Lin, G; Lin, X; Lindenbaum, S J; Lisa, M A; Liu, F; Liu, H; Liu, J; Liu, L; Liu, Z; Ljubicic, T; Llope, W J; Long, H; Longacre, R S; Love, W A; Lu, Y; Ludlam, T; Lynn, D; Ma, G L; Ma, J G; Ma, Y G; Magestro, D; Mahapatra, D P; Majka, R; Mangotra, L K; Manweiler, R; Margetis, S; Markert, C; Martin, L; Matis, H S; Matulenko, Yu A; McClain, C J; McShane, T S; Melnick, Yu; Meschanin, A; Millane, J; Miller, M L; Minaev, N G; Mioduszewski, S; Mironov, C; Mischke, A; Mishra, D K; Mitchell, J; Mohanty, B; Molnar, L; Moore, C F; Morozov, D A; Munhoz, M G; Nandi, B K; Nattrass, C; Nayak, T K; Nelson, J M; Netrakanti, P K; Nogach, L V; Nurushev, S B; Odyniec, G; Ogawa, A; Okorokov, V; Oldenburg, M; Olson, D; Pachr, M; Pal, S K; Panebratsev, Y; Panitkin, S Y; Pavlinov, A I; Pawlak, T; Peitzmann, T; Perevoztchikov, V; Perkins, C; Peryt, W; Phatak, S C; Picha, R; Planinic, M; Pluta, J; Poljak, N; Porile, N; Porter, J; Poskanzer, A M; Potekhin, M; Potrebenikova, E; Potukuchi, B V K S; Prindle, D; Pruneau, C; Putschke, J; Rakness, G; Raniwala, R; Raniwala, S; Ray, R L; Razin, S V; Reinnarth, J; Relyea, D; Ridiger, A; Ritter, H G; Roberts, J B; Rogachevskiy, O V; Romero, J L; Rose, A; Roy, C; Ruan, L; Russcher, M J; Sahoo, R; Sakuma, T; Salur, S; Sandweiss, J; Sarsour, M; Sazhin, P S; Schambach, J; Scharenberg, R P; Schmitz, N; Seger, J; Selyuzhenkov, I; Seyboth, P; Shabetai, A; Shahaliev, E; Shao, M; Sharma, M; Shen, W Q; Shimanskiy, S S; Sichtermann, E P; Simon, F; Singaraju, R N; Smirnov, N; Snellings, R; Sood, G; Sorensen, P; Sowinski, J; Speltz, J; Spinka, H M; Srivastava, B; Stadnik, A; Stanislaus, T D S; Stock, R; Stolpovsky, A; Strikhanov, M; Stringfellow, B; Suaide, A A P; Sugarbaker, E; Sumbera, M; Sun, Z; Surrow, B; Swanger, M; Symons, T J M; Szanto de Toledo, A; Tai, A; Takahashi, J; Tang, A H; Tarnowsky, T; Thein, D; Thomas, J H; Timmins, A R; Timoshenko, S; Tokarev, M; Trainor, T A; Trentalange, S; Tribble, R E; Tsai, O D; Ulery, J; Ullrich, T; Underwood, D G; Buren, G Van; van der Kolk, N; van Leeuwen, M; Molen, A M Vander; Varma, R; Vasilevski, I M; Vasiliev, A N; Vernet, R; Vigdor, S E; Viyogi, Y P; Vokal, S; Voloshin, S A; Waggoner, W T; Wang, F; Wang, G; Wang, J S; Wang, X L; Wang, Y; Watson, J W; Webb, J C; Westfall, G D; Wetzler, A; Whitten, C; Wieman, H; Wissink, S W; Witt, R; Wood, J; Wu, J; Xu, N; Xu, Q H; Xu, Z; Yepes, P; Yoo, I-K; Yurevich, V I; Zhan, W; Zhang, H; Zhang, W M; Zhang, Y; Zhang, Z P; Zhao, Y; Zhong, C; Zoulkarneev, R; Zoulkarneeva, Y; Zubarev, A N; Zuo, J X

    2006-12-22

    We report a measurement of the longitudinal double-spin asymmetry A(LL) and the differential cross section for inclusive midrapidity jet production in polarized proton collisions at square root of s = 200 GeV. The cross section data cover transverse momenta 5 < pT < 50 GeV/c and agree with next-to-leading order perturbative QCD evaluations. The A(LL) data cover 5 < pT < 17 GeV/c and disfavor at 98% C.L. maximal positive gluon polarization in the polarized nucleon.

  2. Enhancing the [13C]bicarbonate signal in cardiac hyperpolarized [1-13C]pyruvate MRS studies by infusion of glucose, insulin and potassium.

    PubMed

    Lauritzen, Mette Hauge; Laustsen, Christoffer; Butt, Sadia Asghar; Magnusson, Peter; Søgaard, Lise Vejby; Ardenkjær-Larsen, Jan Henrik; Åkeson, Per

    2013-11-01

    A change in myocardial metabolism is a known effect of several diseases. MRS with hyperpolarized (13)C-labelled pyruvate is a technique capable of detecting changes in myocardial pyruvate metabolism, and has proven to be useful for the evaluation of myocardial ischaemia in vivo. However, during fasting, the myocardial glucose oxidation is low and the fatty acid oxidation (β-oxidation) is high, which complicates the interpretation of pyruvate metabolism with the technique. The aim of this study was to investigate whether the infusion of glucose, insulin and potassium (GIK) could increase the myocardial glucose oxidation in the citric acid cycle, reflected as an increase in the [(13)C]bicarbonate signal in cardiac hyperpolarized [1-(13)C]pyruvate MRS measurements in fasted rats. Two groups of rats were infused with two different doses of GIK and investigated by MRS after injection of hyperpolarized [1-(13)C]pyruvate. No [(13)C]bicarbonate signal could be detected in the fasted state. However, a significant increase in the [(13)C]bicarbonate signal was observed by the infusion of a high dose of GIK. This study demonstrates that a high [(13)C]bicarbonate signal can be achieved by GIK infusion in fasted rats. The increased [(13)C]bicarbonate signal indicates an increased flux of pyruvate through the pyruvate dehydrogenase enzyme complex and an increase in myocardial glucose oxidation through the citric acid cycle.

  3. 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.

  4. 13C DYNAMIC NUCLEAR POLARIZATION: AN ALTERNATIVE DETECTOR FOR RECYCLED-FLOW NMR EXPERIMENTS. (R824871)

    EPA Science Inventory

    The perspectives, information and conclusions conveyed in research project abstracts, progress reports, final reports, journal abstracts and journal publications convey the viewpoints of the principal investigator and may not represent the views and policies of ORD and EPA. Concl...

  5. Geochemical Approach to Archaeal Ecology: δ13C of GDGTs

    NASA Astrophysics Data System (ADS)

    Lichtin, S.; Warren, C.; Pearson, A.; Pagani, M.

    2015-12-01

    Over the last decade and a half, glycerol dialkyl glycerol tetraethers (GDGTs) have increasingly been used to reconstruct environmental temperatures; proxies like TEX86 that correlate the relative abundance of these archaeal cell membrane lipids to sea surface temperature are omnipresent in paleoclimatology literature. While it has become common to make claims about past temperatures using GDGTs, our present understanding of the organisms that synthesize the compounds is still quite limited. The generally accepted theory states that microorganisms like the Thaumarchaeota modify the structure of membrane lipids to increase intermolecular interactions, strengthening the membrane at higher temperatures. Yet to date, culture experiments have been largely restricted to a single species, Nitrosopumilus maritimes, and recent studies on oceanic archaeal rRNA have revealed that these biomarkers are produced in diverse, heterogeneous, and site-specific communities. This brings up questions as to whether different subclasses of GDGTs, and all subsequent proxies, represent adaptation within a single organismal group or a shift in community composition. To investigate whether GDGTs with different chain structures, from the simple isoprenoidal GDGT-0 to Crenarchaeol with its many cyclopentane groups, are sourced from archaea with similar or disparate metabolic pathways—and if that information is inherited in GDGTs trapped in marine sediments—this study examines the stable carbon isotope values (δ13C) of GDGTs extracted from the uppermost meters of sediment in the Orca Basin, Gulf of Mexico, using spooling-wire microcombustion isotope-ratio mass spectrometer (SWiM-IRMS), tackling a fundamental assumption of the TEX86 proxy that influences the way we perceive the veracity of existing temperature records.

  6. Polarized fluorescence depletion reports orientation distribution and rotational dynamics of muscle cross-bridges.

    PubMed Central

    Bell, Marcus G; Dale, Robert E; van der Heide, Uulke A; Goldman, Yale E

    2002-01-01

    The method of polarized fluorescence depletion (PFD) has been applied to enhance the resolution of orientational distributions and dynamics obtained from fluorescence polarization (FP) experiments on ordered systems, particularly in muscle fibers. Previous FP data from single fluorescent probes were limited to the 2(nd)- and 4(th)-rank order parameters, and , of the probe angular distribution (beta) relative to the fiber axis and , a coefficient describing the extent of rapid probe motions. We applied intense 12-micros polarized photoselection pulses to transiently populate the triplet state of rhodamine probes and measured the polarization of the ground-state depletion using a weak interrogation beam. PFD provides dynamic information describing the extent of motions on the time scale between the fluorescence lifetime (e.g., 4 ns) and the duration of the photoselection pulse and it potentially supplies information about the probe angular distribution corresponding to order parameters above rank 4. Gizzard myosin regulatory light chain (RLC) was labeled with the 6-isomer of iodoacetamidotetramethylrhodamine and exchanged into rabbit psoas muscle fibers. In active contraction, dynamic motions of the RLC on the PFD time scale were intermediate between those observed in relaxation and rigor. The results indicate that previously observed disorder of the light chain region in contraction can be ascribed principally to dynamic motions on the microsecond time scale. PMID:12124286

  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. Methods for metabolic evaluation of prostate cancer cells using proton and 13C HR-MAS spectroscopy and [3-13C] pyruvate as a metabolic substrate

    PubMed Central

    Levin, Yakir S.; Albers, Mark J.; Butler, Thomas N.; Spielman, Daniel; Peehl, Donna M.; Kurhanewicz, John

    2009-01-01

    Prostate cancer has been shown to undergo unique metabolic changes associated with neoplastic transformation, with associated changes in citrate, alanine, and lactate concentrations. 13C HR-MAS spectroscopy provides an opportunity to simultaneously investigate the metabolic pathways implicated in these changes by using 13C labeled substrates as metabolic probes. In this work, a method to reproducibly interrogate metabolism in prostate cancer cells in primary culture was developed using HR-MAS spectroscopy. Optimization of cell culture protocols, labeling parameters, harvesting, storage, and transfer was performed. Using [3-13C] pyruvate as a metabolic probe, 1H and 13C HR-MAS spectroscopy were used to quantify the net amount and fractional enrichment of several labeled metabolites that evolved in multiple cell samples from each of five different prostate cancers. Average enrichment across all cancers was 32.4±5.4% for [3-13C] alanine, 24.5±5.4% for [4-13C] glutamate, 9.1±2.5% for [3-13C] glutamate, 25.2±5.7% for [3-13C] aspartate, and 4.2±1.0% for [3-13C] lactate. Cell samples from the same parent population demonstrated reproducible fractional enrichments of alanine, glutamate, and aspartate to within 12%, 10%, and 10%, respectively. Furthermore, the cells produced a significant amount of [4-13C] glutamate, which supports the bioenergetic theory for prostate cancer. These methods will allow further characterization of metabolic properties of prostate cancer cells in the future. PMID:19780158

  9. Determination of fructose metabolic pathways in normal and fructose-intolerant children: A sup 13 C NMR study using (U- sup 13 C)fructose

    SciTech Connect

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

    1990-07-01

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

  10. Investigation of the elastic and inelastic scattering of α-particles from 13C in the energy range 26.6-65MeV

    NASA Astrophysics Data System (ADS)

    Burtebayev, N.; Sakhiyev, S. K.; Janseitov, D. M.; Kerimkulov, Zh.; Alimov, D.; Danilov, A. N.

    2016-09-01

    We have measured the differential cross-sections for the elastic and inelastic scattering of α-particles on 13C target at the isochronous cyclotron U-150 M INP Republic of Kazakhstan. The beam energies of α-particles were 29MeV and 50MeV. As a result of research we obtained new experimental data for the α + 13C elastic scattering and inelastic one leading to the 3.68 (3/2-), 6.86 (5/2+) and 7.5 (5/2-)MeV excited states of 13C nucleus. The experimental results on elastic scattering were analyzed within the framework of the optical model using Woods-Saxon potential and the double folding one. The theoretical calculations for the concerned excited states were performed using the coupled channel (CC) method. The optimal deformation parameters for the excited states of 13C nucleus were extracted.

  11. PAIN with and without PAR: variants for third-spin assisted heteronuclear polarization transfer.

    PubMed

    Agarwal, Vipin; Sardo, Mariana; Scholz, Ingo; Böckmann, Anja; Ernst, Matthias; Meier, Beat H

    2013-08-01

    In this article, we describe third-spin assisted heteronuclear recoupling experiments, which play an increasingly important role in measuring long-range heteronuclear couplings, in particular (15)N-(13)C, in proteins. In the proton-assisted insensitive nuclei cross polarization (PAIN-CP) experiment (de Paëpe et al. in J Chem Phys 134:095101, 2011), heteronuclear polarization transfer is always accompanied by homonuclear transfer of the proton-assisted recoupling (PAR) type. We present a phase-alternating experiment that promotes heteronuclear (e.g. (15)N → (13)C) polarization transfer while simultaneously minimizing homonuclear (e.g.(13)C → (13)C) transfer (PAIN without PAR). This minimization of homonuclear polarization transfer is based on the principle of the resonant second-order transfer (RESORT) recoupling scheme where the passive proton spins are irradiated by a phase-alternating sequence and the modulation frequency is matched to an integer multiple of the spinning frequency. The similarities and differences between the PAIN-CP and this het-RESORT experiment are discussed here.

  12. Real-time Fluorescence Polarization Microscopy of the Moving Boundary in Cross-Gradient SDS-PAGE

    NASA Astrophysics Data System (ADS)

    Hwang, Jeeseong; Giulian, Gary

    2003-03-01

    Real-time Fluorescence Polarization Microscopy of the Moving Boundary in Cross-Gradient SDS-PAGE Jeeseong Hwang, Jeffrey R. Krogmeier, Angela M. Bardo, Scott N. Goldie, Lori S. Goldner; Optical Technology Division, National Institute of Standards and Technology, Gaithersburg, MD 20899 Gary G. Giulian, Carl R. Merril; National Institute of Mental Health, National Institutes of Health, Bethesda, MD 20892 Sodium Dodecyl Sulfate Polyacrylamide Gel Electrophoresis (SDS-PAGE) is a popular method to separate proteins by their apparent molecular weight. However, it is a limited technique due, in part, to its low spatial resolution. In order to improve the resolution and to enhance the detection sensitivity of proteins separated by SDS-PAGE we are studying the detergent properties at the moving boundary of precast Tris-Tricine-Acetate cross-gradient gels using fluorescent cationic and pH indicating dyes. We have developed real-time full-field fluorescence polarization microscopy to monitor the dynamic fluorescence anisotropy from the cationic tetramethylindocarbocyanine dyes localized in the "extended stack", a concentrated detergent zone. We will present quantitative results of the fluorescence anisotropy. Our system is capable of analyzing local structures of the detergent molecules in the moving boundary of SDS-PAGE and the microenvironment(s) near the boundary. We will discuss the significance of these results and their potential role in enhanced protein separation.

  13. (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.

  14. 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.

  15. Local deposition of 13C tracer in the JET MKII-HD divertor

    NASA Astrophysics Data System (ADS)

    Likonen, Jari; Airila, M. I.; Coad, J. P.; Hakola, A.; Koivuranta, S.; Ahonen, E.; Alves, E.; Barradas, N.; Widdowson, A.; Rubel, M.; Brezinsek, S.; Groth, M.; JET-EFDA Contributors

    2013-07-01

    Migration and deposition of 13C have been investigated at JET by injecting 13C-labelled methane at the outer divertor base at the end of the 2009 campaign. The 13C deposition profile was measured with enhanced proton scattering (EPS) and secondary ion mass spectrometry (SIMS) techniques. A strong toroidal deposition band for 13C was observed experimentally on each of the analysed four outer divertor floor tiles. In addition, 13C was also found on the vertical edge of load bearing tile (LBT) and at the bottom of the LBT tile facing the puffing hole. Local 13C migration in the vicinity of the injection location was modelled by the ERO code. The ERO simulations also produced the strong toroidal 13C deposition band but there is strong deposition also on the vertical edge of the LBT tile and elsewhere on the horizontal part of the outer divertor floor tile.

  16. Propionate metabolism in the rat heart by 13C n.m.r. spectroscopy.

    PubMed Central

    Sherry, A D; Malloy, C R; Roby, R E; Rajagopal, A; Jeffrey, F M

    1988-01-01

    High-resolution 13C n.m.r. spectroscopy has been used to examine propionate metabolism in the perfused rat heart. A number of tricarboxylic acid (TCA) cycle intermediates are observable by 13C n.m.r. in hearts perfused with mixtures of pyruvate and propionate. When the enriched 13C-labelled nucleus originates with pyruvate, the resonances of the intermediates appear as multiplets due to formation of multiply-enriched 13C-labelled isotopomers, whereas when the 13C-labelled nucleus originates with propionate, these same intermediates appear as singlets in the 13C spectrum since entry of propionate into the TCA cycle occurs via succinyl-CoA. An analysis of the isotopomer populations in hearts perfused with [3-13C]pyruvate plus unlabelled propionate indicates that about 27% of the total pyruvate pool available to the heart is derived directly from unlabelled propionate. This was substantiated by perfusing a heart for 2 h with [3-13C]propionate as the only available exogenous substrate. Under these conditions, all of the propionate consumed by the heart, as measured by conventional chemical analysis, ultimately entered the oxidative pathway as [2-13C] or [3-13C]pyruvate. This is consistent with entry of propionate into the TCA cycle intermediate pools as succinyl-CoA and concomitant disposal of malate to pyruvate via the malic enzyme. 13C resonances arising from enriched methylmalonate and propionylcarnitine are also detected in hearts perfused with [3-13C] or [1-13C]propionate which suggests that 13C n.m.r. may be useful as a non-invasive probe in vivo of metabolic abnormalities involving the propionate pathway, such as methylmalonic aciduria or propionic acidaemia. PMID:3178775

  17. Proton-detected 3D (1)H/(13)C/(1)H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz.

    PubMed

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-28

    A proton-detected 3D (1)H/(13)C/(1)H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of (13)C-(1)H connectivities, and proximities of (13)C-(1)H and (1)H-(1)H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including (1)H-(1)H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protons and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) (1)H/(1)H and 2D (13)C/(1)H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of (1)H-(1)H proximity and (13)C-(1)H connectivity. In addition, the 2D (F1/F2) (1)H/(13)C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of (1)H-(1)H dipolar couplings, enables the measurement of proximities between (13)C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of (1)H-(1)H-(13)C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ⋅ H2O ⋅ HCl demonstrate the efficiency of the 3D experiment.

  18. Proton-detected 3D 1H/13C/1H correlation experiment for structural analysis in rigid solids under ultrafast-MAS above 60 kHz

    NASA Astrophysics Data System (ADS)

    Zhang, Rongchun; Nishiyama, Yusuke; Ramamoorthy, Ayyalusamy

    2015-10-01

    A proton-detected 3D 1H/13C/1H chemical shift correlation experiment is proposed for the assignment of chemical shift resonances, identification of 13C-1H connectivities, and proximities of 13C-1H and 1H-1H nuclei under ultrafast magic-angle-spinning (ultrafast-MAS) conditions. Ultrafast-MAS is used to suppress all anisotropic interactions including 1H-1H dipolar couplings, while the finite-pulse radio frequency driven dipolar recoupling (fp-RFDR) pulse sequence is used to recouple dipolar couplings among protons and the insensitive nuclei enhanced by polarization transfer technique is used to transfer magnetization between heteronuclear spins. The 3D experiment eliminates signals from non-carbon-bonded protons and non-proton-bonded carbons to enhance spectral resolution. The 2D (F1/F3) 1H/1H and 2D 13C/1H (F2/F3) chemical shift correlation spectra extracted from the 3D spectrum enable the identification of 1H-1H proximity and 13C-1H connectivity. In addition, the 2D (F1/F2) 1H/13C chemical shift correlation spectrum, incorporated with proton magnetization exchange via the fp-RFDR recoupling of 1H-1H dipolar couplings, enables the measurement of proximities between 13C and even the remote non-carbon-bonded protons. The 3D experiment also gives three-spin proximities of 1H-1H-13C chains. Experimental results obtained from powder samples of L-alanine and L-histidine ṡ H2O ṡ HCl demonstrate the efficiency of the 3D experiment.

  19. Characterization of uniformly and atom-specifically 13C-labeled heparin and heparan sulfate polysaccharide precursors using 13C NMR spectroscopy and ESI mass spectrometry

    PubMed Central

    Nguyen, Thao K. N.; Tran, Vy M.; Victor, Xylophone V.; Skalicky, Jack J.; Kuberan, Balagurunathan

    2010-01-01

    The biological actions of heparin and heparan sulfate, two structurally related glycosaminoglycans, depend on the organization of the complex heparanome. Due to the structural complexity of the heparanome, the sequence of variably sulfonated uronic acid and glucosamine residues is usually characterized by the analysis of smaller oligosaccharide and disaccharide fragments. Even characterization of smaller heparin/heparan sulfate oligosaccharide or disaccharide fragments using simple 1D 1H NMR spectroscopy is often complicated by the extensive signal overlap. 13C NMR signals, on the other hand, overlap less and therefore, 13C NMR spectroscopy can greatly facilitate the structural elucidation of the complex heparanome and provide finer insights into the structural basis for biological functions. This is the first report of the preparation of anomeric carbon-specific 13C-labeled heparin/heparan sulfate precursors from the Escherichia coli K5 strain. Uniformly 13C- and 15N-labeled precursors were also produced and characterized by 13C NMR spectroscopy. Mass spectrometric analysis of enzymatically fragmented disaccharides revealed that anomeric carbon-specific labeling efforts resulted in a minor loss/scrambling of 13C in the precursor backbone, whereas uniform labeling efforts resulted in greater than 95% 13C isotope enrichment in the precursor backbone. These labeled precursors provided high-resolution NMR signals with great sensitivity and set the stage for studying the heparanome–proteome interactions. PMID:20832774

  20. 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

  1. A novel polar-modified post-cross-linked resin: Effect of the porogens on the structure and adsorption performance.

    PubMed

    Wang, Xiaomei; Fu, Zhenyu; Yu, Na; Huang, Jianhan

    2016-03-15

    The porogens used in the polymerization play important roles in the structure and adsorption performance for the polar-modified post-cross-linked resins. A series of novel polar-modified post-cross-linked resins were prepared using different mass percentage of toluene and 3-methyl-1-butanol as the mixed porogens. The results indicated that the resins using a higher mass percentage of toluene in the mixed porogens possessed a higher content of pendent vinyl groups, the greater Brunauer-Emmett-Teller (BET) surface area and t-plot micropore surface area. What's more, the Friedel-Crafts alkylation reaction induced a higher increment of the BET surface area and t-plot micropore surface area before and after the post-cross-linking. The resin p(GMA-co-DVB)-22-pc using 50% (w/w) of toluene and 50% (w/w) of 3-methyl-1-butanol in the mixed porogens held the largest equilibrium capacity to phenol among the four considered resins. The equilibrium data was well characterized by the Freundlich model and the isosteric enthalpy decreased dramatically with increasing of the fractional loading. The resin using a lower mass percentage of toluene in the mixed porogens required less time to reach equilibrium because of its less micropores and the minor diffusion resistance in the pores. p(GMA-co-DVB)-22-pc exhibited a dynamic saturated capacity of 55.4 mg/mL wet resin at an initial concentration of 1250 mg/L and a flow rate of 1.4 mL/min, and it could be completely regenerated by 0.001 mol/L of sodium hydroxide (w/v) and 80% of ethanol (v/v).

  2. 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.

