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Sample records for 14n overtone nmr

  1. 14N overtone NMR under MAS: signal enhancement using symmetry-based sequences and novel simulation strategies† †Electronic supplementary information (ESI) available. See DOI: 10.1039/c4cp03994g Click here for additional data file.

    PubMed Central

    Haies, Ibraheem M.; Jarvis, James A.; Bentley, Harry; Heinmaa, Ivo; Kuprov, Ilya; Williamson, Philip T. F.

    2015-01-01

    Overtone 14N NMR spectroscopy is a promising route for the direct detection of 14N signals with good spectral resolution. Its application is currently limited, however, by the absence of efficient polarization techniques for overtone signal enhancement and the lack of efficient numerical simulation techniques to aid in both the development of new methods and the analysis and interpretation of experimental data. In this paper we report a novel method for the transfer of polarization from 1H to the 14N overtone using symmetry-based R-sequences that overcome many of the limitations of adiabatic approaches that have worked successfully on static samples. Refinement of these sequences and the analysis of the resulting spectra have been facilitated through the development of an efficient simulation strategy for 14N overtone NMR spectroscopy of spinning samples, using effective Hamiltonians on top of Floquet and Fokker–Planck equations. PMID:25662410

  2. Natural abundance 14N and 15N solid-state NMR of pharmaceuticals and their polymorphs

    DOE PAGES

    Veinberg, Stanislav L.; Johnston, Karen E.; Jaroszewicz, Michael J.; Kispal, Brianna M.; Mireault, Christopher R.; Kobayashi, Takeshi; Pruski, Marek; Schurko, Robert W.

    2016-06-08

    14N ultra-wideline (UW), 1H{15N} indirectly-detected HETCOR (idHETCOR) and 15N dynamic nuclear polarization (DNP) solid-state NMR (SSNMR) experiments, in combination with plane-wave density functional theory (DFT) calculations of 14N EFG tensors, were utilized to characterize a series of nitrogen-containing active pharmaceutical ingredients (APIs), including HCl salts of scopolamine, alprenolol, isoprenaline, acebutolol, dibucaine, nicardipine, and ranitidine. Here, a case study applying these methods for the differentiation of polymorphs of bupivacaine HCl is also presented. All experiments were conducted upon samples with naturally-abundant nitrogen isotopes. For most of the APIs, it was possible to acquire frequency-stepped UW 14N SSNMR spectra of stationarymore » samples, which display powder patterns corresponding to pseudo-tetrahedral (i.e., RR'R"NH+ and RR'NH2+) or other (i.e., RNH2 and RNO2) nitrogen environments.« less

  3. Natural abundance (14)N and (15)N solid-state NMR of pharmaceuticals and their polymorphs.

    PubMed

    Veinberg, Stanislav L; Johnston, Karen E; Jaroszewicz, Michael J; Kispal, Brianna M; Mireault, Christopher R; Kobayashi, Takeshi; Pruski, Marek; Schurko, Robert W

    2016-06-29

    (14)N ultra-wideline (UW), (1)H{(15)N} indirectly-detected HETCOR (idHETCOR) and (15)N dynamic nuclear polarization (DNP) solid-state NMR (SSNMR) experiments, in combination with plane-wave density functional theory (DFT) calculations of (14)N EFG tensors, were utilized to characterize a series of nitrogen-containing active pharmaceutical ingredients (APIs), including HCl salts of scopolamine, alprenolol, isoprenaline, acebutolol, dibucaine, nicardipine, and ranitidine. A case study applying these methods for the differentiation of polymorphs of bupivacaine HCl is also presented. All experiments were conducted upon samples with naturally-abundant nitrogen isotopes. For most of the APIs, it was possible to acquire frequency-stepped UW (14)N SSNMR spectra of stationary samples, which display powder patterns corresponding to pseudo-tetrahedral (i.e., RR'R''NH(+) and RR'NH2(+)) or other (i.e., RNH2 and RNO2) nitrogen environments. Directly-excited (14)N NMR spectra were acquired using the WURST-CPMG pulse sequence, which incorporates WURST (wideband, uniform rate, and smooth truncation) pulses and a CPMG (Carr-Purcell Meiboom-Gill) refocusing protocol. In certain cases, spectra were acquired using (1)H → (14)N broadband cross-polarization, via the BRAIN-CP (broadband adiabatic inversion - cross polarization) pulse sequence. These spectra provide (14)N electric field gradient (EFG) tensor parameters and orientations that are particularly sensitive to variations in local structure and intermolecular hydrogen-bonding interactions. The (1)H{(15)N} idHETCOR spectra, acquired under conditions of fast magic-angle spinning (MAS), used CP transfers to provide (1)H-(15)N chemical shift correlations for all nitrogen environments, except for two sites in acebutolol and nicardipine. One of these two sites (RR'NH2(+) in acebutolol) was successfully detected using the DNP-enhanced (15)N{(1)H} CP/MAS measurement, and one (RNO2 in nicardipine) remained elusive due to the absence of

  4. Fast and simple acquisition of solid-state 14N NMR spectra with signal enhancement via population transfer.

    PubMed

    O'Dell, Luke A; Schurko, Robert W

    2009-05-20

    A new approach for the acquisition of static, wideline (14)N NMR powder patterns is outlined. The method involves the use of frequency-swept pulses which serve two simultaneous functions: (1) broad-band excitation of magnetization and (2) signal enhancement via population transfer. The signal enhancement mechanism is described using numerical simulations and confirmed experimentally. This approach, which we call DEISM (Direct Enhancement of Integer Spin Magnetization), allows high-quality (14)N spectra to be acquired at intermediate field strengths in an uncomplicated way and in a fraction of the time required for previously reported methods.

  5. Powder-XRD and (14) N magic angle-spinning solid-state NMR spectroscopy of some metal nitrides.

    PubMed

    Kempgens, Pierre; Britton, Jonathan

    2016-05-01

    Some metal nitrides (TiN, ZrN, InN, GaN, Ca3 N2 , Mg3 N2 , and Ge3 N4 ) have been studied by powder X-ray diffraction (XRD) and (14) N magic angle-spinning (MAS) solid-state NMR spectroscopy. For Ca3 N2 , Mg3 N2 , and Ge3 N4 , no (14) N NMR signal was observed. Low speed (νr  = 2 kHz for TiN, ZrN, and GaN; νr  = 1 kHz for InN) and 'high speed' (νr  = 15 kHz for TiN; νr  = 5 kHz for ZrN; νr  = 10 kHz for InN and GaN) MAS NMR experiments were performed. For TiN, ZrN, InN, and GaN, powder-XRD was used to identify the phases present in each sample. The number of peaks observed for each sample in their (14) N MAS solid-state NMR spectrum matches perfectly well with the number of nitrogen-containing phases identified by powder-XRD. The (14) N MAS solid-state NMR spectra are symmetric and dominated by the quadrupolar interaction. The envelopes of the spinning sidebands manifold are Lorentzian, and it is concluded that there is a distribution of the quadrupolar coupling constants Qcc 's arising from structural defects in the compounds studied.

  6. Sensitivity enhanced (14)N/(14)N correlations to probe inter-beta-sheet interactions using fast magic angle spinning solid-state NMR in biological solids.

    PubMed

    Pandey, Manoj Kumar; Amoureux, Jean-Paul; Asakura, Tetsuo; Nishiyama, Yusuke

    2016-08-10

    (14)N/(14)N correlations are vital for structural studies of solid samples, especially those in which (15)N isotopic enrichment is challenging, time-consuming and expensive. Although (14)N nuclei have high isotopic abundance (99.6%), there are inherent difficulties in observing (14)N/(14)N correlations due to limited resolution and sensitivity related to: (i) low (14)N gyromagnetic ratio (γ), (ii) large (14)N quadrupolar couplings, (iii) integer (14)N spin quantum number (I = 1), and (iv) very weak (14)N-(14)N dipolar couplings. Previously, we demonstrated a proton-detected 3D (14)N/(14)N/(1)H correlation experiment at fast magic angle spinning (MAS) on l-histidine·HCl·H2O utilizing a through-bond (J) and residual dipolar-splitting (RDS) based heteronuclear multiple quantum correlation (J-HMQC) sequence mediated through (1)H/(1)H radio-frequency driven recoupling (RFDR). As an extension of our previous work, in this study we show the utility of dipolar-based HMQC (D-HMQC) in combination with (1)H/(1)H RFDR mixing to obtain sensitivity enhanced (14)N/(14)N correlations in more complex biological solids such as a glycyl-l-alanine (Gly-l-Ala) dipeptide, and parallel (P) and antiparallel (AP) β-strand alanine tripeptides (P-(Ala)3 and AP-(Ala)3, respectively). These systems highlight the mandatory necessity of 3D (14)N/(14)N/(1)H measurements to get (14)N/(14)N correlations when the amide proton resonances are overlapped. Moreover, the application of long selective (14)N pulses, instead of short hard ones, is shown to improve the sensitivity. Globally, we demonstrate that replacing J-scalar with dipolar interaction and hard- with selective-(14)N pulses allows gaining a factor of ca. 360 in experimental time. On the basis of intermolecular NH/NH distances and (14)N quadrupolar tensor orientations, (14)N/(14)N correlations are effectively utilized to make a clear distinction between the parallel and antiparallel arrangements of the β-strands in (Ala)3 through the

  7. Sensitivity enhanced (14)N/(14)N correlations to probe inter-beta-sheet interactions using fast magic angle spinning solid-state NMR in biological solids.

    PubMed

    Pandey, Manoj Kumar; Amoureux, Jean-Paul; Asakura, Tetsuo; Nishiyama, Yusuke

    2016-08-10

    (14)N/(14)N correlations are vital for structural studies of solid samples, especially those in which (15)N isotopic enrichment is challenging, time-consuming and expensive. Although (14)N nuclei have high isotopic abundance (99.6%), there are inherent difficulties in observing (14)N/(14)N correlations due to limited resolution and sensitivity related to: (i) low (14)N gyromagnetic ratio (γ), (ii) large (14)N quadrupolar couplings, (iii) integer (14)N spin quantum number (I = 1), and (iv) very weak (14)N-(14)N dipolar couplings. Previously, we demonstrated a proton-detected 3D (14)N/(14)N/(1)H correlation experiment at fast magic angle spinning (MAS) on l-histidine·HCl·H2O utilizing a through-bond (J) and residual dipolar-splitting (RDS) based heteronuclear multiple quantum correlation (J-HMQC) sequence mediated through (1)H/(1)H radio-frequency driven recoupling (RFDR). As an extension of our previous work, in this study we show the utility of dipolar-based HMQC (D-HMQC) in combination with (1)H/(1)H RFDR mixing to obtain sensitivity enhanced (14)N/(14)N correlations in more complex biological solids such as a glycyl-l-alanine (Gly-l-Ala) dipeptide, and parallel (P) and antiparallel (AP) β-strand alanine tripeptides (P-(Ala)3 and AP-(Ala)3, respectively). These systems highlight the mandatory necessity of 3D (14)N/(14)N/(1)H measurements to get (14)N/(14)N correlations when the amide proton resonances are overlapped. Moreover, the application of long selective (14)N pulses, instead of short hard ones, is shown to improve the sensitivity. Globally, we demonstrate that replacing J-scalar with dipolar interaction and hard- with selective-(14)N pulses allows gaining a factor of ca. 360 in experimental time. On the basis of intermolecular NH/NH distances and (14)N quadrupolar tensor orientations, (14)N/(14)N correlations are effectively utilized to make a clear distinction between the parallel and antiparallel arrangements of the β-strands in (Ala)3 through the

  8. Static solid-state (14)N NMR and computational studies of nitrogen EFG tensors in some crystalline amino acids.

    PubMed

    O'Dell, Luke A; Schurko, Robert W

    2009-08-28

    The recently reported direct enhancement of integer spin magnetization (DEISM) methodology for signal enhancement in solid-state NMR of integer spins has been used to obtain static (14)N powder patterns from alpha-glycine, L-leucine and L-proline in relatively short experimental times at 9.4 T, allowing accurate determination of the quadrupolar parameters. Proton decoupling and deuteration of the nitrogen sites were used to reduce the (1)H-(14)N dipolar contribution to the transverse relaxation time allowing more echoes to be acquired per scan. In addition, ab initio calculations using molecular clusters (Gaussian 03) and the full crystal lattice (CASTEP) have been employed to confirm these results, to obtain the orientation of the electric field gradient (EFG) tensors in the molecular frame, and also to correctly assign the two sets of parameters for L-leucine. The (14)N EFG tensor is shown to be highly sensitive to the surrounding environment, particularly to nearby hydrogen bonding.

  9. Proton zero-quantum 2D NMR of 2-propenenitrile aligned by an electric field. Determination of the 2H and 14N quadrupole coupling constants

    NASA Astrophysics Data System (ADS)

    Ruessink, B. H.; De Kanter, F. J. J.; MaClean, C.

    Zero-quantum NMR, selectively detected by 2D NMR, is applied to observe small 1H- 1H dipolar couplings in a polar liquid partially oriented by a strong electric field. The normal (single-quantum) 1H spectrum is severely broadened, which prevents the observation of small couplings. The results from the zero-quantum proton spectrum are used to calculate the 2H and 14N quadrupole coupling constants of 2-deutero-2-propenenitrile from the 2H and 14N NMR spectra.

  10. Detection of {sup 14}N and {sup 35}Cl in cocaine base and hydrochloride using NQR, NMR, and SQUID techniques

    SciTech Connect

    Yesinowski, J.P.; Buess, M.L.; Garroway, A.N.; Ziegeweid, M.; Pines, A. |

    1995-07-01

    Results from {sup 14}N pure NQR of cocaine in the free base form (cocaine base) yield a nuclear quadrupole coupling constant (NQCC) e{sup 2}Qq/h of 5.0229 ({+-}0.0001) MHz and an asymmetry parameter {eta} of 0.0395 ({+-}0.0001) at 295 K, with corresponding values of 5.0460 ({+-}0.0013) MHz and 0.0353 ({+-}0.0008) at 77 K. Both pure NQR (at 295-77 K) and a superconducting quantum interference device (SQUID) detector (at 4.2 K) were used to measure the very low (<1 MHz) {sup 14}N transition frequencies in cocaine hydrochloride; at 295 K the NQCC is 1.1780 ({+-}0.0014) MHz and the asymmetry parameter is 0.2632 ({+-}0.0034). Stepping the carrier frequency enables one to obtain a powder pattern without the severe intensity distortions that otherwise arise from finite pulse power. A powder pattern simulation using an NQCC value of 5.027 MHz and an asymmetry parameter {eta} of 0.2 agrees reasonably well with the experimental stepped-frequency spectrum. The use of pure NQR for providing nondestructive, quantitative, and highly specific detection of crystalline compounds is discussed, as are experimental strategies. 31 refs., 8 figs., 1 tab.

  11. Polymorphism and disorder in natural active ingredients. Low and high-temperature phases of anhydrous caffeine: Spectroscopic ((1)H-(14)N NMR-NQR/(14)N NQR) and solid-state computational modelling (DFT/QTAIM/RDS) study.

    PubMed

    Seliger, Janez; Žagar, Veselko; Apih, Tomaž; Gregorovič, Alan; Latosińska, Magdalena; Olejniczak, Grzegorz Andrzej; Latosińska, Jolanta Natalia

    2016-03-31

    The polymorphism of anhydrous caffeine (1,3,7-trimethylxanthine; 1,3,7-trimethyl-1H-purine-2,6-(3H,7H)-dione) has been studied by (1)H-(14)N NMR-NQR (Nuclear Magnetic Resonance-Nuclear Quadrupole Resonance) double resonance and pure (14)N NQR (Nuclear Quadrupole Resonance) followed by computational modelling (Density Functional Theory, supplemented Quantum Theory of Atoms in Molecules with Reduced Density Gradient) in solid state. For two stable (phase II, form β) and metastable (phase I, form α) polymorphs the complete NQR spectra consisting of 12 lines were recorded. The assignment of signals detected in experiment to particular nitrogen sites was verified with the help of DFT. The shifts of the NQR frequencies, quadrupole coupling constants and asymmetry parameters at each nitrogen site due to polymorphic transition were evaluated. The strongest shifts were observed at N(3) site, while the smallest at N(9) site. The commercial pharmaceutical sample was found to contain approximately 20-25% of phase I and 75-80% of phase II. The orientational disorder in phase II with a local molecular arrangement mimics that in phase I. Substantial differences in the intermolecular interaction phases I and II of caffeine were analysed using computational (DFT/QTAIM/RDS) approach. The analysis of local environment of each nitrogen nucleus permitted drawing some conclusions on the topology of interactions in both polymorphs. For the most stable orientations in phase I and phase II the maps of the principal component qz of EFG tensor and its asymmetry parameter at each point of the molecular system were calculated and visualized. The relevant maps calculated for both phases I and II indicates small variation in electrostatic potential upon phase change. Small differences between packings in phases slightly disturb the neighbourhood of the N(1) and N(7) nitrogens, thus are meaningless from the biological point of view. The composition of two phases in pharmaceutical material

  12. Ferroelastic phase transitions by 14N NMR spectra in [N(CH3)4]2CoCl4 and [N(CH3)4]2ZnCl4 single crystals

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran

    2016-09-01

    Changes in the structural geometry of [N(CH3)4]2BCl4 (B=Co and Zn) crystals near the phase transition temperatures were studied by analyzing the 14N nuclear magnetic resonance (NMR) spectra. Two physically inequivalent a-N(1)(CH3)4 and b-N(2)(CH3)4 groups were observed in these spectra. Abrupt changes in the resonance frequency and splitting of 14N NMR signals near the phase transition temperatures were attributed to structural phase transitions, and the primary mechanism of these phase transitions exhibited ferroelastic characteristics. In addition, ferroelasticity of [N(CH3)4]2BCl4 was identified at low temperatures using optical polarizing microscopy.

  13. Route No. 1 near east end, view toward Overton Beach ...

    Library of Congress Historic Buildings Survey, Historic Engineering Record, Historic Landscapes Survey

    Route No. 1 near east end, view toward Overton Beach and Lake Mead, view to northeast - Route No. 1-Overton-Lake Mead Road, Between Overton Beach & Park Boundary, 6 miles south of Overton, Overton, Clark County, NV

  14. An innovative method for the non-destructive identification of photodegradation products in solid state: 1H-14N NMR-NQR and DFT/QTAIM study of photodegradation of nifedipine (anti-hypertensive) to nitrosonifedipine (potential anti-oxidative).

    PubMed

    Latosińska, J N; Latosińska, M; Seliger, J; Zagar, V

    2012-08-30

    Stability of the antihypertensive drug nifedipine (NIF) has been studied experimentally in solid state by (1)H-(14)N NMR-NQR double resonance (NQDR) and theoretically by the Density Functional Theory (DFT). Photodegradation of NIF to its metabolite in vivo nitrosonifedipine, NO-NIF (antioxidative agent) upon long term daylight exposure was detected and the changes in the molecular structure of NIF were analysed. The photoconversion of NIF to NO-NIF in solid was found to be accompanied with the electron density redistribution at nitrogen sites (NH to N and NO(2) to NO) and proved to be successfully detected with identification of photoproducts by (1)H-(14)N NQDR and DFT methods. The increase in the e(2)qQ/h and η describing EFG tendency towards non-spherical symmetry was significantly greater upon the reduction of NO(2) site than upon hydrogen abstraction from NH site. The level of sensitivity of detection of the photodegradation product was about 1% of the original sample. The Quantum Theory of Atoms in Molecules (QTAIM) analysis has been found useful in predicting photoreactive sites in the molecules and finding the explanation of differences in reactivity between parent NIF and its photoproduct NO-NIF. Using NIF as a model, this study demonstrates the suitability of NQDR supported by DFT for non-destructive determination of the photodegradation products in solid state.

  15. Scissors modes: The first overtone

    SciTech Connect

    Hatada, Keisuke; Hayakawa, Kuniko; Palumbo, Fabrizio

    2011-07-15

    Scissors modes were predicted in the framework of the two-rotor model. This model has an intrinsic harmonic spectrum, so that the level above the scissors mode, the first overtone, has excitation energy twice that of the scissors mode. Because the latter is of the order of 3 MeV in the rare-earth region, the energy of the overtone is below threshold for nucleon emission, and its width should remain small enough for the overtone to be observable. We find that B(E2){up_arrow}{sub overtone}=(1/64 {theta}{sub 0}{sup 2})B(E2){up_arrow}{sub scissors}, where {theta}{sub 0} is the zero-point oscillation amplitude, which in the rare-earth region is of order 10{sup -1}.

  16. Free radical and overtone spectroscopy

    NASA Technical Reports Server (NTRS)

    Reilly, James P.

    1991-01-01

    In the fall of 1987 during a photoacoustic study of hydrogen peroxide's fourth vibrational overtone band, the remarkably clear and well resolved spectrum was observed. Its periodicity and K subband structure suggested that the spectrum was not of hydrogen peroxide but of a smaller near-prolate symmetric top molecule. Furthermore, the time dependent behavior of the signal indicated that chemical changes were taking place within the photoacoustic apparatus.

  17. Acoustics and perception of overtone singing.

    PubMed

    Bloothooft, G; Bringmann, E; van Cappellen, M; van Luipen, J B; Thomassen, K P

    1992-10-01

    Overtone singing, a technique of Asian origin, is a special type of voice production resulting in a very pronounced, high and separate tone that can be heard over a more or less constant drone. An acoustic analysis is presented of the phenomenon and the results are described in terms of the classical theory of speech production. The overtone sound may be interpreted as the result of an interaction of closely spaced formants. For the lower overtones, these may be the first and second formant, separated from the lower harmonics by a nasal pole-zero pair, as the result of a nasalized articulation shifting from /c/ to /a/, or, as an alternative, the second formant alone, separated from the first formant by the nasal pole-zero pair, again as the result of a nasalized articulation around /c/. For overtones with a frequency higher than 800 Hz, the overtone sound can be explained as a combination of the second and third formant as the result of a careful, retroflex, and rounded articulation from /c/, via schwa /e/ to /y/ and /i/ for the highest overtones. The results indicate a firm and relatively long closure of the glottis during overtone phonation. The corresponding short open duration of the glottis introduces a glottal formant that may enhance the amplitude of the intended overtone. Perception experiments showed that listeners categorized the overtone sounds differently from normally sung vowels, which possibly has its basis in an independent perception of the small bandwidth of the resonance underlying the overtone. Their verbal judgments were in agreement with the presented phonetic-acoustic explanation.

  18. Overtone Mobility Spectrometry: Part 5. Simulations and Analytical Expressions Describing Overtone Limits

    NASA Astrophysics Data System (ADS)

    Ewing, Michael A.; Zucker, Steven M.; Valentine, Stephen J.; Clemmer, David E.

    2013-04-01

    Mathematical expressions for the analytical duty cycle associated with different overtones in overtone mobility spectrometry are derived from the widths of the transmitted packets of ions under different instrumental operating conditions. Support for these derivations is provided through ion trajectory simulations. The outcome of the theory and simulations indicates that under all operating conditions there exists a limit or maximum observable overtone that will result in ion transmission. Implications of these findings on experimental design are discussed.

  19. High overtone spectroscopy of polyatomic molecules

    SciTech Connect

    Wong, J.S.

    1981-12-01

    Overtone spectra of the C-H stretching vibrations were observed using laser photoacoustic spectroscopy in the visible and Fourier transform infrared spectroscopy in the near-infrared. The microcomputer-controlled, laser photoacoustic spectrometer is described in detail. The fifth overtone spectra of gaseous alkanes and alkenes were analyzed using the local mode model, and resolvable peaks were seen for each inequivalent C-H bond. Correlations of overtone transition energies with C-H bond lengths and isolated fundamental frequencies were found. The integrated cross sections per C-H oscillator varied by a factor of two about the average value of (1.08+-0.28) x 10/sup -23/ cm/sup 2/ cm/sup -1/. Local mode spectra of cycloalkanes and cycloalkenes were observed using both gas phase high overtone and isotopically isolated fundamental spectroscopy. The shapes of the bands reflect the changes in the C-H bonds during conformational motion. Absorptions by axial and equatorial type C-H bonds were resolved in cyclobutane, cyclopentane, cyclopentene and cyclohexane and the isotopically isolated fundamentals were close to the frequencies extrapolated from the overtones except for liquid cyclohexane. The equatorial bands are consistently more intense than the axial ones. Spectra of chloroform, fluoroform, dichlorofluoromethane and chlorodifluoromethane are observed from the fundamentals through the fifth overtone of the C-H stretching vibrations. Fermi resonant combination bands with one less C-H stretching quantum plus two quanta of the C-H bending vibrations, along with the C-H stretching overtones, dominate the spectra. The intensities of these combination bands increase with the level of vibrational excitation, indicating strong, intramolecular mode coupling.

  20. Intensities of Fundamental and Overtone Vibrational Transitions

    NASA Astrophysics Data System (ADS)

    Kjaergaard, Henrik G.

    2012-06-01

    We have measured and calculated vibrational XH-stretching overtone spectra (where X is C,N,O,S,..) for a range of molecules and hydrated complexes (e.g. water dimer). Spectroscopic studies of such systems are difficult because: vibrational overtone transitions have low intensities, species that exhibit intramolecular hydrogen bonding typically have low vapor pressures and hydrated complexes have small equilibrium constants. The use of coupled cluster theory including perturbative triples, CCSD(T) or CCSD(T)-F12, as well as a large augmented basis, aug-cc-pVTZ or VDZ-F12, is necessary to obtain calculated vibrational spectra of near experimental accuracy. We explain the interesting intensity patterns in terms of an anharmonic oscillator local mode model. The intensity ratio of the fundamental to first XH-stretching overtone covers a wide range. In the past decade, we have used this local mode model to explain observed spectra of both molecules and complexes. I will show recent results for amines and complexes with amines and will illustrate how the ratio of calculated to measured intensity can provide the room temperature equilibrium constant for formation of the binary complex, a quantity that is difficult to calculate accurately.

  1. Measurements of the CO first overtone bandstrength at elevated temperatures

    NASA Astrophysics Data System (ADS)

    Caledonia, G. E.; Krech, R. H.; Wilkerson, T.

    1985-08-01

    The spectrally resolved emission from the CO first overtone vibration-rotation band has been studied over the temperature range of 1100-2600 K in a shock-tube experiment. First overtone bandstrengths have been deduced from the data. These compare favorably with theoretical expectations.

  2. 2016 ISCB Overton Prize awarded to Debora Marks.

    PubMed

    Fogg, Christiana N; Kovats, Diane E

    2016-01-01

    The International Society for Computational Biology (ISCB) recognizes the achievements of an early- to mid-career scientist with the Overton Prize each year. The Overton Prize was established to honor the untimely loss of Dr. G. Christian Overton, a respected computational biologist and founding ISCB Board member. Winners of the Overton Prize are independent investigators in the early to middle phases of their careers who are selected because of their significant contributions to computational biology through research, teaching, and service. 2016 will mark the fifteenth bestowment of the ISCB Overton Prize.  ISCB is pleased to confer this award the to Debora Marks, Assistant Professor of Systems Biology and director of the Raymond and Beverly Sackler Laboratory for Computational Biology at Harvard Medical School. PMID:27429747

  3. 2016 ISCB Overton Prize awarded to Debora Marks.

    PubMed

    Fogg, Christiana N; Kovats, Diane E

    2016-01-01

    The International Society for Computational Biology (ISCB) recognizes the achievements of an early- to mid-career scientist with the Overton Prize each year. The Overton Prize was established to honor the untimely loss of Dr. G. Christian Overton, a respected computational biologist and founding ISCB Board member. Winners of the Overton Prize are independent investigators in the early to middle phases of their careers who are selected because of their significant contributions to computational biology through research, teaching, and service. 2016 will mark the fifteenth bestowment of the ISCB Overton Prize.  ISCB is pleased to confer this award the to Debora Marks, Assistant Professor of Systems Biology and director of the Raymond and Beverly Sackler Laboratory for Computational Biology at Harvard Medical School.

  4. 2016 ISCB Overton Prize awarded to Debora Marks

    PubMed Central

    Fogg, Christiana N.; Kovats, Diane E.

    2016-01-01

    The International Society for Computational Biology (ISCB) recognizes the achievements of an early- to mid-career scientist with the Overton Prize each year. The Overton Prize was established to honor the untimely loss of Dr. G. Christian Overton, a respected computational biologist and founding ISCB Board member. Winners of the Overton Prize are independent investigators in the early to middle phases of their careers who are selected because of their significant contributions to computational biology through research, teaching, and service. 2016 will mark the fifteenth bestowment of the ISCB Overton Prize.  ISCB is pleased to confer this award the to Debora Marks, Assistant Professor of Systems Biology and director of the Raymond and Beverly Sackler Laboratory for Computational Biology at Harvard Medical School. PMID:27429747

  5. Quartz-enhanced photoacoustic spectroscopy exploiting tuning fork overtone modes

    NASA Astrophysics Data System (ADS)

    Sampaolo, A.; Patimisco, P.; Dong, L.; Geras, A.; Scamarcio, G.; Starecki, T.; Tittel, F. K.; Spagnolo, V.

    2015-12-01

    We report on a quartz-enhanced photoacoustic sensor (QEPAS) based on a custom-made quartz tuning fork (QTF) to operate in both the fundamental and the first overtone vibrational mode resonances. The QTF fundamental mode resonance falls at ˜3 kHz and the first overtone at ˜18 kHz. Electrical tests showed that the first overtone provides a higher quality factor and increased piezoelectric current peak values, with respect to the fundamental flexural mode. To evaluate the QTF acousto-electric energy conversion efficiency, we operated the QEPAS in the near-IR and selected water vapor as the target gas. The first overtone resonance provides a QEPAS signal-to-noise ratio ˜5 times greater with respect to that measured for the fundamental mode. These results open the way to employing QTF overtone vibrational modes for QEPAS based trace gas sensing.

  6. Comparison of various NMR methods for the indirect detection of nitrogen-14 nuclei via protons in solids.

    PubMed

    Shen, Ming; Trébosc, Julien; O'Dell, Luke A; Lafon, Olivier; Pourpoint, Frédérique; Hu, Bingwen; Chen, Qun; Amoureux, Jean-Paul

    2015-09-01

    We present an experimental comparison of several through-space Hetero-nuclear Multiple-Quantum Correlation experiments, which allow the indirect observation of homo-nuclear single- (SQ) or double-quantum (DQ) (14)N coherences via spy (1)H nuclei. These (1)H-{(14)N} D-HMQC sequences differ not only by the order of (14)N coherences evolving during the indirect evolution, t1, but also by the radio-frequency (rf) scheme used to excite and reconvert these coherences under Magic-Angle Spinning (MAS). Here, the SQ coherences are created by the application of center-band frequency-selective pulses, i.e. long and low-power rectangular pulses at the (14)N Larmor frequency, ν0((14)N), whereas the DQ coherences are excited and reconverted using rf irradiation either at ν0((14)N) or at the (14)N overtone frequency, 2ν0((14)N). The overtone excitation is achieved either by constant frequency rectangular pulses or by frequency-swept pulses, specifically Wide-band, Uniform-Rate, and Smooth-Truncation (WURST) pulse shapes. The present article compares the performances of four different (1)H-{(14)N} D-HMQC sequences, including those with (14)N rectangular pulses at ν0((14)N) for the indirect detection of homo-nuclear (i) (14)N SQ or (ii) DQ coherences, as well as their overtone variants using (iii) rectangular or (iv) WURST pulses. The compared properties include: (i) the sensitivity, (ii) the spectral resolution in the (14)N dimension, (iii) the rf requirements (power and pulse length), as well as the robustness to (iv) rf offset and (v) MAS frequency instabilities. Such experimental comparisons are carried out for γ-glycine and l-histidine.HCl monohydrate, which contain (14)N sites subject to moderate quadrupole interactions. We demonstrate that the optimum choice of the (1)H-{(14)N} D-HMQC method depends on the experimental goal. When the sensitivity and/or the robustness to offset are the major concerns, the D-HMQC sequence allowing the indirect detection of (14)N SQ

  7. Comparison of various NMR methods for the indirect detection of nitrogen-14 nuclei via protons in solids

    NASA Astrophysics Data System (ADS)

    Shen, Ming; Trébosc, Julien; O'Dell, Luke A.; Lafon, Olivier; Pourpoint, Frédérique; Hu, Bingwen; Chen, Qun; Amoureux, Jean-Paul

    2015-09-01

    We present an experimental comparison of several through-space Hetero-nuclear Multiple-Quantum Correlation experiments, which allow the indirect observation of homo-nuclear single- (SQ) or double-quantum (DQ) 14N coherences via spy 1H nuclei. These 1H-{14N} D-HMQC sequences differ not only by the order of 14N coherences evolving during the indirect evolution, t1, but also by the radio-frequency (rf) scheme used to excite and reconvert these coherences under Magic-Angle Spinning (MAS). Here, the SQ coherences are created by the application of center-band frequency-selective pulses, i.e. long and low-power rectangular pulses at the 14N Larmor frequency, ν0(14N), whereas the DQ coherences are excited and reconverted using rf irradiation either at ν0(14N) or at the 14N overtone frequency, 2ν0(14N). The overtone excitation is achieved either by constant frequency rectangular pulses or by frequency-swept pulses, specifically Wide-band, Uniform-Rate, and Smooth-Truncation (WURST) pulse shapes. The present article compares the performances of four different 1H-{14N} D-HMQC sequences, including those with 14N rectangular pulses at ν0(14N) for the indirect detection of homo-nuclear (i) 14N SQ or (ii) DQ coherences, as well as their overtone variants using (iii) rectangular or (iv) WURST pulses. The compared properties include: (i) the sensitivity, (ii) the spectral resolution in the 14N dimension, (iii) the rf requirements (power and pulse length), as well as the robustness to (iv) rf offset and (v) MAS frequency instabilities. Such experimental comparisons are carried out for γ-glycine and L-histidine.HCl monohydrate, which contain 14N sites subject to moderate quadrupole interactions. We demonstrate that the optimum choice of the 1H-{14N} D-HMQC method depends on the experimental goal. When the sensitivity and/or the robustness to offset are the major concerns, the D-HMQC sequence allowing the indirect detection of 14N SQ coherences should be employed. Conversely

  8. ir overtone spectrum of the vibrational soliton in crystalline acetanilide

    NASA Astrophysics Data System (ADS)

    Scott, A. C.; Gratton, E.; Shyamsunder, E.; Careri, G.

    1985-10-01

    The self-trapping (soliton) theory which was recently developed to account for the anomalous amide-I band at 1650 cm-1 in crystalline acetanilide (a model system for protein) has been extended to predict the anharmonicity constant of the overtone spectrum. These infrared-active overtones which have been detected at 3250, 4803, and 6304 cm-1 yield an anharmonicity constant that is in good agreement with the theory.

  9. ir overtone spectrum of the vibrational soliton in crystalline acetanilide

    SciTech Connect

    Scott, A.C.; Gratton, E.; Shyamsunder, E.; Careri, G.

    1985-10-15

    The self-trapping (soliton) theory which was recently developed to account for the anomalous amide-I band at 1650 cm/sup -1/ in crystalline acetanilide (a model system for protein) has been extended to predict the anharmonicity constant of the overtone spectrum. These infrared-active overtones which have been detected at 3250, 4803, and 6304 cm/sup -1/ yield an anharmonicity constant that is in good agreement with the theory.

  10. 14 N NQR spectrum of sildenafil citrate

    NASA Astrophysics Data System (ADS)

    Stephenson, David; Singh, Nadia

    2015-04-01

    The 14N nuclear quadrupole resonance (NQR) spectrum of sildenafil citrate tablets has been recorded allowing the quadrupole coupling constants and asymmetry parameters of all six unique nitrogen atoms in its structure to be determined. A density function calculation gives results that are largely in agreement with the experimental values.

  11. Selective dissociation of HCl in Kr from vibrational overtones

    NASA Astrophysics Data System (ADS)

    Berghof, V.; Schwentner, N.

    2002-11-01

    Vibrational levels v=1, 2, and 3 of HCl in Kr matrices are populated with tunable IR radiation and the excited molecules are dissociated by UV excitation to the repulsive A 1x state. Cl fragments are recorded by laser induced fluorescence of Kr2Cl and dissociation rates are determined from the increase in LIF with UV dose. The enlarged UV Franck-Condon range for overtones allows the study of cage exit of H fragments with small kinetic energy Ekin. A threshold at Ekin=1.4 eV and a steep rise indicate a predominant sudden exit. Monomers, different initial rotational states and transients in the relaxation cascade are preselected with overtone excitation and the feasibility of a discrimination between isotopes, aggregates, and local structures is illustrated.

  12. Some nitrogen-14 NMR studies in solids

    SciTech Connect

    Pratum, T.K.

    1983-11-01

    The first order quadrupolar perturbation of the /sup 14/N NMR spectrum yields information regarding the static and dynamic properties of the surrounding electronic environment. Signal to noise problems caused by long /sup 14/N longitudinal relaxation times (T/sub 1/) and small equilibrium polarizations are reduced by rotating frame cross polarization (CP) experiments between /sup 14/N and /sup 1/H. Using quadrupolar echo and CP techniques, the /sup 14/N quadrupolar coupling constants (e/sup 2/qQ/h) and asymmetry parameters (eta) have been obtained for a variety of tetraalkylammonium compounds by observation of their quadrupolar powder patterns at various temperatures. For choline chloride and iodide the /sup 14/N NMR powder patterns exhibit the effects of anisotropic molecular motion, while choline bromide spectra show no such effects.

  13. Determination of cross sections by overtone mobility spectrometry: evidence for loss of unstable structures at higher overtones.

    PubMed

    Lee, Sunyoung; Ewing, Michael A; Nachtigall, Fabiane M; Kurulugama, Ruwan T; Valentine, Stephen J; Clemmer, David E

    2010-09-30

    Overtone mobility spectrometry (OMS) is examined as a means of determining the collision cross sections for multiply charged ubiquitin and substance P ions, as well as for singly charged rafinose and melezitose ions. Overall, values of collision cross section measured by OMS for stable ion conformations are found to be in agreement with values determined by conventional ion mobility spectrometry (IMS) measurements to within ∼1% relative uncertainty. The OMS spectra for ubiquitin ions appear to favor different conformations at higher overtones. We propose that the changes in the distributions as a function of the overtone region in which they are measured arise from the elimination of ions that undergo structural transitions in the drift regions. Kinetics simulations suggest that structural transitions occurring on the order of a few ms and resulting in an ∼4% change in ion collision cross sections are detected by OMS measurements. The unique method of distinguishing ion mobilities with OMS reveals these structural transitions which are not readily apparent from traditional IMS measurements.

  14. Overtone spectroscopy and dynamics in monodeuteroacetylene (C 2HD)

    NASA Astrophysics Data System (ADS)

    Liévin, J.; Abbouti Temsamani, M.; Gaspard, P.; Herman, M.

    1995-01-01

    Complementary experimental, ab initio and dynamical investigations are reported on monodeuteroacetylene, C 2HD (X˜ 1Σ +). All experimental spectroscopic results previously reported in the literature on C 2HD, i.e. from 500 to 16000 cm -1 are gathered. New results are included, which are obtained from the analysis of absorption data recorded with a Fourier transform interferometer at high resolution between 4600 and 9000 cm -1. The presence of numerous weak bands along the whole spectral range is analysed in terms of systematic anharmonic couplings. The entire set of energy data is then used to produce thirty-five vibrational frequencies and anharmonicities from a fit of the vibrational energies to a Dunham-type expansion, and the vibrational level density is extrapolated, up to higher energy. One- and two-dimensional potential energy and dipole moment surfaces refined from new ab initio results are fitted to a selected set among those experimental data, associated to the stretch overtones. The iterative procedure involving an original package of computer programs is described. The evolution of the overtone intensities of the CH and CD stretches, up to η = 4, is interpreted on that basis in terms of electric and mechanical anharmonicity contributions. Eventually, dynamical aspects are studied thanks to the newly introduced vibrograms, which allow to obtain the time recurrences of the vibrational dynamics. Using the Gutzwiller and Berry-Tabor trace formulas, these vibrational recurrences are semiclassically assigned to periodic orbits of the classical Hamiltonian given by the Dunham expansion.

  15. PZT transduction of high-overtone contour-mode resonators.

    PubMed

    Chandrahalim, Hengky; Bhave, Sunil A; Polcawich, Ronald G; Pulskamp, Jeffrey S; Kaul, Roger

    2010-09-01

    This paper presents the Butterworth-van Dyke model and quantitative comparison that explore the design space of lead zirconate titanate-only (PZT) and PZT on 3-, 5-, and 10-μm single-crystal silicon (SCS) high-overtone width-extensional mode (WEM) resonators with identical lateral dimensions for incorporation into radio frequency microelectromechanical systems (RF MEMS) filters and oscillators. A novel fabrication technique was developed to fabricate the resonators with and without a silicon carrier layer using the same mask set on the same wafer. The air-bridge metal routings were implemented to carry electrical signals while avoiding large capacitances from the bond-pads. We theoretically derived and experimentally measured the correlation of motional impedance (RX), quality factor (Q), and resonance frequency (f) with the resonators' silicon layer thickness (tSi) up to frequencies of operation above 1 GHz.

  16. Overtone spectroscopy of benzene derivatives using thermal lensing

    NASA Astrophysics Data System (ADS)

    Vipin Prasad, J.; Rai, S. B.; Thakur, S. N.

    1989-12-01

    The vibrational overtones of CH stretching oscillators are reported as observed by conventional IR spectroscopy and dual-beam thermal lensing spectroscopy for benzene, fluorobenzene, chlorobenzene, bromobenzene and benzonitrile in the liquid phase at room temperature. The stretching frequency ω e, the anharmonicity constant ω eχ e and the change in CH bond length on substitution in benzene have been determined for all these molecules under the local-mode approximation. Effects of substitution on the change in CH stretching frequency have been discussed in terms of the electronegativity of the substituents as well as the inductive part of the Hammett σ. Variation of thermal lensing signal with chopping frequency and laser power has also been studied.

  17. Sediment investigations of the Platte River near Overton, Nebraska

    USGS Publications Warehouse

    Albert, C.D.; Guy, H.P.

    1955-01-01

    This report contains results of sediment-transport investigations on the Platte River near Overton,. Nebr. from January 1950 to September 1953. The basic data of suspended-sediment studies, results of bed-material analyses, and determinations of water-surface slopes from staff readings are given. The data indicate that a reliable determination of suspended sediment, hence total load, is difficult. Because of the nature of the river at the station and the limited scope of the investigations, the suspended-sediment data may not be representative. The Platte River is characterized by a wide braided channel, a small hydraulic radius, low banks, and a wide flood plain. (See figs. 1 and 2.,) The river bed is composed of coarse to fine sands. Near Overton, natural flow of the river is controlled or modified by diversions, storage reservoirs, power development, return flow from irrigation, and withdrawals of ground water. A temporary jetty was extended into the river below the bridge during the summer of 1952 as part of commercial sand pumping operations. Beavers carry on active construction in the narrows and shallows, particularly upstream from the sampling section. Daily fluctuations in water discharge at the gaging station at the bridge are caused by regulation of the flow, mainly from the generation of power by release of water from a reservoir The water discharge at the station begins increasing about 9:30 a.m., reaches a crest about 2:00 p.m and then immediately recede. Weekly water-discharge measurements of alternate high and low stages indicate a daily variation from 200 to more than 1,000 cfs. During spring summer, and fall increases in water dis charge are also caused by thunderstorm activity in the area.

  18. Low energy scattering cross section ratios of 14N(p ,p ) 14N

    NASA Astrophysics Data System (ADS)

    deBoer, R. J.; Bardayan, D. W.; Görres, J.; LeBlanc, P. J.; Manukyan, K. V.; Moran, M. T.; Smith, K.; Tan, W.; Uberseder, E.; Wiescher, M.; Bertone, P. F.; Champagne, A. E.; Islam, M. S.

    2015-04-01

    Background: The slowest reaction in the first CNO cycle is 14N(p ,γ ) 15O , therefore its rate determines the overall energy production efficiency of the entire cycle. The cross section presents several strong resonance contributions, especially for the ground-state transition. Some of the properties of the corresponding levels in the 15O compound nucleus remain uncertain, which affects the uncertainty in extrapolating the capture cross section to the low energy range of astrophysical interest. Purpose: The 14N(p ,γ ) 15O cross section can be described by using the phenomenological R matrix. Over the energy range of interest, only the proton and γ -ray channels are open. Since resonance capture makes significant contributions to the 14N(p ,γ ) 15O cross section, resonant proton scattering data can be used to provide additional constraints on the R -matrix fit of the capture data. Methods: A 4 MV KN Van de Graaff accelerator was used to bombard protons onto a windowless gas target containing enriched 14N gas over the proton energy range from Ep=1.0 to 3.0 MeV. Scattered protons were detected at θlab=90 , 120∘, 135∘, 150∘, and 160∘ using ruggedized silicon detectors. In addition, a 10 MV FN Tandem Van de Graaff accelerator was used to accelerate protons onto a solid Adenine (C5H5N5 ) target, of natural isotopic abundance, evaporated onto a thin self-supporting carbon backing, over the energy range from Ep=1.8 to 4.0 MeV. Scattered protons were detected at 28 angles between θlab=30 .4∘ and 167 .7∘ by using silicon photodiode detectors. Results: Relative cross sections were extracted from both measurements. While the relative cross sections do not provide as much constraint as absolute measurements, they greatly reduce the dependence of the data on otherwise significant systematic uncertainties, which are more difficult to quantify. The data are fit simultaneously using an R -matrix analysis and level energies and proton widths are extracted. Even

  19. Vibrational overtone enhancement of methyl methacrylate polymerization initiated by benzoyl peroxide decomposition

    NASA Astrophysics Data System (ADS)

    Grinevich, Oleg; Snavely, D. L.

    1997-03-01

    Vibrational overtone initiated polymerization has been demonstrated using intracavity photolysis of a benzoyl peroxide/methyl methacrylate mixture. Excitation of the 6 νCH overtone transition of the ground electronic state of benzoyl peroxide creates radicals which subsequently begin the polymerization process. Polymer yield was monitored by comparison of the 2 νCH overtone absorptions for the methyl, methylenic and olefinic CH stretches at 5946 and 6170 cm -1, respectively. Plots of polymer yield versus time demonstrate an autoacceleration of the polymerization rate commencing many hours after the photolysis period. The delay before autoacceleration depends on the duration of the photolysis.

  20. Band strengths of fundamentals and overtones of the CF and CH chromophores in CHD 2F

    NASA Astrophysics Data System (ADS)

    Kormann, C.; Lewerenz, M.; Quack, M.

    1988-08-01

    Large quantities of CHD 2F have been synthesized by a newly developed method. A complete survey of the fundamental and high overtone spectrum of CHD 2F covering the frequency range from 700 to 14000 cm -1 has been measured in part at close to Doppler-limited resolution. The overtone spectrum is found to be dominated by multiple Fermi resonances between CH-stretching and -bending states. The integrated band strengths of the fundamentals and overtones of the CF and CH chromophores have been measured and are interpreted using group additivity models and the Mecke dipole function.

  1. DFT-D study of 14N nuclear quadrupolar interactions in tetra-n-alkyl ammonium halide crystals.

    PubMed

    Dib, Eddy; Alonso, Bruno; Mineva, Tzonka

    2014-05-15

    The density functional theory-based method with periodic boundary conditions and addition of a pair-wised empirical correction for the London dispersion energy (DFT-D) was used to study the NMR quadrupolar interaction (coupling constant CQ and asymmetry parameter ηQ) of (14)N nuclei in a homologous series of tetra-n-alkylammonium halides (C(x)H(2x+1))4N(+)X(-) (x = 1-4), (X = Br, I). These (14)N quadrupolar properties are particularly challenging for the DFT-D computations because of their very high sensitivity to tiny geometrical changes, being negligible for other spectral property calculations as, for example, NMR (14)N chemical shift. In addition, the polarization effect of the halide anions in the considered crystal mesophases combines with interactions of van der Waals type between cations and anions. Comparing experimental and theoretical results, the performance of PBE-D functional is preferred over that of B3LYP-D. The results demonstrated a good transferability of the empirical parameters in the London dispersion formula for crystals with two or more carbons per alkyl group in the cations, whereas the empirical corrections in the tetramethylammonium halides appeared to be inappropriate for the quadrupolar interaction calculation. This is attributed to the enhanced cation-anion attraction, which causes a strong polarization at the nitrogen site. Our results demonstrated that the (14)N CQ and ηQ are predominantly affected by the molecular structures of the cations, adapted to the symmetry of the anion arrangements. The long-range polarization effect of the surrounding anions at the target nitrogen site becomes more important for cells with lower spatial symmetry. PMID:24758512

  2. DFT-D study of 14N nuclear quadrupolar interactions in tetra-n-alkyl ammonium halide crystals.

    PubMed

    Dib, Eddy; Alonso, Bruno; Mineva, Tzonka

    2014-05-15

    The density functional theory-based method with periodic boundary conditions and addition of a pair-wised empirical correction for the London dispersion energy (DFT-D) was used to study the NMR quadrupolar interaction (coupling constant CQ and asymmetry parameter ηQ) of (14)N nuclei in a homologous series of tetra-n-alkylammonium halides (C(x)H(2x+1))4N(+)X(-) (x = 1-4), (X = Br, I). These (14)N quadrupolar properties are particularly challenging for the DFT-D computations because of their very high sensitivity to tiny geometrical changes, being negligible for other spectral property calculations as, for example, NMR (14)N chemical shift. In addition, the polarization effect of the halide anions in the considered crystal mesophases combines with interactions of van der Waals type between cations and anions. Comparing experimental and theoretical results, the performance of PBE-D functional is preferred over that of B3LYP-D. The results demonstrated a good transferability of the empirical parameters in the London dispersion formula for crystals with two or more carbons per alkyl group in the cations, whereas the empirical corrections in the tetramethylammonium halides appeared to be inappropriate for the quadrupolar interaction calculation. This is attributed to the enhanced cation-anion attraction, which causes a strong polarization at the nitrogen site. Our results demonstrated that the (14)N CQ and ηQ are predominantly affected by the molecular structures of the cations, adapted to the symmetry of the anion arrangements. The long-range polarization effect of the surrounding anions at the target nitrogen site becomes more important for cells with lower spatial symmetry.

  3. Pure-tone birdsong by resonance filtering of harmonic overtones

    PubMed Central

    Beckers, Gabriël J. L.; Suthers, Roderick A.; Cate, Carel ten

    2003-01-01

    Pure-tone song is a common and widespread phenomenon in birds. The mechanistic origin of this type of phonation has been the subject of long-standing discussion. Currently, there are three hypotheses. (i) A vibrating valve in the avian vocal organ, the syrinx, generates a multifrequency harmonic source sound, which is filtered to a pure tone by a vocal tract filter (“source-filter” model, analogous to human speech production). (ii) Vocal tract resonances couple with a vibrating valve source, suppressing the normal production of harmonic overtones at this source (“soprano” model, analogous to human soprano singing). (iii) Pure-tone sound is produced as such by a sound-generating mechanism that is fundamentally different from a vibrating valve. Here we present direct evidence of a source-filter mechanism in the production of pure-tone birdsong. Using tracheal thermistors and air sac pressure cannulae, we recorded sound signals close to the syringeal sound source during spontaneous, pure-tone vocalizations of two species of turtledove. The results show that pure-tone dove vocalizations originate through filtering of a multifrequency harmonic sound source. PMID:12764226

  4. Radon, lung cancer, and geology in Livingston, Overton County, Tennessee

    SciTech Connect

    Officer, C.; Shimek, S.; Fitzgerald, F.

    1995-12-31

    During the fall of 1994 tests defined radon levels of 76 piC/l in the basement level of a home in Overton Heights development in Livingston, Tennessee. Subsequent tests confirmed this elevation and also defined a value of 52 PiC/l in the second home tested in the same area. Subsequent discussions with local residents indicated 10 to 15 probable lung cancer cases in the previous +/-5 years in a population of about 100 households. When this situation was brought to the attention of the Tennessee Program the response was to immediately offer support for additional testing. This consisted of the placement of approximately 40 was to immediately offer support for additional testing. This consisted of the placement of approximately 40 Airchek charcoal packets on a somewhat random basis in February and March of 1995. Each house was tested in the location with potential for greatest radon elevation. The results showed that elevated radon levels were widespread with values as high as 105 piC/l. More significantly, most of the homes tested showed elevations. The next phase of the program involved some retesting of previously defined elevations but the majority of this stage concentrated on repeating those tests which were inconclusive and on the extension of the test area to establish the limits of the elevated values. Retesting verified elevations as previously defined but the values were generally lower due to testing main living levels and warmer which encouraged more ventilation.

  5. Diode laser overtone spectroscopy of atmospheric trace species

    SciTech Connect

    Lucchesini, A.; Pelliccia, D.; Longo, I.; Gabbanini, C.; Gozzini, S.

    1994-12-31

    This work is based on the use of diode lasers as spectroscopic sources for the observation and study of weak overtone bands of the NIR. The diode laser emission wavelength can be scanned around a gas resonance by sweeping its injection current, permitting a direct observation of an absorption line-shape. The resolution is limited principally by the effective laser linewidth, generally {approx}20 MHz in free running mode. The signal-to-noise ratio is increased by using the frequency modulation technique, and the excess laser amplitude 1/f noise is reduced by working at high frequencies. Since detectors operating at high frequencies are expensive and less sensitive, a good compromise is the two-tone frequency modulation technique, which uses two close high frequencies and collects the beat signal at lower frequency. Pressure broadening coefficients have been measured for some acetylene and ammonia absorption lines in the 790 nm bands and new lines have been observed. Pressure shift of two acetylene lines have been examined. It is shown that this spectroscopic apparatus can extract very weak signals from the background and can be a good choice when the space occupied by the spectrometer needs to be restricted into small volumes.

  6. Dissociative ionization of liquid water induced by vibrational overtone excitation

    SciTech Connect

    Natzle, W.C.

    1983-03-01

    Photochemistry of vibrationally activated ground electronic state liquid water to produce H/sup +/ and OH/sup -/ ions has been initiated by pulsed, single-photon excitation of overtone and combination transitions. Transient conductivity measurements were used to determine quantum yields as a function of photon energy, isotopic composition, and temperature. The equilibrium relaxation rate following perturbation by the vibrationally activated reaction was also measured as a function of temperature reaction and isotopic composition. In H/sub 2/O, the quantum yield at 283 +- 1 K varies from 2 x 10/sup -9/ to 4 x 10/sup -5/ for wave numbers between 7605 and 18140 cm/sup -1/. In D/sub 2/O, the dependence of quantum yield on wavelength has the same qualitative shape as for H/sub 2/O, but is shifted to lower quantum yields. The position of a minimum in the quantum yield versus hydrogen mole fraction curve is consistent with a lower quantum yield for excitation of HOD in D/sub 2/O than for excitation of D/sub 2/O. The ionic recombination distance of 5.8 +- 0.5 A is constant within experimental error with temperature in H/sub 2/O and with isotopic composition at 25 +- 1/sup 0/C.

  7. Overtone resonance enhanced single-tube on-beam quartz enhanced photoacoustic spectrophone

    NASA Astrophysics Data System (ADS)

    Zheng, Huadan; Dong, Lei; Sampaolo, Angelo; Patimisco, Pietro; Ma, Weiguang; Zhang, Lei; Yin, Wangbao; Xiao, Liantuan; Spagnolo, Vincenzo; Jia, Suotang; Tittel, Frank K.

    2016-09-01

    A single-tube on-beam quartz enhanced photoacoustic spectroscopy (SO-QEPAS) spectrophone, which employs a custom-made quartz tuning fork (QTF) having a prong spacing of 700 μm and operating at the 1st overtone flexural mode, is reported. The design of QTF prong geometry allows the bare QTF to possess twice higher Q-factor values for the 1st overtone resonance mode falling at ˜17.7 kHz than in the fundamental resonance mode at ˜2.8 kHz, resulting in an 8 times higher QEPAS signal amplitude when operating in the 1st overtone resonance mode. Both the vertical position and length of the single-tube acoustic micro-resonator (AmR) were optimized to attain optimal spectrophone performance. Benefiting from the high overtone resonance frequency and the quasi 1st harmonic acoustic standing waves generated in the SO-QEPAS configuration, the AmR length is reduced to 14.5 mm. This allows the realization of compact spectrophone and facilitates the laser beam alignment through the QTF + AmR system. The signal enhancement in the overtone resonance mode and the high acoustic coupling efficiency between the AmR and QTF in the SO-QEPAS configuration yields an overall sensitivity enhancement factor of ˜380 with respect to the bare custom QTF operating in the fundamental resonance mode.

  8. Vibrational spectroscopy of triacetone triperoxide (TATP): Anharmonic fundamentals, overtones and combination bands

    NASA Astrophysics Data System (ADS)

    Brauer, Brina; Dubnikova, Faina; Zeiri, Yehuda; Kosloff, Ronnie; Gerber, R. Benny

    2008-12-01

    The vibrational spectrum of triacetone triperoxide (TATP) is studied by the correlation-corrected vibrational self-consistent field (CC-VSCF) method which incorporates anharmonic effects. Fundamental, overtone, and combination band frequencies are obtained by using a potential based on the PM3 method and yielding the same harmonic frequencies as DFT/cc-pVDZ calculations. Fundamentals and overtones are also studied with anharmonic single-mode (without coupling) DFT/cc-pVDZ calculations. Average deviations from experiment are similar for all methods: 2.1-2.5%. Groups of degenerate vibrations form regions of numerous combination bands with low intensity: the 5600-5800 cm -1 region contains ca. 70 overtones and combinations of CH stretches. Anharmonic interactions are analyzed.

  9. Radiative n 14N capture at astrophysical energies

    NASA Astrophysics Data System (ADS)

    Dubovichenko, S. B.

    2013-06-01

    In the potential cluster model with forbidden states and classification of orbital cluster states according to Young's schemes, the possibility is considered of describing the experimental data for the total cross sections of radiative n 14N capture at energies from 25.0 meV (25•10-3 eV) to 1.0 MeV. It is shown that on the whole it is possible to successfully explain the behavior of these cross sections outside the resonant energy region on the basis of the E1 transition from the 2S1/2 scattering wave with zero phase to the bound 2Р1/2 state of the 15N nucleus in the n14N channel.

  10. Vibrational overtone spectra of metallocenes: effect of the coordinating metal on the CH bond lengths

    NASA Astrophysics Data System (ADS)

    Billinghurst, Brant E.; Gough, Kathleen M.

    2003-03-01

    The first through third overtone spectra of ferrocene, ruthenocene, nickelocene, cobaltocene, dicyclopentadienyl magnesium and sodium cyclopentadienyl are examined with particular attention to the CH stretching of the cyclopentadienyl. Using semi-empirical correlations between CH bond length and CH stretching frequencies in each overtone region, we have determined that the type of metal atom within a metallocene complex has little effect on the CH bond length in the cyclopentadienyl. The only exception is cobaltocene where there is evidence that the Jahn-Teller effect results in several different CH bond lengths. Evidence that bis(cyclopentadienyl) magnesium is not ionic has been observed.

  11. Surface enhanced Raman spectroscopy of pyridine on Ag electrodes. Evidence for overtones

    NASA Astrophysics Data System (ADS)

    Pettinger, B.

    1981-03-01

    An analysis of SER spectra for pyridine in H 2O and D 2O electrolytes yields overtones for six a 1 fundamentals very close to the expected frequency and many combination modes in addition to other unidentified vibrations. All these bands are weak in intensity, but by overlap they form a large part of the enhanced continuum. Implications of these observations are discussed.

  12. Shape resonances, overtones, and electron energy loss spectroscopy of gas phase and physisorbed diatomic molecules

    NASA Astrophysics Data System (ADS)

    Gadzuk, J. W.

    1983-10-01

    Electron energy loss spectra of O2 and N2 physisorbed on metallic substrates showing a series of high overtone losses have recently been reported. In the case of N2, the intense overtone excitation is credited to the formation of a well-known temporary negative ion state with a resonance lifetime ˜10-15 s for gas phase N2-. The principal distinction between the gaseous and physisorbed molecule EELS spectrum is a significant depletion of the overtone intensity which has been attributed to a surface-induced decrease in the resonance lifetime. In the present work, a time dependent quantum mechanical model applicable to vibrational excitation in resonance scattering is outlined which quantitatively accounts for the observed spectra and, in particular, the surface modifications to the gas phase results. The essential feature of the model is one in which the intramolecular dynamics of the intermediate state is characterized by nuclear propagation over a harmonic potential curve spatially displaced from the ground state curve for a time duration equal to the resonance lifetime. The resulting calculated overtone spectra agree well with the experimentally observed ones. The results suggest that the physisorbed N-2 lifetime is about 40% of that of the free molecule.

  13. Molecular dynamic simulations of OH-stretching overtone induced photodissociation of fluorosulfonic and chlorosulfonic acid.

    PubMed

    Gupta, Priyanka; Lane, Joseph R; Kjaergaard, Henrik G

    2010-08-01

    We investigate the OH-stretching overtone dynamics of fluorosulfonic acid (FSO(3)H) and chlorosulfonic acid (ClSO(3)H) using classical trajectory simulations. The initial nuclear coordinates and momenta for the trajectories are sampled from anharmonic correlation-corrected vibrational self consistent field (CC-VSCF) wavefunctions. We consider both OH-stretching overtone states and combination states containing a mix of OH-stretching overtones and SOH-bending or OSOH-torsional modes. Our molecular dynamics simulations confirm that photodissociation of these sulfonic acids to form the corresponding hydrogen halides and sulfur trioxide (HF + SO(3) and HCl + SO(3)), is possible via highly vibrationally excited states on a picosecond timescale. Hydrogen-hopping events are also observed in the trajectories whereby the hydrogen atom of the excited OH group is found to migrate to one of the adjacent S=O groups. The transition states, activation energies and dissociation dynamics of FSO(3)H and ClSO(3)H are found to be similar to those of H(2)SO(4). We suggest that these halogenated sulfonic acids should be suitable proxy molecules for an experimental investigation of the OH-stretching overtone induced photodissociation of H(2)SO(4) thought to be important in Earths' atmosphere. PMID:20526505

  14. AlN/single crystalline diamond piezoelectric structure as a high overtone bulk acoustic resonator

    NASA Astrophysics Data System (ADS)

    Sorokin, B. P.; Kvashnin, G. M.; Volkov, A. P.; Bormashov, V. S.; Aksenenkov, V. V.; Kuznetsov, M. S.; Gordeev, G. I.; Telichko, A. V.

    2013-03-01

    First, the Al/AlN/Al/Cr/diamond single crystal piezoelectric layered structure has been developed, and its properties have been investigated up to 8 GHz. The peculiarities associated with the influence of piezoelectric film on the Q factor of high overtones of substrate have been pointed out. High Q ˜ 104 has been found at 6-7 GHz band.

  15. Unraveling overtone interferences in Love-wave phase velocity measurements by array-based radon transform

    NASA Astrophysics Data System (ADS)

    Yang, Y.; Luo, Y.

    2015-12-01

    Surface waves contain fundamental mode and higher modes, which could interfere with each other. Different modes of surface waves have completely different sensitivities to earth structures. If they are not properly separated, the inverted Earth structures using surface waves could be biased. Especially, for Love waves propagating over oceanic paths, the group velocities of fundamental mod and first/second overtoneS are overlapped with each at periods shorter than 100 sec, resulting in strong overtone interferences in seismograms. Most surface wave tomography studies use dispersion curves of fundamental modes in imaging. One challenge in surface wave tomography is to accurately measure the fundamental-mode phase velocities and avoid the contamination by overtones. In this study, we develop an effective way by applying Linear Radon Transform (LRT) to a seismic array to separate fundamental-mode surface waves from higher modes. We apply this method to both synthetic data and real surface waves from USArray. Analysis on synthetic seismograms shows that two-station measurements on reconstructed data obtained after mode separation can completely retrieve the fundamental-mode Love-wave phase velocities. Results on USArray data show that higher mode contamination effects reach up to ˜10-15 percent for two-station and array-based measurements of Love waves, while two-station measurements on mode-separated data obtained by LRT are very close to the predicted values from a global dispersion model of GDM52, demonstrating that the contamination of overtones on fundamental-mode Love wave phase velocity measurements is effectively mitigated by the LRT method and accurate fundamental-mode Love-wave phase velocities can be measured.

  16. A stochastic streamflow model of the Platte River at Overton, Odessa, and Grand Island, Nebraska

    USGS Publications Warehouse

    Vecchia, A.V., Jr.

    1981-01-01

    A stochastic model is developed to simulate flows for three seasons (September through February, March and April, May through August) at Overton, Odessa, and Grand Island, Nebraska on the Platte River. The model preserves the first and second order moment properties of the historical flow series, including significant autocorrelations within each station and cross-correlations between the stations. Higher order moments are preserved by a transformation technique that allows the residuals from the model to be approximately normal. An algorithm is given for simulation of combined-stations flows, and some simulations are carried out to determine the likelihood of specified flow shortages that could be detrimental to the wildlife habitat in the reach of the Platte River between Overton and Grand Island. (USGS)

  17. Lateral Hopping of CO on Ag(110) by Multiple Overtone Excitation

    NASA Astrophysics Data System (ADS)

    Oh, Junepyo; Lim, Hyunseob; Arafune, Ryuichi; Jung, Jaehoon; Kawai, Maki; Kim, Yousoo

    2016-02-01

    A novel type of action spectrum representing multiple overtone excitations of the v (M -C ) mode was observed for lateral hopping of a CO molecule on Ag(110) induced by inelastically tunneled electrons from the tip of a scanning tunneling microscope. The yield of CO hopping shows sharp increases at 261 ±4 mV , corresponding to the C-O internal stretching mode, and at 61 ±2 , 90 ±2 , and 148 ±7 mV , even in the absence of corresponding fundamental vibrational modes. The mechanism of lateral CO hopping on Ag(110) was explained by the multistep excitation of overtone modes of v (M -C ) based on the numerical fitting of the action spectra, the nonlinear dependence of the hopping rate on the tunneling current, and the hopping barrier obtained from thermal diffusion experiments.

  18. Multiple anharmonic resonances in the vibrational overtone spectra of CHClF2

    NASA Astrophysics Data System (ADS)

    Amrein, A.; Dübal, H.-R.; Quack, M.

    The vibrational spectra of chlorodifluoromethane (Freon 22) have been measured at intermediate and high resolutions between 800 and 12 000 cm-1 by interferometric (FTIR) techniques. The CH overtone spectra exhibit a pronounced multiple-resonance structure which can be understood in terms of the 'universal' anharmonic CH stretching-bending hamiltonian. Quantitative predictions from this hamiltonian agree well (without adjustments) with previous experimental data on the visible spectra, which could not be correctly assigned before.

  19. Peculiarities of high-overtone transition probabilities in carbon monoxide revealed by high-precision calculation

    NASA Astrophysics Data System (ADS)

    Medvedev, Emile S.; Meshkov, Vladimir V.; Stolyarov, Andrey V.; Gordon, Iouli E.

    2015-10-01

    In the recent work devoted to the calculation of the rovibrational line list of the CO molecule [G. Li et al., Astrophys. J., Suppl. Ser. 216, 15 (2015)], rigorous validation of the calculated parameters including intensities was carried out. In particular, the Normal Intensity Distribution Law (NIDL) [E. S. Medvedev, J. Chem. Phys. 137, 174307 (2012)] was employed for the validation purposes, and it was found that, in the original CO line list calculated for large changes of the vibrational quantum number up to Δn = 41, intensities with Δn > 11 were unphysical. Therefore, very high overtone transitions were removed from the published list in Li et al. Here, we show how this type of validation is carried out and prove that the quadruple precision is indispensably required to predict the reliable intensities using the conventional 32-bit computers. Based on these calculations, the NIDL is shown to hold up for the 0 → n transitions till the dissociation limit around n = 83, covering 45 orders of magnitude in the intensity. The low-intensity 0 → n transition predicted in the work of Medvedev [Determination of a new molecular constant for diatomic systems. Normal intensity distribution law for overtone spectra of diatomic and polyatomic molecules and anomalies in overtone absorption spectra of diatomic molecules, Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 1984] at n = 5 is confirmed, and two additional "abnormal" intensities are found at n = 14 and 23. Criteria for the appearance of such "anomalies" are formulated. The results could be useful to revise the high-overtone molecular transition probabilities provided in spectroscopic databases.

  20. The Rates of Change of the Fundamental and Overtone Periods of Sx-Phoenicis

    NASA Astrophysics Data System (ADS)

    Coates, D. W.; Halprin, L.; Thompson, K.

    1982-04-01

    Using existing data for SX Phe, we calculate the rates of change in the fundamental period and the overtone period assuming that both are changing at a constant rate. We find values: dP0 / dt = (-87±5) × 10-13 dP1 / dt = (-174±9) × 10-13 The method used is applicable to any pulsating variable star whose times of maximum light exhibit measurable multiperiodicity.

  1. Peculiarities of high-overtone transition probabilities in carbon monoxide revealed by high-precision calculation

    SciTech Connect

    Medvedev, Emile S.; Meshkov, Vladimir V.; Stolyarov, Andrey V.

    2015-10-21

    In the recent work devoted to the calculation of the rovibrational line list of the CO molecule [G. Li et al., Astrophys. J., Suppl. Ser. 216, 15 (2015)], rigorous validation of the calculated parameters including intensities was carried out. In particular, the Normal Intensity Distribution Law (NIDL) [E. S. Medvedev, J. Chem. Phys. 137, 174307 (2012)] was employed for the validation purposes, and it was found that, in the original CO line list calculated for large changes of the vibrational quantum number up to Δn = 41, intensities with Δn > 11 were unphysical. Therefore, very high overtone transitions were removed from the published list in Li et al. Here, we show how this type of validation is carried out and prove that the quadruple precision is indispensably required to predict the reliable intensities using the conventional 32-bit computers. Based on these calculations, the NIDL is shown to hold up for the 0 → n transitions till the dissociation limit around n = 83, covering 45 orders of magnitude in the intensity. The low-intensity 0 → n transition predicted in the work of Medvedev [Determination of a new molecular constant for diatomic systems. Normal intensity distribution law for overtone spectra of diatomic and polyatomic molecules and anomalies in overtone absorption spectra of diatomic molecules, Institute of Chemical Physics, Russian Academy of Sciences, Chernogolovka, 1984] at n = 5 is confirmed, and two additional “abnormal” intensities are found at n = 14 and 23. Criteria for the appearance of such “anomalies” are formulated. The results could be useful to revise the high-overtone molecular transition probabilities provided in spectroscopic databases.

  2. Concentrations of anesthetics across the water-membrane interface; the Meyer-Overton hypothesis revisited

    NASA Technical Reports Server (NTRS)

    Pohorille, A.; Wilson, M. A.; New, M. H.; Chipot, C.

    1998-01-01

    The free energies of transferring a variety of anesthetic and nonanesthetic compounds across water-oil and water-membrane interfaces were obtained using computer simulations. Anesthetics exhibit greatly enhanced concentrations at these interfaces, compared to nonanesthetics. The substitution of the interfacial solubilites of the anesthetics for their bulk lipid solubilities in the Meyer-Overton relation, was found to give a better correlation, indicating that the potency of an anesthetic is directly proportional to its solubility at the interface.

  3. High-overtone self-focusing acoustic transducers for high-frequency ultrasonic Doppler.

    PubMed

    Zhu, Jie; Lee, Chuangyuan; Kim, Eun Sok; Wu, Dawei; Hu, Changhong; Zhou, Qifa; Shung, K Kirk; Wang, Gaofeng; Yu, Hongyu

    2010-05-01

    This work reports the potential use of high-overtone self-focusing acoustic transducers for high-frequency ultrasonic Doppler. By using harmonic frequencies of a thick bulk Lead Zirconate Titanate (PZT) transducer with a novel air-reflector Fresnel lens, we obtained strong ultrasound signals at 60 MHz (3rd harmonic) and 100 MHz (5th harmonic). Both experimental and theoretical analysis has demonstrated that the transducers can be applied to Doppler systems with high frequencies up to 100 MHz.

  4. Non-radial pulsation in first overtone Cepheids of the Small Magellanic Cloud

    NASA Astrophysics Data System (ADS)

    Smolec, R.; Śniegowska, M.

    2016-06-01

    We analyse photometry for 138 first overtone Cepheids from the Small Magellanic Cloud, in which Optical Gravitational Lensing Experiment team discovered additional variability with period shorter than first overtone period, and period ratios in the P/P1O ∈ (0.60, 0.65) range. In the Petersen diagram, these stars form three well-separated sequences. The additional variability cannot correspond to other radial mode. This form of pulsation is still puzzling. We find that amplitude of the additional variability is small, typically 2-4 per cent of the first overtone amplitude, which corresponds to 2-5 mmag. In some stars, we find simultaneously two close periodicities corresponding to two sequences in the Petersen diagram. The most important finding is the detection of power excess at half the frequency of the additional variability (at subharmonic) in 35 per cent of the analysed stars. Interestingly, power excess at subharmonic frequency is detected mostly for stars of the middle sequence in the Petersen diagram (74 per cent), incidence rate is much lower for stars of the top sequence (31 per cent), and phenomenon is not detected for stars of the bottom sequence. The amplitude and/or phase of the additional periodicities strongly vary in time. Similar form of pulsation is observed in first overtone RR Lyrae stars. Our results indicate that the nature and cause of this form of pulsation is the same in the two groups of classical pulsators; consequently, a common model explaining this form of pulsation should be searched for. Our results favour the theory of the excitation of non-radial modes of angular degrees 7, 8 and 9, proposed recently by Dziembowski.

  5. Repetitively pulsed cryogenically cooled quasi-sealed-off slab RF discharge first-overtone CO laser

    NASA Astrophysics Data System (ADS)

    Ionin, A. A.; Kozlov, A. Yu.; Rulev, O. A.; Seleznev, L. V.; Sinitsyn, D. V.

    2016-07-01

    A slab first-overtone CO laser of improved design excited by repetitively pulsed RF discharge was researched and developed. Its quasi-sealed-off operation appeared to be possible only by using active gas mixture composition with extremely high content of oxygen — up to 50 % with respect to CO concentration. Average output power of the first-overtone CO laser came up to ~2 W with the efficiency of ~2 %. The laser spectrum obtained by using three sets of output couplers consisted of more than 100 vibrational-rotational spectral lines in 28 vibrational first-overtone bands of CO molecule within 2.55÷3.90 μm wavelength range. The number of laser radiation pulses which could be produced by the laser in sealed-off mode of operation (without gas mixture renovation) reached ~5×105 at the averaged output power near its maximum, and ~106 at lower (near its half-maximum) averaged output power. Special features of laser radiation temporal behavior were discussed. Under repetitively pulse pump with repetition rate from 300 up to 7500 Hz, a temporal profile of the CO laser radiation changed from the train of time-separated laser pulses with high peak power to quasi-CW mode of operation.

  6. Diode laser spectroscopy of methyl chloride overtones at 850-860 nm

    NASA Astrophysics Data System (ADS)

    Lucchesini, A.; Gozzini, S.

    2016-01-01

    By using a tunable diode laser (TDL) spectrometer 156 CH3Cl overtone absorption lines have been detected in the range between 11,590 and 11,760 cm-1 (8500-8625 Å). Their strengths range around 10-26 -10-27 cm / molecule and have been measured by utilizing commercial AlGaAs/GaAs laser diodes through the wavelength modulation spectroscopy (WMS) and the 2nd harmonic (2f) detection techniques. For one line the self-broadening coefficient has been obtained.

  7. Cepheids in Magellanic Cloud star clusters - Fundamental and overtone pulsators in NGC 2157

    NASA Technical Reports Server (NTRS)

    Mateo, Mario; Olszewski, Edward W.; Madore, Barry F.

    1990-01-01

    CCD survey data are employed to examine Cepheids in young Magellanic Cloud star clusters. The properties of three Cepheids observed in NGC 2157 are described. It is detected that the two short-period (3 days) Cepheids have photometric properties that correspond to overtone pulsators and the long-period (7.7 days) Cepheid pulses in the fundamental mode. The pulsational masses for the three Cepheids are calculated to be about 5 solar masses. This mass value does not correlate with the average pulsational mass for Cepheids of 3.0 + or - 0.4 solar masses. The potential cause of this deviation in evolutionary/pulsational mass is investigated.

  8. High-overtone black-hole normal modes: A WKB contour-integral approach

    NASA Astrophysics Data System (ADS)

    Guinn, James Williams

    When black holes are perturbed by external sources, they oscillate, or ring, at discrete frequencies corresponding to a set of quasi-normal modes. Gravitational perturbations of the surrounding space-time, as well as 'test' perturbations of electromagnetic and scalar fields in a black hole background space-time, lead to normal modes. In all three cases, the perturbation equations can be reduced to a single Schroedinger-like equation in 1-D, which treats the three types of responses as mathematically equivalent to tunneling of quantum mechanical waves through a potential barrier. Normal modes correspond to tunneling transmission resonances. A high order Wentzel-Kramers-Brillouin (WKB) contour integral technique is shown to apply to the problem of black hole normal modes, first by studying tunneling and normal modes of a model potential barrier, the Poeschl-Teller potential, and then by comparing the contour integral technique with a method derived by Iyer and Will for tunneling near the peak of general potential barriers, which accurately describe low overtone black hole normal modes. The contour WKB technique is then applied to the high overtone normal modes. Results are compared to other techniques.

  9. Origins of IR Intensity in Overtones and Combination Bands in Hydrogen Bonded Systems

    NASA Astrophysics Data System (ADS)

    Horvath, Samantha; McCoy, Anne B.

    2010-06-01

    As the infrared spectra of an increasing number of hydrogen bonded and ion/water complexes have been investigated experimentally, we find that they often contain bands with significant intensity that cannot be attributed to fundamental transitions. In this talk, we explore several sources of the intensity of these overtone and combination bands. A common source of intensity is mode-mode coupling, as is often seen between the proton transfer coordinate and the associated heavy atom vibration. A second important mechanism involves large changes in the dipole moment due the loss of a hydrogen bond. This results in intense overtone transitions involving non-totally symmetric vibrations as well as the introduction of intense combination bands involving intramolecular bending coupled to hindered rotations. These effects will be discussed in the context of several systems, including the spectra of complexes of argon atoms with {H}_3{O}^+, F^-\\cdotH_2O, Cl^-\\cdotH_2O, protonated water clusters,^a and HOONO. T. Guasco, S. Olesen and M. A. Johnson, private communication S. Horvath, A. B. McCoy, J. R. Roscioli and M. A. Johnson, J. Phys. Chem. A, 112, 12337-44 (2008) S. Horvath, A. B. McCoy, B. M. Eliot, G. H. Weddle, J. R. Roscioli and M. A. Johnson, J. Phys. Chem. A, 115, 1556-68 (2010). A. B. McCoy, M. K. Sprague and M. Okumura, J. Phys. Chem. A, 115, 1324-33 (2010)

  10. The Binary Collision-Induced Second Overtone Band of Gaseous Hydrogen: Modelling and Laboratory Measurements

    NASA Technical Reports Server (NTRS)

    Brodbeck, C.; Bouanich, J.-P.; Nguyen, Van Thanh; Borysow, Aleksandra

    1999-01-01

    Collision-induced absorption (CIA) is the major source of the infrared opacity of dense planetary atmospheres which are composed of nonpolar molecules. Knowledge of CIA absorption spectra of H2-H2 pairs is important for modelling the atmospheres of planets and cold stars that are mainly composed of hydrogen. The spectra of hydrogen in the region of the second overtone at 0.8 microns have been recorded at temperatures of 298 and 77.5 K for gas densities ranging from 100 to 800 amagats. By extrapolation to zero density of the absorption coefficient measured every 10 cm(exp -1) in the spectral range from 11100 to 13800 cm(exp -1), we have determined the binary absorption coefficient. These extrapolated measurements are compared with calculations based on a model that was obtained by using simple computer codes and lineshape profiles. In view of the very weak absorption of the second overtone band, we find the agreement between results of the model and experiment to be reasonable.

  11. Period-Luminosity relations derived from the OGLE-III first-overtone mode Cepheids in the Magellanic Clouds

    NASA Astrophysics Data System (ADS)

    Bhardwaj, Anupam; Ngeow, Chow-Choong; Kanbur, Shashi M.; Singh, Harinder P.

    2016-06-01

    We present multiband Period-Luminosity (PL) relations for first-overtone mode Cepheids in the Small Magellanic Cloud (SMC). We derive optical band PL relations and the Wesenheit function using VI mean magnitudes from the Optical Gravitational Lensing Experiment (OGLE-III) survey. We cross-match OGLE-III first-overtone mode Cepheids to the 2MASS and SAGE-SMC catalogues to derive PL relations at near-infrared (JHKs) and mid-infrared (3.6 and 4.5 μm) wavelengths. We test for possible non-linearities in these PL relations using robust statistical tests and find a significant break only in the optical band PL relations at 2.5 d for first-overtone mode Cepheids. We do not find statistical evidence for a non-linearity in these PL relations at 1 d. The multiband PL relations for fundamental-mode Cepheids in the SMC also exhibit a break at 2.5 d. We suggest that the period break around 2.5 d is related to sharp changes in the light-curve parameters for SMC Cepheids. We also derive new optical and mid-infrared band PL relations for first-overtone mode Cepheids in the Large Magellanic Cloud (LMC). We compare multiband PL relations for first-overtone mode Cepheids in the Magellanic Clouds and find a significant difference in the slope of the V-band PL relations but not for I-band PL relations. The slope of PL relations are found to be consistent in most of the infrared bands. A relative distance modulus of Δμ = 0.49 ± 0.02 mag between the two clouds is estimated using multiband PL relations for the first-overtone mode Cepheids in the SMC and LMC.

  12. Protein structure by solid-state NMR of oriented systems

    SciTech Connect

    Stewart, P.L.

    1987-01-01

    A method for determining protein backbone structure from angular information obtainable by solid state NMR spectroscopy is presented. Various spin interactions including quadrupole, dipole, and chemical shift interactions and nuclei including /sup 14/N, /sup 15/N, /sup 13/C, and /sup 2/H may be observed. Angularly dependent measurements can be made when the sample has at least one direction of order along the externally applied magnetic field. Several NMR parameters are used to determine the orientation of each peptide plane with respect to the magnetic field vector, B/sub O/, to within a few symmetry related possibilities. The computer program Totlink can then be used to perform the necessary coordinate transformations and to evaluate the possible backbone structures and select for the most chemically reasonable. Experimental /sup 14/N NMR structural studies of the model peptides n-acetyl-d,l-valine, n-acetyl-l-valyl-l-leucine, and l-alanyl-glycyl-glycine and preliminary /sup 14/N NMR results on a large single crystal of orthorhombic lysozyme are presented.

  13. The fifth overtones of the C-H stretching vibrations and the bond lengths in some heterocyclic compounds

    NASA Astrophysics Data System (ADS)

    Mizugai, Yoshihiro; Katayama, Mikio

    1980-07-01

    The fifth overtones of the C-H stretching vibrations of pyridine, pyrazine, thiophene, 3-methylthiophene, furan and pyrrole in the liquid state have been observed by a thermal lens technique. It was found that their frequency shifts from that of benzene are proportional to the decrease in the relevant C-H bond length.

  14. High overtone quasinormal modes of analog black holes and the small scale structure of the background fluid

    NASA Astrophysics Data System (ADS)

    Daghigh, Ramin G.; Green, Michael D.

    2015-05-01

    The goal of this paper is to build a foundation for, and explore the possibility of, using high overtone quasinormal modes (QNMs) of analog black holes to probe the small scale (microscopic) structure of a background fluid in which an analog black hole is formed. This may provide a tool to study the small scale structure of some interesting quantum systems such as Bose-Einstein condensates (BECs). In order to build this foundation, we first look into the hydrodynamic case where we calculate the high overtone QNM frequencies of a 3+1 dimensional canonical non-rotating acoustic black hole. The leading order calculations have been done earlier in the literature. Here, we obtain the first order correction. We then analyze the high overtone QNMs of acoustic black holes in a BEC using the linearized Gross-Pitaevskii equation. We point out that at the high overtone QNM limit, the only term that is important in the linearized Gross-Pitaevskii equation is the quantum potential term, which is a small scale effect.

  15. Reconstruction of N2O and CH4 Content by Dial Measurements at Wavelengths of Overtone CO Laser

    NASA Astrophysics Data System (ADS)

    Romanovskii, O. A.; Matvienko, G. G.; Kharchenko, O. V.; Yakovlev, S. V.

    2016-06-01

    The paper presents the results of laboratory experiments on measurement of absorption and extinction of radiation of the overtone Co laser at wavelengths used for sensing of methane and N2O in the mid-IR spectral range with the differential absorption (DIAL) method, as well as the concentrations of the studied gases reconstructed from the analysis of experimentally obtained absorption coefficients.

  16. Determination of Pressure Broadening and Shifts for the First Overtone 2←0 of HCL

    NASA Astrophysics Data System (ADS)

    Drouin, Brian; Crawford, Timothy J.; Coffey, Brennan M.

    2014-06-01

    Precise and accurate positions of the line centers of HCl (v = 2 ← 0) have not been reported for quite some time^1, however, using methane as a transferrable standard, we aim to report line positions to an order of magnitude better than previously characterized and enable the use of HCl as a secondary frequency standard. The line centers for the first overtone of (v =2 ← 0) in the spectral region 5500 - 5900 cm-1 have been measured simultaneously with the 2ν_3 band of methane using the JPL Bruker IFS 125HR. The positions are determined through multispectrum analysis to 1×10-5 cm-1. Further analysis using the multispectrum fitting software Labfit allows the determination of the self-broadening, self-shift and Dicke narrowing parameters to high precision as well. This potential new standard is compared to the HITRAN 2012 line parameters. ^1 Guelachvilli, G. Opt. Comm. 19, 150-154. (1976).

  17. Fourier Analysis of First-Overtone RR Lyrae Variables in the LMC

    NASA Astrophysics Data System (ADS)

    Clement, C. M.; Muzzin, A. V.; Rowe, J. F.; MACHO Collaboration

    2002-05-01

    Simon's (1989, ApJ, 343, L17) Fourier decomposition technique has been applied to the V magnitudes of the first-overtone RR Lyrae (RR1) variables in 16 LMC fields observed by the MACHO collaboration. The Fourier coefficients R21 and φ 31 derived for these stars have been compared with the coefficients of RR1 variables in the galactic globular clusters Omega Centauri, M2, M3, M5, M68, M107 (NGC 6171) and NGC 6441. Our analysis indicates that the majority of the LMC RR1 variables have coefficients similar to those in the Oosterhoff type I (OoI) clusters M3 and M5 and to the OoI variables in Omega Centauri. In a study of hydrodynamic pulsation models of first overtone RR Lyrae variables, Simon & Clement (1993, ApJ, 410, 526) found that the Fourier phase parameter φ 31 depends essentially on mass and luminosity. From this, we conclude that the masses and luminosities of most of the RR1 variables in the LMC are comparable to those of the OoI RR1 variables in Omega Centauri, M3 and M5, a fact that should be considered when RR Lyrae variables are used for determining the distance to the LMC. The MACHO collaboration includes C. Alcock, R. A. Allsman, D. R. Alves, T. S. Axelrod, A. C. Becker, D. P. Bennet, K. H. Cook, A. J. Drake, K. C. Freeman, M. Geha, K. Griest, M. J. Lehner, S. L. Marshall, D. Minniti, C. A. Nelson, B. A. Peterson, P. Popowski, M. R. Pratt, P. J. Quinn, C. W. Stubbs, W. Sutherland, T. Vandehel and D. L. Welch. This research has been supported in part by the Natural Sciences and Engineering Research Council of Canada.

  18. Intramolecular vibrational redistribution in aromatic molecules. I. Eigenstate resolved CH stretch first overtone spectra of benzene

    NASA Astrophysics Data System (ADS)

    Callegari, A.; Merker, U.; Engels, P.; Srivastava, H. K.; Lehmann, K. K.; Scoles, G.

    2000-12-01

    We have used infrared-infrared double resonance spectroscopy to record a rovibrational eigenstate resolved spectrum of benzene in the region of the CH stretch first overtone. This experiment is the first of a series aimed at investigating intramolecular vibrational energy redistribution (IVR) in aromatic molecules. The experiment has been carried out in a supersonic molecular beam apparatus using bolometric detection. A tunable resonant cavity was used to enhance the on-beam intensity of the 1.5 μm color center laser used to pump the overtone, and a fixed frequency [R(30)] 13CO2 laser was used to saturate the coinciding ν18 rQ(2) transition of benzene. After assigning the measured lines of the highly IVR fractionated spectrum to their respective rotational quantum number J, analysis of the data reveals that the dynamics occurs on several distinct time scales and is dominated by anharmonic coupling with little contribution from Coriolis coupling. After the fast (˜100 fs) redistribution of the energy among the previously observed "early time resonances" [R. H. Page, Y. R. Shen, and Y. T. Lee, J. Chem. Phys. 88, 4621 (1988) and 88, 5362 (1988)], a slower redistribution (10-20 ps) takes place, which ultimately involves most of the symmetry allowed vibrational states in the energy shell. Level spacing statistics reveal that IVR produces a highly mixed, but nonstatistical, distribution of vibrational excitation, even at infinite time. We propose that this nonintuitive phenomenon may commonly occur in large molecules when the bright state energy is localized in a high-frequency mode.

  19. Overton's Rule Helps To Estimate the Penetration of Anti-Infectives into Patients' Cerebrospinal Fluid

    PubMed Central

    Djukic, Marija; Munz, Martin; Sörgel, Fritz; Holzgrabe, Ulrike; Eiffert, Helmut

    2012-01-01

    In 1900, Ernst Overton found that the entry of anilin dyes through the cell membranes of living cells depended on the lipophilicity of the dyes. The brain is surrounded by barriers consisting of lipid layers that possess several inward and outward active transport systems. In the absence of meningeal inflammation, the cerebrospinal fluid (CSF) penetration of anti-infectives in humans estimated by the ratio of the area under the concentration-time curve (AUC) in CSF (AUCCSF) to that in serum (AUCCSF/AUCS) correlated positively with the lipid-water partition coefficient at pH 7.0 (log D) (Spearman's rank correlation coefficient rS = 0.40; P = 0.01) and negatively with the molecular mass (MM) (rS = −0.33; P = 0.04). The ratio of AUCCSF to the AUC of the fraction in serum that was not bound (AUCCSF/AUCS,free) strongly correlated with log D (rS = 0.67; P < 0.0001). In the presence of meningeal inflammation, AUCCSF/AUCS also correlated positively with log D (rS = 0.46; P = 0.002) and negatively with the MM (rS = −0.37; P = 0.01). The correlation of AUCCSF/AUCS,free with log D (rS = 0.66; P < 0.0001) was as strong as in the absence of meningeal inflammation. Despite these clear correlations, Overton's rule was able to explain only part of the differences in CSF penetration of the individual compounds. The site of CSF withdrawal (lumbar versus ventricular CSF), age of the patients, underlying diseases, active transport, and alterations in the pharmacokinetics by comedications also appeared to strongly influence the CSF penetration of the drugs studied. PMID:22106225

  20. Overton's rule helps to estimate the penetration of anti-infectives into patients' cerebrospinal fluid.

    PubMed

    Djukic, Marija; Munz, Martin; Sörgel, Fritz; Holzgrabe, Ulrike; Eiffert, Helmut; Nau, Roland

    2012-02-01

    In 1900, Ernst Overton found that the entry of anilin dyes through the cell membranes of living cells depended on the lipophilicity of the dyes. The brain is surrounded by barriers consisting of lipid layers that possess several inward and outward active transport systems. In the absence of meningeal inflammation, the cerebrospinal fluid (CSF) penetration of anti-infectives in humans estimated by the ratio of the area under the concentration-time curve (AUC) in CSF (AUC(CSF)) to that in serum (AUC(CSF)/AUC(S)) correlated positively with the lipid-water partition coefficient at pH 7.0 (log D) (Spearman's rank correlation coefficient r(S) = 0.40; P = 0.01) and negatively with the molecular mass (MM) (r(S) = -0.33; P = 0.04). The ratio of AUC(CSF) to the AUC of the fraction in serum that was not bound (AUC(CSF)/AUC(S,free)) strongly correlated with log D (r(S) = 0.67; P < 0.0001). In the presence of meningeal inflammation, AUC(CSF)/AUC(S) also correlated positively with log D (r(S) = 0.46; P = 0.002) and negatively with the MM (r(S) = -0.37; P = 0.01). The correlation of AUC(CSF)/AUC(S,free) with log D (r(S) = 0.66; P < 0.0001) was as strong as in the absence of meningeal inflammation. Despite these clear correlations, Overton's rule was able to explain only part of the differences in CSF penetration of the individual compounds. The site of CSF withdrawal (lumbar versus ventricular CSF), age of the patients, underlying diseases, active transport, and alterations in the pharmacokinetics by comedications also appeared to strongly influence the CSF penetration of the drugs studied. PMID:22106225

  1. Computational High-Frequency Overtone Spectra of the Water Ammonia Complex

    NASA Astrophysics Data System (ADS)

    Sälli, Elina; Halonen, Lauri

    2011-06-01

    We have computed vibrational high-frequency overtone spectra of the water ammonia complex, {H_2O-NH_3}, and its isotopomers. The cluster has been modelled as two independently vibrating monomer units. Our internal coordinate Hamiltonians for each monomer unit have been constructed using exact gas phase kinetic energy operators. The potential energy and dipole moment surfaces have been calculated with the explicitly correlated coupled cluster method CCSD(T)-F12A and valence triple zeta VTZ-F12 basis around the equilibrium geometry of the complex. The vibrational eigenvalues are calculated variationally. The eigenfunctions obtained are used to compute the relative absorption intensities. In {H_2O-NH_3}, water molecule acts as the proton donor and its symmetry is broken. The hydrogen bonded {OH_b} bond oscillator undergoes a large redshift and intensity enhancement compared to the free hydrogen bond. Broken degeneracy of the asymmetric vibrations, quenched inversion splittings, and blueshift of the symmetric bend are the most visible changes in the ammonia unit. Our vibrational model is anharmonic. Therefore, we have been able to calculate not only high-frequency fundamentals but also overtones and combination levels that for this complex have not been detected experimentally. The calculated fundamentals agree well with matrix isolation and helium droplet measurements except for the bonded {OH_b} stretching of the water unit where our model overestimates the clustering induced shift. The same has previously been seen in the bonded {OH_b} stretch of the water dimer and is probably due to the couplings with the low-frequency modes.

  2. NMR study of ferroelastic phase transition of tetramethylammonium tetrabromocobaltate

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran; Kim, Sun Ha

    2016-09-01

    Static and magic angle spinning (MAS) nuclear magnetic resonance (NMR) experiments were carried out on 1H, 13C, and 14N nuclei in order to understand the structural changes of the N(CH3)4 groups in [N(CH3)4]2CoBr4 near the ferroelastic phase transition temperature TC. The two chemically inequivalent N(CH3)4 groups were distinguished using 13C cross-polarization/(CP)MAS and 14N static NMR. The changes in chemical shifts, line intensities, and the spin-lattice relaxation time near TC can be correlated with the changing structural geometry, which underlies the phase transition. The 14N NMR spectra indicated a crystal symmetry change at TC, which is related to the ferroelastic domain with different orientations of the N(CH3)4 groups. The ferroelastic domain walls were confirmed by optical polarizing microscopy, and the wall orientations were described by the Sapriel theory. The transition to the ferroelastic phase was found to be related to the orientational ordering of the N(CH3)4 groups.

  3. Infrared overtone spectroscopy of hydrogen fluoride van der Waals complexes at upsilon (HF) = 3

    NASA Astrophysics Data System (ADS)

    Tsang, Susy Ngan Ping

    1998-11-01

    The dependence of weak intermolecular forces on valence bond excitations is investigated by the spectroscopy and vibrational predissociation dynamics of four hydrogen fluoride van der Waals complexes, N2HF, (HF)2, Ar2HF and Ar3HF, at the second overtone vibrational excitation of the hydrogen bonded HF intramolecular stretch, v HF=3. The formation and detection of these weakly bound complexes are achieved by the unique combination of slit supersonic jet expansion and intracavity Ti:sapphire laser-induced fluorescence. For the four complexes studied, an increase in the red- shift as a function of v HF was observed in the hydrogen bonded HF valence stretch as a result of the strengthening of the hydrogen bond. In addition, changes in the anisotropies of the intermolecular potentials of these weakly bound systems are in accord with those observed in the prototypical studies of ArHF at v HF=3 in this laboratory. However, the van der Waals soft modes have only been completely characterized for N2HF at v HF=3. Moreover, the frequencies of these intermolecular modes were experimentally determined for the first time in the N2HF complex. Of major interest in the N2HF studies is the intermolecular state dependence of the vibrational predissociation in this complex at v HF=3. Intermolecular state dependent vibrational predissociation dynamics is also observed in the (HF)2 studies. In order to further understand the complex internal dynamics in N2HF, ab initio calculations for a highly accurate four-dimensional potential energy surface using the symmetry adapted perturbation theory (SAPT) method were performed at v HF=0 and at v HF=3. A preliminary analysis of the ab initio data for both vibrational states and bound state calculations for the ground state potential energy surface are presented. The work on the Ar2HF and Ar3HF clusters tests the accuracy of pairwise additive intermolecular potentials for these two systems at v HF=3. In particular, the data obtained on these

  4. Importance of Nitrate Attenuation In A Small Wetland Following Forest Harvest: 18O/16O, 15N/14N in nitrate and 15N/14N) in vegetation

    NASA Astrophysics Data System (ADS)

    Spoelstra, J.; Schiff, S. L.; Semkin, R. G.; Jeffries, D. S.; Elgood, R. J.

    2004-05-01

    Forest harvest can result in elevated nitrate concentrations in streams and groundwater affecting forest regeneration and downstream aquatic ecosystems. Turkey Lakes Watershed, located near Sault Ste Marie, Ontario (TLW), exhibits relatively high nitrate export due to naturally high rates of nitrification. During a forest harvest experiment at the TLW, stable isotope techniques were used to investigate nitrate attenuation in an intermediate position natural wetland receiving high concentrations of nitrate following forest clear-cutting. Isotopic analysis of nitrate (18O/16O, 15N/14N) and vegetation (15N/14N) demonstrated that denitrification and plant uptake of nitrate resulted in significantly lower nitrate concentrations in wetland outflow compared to incoming stream water and groundwater. The 0.2-hectare forested swamp, too small to show up on standard topographic maps, retained 65 to 100 percent of upgradient nitrate inputs, elevated due to increased nitrification in soils. The 15N/14N enrichment factor associated with nitrate attenuation in wetland surface water was lower than observed during denitrification in groundwaters, suggesting that denitrification proceeded to completion in some areas of the wetland. Even small, shallow, carbon rich pockets of organic matter in topographic depressions can significantly affect biogeochemical fluxes of C, N, S and Ca. Future forest management practices designed to recognize and preserve small wetlands could significantly reduce the potentially detrimental effects of forest harvest on aquatic systems.

  5. Vibrationally mediated photodissociation of ethene isotopic variants preexcited to the fourth C-H stretch overtone

    NASA Astrophysics Data System (ADS)

    Bespechansky, Evgeny; Portnov, Alexander; Zwielly, Amir; Rosenwaks, Salman; Bar, Ilana

    2006-10-01

    H and D photofragments produced via vibrationally mediated photodissociation of jet-cooled normal ethene (C2H4), 1,2-trans-d2-ethene (HDCCDH), and 1,1-d2-ethene (CH2CD2), initially excited to the fourth C-H stretch overtone region, were studied for the first time. H and D vibrational action spectra and Doppler profiles were measured. The action spectra include partially resolved features due to rotational cooling, while the monitored room temperature photoacoustic spectra exhibit only a very broad feature in each species. Simulation of the spectral contours allowed determination of the band types and origins, limited precision rotational constants, and linewidths, providing time scales for energy redistribution. The H and D Doppler profiles correspond to low average translational energies and show slight preferential C-H over C-D bond cleavage in the deuterated variants. The propensities toward H photofragments emerge even though the energy flow out of the initially prepared C-H stretch is on a picosecond time scale and the photodissociation occurs following internal conversion, indicating a more effective release of the light H atoms.

  6. Unraveling overtone interferences in Love-wave phase velocity measurements by radon transform

    NASA Astrophysics Data System (ADS)

    Luo, Yinhe; Yang, Yingjie; Zhao, Kaifeng; Xu, Yixian; Xia, Jianghai

    2015-10-01

    Surface waves contain fundamental mode and higher modes, which could interfere with each other. If different modes are not properly separated, the inverted Earth structures using surface waves could be biased. In this study, we apply linear radon transform (LRT) to synthetic seismograms and real seismograms from the USArray to demonstrate the effectiveness of LRT in separating fundamental-mode Love waves from higher modes. Analysis on synthetic seismograms shows that two-station measurements on reconstructed data obtained after mode separation can completely retrieve the fundamental-mode Love-wave phase velocities. Results on USArray data show that higher mode contamination effects reach up to ˜10 per cent for two-station measurements of Love waves, while two-station measurements on mode-separated data obtained by LRT are very close to the predicted values from a global dispersion model of GDM52, demonstrating that the contamination of overtones on fundamental-mode Love-wave phase velocity measurements is effectively mitigated by the LRT method and accurate fundamental-mode Love-wave phase velocities can be measured.

  7. Analysis of the CIA Spectra of the Second Overtone Band of D2 at 77 K

    NASA Astrophysics Data System (ADS)

    Abu-Kharma, M.; Shawagfeh, Naseem; Gillard, P.

    2010-10-01

    Quantitative measurements of the collision induced absorption (CIA) spectra of pure D2 gas in the second overtone (v = 3←0) region were made for gas densities in the range 500 to 950 amagat at 77 K for the first time. The observed spectra were modeled with a synthetic profiles; which are composed of the superposition of an overlap-induced profile Q3(overlap)(J = 0 to 3) and a quadrupolar induced profile. The quadrupolar profile is formed of three profiles: a single vibrational transitions of the type X3(J)+X0(J), where X is O(ΔJ = -2), Q(ΔJ = 0) and S(ΔJ = 2) transition, a double vibrational transitions of the type X2(J)+X1(J) and a triple vibrational transitions Q1(J1)+Q1(J2)+Q1(J3) of D2; resulting from simultaneous collision of three D2 molecules. Profile analysis of the spectra was carried out using the Birnbaum—Cohen (BC) line shape function for the quadrupolar transitions and the Levine—Birnbaum (LB) line shape function for the overlap transitions. The fitting parameters were determined from the analysis. The agreement between the experimental and the calculated profiles is satisfactory.

  8. - and H_2-BROADENED Line Parameters of Carbon Monoxide in the First Overtone Band

    NASA Astrophysics Data System (ADS)

    Predoi-Cross, Adriana; Esteki, Koorosh; Naseri, Hossein; Devi, V. Malathy; Smith, Mary Ann H.; Mantz, Arlan; Ivanov, Sergei V.

    2016-06-01

    In this study we have re-analyzed high-resolution spectra of pure CO and CO broadened by hydrogen recorded in the spectral range of the first overtone band. We have used four different line shapes in the multispectrum analysis (Voigt, speed dependent Voigt, Rautian, and Rautian with speed dependence) and compared the resulting line shape parameters. The line mixing coefficients have been calculated using the Exponential Power Gap and the Energy Corrected Sudden scaling laws. A classical approach was applied to calculate CO line widths in CO-H_2 and CO-CO collisions. The formulas of classical impact theory are used for calculation of dipole absorption half-widths along with exact 3D Hamilton equations for simulation of molecular motion. The calculations utilize Monte Carlo averaging over collision parameters and simple interaction potential (Tipping-Herman + electrostatic). Molecules are treated as rigid rotors. The dependences of CO half-widths on rotational quantum number J≤ 24 are computed and compared with measured data at room temperature. V. Malathy Devi et al., J. Mol. Spectrosc. 228 (2004) 580-592. R. G. Gordon, J. Chem. Phys. 44 (1966) 3083-3089; ibid., 45 (1966) 1649-1655. J.-P. Bouanich and A. Predoi-Cross, J. Molec. Structure 742 (2005) 183-190 A. Predoi-Cross, J.-P. Bouanich, D. Chris Benner, A. D. May, and J. R. Drummond, J. Chem. Phys. 113 (2000) 158-168

  9. Overtone spectroscopy of H2D+ and D2H+ using laser induced reactions

    NASA Astrophysics Data System (ADS)

    Asvany, Oskar; Hugo, Edouard; Müller, Frank; Kühnemann, Frank; Schiller, Stephan; Tennyson, Jonathan; Schlemmer, Stephan

    2007-10-01

    The method of laser induced reaction is used to obtain high-resolution IR spectra of H2D+ and D2H+ in collision with n-H2 at a nominal temperature of 17K. For this purpose three cw-laser systems have been coupled to a 22-pole ion trap apparatus, two commercial diode laser systems in the ranges of 6100-6600cm-1 and 6760-7300cm-1, respectively, and a high-power optical parametric oscillator tunable in the range of 2600-3200cm-1. In total, 27 new overtone and combination transitions have been detected for H2D + and D2H+, as well as a weak line in the ν1 vibrational band of H2D+ (220←101) at 3164.118cm-1. The line positions are compared to high accuracy ab initio calculations, showing small but mode-dependent differences, being largest for three vibrational quanta in the ν2 symmetric bending of H2D+. Within the experimental accuracy, the relative values of the ab initio predicted Einstein B coefficients are confirmed.

  10. Synthesis, crystal structure, and photocatalytical properties of Ba3Ta5O14N

    NASA Astrophysics Data System (ADS)

    Anke, B.; Bredow, T.; Soldat, J.; Wark, M.; Lerch, M.

    2016-01-01

    Light yellow Ba3TaV5O14N was successfully synthesized as phase-pure material crystallizing isostructurally to well-known mixed-valence Ba3TaV4TaIVO15. The electronic structure of Ba3Ta5O14N was studied theoretically with a hybrid Hartree-Fock-DFT method. The most stable structure was obtained when nitrogen atoms were placed at 4 h sites having fourfold coordination. By incorporating nitrogen, the band gap decreases from ∼3.8 eV commonly known for barium tantalum(V) oxides to 2.8 eV for the oxide nitride, giving rise to an absorption band well in the visible-light region. Ba3Ta5O14N was also tested for photocatalytic hydrogen formation.

  11. Using near-infrared overtone regions to determine biodiesel content and adulteration of diesel/biodiesel blends with vegetable oils.

    PubMed

    de Vasconcelos, Fernanda Vera Cruz; de Souza, Paulo Fernandes Barbosa; Pimentel, Maria Fernanda; Pontes, Márcio José Coelho; Pereira, Claudete Fernandes

    2012-02-24

    This work evaluates the use of near-infrared (NIR) overtone regions to determine biodiesel content, as well potential adulteration with vegetable oil, in diesel/biodiesel blends. For this purpose, NIR spectra (12,000-6300 cm(-1)) were obtained using three different optical path lengths: 10 mm, 20 mm and 50 mm. Two strategies of regression with variable selection were evaluated: partial least squares (PLS) with significant regression coefficients selected by Jack-Knife algorithm (PLS/JK) and multiple linear regression (MLR) with wavenumber selection by successive projections algorithm (MLR/SPA). For comparison, the results obtained by using PLS full-spectrum models are also presented. In addition, the performance of models using NIR (1.0 mm optical path length, 9000-4000 cm(-1)) and MIR (UATR - universal attenuated total reflectance, 4000-650 cm(-1)) spectral regions was also investigated. The results demonstrated the potential of overtone regions with MLR/SPA regression strategy to determine biodiesel content in diesel/biodiesel blends, considering the possible presence of raw oil as a contaminant. This strategy is simple, fast and uses a fewer number of spectral variables. Considering this, the overtone regions can be useful to develop low cost instruments for quality control of diesel/biodiesel blends, considering the lower cost of optical components for this spectral region.

  12. Fourier Transform Spectrometer observations of solar carbon monoxide. I - The fundamental and first overtone bands in the quiet sun

    NASA Technical Reports Server (NTRS)

    Ayres, T. R.; Testerman, L.

    1981-01-01

    Measurements of the 2200/cm fundamental and 4300/cm first overtone vibration-rotation band systems of solar carbon monoxide, were obtained with the Fourier Transform Spectrometer of the McMath telescope at Kitt Peak. The overtone measurements were taken at the east, north, and west heliocentric limbs, and at disk center. Observations of the strong fundamental bands were obtained at disk center and near the north limb. The low core brightness temperatures of the strongest fundamental carbon monoxide lines near the limb, reported previously by Noyes (1972) and Hall (1974), are confirmed. The possibility that thermal inhomogeneities might be responsible for the unusual behavior of the fundamental carbon dioxide lines have been examined. The somewhat discordant behavior of the fundamental lines at disk center compared with the north limb seems to favor a limb shadowing effect. The first overtone limb equivalent widths and the best-fit thermal and microvelocity models indicate a solar carbon abundance of 0.004 (on the scale with A sub H = 1) for an oxygen-to-carbon abundance ratio of 2.

  13. Measurement of the 14N nuclear quadrupole resonance frequencies by the solid effect

    NASA Astrophysics Data System (ADS)

    Seliger, J.; Žagar, V.

    2008-07-01

    1H- 14N nuclear quadrupole double resonance using magnetic field cycling between high and low magnetic field and solid effect in the low magnetic field is analyzed in details. The transition probabilities per unit time for the solid-effect transitions are calculated. The double resonance spectra are calculated in the limiting cases of fast and slow nitrogen spin-lattice relaxation. The double resonance spectra are measured in histamine and quinolinic acid. The experimental spectra are analyzed and the 14N NQR frequencies are determined.

  14. NMR analysis of biodiesel

    Technology Transfer Automated Retrieval System (TEKTRAN)

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

  15. (1)H-(14)N cross-relaxation spectrum analysis in sildenafil and sildenafil citrate.

    PubMed

    Gregorovič, Alan; Apih, Tomaž; Seliger, Janez

    2016-09-01

    Here we describe a method for the extraction of (14)N quadrupole parameters from a (1)H-(14)N cross-relaxation spectrum by fitting the lineshapes of the (14)N quadrupole transitions. The procedures used typically to fit quadrupole lineshapes are not directly applicable to fit the (1)H-(14)N cross-relaxation spectrum, because the presence of proton homonuclear dipolar interaction broadens the lineshapes considerably and prevents a reliable determination of Cq and η from a single lineshape. Instead, one must fit two or even three lineshapes originating from the same nitrogen site simultaneously. The problem is to identify which lineshapes belong together when many are observed due to the existence of several nitrogen sites. We solve this problem by fitting the spectrum for all possible combinations and find the best-fitting one. This combination then most likely correctly identifies lineshapes belonging to the same nitrogen site. There are two main advantages of our method compared to the typically used method, which relies only on lineshape singularities: (i) the method is "automatic" and does not require knowledge of nitrogen quadrupole parameters in similar environments to aid dip pairing and (ii) the accuracy of quadrupole parameters is better, as proton linewidth is included in the fits. We use sildenafil and sildenafil citrate as model compounds, each with six non-equivalent nitrogen sites.

  16. (1)H-(14)N cross-relaxation spectrum analysis in sildenafil and sildenafil citrate.

    PubMed

    Gregorovič, Alan; Apih, Tomaž; Seliger, Janez

    2016-09-01

    Here we describe a method for the extraction of (14)N quadrupole parameters from a (1)H-(14)N cross-relaxation spectrum by fitting the lineshapes of the (14)N quadrupole transitions. The procedures used typically to fit quadrupole lineshapes are not directly applicable to fit the (1)H-(14)N cross-relaxation spectrum, because the presence of proton homonuclear dipolar interaction broadens the lineshapes considerably and prevents a reliable determination of Cq and η from a single lineshape. Instead, one must fit two or even three lineshapes originating from the same nitrogen site simultaneously. The problem is to identify which lineshapes belong together when many are observed due to the existence of several nitrogen sites. We solve this problem by fitting the spectrum for all possible combinations and find the best-fitting one. This combination then most likely correctly identifies lineshapes belonging to the same nitrogen site. There are two main advantages of our method compared to the typically used method, which relies only on lineshape singularities: (i) the method is "automatic" and does not require knowledge of nitrogen quadrupole parameters in similar environments to aid dip pairing and (ii) the accuracy of quadrupole parameters is better, as proton linewidth is included in the fits. We use sildenafil and sildenafil citrate as model compounds, each with six non-equivalent nitrogen sites. PMID:27379753

  17. Measurement of fibrin concentration by fast field-cycling NMR.

    PubMed

    Broche, Lionel M; Ismail, Saadiya R; Booth, Nuala A; Lurie, David J

    2012-05-01

    The relaxation of (1)H nuclei due to their interaction with quadrupolar (14)N nuclei in gel structures is measured using fast field-cycling NMR. This phenomenon called quadrupolar dips has been reported in different (1)H-(14)N bond-rich species. In this study, we have studied quadrupolar dips in fibrin, an insoluble protein that is the core matrix of thrombi. Fibrin was formed by the addition of thrombin to fibrinogen in 0.2% agarose gel. T(1)-dispersion curves were measured using fast field-cycling NMR relaxometry, over the field range of 1.5-3.5 MHz (proton Larmor frequency), and were analyzed using a curve-fitting algorithm. A linear increase of signal amplitude with increasing fibrin concentration was observed. This agrees with the current theory that predicts a linear relationship of signal amplitude with the concentration of contributing (14)N spins in the sample. Interestingly, fibrin formation gave rise to the signal, regardless of crosslinking induced by the transglutaminase factor XIIIa. To investigate the effect of proteins that might be trapped in the thrombi in vivo, the plasma protein albumin was added to the fibrin gel, and an increase in the quadrupolar signal amplitude was observed. This study can potentially be useful for thrombi classification by fast field-cycling MRI techniques.

  18. Strong Overtones Modes in Inelastic Electron Tunneling Spectroscopy with Cross-Conjugated Molecules: A Prediction from Theory

    PubMed Central

    2013-01-01

    Cross-conjugated molecules are known to exhibit destructive quantum interference, a property that has recently received considerable attention in single-molecule electronics. Destructive quantum interference can be understood as an antiresonance in the elastic transmission near the Fermi energy and leading to suppressed levels of elastic current. In most theoretical studies, only the elastic contributions to the current are taken into account. In this paper, we study the inelastic contributions to the current in cross-conjugated molecules and find that while the inelastic contribution to the current is larger than for molecules without interference, the overall behavior of the molecule is still dominated by the quantum interference feature. Second, an ongoing challenge for single molecule electronics is understanding and controlling the local geometry at the molecule-surface interface. With this in mind, we investigate a spectroscopic method capable of providing insight into these junctions for cross-conjugated molecules: inelastic electron tunneling spectroscopy (IETS). IETS has the advantage that the molecule interface is probed directly by the tunneling current. Previously, it has been thought that overtones are not observable in IETS. Here, overtones are predicted to be strong and, in some cases, the dominant spectroscopic features. We study the origin of the overtones and find that the interference features in these molecules are the key ingredient. The interference feature is a property of the transmission channels of the π system only, and consequently, in the vicinity of the interference feature, the transmission channels of the σ system and the π system become equally transmissive. This allows for scattering between the different transmission channels, which serves as a pathway to bypass the interference feature. A simple model calculation is able to reproduce the results obtained from atomistic calculations, and we use this to interpret these findings

  19. Ultra-Sensitive Instrumentation in the UV-Vis-NIR Spectral Region with Applications on Overtone Spectroscopy

    NASA Astrophysics Data System (ADS)

    Camejo, David

    Fourier transform infrared spectroscopy (FT-IR) is a technique widely used in molecular spectroscopy. Technology advancements are such that FT-IR spectrometers can measure vibrational transitions occurring well within the visible (Vis) region of the electromagnetic spectrum. High overtone transitions of C-H, N-H, and O-H can be measured in the near-infrared (NIR) and the Vis regions using long path cells. Despite the large sensitivity of the FT-IR spectrometers and the use of long path cells, the absorption intensities of these transitions are so low that commercial FT-IR spectrometers would not register the absorption bands. Phase shift cavity ring down (PS-CRD) and thermal lens spectroscopy (TLS) are ultra-sensitive instrumental absorption techniques very commonly used in our laboratory. These are very powerful techniques for the detection of weak absorptions in the NIR-Vis region. In the case of high overtone spectra, CRD is ideal for gas samples whereas TLS is great for liquid samples. In our laboratory we use FT-IR and UV-Vis spectrometers as complementary techniques to CRDS and TLS. In order to simulate conditions in the atmospheres of other planets, we couple our instruments to a low temperature cryostat. In this way, these ultra-sensitive techniques can be applied to the study of gases in the atmosphere and liquid cryo-solutions to simulate the lakes of Saturn's largest moon, Titan. This work shows the use of signal-to-noise ratios to determine the spectral quality of spectra obtained with the PS-CRD technique, particularly in situations where human eye cannot perceive the small differences. We evaluate the impact of some instrumental parameters involved in data acquisition process of the PS-CRD technique, as well as evaluate the spectral quality as a function of the On-Axis/Off-Axis position of the incoming beam. This work also introduces the use of a second pumping laser for the analysis of multi-component samples in thermal lens. The design facilitates

  20. CO 1st overtone spectra of cool evolved stars: Diagnostics for hydrodynamic atmosphere models

    NASA Astrophysics Data System (ADS)

    Bieging, J. H.; Rieke, M. J.; Rieke, G. H.