  3. Local and bulk 13C hyperpolarization in nitrogen-vacancy-centred diamonds at variable fields and orientations

    PubMed Central

    Álvarez, Gonzalo A.; Bretschneider, Christian O.; Fischer, Ran; London, Paz; Kanda, Hisao; Onoda, Shinobu; Isoya, Junichi; Gershoni, David; Frydman, Lucio

    2015-01-01

    Polarizing nuclear spins is of fundamental importance in biology, chemistry and physics. Methods for hyperpolarizing 13C nuclei from free electrons in bulk usually demand operation at cryogenic temperatures. Room temperature approaches targeting diamonds with nitrogen-vacancy centres could alleviate this need; however, hitherto proposed strategies lack generality as they demand stringent conditions on the strength and/or alignment of the magnetic field. We report here an approach for achieving efficient electron-13C spin-alignment transfers, compatible with a broad range of magnetic field strengths and field orientations with respect to the diamond crystal. This versatility results from combining coherent microwave- and incoherent laser-induced transitions between selected energy states of the coupled electron–nuclear spin manifold. 13C-detected nuclear magnetic resonance experiments demonstrate that this hyperpolarization can be transferred via first-shell or via distant 13Cs throughout the nuclear bulk ensemble. This method opens new perspectives for applications of diamond nitrogen-vacancy centres in nuclear magnetic resonance, and in quantum information processing. PMID:26404169

  4. 13C metabolic flux analysis at a genome-scale.

    PubMed

    Gopalakrishnan, Saratram; Maranas, Costas D

    2015-11-01

    Metabolic models used in 13C metabolic flux analysis generally include a limited number of reactions primarily from central metabolism. They typically omit degradation pathways, complete cofactor balances, and atom transition contributions for reactions outside central metabolism. This study addresses the impact on prediction fidelity of scaling-up mapping models to a genome-scale. The core mapping model employed in this study accounts for (75 reactions and 65 metabolites) primarily from central metabolism. The genome-scale metabolic mapping model (GSMM) (697 reaction and 595 metabolites) is constructed using as a basis the iAF1260 model upon eliminating reactions guaranteed not to carry flux based on growth and fermentation data for a minimal glucose growth medium. Labeling data for 17 amino acid fragments obtained from cells fed with glucose labeled at the second carbon was used to obtain fluxes and ranges. Metabolic fluxes and confidence intervals are estimated, for both core and genome-scale mapping models, by minimizing the sum of square of differences between predicted and experimentally measured labeling patterns using the EMU decomposition algorithm. Overall, we find that both topology and estimated values of the metabolic fluxes remain largely consistent between core and GSM model. Stepping up to a genome-scale mapping model leads to wider flux inference ranges for 20 key reactions present in the core model. The glycolysis flux range doubles due to the possibility of active gluconeogenesis, the TCA flux range expanded by 80% due to the availability of a bypass through arginine consistent with labeling data, and the transhydrogenase reaction flux was essentially unresolved due to the presence of as many as five routes for the inter-conversion of NADPH to NADH afforded by the genome-scale model. By globally accounting for ATP demands in the GSMM model the unused ATP decreased drastically with the lower bound matching the maintenance ATP requirement. A non

  5. Scattering forces and electromagnetic momentum density in crossed circularly polarized standing waves.

    PubMed

    Marqués, Manuel I; Saénz, Juan José

    2012-07-01

    We analyze the forces on a small dipolar particle and the electromagnetic momentum density in a configuration consisting in two perpendicular circularly polarized stationary waves. The field distribution shows regions in which the electric and magnetic fields are parallel corresponding to a null Poynting vector. Although the average value of the momentum density, proportional to the Poynting vector, is zero in these regions, there are scattering forces acting on small particles due to light's spin force. The total scattering force suggests a new definition of the average value of the momentum density for free propagating electromagnetic fields.

  6. Scattering forces and electromagnetic momentum density in crossed circularly polarized standing waves.

    PubMed

    Marqués, Manuel I; Saénz, Juan José

    2012-07-15

    We analyze the forces on a small dipolar particle and the electromagnetic momentum density in a configuration consisting in two perpendicular circularly polarized stationary waves. The field distribution shows regions in which the electric and magnetic fields are parallel corresponding to a null Poynting vector. Although the average value of the momentum density, proportional to the Poynting vector, is zero in these regions, there are scattering forces acting on small particles due to light's spin force. The total scattering force suggests a new definition of the average value of the momentum density for free propagating electromagnetic fields.

  7. Cross-stratified Wood: Enigmatic Woody Debris Deposits in Warm-Polar Fluvial Sediments (Pliocene Beaufort Formation, Nunavut)

    NASA Astrophysics Data System (ADS)

    Davies, N. S.; Gosse, J. C.; Rybczynski, N.

    2012-04-01

    Woody debris has been an important sediment component and a significant geomorphic agent in pristine fluvial systems since the Devonian. In recent years a large volume of research has focussed on various aspects of the importance of woody debris within the fluvial realm; from the evolutionary significance of fossil wood accumulations in the rock record to studies of the biogeomorphological and ecological importance of woody debris in modern rivers. In this presentation we describe cross-stratified woody debris deposits comprising organic detritus from a boreal-type treeline forest that included species of pine, birch, poplar, alder, spruce, eastern cedar, and larch, in both shrub and tree form. The cross-stratified wood is an enigmatic subset of fine woody debris which, to our knowledge, has never before been described from either the global stratigraphic record or modern fluvial environments. The deposits we describe are located within the Pliocene Beaufort Formation on Meighen Island, Nunavut, Canada, at a latitude of 80°N, and are compared with other cross-stratified woody debris deposits that have been noted elsewhere in the Pliocene of the Canadian Arctic. We make the robust observation that these deposits appear to be geographically and stratigraphically restricted to polar latitudes from a period of warm climatic conditions during the Pliocene (15-20 °C warmer mean annual temperature than the present day). In this regard it is possible to speculate that the transport of large amounts of woody debris as bedload is potentially a unique feature of forested high latitude rivers. Such bedload deposition requires a large amount of woody debris with a greater density than the fluid transporting it. The softwood composition of the debris suggests that this was most likely attained by saturation and subsequent entrainment of extensive accumulations of deadwood, promoted by unusually high rates of tree mortality and low rates of bacterial decomposition arising from

  8. Pentose cycling and the distribution of 13C in trehalose during glucogenesis from 13C-labelled substrates in an insect.

    PubMed

    Thompson, S N; Scales, V M; Bochardt, D B

    1995-07-26

    Redistribution of 13C in trehalose (Tre) due to pentose cycling was observed in vivo in Manduca sexta during glucogenesis from [3-13C]alanine (Ala) and [2-13C]glycerol (Gly). The extent of cycling was affected by dietary composition. Larvae maintained on a low-carbohydrate diet (LCD) exhibited approximately 13% cycling, while those on a complete-balanced diet (CBD) or low-fat diet (LFD) displayed much higher rates of cycling. Significant incorporation of 13C via reversal of the non-oxidative phase was evident on all diets but was greatest on the CBD and LFD. In contrast to conclusions from previous studies with insects, the present results indicate that under normal conditions the pentose pathway is not the principal source of triose phosphates for oxidative catabolism during larval development.

  9. Isotopic 13C NMR spectrometry to assess counterfeiting of active pharmaceutical ingredients: site-specific 13C content of aspirin and paracetamol.

    PubMed

    Silvestre, Virginie; Mboula, Vanessa Maroga; Jouitteau, Catherine; Akoka, Serge; Robins, Richard J; Remaud, Gérald S

    2009-10-15

    Isotope profiling is a well-established technique to obtain information about the chemical history of a given compound. However, the current methodology using IRMS can only determine the global (13)C content, leading to the loss of much valuable data. The development of quantitative isotopic (13)C NMR spectrometry at natural abundance enables the measurement of the (13)C content of each carbon within a molecule, thus giving simultaneous access to a number of isotopic parameters. When it is applied to active pharmaceutical ingredients, each manufactured batch can be characterized better than by IRMS. Here, quantitative isotopic (13)C NMR is shown to be a very promising and effective tool for assessing the counterfeiting of medicines, as exemplified by an analysis of aspirin (acetylsalicylic acid) and paracetamol (acetaminophen) samples collected from pharmacies in different countries. It is proposed as an essential complement to (2)H NMR and IRMS.

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

    SciTech Connect

    Pahl-Wostl, C.; Seelig, J.

    1986-11-04

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

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

    PubMed Central

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

    2016-01-01

    In order to improve the stiff and brittle characteristics of pure Bombyx mori (B. mori) silk fibroin (SF) film in the dry state, glycerin (Glyc) has been used as a plasticizer. However, there have been very limited studies on the structural characterization of the Glyc-blended SF film. In this study, 13C Cross Polarization/Magic Angle Spinning nuclear magnetic resonance (CP/MAS NMR) was used to monitor the conformational changes in the films by changing the Glyc concentration. The presence of only 5 wt % Glyc in the film induced a significant conformational change in SF where Silk I* (repeated type II β-turn and no α-helix) newly appeared. Upon further increase in Glyc concentration, the percentage of Silk I* increased linearly up to 9 wt % Glyc and then tended to be almost constant (30%). This value (30%) was the same as the fraction of Ala residue within the Silk I* form out of all Ala residues of SF present in B. mori mature silkworm. The 1H DQMAS NMR spectra of Glyc-blended SF films confirmed the appearance of Silk I* in the Glyc-blended SF film. A structural model of Glyc-SF complex including the Silk I* form was proposed with the guidance of the Molecular Dynamics (MD) simulation using 1H–1H distance constraints obtained from the 1H Double-Quantum Magic Angle Spinning (DQMAS) NMR spectra. PMID:27618034

  12. Unilateral NMR, 13C CPMAS NMR spectroscopy and micro-analytical techniques for studying the materials and state of conservation of an ancient Egyptian wooden sarcophagus.

    PubMed

    Proietti, Noemi; Presciutti, Federica; Di Tullio, Valeria; Doherty, Brenda; Marinelli, Anna Maria; Provinciali, Barbara; Macchioni, Nicola; Capitani, Donatella; Miliani, Costanza

    2011-03-01

    A multi-technique approach was employed to study a decorated Egyptian wooden sarcophagus (XXV-XXVI dynasty, Third Intermediate Period), belonging to the Museo del Vicino Oriente of the Sapienza University of Rome. Portable non-invasive unilateral NMR was applied to evaluate the conservation state of the sarcophagus. Moreover, using unilateral NMR, a non-invasive analytical protocol was established to detect the presence of organic substances on the surface and/or embedded in the wooden matrix. This protocol allowed for an educated sampling campaign aimed at further investigating the state of degradation of the wood and the presence of organic substances by (13)C cross polarization magic angle spinning (CPMAS) NMR spectroscopy. The composition of the painted layer was analysed by optical microscopy (OM), scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), Raman and surface enhanced (resonance) Raman spectroscopy (SERS/SERRS), infrared and GC-MS techniques, evidencing original components such as clay minerals, Egyptian green, indigo, natural gums, and also highlighting restoration pigments and alteration compounds. The identification of the wood, of great value for the reconstruction of the history of the artwork, was achieved by means of optical microscopy.

  13. 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.

  14. A 13C NMR spectrometric method for the determination of intramolecular δ13C values in fructose from plant sucrose samples.

    PubMed

    Gilbert, Alexis; Silvestre, Virginie; Robins, Richard J; Tcherkez, Guillaume; Remaud, Gérald S

    2011-07-01

    Recent developments in (13) C NMR spectrometry have allowed the determination of intramolecular (13) C/(12) C ratios with high precision. However, the analysis of carbohydrates requires their derivatization to constrain the anomeric carbon. Fructose has proved to be particularly problematic because of a byproduct occurring during derivatization and the complexity of the NMR spectrum of the derivative. Here, we describe a method to determine the intramolecular (13) C/(12) C ratios in fructose by (13) C NMR analysis of the acetyl-isopropylidene derivative. We have applied this method to measure the intramolecular (13) C/(12) C distribution in the fructosyl moiety of sucrose and have compared this with that in the glucosyl moiety. Three prominent features stand out. First, in sucrose from both C(3) and C(4) plants, the C-1 and C-2 positions of the glucosyl and fructosyl moieties are markedly different. Second, these positions in C(3) and C(4) plants show a similar profile. Third, the glucosyl and fructosyl moieties of sucrose from Crassulacean acid metabolism (CAM) metabolism have a different profile. These contrasting values can be interpreted as a result of the isotopic selectivity of enzymes that break or make covalent bonds in glucose metabolism, whereas the distinctive (13) C pattern in CAM sucrose probably indicates a substantial contribution of gluconeogenesis to glucose synthesis.

  15. Biosynthesis of highly enriched 13C-lycopene for human metabolic studies using repeated batch tomato cell culturing with 13C-glucose.

    PubMed

    Moran, Nancy Engelmann; Rogers, Randy B; Lu, Chi-Hua; Conlon, Lauren E; Lila, Mary Ann; Clinton, Steven K; Erdman, John W

    2013-08-15

    While putative disease-preventing lycopene metabolites are found in both tomato (Solanum lycopersicum) products and in their consumers, mammalian lycopene metabolism is poorly understood. Advances in tomato cell culturing techniques offer an economical tool for generation of highly-enriched (13)C-lycopene for human bioavailability and metabolism studies. To enhance the (13)C-enrichment and yields of labelled lycopene from the hp-1 tomato cell line, cultures were first grown in (13)C-glucose media for three serial batches and produced increasing proportions of uniformly labelled lycopene (14.3±1.2%, 39.6±0.5%, and 48.9±1.5%) with consistent yields (from 5.8 to 9 mg/L). An optimised 9-day-long (13)C-loading and 18-day-long labelling strategy developed based on glucose utilisation and lycopene yields, yielded (13)C-lycopene with 93% (13)C isotopic purity, and 55% of isotopomers were uniformly labelled. Furthermore, an optimised acetone and hexane extraction led to a fourfold increase in lycopene recovery from cultures compared to a standard extraction.

  16. Heavy quarkonium production at collider energies: Partonic cross section and polarization

    SciTech Connect

    Qiu, Jian -Wei; Kang, Zhong -Bo; Ma, Yan -Qing; Sterman, George

    2015-01-27

    We calculate the O(α³s) short-distance, QCD collinear-factorized coefficient functions for all partonic channels that include the production of a heavy quark pair at short distances. Thus, this provides the first power correction to the collinear-factorized inclusive hadronic production of heavy quarkonia at large transverse momentum, pT, including the full leading-order perturbative contributions to the production of heavy quark pairs in all color and spin states employed in NRQCD treatments of this process. We discuss the role of the first power correction in the production rates and the polarizations of heavy quarkonia in high-energy hadronic collisions. The consistency of QCD collinear factorization and nonrelativistic QCD factorization applied to heavy quarkonium production is also discussed.

  17. Heavy quarkonium production at collider energies: Partonic cross section and polarization

    DOE PAGES

    Qiu, Jian -Wei; Kang, Zhong -Bo; Ma, Yan -Qing; ...

    2015-01-27

    We calculate the O(α³s) short-distance, QCD collinear-factorized coefficient functions for all partonic channels that include the production of a heavy quark pair at short distances. Thus, this provides the first power correction to the collinear-factorized inclusive hadronic production of heavy quarkonia at large transverse momentum, pT, including the full leading-order perturbative contributions to the production of heavy quark pairs in all color and spin states employed in NRQCD treatments of this process. We discuss the role of the first power correction in the production rates and the polarizations of heavy quarkonia in high-energy hadronic collisions. The consistency of QCD collinearmore » factorization and nonrelativistic QCD factorization applied to heavy quarkonium production is also discussed.« less

  18. Multi-band polarization insensitive metamaterial absorber with dual cross-wires structure

    NASA Astrophysics Data System (ADS)

    Yao, Li-fang; Li, Min-hua; Zhai, Xiao-min; Wang, Hui-bo; Dong, Jian-feng

    2015-11-01

    A five-band metamaterial absorber (MMA) based on a simple planar structure is proposed. It utilizes different areas of a single unit cell to match impedance, and produces different absorptive frequencies. Numerical calculation shows that the MMA has five different absorption peaks at 3.78 GHz, 7.66 GHz, 10.9 GHz, 14.5 GHz and 16.7 GHz, and their absorption rates reach 95.5%, 98.6%, 95.7%, 96.6% and 99.8%, respectively. The proposed structure is polarization insensitive for transverse electric (TE) and transverse magnetic (TM) incident waves. Also, the absorptive characteristics over large incident angles are examined. In addition, we analyze the absorption mechanism by the surface current density and power flow density distributions. This simple structure provides a way to design multi-band MMA, and also saves the cost of fabrication.

  19. Analyzing Powers and Differential Cross Sections for Polarized Proton Neutron Going to Negative Pion Proton Proton

    NASA Astrophysics Data System (ADS)

    Duncan, Fraser Andrew

    There is considerable interest in the pn to pi^-pp reaction which can proceed by a nonresonant channel from the isospin 0 pn initial state (an NDelta intermediate state cannot be formed). This thesis describes a measurement of analyzing powers and triple differential cross sections for a subset of this reaction, pn to pi^-pp(^1S_0) by isolating the quasifree process in pd to pi^-ppp_{s}. The experimental arrangement selects the relative S-wave component of the outgoing "diproton". The experiment was done on TRIUMF beam line 1B using a LD_2 target; the pion was detected in a magnetic spectrometer, the two outgoing protons in a scintillator bar array. The spectator proton was undetected. Data were taken in August 1989 at 353, 403 and 440 MeV beam energies. Of these the 403 and 440 MeV data are analysed in this thesis and analyzing powers and triple differential cross sections as a function of pion scattering angle extracted at centre of mass kinetic energies, T_{CM}, of 55 and 70 MeV (corresponding to the 403 and 440 MeV beam energies respectively). Partial wave analysis of the data shows that, while the isospin 0 channel dominates the reaction, contributing approximately 75% of the cross section at the energies studied here, there are significant contributions from the s and d-wave pion, isospin 1 channels. Of particular importance is the contribution from the s-wave pion, isospin 1, channel whose interference with the isospin 0 channels produces the characteristic shapes of the cross sections and analyzing powers observed in the data. The d-wave pion, isospin 1 channels, are also required to fully explain the observed analyzing power distributions, and are essential for the T_{CM} = 70MeV data. Comparisons of the pion production data measured in this experiment with pion absorption measurements on ^3He, where the absorption process is pi^-pp(^1S_0) to pn, show a shift in the shape of the differential cross section which can be interpreted as due to differences in

  20. Quantitative evaluation of atherosclerotic plaques using cross-polarization optical coherence tomography, nonlinear, and atomic force microscopy

    NASA Astrophysics Data System (ADS)

    Gubarkova, Ekaterina V.; Kirillin, Mikhail Yu.; Dudenkova, Varvara V.; Timashev, Peter S.; Kotova, Svetlana L.; Kiseleva, Elena B.; Timofeeva, Lidia B.; Belkova, Galina V.; Solovieva, Anna B.; Moiseev, Alexander A.; Gelikonov, Gregory V.; Fiks, Ilya I.; Feldchtein, Felix I.; Gladkova, Natalia D.

    2016-12-01

    A combination of approaches to the image analysis in cross-polarization optical coherence tomography (CP OCT) and high-resolution imaging by nonlinear microscopy and atomic force microscopy (AFM) at the different stages of atherosclerotic plaque development is studied. This combination allowed us to qualitatively and quantitatively assess the disorganization of collagen in the atherosclerotic arterial tissue (reduction and increase of CP backscatter), at the fiber (change of the geometric distribution of fibers in the second-harmonic generation microscopy images) and fibrillar (violation of packing and different nature of a basket-weave network of fibrils in the AFM images) organization levels. The calculated CP channel-related parameters are shown to have a statistically significant difference between stable and unstable (also called vulnerable) plaques, and hence, CP OCT could be a potentially powerful, minimally invasive method for vulnerable plaques detection.

  1. Evaluation of the Effects of Cross-Beam Energy Transfer in NIF Polar-Drive Exploding-Pusher Experiments

    NASA Astrophysics Data System (ADS)

    McKenty, P. W.; Marshall, F. J.; Hohenberger, M.; Craxton, R. S.; Marozas, J. A.; Delettrez, J. A.; Shvydky, A.; Froula, D. H.; Michel, D. T.; Edgell, D. H.; Seka, W.; Olson, P. A.; To, S.; Cao, D.; Moses, G.; Le Pape, S.; MacKinnon, A. J.; Ma, T.

    2013-10-01

    Polar-drive (PD) target implosions have been designed and fielded for neutron diagnostic development on the National Ignition Facility (NIF). Experimental results evaluating the overall hydrodynamic assembly have previously indicated a significant discrepancy with DRACO predictions of the in-flight shell evolution. New physics models, addressing nonlocal electron thermal transport and cross-beam energy transfer within the incoming laser light, have been implemented into DRACO. Results detailing comparisons of experiments with simulations using these models will be presented that indicate significantly better agreement and may provide insight into the application of these models in other inertial confinement fusion experiments. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944. A. M. Cok, R. S. Craxton, and P. W. McKenty, Phys. Plasmas 15, 082705 (2008).

  2. Assessing ex vivo dental biofilms and in vivo composite restorations using cross-polarization optical coherence tomography

    NASA Astrophysics Data System (ADS)

    Jones, R.; Aparicio, C.; Chityala, R.; Chen, R.; Fok, A.; Rudney, J.

    2012-01-01

    A cross-polarization 1310-nm optical coherence tomography system (CP-OCT), using a beam splitter based design, was used to assess ex vivo growth of complex multi-species dental biofilms. These biofilm microcosms were derived from plaque samples along the interface of composite or amalgam restoration in children with a history of early childhood caries. This paper presents a method of measuring the mean biofilm height of mature biofilms using CP-OCT. For our in vivo application, the novel swept source based CP-OCT intraoral probe (Santec Co. Komaki, Japan) dimensions and system image acquisition speed (20 image frames/second) allowed imaging pediatric subjects as young as 4 years old. The subsurface enamel under the interface of composite resin restorations of pediatric subjects were imaged using CP-OCT. Cavitated secondary caries is clearly evident from sound resin composite restorations.

  3. 13cRA regulates the differentiation of antler chondrocytes through targeting Runx3.

    PubMed

    Zhang, Hong-Liang; Cao, Hang; Yang, Zhan-Qing; Geng, Shuang; Wang, Kai; Yu, Hai-Fan; Guo, Bin; Yue, Zhan-Peng

    2017-03-01

    Although 13cRA is involved in the regulation of cellular proliferation and differentiation, its physiological roles in chondrocyte proliferation and differentiation still remain unknown. Here, we showed that 13cRA could induce the proliferation of sika deer antler chondrocytes and expression of Ccnd3 and Cdk6. Administration of 13cRA to antler chondrocytes resulted in an obvious increase in the expression of chondrocyte marker Col II and hypertrophic chondrocyte marker Col X. Silencing of Crabp2 expression by specific siRNA could prevent the 13cRA-induced up-regulation of Col X, whereas overexpression of Crabp2 showed the opposite effects. Further study found that Crabp2 mediated the regulation of 13cRA on the expression of Runx3 which was highly expressed in the antler cartilage and inhibited the differentiation of antler chondrocytes. Moreover, attenuation of Runx3 expression greatly raised 13cRA-induced chondrocyte differentiation. Simultaneously, 13cRA could stimulate the expression of Cyp26a1 and Cyp26b1 in the antler chondrocytes. Inhibition of Cyp26a1 and/or Cyp26b1 reinforced the effects of 13cRA on the expression of Col X and Runx3, while overexpression of Cyp26b1 rendered the antler chondrocytes hyposensitive to 13cRA. Collectively, 13cRA may play an important role in the differentiation of antler chondrocytes through targeting Runx3. Crabp2 enhances the effects of 13cRA on chondrocyte differentiation, while Cyp26a1 and Cyp26b1 weaken the sensitivity of antler chondrocytes to 13cRA.

  4. Synthesis of isotopically labeled R- or S-[.sup.13C, .sup.2H] glycerols

    DOEpatents

    Martinez, Rodolfo A.; Unkefer, Clifford J.; Alvarez, Marc A.

    2008-01-22

    The present invention is directed to asymmetric chiral labeled glycerols including at least one chiral atom, from one to two .sup.13C atoms and from zero to four deuterium atoms bonded directly to a carbon atom, e.g., (2S) [1,2-.sup.13C.sub.2]glycerol and (2R) [1,2-.sup.13C.sub.2]glycerol, and to the use of such chiral glycerols in the preparation of labeled amino acids.

  5. J-refocused 1H PRESS DEPT for localized 13C MR spectroscopy.

    PubMed

    Chen, X; Boesiger, P; Henning, A

    2013-09-01

    Proton point-resolved spectroscopy (PRESS) localization has been combined with distortionless enhanced polarization transfer (DEPT) in multinuclear MRS to overcome the signal contamination problem in image-selected in vivo spectroscopy (ISIS)-combined DEPT, especially for lipid detection. However, homonuclear proton scalar couplings reduce the DEPT enhancement by modifying the spin coherence distribution under J modulation during proton PRESS localization. Herein, a J-refocused proton PRESS-localized DEPT sequence is presented to obtain simultaneously enhanced and localized signals from a large number of metabolites by in vivo (13) C MRS. The suppression of J modulation during PRESS and the substantial recovery of signal enhancement by J-refocused PRESS-localized DEPT were demonstrated theoretically by product operator formalism, numerically by the spin density matrix simulations for different scalar coupling conditions, and experimentally with a glutamate phantom at various TEs, as well as a colza oil phantom. The application of the sequence for localized detection of saturated and unsaturated fatty acids in the calf bone marrow and skeletal muscle of healthy subjects yielded high signal enhancements simultaneously obtained for all components.