    2002-03-01

    We present spectra covering the wavelength range 2.28 to 2.36 mu m at a resolution of Delta lambda = 0.0007 mu m (or R = 3500) for a sample of 24 cool evolved stars. The sample comprises 8 M supergiants, 5 M giants, 3 S stars, 6 carbon stars, and 2 RV Tauri variables. The wavelengths covered include the main parts of the 12C16O v = 2-0 and 3-1 overtone bands, as well as the v = 4-2 and 13CO v = 2-0 bandhead regions. CO lines dominate the spectrum for all the stars observed, and at this resolution most of the observed features can be identified with individual CO R- or P-branch lines or blends. The observed transitions arise from a wide range of energy levels extending from the ground state to E/k > 20 000 K. We looked for correlations between the intensities of various CO absorption line features and other stellar properties, including IR colors and mass loss rates. Two useful CO line features are the v = 2-0 R14 line, and the CO v = 2-0 bandhead. The intensity of the 2-0 bandhead shows a trend with K-[12] color such that the reddest stars (K-[12] > 3 mag) exhibit a wide range in 2-0 bandhead depth, while the least reddened have the deepest 2-0 bandheads, with a small range of variation from star to star. Gas mass loss rates for both the AGB stars and the red supergiants in our sample correlate with the K-[12] color, consistent with other studies. The data imply that stars with dot M_gas < 5x 10-7 Msun y-1 exhibit a much narrower range in the relative strengths of CO 2-0 band features than stars with higher mass loss rates. The range in observed spectral properties implies that there are significant differences in atmospheric structure among the stars in this sample. Figures 4-9, 11-14, 16, 17, 19-21, 23, 24 are only avalaible in electronic form at http://www.edpsciences.org

  1. 10B+α states with chain-like structures in 14N

    NASA Astrophysics Data System (ADS)

    Kanada-En'yo, Yoshiko

    2015-12-01

    I investigate 10B+α -cluster states of 14N with a 10B+α -cluster model. Near the α -decay threshold energy, I obtain Kπ=3+ and Kπ=1+ rotational bands having 10B(3+) +α and 10B(1+) +α components, respectively. I assign the bandhead state of the Kπ=3+ band to the experimental 3+ at Ex=13.19 MeV of 14N observed in α scattering reactions by 10B and show that the calculated α -decay width is consistent with the experimental data. I discuss an α -cluster motion around the 10B cluster and show that the Kπ=3+ and Kπ=1+ rotational bands contain an enhanced component of a linear-chain 3 α configuration, in which an α cluster is localized in the longitudinal direction around the deformed 10B cluster.

  2. Amine templating effect absent in uranyl sulfates synthesized with 1,4-n-butyldiamine

    SciTech Connect

    Jouffret, Laurent J.; Wylie, Ernest M.; Burns, Peter C.

    2013-01-15

    Two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3), were synthesized and their crystal structures determined. NDUS2 was obtained in highly acidic media heat-treated at 373 K and subsequently maintained at 278 K until crystals formed after two months. NDUS3 results from the degradation of NDUS2 over the course of a few days. NDUS2 and NDUS3 crystallize in the monoclinic space group P2{sub 1}/n, a=10.9075(4) A, b=10.4513(4) A, c=17.7881(7) A, {beta}=97.908(2) Degree-Sign , V=2008.52(13) A{sup 3}, Z=4, at 140 K and a=8.8570(4) A, b=7.3299(3) A, c=20.4260(9) A, {beta}=95.140(2) Degree-Sign , V=1320.74(10) A{sup 3}, Z=4, at 140 K, respectively. The compounds contain interlayer 1,4-n-butyldiammonium cations that charge-balance the anionic structural units. - Graphical abstract: Amine templating effect absent in uranyl sulfates synthesized with 1,4-diaminobutane, as shown by the synthesis of two new uranyl sulfates, (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2}){sub 2}(SO{sub 4}){sub 3}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS2) and (C{sub 4}H{sub 14}N{sub 2})[(UO{sub 2})(SO{sub 4}){sub 2}(H{sub 2}O)]{center_dot}2H{sub 2}O (NDUS3). Highlights: Black-Right-Pointing-Pointer Two layered uranyl sulfates were synthesized. Black-Right-Pointing-Pointer Amine molecules are located in the interlayers of the compounds. Black-Right-Pointing-Pointer No templating effect of the amine was observed. Black-Right-Pointing-Pointer Amine molecules are only charge balancing cations in the structures.

  3. Overtone-based pitch selection in hermit thrush song: unexpected convergence with scale construction in human music.

    PubMed

    Doolittle, Emily L; Gingras, Bruno; Endres, Dominik M; Fitch, W Tecumseh

    2014-11-18

    Many human musical scales, including the diatonic major scale prevalent in Western music, are built partially or entirely from intervals (ratios between adjacent frequencies) corresponding to small-integer proportions drawn from the harmonic series. Scientists have long debated the extent to which principles of scale generation in human music are biologically or culturally determined. Data from animal "song" may provide new insights into this discussion. Here, by examining pitch relationships using both a simple linear regression model and a Bayesian generative model, we show that most songs of the hermit thrush (Catharus guttatus) favor simple frequency ratios derived from the harmonic (or overtone) series. Furthermore, we show that this frequency selection results not from physical constraints governing peripheral production mechanisms but from active selection at a central level. These data provide the most rigorous empirical evidence to date of a bird song that makes use of the same mathematical principles that underlie Western and many non-Western musical scales, demonstrating surprising convergence between human and animal "song cultures." Although there is no evidence that the songs of most bird species follow the overtone series, our findings add to a small but growing body of research showing that a preference for small-integer frequency ratios is not unique to humans. These findings thus have important implications for current debates about the origins of human musical systems and may call for a reevaluation of existing theories of musical consonance based on specific human vocal characteristics.

  4. Overtone-based pitch selection in hermit thrush song: Unexpected convergence with scale construction in human music

    PubMed Central

    Doolittle, Emily L.; Gingras, Bruno; Endres, Dominik M.; Fitch, W. Tecumseh

    2014-01-01

    Many human musical scales, including the diatonic major scale prevalent in Western music, are built partially or entirely from intervals (ratios between adjacent frequencies) corresponding to small-integer proportions drawn from the harmonic series. Scientists have long debated the extent to which principles of scale generation in human music are biologically or culturally determined. Data from animal “song” may provide new insights into this discussion. Here, by examining pitch relationships using both a simple linear regression model and a Bayesian generative model, we show that most songs of the hermit thrush (Catharus guttatus) favor simple frequency ratios derived from the harmonic (or overtone) series. Furthermore, we show that this frequency selection results not from physical constraints governing peripheral production mechanisms but from active selection at a central level. These data provide the most rigorous empirical evidence to date of a bird song that makes use of the same mathematical principles that underlie Western and many non-Western musical scales, demonstrating surprising convergence between human and animal “song cultures.” Although there is no evidence that the songs of most bird species follow the overtone series, our findings add to a small but growing body of research showing that a preference for small-integer frequency ratios is not unique to humans. These findings thus have important implications for current debates about the origins of human musical systems and may call for a reevaluation of existing theories of musical consonance based on specific human vocal characteristics. PMID:25368163

  5. Lectures on pulsed NMR

    SciTech Connect

    Pines, A.

    1986-09-01

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

  6. Lectures on pulsed NMR

    SciTech Connect

    Pines, A.

    1988-08-01

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

  7. High sensitivity cavity ring down spectroscopy of N2O near 1.22 μm: (II) 14N216O line intensity modeling and global fit of 14N218O line positions

    NASA Astrophysics Data System (ADS)

    Tashkun, S. A.; Perevalov, V. I.; Karlovets, E. V.; Kassi, S.; Campargue, A.

    2016-06-01

    In a recent work (Karlovets et al., 2016 [1]), we reported the measurement and rovibrational assignments of more than 3300 transitions belonging to 64 bands of five nitrous oxide isotopologues (14N216O, 14N15N16O, 15N14N16O, 14N218O and 14N217O) in the high sensitivity CRDS spectrum recorded in the 7915-8334 cm-1 spectral range. The assignments were performed by comparison with predictions of the effective Hamiltonian models developed for each isotopologue. In the present paper, the large amount of measurements from our previous work mentioned above and literature are gathered to refine the modeling of the nitrous oxide spectrum in two ways: (i) improvement of the intensity modeling for the principal isotopologue, 14N216O, near 8000 cm-1 from a new fit of the relevant effective dipole moment parameters, (ii) global modeling of 14N218O line positions from a new fit of the parameters of the global effective Hamiltonian using an exhaustive input dataset collected in the literature in the 12-8231 cm-1 region. The fitted set of 81 parameters allowed reproducing near 5800 measured line positions with an RMS deviation of 0.0016 cm-1. The dimensionless weighted standard deviation of the fit is 1.22. As an illustration of the improvement of the predictive capabilities of the obtained effective Hamiltonian, two new 14N218O bands could be assigned in the CRDS spectrum in the 7915-8334 cm-1 spectral range. A line list at 296 K has been generated in the 0-10,700 cm-1 range for 14N218O in natural abundance with a 10-30 cm/molecule intensity cutoff.

  8. NMR logging apparatus

    DOEpatents

    Walsh, David O; Turner, Peter

    2014-05-27

    Technologies including NMR logging apparatus and methods are disclosed. Example NMR logging apparatus may include surface instrumentation and one or more downhole probes configured to fit within an earth borehole. The surface instrumentation may comprise a power amplifier, which may be coupled to the downhole probes via one or more transmission lines, and a controller configured to cause the power amplifier to generate a NMR activating pulse or sequence of pulses. Impedance matching means may be configured to match an output impedance of the power amplifier through a transmission line to a load impedance of a downhole probe. Methods may include deploying the various elements of disclosed NMR logging apparatus and using the apparatus to perform NMR measurements.

  9. NMR studies of metalloproteins.

    PubMed

    Li, Hongyan; Sun, Hongzhe

    2012-01-01

    Metalloproteins represent a large share of the proteomes, with the intrinsic metal ions providing catalytic, regulatory, and structural roles critical to protein functions. Structural characterization of metalloproteins and identification of metal coordination features including numbers and types of ligands and metal-ligand geometry, and mapping the structural and dynamic changes upon metal binding are significant for understanding biological functions of metalloproteins. NMR spectroscopy has long been used as an invaluable tool for structure and dynamic studies of macromolecules. Here we focus on the application of NMR spectroscopy in characterization of metalloproteins, including structural studies and identification of metal coordination spheres by hetero-/homo-nuclear metal NMR spectroscopy. Paramagnetic NMR as well as (13)C directly detected protonless NMR spectroscopy will also be addressed for application to paramagnetic metalloproteins. Moreover, these techniques offer great potential for studies of other non-metal binding macromolecules.

  10. NMR methods in combinatorial chemistry.

    PubMed

    Shapiro, M J; Wareing, J R

    1998-06-01

    The use of NMR spectroscopy in combinatorial chemistry has provided a versatile tool for monitoring combinatorial chemistry reactions and for assessing ligand-receptor interactions. The application of magic angle spinning NMR is widespread and has allowed structure determination to be performed on compounds attached to solid supports. A variety of two-dimensional NMR techniques have been applied to enhance the usability of the magic angle spinning NMR data. New developments for solution NMR analysis include high performance liquid chromatography, NMR, mass spectroscopy and flow NMR. NMR based methods currently being investigated may prove valuable as compound screening tools.

  11. Systematic R -matrix analysis of the 13C(p ,γ )14N capture reaction

    NASA Astrophysics Data System (ADS)

    Chakraborty, Suprita; deBoer, Richard; Mukherjee, Avijit; Roy, Subinit

    2015-04-01

    Background: The proton capture reaction 13C(p ,γ )14N is an important reaction in the CNO cycle during hydrogen burning in stars with mass greater than the mass of the Sun. It also occurs in astrophysical sites such as red giant stars: the asymptotic giant branch (AGB) stars. The low energy astrophysical S factor of this reaction is dominated by a resonance state at an excitation energy of around 8.06 MeV (Jπ=1-,T =1 ) in 14N. The other significant contributions come from the low energy tail of the broad resonance with Jπ=0-,T =1 at an excitation of 8.78 MeV and the direct capture process. Purpose: Measurements of the low energy astrophysical S factor of the radiative capture reaction 13C(p ,γ )14N reported extrapolated values of S (0 ) that differ by about 30 % . Subsequent R -matrix analysis and potential model calculations also yielded significantly different values for S (0 ) . The present work intends to look into the discrepancy through a detailed R -matrix analysis with emphasis on the associated uncertainties. Method: A systematic reanalysis of the available decay data following the capture to the Jπ=1-,T =1 resonance state of 14N around 8.06 MeV excitation had been performed within the framework of the R -matrix method. A simultaneous analysis of the 13C(p ,p0 ) data, measured over a similar energy range, was carried out with the capture data. The data for the ground state decay of the broad resonance state (Jπ=0-,T =1 ) around 8.78 MeV excitations was included as well. The external capture model along with the background poles to simulate the internal capture contribution were used to estimate the direct capture contribution. The asymptotic normalization constants (ANCs) for all states were extracted from the capture data. The multichannel, multilevel R -matrix code azure2 was used for the calculation. Results: The values of the astrophysical S factor at zero relative energy, resulting from the present analysis, are found to be consistent within the

  12. Development of solid-state NMR techniques for the characterisation of pharmaceutical compounds

    NASA Astrophysics Data System (ADS)

    Tatton, Andrew S.

    Structural characterisation in the solid state is an important step in understanding the physical and chemical properties of a material. Solid-state NMR techniques applied to solid delivery forms are presented as an alternative to more established structural characterisation methods. The effect of homonuclear decoupling upon heteronuclear couplings is investigated using a combination of experimental and density-matrix simulation results acquired from a 13C-1H spinecho pulse sequence, modulated by scalar couplings. It is found that third-order cross terms under MAS and homonuclear decoupling contribute to strong dephasing effects in the NMR signal. Density-matrix simulations allow access to parameters currently unattainable in experiment, and demonstrate that higher homonuclear decoupling rf nutation frequencies reduce the magnitude of third-order cross terms. 15N-1H spinecho experiments were applied to pharmaceutically relevant samples to differentiate between the number of directly attached protons. Using this method, proton transfer in an acid-base reaction is proven in pharmaceutical salts. The indirect detection of 14N lineshapes via protons obtained using 2D 14N-1H HMQC experiments is presented, where coherence transfer is achieved via heteronuclear through-space dipolar couplings. The importance of fast MAS frequencies is demonstrated, and it is found that increasing the recoupling duration reveals longer range NH proximities. The 2D 14N-1H HMQC method is used to demonstrate the presence of specific hydrogen bonding interactions, and thus aid in identifying molecular association in a cocrystal and an amorphous dispersion. In addition, hydrogen bonding motifs were identified by observing the changes in the 14N quadrupolar parameters between individual molecular components relative to the respective solid delivery form. First-principles calculations of NMR chemical shifts and quadrupolar parameters using the GIPAW method were combined with 14N-1H experimental

  13. Narcotics and explosives detection by 14N pure nuclear quadrupole resonance

    NASA Astrophysics Data System (ADS)

    Garroway, Allen N.; Buess, Michael L.; Yesinowski, James P.; Miller, Joel B.

    1994-03-01

    Pure nuclear quadrupole resonance (NQR) of 14N nuclei is quite promising as a method for detecting explosives such as RDX and contraband narcotics such as cocaine and heroin in quantities of interest. Pure NQR is conducted without an external applied magnetic field, so potential concerns about damage to magnetically encoded data or exposure of personnel to large magnetic fields are not relevant. Because NQR frequencies of different compounds are quite distinct, we do not encounter false alarms from the NQR signals of other benign materials. We have constructed a proof-of-concept NQR explosives detector which interrogates a volume of 300 liters (10 ft3). With minimal modification to the existing explosives detector, we can detect operationally relevant quantities of (free base) cocaine within the 300-liter inspection volume in 6 seconds. We are presently extending this approach to the detection of heroin base and also examining 14N and 35,37Cl pure NQR for detection of the hydrochloride forms of both materials. An adaptation of this NQR approach may be suitable for scanning personnel for externally carried contraband and explosives. We first outline the basics of the NQR approach, highlighting strengths and weaknesses, and then present representative results for RDX and cocaine detection. We also present a partial compendium of relevant NQR parameters measured for some materials of interest.

  14. Neutron scattering cross sections from /sup 14/N and /sup 9/Be at 11, 14, and 17 MeV

    SciTech Connect

    Templon, J.A.; Dave, J.H.; Gould, C.R.; Singkarat, S.

    1985-12-01

    Neutron scattering cross sections were measured for /sup 14/N and /sup 9/Be at incident neutron energies of 11, 14, and 17 MeV using time-of-flight methods. Angular distributions for /sup 14/N and /sup 9/Be elastic scattering and /sup 9/Be inelastic scattering to the 2.429-MeV excited state were obtained betwee 20 and 160 deg in 5-deg increments. The data were corrected for finite geometry effects using a Monte Carlo simulation code. Lengendre polynomial coefficients deduced by fitting the experimental data are tabulated. The results of a spherical optical model analysis for the /sup 14/N data are reported. Coulomb correction terms are obtained from a comparison of neutron and proton elastic scattering data for /sup 14/N.

  15. Pure shift NMR.

    PubMed

    Zangger, Klaus

    2015-04-01

    Although scalar-coupling provides important structural information, the resulting signal splittings significantly reduce the resolution of NMR spectra. Limited resolution is a particular problem in proton NMR experiments, resulting in part from the limited proton chemical shift range (∼10 ppm) but even more from the splittings due to scalar coupling to nearby protons. "Pure shift" NMR spectroscopy (also known as broadband homonuclear decoupling) has been developed for disentangling overlapped proton NMR spectra. The resulting spectra are considerably simplified as they consist of single lines, reminiscent of proton-decoupled C-13 spectra at natural abundance, with no multiplet structure. The different approaches to obtaining pure shift spectra are reviewed here and several applications presented. Pure shift spectra are especially useful for highly overlapped proton spectra, as found for example in reaction mixtures, natural products and biomacromolecules.

  16. On the Ratio of Periods of the Fundamental Harmonic and First Overtone of Magnetic Tube Kink Oscillations

    NASA Astrophysics Data System (ADS)

    Ruderman, M. S.; Petrukhin, N. S.; Pelinovsky, E.

    2016-04-01

    We study kink oscillations of thin magnetic tubes. We assume that the density inside and outside the tube (and possibly also the cross-section radius) can vary along the tube. This variation is assumed to be of such a form that the kink speed is symmetric with respect to the tube centre and varies monotonically from the tube ends to the tube centre. Then we prove a theorem stating that the ratio of periods of the fundamental mode and first overtone is a monotonically increasing function of the ratio of the kink speed at the tube centre and the tube ends. In particular, it follows from this theorem that the period ratio is lower than two when the kink speed increases from the tube ends to its centre, while it is higher than two when the kink speed decreases from the tube ends to its centre. The first case is typical for non-expanding coronal magnetic loops, and the second for prominence threads. We apply the general results to particular problems. First we consider kink oscillations of coronal magnetic loops. We prove that, under reasonable assumptions, the ratio of the fundamental period to the first overtone is lower than two and decreases when the loop size increases. The second problem concerns kink oscillations of prominence threads. We consider three internal density profiles: generalised parabolic, Gaussian, and Lorentzian. Each of these profiles contain the parameter α that is responsible for its sharpness. We calculate the dependence of the period ratio on the ratio of the mean to the maximum density. For all considered values of α we find that a formula relating the period ratio and the ratio of the mean and maximum density suggested by Soler, Goossens, and Ballester ( Astron. Astrophys. 575, A123, 2015) gives a sufficiently good approximation to the exact dependence.

  17. Multiple-overtone resonance Raman scattering and fluorescence from I{sub 2} species adsorbed on silver surfaces

    SciTech Connect

    Sibbald, M.S.; Chumanov, G.; Small, G.; Cotton, T.M.

    1998-07-01

    A detailed excitation profile of a Raman progression consisting of up to six overtones and a fundamental band at 123 cm{sup {minus}1} observed from iodide adsorbed on an electrochemically roughened silver surface at 20 K is analyzed. The excitation profile was constructed from 77 spectra obtained by tuning the laser wavelength in {approximately}0.25 nm steps through the spectral range 409 nm{endash}433 nm. The shift between resonances in the excitation profile, corresponding to the spacing between vibronic levels in the excited state, is also equal to 123 cm{sup {minus}1} indicating that the ground state and excited state potential energy surfaces have the same shape. Only two distinct resonances spaced three vibrational quanta apart were evident in the profile for each band in the progression. Curve fitting of the Raman band shapes indicates that each overtone is composed of one sharp and one broad band, whereas the fundamental contains only one sharp component. The measured width of the fundamental was less than 2.5 cm{sup {minus}1} FWHM, limited by the instrument function. It is proposed that the sharp Raman bands represent a normal vibrational mode of a surface-adsorbed I{sub 2}-like species with the width determined by the intrinsic vibrational dephasing in the ground state. On the other hand, the broad Raman bands reflect vibronic coupling between different I{sub 2}-like species adsorbed on the same Ag cluster. The broad bandwidths result from both dephasing associated with the vibronic coupling and the intrinsic vibrational dephasing. Other weak emission bands are attributed to resonance fluorescence corresponding to direct transitions from higher vibronic levels of the excited state to the ground state. An emission at 429.9 nm is assigned to exciton recombination in small silver iodide clusters which are formed after spontaneous oxidation of the iodide-modified silver surface. {copyright} {ital 1998 American Institute of Physics.}

  18. Fundamental and overtone vibrational spectroscopy, enthalpy of hydrogen bond formation and equilibrium constant determination of the methanol-dimethylamine complex.

    PubMed

    Du, Lin; Mackeprang, Kasper; Kjaergaard, Henrik G

    2013-07-01

    We have measured gas phase vibrational spectra of the bimolecular complex formed between methanol (MeOH) and dimethylamine (DMA) up to about 9800 cm(-1). In addition to the strong fundamental OH-stretching transition we have also detected the weak second overtone NH-stretching transition. The spectra of the complex are obtained by spectral subtraction of the monomer spectra from spectra recorded for the mixture. For comparison, we also measured the fundamental OH-stretching transition in the bimolecular complex between MeOH and trimethylamine (TMA). The enthalpies of hydrogen bond formation (ΔH) for the MeOH-DMA and MeOH-TMA complexes have been determined by measurements of the fundamental OH-stretching transition in the temperature range from 298 to 358 K. The enthalpy of formation is found to be -35.8 ± 3.9 and -38.2 ± 3.3 kJ mol(-1) for MeOH-DMA and MeOH-TMA, respectively, in the 298 to 358 K region. The equilibrium constant (Kp) for the formation of the MeOH-DMA complex has been determined from the measured and calculated transition intensities of the OH-stretching fundamental transition and the NH-stretching second overtone transition. The transition intensities were calculated using an anharmonic oscillator local mode model with dipole moment and potential energy curves calculated using explicitly correlated coupled cluster methods. The equilibrium constant for formation of the MeOH-DMA complex was determined to be 0.2 ± 0.1 atm(-1), corresponding to a ΔG value of about 4.0 kJ mol(-1).

  19. Science to support adaptive habitat management: Overton Bottoms North Unit, Big Muddy National Fish and Wildlife Refuge, Missouri [Volumes 1-6

    USGS Publications Warehouse

    Jacobson, Robert B.

    2006-01-01

    Extensive efforts are underway along the Lower Missouri River to rehabilitate ecosystem functions in the channel and flood plain. Considerable uncertainty inevitably accompanies ecosystem restoration efforts, indicating the benefits of an adaptive management approach in which management actions are treated as experiments, and results provide information to feed back into the management process. The Overton Bottoms North Unit of the Big Muddy National Fish and Wildlife Refuge is a part of the Missouri River Fish and Wildlife Habitat Mitigation Project. The dominant management action at the Overton Bottoms North Unit has been excavation of a side-channel chute to increase hydrologic connectivity and to enhance shallow, slow current-velocity habitat. The side-channel chute also promises to increase hydrologic gradients, and may serve to alter patterns of wetland inundation and vegetation community growth in undesired ways. The U.S. Geological Survey's Central Region Integrated Studies Program (CRISP) undertook interdisciplinary research at the Overton Bottoms North Unit in 2003 to address key areas of scientific uncertainty that were highly relevant to ongoing adaptive management of the site, and to the design of similar rehabilitation projects on the Lower Missouri River. This volume presents chapters documenting the surficial geologic, topographic, surface-water, and ground-water framework of the Overton Bottoms North Unit. Retrospective analysis of vegetation community trends over the last 10 years is used to evaluate vegetation responses to reconnection of the Overton Bottoms North Unit to the river channel. Quasi-experimental analysis of cottonwood growth rate variation along hydrologic gradients is used to evaluate sensitivity of terrestrial vegetation to development of aquatic habitats. The integrated, landscape-specific understanding derived from these studies illustrates the value of scientific information in design and management of rehabilitation projects.

  20. ^14N (p,p) Scattering with the KN Van de Graff Accelerator

    NASA Astrophysics Data System (ADS)

    Lyons, Stephanie; Wiescher, Michael

    2009-03-01

    The ^14N (p,p) scattering experiment was performed with the 4 MV KN Van de Graff Accelerator at the Nuclear Structure Laboratory at the University of Notre Dame. The KN experienced many problems throughout the experiment requiring several belt changes, a change of the drive motor bearings, and a resistor check. The first run of data was converted to cross-sections, and normalized to 30 , which was assumed to be completely Rutherford. Resonances were found at 1.06, 1.55, 1.74, 1.80, 2.34, and 2.47 MeV. These values correlated with previous work done. Further experimentation will be required to clarify the resonances and verify that the scattering at 30 is completely Rutherford.

  1. NMR imaging microscopy

    SciTech Connect

    Not Available

    1986-10-01

    In the past several years, proton nuclear magnetic resonance (NMR) imaging has become an established technique in diagnostic medicine and biomedical research. Although much of the work in this field has been directed toward development of whole-body imagers, James Aguayo, Stephen Blackband, and Joseph Schoeninger of the Johns Hopkins University School of Medicine working with Markus Hintermann and Mark Mattingly of Bruker Medical Instruments, recently developed a small-bore NMR microscope with sufficient resolution to image a single African clawed toad cell (Nature 1986, 322, 190-91). This improved resolution should lead to increased use of NMR imaging for chemical, as well as biological or physiological, applications. The future of NMR microscopy, like that of many other newly emerging techniques, is ripe with possibilities. Because of its high cost, however, it is likely to remain primarily a research tool for some time. ''It's like having a camera,'' says Smith. ''You've got a way to look at things at very fine levels, and people are going to find lots of uses for it. But it is a very expensive technique - it costs $100,000 to add imaging capability once you have a high-resolution NMR, which itself is at least a $300,000 instrument. If it can answer even a few questions that can't be answered any other way, though, it may be well worth the cost.''

  2. Dual Species NMR Oscillator

    NASA Astrophysics Data System (ADS)

    Weber, Joshua; Korver, Anna; Thrasher, Daniel; Walker, Thad

    2016-05-01

    We present progress towards a dual species nuclear magnetic oscillator using synchronous spin exchange optical pumping. By applying the bias field as a sequence of alkali 2 π pulses, we generate alkali polarization transverse to the bias field. The alkali polarization is then modulated at the noble gas resonance so that through spin exchange collisions the noble gas becomes polarized. This novel method of NMR suppresses the alkali field frequency shift by at least a factor of 2500 as compared to longitudinal NMR. We will present details of the apparatus and measurements of dual species co-magnetometry using this method. Research supported by the NSF and Northrop-Grumman Corp.

  3. MULTIPLE-QUANTUM NMR IN SOLIDS

    SciTech Connect

    Yen, Y-S.

    1982-11-01

    Time domain multiple-quantum (MQ) nuclear magnetic resonance (NMR) spectroscopy is a powerful tool for spectral simplification and for providing new information on molecular dynamics. In this thesis, applications of MQ NMR are presented and show distinctly the advantages of this method over the conventional single-quantum NMR. Chapter 1 introduces the spin Hamiltonians, the density matrix formalism and some basic concepts of MQ NMR spectroscopy. In chapter 2, {sup 14}N double-quantum coherence is observed with high sensitivity in isotropic solution, using only the magnetization of bound protons. Spin echoes are used to obtain the homogeneous double-quantum spectrum and to suppress a large H{sub 2}O solvent signal. Chapter 3 resolves the main difficulty in observing high MQ transitions in solids. Due to the profusion of spin transitions in a solid, individual lines are unresolved. Excitation and detection of high quantum transitions by normal schemes are thus difficult. To ensure that overlapping lines add constructively and thereby to enhance sensitivity, time-reversal pulse sequences are used to generate all lines in phase. Up to 22-quantum {sup 1}H absorption in solid adamantane is observed. A time dependence study shows an increase in spin correlations as the excitation time increased. In chapter 4, a statistical theory of MQ second moments is developed for coupled spins of spin I = 1/2. The model reveals that the ratio of the average dipolar coupling to the rms value largely determines the dependence of second moments on the number of quanta. The results of this model are checked against computer-calculated and experimental second moments, and show good agreement. A simple scheme is proposed in chapter 5 for sensitivity improvement in a MQ experiment. The scheme involves acquiring all of the signal energy available in the detection period by applying pulsed spinlocking and sampling between pulses. Using this technique on polycrystalline adamantane, a large

  4. Fourier Transform Infrared Spectroscopy of the First CO-Stretch Overtone Band of 13CH 3OH

    NASA Astrophysics Data System (ADS)

    Predoi-Cross, Adriana; Mellau, G. C.; Lees, R. M.; Winnewisser, B. P.

    1998-06-01

    This paper presents a high-resolution Fourier transform infrared study of the first CO-stretch overtone band of13CH3OH. The spectrum has been recorded at the Justus-Liebig University, Gießsen, Germany on their Bruker IFS 120 HR Fourier transform spectrometer. We have assigned parallel subbands in the torsional staten= 0 forKvalues up to 6. Each individual subband has been fitted to aJ(J+ 1) power series expansion in order to obtain the subband origin and the state-specific energy expansion coefficients for the first CO-stretch overtone state. The average rotational constantBin the CO-stretchvCO= 2 state was found to be 0.768 cm-1, forming a smooth series with that of 0.777 cm-1obtained in thevCO= 1 state and the ground state value of 0.787 cm-1. Modeling of the excited state torsion-vibration energy level structure derived from the subband origins is then discussed and molecular parameters in thevCO= 2 state are proposed. The value obtained for the barrier height to internal rotation is 377.06 ± 0.52 cm-1, nearly indistinguishable from the value 378.65 cm-1reported for the CO-stretchvCO= 1 state. The vibrational energy is found to be 2020.9 ± 1.4 cm-1. The harmonic wavenumber for the CO-stretch vibration in13CH3OH was calculated to be ω = 1029.9 cm-1. The anharmonicity constant of this vibration is ωx= 6.5 cm-1, givingx= 6.3 × 10-3. We have also observed asymmetry-inducedKdoubling for the subbands ofAsymmetry forKvalues from 1 to 3 at sufficiently highJvalues. The size of the splitting coefficients is similar to those observed for the CO-stretch fundamental, with the exception of those for theK= 3Adoublet, where the observed splitting is about 18% larger than that for the ground and CO-stretchvCO= 1 states.

  5. Cross section measurement of 14N(p ,γ )15O in the CNO cycle

    NASA Astrophysics Data System (ADS)

    Li, Q.; Görres, J.; deBoer, R. J.; Imbriani, G.; Best, A.; Kontos, A.; LeBlanc, P. J.; Uberseder, E.; Wiescher, M.

    2016-05-01

    Background: The CNO cycle is the main energy source in stars more massive than our sun; it defines the energy production and the cycle time that lead to the lifetime of massive stars, and it is an important tool for the determination of the age of globular clusters. In our sun about 1.6% of the total solar neutrino flux comes from the CNO cycle. The largest uncertainty in the prediction of this CNO flux from the standard solar model comes from the uncertainty in the 14N(p ,γ )15O reaction rate; thus, the determination of the cross section at astrophysical temperatures is of great interest. Purpose: The total cross section of the 14N(p ,γ )15O reaction has large contributions from the transitions to the Ex=6.79 MeV excited state and the ground state of 15O. The Ex=6.79 MeV transition is dominated by radiative direct capture, while the ground state is a complex mixture of direct and resonance capture components and the interferences between them. Recent studies have concentrated on cross-section measurements at very low energies, but broad resonances at higher energy may also play a role. A single measurement has been made that covers a broad higher-energy range but it has large uncertainties stemming from uncorrected summing effects. Furthermore, the extrapolations of the cross section vary significantly depending on the data sets considered. Thus, new direct measurements have been made to improve the previous high-energy studies and to better constrain the extrapolation. Methods: Measurements were performed at the low-energy accelerator facilities of the nuclear science laboratory at the University of Notre Dame. The cross section was measured over the proton energy range from Ep=0.7 to 3.6 MeV for both the ground state and the Ex=6.79 MeV transitions at θlab=0∘ , 45∘, 90∘, 135∘, and 150∘. Both TiN and implanted-14N targets were utilized. γ rays were detected by using an array of high-purity germanium detectors. Results: The excitation function as

  6. Modern NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Jelinski, Lynn W.

    1984-01-01

    Discusses direct chemical information that can be obtained from modern nuclear magnetic resonance (NMR) methods, concentrating on the types of problems that can be solved. Shows how selected methods provide information about polymers, bipolymers, biochemistry, small organic molecules, inorganic compounds, and compounds oriented in a magnetic…

  7. Temperature induced changes in resonance Raman spectra intensity of all-trans-β-carotene: Changes in the fundamental, combination and overtone modes

    NASA Astrophysics Data System (ADS)

    Liu, Tianyuan; Xu, Shengnan; Li, Zuowei; Wang, Mengzhou; Sun, Chenglin

    2014-10-01

    The resonance Raman spectra of the fundamental, combination and overtone modes around the Csbnd C and Cdbnd C stretches of all-trans-β-carotene in 1,2-dichloroethane solution are obtained from the 293 K to 83 K temperature range. The results indicate that the intensity of the fundamentals in the liquid and solid phases generally increases as the temperature decreases, except for the liquid-solid phase transition, which exhibits a decreasing trend. The Raman intensities ratio between the fundamentals υ1 and υ2, combinations (overtones) and the fundamentals both increases with decreasing temperature. The Raman bandwidths of the Cdbnd C bonds gradually become narrow as the temperature decreases. These varieties of relative intensity are analyzed using the coherent weakly damped electron-lattice vibration mode, the effective conjugation length mode as well as the theory of electron-phonon interaction in this work.

  8. Collision-Induced Absorption by H2 Pairs in the Second Overtone Band at 298 and 77.5 K: Comparison between Experimental and Theoretical Results

    NASA Technical Reports Server (NTRS)

    Brodbeck, C.; Bouanich, J.-P.; van-Thanh, Nguyen; Fu, Y.; Borysow, A.

    1999-01-01

    The collision-induced spectra of hydrogen in the region of the second overtone at 0.8 microns have been recorded at temperatures of 298 and 77.5 K and for gas densities ranging from 100 to 800 amagats. The spectral profile defined by the absorption coefficient per squared density varies significantly with the density, so that the binary absorption coefficient has been determined by extrapolations to zero density of the measured profiles. Our extrapolated measurements and our recent ab initio quantum calculation are in relatively good agreement with one another. Taking into account the very weak absorption of the second overtone band, the agreement is, however, not as good as it has become (our) standard for strong bands.

  9. 17O(p, α) 14N study at the LUNA accelerator

    NASA Astrophysics Data System (ADS)

    Scott, D. A.; Bruno, C.; Caciolli, A.; LUNA Collaboration

    2013-08-01

    Hydrogen burning of 17O sensitively influences nucleosynthesis in a number of stellar sites, including red giants, asymptotic giant branch (AGB) stars, massive stars, and classical novae. In particular, the ratio between reaction rates of 17O(p, α) 14N (Q=1.2 MeV) and 17O(p, γ) 18F (Q=5.6 MeV) channels on 17O is one of the most important parameters for the galactic synthesis of 17O, the stellar production of radioactive 18F, and for predicted O isotopic ratios in premolar grains. Now the LUNA collaboration is preparing a new effort to study the (p, α) channel on 17O at astrophysical energies. To reach this goal a new chamber has been constructed which allows to place 8 silicons detectors in backward directions. The setup improves the efficiency which is a crucial parameter in measuring nuclear reaction at such low energies. Aluminum foils are placed on the silicon in order to stop the elastic backscattered protons which otherwise produce non-negligible background on the silicons.

  10. Real-Time Infrared Overtone Laser Control of Temperature in Picoliter H(2)O Samples: "Nanobathtubs" for Single Molecule Microscopy.

    PubMed

    Holmstrom, Erik D; Nesbitt, David J

    2010-01-01

    An approach for high spatiotemporal control of aqueous sample temperatures in confocal microscopy is reported. This technique exploits near-IR diode-laser illumination to locally heat picoliter volumes of water via first-overtone excitation in the OH-stretch manifold. A thin water cell after the objective resonantly removes any residual IR light from the detection system, allowing for continuous observation of single-molecule fluorescence throughout the heating event. This technique is tested quantitatively by reproducing single-molecule RNA folding results obtained from "bulk" stage heating measurements. Calibration of sample temperatures is obtained from time-correlated single-photon counting studies of Rhodamine B fluorescence decay. We obtain an upper limit to the heating response time (τ(heat) < 20 ms) consistent with even faster estimates (τ(heat) ≈ 0.25 ms) based on laser spot size, H(2)O heat capacit,y and absorption cross section. This combination of fast, noncontact heating of picoliter volumes provides new opportunities for real-time thermodynamic/kinetic studies at the single-molecule level.

  11. Will water act as a photocatalyst for cluster phase chemical reactions? Vibrational overtone-induced dehydration reaction of methanediol

    SciTech Connect

    Kramer, Zeb C.; Takahashi, Kaito; Skodje, Rex T.; Vaida, Veronica

    2012-04-28

    The possibility of water catalysis in the vibrational overtone-induced dehydration reaction of methanediol is investigated using ab initio dynamical simulations of small methanediol-water clusters. Quantum chemistry calculations employing clusters with one or two water molecules reveal that the barrier to dehydration is lowered by over 20 kcal/mol because of hydrogen-bonding at the transition state. Nevertheless, the simulations of the reaction dynamics following OH-stretch excitation show little catalytic effect of water and, in some cases, even show an anticatalytic effect. The quantum yield for the dehydration reaction exhibits a delayed threshold effect where reaction does not occur until the photon energy is far above the barrier energy. Unlike thermally induced reactions, it is argued that competition between reaction and the irreversible dissipation of photon energy may be expected to raise the dynamical threshold for the reaction above the transition state energy. It is concluded that quantum chemistry calculations showing barrier lowering are not sufficient to infer water catalysis in photochemical reactions, which instead require dynamical modeling.

  12. The 2ν{sub 3} Raman overtone of sulfur hexafluoride: Absolute spectra, pressure effects, and polarizability properties

    SciTech Connect

    Chrysos, M. Rachet, F.; Kremer, D.

    2014-03-28

    Of the six normal vibrations of SF{sub 6}, ν{sub 3} has a key role in the mechanisms of radiative forcing. This vibration, though inactive in Raman, shows up through the transition 2ν{sub 3} allowing for a complementary view on the asymmetric stretch of the molecule. Here, we look back into this topic, which has already caught some interest in the past but with some points been left out. We make a systematic incoherent-light-scattering analysis of the overtone with the use of different gas pressures and polarization orientations for the incident beam. Absolute-scale isotropic and anisotropic spectra are reported along with natural and pressure-induced widths and shifts, and other spectral features such as the peaks corresponding to the (experimentally indistinguishable) interfering channels E{sub g} and F{sub 2g} hitherto seen solely as two-photon IR-absorption features. We make the first-ever prediction of the SF{sub 6} polarizability second derivative with respect to the ν{sub 3}-mode coordinate and we develop a heuristic argument to explain why the superposition of the three degenerate stretching motions that are related to the ν{sub 3} mode cannot but generate a polarized Raman band.

  13. Theoretical calculation of the OH vibrational overtone spectra of 1-n alkane diols (n = 2-4): origin of disappearing hydrogen-bonded OH peak.

    PubMed

    Cheng, Yu-Lung; Chen, Hui-Yi; Takahashi, Kaito

    2011-06-01

    In this theoretical study, we simulated the vibrational overtone spectrum of ethylene glycol (EG), 1-3 propanediol (PD), and 1-4 butanediol (BD). Using the local mode model along with the potential energy curve and dipole moment function calculated by B3LYP/6-31+G(d,p) and QCISD/6-311++G(3df,3pd), we obtained the theoretical peak position and integrated absorption coefficient. Furthermore, the vibrational spectra was simulated using a Voigt function using homogeneous and inhomogenous width obtained from quantum chemical calculation methods. Previously, Howard and Kjaergaard recorded the second and third overtone photoacoustic spectra of the three aforementioned alkane diols in the gas phase and observed that the intramolecular hydrogen bonded OH peak becomes difficult to observe as the intramolecular hydrogen bonding strength increased, that is, as the chain length was increased. In this paper we show that the disappearance of the hydrogen-bonded OH peak for the OH stretching overtone excitation for BD is partly due to the increase in homogeneous width due to the increase in the hydrogen bond strength and partly due to the decrease in the relative population of the intramolecular hydrogen-bonded conformers as the chain length is increased. This latter feature is a consequence of the unfavorable strained geometry needed to form the intramolecular hydrogen bond in longer alkane chains. PMID:21568300

  14. COMPARISON OF STABLE-NITROGEN (15N/14N) ISOTOPE RATIOS IN LARGE MOUTH BASS SCALES AND MUSCLE TISSUE

    EPA Science Inventory

    Stable-nitrogen (15N/14N) isotope ratios of fish tissue are currently used to determine trophic structure, contaminant bioaccumulation, and the level of anthropogenic nitrogen enrichment in aquatic systems. The most common tissue used for these measurements is fileted dorsal musc...

  15. Live cell NMR.

    PubMed

    Freedberg, Darón I; Selenko, Philipp

    2014-01-01

    Ever since scientists realized that cells are the basic building blocks of all life, they have been developing tools to look inside them to reveal the architectures and mechanisms that define their biological functions. Whereas "looking into cells" is typically said in reference to optical microscopy, high-resolution in-cell and on-cell nuclear magnetic resonance (NMR) spectroscopy is a powerful method that offers exciting new possibilities for structural and functional studies in and on live cells. In contrast to conventional imaging techniques, in- and on-cell NMR methods do not provide spatial information on cellular biomolecules. Instead, they enable atomic-resolution insights into the native cell states of proteins, nucleic acids, glycans, and lipids. Here we review recent advances and developments in both fields and discuss emerging concepts that have been delineated with these methods.

  16. NMR Studies of Peroxidases.

    NASA Astrophysics Data System (ADS)

    Veitch, Nigel Charles

    Available from UMI in association with The British Library. Requires signed TDF. Peroxidases are a haem-containing group of enzymes with a wide diversity of function within biological systems. While a common characteristic is the ability to catalyse the conversion of hydrogen peroxide to water, it is the accompanying processes of hormone synthesis and degradation which have generated such a high level of interest. However, information at the molecular level is limited to a single well-resolved crystal structure, that of yeast cytochrome c peroxidase. This thesis presents a strategy for the investigation of peroxidase structure and function based on proton nuclear magnetic resonance spectroscopy, a technique which has the ability to address aspects of both protein structure and protein dynamics in solution. The application of one- and two-dimensional NMR techniques has been developed in the context of plant peroxidases, notably the isoenzyme HRP-C derived from the horseradish root. Characterisation of the proton NMR spectra of HRP -C in resting and ligated states provided new information enabling the structure of the binding site for aromatic donor molecules, such as indole-3-propionic, ferulic and benzhydroxamic acids, to be resolved. In order to overcome difficulties encountered with a protein of the complexity of peroxidase, additional information was obtained from chemical shift parameters and the use of peroxidase variants produced by site-directed mutagenesis. A comparative study using NMR spectroscopy was undertaken for wild-type recombinant HRP-C expressed in Escherichia coli, and two protein variants with substitutions made to residues located on the distal side of the haem pocket, Phe41 to Val and Arg38 to Lys. NMR analyses of a plant peroxidase from barley grains and the fungal peroxidase from Coprinus cinereus were also successful using methods conceived with HRP-C. Examination of three specifically constructed recombinant protein variants of C. cinereus

  17. The NMR phased array.

    PubMed

    Roemer, P B; Edelstein, W A; Hayes, C E; Souza, S P; Mueller, O M

    1990-11-01

    We describe methods for simultaneously acquiring and subsequently combining data from a multitude of closely positioned NMR receiving coils. The approach is conceptually similar to phased array radar and ultrasound and hence we call our techniques the "NMR phased array." The NMR phased array offers the signal-to-noise ratio (SNR) and resolution of a small surface coil over fields-of-view (FOV) normally associated with body imaging with no increase in imaging time. The NMR phased array can be applied to both imaging and spectroscopy for all pulse sequences. The problematic interactions among nearby surface coils is eliminated (a) by overlapping adjacent coils to give zero mutual inductance, hence zero interaction, and (b) by attaching low input impedance preamplifiers to all coils, thus eliminating interference among next nearest and more distant neighbors. We derive an algorithm for combining the data from the phased array elements to yield an image with optimum SNR. Other techniques which are easier to implement at the cost of lower SNR are explored. Phased array imaging is demonstrated with high resolution (512 x 512, 48-cm FOV, and 32-cm FOV) spin-echo images of the thoracic and lumbar spine. Data were acquired from four-element linear spine arrays, the first made of 12-cm square coils and the second made of 8-cm square coils. When compared with images from a single 15 x 30-cm rectangular coil and identical imaging parameters, the phased array yields a 2X and 3X higher SNR at the depth of the spine (approximately 7 cm). PMID:2266841

  18. NMR imaging of materials

    SciTech Connect

    Vinegar, H.J.; Rothwell, W.P.

    1988-03-01

    A method for obtaining at least one petrophysical property of a porous material containing therein at least one preselected fluid, is described, comprising: NMR imaging the material to generate signals dependent upon both M(0) and T/sub 1/ and M(0) and T/sub 2/, generating separate M(0), T/sub 1/ and T/sub 2/ images from the signals, and determining at least one petrophysical property from at least one of the images.

  19. 14N Quadrupole Coupling in the Microwave Spectra of N-Vinylformamide

    NASA Astrophysics Data System (ADS)

    Kannengießer, Raphaela; Stahl, Wolfgang; Nguyen, Ha Vinh Lam; Bailey, William C.

    2016-06-01

    The microwave spectra of two conformers, trans and cis, of the title compound were recorded using two molecular beam Fourier transform microwave spectrometers operating in the frequency range 2 GHz to 40 GHz, and aimed at analysis of their 14N quadrupole hyperfine structures. Rotational constants, centrifugal distortion constants, and nuclear quadrupole coupling constants (NQCCs) χaa and χbb - χcc, were all determined with very high accuracy. Two fits including 176 and 117 hyperfine transitions were performed for the trans and cis conformers, respectively. Standard deviations of both fits are close to the measurement accuracy of 2 kHz. The NQCCs of the two conformers are almost exactly the same, and are compared with values found for other saturated and unsaturated formamides. Complementary quantum chemical calculations - MP2/6-311++G(d,p) rotational constants, MP2/cc-pVTZ centrifugal distortion constants, and B3PW91/6-311+G(d,p)//MP2/6-311++G(d,p) nuclear quadrupole coupling constants - give spectroscopic parameters in excellent agreement with the experimental parameters. B3PW91/6-311+G(d,p) calculated electric field gradients, in conjunction with eQ/h = 4.599(12) MHz/a.u., yields more reliable NQCCs for formamides possessing conjugated π-electron systems than does the B3PW91/6-311+G(df,pd) model recommended in Ref., whereas this latter performs better for aliphatic formamides. We conclude from this that f-polarization functions on heavy atoms hinder rather than help with modeling of conjugated π-electron systems. W. C. Bailey, Chem. Phys., 2000, 252, 57 W. C. Bailey, Calculation of Nuclear Quadrupole Coupling Constants in Gaseous State Molecules, http://nqcc.wcbailey.net/index.html.

  20. The Effects of Internal Rotation and 14N Quadrupole Coupling in N-Methyldiacetamide

    NASA Astrophysics Data System (ADS)

    Kannengießer, Raphaela; Eibl, Konrad; Nguyen, Ha Vinh Lam; Stahl, Wolfgang

    2015-06-01

    Acetyl- and nitrogen containing substances play an important role in chemical, physical, and especially biological systems. This applies in particular for acetamides, which are structurally related to peptide bonds. In this work, N-methyldiacetamide, CH_3N(COCH_3)_2, was investigated by a combination of molecular beam Fourier transform microwave spectroscopy and quantum chemical calculations. In N-methyldiacetamide, at least three large amplitude motions are possible: (1) the internal rotation of the methyl group attached to the nitrogen atom and (2, 3) the internal rotations of both acetyl methyl groups. This leads to a rather complicated torsional fine structure of all rotational transitions with additional quadrupole hyperfine splittings caused by the 14N nucleus. Quantum chemical calculations were carried out at the MP2/6-311++G(d,p) level of theory to support the spectral assignment. Conformational analysis was performed by calculating a full potential energy surface depending on the orientation of the two acetyl groups. This yielded three stable conformers with a maximum energy difference of 35.2 kJ/mol. The spectrum of the lowest energy conformer was identified in the molecular beam. The quadrupole hyperfine structure as well as the internal rotation of two methyl groups could be assigned. For the N-methyl group and for one of the two acetyl methyl groups, barriers to internal rotation of 147 cm-1 and of 680 cm-1, respectively, were determined. The barrier of the last methyl group seems to be so high that no additional splittings could be resolved. Using the XIAM program, a global fit with a standard deviation on the order of our experimental accuracy could be achieved.

  1. WURST-QCPMG sequence and "spin-lock" in 14N nuclear quadrupole resonance

    NASA Astrophysics Data System (ADS)

    Gregorovič, Alan; Apih, Tomaž

    2013-08-01

    14N nuclear quadrupole resonance (NQR) is a promising method for the analysis of pharmaceuticals or for the detection of nitrogen based illicit compounds, but so far, the technique is still not widely used, mostly due to the very low sensitivity. This problem is already acute in the preliminary NQR stage, when a compound is being examined for the first time and the NQR frequencies are being searched for, by scanning a wide frequency range step-by-step. In the present work, we experimentally show how to increase the efficiency of this initial stage by using a combination of a wideband excitation achieved with frequency swept pulses (WURST) and a "spin-lock" state obtained with a quadrupolar-CPMG (QCPMG) sequence. In the first part we show that WURST pulses provide a much larger excitation bandwidth compared to common rectangular pulses. This increased bandwidth allows to increase the frequency step and reduces the total number of steps in a scanning stage. In the second part we show that the "spin-lock" decay time T2eff obtained with the WURST-QCPMG combination is practically identical with the T2eff obtained with the most common "spin-lock" sequence, the SLSE, despite a very different nature and length of excitation pulses. This allows for a substantial S/N increase through echo averaging in every individual step and really allows to exploit all the advantages of the wider excitation in the NQR frequency scanning stage. Our experimental results were obtained on a sample of trinitrotoluene, but identical behavior is expected for all compounds where a "spin-lock" state can be created.

  2. Soils, Pores, and NMR

    NASA Astrophysics Data System (ADS)

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

    2010-05-01

    Within Cluster A, Partial Project A1, the pore space exploration by means of Nuclear Magnetic Resonance (NMR) plays a central role. NMR is especially convenient since it probes directly the state and dynamics of the substance of interest: water. First, NMR is applied as relaxometry, where the degree of saturation but also the pore geometry controls the NMR signature of natural porous systems. Examples are presented where soil samples from the Selhausen, Merzenhausen (silt loams), and Kaldenkirchen (sandy loam) test sites are investigated by means of Fast Field Cycling Relaxometry at different degrees of saturation. From the change of the relaxation time distributions with decreasing water content and by comparison with conventional water retention curves we conclude that the fraction of immobile water is characterized by T1 < 5 ms. Moreover, the dependence of the relaxation rate on magnetic field strength allows the identification of 2D diffusion at the interfaces as the mechanism which governs the relaxation process (Pohlmeier et al. 2009). T2 relaxation curves are frequently measured for the rapid characterization of soils by means of the CPMG echo train. Basically, they contain the same information about the pore systems like T1 curves, since mostly the overall relaxation is dominated by surface relaxivity and the surface/volume ratio of the pores. However, one must be aware that T2 relaxation is additionally affected by diffusion in internal gradients, and this can be overcome by using sufficiently short echo times and low magnetic fields (Stingaciu et al. 2009). Second, the logic continuation of conventional relaxation measurements is the 2-dimensional experiment, where prior to the final detection of the CPMG echo train an encoding period is applied. This can be T1-encoding by an inversion pulse, or T2 encoding by a sequence of 90 and 180° pulses. During the following evolution time the separately encoded signals can mix and this reveals information about

  3. Ultrasonic Thermometry Inside Tissues Based on High-resolution Detection of Spectral Shifts in Overtones of Scattering Signals

    NASA Astrophysics Data System (ADS)

    Bazán, I.; Ramos, A.; Ramírez, A.; Leija, L.

    Some research results of cooperation works in biomedical engineering, established among current national projects of Mexico and Spain, are resumed. They are related to coordinated activities of three R & D groups, with the aim to achieve high-resolution ultrasonic thermometry into tissue phantoms with internal reflectors of a non-invasive way. Advanced spectral techniques are being used to extract thermal information in echo-signals acquired from biological phantoms with internal structures having a quasi-regular scattering distribution as, for instance, it happens in the liver tissues where a rather regular separation between scatterers has been reported. These techniques can indicate pathologies related to thermal increases due to the presence of disease. Small changes with temperature can be detected in the location of overtones of the fundamental resonance related to the separation of internal reflectors. But, this requires discarding the influence of the echoes noise on the thermal estimation results. A first evaluation of these spectral analysis techniques is performed, using echo-signals acquired from a phantom in the temperature range with medical interest, where the noise influence is shown for different levels of SNR in the echoes, using signals derived of a mathematical model for hepatic tissue echoes, where the average power, signal to noise ratio and inter-arrival time standard deviation, were taken into account. It seems that our high-resolution spectral option could be applied to detect some pathologies in tissues having regular scattering, but new advances must be performed with real tissues, in order to confirm the potential resolution of this approach.

  4. The Araucaria Project: the First-overtone Classical Cepheid in the Eclipsing System OGLE-LMC-CEP-2532

    NASA Astrophysics Data System (ADS)

    Pilecki, Bogumił; Graczyk, Dariusz; Gieren, Wolfgang; Pietrzyński, Grzegorz; Thompson, Ian B.; Smolec, Radosław; Udalski, Andrzej; Soszyński, Igor; Konorski, Piotr; Taormina, Mónica; Gallenne, Alexandre; Minniti, Dante; Catelan, Márcio

    2015-06-01

    We present here the first spectroscopic and photometric analysis of the double-lined eclipsing binary containing the classical, first-overtone (FO) Cepheid OGLE-LMC-CEP-2532 (MACHO 81.8997.87). The system has an orbital period of 800 days and the Cepheid is pulsating with a period of 2.035 days. Using spectroscopic data from three high-class telescopes and photometry from three surveys spanning 7500 days, we are able to derive the dynamical masses for both stars with an accuracy better than 3%. This makes the Cepheid in this system one of a few classical Cepheids with an accurate dynamical mass determination ({{M}1}=3.90+/- 0.10 {{M}⊙ }). The companion is probably slightly less massive (3.82+/- 0.10 {{M}⊙ }), but may have the same mass within errors ({{M}2}/{{M}1}=0.981+/- 0.015). The system has an age of about 185 million years and the Cepheid is in a more advanced evolutionary stage. For the first time precise parameters are derived for both stars in this system. Due to the lack of the secondary eclipse for many years, not much was known about the Cepheid’s companion. In our analysis, we used extra information from the pulsations and the orbital solution from the radial velocity curve. The best model predicts a grazing secondary eclipse shallower than 1 mmag, hence undetectable in the data, about 370 days after the primary eclipse. The dynamical mass obtained here is the most accurate known for a FO Cepheid and will contribute to the solution of the Cepheid mass discrepancy problem. The research is based on observations obtained with the ESO VLT and 3.6 m telescopes for Programmes 092.D-0295(A), 091.D-0393(A), 089.D-0330(A), 088.D-0447(A), 086.D-0103(A), and 085.D-0398(A), and with the Magellan Clay and Warsaw telescopes at Las Campanas Observatory.

  5. Bayesian reconstruction of projection reconstruction NMR (PR-NMR).

    PubMed

    Yoon, Ji Won

    2014-11-01

    Projection reconstruction nuclear magnetic resonance (PR-NMR) is a technique for generating multidimensional NMR spectra. A small number of projections from lower-dimensional NMR spectra are used to reconstruct the multidimensional NMR spectra. In our previous work, it was shown that multidimensional NMR spectra are efficiently reconstructed using peak-by-peak based reversible jump Markov chain Monte Carlo (RJMCMC) algorithm. We propose an extended and generalized RJMCMC algorithm replacing a simple linear model with a linear mixed model to reconstruct close NMR spectra into true spectra. This statistical method generates samples in a Bayesian scheme. Our proposed algorithm is tested on a set of six projections derived from the three-dimensional 700 MHz HNCO spectrum of a protein HasA. PMID:25218584

  6. IR spectroscopic analysis of polymorphism in C 13H 14N 4O

    NASA Astrophysics Data System (ADS)

    El-Kabbany, F.; Taha, S.; Hafez, M.

    2011-03-01

    IR analysis is used here to investigate the changes in N-N, N-H, C dbnd O modes of thermally treated diphenyl carbazide (DPC) during the variation of temperature from room temperature up to ≈160 °C. Polymorphism in DPC compound has been studied here by detecting the changes in some IR spectroscopic parameters (e.g., mode shift, band contour) during the elevation of temperature. Also, DSC, X-ray, NMR and atomic mass spectra are used as confirming tools for what is obtained by IR. All of the vibrations of DPC were found to be due to ionic fundamentals 3311 cm -1, 3097 cm -1, 3052 cm -1, 1677 cm -1, 1602 cm -1, 1492 cm -1, 1306 cm -1, 1252 cm -1, 887 cm -1 and 755 cm -1. The results revealed for the first time that the thermally treated DPC traverse four different phase transformations at 50 °C, 90 °C, 125 °C and 140 °C. The crystal structure was found to be amorphous, monoclinic, tetragonal, orthorhombic and amorphous within a temperature range (30 °C-160 °C). X-ray diffraction patterns support the results obtained by IR and DSC.

  7. The C14(n,γ) cross section between 10 keV and 1 MeV

    NASA Astrophysics Data System (ADS)

    Reifarth, R.; Heil, M.; Forssén, C.; Besserer, U.; Couture, A.; Dababneh, S.; Dörr, L.; Görres, J.; Haight, R. C.; Käppeler, F.; Mengoni, A.; O'Brien, S.; Patronis, N.; Plag, R.; Rundberg, R. S.; Wiescher, M.; Wilhelmy, J. B.

    2008-01-01

    The neutron capture cross section of C14 is of relevance for several nucleosynthesis scenarios such as inhomogeneous Big Bang models, neutron induced CNO cycles, and neutrino driven wind models for the r process. The C14(n,γ) reaction is also important for the validation of the Coulomb dissociation method, where the (n,γ) cross section can be indirectly obtained via the time-reversed process. So far, the example of C14 is the only case with neutrons where both, direct measurement and indirect Coulomb dissociation, have been applied. Unfortunately, the interpretation is obscured by discrepancies between several experiments and theory. Therefore, we report on new direct measurements of the C14(n,γ) reaction with neutron energies ranging from 20 to 800 keV.

  8. Modelling of Collision Induced Absorption Spectra Of H2-H2 Pairs for the Planetary Atmospheres Structure: The Second Overtone Band

    NASA Technical Reports Server (NTRS)

    Borysow, Aleksandra; Borysow, Jacek I.

    1998-01-01

    The main objective of the proposal was to model the collision induced, second overtone band of gaseous hydrogen at low temperatures. The aim of this work is to assist planetary scientists in their investigation of planetary atmospheres, mainly those of Uranus and Neptune. The recently completed extended database of collision induced dipole moments of hydrogen pairs allowed us, for the first time, to obtain dipole moment matrix elements responsible for the roto-vibrational collision induced absorption spectra of H2-H2 in the second overtone band. Despite our numerous attempts to publish those data, the enormous volume of the database did not allow us to do this. Instead, we deposited the data on a www site. The final part of this work has been partially supported by NASA, Division for Planetary Atmospheres. In order to use our new data for modelling purpose, we first needed to test how well we can reproduce the existing experimental data from theory, when using our new input data. Two papers resulted from this work. The obtained agreement between theoretical results and the measurements appeared to be within 10-30%. The obviously poorer agreement than observed for the first H2 overtone, the fundamental, and the rototranslational bands can be attributed to the fact that dipole moments responsible for the second overtone are much weaker, therefore susceptible to larger numerical uncertainties. At the same time, the intensity of the second overtone band is much weaker and therefore it is much harder to be measured accurately in the laboratory. We need to point out that until now, no dependable model of the 2nd overtone band was available for modelling of the planetary atmospheres. The only one, often referred to in previous works on Uranian and Neptune's atmospheres, uses only one lineshape, with one (or two) parameter(s) deduced at the effective temperature of Uranus (by fitting the planetary observation). After that, the parameter(s) was(were) made temperature

  9. Analysis of the collision-induced absorption spectra in the second overtone region of H2-H2 at 298 K

    NASA Astrophysics Data System (ADS)

    Abu-Kharma, M.

    2015-02-01

    The collision-induced absorption (CIA) spectra of the second overtone band of normal hydrogen in a pure gas were recorded for a number of gas densities up to 750 amagat (1 amagat = 44.614981 mol/m3) with a two meter stainless steel absorption cell at 298 K. The profile analyses of these spectra were carried out using the Birnbaum-Cohen line shape function for the quadrupolar vibrational transitions and the Levine-Birnbaum line shape function for the overlap transitions.

  10. Direct observation of the transitions 2Δ = 1 of the NiH radical by Faraday LMR, employing a CO overtone laser

    NASA Astrophysics Data System (ADS)

    Bachem, E.; Urban, W.; Nelis, Th.

    We report the first direct gas phase observations of the electronic transitions, 2Δ5/2, ν = 0 → 2Π3/2, ν = 0 and 2Δ5/2, ν = 0 → 2Δ3/2, ν = 1, in the NiH radical. From the observed transitions we obtained transition frequencies and electronic g factors. The observation of these electronic transitions by LMR has been possible only by employing the recently developed CO overtone laser. This work forms the first spectroscopic application of this new laser.

  11. Pulse Electron Double Resonance Detected Multinuclear NMR Spectra of Distant and Low Sensitivity Nuclei and Its Application to the Structure of Mn(II) Centers in Organisms.

    PubMed

    Bruch, Eduardo M; Warner, Melissa T; Thomine, Sébastien; Tabares, Leandro C; Un, Sun

    2015-10-29

    The ability to characterize the structure of metal centers beyond their primary ligands is important to understanding their chemistry. High-magnetic-field pulsed electron double resonance detected NMR (ELDOR-NMR) is shown to be a very sensitive approach to measuring the multinuclear NMR spectra of the nuclei surrounding Mn(II) ions. Resolved spectra of intact organisms with resonances arising from (55)Mn, (31)P, (1)H, (39)K, (35)Cl, (23)Na, and (14)N nuclei surrounding Mn(2+) centers were obtained. Naturally abundant cellular (13)C could be routinely measured as well. The amplitudes of the (14)N and (2)H ELDOR-NMR spectra were found to be linearly dependent on the number of nuclei in the ligand sphere. The evolution of the Mn(II) ELDOR-NMR spectra as a function of excitation time was found to be best described by a saturation phenomenon rather than a coherently driven process. Mn(II) ELDOR-NMR revealed details about not only the immediate ligands to the Mn(II) ions but also more distant nuclei, providing a view of their extended structures. This will be important for understanding the speciation and chemistry of the manganese complexes as well as other metals found in organisms.

  12. The Titan 14N/ 15N and 12C/ 13C isotopic ratios in HCN from Cassini/CIRS

    NASA Astrophysics Data System (ADS)

    Vinatier, Sandrine; Bézard, Bruno; Nixon, Conor A.

    2007-11-01

    We report the detection of H 13CN and HC 15N in mid-infrared spectra recorded by the Composite Infrared Spectrometer (CIRS) aboard Cassini, along with the determination of the 12C/ 13C and 14N/ 15N isotopic ratios. We analyzed two sets of limb spectra recorded near 13-15° S (Tb flyby) and 83° N (T4 flyby) at 0.5 cm -1 resolution. The spectral range 1210-1310 cm -1 was used to retrieve the temperature profile in the range 145-490 km at 13° S and 165-300 km at 83° N. These two temperature profiles were then incorporated in the atmospheric model to retrieve the abundance profile of H 12C 14N, H 13CN and HC 15N from their bands at 713, 706 and 711 cm -1, respectively. The HCN abundance profile was retrieved in the range 90-460 km at 15° S and 165-305 km at 83° N. There is no evidence for vertical variations of the isotopic ratios. Constraining the isotopic abundance profiles to be proportional to the HCN one, we find C12/C13=89-18+22 at 15° S, and 68-12+16 at 83° N, two values that are statistically consistent. A combination of these results yields a 12C/ 13C value equal to 75±12. This global result, as well as the 15° S one, envelop the value in Titan's methane ( 82.3±1) [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779-784] measured at 10° S and is slightly lower than the terrestrial inorganic standard value (89). The 14N/ 15N isotopic ratio is found equal to 56-13+16 at 15° S and 56-9+10 at 83° N. Combining the two values yields 14N/ 15N = 56 ± 8, which corresponds to an enrichment in 15N of about 4.9 compared with the terrestrial ratio. These results agree with the values obtained from previous ground-based millimeter observations [Hidayat, T., Marten, A., Bézard, B., Gautier, D., Owen, T., Matthews, H.E., Paubert, G., 1997. Icarus 126, 170-182; Marten, A., Hidayat, T., Biraud, Y., Moreno, R., 2002. Icarus 158, 532-544]. The 15N/ 14N ratio found in HCN is ˜3 times higher than in N 2 [Niemann, H.B., and 17 colleagues, 2005. Nature 438, 779

  13. Achievement of 1020MHz NMR.

    PubMed

    Hashi, Kenjiro; Ohki, Shinobu; Matsumoto, Shinji; Nishijima, Gen; Goto, Atsushi; Deguchi, Kenzo; Yamada, Kazuhiko; Noguchi, Takashi; Sakai, Shuji; Takahashi, Masato; Yanagisawa, Yoshinori; Iguchi, Seiya; Yamazaki, Toshio; Maeda, Hideaki; Tanaka, Ryoji; Nemoto, Takahiro; Suematsu, Hiroto; Miki, Takashi; Saito, Kazuyoshi; Shimizu, Tadashi

    2015-07-01

    We have successfully developed a 1020MHz (24.0T) NMR magnet, establishing the world's highest magnetic field in high resolution NMR superconducting magnets. The magnet is a series connection of LTS (low-Tc superconductors NbTi and Nb3Sn) outer coils and an HTS (high-Tc superconductor, Bi-2223) innermost coil, being operated at superfluid liquid helium temperature such as around 1.8K and in a driven-mode by an external DC power supply. The drift of the magnetic field was initially ±0.8ppm/10h without the (2)H lock operation; it was then stabilized to be less than 1ppb/10h by using an NMR internal lock operation. The full-width at half maximum of a (1)H spectrum taken for 1% CHCl3 in acetone-d6 was as low as 0.7Hz (0.7ppb), which was sufficient for solution NMR. On the contrary, the temporal field stability under the external lock operation for solid-state NMR was 170ppb/10h, sufficient for NMR measurements for quadrupolar nuclei such as (17)O; a (17)O NMR measurement for labeled tri-peptide clearly demonstrated the effect of high magnetic field on solid-state NMR spectra. PMID:25978708

  14. THz Dynamic Nuclear Polarization NMR

    PubMed Central

    Nanni, Emilio A.; Barnes, Alexander B.; Griffin, Robert G.; Temkin, Richard J.

    2013-01-01

    Dynamic nuclear polarization (DNP) increases the sensitivity of nuclear magnetic resonance (NMR) spectroscopy by using high frequency microwaves to transfer the polarization of the electrons to the nuclear spins. The enhancement in NMR sensitivity can amount to a factor of well above 100, enabling faster data acquisition and greatly improved NMR measurements. With the increasing magnetic fields (up to 23 T) used in NMR research, the required frequency for DNP falls into the THz band (140–600 GHz). Gyrotrons have been developed to meet the demanding specifications for DNP NMR, including power levels of tens of watts; frequency stability of a few megahertz; and power stability of 1% over runs that last for several days to weeks. Continuous gyrotron frequency tuning of over 1 GHz has also been demonstrated. The complete DNP NMR system must include a low loss transmission line; an optimized antenna; and a holder for efficient coupling of the THz radiation to the sample. This paper describes the DNP NMR process and illustrates the THz systems needed for this demanding spectroscopic application. THz DNP NMR is a rapidly developing, exciting area of THz science and technology. PMID:24639915

  15. A quantum dynamical study of CH overtones in fluoroform. II. Eigenstate analysis of the vCH = 1 and vCH = 2 regions

    NASA Astrophysics Data System (ADS)

    Maynard, Andrew; Wyatt, Robert E.; Iung, Christopher

    1997-06-01

    In this series, the multiple time scales and mechanisms of intramolecular vibrational-energy redistribution (IVR) present in the CH overtones of fluoroform is investigated. In part II, we analyze the ab initio vibrational spectrum and dynamics of the vCH=1 and vCH=2 regions, explicitly treating all vibrational degrees of freedom. A wave operator sorting algorithm is used to develop an efficient vibrational basis. Spectral transformation, by a filtered-Lanczos method, is used to accelerate eigenstate analysis. The theoretical spectrum of the fundamental is nontrivial, predicting a close triplet of lines (width <6 cm-1) centered at 3048.3 cm-1 and a weak line 20 cm-1 upfield, due to coupling with a small subsystem of background modes: ν4±+ν5±+ν6±, ν2+ν4±+ν6±, and ν3+2ν5. Furthermore, these background states mix with one another and other nearby background states via resonances ω5≈(ω3+ω6), ω2≈ω5, and (ω4+ω6)≈(ω3+ω5). An effective Hamiltonian is used to assess chromophore-background and background-background coupling. In contrast, the first overtone exhibits no strong background resonances, rather the background modes function as a weakly coupled reservoir. IVR time scales and eigenstate convergence, with respect to the active space, are presented.

  16. Non-Linear Thermal Lens Signal of the (Δυ = 6) C-H Vibrational Overtone of Benzene in Liquid Solutions of Hexane

    NASA Astrophysics Data System (ADS)

    Nyaupane, Parashu R.; Manzanares, Carlos

    2016-06-01

    The thermal lens technique is applied to vibrational overtone spectroscopy of solutions of benzene. The pump and probe thermal lens technique has been found to be very sensitive for detecting samples of low concentration in transparent solvents. The C-H fifth vibrational (Δυ = 6) overtone spectrum of benzene is detected at room temperature for compositions per volume in the range (1 to 1× 10-4) using n-C_6H14 as the solvent. By detecting the absorption band in a 100 ppm solution, the peak absorption of the signal is approximately (2.2 ± 0.3)× 10-7 cm-1. The parameters that determine the magnitude of the thermal lens signal such as the pump laser power and the thermodynamic properties of the solvent and solute are discussed. A plot of normalized integrated intensity as a function of composition of benzene in solution reveals a non-linear behavior. The non-linearity cannot be explained assuming solvent enhancement at low concentrations. A two color absorption model that includes the simultaneous absorption of the pump and probe lasers could explain the enhanced magnitude and the non-linear behavior of the thermal lens signal for solutions of composition below 0.01.

  17. Determination of the delta(15N/14N)of Ammonium (NH4+) in Water: RSIL Lab Code 2898

    USGS Publications Warehouse

    Hannon, Janet E.; Böhlke, John Karl

    2008-01-01

    The purpose of the technique described by Reston Stable Isotope Laboratory (RSIL) lab code 2898 is to determine the N isotopic composition, delta(15N/14N), abbreviated as d15N, of ammonium (NH4+) in water (freshwater and saline water). The procedure involves converting dissolved NH4+ into NH3 gas by raising the pH of the sample to above 9 with MgO and subsequently trapping the gas quantitatively as (NH4)2SO4 on a glass fiber (GF) filter. The GF filter is saturated with NaHSO4 and pressure sealed between two gas-permeable polypropylene filters. The GF filter 'sandwich' floats on the surface of the water sample in a closed bottle. NH3 diffuses from the water through the polypropylene filter and reacts with NaHSO4, forming (NH4)2SO4 on the GF filter. The GF filter containing (NH4)2SO4 is dried and then combusted with a Carlo Erba NC 2500 elemental analyzer (EA), which is used to convert total nitrogen in a solid sample into N2 gas. The EA is connected to a continuous-flow isotope-ratio mass spectrometer (CF-IRMS), which determines the relative difference in ratios of the amounts of the stable isotopes of nitrogen (15N and 14N) of the product N2 gas and a reference N2 gas. The filters containing the samples are compressed in tin capsules and loaded into a Costech Zero-Blank Autosampler on the EA. Under computer control, samples then are dropped into a heated reaction tube that contains an oxidant, where combustion takes place in a He atmosphere containing an excess of O2 gas. To remove S-O gases produced from the NaHSO4, a plug of Ag-coated Cu wool is inserted at the bottom of the reaction tube. Combustion products are transported by a He carrier through a reduction furnace to remove excess O2, toconvert all nitrogen oxides to N2, and to remove any remaining S-O gases. The gases then pass through a drying tube to remove water. The gas-phase products, mainly N2 and a small amount of background CO2, are separated by a gas chromatograph (GC). The gas is then introduced

  18. Imaging the dynamical atmosphere of the red supergiant Betelgeuse in the CO first overtone lines with VLTI/AMBER

    NASA Astrophysics Data System (ADS)

    Ohnaka, K.; Weigelt, G.; Millour, F.; Hofmann, K.-H.; Driebe, T.; Schertl, D.; Chelli, A.; Massi, F.; Petrov, R.; Stee, Ph.

    2011-05-01

    Aims: We present one-dimensional aperture synthesis imaging of the red supergiant Betelgeuse (α Ori) with VLTI/AMBER. We reconstructed for the first time one-dimensional images in the individual CO first overtone lines. Our aim is to probe the dynamics of the inhomogeneous atmosphere and its time variation. Methods: Betelgeuse was observed between 2.28 and 2.31 μm with VLTI/AMBER using the 16-32-48 m telescope configuration with a spectral resolution up to 12 000 and an angular resolution of 9.8 mas. The good nearly one-dimensional uv coverage allows us to reconstruct one-dimensional projection images (i.e., one-dimensional projections of the object's two-dimensional intensity distributions). Results: The reconstructed one-dimensional projection images reveal that the star appears differently in the blue wing, line center, and red wing of the individual CO lines. The one-dimensional projection images in the blue wing and line center show a pronounced, asymmetrically extended component up to ~1.3 R⋆, while those in the red wing do not show such a component. The observed one-dimensional projection images in the lines can be reasonably explained by a model in which the CO gas within a region more than half as large as the stellar size is moving slightly outward with 0-5 km s-1, while the gas in the remaining region is infalling fast with 20-30 km s-1. A comparison between the CO line AMBER data taken in 2008 and 2009 shows a significant time variation in the dynamics of the CO line-forming region in the photosphere and the outer atmosphere. In contrast to the line data, the reconstructed one-dimensional projection images in the continuum show only a slight deviation from a uniform disk or limb-darkened disk. We derive a uniform-disk diameter of 42.05 ± 0.05 mas and a power-law-type limb-darkened disk diameter of 42.49 ± 0.06 mas and a limb-darkening parameter of (9.7 ± 0.5) × 10-2. This latter angular diameter leads to an effective temperature of 3690 ± 54 K

  19. Resonance Strength Measurement at Astrophysical Energies: The 17O(p,α)14N Reaction Studied via THM

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Rapisarda, G. G.; Mukhamedzhanov, A.; Irgaziev, B.; Tang, X. D.; Wischer, M.; Mrazek, J.; Kroha, V.

    2016-05-01

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on 17O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the 17O(p,α)14N reaction via the Trojan Horse Method by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. The mean value of the strengths obtained in the two measurements was calculated and compared with the direct data available in literature.

  20. Resonance strength measurement at astrophysical energies: The 17O(p,α)14N reaction studied via Trojan Horse Method

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Rapisarda, G. G.; Mukhamedzhanov, A.; Irgaziev, B.; Tang, X. D.; Wiescher, M.; Mrazek, J.; Kroha, V.

    2015-10-01

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on 17O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the 17O(p,α)14N reaction via the THM by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. Two measurements will be described and the experimental THM cross sections will be shown for both experiments.

  1. Diode laser spectroscopy of the fundamental bands of 12C14N, 13C14N, 12C15N, 13C15N free radicals in the ground 2 Sigma+ electronic state.

    PubMed

    Hübner, M; Castillo, M; Davies, P B; Röpcke, J

    2005-01-01

    Rotationally resolved spectra of the fundamental band of the CN free radical in four isotopic forms have been measured using tunable diode laser absorption spectroscopy. The source of the radical was a microwave discharge in a mixture of isotopically selected methane and nitrogen diluted with argon. The lines were measured to an accuracy of 5 x 10(-4) cm(-1) and fitted to the formula for the vibration rotation spectrum of a diatomic molecule, including quartic distortion constants. The band origins of each of the isotopomers from the five parameter fits were found to be 12C14N: 2042.42115(38) cm(-1), 13C14N: 2000.08479(23) cm(-1), 12C15N: 2011.25594(25) cm(-1), 13C15N: 1968.22093(33) cm(-1) with one standard deviation from the fit given in parenthesis. Some of the lines showed a resolved splitting due to the spin rotation interaction. This was averaged for fitting purposes. The average equilibrium internuclear distance derived from the upsilon = 0 and 1 rotational constants of the four isotopomers is 1.171800(6) A which is in good agreement with the value determined from microwave spectroscopy.

  2. Advanced NMR-based techniques for pore structure analysis of coal. Final project report

    SciTech Connect

    Smith, D.M.; Hua, D.W.

    1996-02-01

    During the 3 year term of the project, new methods have been developed for characterizing the pore structure of porous materials such as coals, carbons, and amorphous silica gels. In general, these techniques revolve around; (1) combining multiple techniques such as small-angle x-ray scattering (SAXS) and adsorption of contrast-matched adsorbates or {sup 129}Xe NMR and thermoporometry (the change in freezing point with pore size), (2) combining adsorption isotherms over several pressure ranges to obtain a more complete description of pore filling, or (3) applying NMR ({sup 129}Xe, {sup 14}N{sub 2}, {sup 15}N{sub 2}) techniques with well-defined porous solids with pores in the large micropore size range (>1 nm).

  3. Polarization transfer NMR imaging

    DOEpatents

    Sillerud, Laurel O.; van Hulsteyn, David B.

    1990-01-01

    A nuclear magnetic resonance (NMR) image is obtained with spatial information modulated by chemical information. The modulation is obtained through polarization transfer from a first element representing the desired chemical, or functional, information, which is covalently bonded and spin-spin coupled with a second element effective to provide the imaging data. First and second rf pulses are provided at first and second frequencies for exciting the imaging and functional elements, with imaging gradients applied therebetween to spatially separate the nuclei response for imaging. The second rf pulse is applied at a time after the first pulse which is the inverse of the spin coupling constant to select the transfer element nuclei which are spin coupled to the functional element nuclei for imaging. In a particular application, compounds such as glucose, lactate, or lactose, can be labeled with .sup.13 C and metabolic processes involving the compounds can be imaged with the sensitivity of .sup.1 H and the selectivity of .sup.13 C.

  4. Compact orthogonal NMR field sensor

    SciTech Connect

    Gerald, II, Rex E.; Rathke, Jerome W.

    2009-02-03

    A Compact Orthogonal Field Sensor for emitting two orthogonal electro-magnetic fields in a common space. More particularly, a replacement inductor for existing NMR (Nuclear Magnetic Resonance) sensors to allow for NMR imaging. The Compact Orthogonal Field Sensor has a conductive coil and a central conductor electrically connected in series. The central conductor is at least partially surrounded by the coil. The coil and central conductor are electrically or electro-magnetically connected to a device having a means for producing or inducing a current through the coil and central conductor. The Compact Orthogonal Field Sensor can be used in NMR imaging applications to determine the position and the associated NMR spectrum of a sample within the electro-magnetic field of the central conductor.

  5. NMR characterization of thin films

    DOEpatents

    Gerald II, Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2010-06-15

    A method, apparatus, and system for characterizing thin film materials. The method, apparatus, and system includes a container for receiving a starting material, applying a gravitational force, a magnetic force, and an electric force or combinations thereof to at least the starting material, forming a thin film material, sensing an NMR signal from the thin film material and analyzing the NMR signal to characterize the thin film of material.

  6. NMR characterization of thin films

    DOEpatents

    Gerald, II, Rex E.; Klingler, Robert J.; Rathke, Jerome W.; Diaz, Rocio; Vukovic, Lela

    2008-11-25

    A method, apparatus, and system for characterizing thin film materials. The method, apparatus, and system includes a container for receiving a starting material, applying a gravitational force, a magnetic force, and an electric force or combinations thereof to at least the starting material, forming a thin film material, sensing an NMR signal from the thin film material and analyzing the NMR signal to characterize the thin film of material.

  7. Optical pumping and xenon NMR

    SciTech Connect

    Raftery, M.D.

    1991-11-01

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

  8. Optical pumping and xenon NMR

    SciTech Connect

    Raftery, M.D.

    1991-11-01

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

  9. [Line intensities of upsilon2 perpendicular band and the change of intensities with temperature for H12C14N].

    PubMed

    Song, Xiao-Shu; Cheng, Xin-Lu; Yang, Xiang-Dong; Li, De-Hua; Ge, Su-Hong

    2008-04-01

    The total internal partition sums (TIPS) were calculated for H12C14N with the product approximation. For rotational partition sums Q(rot), the centrifugal distortion corrections were taken into account. The calculation method for the vibrational partition sums Q(vib) is the harmonic oscillator approximation. The line intensities of upsilon2 perpendicular band (0110-0000 transition) of H12C14N were calculated at normal temperatures and several high temperatures by using the calculated partition functions and experimental transition moment squared and Herman-Waills factor coefficients. Results showed that our line intensities data at 296 and 3 000 K are in excellent agreement with the data in HITRAN, which provide a strong support for the calculations of partition function and line intensity at high temperature. Thereby, the line intensities and spectral simulations of upsilon2 perpendicular band at the higher temperatures 4 000 and 5 000 K were presented and the chang in line intensities with the temperature was discussed. For those transitions corresponding to rotational quantum number J > or = 32 (including P, Q and R branch), the line intensities increase when temperature gradually increase from 296 K. The line intensities are up to the largest at around 1000 K and then weaken rapidly. For J < 32 (also including P, Q and R branch), the line intensities are the largest at 296 K and then weaken rapidly as temperature gradually increase. PMID:18619284

  10. The {sup 14}N(p,{gamma}){sup 15}O reaction studied with a composite germanium detector

    SciTech Connect

    Marta, M.; Bemmerer, D.; Formicola, A.; Gustavino, C.; Junker, M.; Broggini, C.; Menegazzo, R.; Rossi Alvarez, C.; Caciolli, A.; Corvisiero, P.; Costantini, H.; Lemut, A.; Prati, P.; Elekes, Z.; Fueloep, Zs.; Gyuerky, Gy.; Somorjai, E.; Gervino, G.; Guglielmetti, A.; Mazzocchi, C.

    2011-04-15

    The rate of the carbon-nitrogen-oxygen (CNO) cycle of hydrogen burning is controlled by the {sup 14}N(p,{gamma}){sup 15}O reaction. The reaction proceeds by capture to the ground states and several excited states in {sup 15}O. In order to obtain a reliable extrapolation of the excitation curve to astrophysical energy, fits in the R-matrix framework are needed. In an energy range that sensitively tests such fits, new cross-section data are reported here for the four major transitions in the {sup 14}N(p,{gamma}){sup 15}O reaction. The experiment has been performed at the Laboratory for Underground Nuclear Astrophysics (LUNA) 400-kV accelerator placed deep underground in the Gran Sasso facility in Italy. Using a composite germanium detector, summing corrections have been considerably reduced with respect to previous studies. The cross sections for capture to the ground state and to the 5181, 6172, and 6792 keV excited states in {sup 15}O have been determined at 359, 380, and 399 keV beam energy. In addition, the branching ratios for the decay of the 278-keV resonance have been remeasured.

  11. Automated protein NMR resonance assignments.

    PubMed

    Wan, Xiang; Xu, Dong; Slupsky, Carolyn M; Lin, Guohui

    2003-01-01

    NMR resonance peak assignment is one of the key steps in solving an NMR protein structure. The assignment process links resonance peaks to individual residues of the target protein sequence, providing the prerequisite for establishing intra- and inter-residue spatial relationships between atoms. The assignment process is tedious and time-consuming, which could take many weeks. Though there exist a number of computer programs to assist the assignment process, many NMR labs are still doing the assignments manually to ensure quality. This paper presents (1) a new scoring system for mapping spin systems to residues, (2) an automated adjacency information extraction procedure from NMR spectra, and (3) a very fast assignment algorithm based on our previous proposed greedy filtering method and a maximum matching algorithm to automate the assignment process. The computational tests on 70 instances of (pseudo) experimental NMR data of 14 proteins demonstrate that the new score scheme has much better discerning power with the aid of adjacency information between spin systems simulated across various NMR spectra. Typically, with automated extraction of adjacency information, our method achieves nearly complete assignments for most of the proteins. The experiment shows very promising perspective that the fast automated assignment algorithm together with the new score scheme and automated adjacency extraction may be ready for practical use. PMID:16452794

  12. The MACHO Project Large Magellanic Cloud Variable Star Inventory. XIII. Fourier Parameters for the First Overtone RR Lyrae Variables and the LMC Distance

    SciTech Connect

    Alcock, C; Alves, D; Axelrod, T; Becker, A; Bennett, D; Clement, C; Cook, K; Drake, A; Freeman, K; Geha, M; Griest, K; Lehner, M; Marshall, S; Minniti, D; Muzzin, A; Nelson, C; Peterson, B; Popowski, P; Pratt, M; Quinn, P; Rodgers, A; Rowe, J; Sutherland, W; Vandehei, T; Welch, D

    2003-12-31

    Shapes of RR Lyrae light curves can be described in terms of Fourier coefficients which past research has linked with physical characteristics such as luminosity, mass and temperature. Fourier coefficients have been derived for the V and R light curves of 785 overtone RR Lyrae variables in 16 MACHO fields near the bar of the LMC. In general, the Fourier phase differences {phi}{sub 21}, {phi}{sub 31} and {phi}{sub 41} increase and the amplitude ratio R{sub 21} decreases with increasing period. The coefficients for both the V and R magnitudes follow these patterns, but the phase differences for the R curves are on average slightly greater, and their amplitudes are about 20% smaller, than the ones for the V curves. The {phi}{sub 31} and R{sub 21} coefficients have been compared with those of the first overtone RR Lyrae variables in the Galactic globular clusters NGC 6441, M107, M5, M3, M2, {omega} Centauri and M68. The results indicate that many of the LMC variables have properties similar to the ones in M2, M3, M5 and the Oosterhoff type I variables in {omega} Cen, but they are different from the Oosterhoff type II variables in {omega} Cen. Equations derived from hydrodynamic pulsation models have been used to calculate the luminosity and temperature for the 330 bona fide first-overtone variables. The results indicate that they have Log L in the range 1.6 to 1.8 L{sub {center_dot}} and log T{sub eff} between 3.85 and 3.87. Based on these temperatures, a mean color excess E(V-R) = 0.08 mag, equivalent to E(B-V) = 0.14 mag, has been estimated for these 330 stars. The 80 M5-like variables (selected according to their location in the {phi}{sub 31} - log P plot) are used to determine an LMC distance. After correcting for the effects of extinction and crowding, a mean apparent magnitude < V{sub 0} > = 18.99 {+-} 0.02 (statistical) {+-} 0.16 (systematic) has been estimated for these 80 stars. Combining this with a mean absolute magnitude M{sub V} = 0.56 {+-} 0.06 for M5

  13. Polarity-inverted ScAlN film growth by ion beam irradiation and application to overtone acoustic wave (000-1)/(0001) film resonators

    SciTech Connect

    Suzuki, Masashi; Yanagitani, Takahiko; Odagawa, Hiroyuki

    2014-04-28

    Polarity inversion in wurtzite film is generally achieved by the epitaxial growth on a specific under-layer. We demonstrate polarity inversion of c-axis oriented ScAlN films by substrate ion beam irradiation without using buffer layer. Substrate ion beam irradiation was induced by either sputtering a small amount of oxide (as a negative ion source) onto the cathode or by applying a RF bias to the substrate. Polarity of the films was determined by a press test and nonlinear dielectric measurement. Second overtone thickness extensional mode acoustic resonance and suppression of fundamental mode resonance, indicating complete polarity inversion, were clearly observed in bilayer highly oriented (000-1)/(0001) ScAlN film.

  14. The isotropic spectrum of the CO2 Raman 2ν3 overtone: a line-mixing band shape analysis at pressures up to several tens of atmospheres.

    PubMed

    Verzhbitskiy, I A; Kouzov, A P; Rachet, F; Chrysos, M

    2011-06-14

    A line-mixing shape analysis of the isotropic remnant Raman spectrum of the 2ν(3) overtone of CO(2) is reported at room temperature and for densities, ρ, rising up to tens of amagats. The analysis, experimental and theoretical, employs tools of non-resonant light scattering spectroscopy and uses the extended strong collision model (ESCM) to simulate the strong line mixing effects and to evidence motional narrowing. Excellent agreement at any pressure is observed between the calculated spectra and our experiment, which, along with the easy numerical implementation of the ESCM, makes this model stand out clearly above other semiempirical models for band shape calculations. The hitherto undefined, explicit ρ-dependence of the vibrational relaxation rate is given. Our study intends to improve the understanding of pressure-induced phenomena in a gas that is still in the forefront of the news.

  15. Collision-induced infrared spectra of H2-He pairs at temperatures from 18 to 7000 K. II. Overtone and hot bands

    SciTech Connect

    Borysow, A.; Frommhold, L.; Texas Univ., Austin )

    1989-06-01

    The three lowest spectral moments of the collision induced absorption (CIA) spectra of H2-He pairs have been computed from first principles for temperatures T from 18 to 7000 K for a number of hydrogen overtone and hot bands involving vibrational quantum numbers nu = 0, 1, 2, 3 yields nu-prime = 0, 1, 2, 3. The data are given in a form suitable for the computation of CIA spectra of H2-He as function of frequency and temperature, using simple computer codes and model line shapes. The work is of interest for the spectroscopy of the atmospheres of the outer planets and of stars that contain neutral molecular hydrogen and helium (late stars, white dwarfs, and Population II stars) in the infrared and visible region of the spectrum. 13 refs.

  16. Study of the ferroelastic phase transition in the tetraethylammonium compound [N(C2H5)4]2ZnBr4 by magic-angle spinning and static NMR

    NASA Astrophysics Data System (ADS)

    Lim, Ae Ran

    2016-03-01

    The ferroelastic phase transition of tetraethylammonium compound [N(C2H5)4]2ZnBr4 at the phase transition temperature (TC) = 283 K was characterized by magic-angle spinning (MAS) and static nuclear magnetic resonance (NMR), and confirmed by optical polarizing spectroscopy. The structural geometry near TC was studied in terms of the chemical shifts and the spin-lattice relaxation times T1ρ in the rotating frame for 1H MAS NMR and 13C cross-polarization (CP)/MAS NMR. The two inequivalent ethyl groups were distinguishable in the 13C NMR spectrum, and the T1ρ results indicate that they undergo tumbling motion above TC in a coupled manner. From the 14N NMR results, the two nitrogen nuclei in the N(C2H5)4+ ions were distinguishable above TC, and the splitting in the spectra below TC was related to the ferroelastic domains with different orientations.

  17. The ARAUCARIA project. OGLE-LMC-CEP-1718: An exotic eclipsing binary system composed of two classical overtone cepheids in a 413 day orbit

    SciTech Connect

    Gieren, Wolfgang; Pilecki, Bogumił; Pietrzyński, Grzegorz; Graczyk, Dariusz; Gallenne, Alexandre E-mail: pietrzyn@astrouw.edu.pl E-mail: dgallenne@astro-udec.cl; and others

    2014-05-10

    We have obtained extensive high-quality spectroscopic observations of the OGLE-LMC-CEP-1718 eclipsing binary system in the Large Magellanic Cloud that Soszyński et al. had identified as a candidate system for containing two classical Cepheids in orbit. Our spectroscopic data clearly demonstrate binary motion of the Cepheids in a 413 day eccentric orbit, rendering this eclipsing binary system the first ever known to consist of 2 classical Cepheid variables. After disentangling the four different radial velocity variations in the system, we present the orbital solution and the individual pulsational radial velocity curves of the Cepheids. We show that both Cepheids are extremely likely to be first overtone pulsators and determine their respective dynamical masses, which turn out to be equal to within 1.5%. Since the secondary eclipse is not observed in the orbital light curve, we cannot derive the individual radii of the Cepheids, but the sum of their radii derived from the photometry is consistent with overtone pulsation for both variables. The existence of two equal-mass Cepheids in a binary system having different pulsation periods (1.96 and 2.48 days, respectively) may pose an interesting challenge to stellar evolution and pulsation theories, and a more detailed study of this system using additional data sets should yield deeper insight about the physics of stellar evolution of Cepheid variables. Future analysis of the system using additional near-infrared photometry might also lead to a better understanding of the systematic uncertainties in current Baade-Wesselink techniques of distance determinations to Cepheid variables.

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

    SciTech Connect

    Matwiyoff, N.A.

    1983-01-01

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

  19. jsNMR: an embedded platform-independent NMR spectrum viewer.

    PubMed

    Vosegaard, Thomas

    2015-04-01

    jsNMR is a lightweight NMR spectrum viewer written in JavaScript/HyperText Markup Language (HTML), which provides a cross-platform spectrum visualizer that runs on all computer architectures including mobile devices. Experimental (and simulated) datasets are easily opened in jsNMR by (i) drag and drop on a jsNMR browser window, (ii) by preparing a jsNMR file from the jsNMR web site, or (iii) by mailing the raw data to the jsNMR web portal. jsNMR embeds the original data in the HTML file, so a jsNMR file is a self-transforming dataset that may be exported to various formats, e.g. comma-separated values. The main applications of jsNMR are to provide easy access to NMR data without the need for dedicated software installed and to provide the possibility to visualize NMR spectra on web sites.

  20. NMR planar microcoil for microanalysis

    NASA Astrophysics Data System (ADS)

    Sorli, B.; Chateaux, J. F.; Quiquerez, L.; Bouchet-Fakri, L.; Briguet, A.; Morin, P.

    2006-11-01

    This article deals with the analysis of small sample volume by using a planar microcoil and a micromachined cavity. This microcoil is used as a nuclear magnetic resonance (NMR) radio frequency detection coil in order to perform in vitro NMR analysis of the sample introduced into the microcavity. It is a real challenging task to develop microsystem for NMR spectrum extraction for smaller and smaller sample volume. Moreover, it is advantageous that these microsystems could be integrated in a Micro Total Analysing System (μ -TAS) as an analysing tool. In this paper, NMR theory, description, fabrication process and electrical characterization of planar microcoils receiver are described. Results obtained on NMR microspectroscopy experiments have been performed on water and ethanol, using a 1 mm diameter planar coil. This microcoil is tuned and matched at 85.13 MHz which is the Larmor frequency of proton in a 2 T magnetic field. This paper has been presented at “3e colloque interdisciplinaire en instrumentation (C2I 2004)”, École Normale Supérieure de Cachan, 29 30 janvier 2004.

  1. NMR characterization of shocked quartz

    SciTech Connect

    Boslough, M.B.; Cygan, R.T.; Assink, R.A.; Kirkpatrick, R.J.

    1994-03-01

    We have characterized experimentally and naturally-shocked quartz (both synthetic and natural samples) by solid state nuclear magnetic resonance (NMR) spectroscopy. Relaxation analysis of experimentally-shocked samples provides a means for quantitative characterization of the amorphous/disordered silica component NMR spectra demonstrate that magnetization in both the amorphous and crystalline components follows power-law behavior as a function of recycle time. This observation is consistent with the relaxation of nuclear spins by paramagnetic impurities. A fractal dimension can be extracted from the power-law exponent associated with each phase, and relative abundances can be extracted from integrated intensities of deconvolved peaks. NMR spectroscopy of naturally-shocked sandstone from Meteor Crater, Arizona (USA) led to the discovery of a new amorphous hydroxylated silica phase. Solid state NMR spectra of both experimentally and naturally shocked quartz were unexpectedly rich in microstructural information, especially when combined with relaxation analysis and cross-polarization studies. We suggest solid state NMR as a potentially useful tool for examining shock-induced microstructural changes in other inorganic compounds, with possible implications for shock processing of structural ceramics.

  2. Cross sections for n+{sup 14}N from an R-matrix analysis of the {sup 15}N system

    SciTech Connect

    Hale, G.M.; Young, P.G.; Chadwick, M.B.

    1994-06-01

    As part of the Hiroshima-Nagasaki Dose Reevaluation Program, a new evaluation of the neutron cross sections for {sup 14}N was made for ENDF/B-VI, based at energies below 2.5 MeV on a multichannel R-matrix analysis of reactions in the {sup 15}N system. The types of data used in the analysis, and the resulting cross sections and resonance structure for {sup 15}N are briefly described. The resonant features of the neutron cross sections were especially well determined by including precise, high-resolution neutron total cross section measurements from ORNL. While the new evaluated cross section appear to be significant improvements over the earlier ones, they still need to be tested more extensively against recent measurements of the differential elastic cross section from Oak Ridge.

  3. Solution NMR conformation of glycosaminoglycans.

    PubMed

    Pomin, Vitor H

    2014-04-01

    Nuclear magnetic resonance (NMR) spectroscopy has been giving a pivotal contribution to the progress of glycomics, mostly by elucidating the structural, dynamical, conformational and intermolecular binding aspects of carbohydrates. Particularly in the field of conformation, NOE resonances, scalar couplings, residual dipolar couplings, and chemical shift anisotropy offsets have been the principal NMR parameters utilized. Molecular dynamics calculations restrained by NMR-data input are usually employed in conjunction to generate glycosidic bond dihedral angles. Glycosaminoglycans (GAGs) are a special class of sulfated polysaccharides extensively studied worldwide. Besides regulating innumerous physiological processes, these glycans are also widely explored in the global market as either clinical or nutraceutical agents. The conformational aspects of GAGs are key regulators to the quality of interactions with the functional proteins involved in biological events. This report discusses the solution conformation of each GAG type analyzed by one or more of the above-mentioned methods.

  4. Advanced NMR characterization of zeolite catalysts

    NASA Astrophysics Data System (ADS)

    Welsh, L. B.

    1985-04-01

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

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

    NASA Astrophysics Data System (ADS)

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

    2013-01-01

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

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

    ERIC Educational Resources Information Center

    Cavaleiro, Jose A. S.

    1987-01-01

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

  7. Push-through Direction Injectin NMR Automation

    EPA Science Inventory

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

  8. NMR investigations of molecular dynamics

    NASA Astrophysics Data System (ADS)

    Palmer, Arthur

    2011-03-01

    NMR spectroscopy is a powerful experimental approach for characterizing protein conformational dynamics on multiple time scales. The insights obtained from NMR studies are complemented and by molecular dynamics (MD) simulations, which provide full atomistic details of protein dynamics. Homologous mesophilic (E. coli) and thermophilic (T. thermophilus) ribonuclease H (RNase H) enzymes serve to illustrate how changes in protein sequence and structure that affect conformational dynamic processes can be monitored and characterized by joint analysis of NMR spectroscopy and MD simulations. A Gly residue inserted within a putative hinge between helices B and C is conserved among thermophilic RNases H, but absent in mesophilic RNases H. Experimental spin relaxation measurements show that the dynamic properties of T. thermophilus RNase H are recapitulated in E. coli RNase H by insertion of a Gly residue between helices B and C. Additional specific intramolecular interactions that modulate backbone and sidechain dynamical properties of the Gly-rich loop and of the conserved Trp residue flanking the Gly insertion site have been identified using MD simulations and subsequently confirmed by NMR spin relaxation measurements. These results emphasize the importance of hydrogen bonds and local steric interactions in restricting conformational fluctuations, and the absence of such interactions in allowing conformational adaptation to substrate binding.

  9. Deuterium Exchange Kinetics by NMR.

    ERIC Educational Resources Information Center

    Roper, G. C.

    1985-01-01

    Describes a physical chemistry experiment which allows such concepts as kinetics, catalysis, isotope shifts, coupling constants, and the use of nuclear magnetic resonance (NMR) for quantitative work to be covered in the same exercise. Background information, experimental procedures used, and typical results obtained are included. (JN)

  10. Petrophysical applications of NMR imaging

    SciTech Connect

    Rothwell, W.P.; Vinegar, H.J.

    1985-12-01

    A system for obtaining high-resolution NMR images of oil field cores is described. Separate proton density and T/sub 2/ relaxation images are obtained to distinguish spatial variations of fluid-filled porosity and the physical nature of the pores. Results are presented for typical sandstones.

  11. THM determination of the 65 keV resonance strength intervening in the {sup 17}O(p,α){sup 14}N reaction rate

    SciTech Connect

    Sergi, M. L.; La Cognata, M.; Pizzone, R. G.; Spitaleri, C.; Cherubini, S.; Puglia, S. M. R.; Rapisarda, G. G.; Romano, S.; Burjan, S. V.; Hons, Z.; Kroha, V.; Coc, A.; Hammache, F.; Irgaziev, B.; Kiss, G. G.; Somorjai, E.; Lamia, L.; Mukhamedzhanov, A.; and others

    2015-02-24

    The {sup 17}O(p,α){sup 14}N reaction is of paramount importance for the nucleosynthesis in a number of stellar sites, including red giants (RG), asymptotic giant branch (AGB) stars, massive stars and classical novae. We report on the indirect study of the {sup 17}O(p,α){sup 14}N reaction via the Trojan Horse Method by applying the approach recently developed for extracting the resonance strength of the narrow resonance at E{sub c.m.}{sup R} = 65 keV (E{sub X} =5.673 MeV). The strength of the 65 keV resonance in the {sup 17}O(p,α){sup 14}N reaction, measured by means of the THM, has been used to renormalize the corresponding resonance strength in the {sup 17}O+p radiative capture channel.

  12. Resonance strengths in the {sup 14}N(p,gamma){sup 15}O and {sup 15}N(p,alphagamma){sup 12}C reactions

    SciTech Connect

    Marta, Michele; Trompler, Erik; Bemmerer, Daniel; Beyer, Roland; Grosse, Eckart; Hannaske, Roland; Junghans, Arnd R.; Nair, Chithra; Schwengner, Ronald; Wagner, Andreas; Yakorev, Dmitry; Broggini, Carlo; Caciolli, Antonio; Erhard, Martin; Menegazzo, Roberto; Fueloep, Zsolt; Gyuerky, Gyoergy; Szuecs, Tamas; Vezzu, Simone

    2010-05-15

    The {sup 14}N(p,gamma){sup 15}O reaction is the slowest reaction of the carbon-nitrogen-oxygen cycle of hydrogen burning in stars. As a consequence, it determines the rate of the cycle. The {sup 15}N(p,alphagamma){sup 12}C reaction is frequently used in inverse kinematics for hydrogen depth profiling in materials. The {sup 14}N(p,gamma){sup 15}O and {sup 15}N(p,alphagamma){sup 12}C reactions have been studied simultaneously, using titanium nitride targets of natural isotopic composition and a proton beam. The strengths of the resonances at E{sub p} = 1058 keV in {sup 14}N(p,gamma){sup 15}O and at E{sub p} = 897 and 430 keV in {sup 15}N(p,alphagamma){sup 12}C have been determined with improved precision, relative to the well-known resonance at E{sub p} = 278 keV in {sup 14}N(p,gamma){sup 15}O. The new recommended values are omegagamma=0.353+-0.018, 362+-20, and 21.9+-1.0 eV for their respective strengths. In addition, the branching ratios for the decay of the E{sub p} = 1058 keV resonance in {sup 14}N(p,gamma){sup 15}O have been redetermined. The data reported here should facilitate future studies of off-resonant capture in the {sup 14}N(p,gamma){sup 15}O reaction that are needed for an improved R-matrix extrapolation of the cross section. In addition, the data on the 430 keV resonance in {sup 15}N(p,alphagamma){sup 12}C may be useful for hydrogen depth profiling.

  13. 15N/14N Variation in CalCOFI Zooplankton: A 51 year history of Marine Nitrogen Dynamics and Climate Variability off Central California

    NASA Astrophysics Data System (ADS)

    Rau, G. H.; Ohman, M. D.; Pierrot-Bults, A.

    2003-12-01

    Long-term variability in marine zooplankton 15N/14N was investigated in two species of calanoid copepods (Calanus pacificus and Eucalanus californicus) and two chaetognaths (Sagitta bierii and Sagitta euneritica) sampled in the spring of selected years from 1951 to 2001 near Monterey Bay, California. No statistically significant trend in 15N/14N was detected for any of the four species, with isotopic ratios in 2001 resembling those in copepods and chaetognaths sampled from the same area five decades earlier. With respect to proposed oceanographic regime shifts in this region, heterogeneity in 15N/14N was detected only for S. bierii when comparing the periods 1951-1975, 1978-1998, and 1999-2001. In this species the 15N/14N in the most recent, brief period (1999-2001) averaged slightly lower than in the previous period. Three of the four species (C. pacificus, S. bierii, and S. euneritica) showed significant increases in 15N/14N during major El Ninos. El Nino-related enrichment in 15N could arise as a consequence of increased nitrate demand/supply at the base of the food web or advection of 15N-enriched nitrate from more southerly waters. While a range of physical and climate indices were evaluated, anomalies of 15N/14N from the long-term mean were found to be significantly related only to; i) the Southern Oscillation Index in the case of both chaetognath species, ii) a regional surface water temperature record (S. bierii only), iii) an index of wind-driven coastal upwelling for the surface-dwelling C. pacificus, and iv) variability in the Pacific Decadal Oscillation for the somewhat deeper-dwelling E. californicus.

  14. Measurements of 12C/13C, 14N/15N, and 32S/34S ratios in comet Hale-Bopp (C/1995 O1).

    PubMed

    Jewitt, D C; Matthews, H E; Owen, T; Meier, R

    1997-10-01

    The 12C/13C, 14N/15N, and 32S/34S isotope ratios in comet Hale-Bopp (C/1995 O1) were determined through observations taken with the James Clerk Maxwell Telescope. Measurements of rare isotopes in HCN and CS revealed isotope ratios of H12CN/H13CN = 111 +/- 12, HC14N/HC15N = 323 +/- 46, and C32S/C34S = 27 +/- 3. Within the measurement uncertainties, the isotopic ratios are consistent with solar system values. The cometary volatiles thus have an origin in the solar system and show no evidence for an interstellar component.

  15. Steps Toward Experimental Detection of Molecular Parity Violation: Rovibrational Analysis of the Cf-Stretching Mode and First Overtone of CHFBrI

    NASA Astrophysics Data System (ADS)

    Albert, S.; Albert, K. K.; Quack, M.; Bauerecker, S.

    2009-06-01

    The experimental detection of molecular parity violation Δ_{PV}E is of great interest because of its importance in the understanding of fundamental aspects of molecular dynamics and symmetries. One possible method for this is measuring the rovibrational or rotational frequency shifts in the infrared or microwave spectra of enantiomers. A value of 50 mHz is predicted for vibrational frequency shifts in CHFBrI, which is almost within the range of current infrared and submm wave spectroscopic resolution. We report here IR-spectroscopic results and a first high resolution analysis of the infrared spectrum of CHFBrI. The FTIR spectrum of CHFBrI was recorded at 190 K and 295 K in the regions 600-1300 cm^{-1} and 1800-2350 cm^{-1}. We were able to analyse the rovibrational spectra of CHF^{79}BrI (ν_0 = 1060.81569 cm^{-1}) and CHF^{81}BrI (ν_0 = 1060.77864 cm^{-1}) in the CF-stretching (ν_6) and its overtone regions with band centers ν_0 = 2103.75730 cm^{-1} for CHF^{79}BrI and ν_0 = 2103.65974 cm^{-1} for CHF^{81}BrI. We will discuss a possible application of CO_2 laser quasi-resonant two photon transitions in the overtone region of CHFBrI. Finally, we will show submm spectra of CHFBrI recorded with the Zürich-FASSST spectrometer and discuss how submm wave spectroscopy based on FASSST and phase-locked backward wave oscillators can be used to determine line shifts on the order of mHz. M. Quack, J. Stohner and M. Willeke, Annu. Rev. Phys. Chem. 2008, 59, 741, A. Bakasov, T.K. Ha and M. Quack, J. Chem. Phys. 1998, 109, 7263, R. Berger and M. Quack, J. Chem. Phys. 2000, 112, 3148. M. Quack and J. Stohner, PRL 2000, 84, 3807, M. Quack and J. Stohner. J. Chem. Phys. 2003, 119, 11228. J.K. Laerdahl, P. Schwerdtfeger and H.M. Quiney, PRL 2000, 84, 3811, R. Berger and J.L. Stuber, Mol. Phys. 2007, 105, 41. C. Daussy, T. Marrel, A. Amy-Klein, C. Nguyen, C. Borde and C. Chardonnet, Phys. Rev. Lett. 1999, 83, 1554 S. Albert and M. Quack, ChemPhysChem 2007, 8, 1271 D. T. Petkie

  16. Darling-Dennison resonance and Coriolis coupling in the bending overtones of the A 1A(u) state of acetylene, C2H2.

    PubMed

    Merer, Anthony J; Yamakita, Nami; Tsuchiya, Soji; Steeves, Adam H; Bechtel, Hans A; Field, Robert W

    2008-08-01

    Rotational analyses have been carried out for the overtones of the nu(4) (torsion) and nu(6) (in-plane cis-bend) vibrations of the A (1)A(u) state of C(2)H(2). The v(4)+v(6)=2 vibrational polyad was observed in high-sensitivity one-photon laser-induced fluorescence spectra and the v(4)+v(6)=3 polyad was observed in IR-UV double resonance spectra via the ground state nu(3) (Sigma(+) (u)) and nu(3)+nu(4) (Pi(u)) vibrational levels. The structures of these polyads are dominated by the effects of vibrational angular momentum: Vibrational levels of different symmetry interact via strong a-and b-axis Coriolis coupling, while levels of the same symmetry interact via Darling-Dennison resonance, where the interaction parameter has the exceptionally large value K(4466)=-51.68 cm(-1). The K-structures of the polyads bear almost no resemblance to the normal asymmetric top patterns, and many local avoided crossings occur between close-lying levels with nominal K-values differing by one or more units. Least squares analysis shows that the coupling parameters change only slightly with vibrational excitation, which has allowed successful predictions of the structures of the higher polyads: A number of weak bands from the v(4)+v(6)=4 and 5 polyads have been identified unambiguously. The state discovered by Scherer et al. [J. Chem. Phys. 85, 6315 (1986)], which appears to interact with the K=1 levels of the 3(3) vibrational state at low J, is identified as the second highest of the five K=1 members of the v(4)+v(6)=4 polyad. After allowing for the Darling-Dennison resonance, the zero-order bending structure can be represented by omega(4)=764.71, omega(6)=772.50, x(44)=0.19, x(66)=-4.23, and x(46)=11.39 cm(-1). The parameters x(46) and K(4466) are both sums of contributions from the vibrational angular momentum and from the anharmonic force field. For x(46) these contributions are 14.12 and -2.73 cm(-1), respectively, while the corresponding values for K(4466) are -28.24 and -23

  17. Differentiation of Pigment in Eggs Using Carbon ((13)C/(12)C) and Nitrogen ((15)N/(14)N) Stable Isotopes.

    PubMed

    Sun, Feng M; Shi, Guang Y; Wang, Hui W

    2016-07-01

    Consumers prefer natural and healthy food, but artificial pigments are often abused in egg products. The study aimed at differentiating the origin of pigments in eggs by applying the technique of carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) stable isotope analysis. Five hundred sixty laying hens were randomly distributed into 14 treatments, which were divided into four groups: maize, carophyll red pigment, carophyll yellow pigment, and a mixture of carophyll red and yellow pigments. Eggs were collected and pretreated to determe the values of the Roche Yolk Color Fan (RCF), δ(13)C, and δ(15)N. With increasing maize content, the RCF and δ(13)C values of yolks increased. Moreover, the RCF values in the three pigment groups were significantly influenced by the artificial colors, but δ(13)C values were not significantly different, regardless of the existence of pigment. The δ(15)N values in all treatments did not vary as regularly as the carbon stable isotope. A strong positive correlation was found between RCF and δ(13)C in the maize group, but no such correlation was be observed in the pigment groups. It is concluded that carbon stable isotope ratio analysis (δ(13)C) of the yolk can be used to differentiate the origin of the pigment added to eggs. PMID:27302905

  18. The Fundamental Quadrupole Band of (14)N2: Line Positions from High-Resolution Stratospheric Solar Absorption Spectra

    NASA Technical Reports Server (NTRS)

    Rinsland, C. P.; Zander, R.; Goldman, A.; Murcray, F. J.; Murcray, D. G.; Grunson, M. R.; Farmer, C. B.

    1991-01-01

    The purpose of this note is to report accurate measurements of the positions of O- and S-branch lines of the (1-0) vibration-rotation quadrupole band of molecular nitrogen ((14)N2) and improved Dunham coefficients derived from a simultaneous least-squares analysis of these measurements and selected infrared and far infrared data taken from the literature. The new measurements have been derived from stratospheric solar occultation spectra recorded with Fourier transform spectrometer (FTS) instruments operated at unapodized spectral resolutions of 0.002 and 0.01 /cm. The motivation for the present investigation is the need for improved N2 line parameters for use in IR atmospheric remote sensing investigations. The S branch of the N2 (1-0) quadrupole band is ideal for calibrating the line-of-sight airmasses of atmospheric spectra since the strongest lines are well placed in an atmospheric window, their absorption is relatively insensitive to temperature and is moderately strong (typical line center depths of 10 to 50% in high-resolution ground-based solar spectra and in lower stratospheric solar occultation spectra), and the volume mixing ratio of nitrogen is constant in the atmosphere and well known. However, a recent investigation has'shown the need to improve the accuracies of the N2 fine positions, intensities, air-broadened half-widths, and their temperature dependences to fully exploit this calibration capability (1). The present investigation addresses the problem of improving the accuracy of the N2 line positions.