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

    PubMed Central

    2017-01-01

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

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

    PubMed

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

    2017-02-21

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

  8. How to measure a complete set of polarization-dependent differential cross sections in a scattering experiment with aligned reagents?

    SciTech Connect

    Wang, Fengyan E-mail: kliu@po.iams.sinica.edu.tw; Lin, Jui-San; Liu, Kopin E-mail: kliu@po.iams.sinica.edu.tw

    2014-02-28

    Polarization-dependent differential cross section (PDDCS) is one of the three-vector correlations (k, k{sup ′}, j) in molecular collisions, which provides the most detailed insights into the steric requirements of chemical reactions, i.e., how the reactivity depends on the polarization of reagents. Only quite recently has such quantity been fully realized experimentally in the study of the reaction of the aligned CHD{sub 3}(v{sub 1} = 1, |jK〉 = |10〉) molecules with Cl({sup 2}P{sub 3/2}) atoms. Theoretically, PDDCS is a relatively new concept; experimental realization of the theoretical construct requires some careful considerations that are not readily available in the literature. Here, we present the “know-how” behind the full PDDCS measurements to fill the gaps and to provide a clear roadmap for future applications. To make the connection apparent between the methodology presented here and the stereodynamics revealed in previous reports, the same Cl + aligned CHD{sub 3} reaction is used for illustration.

  9. 13C NMR study of halogen bonding of haloarenes: measurements of solvent effects and theoretical analysis.

    PubMed

    Glaser, Rainer; Chen, Naijun; Wu, Hong; Knotts, Nathan; Kaupp, Martin

    2004-04-07

    Solvent effects on the NMR spectra of symmetrical (X = F (1), X = Cl (2), X = Br (3), X = I (4), X = NO2 (5), X = CN (6)) and unsymmetrical (X = I, Y = MeO (7), Y = PhO (8)) para-disubstituted acetophenone azines X-C6H4-CMe=N-N=CMe-C6H4-Y and of models X-C6H4-CMe=N-Z (X = I, Z = H (9), Z = NH2 (10)), 4-iodoacetophenone (11), and iodobenzene (12) were measured in CDCl(3), DMSO, THF, pyridine, and benzene to address one intramolecular and one intermolecular issue. Solvent effects on the (13)C NMR spectra are generally small, and this finding firmly establishes that the azine bridge indeed functions as a "conjugation stopper," an important design concept in our polar materials research. Since intermolecular halogen bonding of haloarenes do occur in polar organic crystalline materials, the NMR solution data pose the question as to whether the absence of solvent shifts indicates the absence of strong halogen bonding in solution. This question was studied by the theoretical analysis of the DMSO complexes of iodoarenes 4, 9-12, and of iodoacetylene. DFT and MP2 computations show iodine bonding, and characteristic structural and electronic features are described. The nonrelativistic complexation shifts and the change in the spin-orbit induced heavy atom effect of iodine compensate each other, and iodine bonding thus has no apparent effect on Ci in the iodoarenes. For iodides, complexation by DMSO occurs and may or may not manifest itself in the NMR spectra. The absence of complexation shifts in the NMR spectra of halides does not exclude the occurrence of halogen bonding in solution.

  10. Lowest bending mode of 13C-substituted C3 and an experimentally derived structure

    NASA Astrophysics Data System (ADS)

    Breier, Alexander A.; Büchling, Thomas; Schnierer, Rico; Lutter, Volker; Fuchs, Guido W.; Yamada, Koichi M. T.; Mookerjea, Bhaswati; Stutzki, Jürgen; Giesen, Thomas F.

    2016-12-01

    The ν2 lowest bending mode of linear C3 and of all its 13C-substituted isotopologues was recorded using a terahertz-supersonic jet spectrometer in combination with a laser ablation source. Sixty-five ro-vibrational transitions between 1.8 and 1.9 THz have been assigned to linear 12C12C12C, 12C12C13, 12C13C12C, 13C13C12C, 13C12C13C, and 13C13C13. For each isotopologue, molecular parameters were obtained and the C-C-bond length was derived experimentally. All results are in excellent agreement with recent ab initio calculations [B. Schröder and P. Sebald, J. Chem. Phys. 144, 044307 (2016)]. The new measurements explain why the interstellar search for singly substituted 12C12C13C has failed so far. A spectral line list with recommended transition frequencies based on global data fits is given to foster future interstellar detections.

  11. Development of a cross-polarization scattering system for the measurement of internal magnetic fluctuations in the DIII-D tokamak

    SciTech Connect

    Rhodes, T. L. Peebles, W. A.; Crocker, N. A.; Nguyen, X.

    2014-11-15

    The design and performance of a new cross-polarization scattering (CPS) system for the localized measurement of internal magnetic fluctuations is presented. CPS is a process whereby magnetic fluctuations scatter incident electromagnetic radiation into a perpendicular polarization which is subsequently detected. A new CPS design that incorporates a unique scattering geometry was laboratory tested, optimized, and installed on the DIII-D tokamak. Plasma tests of signal-to-noise, polarization purity, and frequency response indicate proper functioning of the system. CPS data show interesting features related to internal MHD perturbations known as sawteeth that are not observed on density fluctuations.

  12. Biokinetics of (13)C in the human body after oral administration of (13)C-labeled glucose as an index for the biokinetics of (14)C.

    PubMed

    Masuda, Tsuyoshi; Tako, Yasuhiro; Matsushita, Kensaku; Takeda, Hiroshi; Endo, Masahiro; Nakamura, Yuji; Hisamatsu, Shun'ichi

    2016-09-01

    The retention of (13)C in the human body after oral administration of (13)C-labeled glucose was studied in three healthy volunteer subjects to estimate the 50 year cumulative body burden for (13)C as an index of the committed dose of the radioisotope (14)C. After administration of (13)C-labeled glucose, the volunteers ingested controlled diets with a fixed number of calories for 112 d. Samples of breath and urine were collected up to 112 d after administration. Samples of feces were collected up to 14 d after administration. Hair samples were obtained at 119 d after administration and analyzed as a representative index of the rate of excretion of organic (13)C via pathways such as skin cell exfoliation and mucus secretion. All samples were analyzed for (13)C/(12)C atomic ratio to determine the rate of excretion via each pathway. We then constructed a metabolic model with a total of four pathways (breath, urine, feces, and other) comprising seven compartments. We determined the values of the biokinetic parameters in the model by using the obtained excretion data. From 74% to 94% of the (13)C administered was excreted in breath, whereas  <2% was excreted in urine and feces. In the other pathway, the excretion rate constant in the compartment with the longest residence time stretched to hundreds of days but the rate constant for each subject was not statistically significant (P value  >  0.1). In addition, the dataset for one of the three subjects was markedly different from those of the other two. When we estimated the 50 year cumulative body burden for (13)C by using our model and we included non-statistically significant parameters, a considerable cumulative body burden was found in the compartments excreting to the other pathway. Although our results on the cumulative body burden of (13)C from orally administered carbon as glucose were inconclusive, we found that the compartments excreting to the other pathway had a markedly long residence time and

  13. Scattering of a cross-polarized linear wave by a soliton at an optical event horizon in a birefringent nanophotonic waveguide.

    PubMed

    Ciret, Charles; Gorza, Simon-Pierre

    2016-06-15

    The scattering of a linear wave on an optical event horizon, induced by a cross-polarized soliton, is experimentally and numerically investigated in integrated structures. The experiments are performed in a dispersion-engineered birefringent silicon nanophotonic waveguide. In stark contrast with copolarized waves, the large difference between the group velocity of the two cross-polarized waves enables a frequency conversion almost independent of the soliton wavelength. It is shown that the generated idler is only shifted by 10 nm around 1550 nm over a pump tuning range of 350 nm. Simulations using two coupled full vectorial nonlinear Schrödinger equations fully support the experimental results.

  14. Longitudinal double-spin asymmetry and cross section for inclusivejet production in polarized proton collisions at sqrt(s) = 200 GeV

    SciTech Connect

    Abelev, B.I.; Adams, J.; Aggarwal, M.M.; Ahammed, Z.; Amonett,J.; Anderson, B.D.; Anderson, M.; Arkhipkin, D.; Averichev, G.S.; Bai,Y.; Balewski, J.; Barannikova, O.; Barnby, L.S.; Baudot, J.; Bekele, S.; Belaga, V.V.; Bellingeri-Laurikainen, A.; Bellwied, R.; Benedosso, F.; Bhardwaj, S.; Bhasin, A.; Bhati, A.K.; Bichsel, H.; Bielcik, J.; Bielcikova, J.; Bland, L.C.; Blyth, S.-L.; Bonner, B.E.; Botje, M.; Bouchet, J.; Brandin, A.V.; Bravar, A.; Bystersky, M.; Cadman, R.V.; Cai,X.Z.; Caines, H.; Calderon de la Barca Sanchez, M.; Castillo, J.; Catu,O.; Cebra, D.; Chajecki, Z.; Chaloupka, P.; Chattopadhyay, S.; Chen,H.F.; Chen, J.H.; Cheng, J.; Cherney, M.; Chikanian, A.; Christie, W.; Coffin, J.P.; Cormier, T.M.; Cosentino, M.R.; Cramer, J.G.; Crawford,H.J.; Das, D.; Das, S.; Daugherity, M.; de Moura, M.M.; Dedovich, T.G.; DePhillips, M.; Derevschikov, A.A.; Didenko, L.; Dietel, T.; Djawotho,P.; Dogra, S.M.; Dong, W.J.; Dong, X.; Draper, J.E.; Du, F.; Dunin, V.B.; Dunlop, J.C.; Dutta Mazumdar, M.R.; Eckardt, V.; Edwards, W.R.; Efimov,L.G.; Emelianov, V.; Engelage, J.; Eppley, G.; Erazmus, B.; Estienne, M.; Fachini, P.; Fatemi, R.; Fedorisin, J.; Filimonov, K.; Filip, P.; Finch,E.; Fine, V.; Fisyak, Y.; Fu, J.; Gagliardi, C.A.; Gaillard, L.; Ganti,M.S.; Ghazikhanian, V.; Ghosh, P.; Gonzalez, J.S.; Gorbunov, Y.G.; Gos,H.; Grebenyuk, O.; Grosnick, D.; Guertin, S.M.; Guimaraes, K.S.F.F.; Guo,Y.; Gupta, N.; Gutierrez, T.D.; Haag, B.; Hallman, T.J.; Hamed, A.; Harris, J.W.; He, W.; Heinz, M.; Henry, T.W.; Hepplemann, S.; Hippolyte,B.; Hirsch, A.; Hjort, E.; Hoffman, A.M.; Hoffmann, G.W.; Horner, M.J.; Huang, H.Z.; Huang, S.L.; Hughes, E.W.; Humanic, T.J.; Igo, G.; Jacobs,P.; Jacobs, W.W.; Jakl, P.; Jia, F.; Jiang, H.; Jones, P.G.; Judd, E.G.; Kabana, S.; Kang, K.; Kapitan, J.; Kaplan, M.; Keane, D.; Kechechyan, A.; Khodyrev, V.Yu.; Kim, B.C.; Kiryluk, J.; Kisiel, A.; Kislov, E.M.; Klein,S.R.; Kocoloski, A.; Koetke, D.D.; et al.

    2006-08-10

    We report a measurement of the longitudinal double-spinasymmetry A_LL and the differential cross section for inclusivemidrapidity jet production in polarized proton collisions at sqrt(s)=200GeV. The cross section data cover transverse momenta 5polarization in the polarizednucleon.

  15. Connective tissue polarity. Optical second-harmonic microscopy, crossed-beam summation, and small-angle scattering in rat-tail tendon.

    PubMed Central

    Freund, I; Deutsch, M; Sprecher, A

    1986-01-01

    Connective tissue polarity has remained an intractable enigma for over two decades. We present new data on optical second harmonic generation in native, wet, rat-tail tendon. Scanning second-harmonic microscopy has revealed, for the first time, the existence of a discrete network of fine, polar, filamentous or columnar, structures, and, also, the presence of strongly polar surface, or near-surface patches. The thickness of these features was probed via crossed-beam optical frequency summation and the polar material is estimated to occupy a few percent of the tendon volume. The three-dimensional spatial distribution of filaments was studied with the aid of small-angle second-harmonic scattering, and the filaments were found to permeate the tendon cross-section in an apparently random fashion. These latter measurements also revealed that essentially all polar filaments had the same directionality. Concomitant studies of the polar collagen fibrils that comprise the bulk of tendon were in full accord with prior electron microscope results that had demonstrated that the directionality of these fibrils varies up/down in a purely random fashion, and thus cannot yield a net macroscopic polarity. Quantitative analysis of the second-harmonic data yields the conclusion that the observed polar structures cannot be simply local regions containing some accidental net excess of similarly oriented fibrils. The analytical expressions used in the analysis of the data obtained for this complex tissue were supported by extensive, realistic computer simulations. The discovery that the polarity of rat-tail tendon, and possibly other forms of connective tissue, resides in discrete structures, some of which are located near the tendon surface, should permit the ready isolation of polar-rich material for further study by a variety of techniques. Images FIGURE 2 PMID:3779007

  16. Photobioreactor design for isotopic non-stationary 13C-metabolic flux analysis (INST 13C-MFA) under photoautotrophic conditions.

    PubMed

    Martzolff, Arnaud; Cahoreau, Edern; Cogne, Guillaume; Peyriga, Lindsay; Portais, Jean-Charles; Dechandol, Emmanuel; Le Grand, Fabienne; Massou, Stéphane; Gonçalves, Olivier; Pruvost, Jérémy; Legrand, Jack

    2012-12-01

    Adaptive metabolic behavior of photoautotrophic microorganisms toward genetic and environmental perturbations can be interpreted in a quantitative depiction of carbon flow through a biochemical reaction network using isotopic non-stationary (13) C-metabolic flux analysis (INST (13) C-MFA). To evaluate (13) C-metabolic flux maps for Chlamydomonas reinhardtii, an original experimental framework was designed allowing rapid, reliable collection of high-quality isotopomer data against time. It involved (i) a short-time (13) C labeling injection device based on mixing control in a torus-shaped photobioreactor with plug-flow hydrodynamics allowing a sudden step-change in the (13) C proportion in the substrate feed and (ii) a rapid sampling procedure using an automatic fast filtration method coupled to a manual rapid liquid nitrogen quenching step. (13) C-substrate labeling enrichment was controlled through the total dissolved inorganic carbon concentration in the pulsed solution. First results were obtained from steady-state continuous culture measurements allowing the characterization of the kinetics of label incorporation into light-limited growing cells cultivated in a photobioreactor operating at the maximal biomass productivity for an incident photon flux density of 200 µmol m(-2) s(-1). (13)C label incorporation was measured for 21 intracellular metabolites using IC-MS/MS in 58 samples collected across a labeling experiment duration of 7 min. The fastest labeling rate was observed for 2/3-phosphoglycerate with an apparent isotopic stationary state reached after 300 s. The labeling rate was consistent with the optimized mixing time of about 4.9 s inside the reactor and the shortest reliable sampling period assessed at 5 s.

  17. Estimation of procyanidin/prodelphinidin and cis/trans flavanol ratios of condensed tannin fractions by 1H-13C HSQC NMR spectroscopy: Correlation with thiolysis

    Technology Transfer Automated Retrieval System (TEKTRAN)

    Integration of cross-peak contours of H/C-2’,6’ signals from prodelphinidin (PD) and of H/C-6’ signals from procyanidin (PC) units in 1H-13C HSQC nuclear magnetic resonance (NMR) spectra of condensed tannins yielded nuclei-adjusted PC/PD estimates that were highly correlated with PC/PD ratios obtain...

  18. 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.

  19. The Nature of Carbonate and Organic δ13C Covariance Through Geological Time

    NASA Astrophysics Data System (ADS)

    Oehlert, A. M.; Swart, P. K.

    2014-12-01

    Significant evolutionary, climatic, and oceanographic events in Earth history are often accompanied by excursions in the carbon isotope composition (δ13C) of marine carbonates and co-occurring sedimentary organic material. The observation of synchronous excursions in the δ13C values of marine carbonates and coeval organic matter is commonly thought to prove that the deposit has not been altered by diagenesis, and that the variations in the δ13C records are the result of a significant change in global carbon cycling. Furthermore, this model suggests that the covariance of carbonate and organic δ13C records is driven only by changes in the δ13C value of the dissolved inorganic carbon in the surface waters of the ocean. However, recent work suggests that there may be at least two alternate models for generating covariance between carbonate and organic δ13C values in the geologic record. One of the models invokes sea-level driven syndepositional mixing between isotopically distinct sources of carbonate and organic material to produce positive covariance between carbonate and organic δ13C values. The second model suggests that post-depositional alteration to the carbonate δ13C values during meteoric diagenesis, in concert with concurrent contributions of terrestrial organic material during subaerial exposure, can also produce co-occurring negative excursions with tightly covariant δ13C records. In contrast to earlier interpretations of covariant δ13C values, these models suggest that both syndepositional and post-depositional factors can significantly influence the relationship between carbonate and organic δ13C values in a variety of depositional environments. The implications for reconstructions of ancient global carbon cycle events will be explored within the context of these three models, and their relative importance throughout geologic time will be discussed.

  20. Metabolism of hyperpolarized [1‐13C]pyruvate through alternate pathways in rat liver

    PubMed Central

    Moreno, Karlos X.; Wang, Jian‐Xiong; Fidelino, Leila; Merritt, Matthew E.; Sherry, A. Dean; Malloy, Craig R.

    2016-01-01

    The source of hyperpolarized (HP) [13C]bicarbonate in the liver during metabolism of HP [1‐13C]pyruvate is uncertain and likely changes with physiology. Multiple processes including decarboxylation through pyruvate dehydrogenase or pyruvate carboxylase followed by subsequent decarboxylation via phosphoenolpyruvate carboxykinase (gluconeogenesis) could play a role. Here we tested which metabolic fate of pyruvate contributed to the appearance of HP [13C]bicarbonate during metabolism of HP [1‐13C]pyruvate by the liver in rats after 21 h of fasting compared to rats with free access to food. The 13C NMR of HP [13C]bicarbonate was observed in the liver of fed rats, but not in fasted rats where pyruvate carboxylation and gluconeogenesis was active. To further explore the relative fluxes through pyruvate carboxylase versus pyruvate dehydrogenase in the liver under typical conditions of hyperpolarization studies, separate parallel experiments were performed with rats given non‐hyperpolarized [2,3‐13C]pyruvate. 13C NMR analysis of glutamate isolated from the liver of rats revealed that flux from injected pyruvate through pyruvate dehydrogenase was dominant under fed conditions whereas flux through pyruvate carboxylase dominated under fasted conditions. The NMR signal of HP [13C]bicarbonate does not parallel pyruvate carboxylase activity followed by subsequent decarboxylation reaction leading to glucose production. In the liver of healthy well‐fed rats, the appearance of HP [13C]bicarbonate exclusively reflects decarboxylation of HP [1‐13C]pyruvate via pyruvate dehydrogenase. © 2016 The Authors. NMR in Biomedicine published by John Wiley & Sons Ltd. PMID:26836042

  1. Metabolism of hyperpolarized [1-(13)C]pyruvate through alternate pathways in rat liver.

    PubMed

    Jin, Eunsook S; Moreno, Karlos X; Wang, Jian-Xiong; Fidelino, Leila; Merritt, Matthew E; Sherry, A Dean; Malloy, Craig R

    2016-04-01

    The source of hyperpolarized (HP) [(13)C]bicarbonate in the liver during metabolism of HP [1-(13)C]pyruvate is uncertain and likely changes with physiology. Multiple processes including decarboxylation through pyruvate dehydrogenase or pyruvate carboxylase followed by subsequent decarboxylation via phosphoenolpyruvate carboxykinase (gluconeogenesis) could play a role. Here we tested which metabolic fate of pyruvate contributed to the appearance of HP [(13)C]bicarbonate during metabolism of HP [1-(13)C]pyruvate by the liver in rats after 21 h of fasting compared to rats with free access to food. The (13)C NMR of HP [(13)C]bicarbonate was observed in the liver of fed rats, but not in fasted rats where pyruvate carboxylation and gluconeogenesis was active. To further explore the relative fluxes through pyruvate carboxylase versus pyruvate dehydrogenase in the liver under typical conditions of hyperpolarization studies, separate parallel experiments were performed with rats given non-hyperpolarized [2,3-(13)C]pyruvate. (13)C NMR analysis of glutamate isolated from the liver of rats revealed that flux from injected pyruvate through pyruvate dehydrogenase was dominant under fed conditions whereas flux through pyruvate carboxylase dominated under fasted conditions. The NMR signal of HP [(13)C]bicarbonate does not parallel pyruvate carboxylase activity followed by subsequent decarboxylation reaction leading to glucose production. In the liver of healthy well-fed rats, the appearance of HP [(13)C]bicarbonate exclusively reflects decarboxylation of HP [1-(13)C]pyruvate via pyruvate dehydrogenase.

  2. Robust hyperpolarized (13)C metabolic imaging with selective non-excitation of pyruvate (SNEP).

    PubMed

    Chen, Way Cherng; Teo, Xing Qi; Lee, Man Ying; Radda, George K; Lee, Philip

    2015-08-01

    In vivo metabolic imaging using hyperpolarized [1-(13)C]pyruvate provides localized biochemical information and is particularly useful in detecting early disease changes, as well as monitoring disease progression and treatment response. However, a major limitation of hyperpolarized magnetization is its unrecoverable decay, due not only to T1 relaxation but also to radio-frequency (RF) excitation. RF excitation schemes used in metabolic imaging must therefore be able to utilize available hyperpolarized magnetization efficiently and robustly for the optimal detection of substrate and metabolite activities. In this work, a novel RF excitation scheme called selective non-excitation of pyruvate (SNEP) is presented. This excitation scheme involves the use of a spectral selective RF pulse to specifically exclude the excitation of [1-(13)C]pyruvate, while uniformly exciting the key metabolites of interest (namely [1-(13)C]lactate and [1-(13)C]alanine) and [1-(13)C]pyruvate-hydrate. By eliminating the loss of hyperpolarized [1-(13)C]pyruvate magnetization due to RF excitation, the signal from downstream metabolite pools is increased together with enhanced dynamic range. Simulation results, together with phantom measurements and in vivo experiments, demonstrated the improvement in signal-to-noise ratio (SNR) and the extension of the lifetime of the [1-(13)C]lactate and [1-(13)C]alanine pools when compared with conventional non-spectral selective (NS) excitation. SNEP has also been shown to perform comparably well with multi-band (MB) excitation, yet SNEP possesses distinct advantages, including ease of implementation, less stringent demands on gradient performance, increased robustness to frequency drifts and B0 inhomogeneity as well as easier quantification involving the use of [1-(13)C]pyruvate-hydrate as a proxy for the actual [1-(13)C] pyruvate signal. SNEP is therefore a promising alternative for robust hyperpolarized [1-(13)C]pyruvate metabolic imaging with high

  3. Preliminary studies of a canine 13C-aminopyrine demethylation blood test.

    PubMed Central

    Moeller, E M; Steiner, J M; Williams, D A; Klein, P D

    2001-01-01

    The objectives of this study were to determine whether a 13C-aminopyrine demethylation blood test is technically feasible in clinically healthy dogs, whether oral administration of 13C-aminopyrine causes a detectable increase in percent dose/min (PCD) of 13C administered as 13C-aminopyrine and recovered in gas extracted from blood, and whether gas extraction efficiency has an impact on PCD. A dose of 2 mg/kg body weight of 13C-aminopyrine dissolved in deionized water was administered orally to 6 clinically healthy dogs. Blood samples were taken from each dog 0, 30, 60, and 120 min after administration of the 13C-aminopyrine. Carbon dioxide was extracted from blood samples by addition of acid and analyzed by fractional mass spectrometry. None of the 6 dogs showed any side effects after 13C-aminopyrine administration. All 6 dogs showed a measurable increase of the PCD in gas samples extracted from blood samples at 30 min, 60 min, and 120 min after 13C-aminopyrine administration. Coefficients of variation between the triplicate samples were statistically significantly higher for the %CO2, a measure of extraction efficiency, than for PCD values (P < 0.0001). The 13C-aminopyrine demethylation blood test described here is technically feasible. Oral administration of 13C-aminopyrine did not lead to gross side effects in the 6 dogs. Clinically healthy dogs show a measurable increase of PCD in gas extracted from blood samples after oral administration of 13C-aminopyrine. Efficiency of CO2 extraction from blood samples does not have an impact on PCD determined from these blood samples. This test may prove useful to evaluate hepatic function in dogs. PMID:11227194

  4. Galacto-oligosaccharides have prebiotic activity in a dynamic in vitro colon model using a (13)C-labeling technique.

    PubMed

    Maathuis, Annet J H; van den Heuvel, Ellen G; Schoterman, Margriet H C; Venema, Koen

    2012-07-01

    Galacto-oligosaccharides (GOS) are considered to be prebiotic, although the contribution of specific members of the microbiota to GOS fermentation and the exact microbial metabolites that are produced upon GOS fermentation are largely unknown. We aimed to determine this using uniformly (13)C-labeled GOS. The normal (control) medium and unlabeled or (13)C-labeled GOS was added to a dynamic, validated, in vitro model of the large-intestine containing an adult-type microbiota. Liquid-chromatography MS was used to measure the incorporation of (13)C label into metabolites. 16S-rRNA stable isotope probing coupled to a phylogenetic micro-array was used to determine label incorporation in microbial biomass. The primary members within the complex microbiota that were directly involved in GOS fermentation were shown to be Bifidobacterium longum, B. bifidum, B. catenulatum, Lactobacillus gasseri, and L. salivarius, in line with the prebiotic effect of GOS, although some other species incorporated (13)C label also. GOS fermentation led to an increase in acetate (+49%) and lactate (+23%) compared with the control. Total organic acid production was 8.50 and 7.52 mmol/g of carbohydrate fed for the GOS and control experiments, respectively. At the same time, the cumulative production of putrefactive metabolites (branched-chain fatty acids and ammonia) was reduced by 55%. Cross-feeding of metabolites from primary GOS fermenters to other members of the microbiota was observed. Our findings support a prebiotic role for GOS and its potential to act as a synbiotic in combination with certain probiotic strains.