  19. Radiative Neutron Capture on 9Be, 14C, 14N, 15N and 16O at Thermal and Astrophysical Energies

    NASA Astrophysics Data System (ADS)

    Dubovichenko, Sergey; Dzhazairov-Kakhramanov, Albert; Afanasyeva, Nadezhda

    2013-10-01

    The total cross-sections of the radiative neutron capture processes on 9Be, 14C, 14N, 15N and 16O are described in the framework of the modified potential cluster model with the classification of orbital states according to Young tableaux. The continued interest in the study of these reactions is due, on the one hand, to the important role played by this process in the analysis of many fundamental properties of nuclei and nuclear reactions, and, on the other hand, to the wide use of the capture cross-section data in the various applications of nuclear physics and nuclear astrophysics, and, also, to the importance of the analysis of primordial nucleosynthesis in the Universe. This article is devoted to the description of results for the processes of the radiative neutron capture on certain light atomic nuclei at thermal and astrophysical energies. The considered capture reactions are not part of stellar thermonuclear cycles, but involve in the reaction chains of inhomogeneous Big Bang models.

  20. First direct measurement of the 11C (α ,p )14N stellar reaction by an extended thick-target method

    NASA Astrophysics Data System (ADS)

    Hayakawa, S.; Kubono, S.; Kahl, D.; Yamaguchi, H.; Binh, D. N.; Hashimoto, T.; Wakabayashi, Y.; He, J. J.; Iwasa, N.; Kato, S.; Komatsubara, T.; Kwon, Y. K.; Teranishi, T.

    2016-06-01

    The 11C(α,p ) 14N reaction is an important α -induced reaction competing with β -limited hydrogen-burning processes in high-temperature explosive stars. We directly measured its reaction cross sections both for the ground-state transition (α ,p0) and the excited-state transitions (α ,p1) and (α ,p2) at relevant stellar energies 1.3-4.5 MeV by an extended thick-target method featuring time of flight for the first time. We revised the reaction rate by numerical integration including the (α ,p1) and (α ,p2) contributions and also low-lying resonances of (α ,p0) using both the present and the previous experimental data which were totally neglected in the previous compilation works. The present total reaction rate lies between the previous (α ,p0) rate and the total rate of the Hauser-Feshbach statistical model calculation, which is consistent with the relevant explosive hydrogen-burning scenarios such as the ν p process.

  1. Measurement of the Erc .m .=259 keV resonance in the 14N(p ,γ )15O reaction

    NASA Astrophysics Data System (ADS)

    Daigle, S.; Kelly, K. J.; Champagne, A. E.; Buckner, M. Q.; Iliadis, C.; Howard, C.

    2016-08-01

    The 14N(p ,γ )15O reaction regulates the power generated by the CN cycle and thus impacts the structure and evolution of every star at some point in its life. The lowest positive-energy resonance in this reaction is located at Erc .m .=259 keV, too high in energy to strongly influence quiescent stellar burning. However, the strength of this resonance is used as a cross-section normalization for lower-energy measurements of this reaction. We report on new measurements of the energy, strength, and γ -ray branching ratios for the 259-keV resonance, using different detection and data-analysis schemes. We have also reevaluated previous results, where possible. Our new recommended strength of ω γ =12.6 (3 ) meV is in agreement with the previous value of 13.1(6) meV, but is more precise and thus provides a more reliable normalization for low-energy (p ,γ ) measurements.

  2. INVESTIGATION OF MOLECULAR CLOUD STRUCTURE AROUND INFRARED BUBBLES: CARMA OBSERVATIONS OF N14, N22, AND N74

    SciTech Connect

    Sherman, Reid A.

    2012-11-20

    We present CARMA observations in 3.3 mm continuum and several molecular lines of the surroundings of N14, N22, and N74, three infrared bubbles from the GLIMPSE catalog. We have discovered 28 compact continuum sources and confirmed their associations with the bubbles using velocity information from HCO{sup +} and HCN. We have also mapped small-scale structures of N{sub 2}H{sup +} emission in the vicinity of the bubbles. By combining our data with survey data from GLIMPSE, MIPSGAL, BGPS, and MAGPIS, we establish about half of our continuum sources as star-forming cores. We also use survey data with the velocity information from our molecular line observations to describe the morphology of the bubbles and the nature of the fragmentation. We conclude from the properties of the continuum sources that N74 likely is at the near kinematic distance, which was previously unconfirmed. We also present tentative evidence of molecular clouds being more fragmented on bubble rims compared to dark clouds, suggesting that triggered star formation may occur, though our findings do not conform to a classic collect-and-collapse model.

  3. 15N/14N variations in Cretaceous Atlantic sedimentary sequences: implication for past changes in marine nitrogen biogeochemistry

    USGS Publications Warehouse

    Rau, G.H.; Arthur, M.A.; Dean, W.E.

    1987-01-01

    At two locations in the Atlantic Ocean (DSDP Sites 367 and 530) early to middle Cretaceous organic-carbon-rich beds ("black shales") were found to have significantly lower ??15N values (lower 15N/14N ratios) than adjacent organic-carbon-poor beds (white limestones or green claystones). While these lithologies are of marine origin, the black strata in particular have ??15N values that are significantly lower than those previously found in the marine sediment record and most contemporary marine nitrogen pools. In contrast, black, organic-carbon-rich beds at a third site (DSDP Site 603) contain predominantly terrestrial organic matter and have C- and N-isotopic compositions similar to organic matter of modern terrestrial origin. The recurring 15N depletion in the marine-derived Cretaceous sequences prove that the nitrogen they contain is the end result of an episodic and atypical biogeochemistry. Existing isotopic and other data indicate that the low 15N relative abundance is the consequence of pelagic rather than post-depositional processes. Reduced ocean circulation, increased denitrification, and, hence, reduced euphotic zone nitrate availability may have led to Cretaceous phytoplankton assemblages that were periodically dominated by N2-fixing blue-green algae, a possible source of this sediment 15N-depletion. Lack of parallel isotopic shifts in Cretaceous terrestrially-derived nitrogen (Site 603) argues that the above change in nitrogen cycling during this period did not extend beyond the marine environment. ?? 1987.

  4. Differentiation of Pigment in Eggs Using Carbon ((13)C/(12)C) and Nitrogen ((15)N/(14)N) Stable Isotopes.

    PubMed

    Sun, Feng M; Shi, Guang Y; Wang, Hui W

    2016-07-01

    Consumers prefer natural and healthy food, but artificial pigments are often abused in egg products. The study aimed at differentiating the origin of pigments in eggs by applying the technique of carbon ((13)C/(12)C) and nitrogen ((15)N/(14)N) stable isotope analysis. Five hundred sixty laying hens were randomly distributed into 14 treatments, which were divided into four groups: maize, carophyll red pigment, carophyll yellow pigment, and a mixture of carophyll red and yellow pigments. Eggs were collected and pretreated to determe the values of the Roche Yolk Color Fan (RCF), δ(13)C, and δ(15)N. With increasing maize content, the RCF and δ(13)C values of yolks increased. Moreover, the RCF values in the three pigment groups were significantly influenced by the artificial colors, but δ(13)C values were not significantly different, regardless of the existence of pigment. The δ(15)N values in all treatments did not vary as regularly as the carbon stable isotope. A strong positive correlation was found between RCF and δ(13)C in the maize group, but no such correlation was be observed in the pigment groups. It is concluded that carbon stable isotope ratio analysis (δ(13)C) of the yolk can be used to differentiate the origin of the pigment added to eggs.

  5. Monte Carlo assessment of soil moisture effect on high-energy thermal neutron capture gamma-ray by 14N.

    PubMed

    Pazirandeh, Ali; Azizi, Maryam; Farhad Masoudi, S

    2006-01-01

    Among many conventional techniques, nuclear techniques have shown to be faster, more reliable, and more effective in detecting explosives. In the present work, neutrons from a 5 Ci Am-Be neutron source being in water tank are captured by elements of soil and landmine (TNT), namely (14)N, H, C, and O. The prompt capture gamma-ray spectrum taken by a NaI (Tl) scintillation detector indicates the characteristic photo peaks of the elements in soil and landmine. In the high-energy region of the gamma-ray spectrum, besides 10.829 MeV of (15)N, single escape (SE) and double escape (DE) peaks are unmistakable photo peaks, which make the detection of concealed explosive possible. The soil has the property of moderating neutrons as well as diffusing the thermal neutron flux. Among many elements in soil, silicon is more abundant and (29)Si emits 10.607 MeV prompt capture gamma-ray, which makes 10.829 MeV detection difficult. The Monte Carlo simulation was used to adjust source-target-detector distances and soil moisture content to yield the best result. Therefore, we applied MCNP4C for configuration very close to reality of a hidden landmine in soil.

  6. SEnD NMR: Sensitivity Enhanced n-Dimensional NMR

    PubMed Central

    Gledhill, John M.; Wand, A. Joshua

    2009-01-01

    Sparse sampling offers tremendous potential for overcoming the time limitations imposed by traditional Cartesian sampling of indirectly detected dimensions of multidimensional NMR data. However, in many instances sensitivity rather than time remains of foremost importance when collecting data on protein samples. Here we explore how to optimize the collection of radial sampled multidimensional NMR data to achieve maximal signal-to-noise. A method is presented that exploits a rigorous definition of the minimal set of radial sampling angles required to resolve all peaks of interest in combination with a fundamental statistical property of radial sampled data. The approach appears general and can achieve a substantial sensitivity advantage over Cartesian sampling for the same total data acquisition time. Termed Sensitivity Enhanced n-Dimensional or SEnD NMR, the method involves three basic steps. First, data collection is optimized using routines to determine a minimal set of radial sampling angles required to resolve frequencies in the radially sampled chemical shift evolution dimensions. Second, appropriate combinations of experimental parameters (transients and increments) are defined by simple statistical considerations in order to optimize signal-to-noise in single angle frequency domain spectra. Finally, the data is processed with a direct multidimensional Fourier transform and a statistical artifact and noise removal step is employed. PMID:20004602

  7. REDOR NMR for Drug Discovery

    PubMed Central

    Cegelski, Lynette

    2014-01-01

    Rotational-Echo DOuble-Resonance (REDOR) NMR is a powerful and versatile solid-state NMR measurement that has been recruited to elucidate drug modes of action and to drive the design of new therapeutics. REDOR has been implemented to examine composition, structure, and dynamics in diverse macromolecular and whole-cell systems, including taxol-bound microtubules, enzyme-cofactor-inhibitor ternary complexes, and antibiotic-whole-cell complexes. The REDOR approach involves the integrated design of specific isotopic labeling strategies and the selection of appropriate REDOR experiments. By way of example, this digest illustrates the versatility of the REDOR approach, with an emphasis on the practical considerations of experimental design and data interpretation. PMID:24035486

  8. Real-Time Infrared Overtone Laser Control of Temperature in Picoliter H2O Samples: “Nanobathtubs” for Single Molecule Microscopy

    PubMed Central

    Holmstrom, Erik D.; Nesbitt, David J.

    2011-01-01

    An approach for high spatiotemporal control of aqueous sample temperatures in confocal microscopy is reported. This technique exploits near-IR diode-laser illumination to locally heat picoliter volumes of water via first-overtone excitation in the OH-stretch manifold. A thin water cell after the objective resonantly removes any residual IR light from the detection system, allowing for continuous observation of single-molecule fluorescence throughout the heating event. This technique is tested quantitatively by reproducing single-molecule RNA folding results obtained from “bulk” stage heating measurements. Calibration of sample temperatures is obtained from time-correlated single-photon counting studies of Rhodamine B fluorescence decay. We obtain an upper limit to the heating response time (τheat < 20 ms) consistent with even faster estimates (τheat ≈ 0.25 ms) based on laser spot size, H2O heat capacit,y and absorption cross section. This combination of fast, noncontact heating of picoliter volumes provides new opportunities for real-time thermodynamic/kinetic studies at the single-molecule level. PMID:21814589

  9. Observation of Rayleigh phonon scattering through excitation of extremely high overtones in low-loss cryogenic acoustic cavities for hybrid quantum systems.

    PubMed

    Goryachev, Maxim; Creedon, Daniel L; Galliou, Serge; Tobar, Michael E

    2013-08-23

    The confinement of high frequency phonons approaching 1 GHz is demonstrated in phonon-trapping acoustic cavities at cryogenic temperatures using a low-coupled network approach. The frequency range is extended by nearly an order of magnitude, with excitation at greater than the 200th overtone achieved for the first time. Such a high frequency operation reveals Rayleigh-type phonon scattering losses due to highly diluted lattice impurities and corresponding glasslike behavior, with a maximum Q(L)×f product of 8.6×10(17) at 3.8 K and 4×10(17) at 15 mK. This suggests a limit on the Q×f product due to unavoidable crystal disorder. Operation at 15 mK is high enough in frequency that the average phonon occupation number is less than unity, with a loaded quality factor above half a billion. This work represents significant progress towards the utilization of such acoustic cavities for hybrid quantum systems.

  10. Investigation of the C2H2-CO2 van der Waals complex in the overtone range using cw cavity ring-down spectroscopy.

    PubMed

    Lauzin, C; Didriche, K; Liévin, J; Herman, M; Perrin, A

    2009-05-28

    A slit nozzle supersonic expansion containing acetylene [492 SCCM (SCCM denotes cubic centimeter per minute at STP)] and carbon dioxide (740 SCCM) seeded into Ar (837 SCCM) is investigated using cw-cavity ring-down spectroscopy, in the 1.5 microm range. The C(2)H(2)-CO(2) van der Waals complex is observed around the nu(1) + nu(3) acetylenic band. The rotational temperature is estimated to be close to 60 K from the comparison between observed and simulated spectra. The analysis of the main, perturbed B-type band centered near 6,549.280 cm(-1), is performed. It is attributed to a dimer with the known planar, C(2v) geometry. The present overtone data, involving ground state levels with higher J/K states (J < or = 35 and K(a) < or = 20) than previously reported, are combined to 3 microm data [D. G. Prichard, R. N. Nandi, J. S. Muenter, and B. J. Howard, J. Chem. Phys. 89, 1245 (1988); Z. S. Huang and R. E. Miller, Chem. Phys. 132, 185 (1989)] to determine improved ground state parameters. The major perturbations affecting the upper state are accounted for through C-type Coriolis resonances involving one dark state, whose symmetry must therefore be A(1). Upper state constants are obtained for the bright and dark states. The dependence upon vibrational excitation is demonstrated to arise from excitation in the acetylene unit, only, for the former, but cannot be unravelled for the latter.

  11. Investigation of the C2H2-CO2 van der Waals complex in the overtone range using cw cavity ring-down spectroscopy

    NASA Astrophysics Data System (ADS)

    Lauzin, C.; Didriche, K.; Liévin, J.; Herman, M.; Perrin, A.

    2009-05-01

    A slit nozzle supersonic expansion containing acetylene [492 SCCM (SCCM denotes cubic centimeter per minute at STP)] and carbon dioxide (740 SCCM) seeded into Ar (837 SCCM) is investigated using cw-cavity ring-down spectroscopy, in the 1.5 μm range. The C2H2-CO2 van der Waals complex is observed around the ν1+ν3 acetylenic band. The rotational temperature is estimated to be close to 60 K from the comparison between observed and simulated spectra. The analysis of the main, perturbed B-type band centered near 6 549.280 cm-1, is performed. It is attributed to a dimer with the known planar, C2v geometry. The present overtone data, involving ground state levels with higher J /K states (J ≤35 and Ka≤20) than previously reported, are combined to 3 μm data [D. G. Prichard, R. N. Nandi, J. S. Muenter, and B. J. Howard, J. Chem. Phys. 89, 1245 (1988); Z. S. Huang and R. E. Miller, Chem. Phys. 132, 185 (1989)] to determine improved ground state parameters. The major perturbations affecting the upper state are accounted for through C-type Coriolis resonances involving one dark state, whose symmetry must therefore be A1. Upper state constants are obtained for the bright and dark states. The dependence upon vibrational excitation is demonstrated to arise from excitation in the acetylene unit, only, for the former, but cannot be unravelled for the latter.

  12. The high-resolution infrared spectrum of DC4H from 450 to 1100 cm-1: Overtone, combination, and hot bands

    NASA Astrophysics Data System (ADS)

    Bizzocchi, L.; Tamassia, F.; Esposti, C. Degli; Dore, L.; Fusina, L.; Villa, M.; Canè, E.

    2013-10-01

    The high-resolution infrared spectrum of monodeuterated diacetylene has been recorded in the 450-1100 cm-1 spectral region by Fourier transform infrared spectroscopy. Seven new bands have been identified: the ν3 fundamental (C-C stretch), and the ν8 + ν9, ν7 + ν8, 2ν7, 2ν8, ν8 + ν9 - ν9, and ν6 + ν9 - ν9 combination, overtone, and hot bands. The assigned transitions, together with those previously reported for the fundamental bands [F. Tamassia, L. Bizzocchi, C. Degli Esposti, L. Dore, M. Di Lauro, L. Fusina, M. Villa, and E. Canè, Astron. Astrophys. 549, A38 (2013)], form a comprehensive data set which comprises more than 2500 ro-vibrational transitions, and involves all singly and most doubly excited vibrational states of DC4H lying below 1000 cm-1. Rotational and vibrational l-type resonance effects among the sub-levels of excited bending states were considered in the analysis, which also included a careful treatment of the various anharmonic interactions coupling many vibrational states lying above 600 cm-1. Reliable and unambiguous spectroscopic parameters were obtained for each investigated state, including the rotational and centrifugal distortion constants Bv and Dv, the l-type doubling parameter qt, the anharmonicity constants xL(89), xL(69), and the vibrational l-type terms r89, r69 for the v8 = v9 = 1 and v6 = v9 = 1 bend-bend combination states.

  13. Modeling of collision-induced infrared absorption spectra of H2 pairs in the first overtone band at temperatures from 20 to 500 K

    NASA Technical Reports Server (NTRS)

    Zheng, Chunguang; Borysow, Aleksandra

    1995-01-01

    A simple formalism is presented that permits quick computations of the low-resolution, rotovibrational collision-induced absorption (RV CIA) spectra of H2 pairs in the first overtone band of hydrogen, at temperatures from 20 to 500 K. These spectra account for the free-free transitions. The sharp dimer features, originating from the bound-free, free-bound, and bound-bound transitions are ignored, though their integrated intensities are properly accounted for. The method employs spectral model line- shapes with parameters computed from the three lowest spectral moments. The moments are obtained from first principles expressed as analytical functions of temperature. Except for the sharp dimer features, which are absent in this model, the computed spectra reproduce closely the results of exact quantum mechanical lineshape computations. Comparisons of the computed spectra with existing experimental data also show good agreement. The work interest for the modeling of the atmospheres of the outer planets in the near-infrared region of the spectrum. The user-friendly Fortran program developed here is available on request from the authors.

  14. NMR Hyperpolarization Techniques for Biomedicine

    PubMed Central

    Nikolaou, Panayiotis; Goodson, Boyd M.

    2015-01-01

    Recent developments in NMR hyperpolarization have enabled a wide array of new in vivo molecular imaging modalities—ranging from functional imaging of the lungs to metabolic imaging of cancer. This Concept article explores selected advances in methods for the preparation and use of hyperpolarized contrast agents, many of which are already at or near the phase of their clinical validation in patients. PMID:25470566

  15. NMR Measures of Heterogeneity Length

    NASA Astrophysics Data System (ADS)

    Spiess, Hans W.

    2002-03-01

    Advanced solid state NMR spectroscopy provides a wealth of information about structure and dynamics of complex systems. On a local scale, multidimensional solid state NMR has elucidated the geometry and the time scale of segmental motions at the glass transition. The higher order correlation functions which are provided by this technique led to the notion of dynamic heterogeneities, which have been characterized in detail with respect to their rate memory and length scale. In polymeric and low molar mass glass formers of different fragility, length scales in the range 2 to 4 nm are observed. In polymeric systems, incompatibility of backbone and side groups as in polyalkylmethacrylates leads to heteogeneities on the nm scale, which manifest themselves in unusual chain dynamics at the glass transition involving extended chain conformations. References: K. Schmidt-Rohr and H.W. Spiess, Multidimensional Solid-State NMR and Polymers,Academic Press, London (1994). U. Tracht, M. Wilhelm, A. Heuer, H. Feng, K. Schmidt-Rohr, H.W. Spiess, Phys. Rev. Lett. 81, 2727 (1998). S.A. Reinsberg, X.H. Qiu, M. Wilhelm, M.D. Ediger, H.W. Spiess, J.Chem.Phys. 114, 7299 (2001). S.A. Reinsberg, A. Heuer, B. Doliwa, H. Zimmermann, H.W. Spiess, J. Non-Crystal. Solids, in press (2002)

  16. NMR of fd coat protein.

    PubMed

    Cross, T A; Opella, S J

    1979-01-01

    The conformations of the major coat protein of a filamentous bacteriophage can be described by nuclear magnetic resonance spectroscopy of the protein and the virus. The NMR experiments involve detection of the 13C and 1H nuclei of the coat protein. Both the 13C and 1H nuclear magnetic resonance (NMR) spectra show that regions of the polypeptide chain have substantially more motion than a typical globular protein. The fd coat protein was purified by gel chromatography of the SDA solubilized virus. Natural abundance 13C NMR spectra at 38 MHz resolve all of the nonprotonated aromatic carbons from the three phenylalanines, two tyrosines, and one tryptophan of the coat protein. The alpha carbons of the coat protein show at least two different classes of relaxation behavior, indicative of substantial variation in the motion of the backbone carbons in contrast to the rigidity of the alpha carbons of globular proteins. The 1H spectrum at 360 MHz shows all of the aromatic carbons and many of the amide protons. Titration of a 1H spectra gives the pKas for the tyrosines.

  17. NMR-Based Milk Metabolomics

    PubMed Central

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

    2013-01-01

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

  18. In-cell NMR spectroscopy.

    PubMed

    Serber, Zach; Corsini, Lorenzo; Durst, Florian; Dötsch, Volker

    2005-01-01

    The role of a protein inside a cell is determined by both its location and its conformational state. Although fluorescence techniques are widely used to determine the cellular localization of proteins in vivo, these approaches cannot provide detailed information about a protein's three-dimensional state. This gap, however, can be filled by NMR spectroscopy, which can be used to investigate both the conformation as well as the dynamics of proteins inside living cells. In this chapter we describe technical aspects of these "in-cell NMR" experiments. In particular, we show that in the case of (15)N-labeling schemes the background caused by labeling all cellular components is negligible, while (13)C-based experiments suffer from high background levels and require selective labeling schemes. A correlation between the signal-to-noise ratio of in-cell NMR experiments with the overexpression level of the protein shows that the current detection limit is 150-200 muM (intracellular concentration). We also discuss experiments that demonstrate that the intracellular viscosity is not a limiting factor since the intracellular rotational correlation time is only approximately two times longer than the correlation time in water. Furthermore, we describe applications of the technique and discuss its limitations. PMID:15808216

  19. Genome Sequence of a Novel H14N7 Subtype Influenza A Virus Isolated from a Blue-Winged Teal (Anas discors) Harvested in Texas, USA

    PubMed Central

    Reeves, Andrew B.; Poulson, Rebecca L.; Carter, Deborah L.; Davis-Fields, Nicholas; Stallknecht, David E.

    2016-01-01

    We report here the complete genome sequence of a novel H14N7 subtype influenza A virus (IAV) isolated from a blue-winged teal (Anas discors) harvested in Texas, USA. The genomic characteristics of this IAV strain with a previously undetected subtype combination suggest recent viral evolution within the New World wild-bird IAV reservoir. PMID:27284136

  20. Calculating (14)N(16)O2 spectral line parameters in an infrared range: A comparison of "global" and "local" effective operator methods.

    PubMed

    Voitsekhovskaya, O K; Egorov, O V; Kashirskii, D E

    2016-08-01

    Nitrogen dioxide, (14)N(16)O2, line positions and intensities calculated by us based on a "local" effective operator method are compared to the recent results of the "global" calculation. The comparison was made for theoretical absorption coefficients in the spectral range of 600-3700cm(-1) using the measured data taken from the Pacific Northwest National Laboratory. In order to conduct the calculations, empirical parameters of the effective rotational Hamiltonian of the twenty-one vibrational states were applied from the most recent experimental works. The second order parameters of the dipole moment function of (14)N(16)O2 were determined for the first time. The "local" line list in this research consists of one hundred and four bands and includes the line intensities of the v1+v2+v3 band of (14)N(16)O2 that have not yet been investigated in the literature. Among these bands, only eleven bands are included in HITRAN2012. The reasons behind the disagreements between the theoretical and measured absorption coefficients of (14)N(16)O2 are discussed. PMID:27111152

  1. Calculating 14N16O2 spectral line parameters in an infrared range: A comparison of "global" and "local" effective operator methods

    NASA Astrophysics Data System (ADS)

    Voitsekhovskaya, O. K.; Egorov, O. V.; Kashirskii, D. E.

    2016-08-01

    Nitrogen dioxide, 14N16O2, line positions and intensities calculated by us based on a "local" effective operator method are compared to the recent results of the "global" calculation. The comparison was made for theoretical absorption coefficients in the spectral range of 600-3700 cm- 1 using the measured data taken from the Pacific Northwest National Laboratory. In order to conduct the calculations, empirical parameters of the effective rotational Hamiltonian of the twenty-one vibrational states were applied from the most recent experimental works. The second order parameters of the dipole moment function of 14N16O2 were determined for the first time. The "local" line list in this research consists of one hundred and four bands and includes the line intensities of the v1 + v2 + v3 band of 14N16O2 that have not yet been investigated in the literature. Among these bands, only eleven bands are included in HITRAN2012. The reasons behind the disagreements between the theoretical and measured absorption coefficients of 14N16O2 are discussed.

  2. Linking nitrogen dynamics to climate variability off central California: a 51 year record based on 15N/ 14N in CalCOFI zooplankton

    NASA Astrophysics Data System (ADS)

    Rau, Greg H.; Ohman, Mark D.; Pierrot-Bults, Annelies

    2003-08-01

    Long-term variability in zooplankton 15N/ 14N was investigated in two species of calanoid copepods ( Calanus pacificus and Eucalanus californicus) and two chaetognaths ( Sagitta bierii and Sagitta euneritica) sampled in the spring of selected years from 1951 to 2001 off the central California coast. No statistically significant trend in 15N/ 14N was detected for any of the four species, with isotopic ratios in 2001 resembling those in copepods and chaetognaths sampled five decades earlier. Zooplankton body lengths also showed no long-term trends. With respect to proposed regime shifts in this region, heterogeneity in 15N/ 14N was detected only for S. bierii when comparing the periods 1951-1975, 1978-1998, and 1999-2001. In this species the 15N/ 14N in the most recent, brief period (1999-2001) averaged slightly lower than in the previous period. Three of the four species ( C. pacificus, S. bierii, and S. euneritica) showed significant increases in 15N/ 14N during major El Niños. El Niño-related enrichment in 15N could arise as a consequence of increased nitrate demand:supply at the base of the food web or advection of 15N-enriched nitrate from more southerly waters. While a range of physical and climate indices were evaluated, anomalies of 15N/ 14N from the long-term mean were found to be significantly related only to: (i) the Southern Oscillation Index in the case of both chaetognath species, (ii) a regional surface water temperature record ( S. bierii only), (iii) an index of wind-driven coastal upwelling for the surface-dwelling C. pacificus, and (iv) variability in the Pacific Decadal Oscillation for the somewhat deeper-dwelling E. californicus. The relationships among each species' 15N/ 14N averaged over the total sampling period was: E. californicus≈C. pacificus≪S. euneritica < S. bierii, consistent with trophic 15N biomagnification and the predatory nature of Sagitta.

  3. Probing the Statistical Decay and α-clustering effects in 12C + 12C and 14N + 10B reactions

    NASA Astrophysics Data System (ADS)

    Morelli, L.; Baiocco, G.; D'Agostino, M.; Bruno, M.; Gulminelli, F.; Cinausero, M.; Degerlier, M.; Fabris, D.; Gramegna, F.; Marchi, T.; Barlini, S.; Bini, M.; Casini, G.; Gelli, N.; Lopez, A.; Pasquali, G.; Piantelli, S.; Valdrè, S.

    2014-03-01

    An experimental campaign has been undertaken at Laboratori Nazionali di Legnaro (LNL INFN), Italy, in order to progress in our understanding of the statistical properties of light nuclei at excitation energies above particle emission threshold, by measuring exclusive data from fusion-evaporation reactions. On the experimental side, a first reaction: 12C+12C at 95 MeV beam energy has been measured, using the GARFIELD + Ring Counter (RCo) apparatuses. Fusion-evaporation events have been exclusively selected out of the entire data set. The comparison to a dedicated Hauser-Feshbach calculation allows us to give constraints on the nuclear level density at high excitation energy for light systems ranging from C up to Mg. Out-of-equilibrium aα emission has been evidenced and attributed both to an entrance channel effect (favoured by the cluster nature of reaction partners), and, in more dissipative events, to the persistence of cluster correlations well above the 24Mg threshold for 6 α's decay. In order to study the same 24Mg compound nucleus at similar excitation energy with respect to this first reaction a new measurement, 14N + 10B at 5.7 A.MeV, was performed at LNL laboratories with the same experimental setup. The comparison between the two systems would allow us to further constrain the level density of light nuclei in the mass-excitation energy range of interest. In this perspective, deviations from a statistical behaviour can be used as a tool to get information on nuclear clustering, both in the ground-state for projectile and target and in the hot source formed in the collision.

  4. Discovery of singlet diradicals: theoretical study on the cage species C14N12-H6 and its six derivatives.

    PubMed

    Zhou, Hongwei; Wong, Ning-Bew; Lau, Kai-Chung; Tian, Anmin; Li, Wai-Kee

    2007-10-01

    In this work, the geometries, harmonic vibrational frequencies, and high-energy density material (HEDM) properties of a novel species and its six derivatives with the general formula C14N12-R6 (R = H, OH, F, CN, N3, NH2, and NO2) have been investigated at the restricted and unrestricted B3LYP/cc-pVDZ levels of theory. Natural bond orbital (NBO), natural orbital (NO), and atoms in molecules (AIM) analyses are applied to examine their electronic topologies. It is found that for the four species of R = H, CN, N3, and NO2, (1) there exist high LUMO occupation numbers, (2) there is considerable spin density congregated on the two central carbon atoms, (3) there exists through space interaction (or intramolecular interaction, which is one of the stabilizing factors of a diradicaloid) between the two central carbon atoms, (4) the distance (about 3 A) between the two central carbon atoms (as the apexes of two trigonal pyramids with their bases facing each other) is suitable and favorable for diradical formation. All the results support that these four species are diradicals or diradicaloids. Furthermore, the appreciable singlet-triplet energy gaps indicate that these four diradicals tend to have a singlet ground state. There is a moderate HOMO-LUMO gap (on the order of 1.5 to 2.1 eV) for these four species. These four singlet diradicals may be novel organic semiconductor materials or nonlinear optical materials. On the other hand, the remaining three species, with R = OH, F, and NH2, are not diradicaloids.

  5. FORMATION OF AN O-STAR CLUSTER BY HIERARCHICAL ACCRETION IN G20.08-0.14 N

    SciTech Connect

    Galvan-Madrid, Roberto; Keto, Eric; Zhang Qizhou; Ho, Paul T. P.; Kurtz, Stan; RodrIguez, Luis F.

    2009-12-01

    Spectral line and continuum observations of the ionized and molecular gas in G20.08-0.14 N explore the dynamics of accretion over a range of spatial scales in this massive star-forming region. Very Large Array (VLA) observations of NH{sub 3} at 4'' angular resolution show a large-scale (0.5 pc) molecular accretion flow around and into a star cluster with three small, bright H II regions. Higher resolution (0.''4) observations with the Submillimeter Array in hot core molecules (CH{sub 3}CN, OCS, and SO{sub 2}) and the VLA in NH{sub 3} show that the two brightest and smallest H II regions are themselves surrounded by smaller scale (0.05 pc) accretion flows. The axes of rotation of the large- and small-scale flows are aligned, and the timescale for the contraction of the cloud is short enough, 0.1 Myr, for the large-scale accretion flow to deliver significant mass to the smaller scales within the star formation timescale. The flow structure appears to be continuous and hierarchical from larger to smaller scales. Millimeter radio recombination line (RRL) observations at 0.''4 angular resolution indicate rotation and outflow of the ionized gas within the brightest H II region (A). The broad recombination lines and a continuum spectral energy distribution (SED) that rises continuously from cm to mm wavelengths, are both characteristic of the class of H II regions known as 'broad recombination line objects'. The SED indicates a density gradient inside this H II region, and the RRLs suggest supersonic flows. These observations are consistent with photoevaporation of the inner part of the rotationally flattened molecular accretion flow. We also report the serendipitous detection of a new NH{sub 3} (3,3) maser.

  6. Solving the Tautomeric Equilibrium of Purine Through the Analysis of the Complex Hyperfine Structure of the Four 14N Nuclei

    NASA Astrophysics Data System (ADS)

    Cocinero, Emilio J.; Uriarte, Iciar; Ecija, Patricia; Favero, Laura B.; Spada, Lorenzo; Calabrese, Camilla; Caminati, Walther

    2016-06-01

    Microwave spectroscopy has been restricted to the investigation of small molecules in the last years. However, with the advent of FTMW and CP-FTMW spectroscopies coupled with laser vaporization techniques it has turned into a very competitive methodology in the studies of moderate-size biomolecules. Here, we present the study of purine, characterized by two aromatic rings, one six- and one five-membered, fused together to give a planar aromatic bicycle. Biologically, it is the mainframe of two of the five nucleobases of DNA and RNA. Two tautomers were observed by FTMW spectroscopy coupled to UV ultrafast laser vaporization system. The population ratio of the two main tautomers [N(7)H]/[N(9)H] is about 1/40 in the gas phase. It contrasts with the solid state where only the N(7)H species is present, or in solution where a mixture of both tautomers is observed. For both species, a full quadrupolar hyperfine analysis has been performed. This has led to the determination of the full sets of diagonal quadrupole coupling constants of the four 14N atoms, which have provided crucial information for the unambiguous identification of both species. T. J. Balle and W. H. Flygare Rev. Sci. Instrum. 52, 33-45, 1981 J.-U. Grabow, W. Stahl and H. Dreizler Rev. Sci. Instrum. 67, 4072-4084, 1996 G. G. Brown, B. D. Dian, K. O. Douglass, S. M. Geyer, S. T. Shipman and B. H. Pate Rev. Sci. Instrum. 79, 0531031/1-053103/13, 2008 E. J. Cocinero, A. Lesarri, P. écija, F. J. Basterretxea, J. U. Grabow, J. A. Fernández and F. Castaño Angew. Chem. Int. Ed. 51, 3119-3124, 2012

  7. Scalable NMR spectroscopy with semiconductor chips.

    PubMed

    Ha, Dongwan; Paulsen, Jeffrey; Sun, Nan; Song, Yi-Qiao; Ham, Donhee

    2014-08-19

    State-of-the-art NMR spectrometers using superconducting magnets have enabled, with their ultrafine spectral resolution, the determination of the structure of large molecules such as proteins, which is one of the most profound applications of modern NMR spectroscopy. Many chemical and biotechnological applications, however, involve only small-to-medium size molecules, for which the ultrafine resolution of the bulky, expensive, and high-maintenance NMR spectrometers is not required. For these applications, there is a critical need for portable, affordable, and low-maintenance NMR spectrometers to enable in-field, on-demand, or online applications (e.g., quality control, chemical reaction monitoring) and co-use of NMR with other analytical methods (e.g., chromatography, electrophoresis). As a critical step toward NMR spectrometer miniaturization, small permanent magnets with high field homogeneity have been developed. In contrast, NMR spectrometer electronics capable of modern multidimensional spectroscopy have thus far remained bulky. Complementing the magnet miniaturization, here we integrate the NMR spectrometer electronics into 4-mm(2) silicon chips. Furthermore, we perform various multidimensional NMR spectroscopies by operating these spectrometer electronics chips together with a compact permanent magnet. This combination of the spectrometer-electronics-on-a-chip with a permanent magnet represents a useful step toward miniaturization of the overall NMR spectrometer into a portable platform. PMID:25092330

  8. Advanced NMR technology for bioscience and biotechnology

    SciTech Connect

    Hammel, P.C.; Hernandez, G.; Trewhella, J.; Unkefer, C.J.; Boumenthal, D.K.; Kennedy, M.A.; Moore, G.J.

    1998-11-01

    This is the final report of a three-year, Laboratory Directed Research and Development (LDRD) project at the Los Alamos National Laboratory (LANL). NMR plays critical roles in bioscience and biotechnology in both imaging and structure determination. NMR is limited, however, by the inherent low sensitivity of the NMR experiment and the demands for spectral resolution required to study biomolecules. The authors addressed both of these issues by working on the development of NMR force microscopy for molecular imaging, and high field NMR with isotope labeling to overcome limitations in the size of biomolecules that can be studied using NMR. A novel rf coil design for NMR force microscopy was developed that increases the limits of sensitivity in magnetic resonance detection for imaging, and the authors demonstrated sub-surface spatial imaging capabilities. The authors also made advances in the miniaturization of two critical NMR force microscope components. They completed high field NMR and isotope labeling studies of a muscle protein complex which is responsible for regulating muscle contraction and is too large for study using conventional NMR approaches.

  9. Advanced NMR-based techniques for pore structure analysis of coal

    SciTech Connect

    Smith, D.M.

    1991-01-01

    One of the main problems in coal utilization is the inability to properly characterize its complex pore structure. We propose to investigate the dependence of the common NMR parameters such as chemical shifts and relaxation times of several different nuclei and compounds on the pore structure of model microporous solids, carbons, and coals. In particular, we will study the interaction between several small molecules ({sup 129}Xe, {sup 3}He, {sup 2}H{sub 2}, {sup 14}N{sub 2}, {sup 14}NH{sub 3}, {sup 15}N{sub 2}, {sup 13}CH{sub 4}, {sup 13}CO{sub 2}) and the pore surfaces in coals. These molecules have been selected for their chemical and physical properties.

  10. Fourier Analysis and Structure Determination. Part II: Pulse NMR and NMR Imaging.

    ERIC Educational Resources Information Center

    Chesick, John P.

    1989-01-01

    Uses simple pulse NMR experiments to discuss Fourier transforms. Studies the generation of spin echoes used in the imaging procedure. Shows that pulse NMR experiments give signals that are additions of sinusoids of differing amplitudes, frequencies, and phases. (MVL)

  11. Hyphenated low-field NMR techniques: combining NMR with NIR, GPC/SEC and rheometry.

    PubMed

    Räntzsch, Volker; Wilhelm, Manfred; Guthausen, Gisela

    2016-06-01

    Hyphenated low-field NMR techniques are promising characterization methods for online process analytics and comprehensive offline studies of soft materials. By combining different analytical methods with low-field NMR, information on chemical and physical properties can be correlated with molecular dynamics and complementary chemical information. In this review, we present three hyphenated low-field NMR techniques: a combination of near-infrared spectroscopy and time-domain NMR (TD-NMR) relaxometry, online (1) H-NMR spectroscopy measured directly after size exclusion chromatographic (SEC, also known as GPC) separation and a combination of rheometry and TD-NMR relaxometry for highly viscous materials. Case studies are reviewed that underline the possibilities and challenges of the different hyphenated low-field NMR methods. Copyright © 2015 John Wiley & Sons, Ltd.

  12. Tropine Forming Tropinone Reductase Gene from Withania somnifera (Ashwagandha): Biochemical Characteristics of the Recombinant Enzyme and Novel Physiological Overtones of Tissue-Wide Gene Expression Patterns

    PubMed Central

    Kushwaha, Amit Kumar; Sangwan, Neelam Singh; Trivedi, Prabodh Kumar; Negi, Arvind Singh; Misra, Laxminarain; Sangwan, Rajender Singh

    2013-01-01

    profiles are discussed with respect to their physiological overtones. PMID:24086372

  13. A high-overtone bulk acoustic wave resonator-oscillator-based 4.596 GHz frequency source: Application to a coherent population trapping Cs vapor cell atomic clock

    NASA Astrophysics Data System (ADS)

    Daugey, Thomas; Friedt, Jean-Michel; Martin, Gilles; Boudot, Rodolphe

    2015-11-01

    This article reports on the design and characterization of a high-overtone bulk acoustic wave resonator (HBAR)-oscillator-based 4.596 GHz frequency source. A 2.298 GHz signal, generated by an oscillator constructed around a thermally controlled two-port aluminum nitride-sapphire HBAR resonator with a Q-factor of 24 000 at 68 °C, is frequency multiplied by 2-4.596 GHz, half of the Cs atom clock frequency. The temperature coefficient of frequency of the HBAR is measured to be -23 ppm/ °C at 2.298 GHz. The measured phase noise of the 4.596 GHz source is -105 dB rad2/Hz at 1 kHz offset and -150 dB rad2/Hz at 100 kHz offset. The 4.596 GHz output signal is used as a local oscillator in a laboratory-prototype Cs microcell-based coherent population trapping atomic clock. The signal is stabilized onto the atomic transition frequency by tuning finely a voltage-controlled phase shifter implemented in the 2.298 GHz HBAR-oscillator loop, preventing the need for a high-power-consuming direct digital synthesis. The short-term fractional frequency stability of the free-running oscillator is 1.8 × 10-9 at one second integration time. In locked regime, the latter is improved in a preliminary proof-of-concept experiment at the level of 6.6 × 10-11 τ-1/2 up to a few seconds and found to be limited by the signal-to-noise ratio of the detected CPT resonance.

  14. A high-overtone bulk acoustic wave resonator-oscillator-based 4.596 GHz frequency source: Application to a coherent population trapping Cs vapor cell atomic clock.

    PubMed

    Daugey, Thomas; Friedt, Jean-Michel; Martin, Gilles; Boudot, Rodolphe

    2015-11-01

    This article reports on the design and characterization of a high-overtone bulk acoustic wave resonator (HBAR)-oscillator-based 4.596 GHz frequency source. A 2.298 GHz signal, generated by an oscillator constructed around a thermally controlled two-port aluminum nitride-sapphire HBAR resonator with a Q-factor of 24,000 at 68 °C, is frequency multiplied by 2-4.596 GHz, half of the Cs atom clock frequency. The temperature coefficient of frequency of the HBAR is measured to be -23 ppm/ °C at 2.298 GHz. The measured phase noise of the 4.596 GHz source is -105 dB rad(2)/Hz at 1 kHz offset and -150 dB rad(2)/Hz at 100 kHz offset. The 4.596 GHz output signal is used as a local oscillator in a laboratory-prototype Cs microcell-based coherent population trapping atomic clock. The signal is stabilized onto the atomic transition frequency by tuning finely a voltage-controlled phase shifter implemented in the 2.298 GHz HBAR-oscillator loop, preventing the need for a high-power-consuming direct digital synthesis. The short-term fractional frequency stability of the free-running oscillator is 1.8 × 10(-9) at one second integration time. In locked regime, the latter is improved in a preliminary proof-of-concept experiment at the level of 6.6 × 10(-11) τ(-1/2) up to a few seconds and found to be limited by the signal-to-noise ratio of the detected CPT resonance.

  15. Cross Section of OH Radical Overtone Transition near 7028 cm(-1) and Measurement of the Rate Constant of the Reaction of OH with HO2 Radicals.

    PubMed

    Assaf, Emmanuel; Fittschen, Christa

    2016-09-15

    The absorption cross section of an overtone transition of OH radicals at 7028.831 cm(-1) has been measured using an improved experimental setup coupling laser photolysis to three individual time-resolved detection techniques. Time-resolved relative OH radical profiles were measured by laser-induced fluorescence (LIF), and their absolute profiles have been obtained by cw-cavity ring-down spectroscopy (cw-CRDS). HO2 radicals were quantified simultaneously at the well-characterized absorption line at 6638.21 cm(-1) by a second cw-CRDS absorption path. Initial OH concentrations and thus their absorption cross sections have been deduced from experiments of 248 nm photolysis of H2O2: OH and HO2 profiles have been fitted to a simple kinetic model using well-known rate constants. The rate constant of the reaction between OH and HO2 radicals turned out to be sensitive to the deduction of the initial OH concentration and has been revisited in this work: OH decays have been observed in the presence of varying excess HO2 concentrations. A rate constant of (1.02 ± 0.06) × 10(-10) cm(3) s(-1) has been obtained, in good agreement with previous measurements and recent recommendations. An absorption cross section of σOH = (1.54 ± 0.1) × 10(-19) cm(2) at a total pressure of 50 Torr helium has been obtained from consistent fitting of OH and HO2 profiles in a large range of concentrations.

  16. A high-overtone bulk acoustic wave resonator-oscillator-based 4.596 GHz frequency source: Application to a coherent population trapping Cs vapor cell atomic clock

    SciTech Connect

    Daugey, Thomas; Friedt, Jean-Michel; Martin, Gilles; Boudot, Rodolphe

    2015-11-15

    This article reports on the design and characterization of a high-overtone bulk acoustic wave resonator (HBAR)-oscillator-based 4.596 GHz frequency source. A 2.298 GHz signal, generated by an oscillator constructed around a thermally controlled two-port aluminum nitride-sapphire HBAR resonator with a Q-factor of 24 000 at 68 °C, is frequency multiplied by 2–4.596 GHz, half of the Cs atom clock frequency. The temperature coefficient of frequency of the HBAR is measured to be −23 ppm/ °C at 2.298 GHz. The measured phase noise of the 4.596 GHz source is −105 dB rad{sup 2}/Hz at 1 kHz offset and −150 dB rad{sup 2}/Hz at 100 kHz offset. The 4.596 GHz output signal is used as a local oscillator in a laboratory-prototype Cs microcell-based coherent population trapping atomic clock. The signal is stabilized onto the atomic transition frequency by tuning finely a voltage-controlled phase shifter implemented in the 2.298 GHz HBAR-oscillator loop, preventing the need for a high-power-consuming direct digital synthesis. The short-term fractional frequency stability of the free-running oscillator is 1.8 × 10{sup −9} at one second integration time. In locked regime, the latter is improved in a preliminary proof-of-concept experiment at the level of 6.6 × 10{sup −11} τ{sup −1/2} up to a few seconds and found to be limited by the signal-to-noise ratio of the detected CPT resonance.

  17. A three-dimensional wave-packet method for the CH overtone spectroscopy and intramolecular vibrational relaxation dynamics of the fluoroform molecule

    NASA Astrophysics Data System (ADS)

    Solá, I. R.; Muñoz-Crego, C.; Díaz, A.; Muñoz-Sanz, R.; Santamaría, J.

    1997-01-01

    The overtone spectroscopy and intramolecular vibrational relaxation dynamics of CH chromophore in the fluoroform molecule is studied by a three-dimensional (3D) time-dependent wave-packet method, and the results are compared with the experiment and with those of a 2D (stretch-bend) wave-packet method. A third mode (CF symmetrical stretch) is included in order to explain the long time dynamics and the combination bands between the CF stretch fundamental and the Fermi polyad frequencies. The comparison with the 2D study is carried out by the use of a full set of dynamical and spectroscopic variables, based on the autocorrelation function of the bright states of each polyad. The spectroscopic variables then follow by Fourier transforming the autocorrelation function, while the dynamical ones emerge via survival probability in the frame of the dynamical statistical ensemble. These include several relaxation times and the number of cells and rates of phase-space exploration. The specific effect of the third mode is monitored by following the reduced dynamics of the system irrespective of the polyad stretch-bend dynamics, through population evolution. Dynamical results clearly reveal the third mode effects at very short and long times. In the last regime, we can observe a great span of different behaviors, depending on how the third mode excited states are involved. This richer variety of dynamical patterns cannot be observed in a two-mode model and justifies the present work. The spectroscopic results of both models are in good agreement with the experimental results.

  18. Cross Section of OH Radical Overtone Transition near 7028 cm(-1) and Measurement of the Rate Constant of the Reaction of OH with HO2 Radicals.

    PubMed

    Assaf, Emmanuel; Fittschen, Christa

    2016-09-15

    The absorption cross section of an overtone transition of OH radicals at 7028.831 cm(-1) has been measured using an improved experimental setup coupling laser photolysis to three individual time-resolved detection techniques. Time-resolved relative OH radical profiles were measured by laser-induced fluorescence (LIF), and their absolute profiles have been obtained by cw-cavity ring-down spectroscopy (cw-CRDS). HO2 radicals were quantified simultaneously at the well-characterized absorption line at 6638.21 cm(-1) by a second cw-CRDS absorption path. Initial OH concentrations and thus their absorption cross sections have been deduced from experiments of 248 nm photolysis of H2O2: OH and HO2 profiles have been fitted to a simple kinetic model using well-known rate constants. The rate constant of the reaction between OH and HO2 radicals turned out to be sensitive to the deduction of the initial OH concentration and has been revisited in this work: OH decays have been observed in the presence of varying excess HO2 concentrations. A rate constant of (1.02 ± 0.06) × 10(-10) cm(3) s(-1) has been obtained, in good agreement with previous measurements and recent recommendations. An absorption cross section of σOH = (1.54 ± 0.1) × 10(-19) cm(2) at a total pressure of 50 Torr helium has been obtained from consistent fitting of OH and HO2 profiles in a large range of concentrations. PMID:27556141

  19. Methyl quantum tunneling and nitrogen-14 NQR NMR studies using a SQUID magnetic resonance spectrometer

    SciTech Connect

    Black, B.E. |

    1993-07-01

    Nuclear Magnetic Resonance (NMR) and Nuclear Quadrupole Resonance (NQR) techniques have been very successful in obtaining molecular conformation and dynamics information. Unfortunately, standard NMR and NQR spectrometers are unable to adequately detect resonances below a few megahertz due to the frequency dependent sensitivity of their Faraday coil detectors. For this reason a new spectrometer with a dc SQUID (Superconducting Quantum Interference Device) detector, which has no such frequency dependence, has been developed. Previously, this spectrometer was used to observe {sup 11}B and {sup 27}Al NQR resonances. The scope of this study was increased to include {sup 23}Na, {sup 51}V, and {sup 55}Mn NQR transitions. Also, a technique was presented to observe {sup 14}N NQR resonances through cross relaxation of the nitrogen polarization to adjacent proton spins. When the proton Zeeman splitting matches one nitrogen quadrupoler transition the remaining two {sup 14}N transitions can be detected by sweeping a saturating rf field through resonance. Additionally, simultaneous excitation of two nitrogen resonances provides signal enhancement which helps to connect transitions from the same site. In this way, nitrogen-14 resonances were observed in several amino acids and polypeptides. This spectrometer has also been useful in the direct detection of methyl quantum tunneling splittings at 4.2 K. Tunneling, frequencies of a homologous series of carboxylic acids were measured and for solids with equivalent crystal structures, an exponential correlation between the tunneling frequency and the enthalpy of fusion is observed. This correlation provides information about the contribution of intermolecular interactions to the energy barrier for methyl rotation.

  20. Quantitative 2D liquid-state NMR.

    PubMed

    Giraudeau, Patrick

    2014-06-01

    Two-dimensional (2D) liquid-state NMR has a very high potential to simultaneously determine the absolute concentration of small molecules in complex mixtures, thanks to its capacity to separate overlapping resonances. However, it suffers from two main drawbacks that probably explain its relatively late development. First, the 2D NMR signal is strongly molecule-dependent and site-dependent; second, the long duration of 2D NMR experiments prevents its general use for high-throughput quantitative applications and affects its quantitative performance. Fortunately, the last 10 years has witnessed an increasing number of contributions where quantitative approaches based on 2D NMR were developed and applied to solve real analytical issues. This review aims at presenting these recent efforts to reach a high trueness and precision in quantitative measurements by 2D NMR. After highlighting the interest of 2D NMR for quantitative analysis, the different strategies to determine the absolute concentrations from 2D NMR spectra are described and illustrated by recent applications. The last part of the manuscript concerns the recent development of fast quantitative 2D NMR approaches, aiming at reducing the experiment duration while preserving - or even increasing - the analytical performance. We hope that this comprehensive review will help readers to apprehend the current landscape of quantitative 2D NMR, as well as the perspectives that may arise from it.

  1. NMR studies of isotopically labeled RNA

    SciTech Connect

    Pardi, A.

    1994-12-01

    In summary, the ability to generate NMR quantities of {sup 15}N and {sup 13}C-labeled RNAs has led to the development of heteronuclear multi-dimensional NMR techniques for simplifying the resonance assignment and structure determination of RNAs. These methods for synthesizing isotopically labeled RNAs are only several years old, and thus there are still relatively few applications of heteronuclear multi-dimensional NMR techniques to RNA. However, given the critical role that RNAs play in cellular function, one can expect to see an increasing number of NMR structural studies of biologically active RNAs.

  2. Picoliter H-1 NMR Spectroscopy

    SciTech Connect

    Minard, Kevin R. ); Wind, Robert A. )

    2002-02-01

    A RF probe that fits inside the bore of a small gradient coil package is described for routine 1H-NMR microscopy measurements on small samples. The probe operates at 500 MHz and houses a 267-um-diameter solenoid transceiver. When used in three dimensional chemical shift imaging (3D-CSI) experiments, the measured signal-to-noise ratio (SNR) is shown to be within 20-30 percent of theoretical limits formulated by only considering the solenoid's resistive losses. This is illustrated using a 100-um-diameter globule of triacylglycerols ({approx}900mM) that may be an oocyte precursor in young Xenopus Laevis frogs, and water sample containing choline at a concentration often found in live cells ({approx}33mM). In chemical shift images generated using a few thousand scans, the choline methyl line is found to have an acceptable SNR in resolved from just 5 picoliters in the Xenopus globule. It is concluded that the probe's sensitivity is sufficient for performing 1H-NMR on picoliter-scale volumes in biological cells and tissues.

  3. NMR studies of oriented molecules

    SciTech Connect

    Sinton, S.W.

    1981-11-01

    Deuterium and proton magnetic resonance are used in experiments on a number of compounds which either form liquid crystal mesophases themselves or are dissolved in a liquid crystal solvent. Proton multiple quantum NMR is used to simplify complicated spectra. The theory of nonselective multiple quantum NMR is briefly reviewed. Benzene dissolved in a liquid crystal are used to demonstrate several outcomes of the theory. Experimental studies include proton and deuterium single quantum (..delta..M = +-1) and proton multiple quantum spectra of several molecules which contain the biphenyl moiety. 4-Cyano-4'-n-pentyl-d/sub 11/-biphenyl (5CB-d/sub 11/) is studied as a pure compound in the nematic phase. The obtained chain order parameters and dipolar couplings agree closely with previous results. Models for the effective symmetry of the biphenyl group in 5CB-d/sub 11/ are tested against the experimental spectra. The dihedral angle, defined by the planes containing the rings of the biphenyl group, is found to be 30 +- 2/sup 0/ for 5DB-d/sub 11/. Experiments are also described for 4,4'-d/sub 2/-biphenyl, 4,4' - dibromo-biphenyl, and unsubstituted biphenyl.

  4. Picoliter 1H NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

    Minard, Kevin R.; Wind, Robert A.

    2002-02-01

    In this study, a 267-μm-diameter solenoid transceiver is used to acquire localized 1H NMR spectra and the measured signal-to-noise ratio (SNR) at 500 MHz is shown to be within 20-30% of theoretical limits formulated by considering only its resistive losses. This is illustrated using a 100-μm-diameter globule of triacylglycerols (∼900 mM) that may be an oocyte precursor in young Xenopus laevis frogs and a water sample containing choline at a concentration often found in live mammalian cells (∼33 mM). In chemical shift imaging (CSI) experiments performed using a few thousand total scans, the choline methyl line is shown to have an acceptable SNR in resolved volume elements containing only 50 pL of sample, and localized spectra are resolved from just 5 pL in the Xenopus globule. These findings demonstrate the feasibility of performing 1H NMR on picoliter-scale sample volumes in biological cells and tissues and illustrate how the achieved SNR in spectroscopic images can be predicted with reasonable accuracy at microscopic spatial resolutions.

  5. Analytical Applications of NMR: Summer Symposium on Analytical Chemistry.

    ERIC Educational Resources Information Center

    Borman, Stuart A.