  5. Earth's magnetic field enabled scalar coupling relaxation of 13C nuclei bound to fast-relaxing quadrupolar 14N in amide groups.

    PubMed

    Chiavazza, Enrico; Kubala, Eugen; Gringeri, Concetta V; Düwel, Stephan; Durst, Markus; Schulte, Rolf F; Menzel, Marion I

    2013-02-01

    Scalar coupling relaxation, which is usually only associated with closely resonant nuclei (e.g., (79)Br-(13)C), can be a very effective relaxation mechanism. While working on hyperpolarized [5-(13)C]glutamine, fast liquid-state polarization decay during transfer to the MRI scanner was observed. This behavior could hypothetically be explained by substantial T(1) shortening due to a scalar coupling contribution (type II) to the relaxation caused by the fast-relaxing quadrupolar (14)N adjacent to the (13)C nucleus in the amide group. This contribution is only effective in low magnetic fields (i.e., less than 800 μT) and prevents the use of molecules bearing the (13)C-amide group as hyperpolarized MRS/MRI probes. In the present work, this hypothesis is explored both theoretically and experimentally. The results show that high hyperpolarization levels can be retained using either a (15)N-labeled amide or by applying a magnetic field during transfer of the sample from the polarizer to the MRI scanner.

  6. Economical synthesis of 13C-labeled opiates, cocaine derivatives and selected urinary metabolites by derivatization of the natural products.

    PubMed

    Karlsen, Morten; Liu, Huiling; Johansen, Jon Eigill; Hoff, Bård Helge

    2015-03-25

    The illegal use of opiates and cocaine is a challenge world-wide, but some derivatives are also valuable pharmaceuticals. Reference samples of the active ingredients and their metabolites are needed both for controlling administration in the clinic and to detect drugs of abuse. Especially, (13)C-labeled compounds are useful for identification and quantification purposes by mass spectroscopic techniques, potentially increasing accuracy by minimizing ion alteration/suppression effects. Thus, the synthesis of [acetyl-(13)C4]heroin, [acetyl-(13)C4-methyl-(13)C]heroin, [acetyl-(13)C2-methyl-(13)C]6-acetylmorphine, [N-methyl-(13)C-O-metyl-(13)C]codeine and phenyl-(13)C6-labeled derivatives of cocaine, benzoylecgonine, norcocaine and cocaethylene was undertaken to provide such reference materials. The synthetic work has focused on identifying (13)C atom-efficient routes towards these derivatives. Therefore, the (13)C-labeled opiates and cocaine derivatives were made from the corresponding natural products.

  7. T(2) relaxation times of (13)C metabolites in a rat hepatocellular carcinoma model measured in vivo using (13)C-MRS of hyperpolarized [1-(13)C]pyruvate.

    PubMed

    Yen, Yi-Fen; Le Roux, Patrick; Mayer, Dirk; King, Randy; Spielman, Daniel; Tropp, James; Butts Pauly, Kim; Pfefferbaum, Adolf; Vasanawala, Shreyas; Hurd, Ralph

    2010-05-01

    A single-voxel Carr-Purcell-Meibloom-Gill sequence was developed to measure localized T(2) relaxation times of (13)C-labeled metabolites in vivo for the first time. Following hyperpolarized [1-(13)C]pyruvate injections, pyruvate and its metabolic products, alanine and lactate, were observed in the liver of five rats with hepatocellular carcinoma and five healthy control rats. The T(2) relaxation times of alanine and lactate were both significantly longer in HCC tumors than in normal livers (p < 0.002). The HCC tumors also showed significantly higher alanine signal relative to the total (13)C signal than normal livers (p < 0.006). The intra- and inter-subject variations of the alanine T(2) relaxation time were 11% and 13%, respectively. The intra- and inter-subject variations of the lactate T(2) relaxation time were 6% and 7%, respectively. The intra-subject variability of alanine to total carbon ratio was 16% and the inter-subject variability 28%. The intra-subject variability of lactate to total carbon ratio was 14% and the inter-subject variability 20%. The study results show that the signal level and relaxivity of [1-(13)C]alanine may be promising biomarkers for HCC tumors. Its diagnostic values in HCC staging and treatment monitoring are yet to be explored.

  8. 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.

  9. 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

  10. 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.

  11. Draft Genome Sequence of a Tropical Freshwater Cyanobacterium, Limnothrix sp. Strain P13C2

    PubMed Central

    Tan, Boon Fei; Gin, Karina Yew-Hoong

    2016-01-01

    A nonaxenic unialgal culture of Limnothrix sp. strain P13C2 was obtained through multiple subculturing of an inoculum obtained from a tropical freshwater lake. Here, we report the genome of P13C2 of 4.6 Mbp, extracted from the metagenome of this coculture. PMID:27795269

  12. 13C MRS studies of neuroenergetics and neurotransmitter cycling in humans.

    PubMed

    Rothman, Douglas L; De Feyter, Henk M; de Graaf, Robin A; Mason, Graeme F; Behar, Kevin L

    2011-10-01

    In the last 25 years, (13)C MRS has been established as the only noninvasive method for the measurement of glutamate neurotransmission and cell-specific neuroenergetics. Although technically and experimentally challenging, (13)C MRS has already provided important new information on the relationship between neuroenergetics and neuronal function, the energy cost of brain function, the high neuronal activity in the resting brain state and how neuroenergetics and neurotransmitter cycling are altered in neurological and psychiatric disease. In this article, the current state of (13)C MRS as it is applied to the study of neuroenergetics and neurotransmitter cycling in humans is reviewed. The focus is predominantly on recent findings in humans regarding metabolic pathways, applications to clinical research and the technical status of the method. Results from in vivo (13)C MRS studies in animals are discussed from the standpoint of the validation of MRS measurements of neuroenergetics and neurotransmitter cycling, and where they have helped to identify key questions to address in human research. Controversies concerning the relationship between neuroenergetics and neurotransmitter cycling and factors having an impact on the accurate determination of fluxes through mathematical modeling are addressed. We further touch upon different (13)C-labeled substrates used to study brain metabolism, before reviewing a number of human brain diseases investigated using (13)C MRS. Future technological developments are discussed that will help to overcome the limitations of (13)C MRS, with special attention given to recent developments in hyperpolarized (13)C MRS.

  13. Measuring δ(13)C values of atmospheric acetaldehyde via sodium bisulfite adsorption and cysteamine derivatisation.

    PubMed

    Guo, Songjun; Chen, Mei; Wen, Sheng; Sheng, Guoying; Fu, Jiamo

    2012-01-01

    δ(13)C values of gaseous acetaldehyde were measured by gas chromatograph-combustion-isotope ratio mass spectrometer (GC-C-IRMS) via sodium bisulfite (NaHSO(3)) adsorption and cysteamine derivatisation. Gaseous acetaldehyde was collected via NaHSO(3)-coated Sep-Pak(®) silica gel cartridge, then derivatised with cysteamine, and then the δ(13)C value of the acetaldehyde-cysteamine derivative was measured by GC-C-IRMS. Using two acetaldehydes with different δ(13)C values, derivatisation experiments were carried out to cover concentrations between 0.009×10(-3) and 1.96×10(-3) mg·l(-1)) of atmospheric acetaldehyde, and then δ(13)C fractionation was evaluated in the derivatisation of acetaldehyde based on stoichiometric mass balance after measuring the δ(13)C values of acetaldehyde, cysteamine and the acetaldehyde-cysteamine derivative. δ(13)C measurements in the derivertisation process showed good reproducibility (<0.5 ‰) for gaseous acetaldehyde. The differences between predicted and measured δ(13)C values were 0.04-0.31 ‰ for acetaldehyde-cysteamine derivative, indicating that the derivatisation introduces no isotope fractionation for gaseous acetaldehyde, and obtained δ(13)C values of acetaldehyde in ambient air at the two sites were distinct (-34.00 ‰ at an urban site versus-31.00 ‰ at a forest site), implying potential application of the method to study atmospheric acetaldehyde.

  14. 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

  15. Natural (13) C distribution in oil palm (Elaeis guineensis Jacq.) and consequences for allocation pattern.

    PubMed

    Lamade, Emmanuelle; Tcherkez, Guillaume; Darlan, Nuzul Hijri; Rodrigues, Rosario Lobato; Fresneau, Chantal; Mauve, Caroline; Lamothe-Sibold, Marlène; Sketriené, Diana; Ghashghaie, Jaleh

    2016-01-01

    Oil palm has now become one of the most important crops, palm oil representing nearly 25% of global plant oil consumption. Many studies have thus addressed oil palm ecophysiology and photosynthesis-based models of carbon allocation have been used. However, there is a lack of experimental data on carbon fixation and redistribution within palm trees, and important C-sinks have not been fully characterized yet. Here, we carried out extensive measurement of natural (13) C-abundance (δ(13) C) in oil palm tissues, including fruits at different maturation stages. We find a (13) C-enrichment in heterotrophic organs compared to mature leaves, with roots being the most (13) C-enriched. The δ(13) C in fruits decreased during maturation, reflecting the accumulation in (13) C-depleted lipids. We further used observed δ(13) C values to compute plausible carbon fluxes using a steady-state model of (13) C-distribution including metabolic isotope effects ((12) v/(13) v). The results suggest that fruits represent a major respiratory loss (≈39% of total tree respiration) and that sink organs such as fruits are fed by sucrose from leaves. That is, glucose appears to be a quantitatively important compound in palm tissues, but computations indicate that it is involved in dynamic starch metabolism rather that C-exchange between organs.

  16. Integrated 13C-metabolic flux analysis of 14 parallel labeling experiments in Escherichia coli.

    PubMed

    Crown, Scott B; Long, Christopher P; Antoniewicz, Maciek R

    2015-03-01

    The use of parallel labeling experiments for (13)C metabolic flux analysis ((13)C-MFA) has emerged in recent years as the new gold standard in fluxomics. The methodology has been termed COMPLETE-MFA, short for complementary parallel labeling experiments technique for metabolic flux analysis. In this contribution, we have tested the limits of COMPLETE-MFA by demonstrating integrated analysis of 14 parallel labeling experiments with Escherichia coli. An effort on such a massive scale has never been attempted before. In addition to several widely used isotopic tracers such as [1,2-(13)C]glucose and mixtures of [1-(13)C]glucose and [U-(13)C]glucose, four novel tracers were applied in this study: [2,3-(13)C]glucose, [4,5,6-(13)C]glucose, [2,3,4,5,6-(13)C]glucose and a mixture of [1-(13)C]glucose and [4,5,6-(13)C]glucose. This allowed us for the first time to compare the performance of a large number of isotopic tracers. Overall, there was no single best tracer for the entire E. coli metabolic network model. Tracers that produced well-resolved fluxes in the upper part of metabolism (glycolysis and pentose phosphate pathways) showed poor performance for fluxes in the lower part of metabolism (TCA cycle and anaplerotic reactions), and vice versa. The best tracer for upper metabolism was 80% [1-(13)C]glucose+20% [U-(13)C]glucose, while [4,5,6-(13)C]glucose and [5-(13)C]glucose both produced optimal flux resolution in the lower part of metabolism. COMPLETE-MFA improved both flux precision and flux observability, i.e. more independent fluxes were resolved with smaller confidence intervals, especially exchange fluxes. Overall, this study demonstrates that COMPLETE-MFA is a powerful approach for improving flux measurements and that this methodology should be considered in future studies that require very high flux resolution.

  17. A novel polar-modified post-cross-linked resin and its enhanced adsorption to salicylic acid: Equilibrium, kinetics and breakthrough studies.

    PubMed

    Wang, Xiaomei; Li, Guoqiang; Guo, Deping; Zhang, Yaling; Huang, Jianhan

    2016-05-15

    Improving the surface polarity is of significance for the post-cross-linked resins to enhance their adsorption to polar aromatic compounds. In the present study, we prepared a novel polar-modified post-cross-linked PDEpc_D by the Friedel-Crafts alkylation reaction and the amination reaction, the Brunauer-Emmett-Teller (BET) surface area and pore volume increased significantly after the Friedel-Crafts alkylation reaction and the surface polarity improved greatly after the amination reaction. Batch adsorption showed that PDEpc_D possessed a much enhanced adsorption to salicylic acid as compared the precursors PDE and PDEpc as well as the non-polar post-cross-linked PDVBpc. The equilibrium data was characterized by the Freundlich model, π-π stacking, hydrogen bonding and static interaction were the possible driving forces. The adsorption was a fast process and the kinetic data obeyed the micropore diffusion model. Column adsorption-desorption experiments suggested that PDEpc_D was a potential candidate for adsorptive removal of salicylic acid from aqueous solution.

  18. Sequence-specific 1H, 15N and 13C resonance assignments of Art v 1: a proline-rich allergen of Artemisia vulgaris pollen.

    PubMed

    Razzera, Guilherme; Gadermaier, Gabriele; Almeida, Marcius S; Ferreira, Fatima; Almeida, Fabio C L; Valente, Ana Paula

    2009-06-01

    Art v 1 is the major allergen of Artemisia vulgaris. The IgE raised against Art v 1 not only can cross-react with other proteins from the Asteraceae family members but also with components of various forms of food. Art v 1 is an important target for immunotherapy strategies, including vaccination with hypoallergenic derivatives or chimeras. We report the (1)H, (13)C, and (15)N resonance assignments of the recombinant Art v 1 and identification of secondary structures based on (13)C chemical shifts.

  19. A 13C-NMR study of exopolysaccharide synthesis in Rhizobium meliloti Su47 strain

    NASA Astrophysics Data System (ADS)

    Tavernier, P.; Portais, J.-C.; Besson, I.; Courtois, J.; Courtois, B.; Barbotin, J.-N.

    1998-02-01

    Metabolic pathways implied in the synthesis of succinoglycan produced by the Su47 strain of R. meliloti were evaluated by 13C-NMR spectroscopy after incubation with [1{-}13C] or [2{-}13C] glucose. The biosynthesis of this polymer by R. meliloti from glucose occurred by a direct polymerisation of the introduced glucose and by the pentose phosphate pathway. Les voies métaboliques impliquées dans la synthèse du succinoglycane produit par la souche Su47 de R. meliloti ont été évaluées par la spectroscopie de RMN du carbone 13 après incubation des cellules avec du [1{-}13C] ou [2{-}13C] glucose. La biosynthèse de ce polymère à partir du glucose se produit par polymérisation directe du glucose et par la voie des pentoses phosphate.

  20. Fish Movement and Dietary History Derived from Otolith (delta)13C

    SciTech Connect

    Weber, P K; Finlay, J C; Power, M E; Phillis, C C; Ramon, C E; Eaton, G F; Ingram, B L

    2005-09-08

    Habitat use and food web linkages are critical data for fish conservation and habitat restoration efforts, particularly for threatened salmonids species. Otolith microchemistry has been shown to be a powerful tool for reconstructing fish movement, but over small distances (kilometers), geology-derived differences in otolith chemistry are rare. Here, we demonstrate that otolith {sup 13}C/{sup 12}C ratio (i.e. {delta}{sup 13}C) of anadromous steelhead trout can be used to distinguish residence in small streams from residence in larger streams and rivers. While previous research has shown that water dissolved inorganic carbon {delta}{sup 13}C is the primary source of carbon in otoliths, the downstream change in food {delta}{sup 13}C in this watershed appears to be the primary control on otolith {delta}{sup 13}C. As a result, this method can also be applied to the problem of reconstructing feeding history at a location.

  1. Atmospheric CO2 concentrations and δ13C values across the Antarctic Circumpolar Current between New Zealand and Antarctica

    NASA Astrophysics Data System (ADS)

    Longinelli, Antonio; Giglio, Federico; Langone, Leonardo; Lenaz, Renzo; Ori, Carlo; Selmo, Enricomaria

    2007-02-01

    Measurements of atmospheric CO2 concentrations were repeatedly carried out on the vessel `Italica' of the Italian National Research Program in Antarctica, during cruises from Italy to Antarctica. Discrete air samples were also collected in 4-L Pyrex flasks during these cruises in order to carry out δ13C analyses on atmospheric CO2. The results acquired between New Zealand and Antarctica are reported here. The mean growth rate of the CO2 concentration from 1996 to 2003 in this area of the Southern Oceans is of about 1.8 ppmv yr-1, in good agreement with NOAA/CMDL measurements. The rates of increase from cruise to cruise are rather variable. From 1996-1997 to 1998-1999 cruise the yearly growth rate is 2.75 ppmv yr-1, close to the large growth rates measured in several areas and mainly related to the most severe El Niño event of the last years. The other yearly growth rates are of about 1.3 and 2 ppmv for the periods 1998-1999 to 2001-2002 and 2001-2002 to 2003-2004, respectively. The large difference between these two values is probably related to the uncertainty on the only two 2001-2002 discrete measurements of CO2 concentration in this area. The measured δ13C values show two completely different distributions and a large interannual variability. The 1998-1999, 2002-2003, and 2003-2004 results obtained between about 55°S and 65°S across the Antarctic Polar Front show a marked negativization of up to more than 2‰ when compared to the background values. The results are related to local source regions of CO2, as frequently found in the Southern Ocean by several authors; the negative δ13C values are tentatively related to the possible contribution of different causes. Among them, the southward negative gradient of δ13C of the dissolved inorganic carbon, the contribution from upwelling deep waters and from subsurface processes between the Northern SubAntarctic Front and the Polar Front, and, partly, the contribution of CO2 of biogenic origin, e.g. from

  2. Reconstruction of δ 13C of chemocline CO 2 (aq) in past oceans and lakes using the δ 13C of fossil isorenieratene

    NASA Astrophysics Data System (ADS)

    van Breugel, Yvonne; Schouten, Stefan; Paetzel, Matthias; Ossebaar, Jort; Sinninghe Damsté, Jaap S.

    2005-06-01

    High abundances of the diaromatic carotenoid isorenieratene derived from photosynthetic green sulfur bacteria (Chlorobiaceae) were found just below the chemocline in an anoxic fjord in Norway, throughout the annual cycle. The stable carbon isotope composition of this carotenoid co-varied with the δ 13C of CO 2 (aq) and is independent of the CO 2 and isorenieratene concentration. This constant isotopic fractionation ɛp of isorenieratene versus CO 2, 4 ± 1‰, was subsequently used in the reconstruction of δ 13C of CO 2 at the chemocline in ancient oceans and lakes. These reconstructions indicate that δ 13C of CO 2 at the chemocline is often influenced by isotopically light CO 2, formed by remineralization of organic matter. This process can, depending on the depth and stability of the chemocline, also effect the isotopic composition of the phytoplankton and, thus, isotopic records of sedimentary inorganic and organic carbon.

  3. An overview of methods using (13)C for improved compound identification in metabolomics and natural products.

    PubMed

    Clendinen, Chaevien S; Stupp, Gregory S; Ajredini, Ramadan; Lee-McMullen, Brittany; Beecher, Chris; Edison, Arthur S

    2015-01-01

    Compound identification is a major bottleneck in metabolomics studies. In nuclear magnetic resonance (NMR) investigations, resonance overlap often hinders unambiguous database matching or de novo compound identification. In liquid chromatography-mass spectrometry (LC-MS), discriminating between biological signals and background artifacts and reliable determination of molecular formulae are not always straightforward. We have designed and implemented several NMR and LC-MS approaches that utilize (13)C, either enriched or at natural abundance, in metabolomics applications. For LC-MS applications, we describe a technique called isotopic ratio outlier analysis (IROA), which utilizes samples that are isotopically labeled with 5% (test) and 95% (control) (13)C. This labeling strategy leads to characteristic isotopic patterns that allow the differentiation of biological signals from artifacts and yield the exact number of carbons, significantly reducing possible molecular formulae. The relative abundance between the test and control samples for every IROA feature can be determined simply by integrating the peaks that arise from the 5 and 95% channels. For NMR applications, we describe two (13)C-based approaches. For samples at natural abundance, we have developed a workflow to obtain (13)C-(13)C and (13)C-(1)H statistical correlations using 1D (13)C and (1)H NMR spectra. For samples that can be isotopically labeled, we describe another NMR approach to obtain direct (13)C-(13)C spectroscopic correlations. These methods both provide extensive information about the carbon framework of compounds in the mixture for either database matching or de novo compound identification. We also discuss strategies in which (13)C NMR can be used to identify unknown compounds from IROA experiments. By combining technologies with the same samples, we can identify important biomarkers and corresponding metabolites of interest.

  4. 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.

  5. Electrochemical Performance and Stability of the Cathode for Solid Oxide Fuel Cells. I. Cross Validation of Polarization Measurements by Impedance Spectroscopy and Current-Potential Sweep

    SciTech Connect

    Zhou, Xiao Dong; Pederson, Larry R.; Templeton, Jared W.; Stevenson, Jeffry W.

    2009-12-09

    The aim of this paper is to address three issues in solid oxide fuel cells: (1) cross-validation of the polarization of a single cell measured using both dc and ac approaches, (2) the precise determination of the total areal specific resistance (ASR), and (3) understanding cathode polarization with LSCF cathodes. The ASR of a solid oxide fuel cell is a dynamic property, meaning that it changes with current density. The ASR measured using ac impedance spectroscopy (low frequency interception with real Z´ axis of ac impedance spectrum) matches with that measured from a dc IV sweep (the tangent of dc i-V curve). Due to the dynamic nature of ASR, we found that an ac impedance spectrum measured under open circuit voltage or on a half cell may not represent cathode performance under real operating conditions, particularly at high current density. In this work, the electrode polarization was governed by the cathode activation polarization; the anode contribution was negligible.

  6. 1H and 13C MAS NMR analysis for the role of chemically inequivalent a-N(CH3)4 and b-N(CH3)4 ions in [N(CH3)4]2CuCl4

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran

    2014-01-01

    The spin-lattice relaxation times in the laboratory frame, T1, and in the rotating frame, T1ρ, for 1H and 13C in [N(CH3)4]2CuCl4 were measured by static NMR and magic angle spinning (MAS) NMR as functions of temperature. The intensities of the 1H and 13C signals changed near phase transition temperatures TC1 and TC3, which indicated that N(CH3)4 plays an important role in these phase transitions. It was thus apparent that the T1 and T1ρ for 1H are governed by the same molecular motions. Two inequivalent ions, a-N(CH3)4 and b-N(CH3)4, were identified by 13C cross-polarization (CP)/MAS NMR. From these results, the behaviors of these two chemically inequivalent N(CH3)4 groups in the paraelastic and ferroelastic phases are discussed.

  7. Foliar d13C within a temperate deciduous forest: spatial, temporal, and species sources of variation

    SciTech Connect

    Garten Jr, Charles T; TaylorJr, G. E.

    1992-04-01

    Foliar {sup 13}C-abundance ({delta}{sup 13}C) was analyzed in the dominant trees of a temperate deciduous forest in east Tennessee (Walker Branch Watershed) to investigate the variation in foliar {delta}{sup 13}C as a function of time (within-year and between years), space (canopy height, watershed topography and habitat) and species (deciduous and coniferous taxa). Various hypotheses were tested by analyzing (i) samples collected from the field during the growing season and (ii) foliar tissues maintained in an archived collection. The {delta}{sup 13}C-value for leaves from the tops of trees was 2 to 3%. more positive than for leaves sampled at lower heights in the canopy. Quercus prinus leaves sampled just prior to autumn leaf fall had significantly more negative {delta}{sup 13}C-values than those sampled during midsummer. On the more xeric ridges, needles of Pinus spp. had more positive {delta}{sup 13}C-values than leaves from deciduous species. Foliar {delta}{sup 13}C-values differed significantly as a function of topography. Deciduous leaves from xeric sites (ridges and slopes) had more positive {delta}{sup 13}C-values than those from mesic (riparian and cove) environments. On the more xeric sites, foliar {delta}{sup 13}C was significantly more positive in 1988 (a dry year) relative to that in 1989 (a year with above-normal precipitation). In contrast, leaf {delta}{sup 13}C in trees from mesic valley bottoms did not differ significantly among years with disparate precipitation. Patterns in foliar {delta}{sup 13}C indicated a higher ratio of net CO{sub 2} assimilation to transpiration (A/E) for trees in more xeric versus mesic habitats, and for trees in xeric habitats during years of drought versus years of normal precipitation. However, A/E (units of mmol CO{sub 2} fixed/mol H{sub 2}O transpired) calculated on the basis of {delta}{sup 13}C-values for leaves from the more xeric sites was higher in a wet year (6.6 {+-} 1.2) versus a dry year (3.4 {+-} 0.4). This

  8. Production of hyperpolarized 13CO2 from [1-13C]pyruvate in perfused liver does reflect total anaplerosis but is not a reliable biomarker of glucose production

    PubMed Central

    Moreno, Karlos X.; Moore, Christopher L.; Burgess, Shawn C.; Sherry, A. Dean; Malloy, Craig R.

    2015-01-01

    In liver, 13CO2 can be generated from [1-13C] pyruvate via pyruvate dehydrogenase or anaplerotic entry of pyruvate into the TCA cycle followed by decarboxylation at phosphoenolpyruvate carboxykinase (PEPCK), the malic enzyme, isocitrate dehydrogenase, or α-ketoglutarate dehydrogenase. The purpose of this study was to determine the relative importance of these pathways in production of hyperpolarized (HP) 13CO2 after administration of hyper-polarized pyruvate in livers supplied with a fatty acid plus substrates for gluconeogenesis. Isolated mouse livers were perfused with a mixture of thermally-polarized 13C-enriched pyruvate, lactate and octanoate in various combinations prior to exposure to HP pyruvate. Under all perfusion conditions, HP malate, aspartate and fumarate were detected within ~ 3 s showing that HP [1-13C]pyruvate is rapidly converted to [1-13C]oxaloacetate which can subsequently produce HP 13CO2 via decarboxylation at PEPCK. Measurements using HP [2-13C]pyruvate allowed the exclusion of reactions related to TCA cycle turnover as sources of HP 13CO2. Direct measures of O2 consumption, ketone production, and glucose production by the intact liver combined with 13C isotopomer analyses of tissue extracts yielded a comprehensive profile of metabolic flux in perfused liver. Together, these data show that, even though the majority of HP 13CO2 derived from HP [1-13C]pyruvate in livers exposed to fatty acids reflects decarboxylation of [4-13C]oxaloacetate (PEPCK) or [4-13C]malate (malic enzyme), the intensity of the HP 13CO2 signal is not proportional to glucose production because the amount of pyruvate returned to the TCA cycle via PEPCK and pyruvate kinase is variable, depending upon available substrates. PMID:26543443

  9. Benthic ostracode δ13C as sensor for early Holocene establishment of modern circulation patterns in Central Europe

    NASA Astrophysics Data System (ADS)

    Schwalb, Antje; Dean, Walter; Güde, Hans; Hanisch, Sabine; Sobek, Sebastian; Wessels, Martin

    2013-04-01

    -water-interface, 13C-depleted carbon is added to pore water DIC that is then available for incorporation into ostracode shells. This mechanism suggests that about 9 cal ka the oxygen supply to the bottom waters, especially in summer, decreased. This stimulated methanogenesis close to the sediment-water-interface, and provided δ13C-depleted carbon to benthic dwellers. Independent evidence for methanogenesis is provided by the increase in concentration of tetrahymanol after about 9 cal ka coincident with the decrease in δ13C of L. mirabilis. We suggest that about 9 cal ka the northward retreat of the Northern Hemisphere Ice Sheets, and consequently the polar front, left the alpine region affected by a more oceanic climate, characterized by warmer winters as they occur today especially during the positive North Atlantic Oscillation Index phase. More frequently incomplete mixing of the water column may have shifted the decay of organic matter faster to anaerobic conditions in surficial sediments especially during summer. By about 7 cal ka the North Atlantic region had probably warmed sufficiently to increase precipitation in Central Europe and consequently detrital-clastic runoff to Lake Constance.

  10. Simultaneous imaging of 13C metabolism and 1H structure: technical considerations and potential applications.

    PubMed

    Gordon, Jeremy W; Fain, Sean B; Niles, David J; Ludwig, Kai D; Johnson, Kevin M; Peterson, Eric T

    2015-05-01

    Real-time imaging of (13)C metabolism in vivo has been enabled by recent advances in hyperpolarization. As a result of the inherently low natural abundance of endogenous (13)C nuclei, hyperpolarized (13)C images lack structural information that could be used to aid in motion detection and anatomical registration. Motion before or during the (13)C acquisition can therefore result in artifacts and misregistration that may obscure measures of metabolism. In this work, we demonstrate a method to simultaneously image both (1)H and (13)C nuclei using a dual-nucleus spectral-spatial radiofrequency excitation and a fully coincident readout for rapid multinuclear spectroscopic imaging. With the appropriate multinuclear hardware, and the means to simultaneously excite and receive on both channels, this technique is straightforward to implement requiring little to no increase in scan time. Phantom and in vivo experiments were performed with both Cartesian and spiral trajectories to validate and illustrate the utility of simultaneous acquisitions. Motion compensation of dynamic metabolic measurements acquired during free breathing was demonstrated using motion tracking derived from (1)H data. Simultaneous multinuclear imaging provides structural (1)H and metabolic (13)C images that are correlated both spatially and temporally, and are therefore amenable to joint (1)H and (13)C analysis and correction of structure-function images.

  11. Are accurate computations of the 13C' shielding feasible at the DFT level of theory?

    PubMed

    Vila, Jorge A; Arnautova, Yelena A; Martin, Osvaldo A; Scheraga, Harold A

    2014-02-05

    The goal of this study is twofold. First, to investigate the relative influence of the main structural factors affecting the computation of the (13)C' shielding, namely, the conformation of the residue itself and the next nearest-neighbor effects. Second, to determine whether calculation of the (13)C' shielding at the density functional level of theory (DFT), with an accuracy similar to that of the (13)C(α) shielding, is feasible with the existing computational resources. The DFT calculations, carried out for a large number of possible conformations of the tripeptide Ac-GXY-NMe, with different combinations of X and Y residues, enable us to conclude that the accurate computation of the (13)C' shielding for a given residue X depends on the: (i) (ϕ,ψ) backbone torsional angles of X; (ii) side-chain conformation of X; (iii) (ϕ,ψ) torsional angles of Y; and (iv) identity of residue Y. Consequently, DFT-based quantum mechanical calculations of the (13)C' shielding, with all these factors taken into account, are two orders of magnitude more CPU demanding than the computation, with similar accuracy, of the (13)C(α) shielding. Despite not considering the effect of the possible hydrogen bond interaction of the carbonyl oxygen, this work contributes to our general understanding of the main structural factors affecting the accurate computation of the (13)C' shielding in proteins and may spur significant progress in effort to develop new validation methods for protein structures.

  12. [Determination of 13C enrichment in soil amino acid enantiomers by gas chromatogram/mass spectrometry].

    PubMed

    He, Hong-Bo; Zhang, Wei; Ding, Xue-Li; Bai, Zhen; Liu, Ning; Zhang, Xu-Dong

    2008-06-01

    The transformation and renewal of amino acid enantiomers is of significance in indicating the turnover mechanism of soil organic matter. In this paper, a method of gas chromatogram/mass spectrometry combined with U-13 C-glucose incubation was developed to determine the 13C enrichment in soil amino acid enantiomers, which could effectively differentiate the original and the newly synthesized amino acids in soil matrix. The added U-13 C-glucose was utilized rapidly to structure the amino acid carbon skeleton, and the change of relative abundance of isotope ions could be determined by mass spectrometry. The direct incorporation of U-13 C glucose was estimated by the intensity increase of m/z (F + n) to F (F was parent fragment, and n was the carbon number in the fragment), while the total isotope incorporation from the added 13C could be calculated according to the abundance ratio increment summation from m/z (Fa + 1) through (Fa + T) (Fa was the fragment containing all original skeleton carbons, and T was the carbon number in the amino acid molecule). The 13C enrichment in the target compound was expressed as atom percentage excess (APE), and that of D-amino acid needed to be corrected by the coefficient of hydrolysis-induced racemization. The 13C enrichment reflected the carbon turnover velocity of individual amino acid enantiomers, and was powerful to investigate the dynamics of soil amino acids.

  13. High-throughput backbone resonance assignment of small 13C, 15N-labeled proteins by a triple-resonance experiment with four sequential connectivity pathways using chemical shift-dependent, apparent 1J ( 1H, 13C): HNCACB codedHAHB

    NASA Astrophysics Data System (ADS)

    Pegan, Scott; Kwiatkowski, Witek; Choe, Senyon; Riek, Roland

    2003-12-01

    The proposed three-dimensional triple-resonance experiment HNCACB codedHAHB correlates sequential 15N, 1H moieties via the chemical shifts of 13C α, 13C β, 1H α, and 1H β. The four sequential correlation pathways are achieved by the incorporation of the concept of chemical shift-coding [J. Biomol. NMR 25 (2003) 281] to the TROSY-HNCACB experiment. The monitored 1H α and 1H β chemical shifts are then coded in the line shape of the cross-peaks of 13C α, 13C β along the 13C dimension through an apparent residual scalar coupling, the size of which depends on the attached hydrogen chemical shift. The information of four sequential correlation pathways enables a rapid backbone assignment. The HNCACB codedHAHB experiment was applied to ˜85% labeled 13C, 15N-labeled amino-terminal fragment of Vaccinia virus DNA topoisomerase I comprising residues 1-77. After one day of measurement on a Bruker Avance 700 MHz spectrometer and 8 h of manual analysis of the spectrum 93% of the backbone assignment was achieved.

  14. 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.

  15. Deposition of 13C tracer in the JET MkII-HD divertor

    NASA Astrophysics Data System (ADS)

    Likonen, J.; Airila, M.; Alves, E.; Barradas, N.; Brezinsek, S.; Coad, J. P.; Devaux, S.; Groth, M.; Grünhagen, S.; Hakola, A.; Jachmich, S.; Koivuranta, S.; Makkonen, T.; Rubel, M.; Strachan, J.; Stamp, M.; Widdowson, A.; EFDA contributors, JET-

    2011-12-01

    Migration of 13C has been investigated at JET by injecting 13C-labelled methane at the outer divertor base at the end of the 2009 campaign. The 13C deposition profiles on carbon fibre composite divertor tiles were measured by secondary ion mass spectrometry and Rutherford backscattering techniques. 13C was mainly deposited near the puffing location on the outer divertor base tiles. High amounts of 13C were also found at the outer vertical target: at the bottom of the lower and at the top of the upper plates. Thirty-three percent of puffed 13CH4 was instantly pumped out by the divertor cryopump, which is close to the pump duct entrance. Global 13C transport in the torus was modelled by the EDGE2D/EIRENE and DIVIMP codes, and local 13C migration in the vicinity of the injection location by the ERO code. The DIVIMP and EDGE2D simulations show strong prompt deposition of 13C directly adjacent to the injection point as well as in the far scrape-off layer (SOL) along both the inner and outer divertor targets. In addition, the measured 13C deposition along the outer divertor wall tiles is qualitatively reproduced. However, EDGE2D and DIVIMP do not predict any deposition along the divertor surfaces facing the private plasma on the inner floor tile and inboard of the outer strike point on tile 5. The ERO calculations also indicate that most of the deposition occurs close to the injection location on the vertical face of the LBSRP tile and the horizontal part of tile 6.

  16. Clinical NOE 13C MRS for neuropsychiatric disorders of the frontal lobe

    NASA Astrophysics Data System (ADS)

    Sailasuta, Napapon; Robertson, Larry W.; Harris, Kent C.; Gropman, Andrea L.; Allen, Peter S.; Ross, Brian D.

    2008-12-01

    In this communication, a scheme is described whereby in vivo 13C MRS can safely be performed in the frontal lobe, a human brain region hitherto precluded on grounds of SAR, but important in being the seat of impaired cognitive function in many neuropsychiatric and developmental disorders. By combining two well known features of 13C NMR—the use of low power NOE and the focus on 13C carbon atoms which are only minimally coupled to protons, we are able to overcome the obstacle of SAR and develop means of monitoring the 13C fluxes of critically important metabolic pathways in frontal brain structures of normal volunteers and patients. Using a combination of low-power WALTZ decoupling, variants of random noise for nuclear overhauser effect enhancement it was possible to reduce power deposition to 20% of the advised maximum specific absorption rate (SAR). In model solutions 13C signal enhancement achieved with this scheme were comparable to that obtained with WALTZ-4. In human brain, the low power procedure effectively determined glutamine, glutamate and bicarbonate in the posterior parietal brain after [1- 13C] glucose infusion. The same 13C enriched metabolites were defined in frontal brain of human volunteers after administration of [1- 13C] acetate, a recognized probe of glial metabolism. Time courses of incorporation of 13C into cerebral glutamate, glutamine and bicarbonate were constructed. The results suggest efficacy for measurement of in vivo cerebral metabolic rates of the glutamate-glutamine and tricarboxylic acid cycles in 20 min MR scans in previously inaccessible brain regions in humans at 1.5T. We predict these will be clinically useful biomarkers in many human neuropsychiatric and genetic conditions.

  17. Detecting response of rat C6 glioma tumors to radiotherapy using hyperpolarized [1- 13C]pyruvate and 13C magnetic resonance spectroscopic imaging.

    PubMed

    Day, Sam E; Kettunen, Mikko I; Cherukuri, Murali Krishna; Mitchell, James B; Lizak, Martin J; Morris, H Douglas; Matsumoto, Shingo; Koretsky, Alan P; Brindle, Kevin M

    2011-02-01

    We show here that hyperpolarized [1-(13) C]pyruvate can be used to detect treatment response in a glioma tumor model; a tumor type where detection of response with (18) fluoro-2-deoxyglucose, using positron emission tomography, is limited by the high background signals from normal brain tissue. (13) C chemical shift images acquired following intravenous injection of hyperpolarized [1-(13) C]pyruvate into rats with implanted C6 gliomas showed significant labeling of lactate within the tumors but comparatively low levels in surrounding brain.Labeled pyruvate was observed at high levels in blood vessels above the brain and from other major vessels elsewhere but was detected at only low levels in tumor and brain.The ratio of hyperpolarized (13) C label in tumor lactate compared to the maximum pyruvate signal in the blood vessels was decreased from 0.38 ± 0.16 to 0.23 ± 0.13, (a reduction of 34%) by 72 h following whole brain irradiation with 15 Gy.

  18. Determination of the Orientation and Dynamics of Ergosterol in Model Membranes Using Uniform 13C Labeling and Dynamically Averaged 13C Chemical Shift Anisotropies as Experimental Restraints

    PubMed Central

    Soubias, O.; Jolibois, F.; Massou, S.; Milon, A.; Réat, V.

    2005-01-01

    A new strategy was established to determine the average orientation and dynamics of ergosterol in dimyristoylphosphatidylcholine model membranes. It is based on the analysis of chemical shift anisotropies (CSAs) averaged by the molecular dynamics. Static 13C CSA tensors were computed by quantum chemistry, using the gauge-including atomic-orbital approach within Hartree-Fock theory. Uniformly 13C-labeled ergosterol was purified from Pichia pastoris cells grown on labeled methanol. After reconstitution into dimyristoylphosphatidylcholine lipids, the complete 1H and 13C assignment of ergosterol's resonances was performed using a combination of magic-angle spinning two-dimensional experiments. Dynamically averaged CSAs were determined by standard side-band intensity analysis for isolated 13C resonances (C3 and ethylenic carbons) and by off-magic-angle spinning experiments for other carbons. A set of 18 constraints was thus obtained, from which the sterol's molecular order parameter and average orientation could be precisely defined. The validity of using computed CSAs in this strategy was verified on cholesterol model systems. This new method allowed us to quantify ergosterol's dynamics at three molar ratios: 16 mol % (Ld phase), 30 mol % (Lo phase), and 23 mol % (mixed phases). Contrary to cholesterol, ergosterol's molecular diffusion axis makes an important angle (14°) with the inertial axis of the rigid four-ring system. PMID:15923221

  19. Synthesis of D-[U-{sup 13}C]Glucal, D-[U-{sup 13}C] Galactal, and L-[U-{sup 13}C]Fucose for NMR structure studies of oligosaccharides

    SciTech Connect

    Wu, R.; Unkefer, C.J.; Silks, L.A. III

    1996-12-31

    The role of carbohydrates is well recognized in a variety of important biological phenomena such as cell surface recognition. Recent advances in carbohydrate chemistry, including the development of solid phase synthesis methods, have helped to provide significant quantities of material by offering general protocols for synthesis of well-defined, pure material. However, the study of the solution structure of oligosaccharides by nuclear magnetic resonance techniques have been hampered by the lack of enriched {sup 13}C material. In an effort to help alleviate this situation, we have been interested in the construction of the title compounds from a single economical carbon source, D-[U-{sup 13}C]glucose. Details of the syntheses will be provided.

  20. Synthesis of [.sup.13C] and [.sup.2H] substituted methacrylic acid, [.sup.13C] and [.sup.2H] substituted methyl methacrylate and/or related compounds

    DOEpatents

    Alvarez, Marc A.; Martinez, Rodolfo A.; Unkefer, Clifford J.

    2008-01-22

    The present invention is directed to labeled compounds of the formulae ##STR00001## wherein Q is selected from the group consisting of --S--, --S(.dbd.O)--, and --S(.dbd.O).sub.2--, Z is selected from the group consisting of 1-naphthyl, substituted 1-naphthyl, 2-naphthyl, substituted 2-naphthyl, and phenyl groups with the structure ##STR00002## wherein R.sub.1, R.sub.2, R.sub.3, R.sub.4 and R.sub.5 are each independently selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl, a halogen, and an amino group selected from the group consisting of NH.sub.2, NHR and NRR' where R and R' are each independently selected from the group consisting of a C.sub.1-C.sub.4 lower alkyl, an aryl, and an alkoxy group, and X is selected from the group consisting of hydrogen, a C.sub.1-C.sub.4 lower alkyl group, and a fully-deuterated C.sub.1-C.sub.4 lower alkyl group. The present invention is also directed to a process of preparing labeled compounds, e.g., process of preparing [.sup.13C]methacrylic acid by reacting a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13CH.sub.2)-- aryl sulfone precursor with .sup.13CHI to form a (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate, and, reacting the (CH.sub.3CH.sub.2O--.sup.13C(O)--.sup.13C(.sup.13CH.sub.3).sub.2)-- aryl sulfone intermediate with sodium hydroxide, followed by acid to form [.sup.13C]methacrylic acid. The present invention is further directed to a process of preparing [.sup.2H.sub.8]methyl methacrylate by reacting a (HOOC--C(C.sup.2H.sub.3).sub.2-- aryl sulfinyl intermediate with CD.sub.3I to form a (.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate, and heating the(.sup.2H.sub.3COOC--C(C.sup.2H.sub.3).sub.2)-- aryl sulfinyl intermediate at temperatures and for time sufficient to form [.sup.2H.sub.8]methyl methacrylate.

  1. Two new organic reference materials for δ13C and δ15N measurements and a new value for the δ13C of NBS 22 oil

    USGS Publications Warehouse

    Qi, Haiping; Coplen, Tyler B.; Geilmann, Heike; Brand, Willi A.; Böhlke, John Karl

    2003-01-01

    Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13C and 15N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a δ13C value of −26.24‰ relative to VPDB and a δ15N value of −4.52‰ relative to N2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13C and 15N. USGS41 has a δ13C value of +37.76‰ and a δ15N value of +47.57‰. The δ13C and δ15N values of both materials were measured against the international reference materials NBS 19 calcium carbonate (δ13C = +1.95‰), L-SVEC lithium carbonate (δ13C = −46.48‰), IAEA-N-1 ammonium sulfate (δ15N = 0.43‰), and USGS32 potassium nitrate (δ15N = 180‰) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of δ13C is better than 0.13‰, and that of δ15N is better than 0.13‰ in 100-μg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a δ13C value for NBS 22 oil of −29.91‰, in contrast to the commonly accepted value of −29.78‰ for which off-line blank corrections probably have not been quantified satisfactorily.

  2. Two new organic reference materials for δ13C and δ15N measurements and a new value for the δ13C of NBS 22 oil

    USGS Publications Warehouse

    Qi, Haiping; Coplen, Tyler B.; Geilmann, Heike; Brand, Willi A.; Böhlke, J.K.

    2003-01-01

    Analytical grade L-glutamic acid is chemically stable and has a C/N mole ratio of 5, which is close to that of many of natural biological materials, such as blood and animal tissue. Two L-glutamic acid reference materials with substantially different 13C and 15N abundances have been prepared for use as organic reference materials for C and N isotopic measurements. USGS40 is analytical grade L-glutamic acid and has a δ13C value of −26.24‰ relative to VPDB and a δ15N value of −4.52‰ relative to N2 in air. USGS41 was prepared by dissolving analytical grade L-glutamic acid with L-glutamic acid enriched in 13C and 15N. USGS41 has a δ13C value of +37.76‰ and a δ15N value of +47.57‰. The δ13C and δ15N values of both materials were measured against the international reference materials NBS 19 calcium carbonate (δ13C = +1.95‰), L-SVEC lithium carbonate (δ13C = −46.48‰), IAEA-N-1 ammonium sulfate (δ15N = 0.43‰), and USGS32 potassium nitrate (δ15N = 180‰) by on-line combustion continuous-flow and off-line dual-inlet isotope-ratio mass spectrometry. Both USGS40 and USGS41 are isotopically homogeneous; reproducibility of δ13C is better than 0.13‰, and that of δ15N is better than 0.13‰ in 100-μg amounts. These two isotopic reference materials can be used for (i) calibrating local laboratory reference materials, and (ii) quantifying drift with time, mass-dependent fractionations, and isotope-ratio-scale contraction in the isotopic analysis of various biological materials. Isotopic results presented in this paper yield a δ13C value for NBS 22 oil of −29.91‰, in contrast to the commonly accepted value of −29.78‰ for which off-line blank corrections probably have not been quantified satisfactorily.

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

    PubMed

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

    2009-07-01

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

  4. Isotopic ((13)C) fractionation during plant residue decomposition and its implications for soil organic matter studies.