    1982-01-01

    Highlights a symposium on analytical applications of nuclear magnetic resonance spectroscopy (NMR), discussing pulse Fourier transformation technique, two-dimensional NMR, solid state NMR, and multinuclear NMR. Includes description of ORACLE, an NMR data processing system at Syracuse University using real-time color graphics, and algorithms for…

  6. Access to NMR Spectroscopy for Two-Year College Students: The NMR Site at Trinity University

    ERIC Educational Resources Information Center

    Mills, Nancy S.; Shanklin, Michael

    2011-01-01

    Students at two-year colleges and small four-year colleges have often obtained their exposure to NMR spectroscopy through "canned" spectra because the cost of an NMR spectrometer, particularly a high-field spectrometer, is prohibitive in these environments. This article describes the design of a NMR site at Trinity University in which spectral…

  7. Enzyme dynamics from NMR spectroscopy.

    PubMed

    Palmer, Arthur G

    2015-02-17

    CONSPECTUS: Biological activities of enzymes, including regulation or coordination of mechanistic stages preceding or following the chemical step, may depend upon kinetic or equilibrium changes in protein conformations. Exchange of more open or flexible conformational states with more closed or constrained states can influence inhibition, allosteric regulation, substrate recognition, formation of the Michaelis complex, side reactions, and product release. NMR spectroscopy has long been applied to the study of conformational dynamic processes in enzymes because these phenomena can be characterized over multiple time scales with atomic site resolution. Laboratory-frame spin-relaxation measurements, sensitive to reorientational motions on picosecond-nanosecond time scales, and rotating-frame relaxation-dispersion measurements, sensitive to chemical exchange processes on microsecond-millisecond time scales, provide information on both conformational distributions and kinetics. This Account reviews NMR spin relaxation studies of the enzymes ribonuclease HI from mesophilic (Escherichia coli) and thermophilic (Thermus thermophilus) bacteria, E. coli AlkB, and Saccharomyces cerevisiae triosephosphate isomerase to illustrate the contributions of conformational flexibility and dynamics to diverse steps in enzyme mechanism. Spin relaxation measurements and molecular dynamics (MD) simulations of the bacterial ribonuclease H enzymes show that the handle region, one of three loop regions that interact with substrates, interconverts between two conformations. Comparison of these conformations with the structure of the complex between Homo sapiens ribonuclease H and a DNA:RNA substrate suggests that the more closed state is inhibitory to binding. The large population of the closed conformation in T. thermophilus ribonuclease H contributes to the increased Michaelis constant compared with the E. coli enzyme. NMR spin relaxation and fluorescence spectroscopy have characterized a

  8. Enzyme Dynamics from NMR Spectroscopy

    PubMed Central

    2016-01-01

    Conspectus Biological activities of enzymes, including regulation or coordination of mechanistic stages preceding or following the chemical step, may depend upon kinetic or equilibrium changes in protein conformations. Exchange of more open or flexible conformational states with more closed or constrained states can influence inhibition, allosteric regulation, substrate recognition, formation of the Michaelis complex, side reactions, and product release. NMR spectroscopy has long been applied to the study of conformational dynamic processes in enzymes because these phenomena can be characterized over multiple time scales with atomic site resolution. Laboratory-frame spin-relaxation measurements, sensitive to reorientational motions on picosecond–nanosecond time scales, and rotating-frame relaxation-dispersion measurements, sensitive to chemical exchange processes on microsecond–millisecond time scales, provide information on both conformational distributions and kinetics. This Account reviews NMR spin relaxation studies of the enzymes ribonuclease HI from mesophilic (Escherichia coli) and thermophilic (Thermus thermophilus) bacteria, E. coli AlkB, and Saccharomyces cerevisiae triosephosphate isomerase to illustrate the contributions of conformational flexibility and dynamics to diverse steps in enzyme mechanism. Spin relaxation measurements and molecular dynamics (MD) simulations of the bacterial ribonuclease H enzymes show that the handle region, one of three loop regions that interact with substrates, interconverts between two conformations. Comparison of these conformations with the structure of the complex between Homo sapiens ribonuclease H and a DNA:RNA substrate suggests that the more closed state is inhibitory to binding. The large population of the closed conformation in T. thermophilus ribonuclease H contributes to the increased Michaelis constant compared with the E. coli enzyme. NMR spin relaxation and fluorescence spectroscopy have characterized a

  9. {sup 4}He fragments from the {sup 14}N + {sup 12}C collision at 35 MeV/nucleon and clustering in colliding nuclei

    SciTech Connect

    Takemoto, H.; Horiuchi, H.; Engel, A.; Ono, A.

    1996-07-01

    In order to study effects of clustering of colliding nuclei in the fragmentation process, the fragmentation of the {sup 14}N+{sup 12}C reaction at 35 MeV/nucleon is analyzed by antisymmetrized molecular dynamics. It is found that {sup 4}He fragments from {sup 12}C fragmentation are much more abundant than those from {sup 14}N fragmentation. Characters of {sup 4}He fragments from {sup 12}C fragmentation are investigated and it is found that this abundance in {sup 12}C fragmentation results from the three-alpha breakup in a short time scale where the excited states with excitation energy 7{endash}15 MeV play an important role. {copyright} {ital 1996 The American Physical Society.}

  10. FOURIER TRANSFORM EMISSION SPECTROSCOPY OF THE B {sup 2}{Sigma}{sup +}-X {sup 2}{Sigma}{sup +} (VIOLET) SYSTEM OF {sup 13}C{sup 14}N

    SciTech Connect

    Ram, R. S.; Bernath, P. F.

    2011-06-01

    Emission spectra of the B {sup 2}{Sigma}{sup +}-X {sup 2}{Sigma}{sup +} transition of {sup 13}C{sup 14}N have been observed at high resolution using the Fourier transform spectrometer associated with the McMath-Pierce Solar Telescope of the National Solar Observatory. The spectra have been measured in the 21000-30000 cm{sup -1} region and a total of 52 vibrational bands involving vibrational levels up to v = 15 of the ground and excited states have been rotationally analyzed to provide a much improved set of spectroscopic constants. An experimental line list and calculated term values are provided. The results of the present analysis should prove useful in the identification of additional {sup 13}C{sup 14}N lines in comets and cool stars, and will help in the determination of the {sup 12}C/{sup 13}C abundance ratio.

  11. Experimental Study of 17O(p,{alpha})14N and 17O(p,{gamma})18F for Classical Nova Nucleosynthesis

    SciTech Connect

    Chafa, A.; Ouichaoui, S.; Tatischeff, V.; Coc, A.; Garrido, F.; Kiener, J.; Lefebvre-Schuhl, A.; Thibaud, J.-P.; Aguer, P.; Barhoumi, S.; Hernanz, M.; Jose, J.; Sereville, N. de

    2006-04-26

    We investigated the proton-capture reactions on 17O occurring in classical nova explosions. We observed a previously undiscovered resonance at E{sub R}{sup lab}=194.1{+-}0.6 keV in the 17O(p,{alpha})14N reaction, with a measured resonance strength {omega}{gamma}p{alpha}=1.6{+-}0.2 meV. We studied in the same experiment the 17O(p,{gamma})18F reaction by an activation method and the resonance-strength ratio was found to be {omega}{gamma}p{alpha}/{omega}{gamma}p{gamma}=470{+-}50. The corresponding excitation energy in the 18F compound nucleus was determined to be 5789.8{+-}0.3 keV by {gamma}-ray measurements using the 14N({alpha},{gamma})18F reaction. These new resonance properties have important consequences for 17O nucleosynthesis and {gamma}-ray astronomy of classical novae.

  12. Interactions of /sup 14/N:/sup 15/N stearic acid spin-label pairs: effects of host lipid alkyl chain length and unsaturation

    SciTech Connect

    Feix, J.B.; Yin, J.J.; Hyde, J.S.

    1987-06-30

    Electron-electron double resonance (ELDOR) and saturation recovery electron paramagnetic resonance (EPR) spectroscopy have been employed to examine the interactions of /sup 14/N:/sup 15/N stearic acid spin-label pairs in fluid-phase model membrane bilayers composed of a variety of phospholipids. The (/sup 14/N)-16-doxylstearate:(/sup 15/N)-16-doxylstearate (16:16) pair was utilized to measure lateral diffusion of the spin-labels, while the (/sup 14/N)-16-doxylstearate:(/sup 15/N)-5-doxylstearate (16:5) pair provided information on vertical fluctuations of the 16-doxylstearate nitroxide moiety toward the membrane surface. Three saturated host lipids of varying alkyl chain length (dimyristoylphosphatidylcholine (DMPC), dipalmitoylphosphatidylcholine (DPPC), and distearoylphosphatidylcholine (DSPC)), an ..cap alpha..-saturated, ..beta..-unsaturated lipid (1-palmitoyl-2-oleoylphosphatidylcholine (POPC)), and phosphatidylcholine from a natural source (egg yolk phosphatidylcholine (egg PC)) were utilized as host lipids. Lateral diffusion of the stearic acid spin-labels was only slightly affected by alkyl chain length at a given reduced temperature (T/sub r/) in the saturated host lipids but was significantly decreased in POPC at the same T/sub r/. Lateral diffusion in DMPC, POPC, and egg PC was quite similar at 37/sup 0/C. A strong correlation was noted between lateral diffusion constants and rotational mobility of (/sup 14/N)-16-doxylstearate. Vertical fluctuations were likewise only slightly influenced by alklyl chain length but were strongly diminished in POPC and egg PC relative to the saturated systems. This diminution of the 16:5 interaction was observed even under conditions where no differences were discernible by conventional EPR.

  13. Carbon-rich presolar grains from massive stars. Subsolar 12 C/ 13 C and 14 N/ 15 N ratios and the mystery of 15 N

    DOE PAGES

    Pignatari, M.; Zinner, E.; Hoppe, P.; Jordan, C. J.; Gibson, B. K.; Trappitsch, R.; Herwig, F.; Fryer, C.; Hirschi, R.; Timmes, F. X.

    2015-07-30

    We compared carbon-rich grains with isotopic anomalies to the Sun are found in primitive meteorites. They were made by stars, and carry the original stellar nucleosynthesis signature. Silicon carbide grains of Type X and C and low-density (LD) graphites condensed in the ejecta of core-collapse supernovae. Furthermore, we present a new set of models for the explosive He shell and compare them with the grains showing 12C/13C and 14N/15N ratios lower than solar. In the stellar progenitor H was ingested into the He shell and not fully destroyed before the explosion. All of the explosion energies and H concentrations aremore » considered. If the supernova shock hits the He-shell region with some H still present, the models can reproduce the C and N isotopic signatures in C-rich grains. Hot-CNO cycle isotopic signatures are obtained, including a large production of 13C and 15N. The short-lived radionuclides 22Na and 26Al are increased by orders of magnitude. The production of radiogenic 22Ne from the decay of 22Na in the He shell might solve the puzzle of the Ne-E(L) component in LD graphite grains. This scenario is attractive for the SiC grains of type AB with 14N/15N ratios lower than solar, and provides an alternative solution for SiC grains originally classified as nova grains. Finally, this process may contribute to the production of 14N and 15N in the Galaxy, helping to produce the 14N/15N ratio in the solar system.« less

  14. Direct measurement of the breakout reaction {sup 11}C({alpha},p){sup 14}N in explosive hydrogen-burning process

    SciTech Connect

    Hayakawa, S.; Kubono, S.; Kahl, D.; Yamaguchi, H.; Binh, Dam N.; Hashimoto, T.; Wakabayashi, Y.; He, J. J.; Iwasa, N.; Kato, S.; Komatsubara, T.; Kwon, Y. K.; Teranishi, T.; Wanajo, S.

    2012-11-12

    We determined the {sup 11}C({alpha},p){sup 14}N reaction rate relevant to the nucleosynthesis in explosive hydrogen-burning stars. The measurement was performed by means of the thick target method in inverse kinematics with {sup 11}C RI beams. We derived the excitation functions for the ground-state transition and excited-state transitions using time-of-flight information for the first time. The present reaction rate is compared to the previous one.

  15. Genome sequence of a novel H14N7 subtype influenza A virus isolated from a blue-winged teal (Anas discors) harvested in Texas, USA

    USGS Publications Warehouse

    Ramey, Andy M.; Reeves, Andrew; Poulson, Rebecca L.; Carter, Deborah L.; Davis-Fields, Nicholas; Stallknecht, David E.

    2016-01-01

    We report here the complete genome sequence of a novel H14N7 subtype influenza A virus (IAV) isolated from a blue-winged teal (Anas discors) harvested in Texas, USA. The genomic characteristics of this IAV strain with a previously undetected subtype combination suggest recent viral evolution within the New World wild-bird IAV reservoir.                   

  16. Carbon-rich Presolar Grains from Massive Stars: Subsolar 12C/13C and 14N/15N Ratios and the Mystery of 15N

    NASA Astrophysics Data System (ADS)

    Pignatari, M.; Zinner, E.; Hoppe, P.; Jordan, C. J.; Gibson, B. K.; Trappitsch, R.; Herwig, F.; Fryer, C.; Hirschi, R.; Timmes, F. X.

    2015-08-01

    Carbon-rich grains with isotopic anomalies compared to the Sun are found in primitive meteorites. They were made by stars, and carry the original stellar nucleosynthesis signature. Silicon carbide grains of Type X and C and low-density (LD) graphites condensed in the ejecta of core-collapse supernovae. We present a new set of models for the explosive He shell and compare them with the grains showing 12C/13C and 14N/15N ratios lower than solar. In the stellar progenitor H was ingested into the He shell and not fully destroyed before the explosion. Different explosion energies and H concentrations are considered. If the supernova shock hits the He-shell region with some H still present, the models can reproduce the C and N isotopic signatures in C-rich grains. Hot-CNO cycle isotopic signatures are obtained, including a large production of 13C and 15N. The short-lived radionuclides 22Na and 26Al are increased by orders of magnitude. The production of radiogenic 22Ne from the decay of 22Na in the He shell might solve the puzzle of the Ne-E(L) component in LD graphite grains. This scenario is attractive for the SiC grains of type AB with 14N/15N ratios lower than solar, and provides an alternative solution for SiC grains originally classified as nova grains. Finally, this process may contribute to the production of 14N and 15N in the Galaxy, helping to produce the 14N/15N ratio in the solar system.

  17. Direct measurement of the {sup 11}C({alpha},p){sup 14}N reaction at CRIB: A path from pp-chain to CNO

    SciTech Connect

    Hayakawa, S.; Kubono, S.; Kahl, D.; Yamaguchi, H.; Binh, D. N.; Hashimoto, T.; Wakabayashi, Y.; He, J. J.; Iwasa, N.; Kato, S.; Komatsubara, T.; Kwon, Y. K.; Teranishi, T.; Wanajo, S.

    2012-11-20

    We determined the total reaction rate of the {sup 11}C({alpha},p){sup 14}N reaction relevant to the nucleosynthesis in explosive hydrogen-burning stars. The measurement was performed by means of the thick target method in inverse kinematics with {sup 11}C RI beams. We performed the identification of the ground-state transition and excited-state transitions using time-of-flight information for the first time.

  18. Millimeter-Wave Observations of Circumstellar 14N/15N and 12C/13C Ratios: New Insights into J-Type Stars

    NASA Astrophysics Data System (ADS)

    Adande, Gilles; Ziurys, Lucy M.; Woolf, Neville

    2016-06-01

    Measurements of 14N/15N and 12C/13C isotopic ratios have been conducted towards circumstellar envelopes of a sample of evolved stars using the J = 3→2 rotational transitions of the isotopologues of HCN, observed with the Submillimeter Telescope (SMT) of the Arizona Radio Observatory (ARO). Towards the J-type stars Y CVn and RY Dra, where 12C/13C ~ 3, the 14N/15N ratios were found to be 120-180 and 225, respectively. The 14N/15N ratio is thus anomalously low relative to interstellar values and a factor ~100 lower than equilibrium values predicted from the CNO cycle. Combining these results with previous chemical and isotopic prior observations of these stars, we conclude that two anomalous behaviors are likely to have occurred in Y CVn and RY Dra. First, the stellar envelope failed to participate in the normal mixing seen in low mass red giants, in which C and then O are substantially converted to N. Secondly, both the carbon enrichment and anomalous isotopic composition of both 13C and15N could have been caused by a plume of hot gas, hydrogen poor but enriched in 12C, from a helium flash mixing into the envelope.

  19. Differential 14N/15N-Labeling of Peptides Using N-Terminal Charge Derivatization with a High-Proton Affinity for Straightforward de novo Peptide Sequencing

    PubMed Central

    Nihashi, Yoichiro; Miyashita, Masahiro; Awane, Hiroyuki; Miyagawa, Hisashi

    2013-01-01

    While de novo peptide sequencing is essential in many situations, it remains a difficult task. This is because peptide fragmentation results in complicated and often incomplete product ion spectra. In a previous study, we demonstrated that N-terminal charge derivatization with 4-amidinobenzoic acid (Aba) resulted in improved peptide fragmentation under low-energy CID conditions. However, even with this derivatization, some ambiguity exists, due to difficulties in discriminating between N- and C-terminal fragments. In this study, to specifically identify b-ions from complex product ion spectra, the differential 14N/15N-labeling of peptides was performed using Aba derivatization. 15N-Labeled Aba was synthesized in the form of a succinimide ester. Peptides were derivatized individually with 14N-Aba or 15N-Aba and analyzed by ESI-MS/MS using a linear ion trap-Orbitrap hybrid FTMS system. The N-terminal fragments (i.e., b-ions) were then identified based on m/z differences arising from isotope labeling. By comparing the spectra between 14N- and 15N-Aba derivatized peptides, b-ions could be successfully identified based on the m/z shifts, which provided reliable sequencing results for all of the peptides examined in this study. The method developed in this study allows the easy and reliable de novo sequencing of peptides, which is useful in peptidomics and proteomics studies. PMID:24860714

  20. An analytical method for estimating the {sup 14}N nuclear quadrupole resonance parameters of organic compounds with complex free induction decays for radiation effects studies

    SciTech Connect

    Iselin, L.H.

    1992-12-31

    The use of {sup 14}N nuclear quadrupole resonance (NQR) as a radiation dosimetry tool has only recently been explored. An analytical method for analyzing {sup 14}N NQR complex free induction decays is presented with the background necessary to conduct pulsed NQR experiments. The {sup 14}N NQR energy levels and possible transitions are derived in step-by-step detail. The components of a pulsed NQR spectrometer are discussed along with the experimental techniques for conducting radiation effects experiments using the spectrometer. Three data analysis techniques -- the power spectral density Fourier transform, state space singular value decomposition (HSVD), and nonlinear curve fitting (using the downhill simplex method of global optimization and the Levenberg-Marquart method) -- are explained. These three techniques are integrated into an analytical method which uses these numerical techniques in this order to determine the physical NQR parameters. Sample data sets of urea and guanidine sulfate data are used to demonstrate how these methods can be employed to analyze both simple and complex free induction decays. By determining baseline values for biologically significant organics, radiation effects on the NQR parameters can be studied to provide a link between current radiation dosimetry techniques and the biological effects of radiation.

  1. A Guided Inquiry Approach to NMR Spectroscopy

    NASA Astrophysics Data System (ADS)

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

    1998-04-01

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

  2. NMR Spectroscopy and Its Value: A Primer

    ERIC Educational Resources Information Center

    Veeraraghavan, Sudha

    2008-01-01

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

  3. An Inversion Recovery NMR Kinetics Experiment

    ERIC Educational Resources Information Center

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

    2011-01-01

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

  4. Using Cloud Storage for NMR Data Distribution

    ERIC Educational Resources Information Center

    Soulsby, David

    2012-01-01

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

  5. An Integrated Laboratory Project in NMR Spectroscopy.

    ERIC Educational Resources Information Center

    Hudson, Reggie L.; Pendley, Bradford D.

    1988-01-01

    Describes an advanced NMR project that can be done with a 60-MHz continuous-wave proton spectrometer. Points out the main purposes are to give students experience in second-order NMR analysis, the simplification of spectra by raising the frequency, and the effect of non-hydrogen nuclei on proton resonances. (MVL)

  6. NMR and MRI apparatus and method

    DOEpatents

    Clarke, John; Kelso, Nathan; Lee, SeungKyun; Moessle, Michael; Myers, Whittier; McDermott, Robert; ten Haken, Bernard; Pines, Alexander; Trabesinger, Andreas

    2007-03-06

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

  7. Experimental determination of the {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates

    SciTech Connect

    Chafa, A.; Ouichaoui, S.; Tatischeff, V.; Coc, A.; Garrido, F.; Kiener, J.; Lefebvre-Schuhl, A.; Thibaud, J.-P.; Aguer, P.; Barhoumi, S.; Hernanz, M.; Jose, J.; Sereville, N. de

    2007-03-15

    The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reactions are of major importance to hydrogen-burning nucleosynthesis in a number of different stellar sites. In particular, {sup 17}O and {sup 18}F nucleosynthesis in classical novae is strongly dependent on the thermonuclear rates of these two reactions. The previously estimated rate for {sup 17}O(p,{alpha}){sup 14}N carries very large uncertainties in the temperature range of classical novae (T=0.01-0.4 GK), whereas a recent measurement has reduced the uncertainty of the {sup 17}O(p,{gamma}){sup 18}F rate. We report on the observation of a previously undiscovered resonance at E{sub c.m.}=183.3 keV in the {sup 17}O(p,{alpha}){sup 14}N reaction, with a measured resonance strength {omega}{gamma}{sub p{alpha}}=(1.6{+-}0.2)x10{sup -3} eV. We studied in the same experiment the {sup 17}O(p,{gamma}){sup 18}F reaction by an activation method, and the resonance strength was found to amount to {omega}{gamma}{sub p{gamma}}=(2.2{+-}0.4)x10{sup -6} eV. The excitation energy of the corresponding level in {sup 18}F was determined to be 5789.8{+-}0.3 keV in a Doppler shift attenuation method measurement, which yielded a value of {tau}<2.6 fs for the level lifetime. The {sup 17}O(p,{alpha}){sup 14}N and {sup 17}O(p,{gamma}){sup 18}F reaction rates were calculated using the measured resonance properties and reconsidering some previous analyses of the contributions of other levels or processes. The {sup 17}O(p,{alpha}){sup 14}N rate is now well established below T=1.5 GK, with uncertainties reduced by orders of magnitude in the temperature range T=0.1-0.4 GK. The uncertainty in the {sup 17}O(p,{gamma}){sup 18}F rate is somewhat larger because of remaining obscurities in the knowledge of the direct capture process. These new resonance properties have important consequences for {sup 17}O nucleosynthesis and {gamma}-ray emission of classical novae.

  8. Preprocessing of NMR metabolomics data.

    PubMed

    Euceda, Leslie R; Giskeødegård, Guro F; Bathen, Tone F

    2015-05-01

    Metabolomics involves the large scale analysis of metabolites and thus, provides information regarding cellular processes in a biological sample. Independently of the analytical technique used, a vast amount of data is always acquired when carrying out metabolomics studies; this results in complex datasets with large amounts of variables. This type of data requires multivariate statistical analysis for its proper biological interpretation. Prior to multivariate analysis, preprocessing of the data must be carried out to remove unwanted variation such as instrumental or experimental artifacts. This review aims to outline the steps in the preprocessing of NMR metabolomics data and describe some of the methods to perform these. Since using different preprocessing methods may produce different results, it is important that an appropriate pipeline exists for the selection of the optimal combination of methods in the preprocessing workflow.

  9. Spectroscopic observations of 14N/15N ratios in both NH2 and CN in comet C/2013 US10 (Catalina)

    NASA Astrophysics Data System (ADS)

    Shinnaka, Yoshiharu; Kawakita, Hideyo

    2016-10-01

    Comet is one of the primordial small bodies in the solar system and probably it has kept the information about the evolution of materials from the pre-solar molecular cloud to the solar nebula.Isotopic ratio in volatiles is one of the primordial properties of comets. A heavier isotopes trend to be captured into a molecule by chemical reactions under very low-temperature conditions (called as fractionation). For instance, D/H ratio of water (HDO/H2O) in comet is enriched in D atom than the elemental abundance ratios of D/H in entire solar system [1]. Based on the observed D/H ratios in cometary water, a presumed temperature is ~20–50 K as the formation temperature of water (most abundant volatiles in cometary nucleus), by assuming water formed in gas-phase chemistry [2].Besides, the nitrogen isotopic ratios (14N/15N) have been determined from CN and HCN (which is believed a dominant "parent" species of CN in the coma) in >20 comets [3,4]. They demonstrated cometary HCN and CN show high 15N-fractionation with respect to the proto-solar value by a factor of ~3 and with a small diversity. Moreover, 14N/15N ratios in NH3 in comets has been determined from intensity ratios of NH2 isotopologues [5,6,7], and both 15N-fractionation as much as HCN in comets and a small diversity are seen in those 14N/15N ratios in NH3. However, there is a few reports about 14N/15N ratios in both HCN and NH3 in the same comets, and discussions about the relationship between these 14N/15N ratios have not been yet.We present 14N/15N ratios in both NH2 and CN in comet C/2013 US10 (Catalina). High-resolution optical spectra of the comet were taken with the HDS spectrograph mounted on the Subaru Telescope (Hawaii) on UT 2016 January 2–3. We will discuss about the origins of these volatiles based on the 14N/15N ratios.This work was supported by Graint-in-Aid for JSPS Fellows, 15J10864 (YS).References:[1] Lis et al., 2013, ApJ 774, L3[2] Millar et al., 1989, ApJ 340, 906[3] Bockelée-Morvan et

  10. Overtone vibrational spectroscopy in H2-H2O complexes: A combined high level theoretical ab initio, dynamical and experimental study

    NASA Astrophysics Data System (ADS)

    Ziemkiewicz, Michael P.; Pluetzer, Christian; Nesbitt, David J.; Scribano, Yohann; Faure, Alexandre; van der Avoird, Ad

    2012-08-01

    First results are reported on overtone (vOH = 2 ← 0) spectroscopy of weakly bound H2-H2O complexes in a slit supersonic jet, based on a novel combination of (i) vibrationally mediated predissociation of H2-H2O, followed by (ii) UV photodissociation of the resulting H2O, and (iii) UV laser induced fluorescence on the nascent OH radical. In addition, intermolecular dynamical calculations are performed in full 5D on the recent ab initio intermolecular potential of Valiron et al. [J. Chem. Phys. 129, 134306 (2008), 10.1063/1.2988314] in order to further elucidate the identity of the infrared transitions detected. Excellent agreement is achieved between experimental and theoretical spectral predictions for the most strongly bound van der Waals complex consisting of ortho (I = 1) H2 and ortho (I = 1) H2O (oH2-oH2O). Specifically, two distinct bands are seen in the oH2-oH2O spectrum, corresponding to internal rotor states in the upper vibrational manifold of Σ and Π rotational character. However, none of the three other possible nuclear spin modifications (pH2-oH2O, pH2-pH2O, or oH2-pH2O) are observed above current signal to noise level, which for the pH2 complexes is argued to arise from displacement by oH2 in the expansion mixture to preferentially form the more strongly bound species. Direct measurement of oH2-oH2O vibrational predissociation in the time domain reveals lifetimes of 15(2) ns and <5(2) ns for the Σ and Π states, respectively. Theoretical calculations permit the results to be interpreted in terms of near resonant energy levels and intermolecular alignment of the H2 and H2O wavefunctions, providing insight into predissociation dynamical pathways from these metastable levels.

  11. An introduction to biological NMR spectroscopy.

    PubMed

    Marion, Dominique

    2013-11-01

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

  12. An Introduction to Biological NMR Spectroscopy*

    PubMed Central

    Marion, Dominique

    2013-01-01

    NMR spectroscopy is a powerful tool for biologists interested in the structure, dynamics, and interactions of biological macromolecules. This review aims at presenting in an accessible manner the requirements and limitations of this technique. As an introduction, the history of NMR will highlight how the method evolved from physics to chemistry and finally to biology over several decades. We then introduce the NMR spectral parameters used in structural biology, namely the chemical shift, the J-coupling, nuclear Overhauser effects, and residual dipolar couplings. Resonance assignment, the required step for any further NMR study, bears a resemblance to jigsaw puzzle strategy. The NMR spectral parameters are then converted into angle and distances and used as input using restrained molecular dynamics to compute a bundle of structures. When interpreting a NMR-derived structure, the biologist has to judge its quality on the basis of the statistics provided. When the 3D structure is a priori known by other means, the molecular interaction with a partner can be mapped by NMR: information on the binding interface as well as on kinetic and thermodynamic constants can be gathered. NMR is suitable to monitor, over a wide range of frequencies, protein fluctuations that play a crucial role in their biological function. In the last section of this review, intrinsically disordered proteins, which have escaped the attention of classical structural biology, are discussed in the perspective of NMR, one of the rare available techniques able to describe structural ensembles. This Tutorial is part of the International Proteomics Tutorial Programme (IPTP 16 MCP). PMID:23831612

  13. Saturation transfer difference NMR for fragment screening.

    PubMed

    Begley, Darren W; Moen, Spencer O; Pierce, Phillip G; Zartler, Edward R

    2013-01-01

    Fragment screening by saturation transfer difference nuclear magnetic resonance (STD-NMR) is a robust method for identifying small molecule binders and is well suited to a broad set of biological targets. STD-NMR is exquisitely sensitive for detecting weakly binding compounds (a common characteristic of fragments), which is a crucial step in finding promising compounds for a fragment-based drug discovery campaign. This protocol describes the development of a library suitable for STD-NMR fragment screening, as well as preparation of protein samples, optimization of experimental conditions, and procedures for data collection and analysis. PMID:24391096

  14. Scalar operators in solid-state NMR

    SciTech Connect

    Sun, Boqin

    1991-11-01

    Selectivity and resolution of solid-state NMR spectra are determined by dispersion of local magnetic fields originating from relaxation effects and orientation-dependent resonant frequencies of spin nuclei. Theoretically, the orientation-dependent resonant frequencies can be represented by a set of irreducible tensors. Among these tensors, only zero rank tensors (scalar operators) are capable of providing high resolution NMR spectra. This thesis presents a series of new developments in high resolution solid-state NMR concerning the reconstruction of various scalar operators motion in solid C{sub 60} is analyzed.

  15. Probing porous media with gas diffusion NMR.

    PubMed

    Mair, R W; Wong, G P; Hoffmann, D; Hurlimann, M D; Patz, S; Schwartz, L M; Walsworth, R L

    1999-10-18

    We show that gas diffusion nuclear magnetic resonance (GD-NMR) provides a powerful technique for probing the structure of porous media. In random packs of glass beads, using both laser-polarized and thermally polarized xenon gas, we find that GD-NMR can accurately measure the pore space surface-area-to-volume ratio, S/V rho, and the tortuosity, alpha (the latter quantity being directly related to the system's transport properties). We also show that GD-NMR provides a good measure of the tortuosity of sandstone and complex carbonate rocks. PMID:11543587

  16. MAS NMR of HIV-1 protein assemblies

    NASA Astrophysics Data System (ADS)

    Suiter, Christopher L.; Quinn, Caitlin M.; Lu, Manman; Hou, Guangjin; Zhang, Huilan; Polenova, Tatyana

    2015-04-01

    The negative global impact of the AIDS pandemic is well known. In this perspective article, the utility of magic angle spinning (MAS) NMR spectroscopy to answer pressing questions related to the structure and dynamics of HIV-1 protein assemblies is examined. In recent years, MAS NMR has undergone major technological developments enabling studies of large viral assemblies. We discuss some of these evolving methods and technologies and provide a perspective on the current state of MAS NMR as applied to the investigations into structure and dynamics of HIV-1 assemblies of CA capsid protein and of Gag maturation intermediates.

  17. Probing porous media with gas diffusion NMR

    NASA Technical Reports Server (NTRS)

    Mair, R. W.; Wong, G. P.; Hoffmann, D.; Hurlimann, M. D.; Patz, S.; Schwartz, L. M.; Walsworth, R. L.

    1999-01-01

    We show that gas diffusion nuclear magnetic resonance (GD-NMR) provides a powerful technique for probing the structure of porous media. In random packs of glass beads, using both laser-polarized and thermally polarized xenon gas, we find that GD-NMR can accurately measure the pore space surface-area-to-volume ratio, S/V rho, and the tortuosity, alpha (the latter quantity being directly related to the system's transport properties). We also show that GD-NMR provides a good measure of the tortuosity of sandstone and complex carbonate rocks.

  18. NMR mechanisms in gel dosimetry

    NASA Astrophysics Data System (ADS)

    Schreiner, L. J.

    2009-05-01

    Nuclear magnetic resonance was critical to the development of gel dosimetry, as it established the potential for three dimensional dosimetry with chemical dosimeter systems through magnetic resonance imaging [1]. In the last two decades MRI has served as the gold standard for imaging, while NMR relaxometry has played an important role in the development and understanding of the behaviour of new gel dosimetry systems. Therefore, an appreciation of the relaxation mechanisms determining the NMR behaviour of irradiated gel dosimeters is important for a full comprehension of a considerable component of the literature on gel dosimetry. A number of excellent papers have presented this important theory, this brief review will highlight some of the salient points made previously [1-5]. The spin relaxation of gel dosimeters (which determines the dose dependence in most conventional MR imaging) is determined principally by the protons on water molecules in the system. These water protons exist in different environments, or groups (see Figure 1): on bulk water, on water hydrating the chemical species that are being modified under irradiation, and on water hydrating the gel matrix used to spatially stabilize the dosimeter (e.g., gelatin, agarose, etc). The spin relaxation depends on the inherent relaxation rate of each spin group, that is, on the relaxation rate which would be observed for the specific group if it were isolated. Also, the different water environments are not isolated from each other, and the observed relaxation rate also depends on the rate of exchange of magnetization between the groups, and on the fraction of protons in each group. In fact, the water exchanges quickly between the environments, so that relaxation is in what is usually termed the fast exchange regime. In the limit of fast exchange, the relaxation of the water protons is well characterized by a single exponential and hence by a single apparent relaxation rate. In irradiated gel dosimeters this

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

    PubMed

    Jang, Richard; Wang, Yan; Xue, Zhidong; Zhang, Yang

    2015-08-01

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

  20. Improvement of the high-accuracy 17O(p ,α )14N reaction-rate measurement via the Trojan Horse method for application to 17O nucleosynthesis

    NASA Astrophysics Data System (ADS)

    Sergi, M. L.; Spitaleri, C.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Rapisarda, G. G.; Tang, X. D.; Bucher, B.; Couder, M.; Davies, P.; deBoer, R.; Fang, X.; Lamm, L.; Ma, C.; Notani, M.; O'Brien, S.; Roberson, D.; Tan, W.; Wiescher, M.; Irgaziev, B.; Mukhamedzhanov, A.; Mrazek, J.; Kroha, V.

    2015-06-01

    The 17O(p ,α )14N and 17O(p ,γ )18F reactions are of paramount importance for the nucleosynthesis in a number of stellar sites, including red giants (RGs), asymptotic giant branch (AGB) stars, massive stars, and classical novae. In particular, they govern the destruction of 17O and the formation of the short-lived radioisotope 18F, which is of special interest for γ -ray astronomy. At temperatures typical of the above-mentioned astrophysical scenario, T =0.01 -0.1 GK for RG, AGB, and massive stars and T =0.1 -0.4 GK for a classical nova explosion, the 17O(p ,α )14N reaction cross section is dominated by two resonances: one at about ERc m=65 keV above the 18F proton threshold energy, corresponding to the EX=5.673 MeV level in 18F, and another one at ERc m=183 keV (EX=5.786 MeV). We report on the indirect study of the 17O(p ,α )14N reaction via the Trojan Horse method by applying the approach recently developed for extracting the strength of narrow resonance at ultralow energies. The mean value of the strengths obtained in the two measurements was calculated and compared with the direct data available in literature. This value was used as input parameter for reaction-rate determination and its comparison with the result of the direct measurement is also discussed in the light of the electron screening effect.

  1. Nonlinear thermal lens signal of the (Δυ = 6) C-H vibrational overtone of C6H6 in liquid solutions of n-C6H14 and CCl4

    NASA Astrophysics Data System (ADS)

    Nyaupane, Parashu R.; Diez-y-Riega, Helena; Camejo, David; Manzanares, Carlos E.

    2016-05-01

    The thermal lens technique is applied to vibrational overtone spectroscopy of solutions of benzene. The pump and probe thermal lens technique has been found to be very sensitive for detecting samples of low concentration in transparent solvents. The C-H fifth vibrational (Δ υ = 6) overtone spectrum of benzene is detected at room temperature for compositions per volume in the range (1 to 1 × 10-4) using CCl4 and n-C6H14 as solvents. By detecting the absorption band in a 100-ppm solution, the peak absorption of the signal is approximately (2.2 ± 0.3) × 10-7 cm-1. The parameters that determine the magnitude of the thermal lens signal such as the pump laser power and the thermodynamic properties of the solvent and solute are discussed. A plot of normalized integrated intensity as a function of composition of benzene in solution reveals a nonlinear behavior. The nonlinearity cannot be explained assuming solvent enhancement at low concentrations. A two-color absorption model that includes the simultaneous absorption of the pump and probe lasers explains the enhanced magnitude and the nonlinear behavior of the thermal lens signal for solutions of composition below 0.01.

  2. 14N Quadrupole Resonance in the presence of a weak static magnetic field. Direct determination of the electric field gradient tensor

    NASA Astrophysics Data System (ADS)

    Aissani, Sarra; Guendouz, Laouès; Canet, Daniel

    2014-02-01

    The electric field gradient tensor (considered here at the level of a nitrogen nucleus) can be described by two parameters: the largest element in the (x, y, z) principal axis system, denoted by Vzz, and the asymmetry parameter η=(Vyy-Vxx)/Vzz. The frequencies of the three nitrogen-14 NQR transitions depend on both parameters and two of them are, a priori, necessary for their determination. We demonstrate that, if a weak static magnetic field is applied during a NQR experiment, both parameters can be obtained from a single transition thus alleviating the difficulties for finding out 14N Quadrupole Resonance lines.

  3. Assessment of experimental d-PIGE γ-ray production cross sections for 12C, 14N and 16O and comparison with absolute thick target yields

    NASA Astrophysics Data System (ADS)

    Csedreki, L.; Halász, Z.; Kiss, Á. Z.

    2016-08-01

    Measured differential cross sections for deuteron induced γ-ray emission from the reactions 12C(d,pγ)13C, (Eγ = 3089 keV), 14N(d,pγ)15N (Eγ = 8310 keV) and 16O(d,pγ)17O (Eγ = 871 keV) available in the literature were assessed. In order to cross check the assessed γ-ray production cross section data, thick target γ-yields calculated from the differential cross sections were compared with available measured thick target yields. Recommended differential cross section data for each reaction were deduced for particle induced γ-ray emission (PIGE) applications.

  4. Resonance strength measurement at astrophysical energies: The {sup 17}O(p,α){sup 14}N reaction studied via Trojan Horse Method

    SciTech Connect

    Sergi, M. L. La Cognata, M.; Pizzone, R. G.; Spitaleri, C.; Lamia, L.; Rapisarda, G. G.; Mukhamedzhanov, A.; Irgaziev, B.; Tang, X. D.; Wiescher, M.; Mrazek, J.; Kroha, V.

    2015-10-15

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on {sup 17}O nuclei, overcoming extrapolation procedures and enhancement effects due to electron screening. We will report on the indirect study of the {sup 17}O(p,α){sup 14}N reaction via the THM by applying the approach developed for extracting the resonance strength of narrow resonance in the ultralow energy region. Two measurements will be described and the experimental THM cross sections will be shown for both experiments.

  5. A direct underground measurement of the {sup 17}O(p,α){sup 14}N reaction cross-section at energies of astrophysical interest

    SciTech Connect

    Bruno, C. G.; Collaboration, LUNA

    2014-05-09

    The {sup 17}O(p,α){sup 14}N reaction plays a key role in many stellar sites, including classical novae and massive stars. Our knowledge of these scenarios might be improved by a precise measurement of the reaction’s cross-section at astrophysical energies. A direct attempt is currently underway in the Gran Sasso Laboratory, Italy, using the underground LUNA 400kV accelerator. The background reduction afforded by the underground environment is essential to the success of this challenging measurement. A purpose-built experimental setup has been simulated and commissioned. Preliminary results are presented.

  6. 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.

  7. Imaging of complex NMR spectra.

    PubMed

    Harrison, C G; Adams, D F; Kramer, P B

    1985-01-01

    The Point Spread Function (PSF) in NMR imaging is the result of both the line broadening due to magnet field inhomogeneity and the intrinsic spectrum of the nucleus at resonance. In the case of proton imaging, the line broadening dominates the small chemical shifts and the spectral lines are not resolved. This is not generally the case with other nuclei having strong chemical shifts and the PSF then has a complex structure. During imaging, the complex PSF is convolved with the spatial distribution of the nucleus at resonance and this leads to halo artifacts which are dependent on the imaging technique employed. The images due to the ensemble of spectral lines can be separated in principle by deconvolution of the data with the PSF before reconstruction. In the special case where the complex PSF is spatially independent, it can be obtained from the Free Induction Decay (FID) data produced in the absence of a spatially encoding gradient field. This technique has been successfully applied to in-vivo imaging of exogenous perfluorocarbon material. PMID:3988470

  8. NMR-Assisted Molecular Docking Methodologies.

    PubMed

    Sturlese, Mattia; Bellanda, Massimo; Moro, Stefano

    2015-08-01

    Nuclear magnetic resonance (NMR) spectroscopy and molecular docking are regularly being employed as helpful tools of drug discovery research. Molecular docking is an extremely rapid method to evaluate possible binders from a large chemical library in a fast and cheap manner. NMR techniques can directly detect a protein-ligand interaction, can determine the corresponding association constant, and can consistently identify the ligand binding cavity. Consequently, molecular docking and NMR techniques are naturally complementary techniques where the combination of the two has the potential to improve the overall efficiency of drug discovery process. In this review, we would like to summarize the state of the art of docking methods which have been recently bridged to NMR experiments to identify novel and effective therapeutic drug candidates.

  9. A New Microcell Technique for NMR Analysis.

    ERIC Educational Resources Information Center

    Yu, Sophia J.

    1987-01-01

    Describes a new laboratory technique for working with small samples of compounds used in nuclear magnetic resonance (NMR) analysis. Demonstrates how microcells can be constructed for each experiment and samples can be recycled. (TW)

  10. NMR-Assisted Molecular Docking Methodologies.

    PubMed

    Sturlese, Mattia; Bellanda, Massimo; Moro, Stefano

    2015-08-01

    Nuclear magnetic resonance (NMR) spectroscopy and molecular docking are regularly being employed as helpful tools of drug discovery research. Molecular docking is an extremely rapid method to evaluate possible binders from a large chemical library in a fast and cheap manner. NMR techniques can directly detect a protein-ligand interaction, can determine the corresponding association constant, and can consistently identify the ligand binding cavity. Consequently, molecular docking and NMR techniques are naturally complementary techniques where the combination of the two has the potential to improve the overall efficiency of drug discovery process. In this review, we would like to summarize the state of the art of docking methods which have been recently bridged to NMR experiments to identify novel and effective therapeutic drug candidates. PMID:27490497

  11. NMR studies of borates and borides

    NASA Astrophysics Data System (ADS)

    Bray, P. J.

    1986-04-01

    Nuclear magnetic resonance (NMR) has been employed for some 25 years to study the structure of boron-containing compounds.1-3 The earliest works employed the 11B nuclear isotope in a study of glasses containing boron oxide. Many additional NMR studies3-10 of boron-containing glasses have utilized both the 11B and 10B isotopes. Crystalline materials were also studied2,3 at an early date, with particular attention given to borides and boron carbide. After a discussion of the features of NMR spectroscopy particularly pertinent for the study of boron-containing compounds, highlights of the early work and more recent studies will be summarized to indicate the usefulness of 10B and 11B NMR for structural studies.

  12. Solvent signal as an NMR concentration reference.

    PubMed

    Mo, Huaping; Raftery, Daniel

    2008-12-15

    We propose that the NMR solvent signal be utilized as a universal concentration reference because most solvents can be observed by NMR and solvent concentrations can be readily calculated or determined independently. In particular, a highly protonated solvent such as water can serve as a primary concentration standard for its stability, availability, and ease of observation. The potential problems of radiation damping associated with a strong NMR signal can be alleviated by small pulse angle excitation. The solvent signal then can be detected by the NMR receiver with the same efficiency as a dilute analyte. We demonstrated that the analyte's proton concentration can be accurately determined from 4 microM to more than 100 M, referenced by solvent (water) protons of concentrations more than 10 M. The proposed method is robust and indifferent to probe tuning and does not require any additional concentration standard.

  13. Frontiers of NMR in Molecular Biology

    SciTech Connect

    1999-08-25

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

  14. NMR of Membrane Proteins: Beyond Crystals.

    PubMed

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

    2016-01-01

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

  15. NMR studies of multiphase flows II

    SciTech Connect

    Altobelli, S.A.; Caprihan, A.; Fukushima, E.

    1995-12-31

    NMR techniques for measurements of spatial distribution of material phase, velocity and velocity fluctuation are being developed and refined. Versions of these techniques which provide time average liquid fraction and fluid phase velocity have been applied to several concentrated suspension systems which will not be discussed extensively here. Technical developments required to further extend the use of NMR to the multi-phase flow arena and to provide measurements of previously unobtainable parameters are the focus of this report.

  16. NMR of Membrane Proteins: Beyond Crystals.

    PubMed

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

    2016-01-01

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

  17. Multidimensional NMR spectroscopy in a single scan.

    PubMed

    Gal, Maayan; Frydman, Lucio

    2015-11-01

    Multidimensional NMR has become one of the most widespread spectroscopic tools available to study diverse structural and functional aspects of organic and biomolecules. A main feature of multidimensional NMR is the relatively long acquisition times that these experiments demand. For decades, scientists have been working on a variety of alternatives that would enable NMR to overcome this limitation, and deliver its data in shorter acquisition times. Counting among these methodologies is the so-called ultrafast (UF) NMR approach, which in principle allows one to collect arbitrary multidimensional correlations in a single sub-second transient. By contrast to conventional acquisitions, a main feature of UF NMR is a spatiotemporal manipulation of the spins that imprints the chemical shift and/or J-coupling evolutions being sought, into a spatial pattern. Subsequent gradient-based manipulations enable the reading out of this information and its multidimensional correlation into patterns that are identical to those afforded by conventional techniques. The current review focuses on the fundamental principles of this spatiotemporal UF NMR manipulation, and on a few of the methodological extensions that this form of spectroscopy has undergone during the years. PMID:26249041

  18. Artifact suppression in electron paramagnetic resonance imaging of 14N- and 15N-labeled nitroxyl radicals with asymmetric absorption spectra

    NASA Astrophysics Data System (ADS)

    Takahashi, Wataru; Miyake, Yusuke; Hirata, Hiroshi

    2014-10-01

    This article describes an improved method for suppressing image artifacts in the visualization of 14N- and 15N-labeled nitroxyl radicals in a single image scan using electron paramagnetic resonance (EPR). The purpose of this work was to solve the problem of asymmetric EPR absorption spectra in spectral processing. A hybrid function of Gaussian and Lorentzian lineshapes was used to perform spectral line-fitting to successfully separate the two kinds of nitroxyl radicals. This approach can process the asymmetric EPR absorption spectra of the nitroxyl radicals being measured, and can suppress image artifacts due to spectral asymmetry. With this improved visualization method and a 750-MHz continuous-wave EPR imager, a temporal change in the distributions of a two-phase paraffin oil and water/glycerin solution system was visualized using lipophilic and hydrophilic nitroxyl radicals, i.e., 2-(14-carboxytetradecyl)-2-ethyl-4,4-dimethyl-3-oxazolidinyloxy (16-DOXYL stearic acid) and 4-hydroxyl-2,2,6,6-tetramethylpiperidine-d17-1-15N-1-oxyl (TEMPOL-d17-15N). The results of the two-phase separation experiment verified that reasonable artifact suppression could be achieved by the present method that deals with asymmetric absorption spectra in the EPR imaging of 14N- and 15N-labeled nitroxyl radicals.

  19. A theoretical study of 17O, 14N and 2H nuclear quadrupole coupling tensors in the real crystalline structure of acetaminophen

    NASA Astrophysics Data System (ADS)

    Behzadi, Hadi; Esrafili, Mehdi D.; Hadipour, Nasser L.

    2007-03-01

    A systematic computational investigation was carried out to characterize the 17O, 14N and 2H electric field gradient, EFG, tensors in the acetaminophen real crystalline structure. To include the hydrogen bonding effects in the calculations, the most probable interacting molecules with the target molecule in the crystalline phase were considered through the various molecular clusters. The calculations were performed with the B3LYP method and 6-311++G ∗∗ and 6-311+G ∗ standard basis sets using the Gaussian 98 suite of programs. Calculated EFG tensors were used to evaluate the 17O, 14N, and 2H nuclear quadrupole resonance, NQR, parameters in acetaminophen crystalline structure, which are in good agreement with the available experimental data. The difference between the calculated NQR parameters of the monomer and molecular clusters shows how much hydrogen bonding interactions affect the EFG tensors of each nucleus. These results indicate that both O-H⋯O and N-H⋯O hydrogen bonding have major influence on the NQR parameters. Moreover, the quantum chemical calculation indicated that the intermolecular hydrogen bonding interactions play an essential role in determining the relative orientation of quadrupole coupling principal components in the molecular frame axes.

  20. The effects of methyl internal rotation and {sup 14}N quadrupole coupling in the microwave spectra of two conformers of N,N-diethylacetamide

    SciTech Connect

    Kannengießer, Raphaela; Klahm, Sebastian; Vinh Lam Nguyen, Ha Lüchow, Arne; Stahl, Wolfgang

    2014-11-28

    The gas phase structures and internal dynamics of N,N-diethylacetamide were determined with very high accuracy using a combination of molecular beam Fourier-transform microwave spectroscopy and quantum chemical calculations at high levels. Conformational studies yielded five stable conformers with C{sub 1} symmetry. The two most energetically favorable conformers, conformer I and II, could be found in the experimental spectrum. For both conformers, quadrupole hyperfine splittings of the {sup 14}N nucleus and torsional fine splittings due to the internal rotation of the acetyl methyl group occurred in the same order of magnitude and were fully assigned. The rotational constants, centrifugal distortion constants as well as the quadrupole coupling constants of the {sup 14}N nucleus were determined and fitted to experimental accuracy. The V{sub 3} potentials were found to be 517.04(13) cm{sup −1} and 619.48(91) cm{sup −1} for conformer I and II, respectively, and compared to the V{sub 3} potentials found in other acetamides. Highly accurate CCSD(T) and DMC calculations were carried out for calculating the barriers to internal rotation in comparison with the experimentally deduced V{sub 3} values.

  1. 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.

  2. Improved Direct Measurement of the 64.5 keV Resonance Strength in the 17O (p ,α )14N Reaction at LUNA

    NASA Astrophysics Data System (ADS)

    Bruno, C. G.; Scott, D. A.; Aliotta, M.; Formicola, A.; Best, A.; Boeltzig, A.; Bemmerer, D.; Broggini, C.; Caciolli, A.; Cavanna, F.; Ciani, G. F.; Corvisiero, P.; Davinson, T.; Depalo, R.; Di Leva, A.; Elekes, Z.; Ferraro, F.; Fülöp, Zs.; Gervino, G.; Guglielmetti, A.; Gustavino, C.; Gyürky, Gy.; Imbriani, G.; Junker, M.; Menegazzo, R.; Mossa, V.; Pantaleo, F. R.; Piatti, D.; Prati, P.; Somorjai, E.; Straniero, O.; Strieder, F.; Szücs, T.; Takács, M. P.; Trezzi, D.; LUNA Collaboration

    2016-09-01

    The 17O (p ,α ) 14N reaction plays a key role in various astrophysical scenarios, from asymptotic giant branch stars to classical novae. It affects the synthesis of rare isotopes such as 17O and 18F, which can provide constraints on astrophysical models. A new direct determination of the ER=64.5 keV resonance strength performed at the Laboratory for Underground Nuclear Astrophysics (LUNA) accelerator has led to the most accurate value to date ω γ =10.0 ±1. 4stat±0. 7syst neV , thanks to a significant background reduction underground and generally improved experimental conditions. The (bare) proton partial width of the corresponding state at Ex=5672 keV in 18F is Γp=35 ±5stat±3syst neV . This width is about a factor of 2 higher than previously estimated, thus leading to a factor of 2 increase in the 17O (p , α ) 14N reaction rate at astrophysical temperatures relevant to shell hydrogen burning in red giant and asymptotic giant branch stars. The new rate implies lower 17O/16O ratios, with important implications on the interpretation of astrophysical observables from these stars.

  3. Submillimeter Observations of Titan: Global Measures of Stratospheric Temperature, CO, HCN, HC3N, and the Isotopic Ratios 12C/13C and 14N/15N

    NASA Astrophysics Data System (ADS)

    Gurwell, Mark A.

    2004-11-01

    Interferometric observations of the atmosphere of Titan were performed with the Submillimeter Array on two nights in 2004 February to investigate the global average vertical distributions of several molecular species above the tropopause. Rotational transitions of CO, isomers of HCN, and HC3N were simultaneously recorded. The abundance of CO is determined to be 51+/-4 parts per million (ppm), constant with altitude. The vertical profile of HCN is dependent on the assumed temperature but generally increases from 30 parts per billion at the condensation altitude (~83 km) to 5 ppm at ~300 km. Furthermore, the central core of the HCN emission is strong and can be reproduced only if the upper stratospheric temperature increases with altitude. The isotopic ratios are determined to be 12C/13C=132+/-25 and 14N/15N=94+/-13 assuming the Coustenis & Bézard temperature profile. If the Lellouch temperature profile is assumed, the ratios decrease to 12C/13C=108+/-20 and 14N/15N=72+/-9. The vertical profile of HC3N is consistent with that derived by Marten et al.

  4. 33S NMR cryogenic probe for taurine detection

    NASA Astrophysics Data System (ADS)

    Hobo, Fumio; Takahashi, Masato; Maeda, Hideaki

    2009-03-01

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

  5. Achievement of a 920-MHz High Resolution NMR

    NASA Astrophysics Data System (ADS)

    Hashi, Kenjiro; Shimizu, Tadashi; Goto, Atsushi; Kiyoshi, Tsukasa; Matsumoto, Shinji; Wada, Hitoshi; Fujito, Teruaki; Hasegawa, Ken-ichi; Yoshikawa, Masatoshi; Miki, Takashi; Ito, Satoshi; Hamada, Mamoru; Hayashi, Seiji

    2002-06-01

    We have developed a 920-MHz NMR system and performed the proton NMR measurement of H 2O and ethylbenzene using the superconducting magnet operating at 21.6 T (920 MHz for proton), which is the highest field produced by a superconducting NMR magnet in the persistent mode. From the NMR measurements, it is verified that both homogeneity and stability of the magnet have a specification sufficient for a high resolution NMR.

  6. The structural transformation of monoclinic [(R)-C5H14N2][Cu(SO4)2(H2O)4].2H2O into orthorhombic [(R)-C5H14N2]2[Cu(H2O)6](SO4)3: crystal structures and thermal behavior

    NASA Astrophysics Data System (ADS)

    Saïd, Salem; Mhadhbi, Noureddine; Hajlaoui, Fadhel; Yahyaoui, Samia; Norquist, Alexander J.; Mhiri, Tahar; Bataille, Thierry; Naïli, Houcine

    2014-01-01

    Single crystals of [(R)-C5H14N2][Cu(SO4)2(H2O)4].2H2O (1) were grown through the slow evaporation of a solution containing H2SO4, (R)-C5H12N2 and CuSO4.5H2O. These crystals spontaneously transform to [(R)-C5H14N2]2[Cu(H2O)6](SO4)3 (2) over the course of four days at room temperature. The same single crystal on the same mounting was used for the determination of the structure of (1) and the unit cell determination of (2). A second single crystal of the transformed batch has served for the structural determination of (2). Compound 1 crystallizes in the noncentrosymmetric space group P21 (No. 4) and consists of trimeric [Cu(SO4)2(H2O)4]2- anions, [(R)-C5H14N2]2+ cations and occluded water molecules. Compound 2 crystallizes in P21212 (No. 18) and contains [Cu(H2O)6]2+ cations, [SO4]2- anions and occluded water molecules. The thermal decompositions of compounds 1 and 2 were studied by thermogravimetric analyses and temperature-dependent X-ray diffraction.

  7. Advanced NMR-based techniques for pore structure analysis of coal. Quarterly report No. 9, October 1, 1993--December 30, 1993

    SciTech Connect

    Smith, D.M.

    1993-12-31

    One of the main problems in coal utilization is the inability to properly characterize its complex pore structure. Coals typically have micro/ultra-micro pores but they also exhibit meso and macroporosity. Conventional pore size techniques (adsorption/condensation, mercury porosimetry) are limited because of this broad pore size range, microporosity, reactive nature of coal, samples must be completely dried, and network/percolation effects. Small angle scattering is limited because it probes both open and dosed pores. Although one would not expect any single technique to provide a satisfactory description of a coal`s structure, it is apparent that better techniques are necessary. Small angle scattering could be improved by combining scattering and adsorption measurements. Also, the measurement of NMR parameters of various gas phase and adsorbed phase NMR active probes can provide pore structure information. We will investigate the dependence of the common NMR parameters such as chemical shifts and relaxation times of several different nuclei and compounds on the pore structure of model microporous solids, carbons, and coals. In particular, we will study the interaction between several small molecules ({sup 129}Xe, {sup 3}He, {sup 14}N{sub 2}, {sup 14}NH{sub 3}, {sup 15}N{sub 2}, {sup 13}CH{sub 4}, {sup 13}CO{sub 2}) and pore surface. Our current work may be divided into three areas: small-angle X-ray scattering (SAXS), adsorption, and NMR.

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

    ERIC Educational Resources Information Center

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

    2009-01-01

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

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

    PubMed

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

    2015-08-01

    We present here the performance of the WeNMR CS-Rosetta3 web server in CASD-NMR, the critical assessment of automated structure determination by NMR. The CS-Rosetta server uses only chemical shifts for structure prediction, in combination, when available, with a post-scoring procedure based on unassigned NOE lists (Huang et al. in J Am Chem Soc 127:1665-1674, 2005b, doi: 10.1021/ja047109h). We compare the original submissions using a previous version of the server based on Rosetta version 2.6 with recalculated targets using the new R3FP fragment picker for fragment selection and implementing a new annotation of prediction reliability (van der Schot et al. in J Biomol NMR 57:27-35, 2013, doi: 10.1007/s10858-013-9762-6), both implemented in the CS-Rosetta3 WeNMR server. In this second round of CASD-NMR, the WeNMR CS-Rosetta server has demonstrated a much better performance than in the first round since only converged targets were submitted. Further, recalculation of all CASD-NMR targets using the new version of the server demonstrates that our new annotation of prediction quality is giving reliable results. Predictions annotated as weak are often found to provide useful models, but only for a fraction of the sequence, and should therefore only be used with caution. PMID:25982706

  10. Nuclear magnetic resonance apparatus having semitoroidal rf coil for use in topical NMR and NMR imaging

    DOEpatents

    Fukushima, Eiichi; Roeder, Stephen B. W.; Assink, Roger A.; Gibson, Atholl A. V.

    1986-01-01

    An improved nuclear magnetic resonance (NMR) apparatus for use in topical magnetic resonance (TMR) spectroscopy and other remote sensing NMR applications includes a semitoroidal radio-frequency (rf) coil. The semitoroidal rf coil produces an effective alternating magnetic field at a distance from the poles of the coil, so as to enable NMR measurements to be taken from selected regions inside an object, particularly including human and other living subjects. The semitoroidal rf coil is relatively insensitive to magnetic interference from metallic objects located behind the coil, thereby rendering the coil particularly suited for use in both conventional and superconducting NMR magnets. The semitoroidal NMR coil can be constructed so that it emits little or no excess rf electric field associated with the rf magnetic field, thus avoiding adverse effects due to dielectric heating of the sample or to any other interaction of the electric field with the sample.