    PubMed

    Schweizer; Fear; Cadisch

    1999-07-01

    Carbon isotopic fractionations in plant materials and those occurring during decomposition have direct implications in studies of short-and longer-term soil organic matter dynamics. Thus the products of decomposition, the evolved CO(2) and the newly formed soil organic matter, may vary in their (13)C signature from that of the original plant material. To evaluate the importance of such fractionation processes, the variations in (13)C signatures between and within plant parts of a tropical grass (Brachiaria humidicola) and tropical legume (Desmodium ovalifolium) were measured and the changes in (13)C content (signatures) during decomposition were monitored over a period of four months. As expected the grass materials were less depleted in (13)C (-11.4 to -11.9 per thousand) than those of the legume (-27.3 to -25.8 per thousand). Root materials of the legume were less (1.5 per thousand) depleted in (13)C compared with the leaves. Plant lignin-C was strongly depleted in (13)C compared with the bulk material by up to 2.5 per thousand in the legume and up to 4.7 per thousand in the grass. Plant materials were subsequently incubated in a sand/nutrient-solution/microbial inoculum mixture. The respiration product CO(2) was trapped in NaOH and precipitated as CaCO(3), suitable for analysis using an automated C/N analyser coupled to an isotope ratio mass spectrometer. Significant depletion in (13)C of the evolved CO(2) was observed during the initial stages of decomposition probably as a result of microbial fractionation as it was not associated with the (13)C signatures of the measured more decomposable fractions (non-acid detergent fibre and cellulose). While the cumulative CO(2)-(13)C signatures of legume materials became slightly enriched with ongoing decomposition, the CO(2)-C of the grass materials remained depleted in (13)C. Associated isotopic fractionation correction factors for source identification of CO(2-)C varied with time and suggested errors of 2-19% in the

  5. Isotopomer studies of gluconeogenesis and the Krebs cycle with 13C-labeled lactate.

    PubMed

    Katz, J; Wals, P; Lee, W N

    1993-12-05

    Fasted rats were intragastrically infused with either [2,3-13C]lactate or [1,2,3-13C]lactate. The infusate also contained 14C-labeled lactate and [3-3H]glucose. Glucose, alanine, glutamate, and glutamine were isolated from liver and blood. There was near complete equilibration of lactate and alanine, and the relative specific activities and relative enrichments were the same in blood and liver. Glucose was cleaved enzymatically to lactate. The compounds were examined by gas chromatography-mass spectroscopy. From the mass isotopomer spectra of the lactate, glutamate, and glutamine and their cleavage fragments the positional isotopomer composition of these compounds was obtained. The enrichment and isotopomer pattern in the lactate from cleaved glucose represents that in phosphoenolpyruvate (PEP). When [1,2,3-13C]lactate was infused the mass isotopomer spectrum of glutamates consisted only of compounds containing either one, two, or three 13C carbons per molecule (m1, m2, and m3). There was little 13C in C-4 and C-5 of glutamate. The rate of pyruvate decarboxylation is low, and 3-4% of the acetyl-CoA flux in the Krebs cycle is contributed by lactate carbon. The major isotopomers in lactate, alanine, and PEP were m3 and m2 with 13C in C-2 and C-3. The predominant isotopomer in PEP from [2,3-13C]lactate was m2 with 13C in C-2 and C-3. There was much more of m1 isotopomer with 13C in C-3 and C-2 than the m1 isotopomer with 13C in C-1. There was very little m3, the isotopomer with 13C in all three carbons. Most of the 13C in C-3 and C-4 of glucose and C-1 of glutamate was introduced via 13CO2 fixation. From the isotopomer distribution and the rate of glucose turnover we deduced, applying the analysis described in the "Appendix," the absolute rates of gluconeogenic pathways, recycling of PEP and the Cori cycle, and flux in the Krebs cycle. The flux from oxaloacetate (OAA)-->PEP was seven times that of OAA-->citrate, and about half of PEP was recycled to pyruvate via

  6. A roadmap for interpreting 13C metabolite labeling patterns from cells

    PubMed Central

    Buescher, Joerg M.; Antoniewicz, Maciek R.; Boros, Laszlo G.; Burgess, Shawn C.; Brunengraber, Henri; Clish, Clary B.; DeBerardinis, Ralph J.; Feron, Olivier; Frezza, Christian; Ghesquiere, Bart; Gottlieb, Eyal; Hiller, Karsten; Jones, Russell G.; Kamphorst, Jurre J.; Kibbey, Richard G.; Kimmelman, Alec C.; Locasale, Jason W.; Lunt, Sophia Y.; Maddocks, Oliver D. K.; Malloy, Craig; Metallo, Christian M.; Meuillet, Emmanuelle J.; Munger, Joshua; Nöh, Katharina; Rabinowitz, Joshua D.; Ralser, Markus; Sauer, Uwe; Stephanopoulos, Gregory; St-Pierre, Julie; Tennant, Daniel A.; Wittmann, Christoph; Vander Heiden, Matthew G.; Vazquez, Alexei; Vousden, Karen; Young, Jamey D.; Zamboni, Nicola; Fendt, Sarah-Maria

    2015-01-01

    Measuring intracellular metabolism has increasingly led to important insights in biomedical research. 13C tracer analysis, although less information-rich than quantitative 13C flux analysis that requires computational data integration, has been established as a time-efficient method to unravel relative pathway activities, qualitative changes in pathway contributions, and nutrient contributions. Here, we review selected key issues in interpreting 13C metabolite labeling patterns, with the goal of drawing accurate conclusions from steady state and dynamic stable isotopic tracer experiments. PMID:25731751

  7. 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

  8. Modular video endoscopy for in vivo cross-polarized and vital-dye fluorescence imaging of Barrett's-associated neoplasia

    NASA Astrophysics Data System (ADS)

    Thekkek, Nadhi; Pierce, Mark C.; Lee, Michelle H.; Polydorides, Alexandros D.; Flores, Raja M.; Anandasabapathy, Sharmila; Richards-Kortum, Rebecca R.

    2013-02-01

    A modular video endoscope is developed and tested to allow imaging in different modalities. This system incorporates white light imaging (WLI), cross-polarized imaging (CPI), and vital-dye fluorescence imaging (VFI), using interchangeable filter modules. CPI and VFI are novel endoscopic modalities that probe mucosal features associated with Barrett's neoplasia. CPI enhances vasculature, while VFI enhances glandular architecture. In this pilot study, we demonstrate the integration of these modalities by imaging areas of Barrett's metaplasia and neoplasia in an esophagectomy specimen. We verify that those key image features are also observed during an in vivo surveillance procedure. CPI images demonstrate improved visualization of branching blood vessels associated with neoplasia. VFI images show glandular architecture with increased glandular effacement associated with neoplasia. Results suggests that important pathologic features seen in CPI and VFI are not visible during standard endoscopic white light imaging, and thus the modalities may be useful in future in vivo studies for discriminating neoplasia from Barrett's metaplasia. We further demonstrate that the integrated WLI/CPI/VFI endoscope is compatible with complementary high-resolution endomicroscopy techniques such as the high-resolution microendoscope, potentially enabling two-step ("red-flag" widefield plus confirmatory high-resolution imaging) protocols to be enhanced.

  9. Solar wind density controlling penetration electric field at the equatorial ionosphere during a saturation of cross polar cap potential

    NASA Astrophysics Data System (ADS)

    Wei, Y.; Wan, W.; Zhao, B.; Hong, M.; Ridley, A.; Ren, Z.; Fraenz, M.; Dubinin, E.; He, M.

    2012-09-01

    The most important source of electrodynamic disturbances in the equatorial ionosphere during the main phase of a storm is the prompt penetration electric field (PPEF) originating from the high-latitude region. It has been known that such an electric field is correlated with the magnetospheric convection or interplanetary electric field. Here we show a unique case, in which the electric field disturbance in the equatorial ionosphere cannot be interpreted by this concept. During the superstorm on Nov. 20-21, 2003, the cross polar cap potential (CPCP) saturated at least for 8.2 h. The CPCP reconstructed by Assimilative Mapping of Ionospheric Electrodynamics (AMIE) procedure suggested that the PPEF at the equatorial ionosphere still correlated with the saturated CPCP, but the CPCP was controlled by the solar wind density instead of the interplanetary electric field. However, the predicted CPCPs by Hill-Siscoe-Ober (HSO) model and Boyle-Ridley (BR) model were not fully consistent with the AMIE result and PPEF. The PPEF also decoupled from the convection electric field in the magnetotail. Due to the decoupling, the electric field in the ring current was not able to comply with the variations of PPEF, and this resulted in a long-duration electric field penetration without shielding.

  10. Confocal microscopy of excised human skin using acetic acid and crossed polarization: rapid detection of nonmelanoma skin cancers

    NASA Astrophysics Data System (ADS)

    Rajadhyaksha, Milind M.; Menaker, Gregg; Gonzalez, Salvador

    2000-05-01

    Moh's micrographic surgery for basal- and squamous-cell cancers (BCCs, SCCs) involves precise excision of the tumor with minimal damage to the surrounding normal skin. Precise excision is guided by histopathologic examination for tumor margins; typically, 2 - 4 slices of skin are excised, and there is a waiting time of 15 - 45 minutes for the surgeon and patient while each slice is being processed for histopathology. We can avoid the processing by using a confocal reflectance microscope; confocal detection of BCCs and SCCs is possible after staining the nuclei in the excised skin with 5% acetic acid, and imaging in crossed polarization. The cancerous nuclei appear bright against the dark surrounding normal dermis. The contrast is due to increased back-scattering as well as increased depolarization from the intra-nuclear structure relative to that from the surrounding normal dermis. As in conventional histopathology, the tumors are first detected at low resolution (section thickness 20 micrometer) in a wide field (1-2 mm); nuclear morphology is then viewed at high resolution (section thickness 2 micrometer) in a small field (0.25 - 0.50 mm). Mosaics of images are assembled to produce confocal maps of the BCCs or SCCs within large excised tissue. Rapid detection (within minutes) is possible.

  11. Broadband cross-polarization-based heteronuclear dipolar recoupling for structural and dynamic NMR studies of rigid and soft solids

    SciTech Connect

    Kharkov, B. B.; Chizhik, V. I.; Dvinskikh, S. V.

    2016-01-21

    Dipolar recoupling is an essential part of current solid-state NMR methodology for probing atomic-resolution structure and dynamics in solids and soft matter. Recently described magic-echo amplitude- and phase-modulated cross-polarization heteronuclear recoupling strategy aims at efficient and robust recoupling in the entire range of coupling constants both in rigid and highly dynamic molecules. In the present study, the properties of this recoupling technique are investigated by theoretical analysis, spin-dynamics simulation, and experimentally. The resonance conditions and the efficiency of suppressing the rf field errors are examined and compared to those for other recoupling sequences based on similar principles. The experimental data obtained in a variety of rigid and soft solids illustrate the scope of the method and corroborate the results of analytical and numerical calculations. The technique benefits from the dipolar resolution over a wider range of coupling constants compared to that in other state-of-the-art methods and thus is advantageous in studies of complex solids with a broad range of dynamic processes and molecular mobility degrees.

  12. Dynamic structures of intact chicken erythrocyte chromatins as studied by 1H-31P cross-polarization NMR.

    PubMed Central

    Akutsu, H; Nishimoto, S; Kyogoku, Y

    1994-01-01

    The dynamic properties of DNA in intact chicken erythrocyte cells, nuclei, nondigested chromatins, digested soluble chromatins, H1, H5-depleted soluble chromatins and nucleosome cores were investigated by means of single-pulse and 1H-31P cross-polarization NMR. The temperature dependence of the phosphorus chemical shift anisotropy was identical for the former three in the presence of 3 mM MgCl2, suggesting that the local higher order structure is identical for these chromatins. The intrinsic phosphorus chemical shift anisotropy of the nucleosome cores was -159 ppm. The chemical shift anisotropy of DNA in the chromatins can be further averaged by the motion of the linker DNA. The spin-lattice relaxation time in the rotating frame of the proton spins (T1p) of the nondigested chromatins was measured at various locking fields. The result was analyzed on the assumption of the isotropic motion to get a rough value of the correlation time of the motion efficient for the relaxation, which was eventually ascribed to the segmental motion of the linker DNA with restricted amplitude. The 30 nm filament structure induced by NaCl was shown to be dynamically different from that induced by MgCl2. Side-by-side compaction of 30-nm filaments was suggested to be induced in the MgCl2 concentration range higher than 0.3 mM. Biological significance of the dynamic structure was discussed in connection with the results obtained. PMID:7948693

  13. Broadband cross-polarization-based heteronuclear dipolar recoupling for structural and dynamic NMR studies of rigid and soft solids

    NASA Astrophysics Data System (ADS)

    Kharkov, B. B.; Chizhik, V. I.; Dvinskikh, S. V.

    2016-01-01

    Dipolar recoupling is an essential part of current solid-state NMR methodology for probing atomic-resolution structure and dynamics in solids and soft matter. Recently described magic-echo amplitude- and phase-modulated cross-polarization heteronuclear recoupling strategy aims at efficient and robust recoupling in the entire range of coupling constants both in rigid and highly dynamic molecules. In the present study, the properties of this recoupling technique are investigated by theoretical analysis, spin-dynamics simulation, and experimentally. The resonance conditions and the efficiency of suppressing the rf field errors are examined and compared to those for other recoupling sequences based on similar principles. The experimental data obtained in a variety of rigid and soft solids illustrate the scope of the method and corroborate the results of analytical and numerical calculations. The technique benefits from the dipolar resolution over a wider range of coupling constants compared to that in other state-of-the-art methods and thus is advantageous in studies of complex solids with a broad range of dynamic processes and molecular mobility degrees.

  14. Improved Wavelength Detuning Cross-Beam Energy Transfer Mitigation Strategy for Polar Direct Drive at the National Ignition Facility

    NASA Astrophysics Data System (ADS)

    Marozas, J. A.; Collins, T. J. B.; McKenty, P. W.; Zuegel, J. D.

    2015-11-01

    Cross-beam energy transfer (CBET) reduces absorbed light and implosion velocity, alters time-resolved scattered-light spectra, and redistributes absorbed and scattered light. These effects reduce target performance in both symmetric direct-drive and polar-direct-drive (PDD) experiments on the OMEGA Laser System and the National Ignition Facility (NIF). The CBET package (Adaawam) incorporated into the 2-D hydrodynamics code DRACO is an integral part of the 3-D ray-trace package (Mazinisin). The CBET exchange occurs primarily over the equatorial region in PDD, where successful mitigation strategies concentrate. Detuning the initial laser wavelength (dλ0) reduces the CBET interaction volume, which can be combined with other mitigation domains (e.g., spatial and temporal). By judiciously selecting the ring and/or port +/-dλ0 in each hemisphere, using new DRACO diagnostic abilities, improved wavelength detuning strategies trade-off overall energy absorption for improved hemispherical energy balance control. These balanced-wavelength detuning strategies improve performance for high-convergence implosions. Simulations (2-D DRACO) predict improved implosion performance and control in both the shell trajectory and morphology for planned intermediate PDD experiments on the NIF. This material is based upon work supported by the Department of Energy National Nuclear Security Administration under Award Number DE-NA0001944.

  15. Broadband cross-polarization-based heteronuclear dipolar recoupling for structural and dynamic NMR studies of rigid and soft solids.

    PubMed

    Kharkov, B B; Chizhik, V I; Dvinskikh, S V

    2016-01-21

    Dipolar recoupling is an essential part of current solid-state NMR methodology for probing atomic-resolution structure and dynamics in solids and soft matter. Recently described magic-echo amplitude- and phase-modulated cross-polarization heteronuclear recoupling strategy aims at efficient and robust recoupling in the entire range of coupling constants both in rigid and highly dynamic molecules. In the present study, the properties of this recoupling technique are investigated by theoretical analysis, spin-dynamics simulation, and experimentally. The resonance conditions and the efficiency of suppressing the rf field errors are examined and compared to those for other recoupling sequences based on similar principles. The experimental data obtained in a variety of rigid and soft solids illustrate the scope of the method and corroborate the results of analytical and numerical calculations. The technique benefits from the dipolar resolution over a wider range of coupling constants compared to that in other state-of-the-art methods and thus is advantageous in studies of complex solids with a broad range of dynamic processes and molecular mobility degrees.

  16. Assessing Oxidative Stress in Tumors by Measuring the Rate of Hyperpolarized [1-13C]Dehydroascorbic Acid Reduction Using 13C Magnetic Resonance Spectroscopy*

    PubMed Central

    Timm, Kerstin N.; Hu, De-En; Williams, Michael; Wright, Alan J.; Kettunen, Mikko I.; Kennedy, Brett W. C.; Larkin, Timothy J.; Dzien, Piotr; Marco-Rius, Irene; Bohndiek, Sarah E.; Brindle, Kevin M.

    2017-01-01

    Rapid cancer cell proliferation promotes the production of reducing equivalents, which counteract the effects of relatively high levels of reactive oxygen species. Reactive oxygen species levels increase in response to chemotherapy and cell death, whereas an increase in antioxidant capacity can confer resistance to chemotherapy and is associated with an aggressive tumor phenotype. The pentose phosphate pathway is a major site of NADPH production in the cell, which is used to maintain the main intracellular antioxidant, glutathione, in its reduced state. Previous studies have shown that the rate of hyperpolarized [1-13C]dehydroascorbic acid (DHA) reduction, which can be measured in vivo using non-invasive 13C magnetic resonance spectroscopic imaging, is increased in tumors and that this is correlated with the levels of reduced glutathione. We show here that the rate of hyperpolarized [1-13C]DHA reduction is increased in tumors that have been oxidatively prestressed by depleting the glutathione pool by buthionine sulfoximine treatment. This increase was associated with a corresponding increase in pentose phosphate pathway flux, assessed using 13C-labeled glucose, and an increase in glutaredoxin activity, which catalyzes the glutathione-dependent reduction of DHA. These results show that the rate of DHA reduction depends not only on the level of reduced glutathione, but also on the rate of NADPH production, contradicting the conclusions of some previous studies. Hyperpolarized [1-13C]DHA can be used, therefore, to assess the capacity of tumor cells to resist oxidative stress in vivo. However, DHA administration resulted in transient respiratory arrest and cardiac depression, which may prevent translation to the clinic. PMID:27994059

  17. 1H, 13C NMR and DFT Study of Hydrogen Bonding in Imidazolium-based Ionic Liquids.

    PubMed

    Balevičius, Vytautas; Gdaniec, Zofia; Džiaugys, Lukas; Kuliešius, Feliksas; Maršalka, Arūnas

    2011-09-01

    The ionic liquid 1-decyl-3-methyl-imidazolium bromide [C10mim][Br], the neat material, and also dissolved (~0.01 mole fraction) in various dielectric media (acetonitrile, benzene, chloroform, dichloromethane, methanol, 2-butanol and H2O) was studied using 1H and 13C NMR spectroscopy. The most important interaction in this compound is considered to be the Br-...H-C2+ hydrogen bond, which is formed between the anions and cations. The obtained results show that dielectric medium influence mostly the behavior of the Br-...H-C2+ bridge proton. The changes observed in 1H and 13C NMR spectra of [C10mim][Br] with increasing solvents polarity and temperature can be explained applying the model of the lengthening of the H2...Br- bond with the accompanying thickening of the solvation shell of bromine anion and C2-H bond contraction. The short-range order effects related to the configuration of neighboring dipoles of solvent molecules are more important for the solvation ability of small anions than the bulk solvent field effect. However, the solvents, molecules of which tend to associate via hydrogen bonding, can significantly affect the dynamics of anions.

  18. 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.

  19. 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

  20. Real-time assessment of Krebs cycle metabolism using hyperpolarized 13C magnetic resonance spectroscopy.

    PubMed

    Schroeder, Marie A; Atherton, Helen J; Ball, Daniel R; Cole, Mark A; Heather, Lisa C; Griffin, Julian L; Clarke, Kieran; Radda, George K; Tyler, Damian J

    2009-08-01

    The Krebs cycle plays a fundamental role in cardiac energy production and is often implicated in the energetic imbalance characteristic of heart disease. In this study, we measured Krebs cycle flux in real time in perfused rat hearts using hyperpolarized magnetic resonance spectroscopy (MRS). [2-(13)C]Pyruvate was hyperpolarized and infused into isolated perfused hearts in both healthy and postischemic metabolic states. We followed the enzymatic conversion of pyruvate to lactate, acetylcarnitine, citrate, and glutamate with 1 s temporal resolution. The appearance of (13)C-labeled glutamate was delayed compared with that of other metabolites, indicating that Krebs cycle flux can be measured directly. The production of (13)C-labeled citrate and glutamate was decreased postischemia, as opposed to lactate, which was significantly elevated. These results showed that the control and fluxes of the Krebs cycle in heart disease can be studied using hyperpolarized [2-(13)C]pyruvate.

  1. Nanotwins soften boron-rich boron carbide (B13C2)

    NASA Astrophysics Data System (ADS)

    An, Qi; Goddard, William A.

    2017-03-01

    Extensive studies of metals and alloys have observed that nanotwins lead to strengthening, but the role of nanotwins in ceramics is not well established. We compare here the shear strength and the deformation mechanism of nanotwinned boron-rich boron carbide (B13C2) with the perfect crystal under both pure shear and biaxial shear deformations. We find that the intrinsic shear strength of crystalline B13C2 is higher than that of crystalline boron carbide (B4C). But nanotwins in B13C2 lower the strength, making it softer than crystalline B4C. This reduction in strength of nanotwinned B13C2 arises from the interaction of the twin boundary with the C-B-C chains that connect the B12 icosahedra.

  2. Deposition of 13C tracer in the JET MkII-HD divertor

    NASA Astrophysics Data System (ADS)

    Jet-Efda Contributors Likonen, J.; Hakola, A.; Strachan, J.; Coad, J. P.; Widdowson, A.; Koivuranta, S.; Hole, D. E.; Mizohata, K.; Rubel, M.; Jachmich, S.; Stamp, M.

    2011-08-01

    Migration of 13C has been investigated at JET by puffing 13CH4 into the outer midplane at the end of the 2007 campaign. The 13C deposition profile was measured with secondary ion mass spectrometry (SIMS) and Rutherford backscattering (RBS) techniques. 13C was mainly found on Tile 1 and near the outer strike point (OSP) on Tile 7. The 13C transport was modelled with the EDGE2D/NIMBUS code. Previous work indicates that migration pathways are: (1) through the main chamber scrape-off layer (SOL), (2) migration through the private flux region (PFR) aided by E × B drifts and (3) neutral migration originating near the strike points. The main contribution of this paper is to further describe the neutral migration.

  3. Preparation of 13C/15N-labeled oligomers using the polymerase chain reaction

    DOEpatents

    Chen, Xian; Gupta, Goutam; Bradbury, E. Morton

    2001-01-01

    Preparation of .sup.13 C/.sup.15 N-labeled DNA oligomers using the polymerase chain reaction (PCR). A PCR based method for uniform (.sup.13 C/.sup.15 N)-labeling of DNA duplexes is described. Multiple copies of a blunt-ended duplex are cloned into a plasmid, each copy containing the sequence of interest and restriction Hinc II sequences at both the 5' and 3' ends. PCR using bi-directional primers and uniformly .sup.13 C/.sup.15 N-labeled dNTP precursors generates labeled DNA duplexes containing multiple copies of the sequence of interest. Twenty-four cycles of PCR, followed by restriction and purification, gave the uniformly .sup.13 C/.sup.15 N-labeled duplex sequence with a 30% yield. Such labeled duplexes find significant applications in multinuclear magnetic resonance spectroscopy.

  4. Separation of extra- and intracellular metabolites using hyperpolarized 13C diffusion weighted MR

    NASA Astrophysics Data System (ADS)

    Koelsch, Bertram L.; Sriram, Renuka; Keshari, Kayvan R.; Leon Swisher, Christine; Van Criekinge, Mark; Sukumar, Subramaniam; Vigneron, Daniel B.; Wang, Zhen J.; Larson, Peder E. Z.; Kurhanewicz, John

    2016-09-01

    This work demonstrates the separation of extra- and intracellular components of glycolytic metabolites with diffusion weighted hyperpolarized 13C magnetic resonance spectroscopy. Using b-values of up to 15,000 s mm-2, a multi-exponential signal response was measured for hyperpolarized [1-13C] pyruvate and lactate. By fitting the fast and slow asymptotes of these curves, their extra- and intracellular weighted diffusion coefficients were determined in cells perfused in a MR compatible bioreactor. In addition to measuring intracellular weighted diffusion, extra- and intracellular weighted hyperpolarized 13C metabolites pools are assessed in real-time, including their modulation with inhibition of monocarboxylate transporters. These studies demonstrate the ability to simultaneously assess membrane transport in addition to enzymatic activity with the use of diffusion weighted hyperpolarized 13C MR. This technique could be an indispensible tool to evaluate the impact of microenvironment on the presence, aggressiveness and metastatic potential of a variety of cancers.

  5. Wheat Bran Does Not Affect Postprandial Plasma Short-Chain Fatty Acids from 13C-inulin Fermentation in Healthy Subjects

    PubMed Central

    Deroover, Lise; Verspreet, Joran; Luypaerts, Anja; Vandermeulen, Greet; Courtin, Christophe M.; Verbeke, Kristin

    2017-01-01

    Wheat bran (WB) is a constituent of whole grain products with beneficial effects for human health. Within the human colon, such insoluble particles may be colonized by specific microbial teams which can stimulate cross-feeding, leading to a more efficient carbohydrate fermentation and an increased butyrate production. We investigated the extent to which WB fractions with different properties affect the fermentation of other carbohydrates in the colon. Ten healthy subjects performed four test days, during which they consumed a standard breakfast supplemented with 10 g 13C-inulin. A total of 20 g of a WB fraction (unmodified WB, wheat bran with a reduced particle size (WB RPS), or de-starched pericarp-enriched wheat bran (PE WB)) was also added to the breakfast, except for one test day, which served as a control. Blood samples were collected at regular time points for 14 h, in order to measure 13C-labeled short-chain fatty acid (SCFA; acetate, propionate and butyrate) concentrations. Fermentation of 13C-inulin resulted in increased plasma SCFA for about 8 h, suggesting that a sustained increase in plasma SCFA can be achieved by administering a moderate dose of carbohydrates, three times per day. However, the addition of a single dose of a WB fraction did not further increase the 13C-SCFA concentrations in plasma, nor did it stimulate cross-feeding (Wilcoxon signed ranks test). PMID:28117694

  6. 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.

  7. Investigation of a marine magnetic polarity reversal boundary in cross section at the northern boundary of the Kane Megamullion, Mid-Atlantic Ridge, 23°40'N

    NASA Astrophysics Data System (ADS)

    Xu, Min; Tivey, M. A.

    2016-05-01

    Near-bottom magnetic field measurements made by the submersible Nautile during the 1992 Kanaut Expedition define the cross-sectional geometry of magnetic polarity reversal boundaries and the vertical variation of crustal magnetization in lower oceanic crust exposed along the Kane Transform Fault (TF) at the northern boundary of the Kane Megamullion (KMM). The KMM exposes lower crust and upper mantle rocks on a low-angle normal fault that was active between 3.3 Ma and 2.1 Ma. The geometry of the polarity boundaries is estimated from an inversion of the submarine magnetic data for crustal magnetization. In general, the polarity boundaries dip away from the ridge axis along the Kane TF scarp, with a west dipping angle of ~45° in the shallow (<1 km) crust and <20° in the deeper crust. The existence of the magnetic polarity boundaries (e.g., C2r.2r/C2An.1n, ~2.581 Ma) indicates that the lower crustal gabbros and upper mantle serpentinized peridotites are able to record a coherent magnetic signal. Our results support the conclusion of Williams (2007) that the lower crust cools through the Curie temperature of magnetite to become magnetic, with the polarity boundaries representing both frozen isotherms and isochrons. We also test the effects of the rotation of this isotherm structure and/or footwall rotation and find that the magnetic polarity boundary geometry is not sensitive to these directional changes.

  8. Wingless-type family member 3A triggers neuronal polarization via cross-activation of the insulin-like growth factor-1 receptor pathway.

    PubMed

    Bernis, María E; Oksdath, Mariana; Dupraz, Sebastián; Nieto Guil, Alvaro; Fernández, Marisa M; Malchiodi, Emilio L; Rosso, Silvana B; Quiroga, Santiago

    2013-01-01

    Initial axonal elongation is essential for neuronal polarization and requires polarized activation of IGF-1 receptors (IGF-1r) and the phosphatidylinositol 3 kinase (PI3k) pathway. Wingless-type family growth factors (Wnts) have also been implied in the regulation of axonal development. It is not known, however, if Wnts have any participation in the regulation of initial axonal outgrowth and the establishment of neuronal polarity. We used cultured hippocampal neurons and growth cone particles (GCPs) isolated from fetal rat brain to show that stimulation with the wingless family factor 3A (Wnt3a) was sufficient to promote neuronal polarization in the absence of IGF-1 or high insulin. We also show that Wnt3a triggered a strong activation of IGF-1r, PI3k, and Akt in developmental Stage 2 neurons and that the presence of activatable IGF-1r and PI3k activation were necessary for Wnt3a polarizing effects. Surface plasmon resonance (SPR) experiments show that Wnt3a did not bind specifically to the IGF-1r. Using crosslinking and immuno-precipitation experiments, we show that stimulation with Wnt3a triggered the formation of a complex including IGF-1r-Wnt3a-Frizzled-7. We conclude that Wnt3a triggers polarization of neurons via cross-activation of the IGF-1r/PI3k pathway upon binding to Fz7.

  9. Wingless-type family member 3A triggers neuronal polarization via cross-activation of the insulin-like growth factor-1 receptor pathway

    PubMed Central

    Bernis, María E.; Oksdath, Mariana; Dupraz, Sebastián; Nieto Guil, Alvaro; Fernández, Marisa M.; Malchiodi, Emilio L.; Rosso, Silvana B.; Quiroga, Santiago

    2013-01-01

    Initial axonal elongation is essential for neuronal polarization and requires polarized activation of IGF-1 receptors (IGF-1r) and the phosphatidylinositol 3 kinase (PI3k) pathway. Wingless-type family growth factors (Wnts) have also been implied in the regulation of axonal development. It is not known, however, if Wnts have any participation in the regulation of initial axonal outgrowth and the establishment of neuronal polarity. We used cultured hippocampal neurons and growth cone particles (GCPs) isolated from fetal rat brain to show that stimulation with the wingless family factor 3A (Wnt3a) was sufficient to promote neuronal polarization in the absence of IGF-1 or high insulin. We also show that Wnt3a triggered a strong activation of IGF-1r, PI3k, and Akt in developmental Stage 2 neurons and that the presence of activatable IGF-1r and PI3k activation were necessary for Wnt3a polarizing effects. Surface plasmon resonance (SPR) experiments show that Wnt3a did not bind specifically to the IGF-1r. Using crosslinking and immuno-precipitation experiments, we show that stimulation with Wnt3a triggered the formation of a complex including IGF-1r-Wnt3a-Frizzled-7. We conclude that Wnt3a triggers polarization of neurons via cross-activation of the IGF-1r/PI3k pathway upon binding to Fz7. PMID:24298236

  10. Water availability and branch length determine delta(13)C in foliage of Pinus pinaster.

    PubMed

    Warren, Charles R.; Adams, Mark A.

    2000-05-01

    The stable carbon isotope composition (delta(13)C) of foliage integrates signals resulting from environmental and hydraulic constraints on water movement and photosynthesis. We used branch length as a simple predictor of hydraulic constraints to water fluxes and determined the response of delta(13)C to varying water availability. Foliage up to 6 years old was taken from Pinus pinaster Ait. trees growing at four sites differing in precipitation (P; 414-984 mm year(-1)) and potential evaporation (ET; 1091-1750 mm year(-1)). Branch length was the principal determinant of temporal trends in delta(13)C. The strong relationship between delta(13)C and branch length was a function of hydraulic conductance, which was negatively correlated with branch length (r(2) = 0.84). Variation in P and ET among sites was reflected in delta(13)C, which was negatively correlated with P/ET (r(2) = 0.66). However, this analysis was confounded by differences in branch length. If the effects of branch length on delta(13)C were first removed, then the 'residual' delta(13)C was more closely related to P/ET (r(2) = 0.99), highlighting the importance of accounting for variation in hydraulic constraints to water flux between sites and years. For plant species that exhibit considerable phenotypic plasticity in response to changes in environment (e.g., variation in leaf area, branch length and number, or stem form), the environmental effects on delta(13)C in foliage can only be reliably assessed if deconvoluted from hydraulic constraints.

  11. Parallel labeling experiments validate Clostridium acetobutylicum metabolic network model for (13)C metabolic flux analysis.

    PubMed

    Au, Jennifer; Choi, Jungik; Jones, Shawn W; Venkataramanan, Keerthi P; Antoniewicz, Maciek R

    2014-11-01

    In this work, we provide new insights into the metabolism of Clostridium acetobutylicum ATCC 824 obtained using a systematic approach for quantifying fluxes based on parallel labeling experiments and (13)C-metabolic flux analysis ((13)C-MFA). Here, cells were grown in parallel cultures with [1-(13)C]glucose and [U-(13)C]glucose as tracers and (13)C-MFA was used to quantify intracellular metabolic fluxes. Several metabolic network models were compared: an initial model based on current knowledge, and extended network models that included additional reactions that improved the fits of experimental data. While the initial network model did not produce a statistically acceptable fit of (13)C-labeling data, an extended network model with five additional reactions was able to fit all data with 292 redundant measurements. The model was subsequently trimmed to produce a minimal network model of C. acetobutylicum for (13)C-MFA, which could still reproduce all of the experimental data. The flux results provided valuable new insights into the metabolism of C. acetobutylicum. First, we found that TCA cycle was effectively incomplete, as there was no measurable flux between α-ketoglutarate and succinyl-CoA, succinate and fumarate, and malate and oxaloacetate. Second, an active pathway was identified from pyruvate to fumarate via aspartate. Third, we found that isoleucine was produced exclusively through the citramalate synthase pathway in C. acetobutylicum and that CAC3174 was likely responsible for citramalate synthase activity. These model predictions were confirmed in several follow-up tracer experiments. The validated metabolic network model established in this study can be used in future investigations for unbiased (13)C-flux measurements in C. acetobutylicum.

  12. Tracing the biosynthetic source of essential amino acids in marine turtles using delta13C fingerprints.

    PubMed

    Arthur, Karen E; Kelez, Shaleyla; Larsen, Thomas; Choy, C Anela; Popp, Brian N

    2014-05-01

    Plants, bacteria, and fungi produce essential amino acids (EAAs) with distinctive patterns of delta13C values that can be used as naturally occurring fingerprints of biosynthetic origin of EAAs in a food web. Because animals cannot synthesize EAAs and must obtain them from food, their tissues reflect delta13C(EAA) patterns found in diet, but it is not known how microbes responsible for hindgut fermentation in some herbivores influence the delta13C values of EAAs in their hosts' tissues. We examined whether distinctive delta13C fingerprints of hindgut flora are evident in the tissues of green turtles (Chelonia mydas), which are known to be facultative hindgut fermenters. We determined delta13C(EAA) values in tissues of green turtles foraging herbivorously in neritic habitats of Hawaii and compared them with those from green, olive ridley, and loggerhead turtles foraging carnivorously in oceanic environments of the central and southeast Pacific Ocean. Results of multivariate statistical analysis revealed two distinct groups that could be distinguished based on unique delta13C(EAA) patterns. A three-end-member predictive linear discriminant model indicated that delta13C(EAA) fingerprints existed in the tissues of carnivorous turtles that resembled patterns found in microalgae, which form the base of an oceanic food web, whereas herbivorous turtles derive EAAs from a bacterial or seagrass source. This study demonstrates the capacity for delta13C fingerprinting to establish the biosynthetic origin of EAAs in higher consumers, and that marine turtles foraging on macroalgal diets appear to receive nutritional supplementation from bacterial symbionts in their digestive system.

  13. Soil compaction effects on water status of ponderosa pine assessed through 13C/12C composition.

    PubMed

    Gomez, G Armando; Singer, Michael J; Powers, Robert F; Horwath, William R

    2002-05-01

    Soil compaction is a side effect of forest reestablishment practices resulting from use of heavy equipment and site preparation. Soil compaction often alters soil properties resulting in changes in plant-available water. The use of pressure chamber methods to assess plant water stress has two drawbacks: (1) the measurements are not integrative; and (2) the method is difficult to apply extensively to establish seasonal soil water status. We evaluated leaf carbon isotopic composition (delta13C) as a means of assessing effects of soil compaction on water status and growth of young ponderosa pine (Pinus ponderosa var. ponderosa Dougl. ex Laws) stands across a range of soil textures. Leaf delta13C in cellulose and whole foliar tissue were highly correlated. Leaf delta13C in both whole tissue and cellulose (holocellulose) was up to 1.0 per thousand lower in trees growing in non-compacted (NC) loam or clay soils than in compacted (SC) loam or clay soils. Soil compaction had the opposite effect on leaf delta13C in trees growing on sandy loam soil, indicating that compaction increased water availability in this soil type. Tree growth response to compaction also varied with soil texture, with no effect, a negative effect and a positive effect as a result of compaction of loam, clay and sandy loam soils, respectively. There was a significant correlation between 13C signature and tree growth along the range of soil textures. Leaf delta13C trends were correlated with midday stem water potentials. We conclude that leaf delta13C can be used to measure retrospective water status and to assess the impact of site preparation on tree growth. The advantage of the leaf delta13C approach is that it provides an integrative assessment of past water status in different aged leaves.

  14. The effect of chemical processing on the δ 13C value of plant tissue

    NASA Astrophysics Data System (ADS)

    Van de Water, Peter K.

    2002-04-01

    The effect of standard processing techniques on the δ 13C value of plant tissue was tested using species representing the three photosynthetic pathways, including angiosperms and gymnosperms within the C 3 taxonomic division. The species include Cowania mexicana (C 3 angiosperm), Juniperus osteosperma (C 3 gymnosperm), Opuntia spp. (crassulacean acid metabolism [CAM] angiosperm), and Atriplex canescens (C 4 angiosperm). Each species is represented by 5 plants collected at two different sites, for a total of 10 samples. The samples were processed to whole plant tissue, holocellulose, α-cellulose, and nitrocellulose. An additional process was added with the discovery of residual Ca-oxalate crystals in holocellulose samples. Both C 3 species show δ 13C values becoming 13C enriched with increased processing. The CAM representative shows the opposite trend, with 13C depletion during the progression of treatments. The greatest range of values and most inconsistent trends occur in the C 4 representative. Removal of the Ca-oxalate fraction resulted in different mean weight percentages and δ 13C values among the species. Calculated δ 13C values of the Ca-oxalate crystals show depletion from the tissue values in the two C 3 species and enrichment in the C 4 and CAM representatives. The C. mexicana samples show the greatest change between the tissue and Ca-oxalates (7.3‰) but the least mean weight percentage (11%), whereas A. canescens shows the greatest overall change, with a -2.8‰ isotopic shift and over 48% mean weight percentage. Variability within the samples undergoing each treatment remained relatively unchanged even with increased cellulose purity. This paper provides estimates of isotopic offsets necessary to correct from one treatment to another. Significant differences in δ 13C among different treatments confirm the need to state the tissue fraction analyzed when reporting δ 13C results.

  15. 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.

  16. Concentric Rings K-Space Trajectory for Hyperpolarized 13C MR Spectroscopic Imaging

    PubMed Central

    Jiang, Wenwen; Lustig, Michael; Larson, Peder E.Z.

    2014-01-01

    Purpose To develop a robust and rapid imaging technique for hyperpolarized 13C MR Spectroscopic Imaging (MRSI) and investigate its performance. Methods A concentric rings readout trajectory with constant angular velocity is proposed for hyperpolarized 13C spectroscopic imaging and its properties are analyzed. Quantitative analyses of design tradeoffs are presented for several imaging scenarios. The first application of concentric rings on 13C phantoms and in vivo animal hyperpolarized 13C MRSI studies were performed to demonstrate the feasibility of the proposed method. Finally, a parallel imaging accelerated concentric rings study is presented. Results The concentric rings MRSI trajectory has the advantages of acquisition timesaving compared to echo-planar spectroscopic imaging (EPSI). It provides sufficient spectral bandwidth with relatively high SNR efficiency compared to EPSI and spiral techniques. Phantom and in vivo animal studies showed good image quality with half the scan time and reduced pulsatile flow artifacts compared to EPSI. Parallel imaging accelerated concentric rings showed advantages over Cartesian sampling in g-factor simulations and demonstrated aliasing-free image quality in a hyperpolarized 13C in vivo study. Conclusion The concentric rings trajectory is a robust and rapid imaging technique that fits very well with the speed, bandwidth, and resolution requirements of hyperpolarized 13C MRSI. PMID:25533653

  17. Tracing carbon monoxide uptake by Clostridium ljungdahlii during ethanol fermentation using (13)C-enrichment technique.

    PubMed

    Yun, Seok-In; Gang, Seong-Joo; Ro, Hee-Myong; Lee, Min-Jin; Choi, Woo-Jung; Hong, Seong-Gu; Kang, Kwon-Kyoo

    2013-05-01

    Conversion of synthesis gas (CO and H2) to ethanol can be an alternative, promising technology to produce biofuels from renewable biomass. To distinguish microbial utilization of carbon source between fructose and synthesis gas CO and to evaluate biological production of ethanol from CO, we adopted the (13)C-enrichment of the CO substrate and hypothesized that the residual increase in δ(13)C of the cell biomass would reflect the increased contribution of (13)C-enriched CO. Addition of synthesis gas to live culture medium for ethanol fermentation by Clostridum ljungdahlii increased the microbial growth and ethanol production. Despite the high (13)C-enrichment in CO (99 atom % (13)C), however, microbial δ(13)C increased relatively small compared to the microbial growth. The uptake efficiency of CO estimated using the isotope mass balance equation was also very low: 0.0014 % for the low CO and 0.0016 % for the high CO treatment. Furthermore, the fast production of ethanol in the early stage indicated that the presence of sugar in fermentation medium would limit the utilization of CO as a carbon source by C. ljungdahlii.

  18. Extreme (13)C depletion of carbonates formed during oxidation of biogenic methane in fractured granite.

    PubMed

    Drake, Henrik; Åström, Mats E; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-05-07

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

  19. Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

    PubMed Central

    Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-01-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C13C as light as −69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to −125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane. PMID:25948095

  20. Extreme 13C depletion of carbonates formed during oxidation of biogenic methane in fractured granite

    NASA Astrophysics Data System (ADS)

    Drake, Henrik; Åström, Mats E.; Heim, Christine; Broman, Curt; Åström, Jan; Whitehouse, Martin; Ivarsson, Magnus; Siljeström, Sandra; Sjövall, Peter

    2015-05-01

    Precipitation of exceptionally 13C-depleted authigenic carbonate is a result of, and thus a tracer for, sulphate-dependent anaerobic methane oxidation, particularly in marine sediments. Although these carbonates typically are less depleted in 13C than in the source methane, because of incorporation of C also from other sources, they are far more depleted in 13C13C as light as -69‰ V-PDB) than in carbonates formed where no methane is involved. Here we show that oxidation of biogenic methane in carbon-poor deep groundwater in fractured granitoid rocks has resulted in fracture-wall precipitation of the most extremely 13C-depleted carbonates ever reported, δ13C down to -125‰ V-PDB. A microbial consortium of sulphate reducers and methane oxidizers has been involved, as revealed by biomarker signatures in the carbonates and S-isotope compositions of co-genetic sulphide. Methane formed at shallow depths has been oxidized at several hundred metres depth at the transition to a deep-seated sulphate-rich saline water. This process is so far an unrecognized terrestrial sink of methane.

  1. 13C-labelled microdialysis studies of cerebral metabolism in TBI patients☆

    PubMed Central

    Carpenter, Keri L.H.; Jalloh, Ibrahim; Gallagher, Clare N.; Grice, Peter; Howe, Duncan J.; Mason, Andrew; Timofeev, Ivan; Helmy, Adel; Murphy, Michael P.; Menon, David K.; Kirkpatrick, Peter J.; Carpenter, T. Adrian; Sutherland, Garnette R.; Pickard, John D.; Hutchinson, Peter J.

    2014-01-01

    Human brain chemistry is incompletely understood and better methodologies are needed. Traumatic brain injury (TBI) causes metabolic perturbations, one result of which includes increased brain lactate levels. Attention has largely focussed on glycolysis, whereby glucose is converted to pyruvate and lactate, and is proposed to act as an energy source by feeding into neurons’ tricarboxylic acid (TCA) cycle, generating ATP. Also reportedly upregulated by TBI is the pentose phosphate pathway (PPP) that does not generate ATP but produces various molecules that are putatively neuroprotective, antioxidant and reparative, in addition to lactate among the end products. We have developed a novel combination of 13C-labelled cerebral microdialysis both to deliver 13C-labelled substrates into brains of TBI patients and recover the 13C-labelled metabolites, with high-resolution 13C NMR analysis of the microdialysates. This methodology has enabled us to achieve the first direct demonstration in humans that the brain can utilise lactate via the TCA cycle. We are currently using this methodology to make the first direct comparison of glycolysis and the PPP in human brain. In this article, we consider the application of 13C-labelled cerebral microdialysis for studying brain energy metabolism in patients. We set this methodology within the context of metabolic pathways in the brain, and 13C research modalities addressing them. PMID:24361470

  2. sup 13 C and sup 18 O isotopic disequilibrium in biological carbonates: I. Patterns

    SciTech Connect

    McConnaughey, T. )

    1989-01-01

    Biological carbonates frequently precipitate out of {sup 18}O and {sup 13}C equilibrium with ambient waters. Two patterns of isotopic disequilibrium are particularly common. Kinetic disequilibria, so designated because they apparently result from kinetic isotope effects during CO{sub 2} hydration and hydroxylation, involve simultaneous depletions of {sup 18}O and {sup 13}C as large as 4{per thousand} and 10 to 15{per thousand}, respectively. Rapid skeletogenesis favors strong kinetic effects, and approximately linear correlations between skeletal {delta}{sup 18}O and {delta}{sup 13}C are common in carbonates showing mainly the kinetic pattern. Metabolic effects involve additional positive or negative modulation of skeletal {delta}{sup 13}C, reflecting changes in the {delta}{sup 13}C of dissolved inorganic carbon, caused mainly by photosynthesis and respiration. Kinetic isotope disequilibria tend to be fairly consistent in rapidly growing parts of photosynthetic corals, and time dependent isotopic variations therefore reflect changes in environmental conditions. {delta}{sup 18}O variations from Galapagos corals yields meaningful clues regarding seawater temperature, while {delta}{sup 13}C variations reflect changes in photosynthesis, modulated by cloudiness.

  3. The paper trail of the 13C of atmospheric CO2 since the industrial revolution period

    NASA Astrophysics Data System (ADS)

    Yakir, Dan

    2011-07-01

    The 13C concentration in atmospheric CO2 has been declining over the past 150 years as large quantities of 13C-depleted CO2 from fossil fuel burning are added to the atmosphere. Deforestation and other land use changes have also contributed to the trend. Looking at the 13C variations in the atmosphere and in annual growth rings of trees allows us to estimate CO2 uptake by land plants and the ocean, and assess the response of plants to climate. Here I show that the effects of the declining 13C trend in atmospheric CO2 are recorded in the isotopic composition of paper used in the printing industry, which provides a well-organized archive and integrated material derived from trees' cellulose. 13C analyses of paper from two European and two American publications showed, on average, a - 1.65 ± 1.00‰ trend between 1880 and 2000, compared with - 1.45 and - 1.57‰ for air and tree-ring analyses, respectively. The greater decrease in plant-derived 13C in the paper we tested than in the air is consistent with predicted global-scale increases in plant intrinsic water-use efficiency over the 20th century. Distinct deviations from the atmospheric trend were observed in both European and American publications immediately following the World War II period.

  4. (13) C Breath Tests Are Feasible in Patients With Extracorporeal Membrane Oxygenation Devices.

    PubMed

    Bednarsch, Jan; Menk, Mario; Malinowski, Maciej; Weber-Carstens, Steffen; Pratschke, Johann; Stockmann, Martin

    2016-07-01

    Temporary extracorporeal membrane oxygenation (ECMO) has been established as an essential part of therapy in patients with pulmonary or cardiac failure. As physiological gaseous exchange is artificially altered in this patient group, it is debatable whether a (13) C-breath test can be carried out. In this proof of technical feasibility report, we assess the viability of the (13) C-breath test LiMAx (maximum liver function capacity) in patients on ECMO therapy. All breath probes for the test device were obtained directly via the membrane oxygenator. Data of four patients receiving liver function assessment with the (13) C-breath test LiMAx while having ECMO therapy were analyzed. All results were compared with validated scenarios of the testing procedures. The LiMAx test could successfully be carried out in every case without changing ECMO settings. Clinical course of the patients ranging from multiorgan failure to no sign of liver insufficiency was in accordance with the results of the LiMAx liver function test. The (13) C-breath test is technically feasible in the context of ECMO. Further evaluation of (13) C-breath test in general would be worthwhile. The LiMAx test as a (13) C-breath test accessing liver function might be of particular predictive interest if patients with ECMO therapy develop multiorgan failure.

  5. (13)C-labelled microdialysis studies of cerebral metabolism in TBI patients.

    PubMed

    Carpenter, Keri L H; Jalloh, Ibrahim; Gallagher, Clare N; Grice, Peter; Howe, Duncan J; Mason, Andrew; Timofeev, Ivan; Helmy, Adel; Murphy, Michael P; Menon, David K; Kirkpatrick, Peter J; Carpenter, T Adrian; Sutherland, Garnette R; Pickard, John D; Hutchinson, Peter J

    2014-06-16

    Human brain chemistry is incompletely understood and better methodologies are needed. Traumatic brain injury (TBI) causes metabolic perturbations, one result of which includes increased brain lactate levels. Attention has largely focussed on glycolysis, whereby glucose is converted to pyruvate and lactate, and is proposed to act as an energy source by feeding into neurons' tricarboxylic acid (TCA) cycle, generating ATP. Also reportedly upregulated by TBI is the pentose phosphate pathway (PPP) that does not generate ATP but produces various molecules that are putatively neuroprotective, antioxidant and reparative, in addition to lactate among the end products. We have developed a novel combination of (13)C-labelled cerebral microdialysis both to deliver (13)C-labelled substrates into brains of TBI patients and recover the (13)C-labelled metabolites, with high-resolution (13)C NMR analysis of the microdialysates. This methodology has enabled us to achieve the first direct demonstration in humans that the brain can utilise lactate via the TCA cycle. We are currently using this methodology to make the first direct comparison of glycolysis and the PPP in human brain. In this article, we consider the application of (13)C-labelled cerebral microdialysis for studying brain energy metabolism in patients. We set this methodology within the context of metabolic pathways in the brain, and (13)C research modalities addressing them.