  11. Calibration of NMR well logs from carbonate reservoirs with laboratory NMR measurements and μXRCT

    SciTech Connect

    Mason, Harris E.; Smith, Megan M.; Hao, Yue; Carroll, Susan A.

    2014-12-31

    The use of nuclear magnetic resonance (NMR) well log data has the potential to provide in-situ porosity, pore size distributions, and permeability of target carbonate CO₂ storage reservoirs. However, these methods which have been successfully applied to sandstones have yet to be completely validated for carbonate reservoirs. Here, we have taken an approach to validate NMR measurements of carbonate rock cores with independent measurements of permeability and pore surface area to volume (S/V) distributions using differential pressure measurements and micro X-ray computed tomography (μXRCT) imaging methods, respectively. We observe that using standard methods for determining permeability from NMR data incorrectly predicts these values by orders of magnitude. However, we do observe promise that NMR measurements provide reasonable estimates of pore S/V distributions, and with further independent measurements of the carbonate rock properties that universally applicable relationships between NMR measured properties may be developed for in-situ well logging applications of carbonate reservoirs.

  12. BOOK REVIEW: NMR Imaging of Materials

    NASA Astrophysics Data System (ADS)

    Blümich, Bernhard

    2003-09-01

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

  13. SU-E-J-142: Prompt Gamma Emission Measurements From a Passively Scattered Proton Beam On Targets Containing 16O, 12C and 14N

    SciTech Connect

    Jeyasugiththan, J; Peterson, S

    2015-06-15

    Purpose: To measure the prompt gamma emission from the important elements found in tissue ({sup 16}O,{sup 12}C and {sup 14}N) in a clinical passive-scatter treatment environment. Methods: The targets (composed of water, Perspex, graphite and liquid nitrogen) were irradiated with a 200 MeV passive-scatter proton beam and the discrete prompt gamma energy spectra was detected by a high resolution 2′ × 2′ LaBr. detector. In order to reduce the high level of radiation produced by the beam line elements, the detector was surrounded by 10 cm of lead to attenuate the scattered gamma-rays entering the detector with an extra 5 cm thick layer of lead added along the beam direction. A 10 cm thick collimator with a 5 cm × 10 cm rectangular opening was also used. Results: The prompt gamma peaks at 6.13 MeV and 4.44 MeV were clearly identified as a Result of the inelastic nuclear reaction between the protons and the 16O atoms found in the water target. The 6.13 MeV peak was 5% higher than the peak at 4.44 MeV for the water target. The 4.44 MeV peak was the only identified emission in the prompt gamma energy spectra from the graphite target ({sup 12}C). The expected 2.313 MeV peak form the{sup 14}N (liquid nitrogen target) was identified, but the other expected {sup 14}N peaks could not be resolved. Conclusion: Prompt gamma measurements with a passive-scatter proton beam are possible, but the presence of a high amount of background radiation from the patient final collimator presents a challenge at the treatment isocenter. The prominent prompt gamma peaks at 6.13 MeV and 4.44 MeV were identified from the water, Perspex and graphite targets. The prompt gammas from the liquid nitrogen target were difficult to see, but may not be significant in the in-vivo verification process.

  14. NMR studies of cation transport across membranes

    SciTech Connect

    Shochet, N.R.

    1985-01-01

    /sup 23/Na NMR Studies of cation transport across membranes were conducted both on model and biological membranes. Two ionophores, the carrier monensin and the channel-former gramicidin, were chosen to induce cation transport in large unilamellar phosphatidylcholine vesicles. The distinction between the NMR signals arising from the two sides of the membrane was achieved by the addition of an anionic paramagnetic shift reagent to the outer solution. The kinetics of the cation transport across the membrane was observed simultaneously monitoring the changes in the /sup 23/Na NMR signals of both compartments. Two mathematical models were developed for the estimation of the transport parameters of the monensin- and gramicidin-induced cation transport. The models were able to fit the experimental data very well. A new method for the estimation of the volume trapped inside the vesicles was developed. The method uses the relative areas of the intra- and extravesicular NMR signals arising from a suspension of vesicles bathed in the same medium they contain, as a measure for the relative volumes of these compartments. Sodium transport across biological membranes was studied by /sup 23/ NMR, using suspensions of cultured nerve cells. The sodium influx through voltage-gated channels was studied using the channel modifier batrachotoxin in combination with scorpion toxin.

  15. NMR methodologies in the analysis of blueberries.

    PubMed

    Capitani, Donatella; Sobolev, Anatoly P; Delfini, Maurizio; Vista, Silvia; Antiochia, Riccarda; Proietti, Noemi; Bubici, Salvatore; Ferrante, Gianni; Carradori, Simone; De Salvador, Flavio Roberto; Mannina, Luisa

    2014-06-01

    An NMR analytical protocol based on complementary high and low field measurements is proposed for blueberry characterization. Untargeted NMR metabolite profiling of blueberries aqueous and organic extracts as well as targeted NMR analysis focused on anthocyanins and other phenols are reported. Bligh-Dyer and microwave-assisted extractions were carried out and compared showing a better recovery of lipidic fraction in the case of microwave procedure. Water-soluble metabolites belonging to different classes such as sugars, amino acids, organic acids, and phenolic compounds, as well as metabolites soluble in organic solvent such as triglycerides, sterols, and fatty acids, were identified. Five anthocyanins (malvidin-3-glucoside, malvidin-3-galactoside, delphinidin-3-glucoside, delphinidin-3-galactoside, and petunidin-3-glucoside) and 3-O-α-l-rhamnopyranosyl quercetin were identified in solid phase extract. The water status of fresh and withered blueberries was monitored by portable NMR and fast-field cycling NMR. (1) H depth profiles, T2 transverse relaxation times and dispersion profiles were found to be sensitive to the withering.

  16. Review of advances in coupling electrochemistry and liquid state NMR.

    PubMed

    Bussy, Ugo; Boujtita, Mohammed

    2015-05-01

    The coupling of electrochemistry and NMR spectroscopy (EC-NMR) may present an interesting approach in the environmental oxidative degradation or metabolism studies. This review presents experimental advances in the field of EC-NMR and highlights the main advantages and drawbacks of in situ and on line of NMR spectroelectrochemistry. The analysis of NMR spectra recorded in situ or on line EC-NMR permits to elucidate the reaction pathway of the electrochemical oxidation reactions and could constitute a fast way for monitoring unstable species as for instance quinone and quinone imine structures without using any coupling agents. The use of 1D and 2D NMR coupled with electrochemistry may leads to the elucidation of the major species produced from the electrochemical oxidation process. The present review gives an overview about the development of the electrochemical cells which can operate on line or in situ with NMR measurements. Future developments and potential applications of EC-NMR are also discussed.

  17. NMR techniques in the study of cardiovascular structure and functions

    SciTech Connect

    Osbakken, M.; Haselgrove, J.

    1987-01-01

    The chapter titles of this book are: Introduction to NMR Techniques;Theory of NMR Probe Design;Overview of Magnetic Resonance Imaging to Study the Cardiovascular System;Vascular Anatomy and Physiology Studied with NMR Techniques;Assessment of Myocardial Ischemia and Infarction by Nuclear Magnetic Resonance Imaging;The Use of MRI in Congenital Heart Disease;Cardiomyopathies and Myocarditis Studied with NMR Techniques;Determination of Myocardial Mechanical Function with Magnetic Resonance Imaging Techniques;Determination of Flow Using NMR Techniques;The Use of Contrast Agents in Cardiac MRI;Can Cardiovascular Disease Be Effectively Evaluated with NMR Spectroscopy. NMR Studies of ATP Synthesis Reactions in the Isolated Heart;Studies of Intermediary Metabolism in the Heart by 13C NMR Spectroscopy;23Na and 39K NMR Spectroscopic Studies of the Intact Beating Heart;and Evaluation of Skeletal Muscle Metabolism in Patients with Congestive Heart Failure Using Phosphorus Nuclear Magnetic Resonance.

  18. Radiative neutron capture by {sup 2}H, {sup 7}Li, {sup 14}C, and {sup 14}N nuclei at astrophysical energies

    SciTech Connect

    Dubovichenko, S. B.

    2013-07-15

    The possibility of describing experimental data on the total cross sections for the n{sup 2}H, n{sup 7}Li, n{sup 14}C, and n{sup 14}N radiative-capture processes within the potential cluster model involving forbidden states and their classification according to Young's tableaux is considered. It is shown that this model and the methods used here to construct potentials make it possible to describe correctly the behavior of the experimental cross sections at energies between 5 to 10 meV (5 Multiplication-Sign 10{sup -3}-10 Multiplication-Sign 10{sup -3} eV) and 1 to 15MeV.

  19. NO3- Coordination in Aqueous Solutions by 15N/14N and 18O/natO Isotopic Substitution: What Can We Learn from Molecular Simulation?

    DOE PAGES

    Chialvo, Ariel A.; Vlcek, Lukas

    2014-12-16

    We explore the deconvolution of the water-nitrate correlations by the first-order difference approach involving neutron diffraction of heavy- and null-aqueous solutions of KNO3 under 14N 15N and natON 18ON substitutions to achieve a full characterization of the first water coordination around the nitrate ion. For that purpose we performed isobaric-isothermal simulations of 3.5m KNO3 aqueous solutions at ambient conditions to generate the relevant radial distribution functions (RDF) required in the analysis (a) to identify the individual partial contributions to the total neutron weighted distribution function, (b) to isolate and assess the contribution of NO3 -!K+ pair formation, (c) to testmore » the accuracy of the NDIS-based coordination calculations and XRDbased assumptions, and (d) to describe the water coordination around both the nitrogen and oxygen sites of the nitrate ion.« less

  20. Conformational NMR Study of Bistriazolyl Anion Receptors.

    PubMed

    Makuc, Damjan; Merckx, Tamara; Dehaen, Wim; Plavec, Janez

    2016-01-01

    Conformational features of pyridine- and pyrimidine-based bistriazolyl anion receptors dissolved in acetonitrile-d3 were assessed by multidimensional, heteronuclear NMR spectroscopy. NOESY correlation signals suggested preorganization of both host molecules in solution in the absence of anions. In addition, only a single set of signals was observed in the 1H NMR spectra, which suggested a symmetrical conformation of anion receptors or their conformational exchange that is fast on the NMR time-scale. Furthermore, the predominant conformations of the pyridine- and pyrimidine-based anion receptors are preserved upon addition of chloride, bromide, and acetate anions. Chemical shift changes observed upon addition of anions showed that the NH (thio)urea and triazole protons are involved in anion-receptor interactions through hydrogen bonding. PMID:27640375

  1. Review of NMR characterization of pyrolysis oils

    DOE PAGES

    Hao, Naijia; Ben, Haoxi; Yoo, Chang Geun; Adhikari, Sushil; Ragauskas, Arthur J.

    2016-08-24

    Here, pyrolysis of renewable biomass has been developed as a method to produce green fuels and chemicals in response to energy security concerns as well as to alleviate environmental issues incurred with fossil fuel usage. However, pyrolysis oils still have limited commercial application, mainly because unprocessed oils cannot be readily blended with current petroleum-based transportation fuels. To better understand these challenges, researchers have applied diverse characterization techniques in the development of bio-oil studies. In particular, nuclear magnetic resonance (NMR) is a key spectroscopic characterization method through analysis of bio-oil components. This review highlights the NMR strategies for pyrolysis oil characterizationmore » and critically discusses the applications of 1H, 13C, 31P, 19F, and two-dimensional (2-D NMR) analyses such as heteronuclear single quantum correlation (HSQC) in representative pyrolysis oil studies.« less

  2. NMR Spectroscopy: Processing Strategies (by Peter Bigler)

    NASA Astrophysics Data System (ADS)

    Mills, Nancy S.

    1998-06-01

    Peter Bigler. VCH: New York, 1997. 249 pp. ISBN 3-527-28812-0. $99.00. This book, part of a four-volume series planned to deal with all aspects of a standard NMR experiment, is almost the exact book I have been hoping to find. My department has acquired, as have hundreds of other undergraduate institutions, high-field NMR instrumentation and the capability of doing extremely sophisticated experiments. However, the training is often a one- or two-day experience in which the material retained by the faculty trained is garbled and filled with holes, not unlike the information our students seem to retain. This text, and the accompanying exercises based on data contained on a CD-ROM, goes a long way to fill in the gaps and clarify misunderstandings about NMR processing.

  3. NMR phase noise in bitter magnets.

    PubMed

    Sigmund, E E; Calder, E S; Thomas, G W; Mitrović, V F; Bachman, H N; Halperin, W P; Kuhns, P L; Reyes, A P

    2001-02-01

    We have studied the temporal instability of a high field resistive Bitter magnet through nuclear magnetic resonance (NMR). This instability leads to transverse spin decoherence in repeated and accumulated NMR experiments as is normally performed during signal averaging. We demonstrate this effect via Hahn echo and Carr--Purcell--Meiboom--Gill (CPMG) transverse relaxation experiments in a 23-T resistive magnet. Quantitative analysis was found to be consistent with separate measurements of the magnetic field frequency fluctuation spectrum, as well as with independent NMR experiments performed in a magnetic field with a controlled instability. Finally, the CPMG sequence with short pulse delays is shown to be successful in recovering the intrinsic spin--spin relaxation even in the presence of magnetic field temporal instability.

  4. A modularized pulse programmer for NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Mao, Wenping; Bao, Qingjia; Yang, Liang; Chen, Yiqun; Liu, Chaoyang; Qiu, Jianqing; Ye, Chaohui

    2011-02-01

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

  5. Theory of 14N and 17O Nuclear Quadrupole Interactions in the Single Amino Acids Occurring in the Protein Chain of Cytochrome c

    NASA Astrophysics Data System (ADS)

    Scheicher, R. H.; Cammarere, D.; Sahoo, N.; Nagamine, K.; Das, T. P.

    2002-07-01

    The understanding of electron transport in proteins based on a novel technique involving muon spin rotation (μSR)measurements is a topic of great current interest. The technique, which involves study of spin relaxation of a positive muon (μ+) trapped in amino acids in protein chains due to the fluctuating magnetic field that the moving electron produces, is based on the premise that the electron is generated by ionization of a muonium (Mu) which was trapped at the same site as the μ+ left behind. In attempting to test this premise from first-principles for the Cytochrome c (Cyt c) system in which recent μSR measurements have been made, we have carried out Hartree- Fock investigations of the electronic structures of the bare amino acids and amino acids with + and Mu trapped at the oxygen of the C=O group common to all amino acids. With the aim that the comparison of theoretically predicted experimental nuclear quadrupole interaction (NQI) parameters will provide a useful test of the electron distribution in the amino acids of Cyt c, we present results for the nuclear quadrupole coupling constants (e2qQ) and asymmetry parameters (η) for the bare amino acids and the amino acids with trapped μ+ and Mu. The trends in 2 and for 14N and 17O between the various amino acids, as well as the changes in these parameters in the presence of μ+ and Mu are being analyzed. It would be helpful to have experimental data for e2qQ and to η compare with our predictions for the amino acids as they occur in vitro in polycrystalline Cyt c in which the SR measurements have been carried out. It is also hoped that the μSR technique will be able to provide experimental data on e2qQ and for the 14N and 17O nuclei to compare with our predictions

  6. An NMR Study of Microvoids in Polymers

    NASA Technical Reports Server (NTRS)

    Toy, James; Mattrix, Larry

    1996-01-01

    An understanding of polymer defect structures, like microvoids in polymeric matrices, is most crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally not be found naturally in polymer or in NMR probe materials. There are two NMR active Xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb and Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe-129-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts in Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of Xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A series of spectra were obtained interspersed with applications of vacuum and heating to drive out the adsorbed Xe and determine the role of Xe-Xe interactions in the observed chemical shift.

  7. The Quiet Renaissance of Protein NMR

    PubMed Central

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

    2013-01-01

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

  8. Tritiation methods and tritium NMR spectroscopy

    SciTech Connect

    Jaiswal, D.K.; Morimoto, H.; Salijoughian, M.; Williams, P.G.

    1991-09-01

    We have used a simple process for the production of highly tritiated water and characterized the product species by {sup 1}H and {sup 3}H NMR spectroscopy. The water is readily manipulated and used in subsequent reactions either as T{sub 2}O, CH{sub 3}COOT or CF{sub 3}COOT. Development of tritiated diimide has progressed to the point where cis-hydrogenated products at 1-20 Ci/mmole S.A. are possible. Tri-n-butyl tin tritide has been produced at >95% tritium content and well characterized by multinuclear NMR techniques. 27 refs., 3 figs.

  9. NMR investigation of the quantum pigeonhole effect

    NASA Astrophysics Data System (ADS)

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

    2016-02-01

    NMR quantum simulators have been used for studying various quantum phenomena. Here, using a four-qubit NMR quantum simulator, we investigate the recently postulated quantum pigeonhole effect. In this phenomenon, a set of three particles in a two-path interferometer often appears to be in such a superposition that no two particles can be assigned a single path, thus exhibiting the nonclassical behavior. In our experiments, quantum pigeons are emulated by three nuclear qubits whose states are probed jointly and noninvasively by an ancillary spin. The experimental results are in good agreement with quantum theoretical predictions.

  10. Magic angle spinning NMR of viruses.

    PubMed

    Quinn, Caitlin M; Lu, Manman; Suiter, Christopher L; Hou, Guangjin; Zhang, Huilan; Polenova, Tatyana

    2015-04-01

    Viruses, relatively simple pathogens, are able to replicate in many living organisms and to adapt to various environments. Conventional atomic-resolution structural biology techniques, X-ray crystallography and solution NMR spectroscopy provided abundant information on the structures of individual proteins and nucleic acids comprising viruses; however, viral assemblies are not amenable to analysis by these techniques because of their large size, insolubility, and inherent lack of long-range order. In this article, we review the recent advances in magic angle spinning NMR spectroscopy that enabled atomic-resolution analysis of structure and dynamics of large viral systems and give examples of several exciting case studies. PMID:25919197

  11. Magic Angle Spinning NMR of Viruses

    PubMed Central

    Quinn, Caitlin; Lu, Manman; Suiter, Christopher L.; Hou, Guangjin; Zhang, Huilan; Polenova, Tatyana

    2015-01-01

    Viruses, relatively simple pathogens, are able to replicate in many living organisms and to adapt to various environments. Conventional atomic-resolution structural biology techniques, X-ray crystallography and solution NMR spectroscopy provided abundant information on the structures of individual proteins and nucleic acids comprising viruses; however, viral assemblies are not amenable to analysis by these techniques because of their large size, insolubility, and inherent lack of long-range order. In this article, we review the recent advances in magic angle spinning NMR spectroscopy that enabled atomic-resolution analysis of structure and dynamics of large viral systems and give examples of several exciting case studies. PMID:25919197

  12. NMR spectra of androstane analogs of brassinosteroids

    NASA Astrophysics Data System (ADS)

    Baranovskii, A. V.; Litvinovskaya, R. P.; Aver'kova, M. A.; Khripach, N. B.; Khripach, V. A.

    2007-09-01

    We have used two-dimensional NMR spectroscopy to make a complete assignment of signals from the nuclei of hydrogen and carbon atoms in the spectra of brassinosteroids in the androstane series. We have confirmed the stereochemistry of the chiral centers and the structure of the molecules. We have studied the effect of the configuration of the 2,3-diol groups in the A ring of the steroids on the chemical shift of adjacent atoms in the 13C and 1H NMR spectra.

  13. NMR Microscopy - Micron-Level Resolution.

    NASA Astrophysics Data System (ADS)

    Kwok, Wing-Chi Edmund

    1990-01-01

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

  14. NMR Stark Spectroscopy: New Methods to Calibrate NMR Sensitivity to Electric Fields

    NASA Astrophysics Data System (ADS)

    Tarasek, Matthew R.

    The influence of electrostatics on NMR parameters is well accepted. Thus, NMR is a promising route to probe electrical features within molecules and materials. However, applications of NMR Stark effects (E-field induced changes in spin energy levels) have been elusive. I have developed new approaches to resolve NMR Stark effects from an applied E field. This calibrates nuclear probes whose spectral response might later be used to evaluate internal E fields that are critical to function, such as those due to local charge distributions or sample structure. I will present two novel experimental approaches for direct calibration of NMR quadrupolar Stark effects (QSEs). In the first, steady-state (few-second) excitation by an E field at twice the NMR frequency (2ω 0) is used to saturate spin magnetization. The extent of saturation vs. E-field amplitude calibrates the QSE response rate, while measurements vs sample orientation determine tensorial character. The second method instead synchronizes short (few µs) pulses of the 2ω0 E field with a multiple-pulse NMR sequence. This, “POWER” (Perturbations Observed With Enhanced Resolution) approach enables more accurate measure of small QSEs (i.e. few Hz spectral changes). A 2nd key advantage is the ability to define tensorial response without reorienting the sample, but instead varying the phase of the 2ω0 field. I will describe these experiments and my home-built NMR “Stark probe”, employed on a conventional wide-bore solid-state NMR system. Results with GaAs demonstrate each method, while extensions to a wider array of molecular and material systems may now be possible using these methods.

  15. NMR blood vessel imaging method and apparatus

    SciTech Connect

    Riederer, S.J.

    1988-04-26

    A high speed method of forming computed images of blood vessels based on measurements of characteristics of a body is described comprising the steps of: subjecting a predetermined body area containing blood vessels of interest to, successively, applications of a short repetition time (TR) NMR pulse sequence during the period of high blood velocity and then to corresponding applications during the period of low blood velocity for successive heart beat cycles; weighting the collected imaging data from each application of the NMR pulse sequence according to whether the data was acquired during the period of high blood velocity or a period of low blood velocity of the corresponding heart beat cycle; accumulating weighted imaging data from a plurality of NMR pulse sequences corresponding to high blood velocity periods and from a plurality of NMR pulse sequences corresponding to low blood velocity periods; subtracting the weighted imaging data corresponding to each specific phase encoding acquired during the high blood velocity periods from the weighted imaging data for the same phase encoding corresponding to low blood velocity periods in order to compute blood vessel imaging data; and forming an image of the blood vessels of interest from the blood vessel imaging data.

  16. Solid-state NMR imaging system

    SciTech Connect

    Gopalsami, N.; Dieckman, S.L.; Ellingson, W.A.

    1990-01-01

    An accessory for use with a solid-state NMR spectrometer includes a special imaging probe with linear, high-field strength gradient fields and high-power broadband RF coils using a back projection method for data acquisition and image reconstruction, and a real-time pulse programmer adaptable for use by a conventional computer for complex high speed pulse sequences.

  17. Structural Studies of Biological Solids Using NMR

    NASA Astrophysics Data System (ADS)

    Ramamoorthy, Ayyalusamy

    2011-03-01

    High-resolution structure and dynamics of biological molecules are important in understanding their function. While studies have been successful in solving the structures of water-soluble biomolecules, it has been proven difficult to determine the structures of membrane proteins and fibril systems. Recent studies have shown that solid-state NMR is a promising technique and could be highly valuable in studying such non-crystalline and non-soluble biosystems. I will present strategies to study the structures of such challenging systems and also about the applications of solid-state NMR to study the modes of membrane-peptide interactions for a better assessment of the prospects of antimicrobial peptides as substitutes to antibiotics in the control of human disease. Our studies on the mechanism of membrane disruption by LL-37 (a human antimicrobial peptide), analogs of the naturally occurring antimicrobial peptide magainin2 extracted from the skin of the African frog Xenopus Laevis, and pardaxin will be presented. Solid-state NMR experiments were used to determine the secondary structure, dynamics and topology of these peptides in lipid bilayers. Similarities and difference in the cell-lysing mechanism, and their dependence on the membrane composition, of these peptides will be discussed. Atomic-level resolution NMR structures of amyloidogenic proteins revealing the misfolding pathway and early intermediates that play key roles in amyloid toxicity will also be presented.

  18. Advanced Laboratory NMR Spectrometer with Applications.

    ERIC Educational Resources Information Center

    Biscegli, Clovis; And Others

    1982-01-01

    A description is given of an inexpensive nuclear magnetic resonance (NMR) spectrometer suitable for use in advanced laboratory courses. Applications to the nondestructive analysis of the oil content in corn seeds and in monitoring the crystallization of polymers are presented. (SK)

  19. NMR in a Diamond Anvil Pressure Cell

    NASA Astrophysics Data System (ADS)

    Lawson, Matthew; Dioguardi, Adam; Weir, Samuel; Bush, Blaine; Dunuwille, Mihindra; Deemyad, Shanti; Curro, Nichlas

    We present recent advances in the use of diamond anvil pressure cells in nuclear magnetic resonance measurements. This technique allows access to new regions of the phase diagrams of iron pnictide and heavy fermion materials, and promises to allow NMR experiments under pressures not previously accessible.

  20. Increasing the quantitative bandwidth of NMR measurements.

    PubMed

    Power, J E; Foroozandeh, M; Adams, R W; Nilsson, M; Coombes, S R; Phillips, A R; Morris, G A

    2016-02-18

    The frequency range of quantitative NMR is increased from tens to hundreds of kHz by a new pulse sequence, CHORUS. It uses chirp pulses to excite uniformly over very large bandwidths, yielding accurate integrals even for nuclei such as (19)F that have very wide spectra. PMID:26789115

  1. A Primer of Fourier Transform NMR.

    ERIC Educational Resources Information Center

    Macomber, Roger S.

    1985-01-01

    Fourier transform nuclear magnetic resonance (NMR) is a new spectroscopic technique that is often omitted from undergraduate curricula because of lack of instructional materials. Therefore, information is provided to introduce students to the technique of data collection and transformation into the frequency domain. (JN)

  2. NMR characterization of polymers: Review and update

    Technology Transfer Automated Retrieval System (TEKTRAN)

    NMR spectroscopy is a major technique for the characterization and analysis of polymers. A large number of methodologies have been developed in both the liquid and the solid state, and the literature has grown considerably (1-5). The field now covers a broad spectrum of activities, including polym...

  3. Hyperpolarized NMR Probes for Biological Assays

    PubMed Central

    Meier, Sebastian; Jensen, Pernille R.; Karlsson, Magnus; Lerche, Mathilde H.

    2014-01-01

    During the last decade, the development of nuclear spin polarization enhanced (hyperpolarized) molecular probes has opened up new opportunities for studying the inner workings of living cells in real time. The hyperpolarized probes are produced ex situ, introduced into biological systems and detected with high sensitivity and contrast against background signals using high resolution NMR spectroscopy. A variety of natural, derivatized and designed hyperpolarized probes has emerged for diverse biological studies including assays of intracellular reaction progression, pathway kinetics, probe uptake and export, pH, redox state, reactive oxygen species, ion concentrations, drug efficacy or oncogenic signaling. These probes are readily used directly under natural conditions in biofluids and are often directly developed and optimized for cellular assays, thus leaving little doubt about their specificity and utility under biologically relevant conditions. Hyperpolarized molecular probes for biological NMR spectroscopy enable the unbiased detection of complex processes by virtue of the high spectral resolution, structural specificity and quantifiability of NMR signals. Here, we provide a survey of strategies used for the selection, design and use of hyperpolarized NMR probes in biological assays, and describe current limitations and developments. PMID:24441771

  4. Increasing the quantitative bandwidth of NMR measurements.

    PubMed

    Power, J E; Foroozandeh, M; Adams, R W; Nilsson, M; Coombes, S R; Phillips, A R; Morris, G A

    2016-02-18

    The frequency range of quantitative NMR is increased from tens to hundreds of kHz by a new pulse sequence, CHORUS. It uses chirp pulses to excite uniformly over very large bandwidths, yielding accurate integrals even for nuclei such as (19)F that have very wide spectra.

  5. Hyperpolarized NMR probes for biological assays.

    PubMed

    Meier, Sebastian; Jensen, Pernille R; Karlsson, Magnus; Lerche, Mathilde H

    2014-01-16

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

  6. NMR analysis of a fluorocarbon copolymer

    SciTech Connect

    Smith, R.E.; Smith, C.H.

    1987-10-01

    Vinylidene fluoride (VF/sub 2/) can be copolymerized with chlorotrifluoroethylene (CTFE) in an aqueous emulsion using a peroxide chain initiator. The physical properties of the resulting fluorocarbon polymer depend on the ratio of VF/sub 2/ to CTFE and the randomness of the copolymerization. When CTFE and VF are polymerized in an approximately 3:1 mole ratio, the resulting polymer is soluble in acetone (and other solvents) at room temperature. Using proton and fluorine-19 NMR, the mole ratio of CTFE to VF/sub 2/, the emulsifier (perfluorodecanoate) concentration, and the randomness of copolymerization can be determined. A trifluorotoluene internal standard is added to a d/sub 6/-acetone solution of the fluoropolymer. Proton NMR is used to determine the amount of VF/sub 2/. Fluorine-19 NMR is used to measure the amount of emulsifier and the randomness of copolymerization. Each analysis requires about 5 minutes, and is quite precise, with relative standard deviations from 3 to 10% (10 replicates analyzed). In addition, the results from NMR analyses agree well with wet chemical analyses. 4 refs., 3 figs., 3 tabs.

  7. RNA Secondary Structure Determination by NMR.

    PubMed

    Chen, Jonathan L; Bellaousov, Stanislav; Turner, Douglas H

    2016-01-01

    Dynamic programming methods for predicting RNA secondary structure often use thermodynamics and experimental restraints and/or constraints to limit folding space. Chemical mapping results typically restrain certain nucleotides not to be in AU or GC pairs. Two-dimensional nuclear magnetic resonance (NMR) spectra can reveal the order of AU, GC, and GU pairs in double helixes. This chapter describes a program, NMR-assisted prediction of secondary structure and chemical shifts (NAPSS-CS), that constrains possible secondary structures on the basis of the NMR determined order and 5'-3' direction of AU, GC, and GU pairs in helixes. NAPSS-CS minimally requires input of the order of base pairs as determined from nuclear Overhauser effect spectroscopy (NOESY) of imino protons. The program deduces the 5'-3' direction of the base pairs if certain chemical shifts are also input. Secondary structures predicted by the program provide assignments of input chemical shifts to particular nucleotides in the sequence, thus facilitating an important step for determination of the three dimensional structure by NMR. The method is particularly useful for revealing pseudoknots and an example is provided. The method may also allow determination of secondary structures when a sequence folds into two structures that exchange slowly. PMID:27665599

  8. The spectroscopic (FTIR, FT-Raman, NMR and UV), first-order hyperpolarizability and HOMO-LUMO analysis of methylboronic acid

    NASA Astrophysics Data System (ADS)

    Rani, Usha; Karabacak, M.; Tanrıverdi, O.; Kurt, M.; Sundaraganesan, N.

    2012-06-01

    The solid phase FTIR and FT-Raman spectra of methylboronic acid (MBA) have been recorded in the regions 400-4000 and 50-4000 cm-1, respectively. The spectra were interpreted interms of fundamentals modes, combination and overtone bands. The structure of the molecule was optimized and the structural characteristics were determined by density functional theory (B3LYP) and HF method with 6-311++G(d,p) as basis set. The vibrational frequencies were calculated for most stable conformer and were compared with the experimental frequencies, which yield good agreement between observed and calculated frequencies. The infrared and Raman spectra were also predicted from the calculated intensities. 1H and 13C NMR spectra were recorded and 1H and 13C nuclear magnetic resonance chemical shifts of the molecule were calculated using the gauge independent atomic orbital (GIAO) method. UV-visible spectrum of the compound was recorded in the region 200-400 nm and the electronic properties HOMO and LUMO energies were calculated by time-dependent TD-DFT approach. Mulliken charges of the MBA molecule was also calculated and interpreted. The geometric parameters, energies, harmonic vibrational frequencies, IR intensities, Raman intensities and absorption wavelengths were compared with the available experimental data of the molecule.

  9. An NMR study of microvoids in polymers

    NASA Technical Reports Server (NTRS)

    Toy, James; Mattix, Larry

    1995-01-01

    An understanding of polymer defect structures, like microvoids in polymeric matrices, is crucial to their fabrication and application potential. In this project guest atoms are introduced into the microvoids in PMR-15 and NMR is used to determine microvoid sizes and locations. Xenon is a relatively inert probe that would normally be found naturally in polymer or in NMR probe materials. There are two NMR active xenon isotopes, Xe-129 and Xe-131. The Xe atom has a very high polarizability, which makes it sensitive to the intracrystalline environment of polymers. Interactions between the Xe atoms and the host matrix perturb the Xe electron cloud, deshielding the nuclei, and thereby expanding the range of the observed NMR chemical shifts. This chemical shift range which may be as large as 5000 ppm, permits subtle structural and chemical effects to be studied with high sensitivity. The Xe(129)-NMR line shape has been found to vary in response to changes in the pore symmetry of the framework hosts line Zeolites and Clathrasil compounds. Before exposure to Xe gas, the PMR-15 samples were dried in a vacuum oven at 150 C for 48 hours. The samples were then exposed to Xe gas at 30 psi for 72 hours and sealed in glass tubes with 1 atmosphere of xenon gas. Xenon gas at 1 atmosphere was used to tune up the spectrometer and to set up the appropriate NMR parameters. A single Xe-129 line at 83.003498 Mhz (with protons at 300 Mhz) was observed for the gas. With the xenon charged PMR-15 samples, a second broader line is observed 190 ppm downfield from the gas line (also observed). The width of the NMR line from the Xe-129 absorbed in the polymer is at least partially due to the distribution of microvoid sizes. From the chemical shift (relative to the gas line) and the line width, we estimate the average void sizes to be 2.74 +/- 0.20 angstroms. Since Xe-129 has such a large chemical shift range (approximately 5000 ppm), we expect the chemical shift anisotropy to contribute to the

  10. Dynamic nuclear polarization surface enhanced NMR spectroscopy.

    PubMed

    Rossini, Aaron J; Zagdoun, Alexandre; Lelli, Moreno; Lesage, Anne; Copéret, Christophe; Emsley, Lyndon

    2013-09-17

    Many of the functions and applications of advanced materials result from their interfacial structures and properties. However, the difficulty in characterizing the surface structure of these materials at an atomic level can often slow their further development. Solid-state NMR can probe surface structure and complement established surface science techniques, but its low sensitivity often limits its application. Many materials have low surface areas and/or low concentrations of active/surface sites. Dynamic nuclear polarization (DNP) is one intriguing method to enhance the sensitivity of solid-state NMR experiments by several orders of magnitude. In a DNP experiment, the large polarization of unpaired electrons is transferred to surrounding nuclei, which provides a maximum theoretical DNP enhancement of ∼658 for (1)H NMR. In this Account, we discuss the application of DNP to enhance surface NMR signals, an approach known as DNP surface enhanced NMR spectroscopy (DNP SENS). Enabling DNP for these systems requires bringing an exogeneous radical solution into contact with surfaces without diluting the sample. We proposed the incipient wetness impregnation technique (IWI), a well-known method in materials science, to impregnate porous and particulate materials with just enough radical containing solution to fill the porous volume. IWI offers several advantages: it is extremely simple, provides a uniform wetting of the surface, and does not increase the sample volume or substantially reduce the concentration of the sample. This Account describes the basic principles behind DNP SENS through results obtained for mesoporous and nanoparticulate samples impregnated with radical solutions. We also discuss the quantification of the overall sensitivity enhancements obtained with DNP SENS and compare that with ordinary room temperature NMR spectroscopy. We then review the development of radicals and solvents that give the best possible enhancements today. With the best

  11. A mobile one-sided NMR sensor with a homogeneous magnetic field: the NMR-MOLE.

    PubMed

    Manz, B; Coy, A; Dykstra, R; Eccles, C D; Hunter, M W; Parkinson, B J; Callaghan, P T

    2006-11-01

    A new portable NMR sensor with a novel one-sided access magnet design, termed NMR-MOLE (MObile Lateral Explorer), has been characterised in terms of sensitivity and depth penetration. The magnet has been designed to be portable and create a volume with a relatively homogeneous magnetic field, 15,000 ppm over a region from 4 to 16 mm away from the probe, with maximum sensitivity at a depth of 10 mm. The proton NMR frequency is 3.3 MHz. We have demonstrated that with this approach a highly sensitive, portable, unilateral NMR sensor can be built. Such a design is especially suited for the characterisation of liquids in situations where unilateral or portable access is required.

  12. Using NMR to study full intact wine bottles

    NASA Astrophysics Data System (ADS)

    Weekley, A. J.; Bruins, P.; Sisto, M.; Augustine, M. P.

    2003-03-01

    A nuclear magnetic resonance (NMR) probe and spectrometer capable of investigating full intact wine bottles is described and used to study a series of Cabernet Sauvignons with high resolution 1H NMR spectroscopy. Selected examples of full bottle 13C NMR spectra are also provided. The application of this full bottle NMR method to the measurement of acetic acid content, the detection of complex sugars, phenols, and trace elements in wine is discussed.

  13. Solid-state NMR studies of supercapacitors.

    PubMed

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

    2016-01-01

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

  14. Solid-state NMR studies of supercapacitors.

    PubMed

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

    2016-01-01

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

  15. Superoxygenated Water as an Experimental Sample for NMR Relaxometry

    ERIC Educational Resources Information Center

    Nestle, Nikolaus; Dakkouri, Marwan; Rauscher, Hubert

    2004-01-01

    The increase in NMR relaxation rates as a result of dissolved paramagnetic species on the sample of superoxygenated drinking water is demonstrated. It is concluded that oxygen content in NMR samples is an important issue and can give rise to various problems in the interpretation of both spectroscopic and NMR imaging or relaxation experiments.

  16. Foliar and fungal 15N:14N ratios reflect development of mycorrhizae and nitrogen supply during primary succession: testing analytical models.

    PubMed

    Hobbie, Erik A; Jumpponen, Ari; Trappe, Jim

    2005-12-01

    Nitrogen isotopes (15N/14N ratios, expressed as delta15N values) are useful markers of the mycorrhizal role in plant nitrogen supply because discrimination against 15N during creation of transfer compounds within mycorrhizal fungi decreases the 15N/14N in plants (low delta15N) and increases the 15N/14N of the fungi (high delta15N). Analytical models of 15N distribution would be helpful in interpreting delta15N patterns in fungi and plants. To compare different analytical models, we measured nitrogen isotope patterns in soils, saprotrophic fungi, ectomycorrhizal fungi, and plants with different mycorrhizal habits on a glacier foreland exposed during the last 100 years of glacial retreat and on adjacent non-glaciated terrain. Since plants during early primary succession may have only limited access to propagules of mycorrhizal fungi, we hypothesized that mycorrhizal plants would initially be similar to nonmycorrhizal plants in delta15N and then decrease, if mycorrhizal colonization were an important factor influencing plant delta15N. As hypothesized, plants with different mycorrhizal habits initially showed similar delta15N values (-4 to -6 per thousand relative to the standard of atmospheric N2 at 0 per thousand), corresponding to low mycorrhizal colonization in all plant species and an absence of ectomycorrhizal sporocarps. In later successional stages where ectomycorrhizal sporocarps were present, most ectomycorrhizal and ericoid mycorrhizal plants declined by 5-6 per thousand in delta15N, suggesting transfer of 15N-depleted N from fungi to plants. The values recorded (-8 to -11 per thousand) are among the lowest yet observed in vascular plants. In contrast, the delta15N of nonmycorrhizal plants and arbuscular mycorrhizal plants declined only slightly or not at all. On the forefront, most ectomycorrhizal and saprotrophic fungi were similar in delta15N (-1 to -3 per thousand), but the host-specific ectomycorrhizal fungus Cortinarius tenebricus had values of up to 7

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

    PubMed

    Heller, Davide Martin; Giorgetti, Alejandro

    2010-07-01

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

  18. Structural investigations on betacyanin pigments by LC NMR and 2D NMR spectroscopy.

    PubMed

    Stintzing, Florian C; Conrad, Jürgen; Klaiber, Iris; Beifuss, Uwe; Carle, Reinhold

    2004-02-01

    Four betacyanin pigments were analysed by LC NMR and subjected to extensive NMR characterisation after isolation. Previously, low pH values were applied for NMR investigations of betalains resulting in rapid degradation of the purified substances thus preventing extensive NMR studies. Consequently, up to now only one single (13)C NMR spectrum of a betalain pigment, namely that of neobetanin (=14,15-dehydrobetanin), was available. Because of its sufficient stability under highly acidic conditions otherwise detrimental for betacyanins, this pigment remained an exemption. Since betalains are most stable in the pH range of 5-7, a new solvent system has been developed allowing improved data acquisition through improved pigment stability at near neutral pH. Thus, not only (1)H, but for the first time also partial (13)C data of betanin, isobetanin, phyllocactin and hylocerenin isolated from red-purple pitaya [Hylocereus polyrhizus (Weber) Britton & Rose, Cactaceae] could be indirectly obtained by gHSQC- and gHMQC-NMR experiments.

  19. OPENCORE NMR: Open-source core modules for implementing an integrated FPGA-based NMR spectrometer

    NASA Astrophysics Data System (ADS)

    Takeda, Kazuyuki

    2008-06-01

    A tool kit for implementing an integrated FPGA-based NMR spectrometer [K. Takeda, A highly integrated FPGA-based nuclear magnetic resonance spectrometer, Rev. Sci. Instrum. 78 (2007) 033103], referred to as the OPENCORE NMR spectrometer, is open to public. The system is composed of an FPGA chip and several peripheral boards for USB communication, direct-digital synthesis (DDS), RF transmission, signal acquisition, etc. Inside the FPGA chip have been implemented a number of digital modules including three pulse programmers, the digital part of DDS, a digital quadrature demodulator, dual digital low-pass filters, and a PC interface. These FPGA core modules are written in VHDL, and their source codes are available on our website. This work aims at providing sufficient information with which one can, given some facility in circuit board manufacturing, reproduce the OPENCORE NMR spectrometer presented here. Also, the users are encouraged to modify the design of spectrometer according to their own specific needs. A home-built NMR spectrometer can serve complementary roles to a sophisticated commercial spectrometer, should one comes across such new ideas that require heavy modification to hardware inside the spectrometer. This work can lower the barrier of building a handmade NMR spectrometer in the laboratory, and promote novel and exciting NMR experiments.

  20. Solid-State NMR Reveals the Hydrophobic-Core Location of Poly(amidoamine) Dendrimers in Biomembranes

    PubMed Central

    Smith, Pieter E. S.; Brender, Jeffrey R.; Dürr, Ulrich H. N.; Xu, Jiadi; Mullen, Douglas G.; Banaszak Holl, Mark M.; Ramamoorthy, Ayyalusamy

    2010-01-01

    Poly(amidoamine) (PAMAM) dendrimer nanobiotechnology shows great promise in targeted drug delivery and gene therapy. Because of the involvement of cell membrane lipids with the pharmacological activity of dendrimer nanomedicines, the interactions between dendrimers and lipids are of particular relevance to the pharmaceutical applications of dendrimers. In this study, solid-state NMR was used to obtain a molecular image of the complex of generation 5 PAMAM dendrimer with the lipid bilayer. Using 1H radio frequency driven dipolar recoupling (RFDR) and 1H magic angle spinning (MAS) nuclear Overhauser effect spectroscopy (NOESY) techniques, we show that dendrimers are thermodynamically stable when inserted into zwitterionic lipid bilayers. 14N and 31P NMR experiments on static samples and measurements of the mobility of C–H bonds using a 2D proton detected local field protocol under MAS corroborate these results. The localization of dendrimers in the hydrophobic core of lipid bilayers restricts the motion of bilayer lipid tails, with the smaller G5 dendrimer having more of an effect than the larger G7 dendrimer. Fragmentation of the membrane does not occur at low dendrimer concentrations in zwitterionic membranes. Because these results show that the amphipathic dendrimer molecule can be stably incorporated in the interior of the bilayer (as opposed to electrostatic binding at the surface), they are expected to be useful in the design of dendrimer-based nanobiotechnologies. PMID:20481633

  1. Lifetime Measurement of the 6.79 MeV Excited State of 15O to Help Constrain the 14N(p,gamma)15O Reaction Rate

    NASA Astrophysics Data System (ADS)

    Galinski, Naomi

    2013-12-01

    In main sequence stars such as our Sun, the source of energy comes from converting hydrogen into helium. There are two competing mechanisms via which this can happen: the pp chain and CNO cycle. The latter is a cycle of reactions involving carbon, nitrogen and oxygen which are catalysts for the conversion of hydrogen into helium. The slowest reaction 14N(p, gamma) 15O in the cycle will affect the energy generation timescale and the amount of helium ash produced via the CNO cycle. This has several astrophysical impacts. It affects the evolutionary timescale of main sequence stars from which the ages of globular clusters can be calculated, the nucleosynthesis of heavier elements in H burning shells of red giant stars, and the fraction of energy produced by the CNO cycle compared to the pp chain in our Sun which helps determine the interior composition of the Sun. For main sequence stars the CNO cycle dominates over the pp chain for core temperatures T ≳ 0.02 GK. For the 14N(p, gamma)15O reaction this corresponds to a low center of mass energy Ecm = 30 keV. This is lower than the low energy limit of the reaction rate measurable in the laboratory. This means that we need to extrapolate down to low energy using theory. The largest remaining uncertainty in the theoretical calculations is due to the lifetime tau of the 6.79 MeV state of 15O. In this work the lifetimes of three excited states of 15O were measured using the Doppler shift attenuation method (DSAM) populating the states via the 3He(16O,alpha)15O reaction at a beam energy of 50 MeV. The low lifetime limit measurable using the DSAM is ˜1 fs. The lifetime of the 6.79 MeV state is near that limit, making this measurement challenging. A 1.8 fs upper limit (68.3% C.L.) on this lifetime is reported here. In addition we measured the lifetimes of the 6.17 and 6.86 MeV state in 15O which were < 2.5 fs and 13.3+0.8-1.2 fs (68.3% C.L.) respectively. iii Acknowledgments

  2. Humic acids from particulate organic matter in the Saguenay Fjord and the St. Lawrence Estuary investigated by advanced solid-state NMR

    NASA Astrophysics Data System (ADS)

    Mao, J.-D.; Tremblay, L.; Gagné, J.-P.; Kohl, S.; Rice, J.; Schmidt-Rohr, K.

    2007-11-01

    Detailed structural information on two humic acids extracted from two sinking particulate matter samples at a water depth of 20 m in the Saguenay Fjord (F-20-HA) and the St. Lawrence Estuary (E-20-HA) (Canada), was obtained by advanced solid-state NMR. Spectral-editing analyses provided numerous structural details rarely reported in geochemical studies. The NMR data account almost quantitatively for the elemental compositions. The two humic acids were found to be quite similar, consisting of four main structural components: peptides (ca. 39 ± 3% vs. 34 ± 3% of all C for E-20-HA and F-20-HA, respectively); aliphatic chains, 14-20 carbons long (ca. 25 ± 5% vs. 17 ± 5% of all C); aromatic structures (ca. 17 ± 2% vs. 26 ± 2% of all C); and sugar rings (14 ± 2% vs. 15 ± 2% of all C). Peptides were identified by 13C{ 14N} SPIDER NMR, which selects signals of carbons bonded to nitrogen, and by dipolar DEPT, which selects CH-group signals, in particular the NCH band of peptides. The SPIDER spectra also indicate that heterocycles constitute a significant fraction of the aromatic structures. The aliphatic (CH 2) n chains, which are highly mobile, contain at least one double bond per two chains and end in methyl groups. 1H spin diffusion NMR experiments showed that these mobile aliphatic chains are in close (<10 nm) proximity to the other structural components. A major bacterial contribution to these two samples could explain why the samples, which have different dominant organic matter sources (terrestrial vs. marine), are similar to each other as well as to degraded algae and particles from other waters. The NMR data suggest structures containing mobile lipids in close proximity to peptides and carbohydrates (e.g., peptidoglycan) as found in bacterial cell walls. Measured yields of muramic acid and D-amino acids confirmed the presence of bacterial cell wall components in the studied samples.

  3. NMR CHARACTERIZATIONS OF PROPERTIES OF HETEROGENEOUS MEDIA

    SciTech Connect

    C.T. Philip Chang; Changho Choi; Jeromy T. Hollenshead; Rudi Michalak; Jack Phan; Ramon Saavedra; John C. Slattery; Jinsoo Uh; Randi Valestrand; A. Ted Watson; Song Xue

    2005-01-01

    A critical and long-standing need within the petroleum industry is the specification of suitable petrophysical properties for mathematical simulation of fluid flow in petroleum reservoirs (i.e., reservoir characterization). The development of accurate reservoir characterizations is extremely challenging. Property variations may be described on many scales, and the information available from measurements reflect different scales. In fact, experiments on laboratory core samples, well-log data, well-test data, and reservoir-production data all represent information potentially valuable to reservoir characterization, yet they all reflect information about spatial variations of properties at different scales. Nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI) provide enormous potential for developing new descriptions and understandings of heterogeneous media. NMR has the rare capability to probe permeable media non-invasively, with spatial resolution, and it provides unique information about molecular motions and interactions that are sensitive to morphology. NMR well-logging provides the best opportunity ever to resolve permeability distributions within petroleum reservoirs. We develop MRI methods to determine, for the first time, spatially resolved distributions of porosity and permeability within permeable media samples that approach the intrinsic scale: the finest resolution of these macroscopic properties possible. To our knowledge, this is the first time that the permeability is actually resolved at a scale smaller than the sample. In order to do this, we have developed a robust method to determine of relaxation distributions from NMR experiments and a novel implementation and analysis of MRI experiments to determine the amount of fluid corresponding to imaging regions, which are in turn used to determine porosity and saturation distributions. We have developed a novel MRI experiment to determine velocity distributions within flowing experiments, and

  4. Multinuclear NMR studies of relaxor ferroelectrics

    NASA Astrophysics Data System (ADS)

    Zhou, Donghua

    Multinuclear NMR of 93Nb, 45Sc, and 207Pb has been carried out to study the structure, disorder, and dynamics of a series of important solid solutions: perovskite relaxor ferroelectric materials (1-x) Pb(Mg1/3Nb 2/3)O3-x Pb(Sc1/2Nb1/2)O 3 (PMN-PSN). 93Nb NMR investigations of the local structure and cation order/disorder are presented as a function of PSN concentration, x. The superb fidelity and accuracy of 3QMAS allows us to make clear and consistent assignments of spectral intensities to the 28 possible nearest B-site neighbor (nBn) configurations, (NMg, NSc, NNb), where each number ranges from 0 to 6 and their sum is 6. For most of the 28 possible nBn configurations, isotropic chemical shifts and quadrupole product constants have been extracted from the data. The seven configurations with only larger cations, Mg 2+ and Sc3+ (and no Nb5+) are assigned to the seven observed narrow peaks, whose deconvoluted intensities facilitate quantitative evaluation of, and differentiation between, different models of B-site (chemical) disorder. The "completely random" model is ruled out and the "random site" model is shown to be in qualitative agreement with the NMR experiments. To obtain quantitative agreement with observed NMR intensities, the random site model is slightly modified by including unlike-pair interaction energies. To date, 45Sc studies have not been as fruitful as 93Nb NMR because the resolution is lower in the 45Sc spectra. The lower resolution of 45Sc spectra is due to a smaller span of isotropic chemical shift (40 ppm for 45Sc vs. 82 ppm for 93Nb) and to the lack of a fortuitous mechanism that simplifies the 93Nb spectra; for 93Nb the overlap of the isotropic chemical shifts of 6-Sc and 6-Nb configurations results in the alignment of all the 28 configurations along only seven quadrupole distribution axes. Finally we present variable temperature 207Pb static, MAS, and 2D-PASS NMR studies. Strong linear correlations between isotropic and anisotropic chemical

  5. Sodium ion effect on silk fibroin conformation characterized by solid-state NMR and generalized 2D NMR NMR correlation

    NASA Astrophysics Data System (ADS)

    Ruan, Qing-Xia; Zhou, Ping

    2008-07-01

    In the present work, we investigated Na + ion effect on the silk fibroin (SF) conformation. Samples are Na +-involved regenerated silk fibroin films. 13C CP-MAS NMR demonstrates that as added [Na +] increases, partial silk fibroin conformation transit from helix-form to β-form at certain Na + ion concentration which is much higher than that in Bombyx mori silkworm gland. The generalized two-dimensional NMR-NMR correlation analysis reveals that silk fibroin undergoes several intermediate states during its conformation transition process as [Na +] increase. The appearance order of the intermediates is followed as: helix and/or random coil → helix-like → β-sheet-like → β-sheet, which is the same as that produced by pH decrease from 6.8 to 4.8 in the resultant regenerated silk fibroin films. The binding sites of Na + to silk fibroin might involve the carbonyl oxygen atom of certain amino acids sequence which could promote the formation of β-sheet conformation. Since the Na +sbnd O bond is weak, the ability of Na + inducing the secondary structure transition is weaker than those of Ca 2+, Cu 2+ and even K +. It is maybe a reason why the sodium content is much lower than potassium in the silkworm gland.

  6. SQUID detected NMR and MRI at ultralow fields

    SciTech Connect

    Clarke, John; McDermott, Robert; Pines, Alexander; Trabesinger, Andreas Heinz

    2006-10-03

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

  7. Squid detected NMR and MRI at ultralow fields

    DOEpatents

    Clarke, John; McDermott, Robert; Pines, Alexander; Trabesinger, Andreas Heinz

    2006-05-30

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

  8. Squid detected NMR and MRI at ultralow fields

    DOEpatents

    Clarke, John; McDermott, Robert; Pines, Alexander; Trabesinger, Andreas Heinz

    2007-05-15

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

  9. Squid detected NMR and MRI at ultralow fields

    SciTech Connect

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

    2008-12-16

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

  10. Disentangling scalar coupling patterns by real-time SERF NMR.

    PubMed

    Gubensäk, Nina; Fabian, Walter M F; Zangger, Klaus

    2014-10-21

    Scalar coupling constants and signal splitting patterns in NMR spectra contain a wealth of short-range structural information. The extraction of these parameters from (1)H NMR spectra is often prohibited by simultaneous scalar coupling interactions with several other protons. Here we present a high-resolution NMR experiment where scalar coupling to only one selected signal is visible. All other couplings are removed from the spectrum. This real-time selectively refocused NMR experiment is achieved by spatially selective homonuclear broadband decoupling combined with selective refocusing during acquisition. It allows the unperturbed extraction of scalar coupling constants from the highly resolved acquisition dimension of NMR spectra.

  11. Theoretical 13C chemical shift, 14N, and 2H quadrupole coupling- constant studies of hydrogen bonding in L-alanylglycine dipeptide.

    PubMed

    Tafazzoli, M; Amini, S K

    2008-04-01

    (13)C chemical shieldings and (14)N and (2)H electric field gradient (EFG) tensors of L-alanylglycine (L-alagly) dipeptide were calculated at RHF/6-31 + + G** and B3LYP/6-31 + + G** levels of theory respectively. For these calculations a crystal structure of this dipeptide obtained from X-ray crystallography was used. Atomic coordinates of different clusters containing several L-alagly molecules were used as input files for calculations. These clusters consist of central and surrounding L-alagly molecules, the latter forming short, strong, hydrogen bonds with the central molecule. Since the calculations did not converge for these clusters, the surrounding L-alagly molecules were replaced by glycine molecules. In order to improve the accuracy of calculated chemical shifts and nuclear quadrupole coupling constants (NQCCs), different geometry-optimization strategies were applied for hydrogen nuclei. Agreement between calculated and experimental data confirms that our optimized coordinates for hydrogen nuclei are more accurate than those obtained by X-ray diffraction.

  12. beta1,4-N-Acetylglucosaminyltransferase III potentiates beta1 integrin-mediated neuritogenesis induced by serum deprivation in Neuro2a cells.

    PubMed

    Shigeta, Masaki; Shibukawa, Yukinao; Ihara, Hideyuki; Miyoshi, Eiji; Taniguchi, Naoyuki; Gu, Jianguo

    2006-06-01

    Aspects of the biological significance of the bisecting N-acetylglucosamine (GlcNAc) structure on N-glycans introduced by beta1,4-N-acetylglucosaminyltransferase III (GnT-III) in Neuro2a cell differentiation are demonstrated. The overexpression of GnT-III in the cells led to the induction of axon-like processes with numerous neurites and swellings, in which beta1 integrin was localized, under conditions of serum starvation. This enhancement in neuritogenesis was suppressed by either the addition of a bisecting GlcNAc-containing N-glycan or erythroagglutinating phytohemagglutinin (E(4)-PHA), which preferentially recognizes the bisecting GlcNAc. GnT-III-promoted neuritogenesis was also significantly perturbed by treatment with a functional blocking anti-beta1 integrin antibody. In fact, beta1 integrin was found to be one of the target proteins of GnT-III, as confirmed by a pull-down assay with E(4)-PHA. These data suggest that N-glycans with a bisecting GlcNAc on target molecules, such as beta1 integrin, play important roles in the regulation of neuritogenesis. PMID:16531477

  13. Haldane-gap excitations in the low-Hc one-dimensional quantum antiferromagnet Ni(C5D14N2)2N3(PF6)

    NASA Astrophysics Data System (ADS)

    Zheludev, A.; Chen, Y.; Broholm, C. L.; Honda, Z.; Katsumata, K.

    2001-03-01

    Inelastic neutron scattering on deuterated single-crystal samples is used to study Haldane-gap excitations in the new S=1 one-dimensional quantum antiferromagnet Ni(C5D14N2)2N3(PF6), that was recently recognized as an ideal model system for high-field studies. The Haldane gap energies Δx=0.42(3) meV, Δy=0.52(6) meV, and Δz=1.9(1) meV, for excitations polarized along the a, b, and c crystallographic axes, respectively, are measured. The dispersion relation is studied for momentum transfers both along and perpendicular to the chains' direction. The in-chain exchange constant J=2.8 meV is found to be much larger than interchain coupling, Jy=1.8(4)×10-3 meV and Jx=4(3)×10-4 meV, along the b and a axes, respectively. The results are discussed in the context of future experiments in high magnetic fields.