  6. OEDGE Modeling of {sup 13}C Deposition in the Inner Divertor of DIII-D

    SciTech Connect

    Elder, J; Stangeby, P; Whyte, D; Allen, S; McLean, A; Boedo, J; Bray, B; Brooks, N; Fenstermacher, M; Groth, M; Lasnier, C; Lisgo, S; Rudakov, D; Wampler, W; Watkins, J; West, W

    2004-12-01

    Use of carbon in tokamaks leads to a major tritium retention issue due to co-deposition. To investigate this process a low power (no beams) L-mode experiment was performed on DIII-D in which {sup 13}CH{sub 4} was puffed into the main vessel through the toroidally-symmetric pumping plenum at the top of lower single-null discharges. Subsequently, the {sup 13}C content of tiles taken from the vessel wall was measured. The interpretive OEDGE code was used to model the results. It was found that the {sup 13}C deposition pattern is controlled by: (a) source strength of {sup 13}C{sup +}, (b) radial location of the {sup 13}C{sup +} source, (c) D{sub {perpendicular}}, (d) M{sub {parallel}}, the scrape-off layer parallel Mach number. Best agreement was found for (a) {approx}50% conversion efficiency {sup 13}CH{sub 4} {yields} {sup 13}C{sup +}, (b) {sup 13}C{sup +} source {approx}3.5 cm outboard of separatrix near {sup 13}CH{sub 4} injection location, (c)D{sub {perpendicular}} {approx} 0.3 m{sup 2}s{sup -1}, (d) M{sub {parallel}} {approx} 0.4 toward inside.

  7. NMR quantum computation with optically polarized molecules

    NASA Astrophysics Data System (ADS)

    Verhulst, Anne; Yannoni, Constantino; Sherwood, Mark; Pomerantz, Drew; Vandersypen, Lieven; Chuang, Isaac

    2000-03-01

    Current methods for bulk NMR quantum computation rely on nuclear spin polarization present at high temperature equilibrium. This presents a challenging obstacle as the probability to find a spin in a specific state decreases exponentially in the number of spins used as qubits, causing a corresponding decrease in the signal to noise ratio of the desired NMR signal. One way to address this problem is to provide an artificial source of high polarization, such as optically pumped ^129Xe. For comparison, thermal equilibrium polarizations are only about 10-3% for ^1H in a typical NMR experiment at room temperature and in a 10 Tesla magnetic field, but with ^129Xe polarizations as high as 18% have been achieved [Happer et. al., Chem.Phys.Lett., 284, p.87-92, Feb 1998]. Using this technique, we prepare hyperpolarized liquid Xe and use it as a solvent for chloroform molecules (CHCl_3). Cross polarization (SPINOE) between ^129Xe and ^1H results in measured enhancements of the proton signal of over 300%, and evidence of transfer to ^13C. These results provide hope for the scalability of quantum computation.

  8. Correction algorithm for online continuous flow δ13C and δ18O carbonate and cellulose stable isotope analyses

    NASA Astrophysics Data System (ADS)

    Evans, M. N.; Selmer, K. J.; Breeden, B. T.; Lopatka, A. S.; Plummer, R. E.

    2016-09-01

    We describe an algorithm to correct for scale compression, runtime drift, and amplitude effects in carbonate and cellulose oxygen and carbon isotopic analyses made on two online continuous flow isotope ratio mass spectrometry (CF-IRMS) systems using gas chromatographic (GC) separation. We validate the algorithm by correcting measurements of samples of known isotopic composition which are not used to estimate the corrections. For carbonate δ13C (δ18O) data, median precision of validation estimates for two reference materials and two calibrated working standards is 0.05‰ (0.07‰); median bias is 0.04‰ (0.02‰) over a range of 49.2‰ (24.3‰). For α-cellulose δ13C (δ18O) data, median precision of validation estimates for one reference material and five working standards is 0.11‰ (0.27‰); median bias is 0.13‰ (-0.10‰) over a range of 16.1‰ (19.1‰). These results are within the 5th-95th percentile range of subsequent routine runtime validation exercises in which one working standard is used to calibrate the other. Analysis of the relative importance of correction steps suggests that drift and scale-compression corrections are most reliable and valuable. If validation precisions are not already small, routine cross-validated precision estimates are improved by up to 50% (80%). The results suggest that correction for systematic error may enable these particular CF-IRMS systems to produce δ13C and δ18O carbonate and cellulose isotopic analyses with higher validated precision, accuracy, and throughput than is typically reported for these systems. The correction scheme may be used in support of replication-intensive research projects in paleoclimatology and other data-intensive applications within the geosciences.

  9. Determination of glucan phosphorylation using heteronuclear 1H, 13C double and 1H, 13C, 31P triple-resonance NMR spectra.

    PubMed

    Schmieder, Peter; Nitschke, Felix; Steup, Martin; Mallow, Keven; Specker, Edgar

    2013-10-01

    Phosphorylation and dephosphorylation of starch and glycogen are important for their physicochemical properties and also their physiological functions. It is therefore desirable to reliably determine the phosphorylation sites. Heteronuclear multidimensional NMR-spectroscopy is in principle a straightforward analytical approach even for complex carbohydrate molecules. With heterogeneous samples from natural sources, however, the task becomes more difficult because a full assignment of the resonances of the carbohydrates is impossible to obtain. Here, we show that the combination of heteronuclear (1) H,(13) C and (1) H,(13) C,(31) P techniques and information derived from spectra of a set of reference compounds can lead to an unambiguous determination of the phosphorylation sites even in heterogeneous samples.

  10. Interference effects between /sup 17/O states populated in the /sup 13/C(/sup 6/Li,d)/sup 17/O*. --> cap alpha. +/sup 13/C reaction

    SciTech Connect

    Cardella, G.; Cunsolo, A.; Foti, A.; Imme, G.; Pappalardo, G.; Raciti, G.; Rizzo, F.; Alamanos, N.; Berthier, B.; Saunier, N.

    1987-12-01

    An analysis of the /sup 13/C(/sup 6/Li,d..cap alpha..)/sup 13/C reaction in the collinear (theta/sub d/ = 0/sup 0/) and noncollinear (theta/sub d/ = 10/sup 0/,8/sup 0/) geometry is made for two peaks observed in the deuteron energy spectrum and corresponding to excitation energies of 16.1 and 13.6 MeV in the /sup 17/O nucleus. It is shown that the reaction proceeds via a direct alpha-transfer process which populates doublets of interfering /sup 17/O levels. Spins, weights, and parities of these levels are obtained by means of a least square procedure.

  11. Indirect study of the {sup 13}C({alpha},n){sup 16}O reaction via the {sup 13}C({sup 7}Li,t){sup 17}O transfer reaction

    SciTech Connect

    Pellegriti, M. G.; Hammache, F.; Roussel, P.; Audouin, L.; Beaumel, D.; Fortier, S.; Vilmay, M.; Descouvemont, P.; Gaudefroy, L.; Kiener, J.; Lefebvre-Schuhl, A.; Tatischeff, V.; Stanoiu, M.

    2008-04-15

    The {sup 13}C({alpha},n){sup 16}O reaction is considered the main neutron source for the s process in low mass asymptotic giant branch (AGB) stars. In the Gamow peak, the cross section sensitively depends on the 1/2{sup +} subthreshold state of {sup 17}O (E{sub x}=6.356 MeV). In this work, we determined the astrophysical S factor through an evaluation of the {alpha} spectroscopic factor and the corresponding asymptotic normalization factor (ANC) of the 6.356 MeV state using the transfer reaction {sup 13}C({sup 7}Li,t){sup 17}O at two different incident energies. Our result confirms that the contribution of the 1/2{sup +} state is dominant at astrophysical energies. Our reaction rate at T=0.09 GK is slightly lower than the value adopted in the Nuclear Astrophysics Compilation of REaction rates (NACRE), but two times larger than the one obtained in a recent ANC measurement.

  12. Charged-pion cross sections and double-helicity asymmetries in polarized p + p collisions at √s = 200 GeV

    SciTech Connect

    Adare, A.; Aidala, C.; Ajitanand, N. N.; Akiba, Y.; Akimoto, R.; Al-Ta’ani, H.; Alexander, J.; Andrews, K. R.; Angerami, A.; Aoki, K.; Apadula, N.; Appelt, E.; Aramaki, Y.; Armendariz, R.; Aschenauer, E. C.; Atomssa, E. T.; Awes, T. C.; Azmoun, B.; Babintsev, V.; Bai, M.; Bannier, B.; Barish, K. N.; Bassalleck, B.; Basye, A. T.; Bathe, S.; Baublis, V.; Baumann, C.; Bazilevsky, A.; Belmont, R.; Ben-Benjamin, J.; Bennett, R.; Blau, D. S.; Bok, J. S.; Boyle, K.; Brooks, M. L.; Broxmeyer, D.; Buesching, H.; Bumazhnov, V.; Bunce, G.; Butsyk, S.; Campbell, S.; Castera, P.; Chen, C. -H.; Chi, C. Y.; Chiu, M.; Choi, I. J.; Choi, J. B.; Choudhury, R. K.; Christiansen, P.; Chujo, T.; Chvala, O.; Cianciolo, V.; Citron, Z.; Cole, B. A.; Conesa del Valle, Z.; Connors, M.; Csanád, M.; Csörgő, T.; Dairaku, S.; Datta, A.; David, G.; Dayananda, M. K.; Denisov, A.; Deshpande, A.; Desmond, E. J.; Dharmawardane, K. V.; Dietzsch, O.; Dion, A.; Donadelli, M.; Drapier, O.; Drees, A.; Drees, K. A.; Durham, J. M.; Durum, A.; D’Orazio, L.; Efremenko, Y. V.; Engelmore, T.; Enokizono, A.; En’yo, H.; Esumi, S.; Fadem, B.; Fields, D. E.; Finger, M.; Finger, M.; Fleuret, F.; Fokin, S. L.; Frantz, J. E.; Franz, A.; Frawley, A. D.; Fukao, Y.; Fusayasu, T.; Gal, C.; Garishvili, I.; Giordano, F.; Glenn, A.; Gong, X.; Gonin, M.; Goto, Y.; Granier de Cassagnac, R.; Grau, N.; Greene, S. V.; Grosse Perdekamp, M.; Gunji, T.; Guo, L.; Gustafsson, H. -Å.; Haggerty, J. S.; Hahn, K. I.; Hamagaki, H.; Hamblen, J.; Han, R.; Hanks, J.; Harper, C.; Hashimoto, K.; Haslum, E.; Hayano, R.; He, X.; Hemmick, T. K.; Hester, T.; Hill, J. C.; Hollis, R. S.; Holzmann, W.; Homma, K.; Hong, B.; Horaguchi, T.; Hori, Y.; Hornback, D.; Huang, S.; Ichihara, T.; Ichimiya, R.; Iinuma, H.; Ikeda, Y.; Imai, K.; Inaba, M.; Iordanova, A.; Isenhower, D.; Ishihara, M.; Issah, M.; Ivanischev, D.; Iwanaga, Y.; Jacak, B. V.; Jia, J.; Jiang, X.; John, D.; Johnson, B. M.; Jones, T.; Joo, K. S.; Jouan, D.; Kamin, J.; Kaneti, S.; Kang, B. H.; Kang, J. H.; Kang, J. S.; Kapustinsky, J.; Karatsu, K.; Kasai, M.; Kawall, D.; Kazantsev, A. V.; Kempel, T.; Khanzadeev, A.; Kijima, K. M.; Kim, B. I.; Kim, D. J.; Kim, E. -J.; Kim, Y. -J.; Kim, Y. K.; Kinney, E.; Kiss, Á.; Kistenev, E.; Kleinjan, D.; Kline, P.; Kochenda, L.; Komkov, B.; Konno, M.; Koster, J.; Kotov, D.; Král, A.; Kunde, G. J.; Kurita, K.; Kurosawa, M.; Kwon, Y.; Kyle, G. S.; Lacey, R.; Lai, Y. S.; Lajoie, J. G.; Lebedev, A.; Lee, D. M.; Lee, J.; Lee, K. B.; Lee, K. S.; Lee, S. H.; Lee, S. R.; Leitch, M. J.; Leite, M. A. L.; Li, X.; Lim, S. H.; Linden Levy, L. A.; Liu, H.; Liu, M. X.; Love, B.; Lynch, D.; Maguire, C. F.; Makdisi, Y. I.; Manion, A.; Manko, V. I.; Mannel, E.; Mao, Y.; Masui, H.; McCumber, M.; McGaughey, P. L.; McGlinchey, D.; McKinney, C.; Means, N.; Mendoza, M.; Meredith, B.; Miake, Y.; Mibe, T.; Mignerey, A. C.; Miki, K.; Milov, A.; Mitchell, J. T.; Miyachi, Y.; Mohanty, A. K.; Moon, H. J.; Morino, Y.; Morreale, A.; Morrison, D. P.; Motschwiller, S.; Moukhanova, T. V.; Murakami, T.; Murata, J.; Nagamiya, S.; Nagle, J. L.; Naglis, M.; Nagy, M. I.; Nakagawa, I.; Nakamiya, Y.; Nakamura, K. R.; Nakamura, T.; Nakano, K.; Newby, J.; Nguyen, M.; Nihashi, M.; Nouicer, R.; Nyanin, A. S.; Oakley, C.; O’Brien, E.; Ogilvie, C. A.; Oka, M.; Okada, K.; Oskarsson, A.; Ouchida, M.; Ozawa, K.; Pak, R.; Pantuev, V.; Papavassiliou, V.; Park, B. H.; Park, I. H.; Park, S. K.; Pate, S. F.; Patel, L.; Pei, H.; Peng, J. -C.; Pereira, H.; Peressounko, D. Yu.; Petti, R.; Pinkenburg, C.; Pisani, R. P.; Proissl, M.; Purschke, M. L.; Qu, H.; Rak, J.; Ravinovich, I.; Read, K. F.; Reygers, K.; Riabov, V.; Riabov, Y.; Richardson, E.; Roach, D.; Roche, G.; Rolnick, S. D.; Rosati, M.; Rosendahl, S. S. E.; Rubin, J. G.; Sahlmueller, B.; Saito, N.; Sakaguchi, T.; Samsonov, V.; Sano, S.; Sarsour, M.; Sato, T.; Savastio, M.; Sawada, S.; Sedgwick, K.; Seidl, R.; Seto, R.; Sharma, D.; Shein, I.; Shibata, T. -A.; Shigaki, K.; Shim, H. H.; Shimomura, M.; Shoji, K.; Shukla, P.; Sickles, A.; Silva, C. L.; Silvermyr, D.; Silvestre, C.; Sim, K. S.; Singh, B. K.; Singh, C. P.; Singh, V.; Slunečka, M.; Sodre, T.; Soltz, R. A.; Sondheim, W. E.; Sorensen, S. P.; Sourikova, I. V.; Stankus, P. W.; Stenlund, E.; Stoll, S. P.; Sugitate, T.; Sukhanov, A.; Sun, J.; Sziklai, J.; Takagui, E. M.; Takahara, A.; Taketani, A.; Tanabe, R.; Tanaka, Y.; Taneja, S.; Tanida, K.; Tannenbaum, M. J.; Tarafdar, S.; Taranenko, A.; Tennant, E.; Themann, H.; Thomas, D.; Togawa, M.; Tomášek, L.; Tomášek, M.; Torii, H.; Towell, R. S.; Tserruya, I.; Tsuchimoto, Y.; Utsunomiya, K.; Vale, C.; van Hecke, H. W.; Vazquez-Zambrano, E.; Veicht, A.; Velkovska, J.; Vértesi, R.; Virius, M.; Vossen, A.; Vrba, V.; Vznuzdaev, E.; Wang, X. R.; Watanabe, D.; Watanabe, K.; Watanabe, Y.; Watanabe, Y. S.; Wei, F.; Wei, R.; Wessels, J.; White, S. N.; Winter, D.; Woody, C. L.; Wright, R. M.; Wysocki, M.; Yamaguchi, Y. L.; Yang, R.; Yanovich, A.; Ying, J.; Yokkaichi, S.; Yoo, J. S.; You, Z.; Young, G. R.; Younus, I.; Yushmanov, I. E.; Zajc, W. A.; Zelenski, A.; Zhou, S.

    2015-02-02

    We present midrapidity charged-pion invariant cross sections, the ratio of the π⁻ to π⁺ cross sections and the charge-separated double-spin asymmetries in polarized p+p collisions at √s = 200 GeV. While the cross section measurements are consistent within the errors of next-to-leadingorder (NLO) perturbative quantum chromodynamics predictions (pQCD), the same calculations over estimate the ratio of the charged-pion cross sections. This discrepancy arises from the cancellation of the substantial systematic errors associated with the NLO-pQCD predictions in the ratio and highlights the constraints these data will place on flavor dependent pion fragmentation functions. Thus, the charge-separated pion asymmetries presented here sample an x range of ~0.03–0.16 and provide unique information on the sign of the gluon-helicity distribution.

  13. Charged-pion cross sections and double-helicity asymmetries in polarized p + p collisions at √s = 200 GeV

    DOE PAGES

    Adare, A.; Aidala, C.; Ajitanand, N. N.; ...

    2015-02-02

    We present midrapidity charged-pion invariant cross sections, the ratio of the π⁻ to π⁺ cross sections and the charge-separated double-spin asymmetries in polarized p+p collisions at √s = 200 GeV. While the cross section measurements are consistent within the errors of next-to-leadingorder (NLO) perturbative quantum chromodynamics predictions (pQCD), the same calculations over estimate the ratio of the charged-pion cross sections. This discrepancy arises from the cancellation of the substantial systematic errors associated with the NLO-pQCD predictions in the ratio and highlights the constraints these data will place on flavor dependent pion fragmentation functions. Thus, the charge-separated pion asymmetries presented heremore » sample an x range of ~0.03–0.16 and provide unique information on the sign of the gluon-helicity distribution.« less

  14. Paleoclimate Reconstruction From the d13C Organic and d13C Carbonate Proxies in Triassic Paleosols and Sediments, Ischigualasto Basin Argentina

    NASA Astrophysics Data System (ADS)

    Moore, K. A.; Tabor, N. J.; Montañez, I. P.; Currie, B.; Shipman, T.

    2001-12-01

    Stable carbon isotopes of organic matter and paleosol carbonate from the Triassic Ischigualasto Formation, Argentina are used as a proxy of paleoatmospheric pCO2 and d13CO2. Carbon and Oxygen isotope values were determined for over 100 Triassic pedogenic carbonate nodules and associated organic matter. The d13C of carbonate ranges from -3.29 per mil to -10.56 per mil. The d13C of organic matter ranges from -21.07 per mil to -24.24 per mil. The Hydrogen and Oxygen indices and TOC values indicate that the best preserved organic matter samples yield the most negative d13C values. Reconstructed pCO2 levels were around 1000 ppm V in the early to mid- Triassic and increased to around 2000 ppm V later in the Triassic. This maximum is followed by a fall in pCO2 in the late Triassic. This previously undocumented rapid change in paleo-CO2 levels likely accompanied the evolution of mammal-like reptiles to true dinosaurs as well as rapid climate change.

  15. Metabolite channeling and compartmentation in the human cell line AGE1.HN determined by 13C labeling experiments and 13C metabolic flux analysis.

    PubMed

    Niklas, Jens; Sandig, Volker; Heinzle, Elmar

    2011-12-01

    This study focused on analyzing active pathways and the metabolic flux distribution in human neuronal AGE1.HN cells that is a desirable basis for a rational design and optimization of producing cell lines and production processes for biopharmaceuticals. (13)C-labeling experiments and (13)C metabolic flux analysis were conducted using glucose, glutamine, alanine and lactate tracers in parallel experiments. Connections between cytosolic and mitochondrial metabolite pools were verified, e.g., flux from TCA cycle metabolite (13)C to glycolytic metabolites. It was also found that lactate and alanine are produced from the same pyruvate pool and that consumed alanine is mainly directly metabolized and secreted as lactate. Activity of the pentose phosphate pathway was low being around 2.3% of the glucose uptake flux. This might be compensated in AGE1.HN by high mitochondrial malic enzyme flux producing NADPH. Mitochondrial pyruvate transport was almost zero. Instead pyruvate carbons were channeled via oxaloacetate into the TCA cycle which was mainly fed via α-ketoglutarate and oxaloacetate during the investigated phase. The data indicate that further optimization of this cell line should focus on the improved substrate usage which can be accomplished by an improved connectivity between glycolytic and mitochondrial pyruvate pools or by better control of the substrate uptake.

  16. On the use of phloem sap δ13C to estimate canopy carbon discrimination

    NASA Astrophysics Data System (ADS)

    Rascher, Katherine; Máguas, Cristina; Werner, Christiane

    2010-05-01

    Although the carbon stable isotope composition (d13C) of bulk leaf material is a good integrative parameter of photosynthetic discrimination and can be used as a reliable ecological index of plant functioning; it is not a good tracer of short-term changes in photosynthetic discrimination. In contrast, d13C of phloem sap is potentially useful as an indicator of short-term changes in canopy photosynthetic discrimination. However, recent research indicates that d13C signatures may be substantially altered by metabolic processes downstream of initial leaf-level carbon fixation (e.g. post-photosynthetic fractionation). Accordingly, before phloem sap d13C can be used as a proxy for canopy level carbon discrimination an understanding of factors influencing the degree and magnitude of post-photosynthetic fractionation and how these vary between species is of paramount importance. In this study, we measured the d13C signature along the basipetal transport pathway in two co-occurring tree species in the field - an understory invasive exotic legume, Acacia longifolia, and a native pine, Pinus pinaster. We measured d13C of bulk leaf and leaf water soluble organic matter (WSOM), phloem sap sampled at two points along the plant axis and leaf and root dark respiration. In general, species differences in photosynthetic discrimination resulted in more enriched d13C values in the water-conserving P. pinaster relative to the water-spending A. longifolia. Post-photosynthetic fractionation led to differences in d13C of carbon pools along the plant axis with progressively more depleted d13C from the canopy to the trunk (~6.5 per mil depletion in A. longifolia and ~0.8per mil depletion in P. pinaster). Leaf and root respiration, d13C, were consistently enriched relative to putative substrates. We hypothesize that the pronounced enrichment of leaf respired CO2 relative to leaf WSOM may have left behind relatively depleted carbon to be loaded into the phloem resulting in d13C depletion

  17. POLARIZED SCATTERING OF LIGHT FOR ARBITRARY MAGNETIC FIELDS WITH LEVEL-CROSSINGS FROM THE COMBINATION OF HYPERFINE AND FINE STRUCTURE SPLITTINGS

    SciTech Connect

    Sowmya, K.; Nagendra, K. N.; Sampoorna, M.; Stenflo, J. O. E-mail: knn@iiap.res.in E-mail: stenflo@astro.phys.ethz.ch

    2015-12-01

    Interference between magnetic substates of the hyperfine structure states belonging to different fine structure states of the same term influences the polarization for some of the diagnostically important lines of the Sun's spectrum, like the sodium and lithium doublets. The polarization signatures of this combined interference contain information on the properties of the solar magnetic fields. Motivated by this, in the present paper, we study the problem of polarized scattering on a two-term atom with hyperfine structure by accounting for the partial redistribution in the photon frequencies arising due to the Doppler motions of the atoms. We consider the scattering atoms to be under the influence of a magnetic field of arbitrary strength and develop a formalism based on the Kramers–Heisenberg approach to calculate the scattering cross section for this process. We explore the rich polarization effects that arise from various level-crossings in the Paschen–Back regime in a single scattering case using the lithium atomic system as a concrete example that is relevant to the Sun.

  18. 13C-phenylalanine breath test detects altered phenylalanine kinetics in schizophrenia patients

    PubMed Central

    Teraishi, T; Ozeki, Y; Hori, H; Sasayama, D; Chiba, S; Yamamoto, N; Tanaka, H; Iijima, Y; Matsuo, J; Kawamoto, Y; Kinoshita, Y; Hattori, K; Ota, M; Kajiwara, M; Terada, S; Higuchi, T; Kunugi, H

    2012-01-01

    Phenylalanine is an essential amino acid required for the synthesis of catecholamines including dopamine. Altered levels of phenylalanine and its metabolites in blood and cerebrospinal fluid have been reported in schizophrenia patients. This study attempted to examine for the first time whether phenylalanine kinetics is altered in schizophrenia using L-[1-13C]phenylalanine breath test (13C-PBT). The subjects were 20 chronically medicated schizophrenia patients (DSM-IV) and the same number of age- and sex-matched controls. 13C-phenylalanine (99 atom% 13C; 100 mg) was administered orally and the breath 13CO2 /12CO2 ratio was monitored for 120 min. The possible effect of antipsychotic medication (risperidone (RPD) or haloperidol (HPD) treatment for 21 days) on