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

    NASA Astrophysics Data System (ADS)

    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., 79Br-13C), can be a very effective relaxation mechanism. While working on hyperpolarized [5-13C]glutamine, fast liquid-state polarization decay during transfer to the MRI scanner was observed. This behavior could hypothetically be explained by substantial T1 shortening due to a scalar coupling contribution (type II) to the relaxation caused by the fast-relaxing quadrupolar 14N adjacent to the 13C 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 13C-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 15N-labeled amide or by applying a magnetic field during transfer of the sample from the polarizer to the MRI scanner.

  15. Sensitive measurement of NH4+ 15N/14N (delta 15NH4+) at natural abundance levels in fresh and saltwaters.

    PubMed

    Zhang, Lin; Altabet, Mark A; Wu, Taixing; Hadas, Ora

    2007-07-15

    We report a new method for determining the 15N/14N of NH4+ at natural abundance level in both freshwater and seawater. NH4+ is first quantitatively oxidized to NO2- by hypobromite (BrO-) at pH approximately 12. After the addition of sodium arsenite to consume excess BrO-, yield is verified by colorimetric NO2- determination. NO2- is further reduced to N2O using a 1:1 sodium azide and acetic acid buffer solution using previously established procedures. The product N2O is then analyzed for isotopic composition using a continuous flow purge and cryogenic trap system coupled to an isotope ratio mass spectrometer. Reliable delta 15N values (standard deviation is 0.3 per thousand or better) are obtained over an NH4+ concentration range of 0.5-10 microM using 20 mL volumes of either freshwater or seawater samples. Higher concentration samples are readily diluted to lower concentration. Preexisting NO2- is removed by treatment with sulfanilic acid. There is no interference from any of the nitrogen-containing compounds tested except short-chain aliphatic amino acids (i.e., glycine) which typically are present at very low environmental concentrations. As compared to published methods, our approach is more robust, readily applicable at low concentrations and small sample volumes, and requires less time for preparation and analysis.

  16. NMR shielding calculations across the periodic table: diamagnetic uranium compounds. 2. Ligand and metal NMR.

    PubMed

    Schreckenbach, Georg

    2002-12-16

    In this and a previous article (J. Phys. Chem. A 2000, 104, 8244), the range of application for relativistic density functional theory (DFT) is extended to the calculation of nuclear magnetic resonance (NMR) shieldings and chemical shifts in diamagnetic actinide compounds. Two relativistic DFT methods are used, ZORA ("zeroth-order regular approximation") and the quasirelativistic (QR) method. In the given second paper, NMR shieldings and chemical shifts are calculated and discussed for a wide range of compounds. The molecules studied comprise uranyl complexes, [UO(2)L(n)](+/-)(q); UF(6); inorganic UF(6) derivatives, UF(6-n)Cl(n), n = 0-6; and organometallic UF(6) derivatives, UF(6-n)(OCH(3))(n), n = 0-5. Uranyl complexes include [UO(2)F(4)](2-), [UO(2)Cl(4)](2-), [UO(2)(OH)(4)](2-), [UO(2)(CO(3))(3)](4-), and [UO(2)(H(2)O)(5)](2+). For the ligand NMR, moderate (e.g., (19)F NMR chemical shifts in UF(6-n)Cl(n)) to excellent agreement [e.g., (19)F chemical shift tensor in UF(6) or (1)H NMR in UF(6-n)(OCH(3))(n)] has been found between theory and experiment. The methods have been used to calculate the experimentally unknown (235)U NMR chemical shifts. A large chemical shift range of at least 21,000 ppm has been predicted for the (235)U nucleus. ZORA spin-orbit appears to be the most accurate method for predicting actinide metal chemical shifts. Trends in the (235)U NMR chemical shifts of UF(6-n)L(n) molecules are analyzed and explained in terms of the calculated electronic structure. It is argued that the energy separation and interaction between occupied and virtual orbitals with f-character are the determining factors.

  17. I: Low Frequency NMR and NQR Using a dc SQUID. II: Variable-temperature 13C CP/MAS of Organometallics

    SciTech Connect

    Ziegeweid, M.A.

    1995-11-29

    NMR and NQR at low frequencies are difficult prospects due to small nuclear spin polarization. Furthermore, the sensitivity'of the inductive pickup circuitry of standard spectrometers is reduced as the frequency is lowered. I have used a cw-SQUID (Superconducting QUantum Interference Device) spectrometer, which has no such frequency dependence, to study the local atomic environment of {sup 14}N via the quadrupolar interaction. Because {sup 14}N has spin I = 1 and a 0-6 MHz frequency range, it is not possible to obtain well-resolved spectra in high magnetic fields. I have used a technique to observe {sup 14}N NQR resonances via their effect on neighboring protons mediated by the heteronuclear dipolar interaction to study peptides and narcotics. The sensitivity of the SQUID is not enough to measure low-frequency surface (or other low spin density) systems. The application of spin-polarized xenon has been previously used to enhance polarization in conventional NMR experiments. Because xenon only polarizes spins with which it is in contact, it is surface selective. While differences in chemical shifts between surface and bulk spins are not large, it is expected that the differences in quadrupole coupling constant should be very large due to the drastic change of the electric field gradient surrounding spins at the surface. With this in mind, I have taken preliminary steps to measure SQUID detected polarization transfer from Xe to another spin species at 4.2 K and in small magnetic fields (<50 G). In this regime, the spin-lattice relaxation of xenon is dependent on the applied magnetic field. The results of our efforts to characterize the relaxation of xenon are presented. The final section describes the solid-state variable-temperature (VT) one- and two-dimensional {sup 13}C cross polarization (CP)/magic angle spinning (MAS) NMR of Hf({eta}{sup 5}-C{sub 5}H{sub 5}){sub 2}({eta}{sup 1}-C{sub 5}H{sub 5}){sub 2}, Zr({eta}{sup 5}-C{sub 5}H{sub 5}){sub 3}({eta}{sup 1}-C

  18. Advanced NMR-based techniques for pore structure analysis of coal. Quarterly report No. 7, April 1, 1993--June 31, 1993

    SciTech Connect

    Smith, D.M.

    1993-09-01

    One of the main problems in coal utilization is the inability to properly characterize its complex pore structure. Coals typically have micro/ultramicro pores but they also exhibit meso and macroporosity. Conventional pore size techniques (adsorption/condensation, mercury porosimetry) are limited because of this broad pore size range, microporosity, reactive nature of coal, samples must be completely dried, and network/percolation effects. Small angle scattering is limited because it probes both open and closed pores. Although one would not expect any single technique to provide a satisfactory description of a coal`s structure, it is apparent that better techniques are necessary. Small angle scattering could be improved by combining scattering and adsorption measurements. Also, the measurement of NMR parameters of various gas phase and adsorbed phase NMR active probes can provide pore structure information. We will investigate the dependence of the common NMR parameters such as chemical shifts and relaxation times of several different nuclei and compounds on the pore structure of model microporous solids, carbons, and coals. In particular, we will study the interaction between several small molecules ({sup 129}Xe, {sup 3}He, {sup 2}H{sub 2},{sup 14}N{sub 2}, {sup 14}NH{sub 3}, {sup 15}N{sub 2},{sup 13}CH{sub 4}, {sup 13}CO{sub 2}) and the pore surfaces in coals.

  19. Advanced NMR-based techniques for pore structure analysis of coal. Quarter report {number_sign}8, 7/1/93--9/30/93

    SciTech Connect

    Smith, D.M.

    1993-12-31

    One of the main problems in coal utilization is the inability to properly characterize its complex pore structure. Coals typically have micro/ultramicro pores but they also exhibit meso and macroporosity. Conventional pore size techniques (adsorption/condensation, mercury porosimetry) are limited because of this broad pore size range, microporosity, reactive nature of coal, samples must be completely dried, and network/percolation effects. Small angle scattering is limited because it probes both open and closed pores. Although one would not expect any single technique to provide a satisfactory description of a coal`s structure, it is apparent that better techniques are necessary. Small angle scattering could be improved by combining scattering and adsorption measurements. Also, the measurement of NMR parameters of various gas phase and adsorbed phase NMR active probes can provide pore structure information. The dependence of the common NMR parameters such as chemical shifts and relaxation times of several different nuclei and compounds on the pore structure of model microporous solids, carbons, and coals is investigated. In particular, the interaction between several small molecules ({sup 129}Xe, {sup 3}He, {sup 14}N{sub 2},{sup 14}NH{sub 3},{sup 15}N{sub 2},{sup 13} CH{sub 4}, {sup 13}CO{sub 2}) and pore surface is studied.

  20. Advanced NMR-based techniques for pore structure analysis of coal. Quarterly report No. 6, January 1, 1993--March 31, 1993

    SciTech Connect

    Smith, D.M.

    1993-08-01

    One of the main problems in coal utilization is the inability to properly characterize its complex pore structure. Coals typically have micro/ultra-micro pores but they also exhibit meso and macroporosity. Conventional pore size techniques (adsorption/condensation, mercury porosimetry) are limited because of this broad pore size range, microporosity, reactive nature of coal, samples must be completely dried, and network/percolation effects. Small angle scattering is limited because it probes both open and closed pores. Although one would not expect any single technique to provide a satisfactory description of a coal`s structure, it is apparent that better techniques are necessary. Small angle scattering could be improved by combining scattering and adsorption measurements. Also, the measurement of NMR parameters of various gas phase and adsorbed phase NMR active probes can provide pore structure information. We will investigate the dependence of the common NMR parameters such as chemical shifts and relaxation times of several different nuclei and compounds on the pore structure of model microporous solids, carbons, and coals. In particular, we will study the interaction between several small molecules ({sup 129}Xe, {sup 3}He, {sup 2}H{sub 2}, {sup 14}N{sub 2},{sup 14}NH{sub 3}, {sup 15}N{sup 2}, {sup 13}CH{sub 4}, {sup 13}CO{sub 2}) and the pore surfaces in coals.

  1. Nuclear spin noise in NMR revisited

    SciTech Connect

    Ferrand, Guillaume; Luong, Michel

    2015-09-07

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

  2. NMR studies of nucleic acid dynamics

    PubMed Central

    Al-Hashimi, Hashim M.

    2014-01-01

    Nucleic acid structures have to satisfy two diametrically opposite requirements; on one hand they have to adopt well-defined 3D structures that can be specifically recognized by proteins; on the other hand, their structures must be sufficiently flexible to undergo very large conformational changes that are required during key biochemical processes, including replication, transcription, and translation. How do nucleic acids introduce flexibility into their 3D structure without losing biological specificity? Here, I describe the development and application of NMR spectroscopic techniques in my laboratory for characterizing the dynamic properties of nucleic acids that tightly integrate a broad set of NMR measurements, including residual dipolar couplings, spin relaxation, and relaxation dispersion with sample engineering and computational approaches. This approach allowed us to obtain fundamental new insights into directional flexibility in nucleic acids that enable their structures to change in a very specific functional manner. PMID:24149218

  3. High Resolution non-Markovianity in NMR

    PubMed Central

    Bernardes, Nadja K.; Peterson, John P. S.; Sarthour, Roberto S.; Souza, Alexandre M.; Monken, C. H.; Roditi, Itzhak; Oliveira, Ivan S.; Santos, Marcelo F.

    2016-01-01

    Memoryless time evolutions are ubiquitous in nature but often correspond to a resolution-induced approximation, i.e. there are correlations in time whose effects are undetectable. Recent advances in the dynamical control of small quantum systems provide the ideal scenario to probe some of these effects. Here we experimentally demonstrate the precise induction of memory effects on the evolution of a quantum coin (qubit) by correlations engineered in its environment. In particular, we design a collisional model in Nuclear Magnetic Resonance (NMR) and precisely control the strength of the effects by changing the degree of correlation in the environment and its time of interaction with the qubit. We also show how these effects can be hidden by the limited resolution of the measurements performed on the qubit. The experiment reinforces NMR as a test bed for the study of open quantum systems and the simulation of their classical counterparts. PMID:27669652

  4. NMR spectral analysis using prior knowledge

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  5. NMR-based diffusion lattice imaging

    NASA Astrophysics Data System (ADS)

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

    2016-03-01

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

  6. Quantitative calibration of radiofrequency NMR Stark effects

    NASA Astrophysics Data System (ADS)

    Tarasek, Matthew R.; Kempf, James G.

    2011-10-01

    Nuclear magnetic resonance (NMR) Stark responses can occur in quadrupolar nuclei for an electric field oscillating at twice the usual NMR frequency (2ω0). Calibration of responses to an applied E field is needed to establish nuclear spins as probes of native E fields within material and molecular systems. We present an improved approach and apparatus for accurate measurement of quadrupolar Stark effects. Updated values of C14 (the response parameter in cubic crystals) were obtained for both 69Ga and 75As in GaAs. Keys to improvement include a modified implementation of voltage dividers to assess the 2ω0 amplitude, |E|, and the stabilization of divider response by reduction of stray couplings in 2ω0 circuitry. Finally, accuracy was enhanced by filtering sets of |E| through a linear response function that we established for the radiofrequency amplifier. Our approach is verified by two types of spectral results. Steady-state 2ω0 excitation to presaturate NMR spectra yielded C14 = (2.59 ± 0.06) × 1012 m-1 for 69Ga at room-temperature and 14.1 T. For 75As, we obtained (3.1 ± 0.1) × 1012 m-1. Both values reconcile with earlier results from 77 K and below 1 T, whereas current experiments are at room temperature and 14.1 T. Finally, we present results where few-microsecond pulses of the 2ω0 field induced small (tens of Hz) changes in high-resolution NMR line shapes. There too, spectra collected vs |E| agree with the model for response, further establishing the validity of our protocols to specify |E|.

  7. Water absorption in mortar determined by NMR.

    PubMed

    Pel, L; Hazrati, K; Kopinga, K; Marchand, J

    1998-01-01

    Nuclear magnetic resonance (NMR) offers the possibility to determine moisture profiles in porous building materials. Moreover, the relaxation of the nuclear magnetic resonance signal can provide additional information on the water distribution in the microstructure. For mortar, it is shown that the transverse relaxation yields information on the distribution of water in the gel pores and capillary pores. Moisture profiles and relaxation were measured during water absorption. The effect of the drying treatment on the microstructure and the water absorption was investigated.

  8. The Cheshire-cat-like Behavior of 2nu(sub 3) Overtone of Co2 near 2.134 micron: NIR Lab Spectra of Solid CO2 in H2O and CH3OH

    NASA Technical Reports Server (NTRS)

    Bernstein, Max; Sandford, Scott; Cruikshank, Dale

    2005-01-01

    Infrared (IR) spectra have demonstrated that solid H2O is very common in the outer Solar System, and solid carbon dioxide (CO2) has been detected on icy satellites, comets, and planetismals throughout the outer Solar System. In such environments, CO2 and H2O must sometimes be mixed at a molecular level, changing their IR absorption features. In fact, the IR spectra of CO2-H2O mixtures are not equivalent to a linear combination of the spectra of the pure materials. Laboratory IR spectra of pure CO2 and H2O have been published but a lack of near-IR spectra of CO2-H2O mixtures has made the interpretation of outer Solar System spectra more difficult. We present near infrared (IR) spectra of CO2 in H2O and in CH3OH compared to that of pure solid CO2 and find significant differences. Peaks not present in either pure H2O or pure CO2 spectra become evident. First, the CO2 (2nu(sub 3)) overtone near 2.134 micron (4685/ cm) that is not seen in pure solid CO2 is prominent in the spectrum of a CO2/H2O = 25 mixture. Second, a 2.74 micron (3650/ cm) dangling OH feature of water (and a potentially related peak at 1.89 micron) appear in the spectra of CO2-H2O ice mixtures, but may not be specific to the presence of CO2. Other CO2 peaks display shifts in position and increased width because of intermolecular interactions with water. Changes in CO2 peak positions and profiles on warming of a CO2/H2O = 5 mixture are consistent with 'segregation' of the ice into nearly pure separate components. Absolute strengths for absorptions of CO2 in solid H2O are estimated. Similar results are observed for CO2 in solid CH3OH. Since the CO2 ( 2nu(sub 3)) overtone near 2.134 micron (4685/ cm) is not present in pure CO2 but prominent in mixtures it may be a good observational indicator of whether solid CO2 is a pure material or intimately mixed with other molecules. Significant changes in the near IR spectrum of solid CO2 in the presence of H2O and CH3OH means that the abundance of solid CO2 in the

  9. Protein NMR structures refined without NOE data.

    PubMed

    Ryu, Hyojung; Kim, Tae-Rae; Ahn, SeonJoo; Ji, Sunyoung; Lee, Jinhyuk

    2014-01-01

    The refinement of low-quality structures is an important challenge in protein structure prediction. Many studies have been conducted on protein structure refinement; the refinement of structures derived from NMR spectroscopy has been especially intensively studied. In this study, we generated flat-bottom distance potential instead of NOE data because NOE data have ambiguity and uncertainty. The potential was derived from distance information from given structures and prevented structural dislocation during the refinement process. A simulated annealing protocol was used to minimize the potential energy of the structure. The protocol was tested on 134 NMR structures in the Protein Data Bank (PDB) that also have X-ray structures. Among them, 50 structures were used as a training set to find the optimal "width" parameter in the flat-bottom distance potential functions. In the validation set (the other 84 structures), most of the 12 quality assessment scores of the refined structures were significantly improved (total score increased from 1.215 to 2.044). Moreover, the secondary structure similarity of the refined structure was improved over that of the original structure. Finally, we demonstrate that the combination of two energy potentials, statistical torsion angle potential (STAP) and the flat-bottom distance potential, can drive the refinement of NMR structures.

  10. NMR Studies of Cartilage Dynamics, Diffusion, Degradation

    NASA Astrophysics Data System (ADS)

    Huster, Daniel; Schiller, Jurgen; Naji, Lama; Kaufmann Jorn; Arnold, Klaus

    An increasing number of people is suffering from rheumatic diseases, and, therefore, methods of early diagnosis of joint degeneration are urgently required. For their establishment, however, an improved knowledge about the molecular organisation of cartilage would be helpful. Cartilage consists of three main components: Water, collagen and chondroitin sulfate (CS) that is (together with further polysaccharides and proteins) a major constituent of the proteoglycans of cartilage. 1H and 13C MAS (magic-angle spinning) NMR (nuclear magnetic resonance) opened new perspectives for the study of the macromolecular components in cartilage. We have primarily studied the mobilities of CS and collagen in bovine nasal and pig articular cartilage (that differ significantly in their collagen/polysaccharide content) by measuring 13C NMR relaxation times as well as the corresponding 13C CP (cross polarisation) MAS NMR spectra. These data clearly indicate that the mobility of cartilage macromolecules is broadly distributed from almost completely rigid (collagen) to highly mobile (polysaccharides), which lends cartilage its mechanical strength and shock-absorbing properties.

  11. NMR Studies of Dynamic Biomolecular Conformational Ensembles

    PubMed Central

    Torchia, Dennis A.

    2015-01-01

    Multidimensional heteronuclear NMR approaches can provide nearly complete sequential signal assignments of isotopically enriched biomolecules. The availability of assignments together with measurements of spin relaxation rates, residual spin interactions, J-couplings and chemical shifts provides information at atomic resolution about internal dynamics on timescales ranging from ps to ms, both in solution and in the solid state. However, due to the complexity of biomolecules, it is not possible to extract a unique atomic-resolution description of biomolecular motions even from extensive NMR data when many conformations are sampled on multiple timescales. For this reason, powerful computational approaches are increasingly applied to large NMR data sets to elucidate conformational ensembles sampled by biomolecules. In the past decade, considerable attention has been directed at an important class of biomolecules that function by binding to a wide variety of target molecules. Questions of current interest are: “Does the free biomolecule sample a conformational ensemble that encompasses the conformations found when it binds to various targets; and if so, on what time scale is the ensemble sampled?” This article reviews recent efforts to answer these questions, with a focus on comparing ensembles obtained for the same biomolecules by different investigators. A detailed comparison of results obtained is provided for three biomolecules: ubiquitin, calmodulin and the HIV-1 trans-activation response RNA. PMID:25669739

  12. Discrete analysis of stochastic NMR.II

    NASA Astrophysics Data System (ADS)

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

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

  13. Calibration of NMR well logs from carbonate reservoirs with laboratory NMR measurements and μXRCT

    DOE PAGES

    Mason, Harris E.; Smith, Megan M.; Hao, Yue; Carroll, Susan A.

    2014-12-31

    The use of nuclear magnetic resonance (NMR) well log data has the potential to provide in-situ porosity, pore size distributions, and permeability of target carbonate CO₂ storage reservoirs. However, these methods which have been successfully applied to sandstones have yet to be completely validated for carbonate reservoirs. Here, we have taken an approach to validate NMR measurements of carbonate rock cores with independent measurements of permeability and pore surface area to volume (S/V) distributions using differential pressure measurements and micro X-ray computed tomography (μXRCT) imaging methods, respectively. We observe that using standard methods for determining permeability from NMR data incorrectlymore » predicts these values by orders of magnitude. However, we do observe promise that NMR measurements provide reasonable estimates of pore S/V distributions, and with further independent measurements of the carbonate rock properties that universally applicable relationships between NMR measured properties may be developed for in-situ well logging applications of carbonate reservoirs.« less

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

    PubMed

    Huang, Yuanpeng Janet; Mao, Binchen; Xu, Fei; Montelione, Gaetano T

    2015-08-01

    ASDP is an automated NMR NOE assignment program. It uses a distinct bottom-up topology-constrained network anchoring approach for NOE interpretation, with 2D, 3D and/or 4D NOESY peak lists and resonance assignments as input, and generates unambiguous NOE constraints for iterative structure calculations. ASDP is designed to function interactively with various structure determination programs that use distance restraints to generate molecular models. In the CASD-NMR project, ASDP was tested and further developed using blinded NMR data, including resonance assignments, either raw or manually-curated (refined) NOESY peak list data, and in some cases (15)N-(1)H residual dipolar coupling data. In these blinded tests, in which the reference structure was not available until after structures were generated, the fully-automated ASDP program performed very well on all targets using both the raw and refined NOESY peak list data. Improvements of ASDP relative to its predecessor program for automated NOESY peak assignments, AutoStructure, were driven by challenges provided by these CASD-NMR data. These algorithmic improvements include (1) using a global metric of structural accuracy, the discriminating power score, for guiding model selection during the iterative NOE interpretation process, and (2) identifying incorrect NOESY cross peak assignments caused by errors in the NMR resonance assignment list. These improvements provide a more robust automated NOESY analysis program, ASDP, with the unique capability of being utilized with alternative structure generation and refinement programs including CYANA, CNS, and/or Rosetta. PMID:26081575

  15. The Trojan Horse Method as a tool to investigate low-energy resonances: the {sup 18}O(p, {alpha}){sup 15}N and {sup 17}O(p, {alpha}){sup 14}N cases

    SciTech Connect

    La Cognata, M.; Sergi, M. L.; Spitaleri, C.; Cherubini, S.; Gulino, M.; Kiss, G.; Lamia, L.; Pizzone, R. G.; Romano, S.; Mukhamedzhanov, A.; Goldberg, V.; Tribble, R.; Coc, A.; Hammache, F.; Sereville, N. de; Tumino, A.

    2010-08-12

    The {sup 18}O(p, {alpha}){sup 15}N and {sup 17}O(p, {alpha}){sup 14}N reactions are of primary importance in several as-trophysical scenarios, including nucleosynthesis inside Asymptotic Giant Branch stars and oxygen and nitrogen isotopic ratios in meteorite grains. They are also key reactions to understand exotic systems such as R-Coronae Borealis stars and novae. Thus, the measurement of their cross sections in the low energy region can be crucial to reduce the nuclear uncertainty on theoretical predictions, because the resonance parameters are poorly determined. The Trojan Horse Method, in its newly developed form particularly suited to investigate low-energy resonances, has been applied to the {sup 2}H({sup 18}O, {alpha}{sup 15}N)n and {sup 2}H({sup 17}O, {alpha}{sup 14}N)n reactions to deduce the {sup 18}O(p, {alpha}){sup 15}N and {sup 17}O(p, {alpha}){sup 14}N cross sections at low energies. Resonances in the {sup 18}O(p, {alpha}){sup 15}N and {sup 17}O(p, {alpha}){sup 14}N excitation functions have been studied and the resonance parameters deduced.

  16. NMR spectroscopy of experimentally shocked single crystal quartz: A reexamination of the NMR shock barometer

    NASA Technical Reports Server (NTRS)

    Fiske, P. S.; Gratz, A. J.; Nellis, W. J.

    1993-01-01

    Cygan and others report a broadening of the Si-29 nuclear magnetic resonance (NMR) peak for synthetic quartz powders with increasing shock pressure which they propose as a shock wave barometer for natural systems. These results are expanded by studying single crystal quartz shocked to 12 and 33 GPa using the 6.5 m two-stage light-gas gun at Lawrence Livermore National Laboratories. Our NMR results differ substantially from those of Cygan and others and suggest that the proposed shock wave barometer may require refinement. The difference in results between this study and that of Cygan and others is most likely caused by different starting materials (single crystal vs. powder) and different shock loading histories. NMR results from single crystal studies may be more applicable to natural systems.

  17. Radical Prostatectomy versus External Beam Radiotherapy for cT1-4N0M0 Prostate Cancer: Comparison of Patient Outcomes Including Mortality

    PubMed Central

    Taguchi, Satoru; Fukuhara, Hiroshi; Shiraishi, Kenshiro; Nakagawa, Keiichi; Morikawa, Teppei; Kakutani, Shigenori; Takeshima, Yuta; Miyazaki, Hideyo; Fujimura, Tetsuya; Nakagawa, Tohru; Kume, Haruki; Homma, Yukio

    2015-01-01

    Background Although radical prostatectomy (RP) and external beam radiotherapy (EBRT) have been considered as comparable treatments for localized prostate cancer (PC), it is controversial which treatment is better. The present study aimed to compare outcomes, including mortality, of RP and EBRT for localized PC. Methods We retrospectively analyzed 891 patients with cT1-4N0M0 PC who underwent either RP (n = 569) or EBRT (n = 322) with curative intent at our single institution between 2005 and 2012. Of the EBRT patients, 302 (93.8%) underwent intensity-modulated radiotherapy. Primary endpoints were overall survival (OS) and cancer-specific survival (CSS). Related to these, other-cause mortality (OCM) was also calculated. Biochemical recurrence-free survival was assessed as a secondary endpoint. Cox proportional hazards model was used for multivariate analysis. Results Median follow-up durations were 53 and 45 months, and median ages were 66 and 70 years (P <0.0001), in the RP and EBRT groups, respectively. As a whole, significantly better prognoses of the RP group than the EBRT group were observed for both OS and CSS, although OCM was significantly higher in the EBRT group. There was no death from PC in men with low and intermediate D’Amico risks, except one with intermediate-risk in the EBRT group. In high-risk patients, significantly more patients died from PC in the EBRT group than the RP group. Multivariate analysis demonstrated the RP group to be an independent prognostic factor for better CSS. On the other hand, the EBRT group had a significantly longer biochemical recurrence-free survival than the RP group. Conclusions Mortality outcomes of both RP and EBRT were generally favorable in low and intermediate risk patients. Improvement of CSS in high risk patients was seen in patients receiving RP over those receiving EBRT. PMID:26506569

  18. Analysis of microearthquakes at the non-transform offset of the Mid-Atlantic Ridge hosting the Rainbow hydrothermal system (36°14'N)

    NASA Astrophysics Data System (ADS)

    Horning, G.; Canales, J. P.; Sohn, R. A.; Dunn, R. A.

    2015-12-01

    The Rainbow hydrothermal field is an active, ultramafic-hosted system located on the Mid-Atlantic Ridge (MAR) at 36° 14'N. It is located at a non-transform discontinuity (NTD) of the MAR at the AMAR-AMAR minor segment intersection [German et al., 1996]. Rainbow, in contrast to other ultramafic-hosted systems such as Lost City, is a high-temperature site with fluids up to 365 °C [Douville et al., 2002]. A magmatic heat source must be present to account for the long-lived, high-temperature, heat flux of 1-5 GW [Thurnherr and Richards, 2001], but the nearest, known neovolcanic activity is 15-20 km away on the AMAR segment [German and Parson, 1998]. In 2013, a long-term, ocean bottom seismometer (OBS) microearthquake network of 13 instruments was deployed as part of the MARINER geophysical experiment [Dunn et al., 2013]. Over 40,000 events were detected and located within ~16 km of the active hydrothermal field during the ~200 day deployment. We present hypocenters estimated using P- and S-wave arrival times and a crustal velocity model derived from the active-source tomography component of the MARINER experiment. Moment/magnitude estimates from spectral methods indicate that the majority of events have local magnitudes (ML) of 0-1, with the largest events approaching ML ~2. First arrival polarity data demonstrate that many of the events have non-double couple source mechanisms, and we explore the use of P/S-wave amplitude ratios to constrain these focal mechanisms. The detection of predominantly non-double events indicates processes other than simple fault slip (e.g., serpentinization) are contributing to the observed seismicity and deformation. We use the spatial distribution, magnitudes, rate, and source mechanisms of the seismic events to constrain the coupled processes of hydrothermal circulation and deformation at the Rainbow massif.

  19. Study of the Q branch structure of the 14N and 15N isotopologues of the ν4 band of ammonia using frequency chirped quantum cascade lasers.

    PubMed

    Duxbury, Geoffrey; Wilson, David; Hay, Kenneth; Langford, Nigel

    2013-10-01

    Intrapulse quantum cascade (QC) laser spectrometers are able to produce both saturation and molecular alignment of a gas sample owing to the rapid sweep of the radiation through the absorption features. In the QC lasers used to study the (14)N and (15)N isotopologues of the ν4 band of ammonia centered near 1625 cm(-1), the variation of the chirp rate during the scan is very large, from ca. 85 to ca. 15 MHz ns(-1). In the rapid chirp zone the collisional interaction time of the laser radiation with the gas molecules is short, and large rapid passage effects are seen, whereas at the slow chirp end the line shape resembles that of a Doppler broadened line. The total scan range of the QC laser of ca. 10 cm(-1) is sufficient to allow the spectra of both isotopologues to be recorded and the rapid and slow interactions with the laser radiation to be seen. The rapid passage effects are enhanced by the use of an off axis Herriott cell with an effective path length of 62 m, which allows a buildup of polarization to occur. The effective resolution of the chirped QC laser is ca. 0.012 cm(-1) full width at half-maximum in the 1625 cm(-1) region. The results of these experiments are compared with those of other studies of the ν4 band of ammonia carried out using Fourier transform and Laser Stark spectroscopy. They also demonstrate the versatility of the down chirped QC laser for investigating collisional effects in low pressure gases using long absorbing path lengths.

  20. Modelling of hydrothermal fluid circulation in a heterogeneous medium: Application to the Rainbow Vent site (Mid-Atlantic-Ridge, 36°14N)

    NASA Astrophysics Data System (ADS)

    Perez, F.; Mügler, C.; Jean-Baptiste, P.; Charlou, J. L.

    2012-04-01

    Hydrothermal activity at the axis of mid-ocean ridges is a key driver for energy and matter transfer from the interior of the Earth to the ocean floor. At mid-ocean ridges, seawater penetrates through the permeable young crust, warms at depth and exchanges chemicals with the surrounding rocks. This hot fluid focuses and flows upwards, then is expelled from the crust at hydrothermal vent sites in the form of black or white smokers completed by diffusive emissions. We developed a new numerical tool in the Cast3M software framework to model such hydrothermal circulations. Thermodynamic properties of one-phase pure water were calculated from the IAPWS formulation. This new numerical tool was validated on several test cases of convection in closed-top and open-top boxes. Simulations of hydrothermal circulation in a homogeneous-permeability porous medium also gave results in good agreement with already published simulations. We used this new numerical tool to construct a geometric and physical model configuration of the Rainbow Vent site at 36°14'N on the Mid-Atlantic Ridge. In this presentation, several configurations will be discussed, showing that high temperatures and high mass fluxes measured at the Rainbow site cannot be modelled with hydrothermal circulation in a homogeneous-permeability porous medium. We will show that these high values require the presence of a fault or a preferential pathway right below the venting site. We will propose and discuss a 2-D one-path model that allows us to simulate both high temperatures and high mass fluxes. This modelling of the hydrothermal circulation at the Rainbow site constitutes a first but necessary step to understand the origin of high concentrations of hydrogen issued from this ultramafic-hosted vent field.

  1. 13C/12C and 15N/14N Isotope Analysis to Characterize Natural Degradation of Atrazine: Evidence from Parent and Daughter Compound Values

    NASA Astrophysics Data System (ADS)

    Elsner, Martin; Meyer, Armin

    2013-04-01

    The mobile and still herbicidal metabolites desethylatrazine (DEA) and desisopropylatrazine (DIA) are frequently detected together with its parent compound atrazine (Atz) in the aquatic environment. Interpretation of their transformation state is often difficult with current methods, which are mainly measuring concentrations. Alternatively, compound specific isotope analyses (CSIA) has become a novel tool to detect degradation processes of contaminants in groundwater. The aim of our study was to investigate on the lab scale 13C/12C and 15N/14N isotope trends in parent and daughter compounds associated with different degradation scenarios of atrazine likely to occur in the environment. Thus atrazine was dealkylated with (i) permanganate and (ii) the bacterium Rhodococcus sp. NI86/21. In both transformations, 13C/12C ratios of atrazine increased strongly (epsilon carbon/permanganate = -4.6 ± 0.6 ‰ and epsilon carbon/Rhodoccoccus = -3.8 ± 0.2 ‰) whereas nitrogen isotope fractionation was small. 13C/12C ratios of DEA showed the following trends. (i) When DEA was formed as only product (Atz + permanganate) 13C/12C remained constant, close to the initial value of Atz. (ii) When DEA was formed together with deisopropylatrazine (biodegradation of Atz) 13C/12C increased, but only within 2‰. (iii) When DEA and DIA was further biodegraded, 13C/12C increased for both metabolites up to 9‰. Thus strong enrichment of 13C/12C in the metabolites in comparison to Atz can give strong testimony for further breakdown of the metabolite.

  2. Protein Structure Determination Using Protein Threading and Sparse NMR Data

    SciTech Connect

    Crawford, O.H.; Einstein, J.R.; Xu, D.; Xu, Y.

    1999-11-14

    It is well known that the NMR method for protein structure determination applies to small proteins and that its effectiveness decreases very rapidly as the molecular weight increases beyond about 30 kD. We have recently developed a method for protein structure determination that can fully utilize partial NMR data as calculation constraints. The core of the method is a threading algorithm that guarantees to find a globally optimal alignment between a query sequence and a template structure, under distance constraints specified by NMR/NOE data. Our preliminary tests have demonstrated that a small number of NMR/NOE distance restraints can significantly improve threading performance in both fold recognition and threading-alignment accuracy, and can possibly extend threading's scope of applicability from structural homologs to structural analogs. An accurate backbone structure generated by NMR-constrained threading can then provide a significant amount of structural information, equivalent to that provided by the NMR method with many NMR/NOE restraints; and hence can greatly reduce the amount of NMR data typically required for accurate structure determination. Our preliminary study suggests that a small number of NMR/NOE restraints may suffice to determine adequately the all-atom structure when those restraints are incorporated in a procedure combining threading, modeling of loops and sidechains, and molecular dynamics simulation. Potentially, this new technique can expand NMR's capability to larger proteins.

  3. Synthesis and Characterization of New Iron Phosphatooxalates: [( - 5H 14N 2] [Fe 4(C 2O 4) 3(HPO 4) 2(H 2O) 2] and [( - 5H 14N 2] [Fe 4(C 2O 4) 3(HPO 4) 2

    NASA Astrophysics Data System (ADS)

    Chang, Wen-Jung; Lin, Hsiu-Mei; Lii, Kwang-Hwa

    2001-02-01

    Two new organically templated iron(II) phosphatooxalates, [(S)-C5H14N2] [Fe4(C2O4)3(HPO4)2(H2O)2] (1) and [(S)-C5H14 N2] [Fe4(C2O4)3(HPO4)2] (2), have been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction and Mössbauer spectroscopy. Crystal data are as follows: compound 1, triclinic, P1 (No. 1), a=7.6999(4) Å, b=7.9542(4) Å, c=9.8262(5) Å, α=74.8444(7)°, β=81.7716(8)°, γ=85.4075(8)°, V=574.34(8) Å3, Z=1, and R1=0.0255; compound 2, monoclinic, P21 (No. 4), a=7.5943(8) Å, b=7.8172(8) Å, c=18.318(2) Å, β=99.111(2)°, V=1073.8(3) Å3, Z=2, and R1=0.0281. The structure of 1 consists of dimers of edge-sharing FeO6 octahedra that are linked by phosphate and oxalate groups to generate a three-dimensional framework with intersecting tunnels parallel to the [100] and [010] directions. Diprotonated (S)-2-methylpiperazinium cations are located at the intersections of these tunnels. Compound 1 crystallizes as a minor product when a racemic mixture of 2-methylpiperazine is used in the synthesis, and can be prepared as a major product with a small amount of 2 if optically pure (S)-2-methylpiperzine is used. The structure of 2 is similar to that of 1 except that the coordination around the iron centers in the dimer are square pyramidal and octahedral. The two compounds are the first 3-dimensional phosphatooxalates containing a chiral amine.

  4. MILLIMETER-WAVE OBSERVATIONS OF CN AND HNC AND THEIR {sup 15}N ISOTOPOLOGUES: A NEW EVALUATION OF THE {sup 14}N/{sup 15}N RATIO ACROSS THE GALAXY

    SciTech Connect

    Adande, G. R.; Ziurys, L. M.

    2012-01-10

    The N = 1 {yields} 0 transitions of CN and C{sup 15}N (X{sup 2}{Sigma}{sup +}), as well as the J = 1 {yields} 0 lines of HN{sup 13}C and H{sup 15}NC, have been observed toward 11 molecular clouds using the new 3 mm ALMA-type receiver of the 12 m telescope of the Arizona Radio Observatory. These sources span a wide range of distances from the Galactic center and are all regions of star formation. From these observations, {sup 14}N/{sup 15}N ratios have been determined using two independent methods. First, the measurements of C{sup 14}N and C{sup 15}N were directly compared to establish this ratio, correcting for high opacities when needed, as indicated by the nitrogen hyperfine intensities. Second, the ratio was calculated from the quantity [HN{sup 13}C]/[H{sup 15}NC], determined from the HNC data, and then scaled by {sup 12}C/{sup 13}C ratios previously established, i.e., the so-called double isotope method. Values from both methods are in reasonable agreement, and fall in the range {approx}120-400, somewhat lower than previous {sup 14}N/{sup 15}N ratios derived from HCN. The ratios exhibit a distinct positive gradient with distance from the Galactic center, following the relationship{sup 14}N/{sup 15}N = 21.1 (5.2) kpc{sup -1} D{sub GC} + 123.8 (37.1). This gradient is consistent with predictions of Galactic chemical evolution models in which {sup 15}N has a secondary origin in novae, while primary and secondary sources exist for {sup 14}N. The local interstellar medium value was found to be {sup 4}N/{sup 15}N = 290 {+-} 40, in agreement with the ratio found in nearby diffuse clouds and close to the value of 272 found in Earth's atmosphere.

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

    PubMed

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

    2013-11-01

    ADAPT-NMR (Assignment-directed Data collection Algorithm utilizing a Probabilistic Toolkit in NMR) supports automated NMR data collection and backbone and side chain assignment for [U-(13)C, U-(15)N]-labeled proteins. Given the sequence of the protein and data for the orthogonal 2D (1)H-(15)N and (1)H-(13)C planes, the algorithm automatically directs the collection of tilted plane data from a variety of triple-resonance experiments so as to follow an efficient pathway toward the probabilistic assignment of (1)H, (13)C, and (15)N signals to specific atoms in the covalent structure of the protein. Data collection and assignment calculations continue until the addition of new data no longer improves the assignment score. ADAPT-NMR was first implemented on Varian (Agilent) spectrometers [A. Bahrami, M. Tonelli, S.C. Sahu, K.K. Singarapu, H.R. Eghbalnia, J.L. Markley, PLoS One 7 (2012) e33173]. Because of broader interest in the approach, we present here a version of ADAPT-NMR for Bruker spectrometers. We have developed two AU console programs (ADAPT_ORTHO_run and ADAPT_NMR_run) that run under TOPSPIN Versions 3.0 and higher. To illustrate the performance of the algorithm on a Bruker spectrometer, we tested one protein, chlorella ubiquitin (76 amino acid residues), that had been used with the Varian version: the Bruker and Varian versions achieved the same level of assignment completeness (98% in 20 h). As a more rigorous evaluation of the Bruker version, we tested a larger protein, BRPF1 bromodomain (114 amino acid residues), which yielded an automated assignment completeness of 86% in 55 h. Both experiments were carried out on a 500 MHz Bruker AVANCE III spectrometer equipped with a z-gradient 5 mm TCI probe. ADAPT-NMR is available at http://pine.nmrfam.wisc.edu/ADAPT-NMR in the form of pulse programs, the two AU programs, and instructions for installation and use. PMID:24091140

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

    NASA Astrophysics Data System (ADS)

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

    2013-11-01

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

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

    PubMed

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

    2013-11-01

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

  8. Chemical shift and electric field gradient tensors for the amide and carboxyl hydrogens in the model peptide N-acetyl-D,L-valine. Single-crystal deuterium NMR study.

    SciTech Connect

    Gerald, R. E., II; Bernhard, T.; Haeberlen, U.; Rendell, J.; Opella, S.; Chemical Engineering

    1993-01-01

    Solid-state NMR spectroscopy is well established as a method for describing molecular structure with resolution on the atomic scale. Many of the NMR observables result from anisotropic interactions between the nuclear spin and its environment. These observables can be described by second-rank tensors. For example, the eigenvalues of the traceless symmetric part of the hydrogen chemical shift (CS) tensor provide information about the strength of inter- or intramolecular hydrogen bonding. On the other hand, the eigenvectors of the deuterium electric field gradient (EFG) tensor give deuteron/proton bond directions with an accuracy rivalled only by neutron diffraction. In this paper the authors report structural information of this type for the amide and carboxyl hydrogen sites in a single crystal of the model peptide N-acetyl-D,L-valine (NAV). They use deuterium NMR to infer both the EFG and CS tensors at the amide and carboxyl hydrogen sites in NAV. Advantages of this technique over multiple-pulse proton NMR are that it works in the presence of {sup 14}N spins which are very hard to decouple from protons and that additional information in form of the EFG tensors can be derived. The change in the CS and EFG tensors upon exchange of a deuteron for a proton (the isotope effect) is anticipated to be very small; the effect on the CS tensors is certainly smaller than the experimental errors. NAV has served as a model peptide before in a variety of NMR studies, including those concerned with developing solid-state NMR spectroscopy as a method for determining the structure of proteins. NMR experiments on peptide or protein samples which are oriented in at least one dimension can provide important information about the three-dimensional structure of the peptide or the protein. In order to interpret the NMR data in terms of the structure of the polypeptide, the relationship of the CS and EFG tensors to the local symmetry elements of an amino acide, e.g., the peptide plane, is

  9. Direct Comparison of (19)F qNMR and (1)H qNMR by Characterizing Atorvastatin Calcium Content.

    PubMed

    Liu, Yang; Liu, Zhaoxia; Yang, Huaxin; He, Lan

    2016-01-01

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

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

    PubMed Central

    Liu, Yang; Liu, Zhaoxia; Yang, Huaxin

    2016-01-01

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

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

    PubMed Central

    Liu, Yang; Liu, Zhaoxia; Yang, Huaxin

    2016-01-01

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

  12. NMR study of magnetism and superparamagnetism

    NASA Astrophysics Data System (ADS)

    Yuan, Shaojie

    The research described in this dissertation is concerned with two different types of magnetic materials. Both types of systems involve competing interactions between transition metal ions. New approaches involving magnetic resonance in the large hyperfine fields at nuclear sites have been developed. The interactions responsible for the properties that have been investigated in the materials studied are geometric frustration in an insulator and ferromagnetic and antiferromagnetic interactions in a metal alloy. Further details are given below. The extended kagome frustrated system YBaCo4O7 has 2D kagome and triangular lattices of Co ions stacked along the c-axis. Antiferromagnetic (AF) ordering accompanied by a structural transition has been reported in the literature. From a zero field (ZF) NMR single crystal rotation experiment, we have obtained the Co spin configurations for both the kagome and triangular layers. A 'spin-flop' configuration between the spins on the kagome layer and the spins on the triangular layer is indicated by our results. Our NMR findings are compared with neutron scattering results for this intriguing frustrated AF spin system. The non-stoichiometric oxygenated sister compound YBaCo4O7.1 has application potential for oxygen storage. While, its' magnetic properties are quite different from those of the stoichiometric compound, in spite of their similar structures of alternating kagome and triangular Co layers. Various techniques, including ZF NMR have been used to investigate the spin dynamics and spin configuration in a single crystal of YBaCo4O7.1. A magnetic transition at 80 K is observed, which is interpreted as the freezing out of spins in the triangular layers. At low temperatures (below 50 K), the spin dynamics persists and a fraction of spins in the kagome layers form a viscous spin liquid. Below 10 K, a glass-like spin structure forms and a large distribution of spin correlation times are suggested by nuclear spin lattice relaxation

  13. Lithium Polymer Electrolytes and Solid State NMR

    NASA Technical Reports Server (NTRS)

    Berkeley, Emily R.

    2004-01-01

    Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for

  14. Advanced NMR-based techniques for pore structure analysis of coal. Quarterly report No. 1, September 1, 1991--November 30, 1991

    SciTech Connect

    Smith, D.M.

    1991-12-31

    One of the main problems in coal utilization is the inability to properly characterize its complex pore structure. We propose to investigate the dependence of the common NMR parameters such as chemical shifts and relaxation times of several different nuclei and compounds on the pore structure of model microporous solids, carbons, and coals. In particular, we will study the interaction between several small molecules ({sup 129}Xe, {sup 3}He, {sup 2}H{sub 2}, {sup 14}N{sub 2}, {sup 14}NH{sub 3}, {sup 15}N{sub 2}, {sup 13}CH{sub 4}, {sup 13}CO{sub 2}) and the pore surfaces in coals. These molecules have been selected for their chemical and physical properties.

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

    SciTech Connect

    Wright, P.E.

    1994-12-01

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

  16. NMR and NQR study of Si-doped (6,0) zigzag single-walled aluminum nitride nanotube as n or P-semiconductors.

    PubMed

    Baei, Mohammad T; Peyghan, Ali Ahmadi; Tavakoli, Khadijeh; Babaheydari, Ali Kazemi; Moghimi, Masoumeh

    2012-09-01

    Density functional theory (DFT) calculations were performed to investigate the electronic structure properties of pristine and Si-doped aluminum nitride nanotubes as n or P-semiconductors at the B3LYP/6-31G* level of theory in order to evaluate the influence of Si-doped in the (6,0) zigzag AlNNTs. We extended the DFT calculation to predict the electronic structure properties of Si-doped aluminum nitride nanotubes, which are very important for production of solid-state devices and other applications. To this aim, pristine and Si-doped AlNNT structures in two models (Si(N) and Si(Al)) were optimized, and then the electronic properties, the isotropic (CS(I)) and anisotropic (CS(A)) chemical shielding parameters for the sites of various (27)Al and (14)N atoms, NQR parameters for the sites of various of (27)Al and (14)N atoms, and quantum molecular descriptors were calculated in the optimized structures. The optimized structures, the electronic properties, NMR and NQR parameters, and quantum molecular descriptors for the Si(N) and Si(Al) models show that the Si(N) model is a more reactive material than the pristine or Si(Al) model.

  17. Measurement of vorticity diffusion by NMR microscopy.

    PubMed

    Brown, Jennifer R; Callaghan, Paul T

    2010-05-01

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

  18. Quenched Hydrogen Exchange NMR of Amyloid Fibrils.

    PubMed

    Alexandrescu, Andrei T

    2016-01-01

    Amyloid fibrils are associated with a number of human diseases. These aggregatively misfolded intermolecular β-sheet assemblies constitute some of the most challenging targets in structural biology because to their complexity, size, and insolubility. Here, protocols and controls are described for experiments designed to study hydrogen-bonding in amyloid fibrils indirectly, by transferring information about amide proton occupancy in the fibrils to the dimethyl sulfoxide-denatured state. Since the denatured state is amenable to solution NMR spectroscopy, the method can provide residue-level-resolution data on hydrogen exchange for the monomers that make up the fibrils. PMID:26453215

  19. Quenched Hydrogen Exchange NMR of Amyloid Fibrils.

    PubMed

    Alexandrescu, Andrei T

    2016-01-01

    Amyloid fibrils are associated with a number of human diseases. These aggregatively misfolded intermolecular β-sheet assemblies constitute some of the most challenging targets in structural biology because to their complexity, size, and insolubility. Here, protocols and controls are described for experiments designed to study hydrogen-bonding in amyloid fibrils indirectly, by transferring information about amide proton occupancy in the fibrils to the dimethyl sulfoxide-denatured state. Since the denatured state is amenable to solution NMR spectroscopy, the method can provide residue-level-resolution data on hydrogen exchange for the monomers that make up the fibrils.

  20. NMR measurements of intracellular ions in hypertension

    NASA Astrophysics Data System (ADS)

    Veniero, Joseph C.; Gupta, R. K.

    1993-08-01

    The NMR methods for the measurement of intracellular free Na+, K+, Mg2+, Ca2+, and H+ are introduced. The recent literature is then presented showing applications of these methods to cells and tissues from hypertensive animal model systems, and humans with essential hypertension. The results support the hypothesis of consistent derangement of the intracellular ionic environment in hypertension. The theory that this derangement may be a common link in the disease states of high blood pressure and abnormal insulin and glucose metabolism, which are often associated clinically, is discussed.

  1. A NMR characterisation of a banded sandstone.

    PubMed

    Bolam, A C; Packer, K J

    1998-01-01

    1H-nuclear magnetic resonance (NMR) measurements have been carried out on a banded sandstone to investigate the effects of structural inhomogeneities on the fluid dynamics of the sample as a whole. The results obtained from average propagator measurements (the probability of a displacement z in a time delta or P delta (z)) using pulsed-field-gradient techniques have been compared to those obtained from a study of a homogeneous sandstone. Relaxation has been used to derive the pore sizes for the differing bands and have been found to correlate with flow velocities within the bands.

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

    SciTech Connect

    Hirasaki, George J.; Mohanty, Kishore K.

    2003-02-10

    The objective of this project was to characterize the fluid properties and fluid-rock interactions that are needed for formation evaluation by NMR well logging. The advances made in the understanding of NMR fluid properties are summarized in a chapter written for an AAPG book on NMR well logging. This includes live oils, viscous oils, natural gas mixtures, and the relation between relaxation time and diffusivity.

  3. On the sensitivity of running-fluid NMR magnetometers

    NASA Astrophysics Data System (ADS)

    Davydov, V. V.; Dudkin, V. I.; Petrov, A. A.; Myazin, N. S.

    2016-07-01

    A new procedure for determining the sensitivity of running-fluid NMR magnetometers is considered. The procedure is based on mathematical processing of experimental data that are related to measuring the gradient of a nutation-line slope at the point at which an inverted NMR signal crosses zero. The procedure allows one to determine the sensitivity of running-fluid NMR magnetometers for resonance frequencies of magnetic-field measurements within a range of 0.5 Hz to 840 MHz.

  4. Touch NMR: An NMR Data Processing Application for the iPad

    ERIC Educational Resources Information Center

    Li, Qiyue; Chen, Zhiwei; Yan, Zhiping; Wang, Cheng; Chen, Zhong

    2014-01-01

    Nuclear magnetic resonance (NMR) spectroscopy has become one of the most powerful technologies to aid research in numerous scientific disciplines. With the development of consumer electronics, mobile devices have played increasingly important roles in our daily life. However, there is currently no application available for mobile devices able to…

  5. Monitoring and understanding the paraelectric-ferroelectric phase transition in the metal-organic framework [NH4 ][M(HCOO)3 ] by solid-state NMR spectroscopy.

    PubMed

    Xu, Jun; Lucier, Bryan E G; Sinelnikov, Regina; Terskikh, Victor V; Staroverov, Viktor N; Huang, Yining

    2015-10-01

    The paraelectric-ferroelectric phase transition in two isostructural metal-organic frameworks (MOFs) [NH4 ][M(HCOO)3 ] (M=Mg, Zn) was investigated by in situ variable-temperature (25) Mg, (67) Zn, (14) N, and (13) C solid-state NMR (SSNMR) spectroscopy. With decreasing temperature, a disorder-order transition of NH4 (+) cations causes a change in dielectric properties. It is thought that [NH4 ][Mg(HCOO)3 ] exhibits a higher transition temperature than [NH4 ][Zn(HCOO)3 ] due to stronger hydrogen-bonding interactions between NH4 (+) ions and framework oxygen atoms. (25) Mg and (67) Zn NMR parameters are very sensitive to temperature-induced changes in structure, dynamics, and dielectric behavior; stark spectral differences across the paraelectric-ferroelectric phase transition are intimately related to subtle changes in the local environment of the metal center. Although (25) Mg and (67) Zn are challenging nuclei for SSNMR experiments, the highly spherically symmetric metal-atom environments in [NH4 ][M(HCOO)3 ] give rise to relatively narrow spectra that can be acquired in 30-60 min at a low magnetic field of 9.4 T. Complementary (14) N and (13) C SSNMR experiments were performed to probe the role of NH4 (+) -framework hydrogen bonding in the paraelectric-ferroelectric phase transition. This multinuclear SSNMR approach yields new physical insights into the [NH4 ][M(HCOO)3 ] system and shows great potential for molecular-level studies on electric phenomena in a wide variety of MOFs.

  6. NMR-based dynamics of free glycosaminoglycans in solution.

    PubMed

    Pomin, Vitor H

    2014-08-01

    Glycosaminoglycans (GAGs) comprise a special class of complex carbohydrates endowed with numerous biological functions. Most of these functions are regulated by conformational arrangements or dynamical properties of GAGs in solution. Nuclear magnetic resonance (NMR) is a powerful technique used for dynamic analyses. Spin relaxation, scalar couplings, chemical shifts and nuclear Overhauser effect resonances are the commonest NMR parameters utilized in such analyses. Computational molecular dynamics are also very often employed in conjunction with, or restrained by, the NMR dataset. This report aims at describing the major NMR-based information available so far concerning the dynamical properties of free GAGs in solution.

  7. Rotational Doppler Effect and Barnett Field in Spinning NMR

    NASA Astrophysics Data System (ADS)

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

    2015-04-01

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

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

    SciTech Connect

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

    2014-06-20

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

  9. NMR measurements in solutions of dialkylimidazolium haloaluminates

    SciTech Connect

    Takahashi, S.; Saboungi, M.L.; Klingler, R.J.; Chen, M.J.; Rathke, J.W.

    1992-06-01

    {sup 27}Al and {sup 35}Cl NMR spectra of AlCl{sub 3}-1-ethyl-3-methyl imidazolium chloride (EMIC) melts were measured for initial compositions ranging from 50 to 67 mol % AlCl{sub 3} at various temperatures. It was shown by changing the preaquisition delay time (DE value) that the dominant aluminum species are AlCl{sub 4}{sup {minus}} in the melt formed by mixing 50 mol % with EMIC and Al{sub 2}Cl{sub 7}{sup {minus}} in the 67 mol % AlCl{sub 3} melt. In the equimolar mixture, the chemical shift of {sup 27}Al NMR spectrum is 103.28 ppm and the line width is 22.83Hz. In the 67 mol % AlCl{sub 3} mixture, the chemical shift is 103.41 ppm and the line width is 2624Hz. A third species observed at 97 ppm in the {sup 27}Al spectra for the 55 and 60 mol % AlCl{sub 3} mixtures is identified to be a product of the reaction with residual water. The relaxation rates for each species in the melts were determined.

  10. NMR investigation of iron-based superconductors

    NASA Astrophysics Data System (ADS)

    Imai, Takashi

    2010-03-01

    We report NMR investigation of the electronic properties of iron-based superconductors with primary focus on the 11 (FeSe) and 122 (Co-doped BaFe2As2) systems. From the ^77Se and ^75As NMR Knight shift K measurements, we will deduce the intrinsic temperature and concentration dependences of the uniform spin susceptibility, χspin, in these systems. We will also demonstrate the evolution of antiferromagnetic spin fluctuations (AFSF) as a function of pressure (in FeSe) or the doping level (in Ba[Fe1-xCox]2As2). Our results show that the optimal superconducting phase exists in close proximity with SDW order; superconductivity sets in only after AFSF grow toward Tc. This work was carried out in collaboration with F.L. Ning and K. Ahilan (McMaster), T. McQueen and R.J. Cava (Princeton), A.S. Sefat, M.A. McGuire, B. C. Sales, and D. Mandrus (Oak Ridge), P. Cheng, B. Shen, and H.-H Wen (Chinese Academy of Sciences). The work at McMaster was supported by NSERC, CIFAR, and CFI.

  11. Characterizing carbohydrate-protein interactions by NMR

    PubMed Central

    Bewley, Carole A.; Shahzad-ul-Hussan, Syed

    2013-01-01

    Interactions between proteins and soluble carbohydrates and/or surface displayed glycans are central to countless recognition, attachment and signaling events in biology. The physical chemical features associated with these binding events vary considerably, depending on the biological system of interest. For example, carbohydrate-protein interactions can be stoichiometric or multivalent, the protein receptors can be monomeric or oligomeric, and the specificity of recognition can be highly stringent or rather promiscuous. Equilibrium dissociation constants for carbohydrate binding are known to vary from micromolar to millimolar, with weak interactions being far more prevalent; and individual carbohydrate binding sites can be truly symmetrical or merely homologous, and hence, the affinities of individual sites within a single protein can vary, as can the order of binding. Several factors, including the weak affinities with which glycans bind their protein receptors, the dynamic nature of the glycans themselves, and the non-equivalent interactions among oligomeric carbohydrate receptors, have made NMR an especially powerful tool for studying and defining carbohydrate-protein interactions. Here we describe those NMR approaches that have proven to be the most robust in characterizing these systems, and explain what type of information can (or cannot) be obtained from each. Our goal is to provide to the reader the information necessary for selecting the correct experiment or sets of experiments to characterize their carbohydrate-protein interaction of interest. PMID:23784792

  12. NMR imaging of density distributions in tablets.

    PubMed

    Djemai, A; Sinka, I C

    2006-08-17

    This paper describes the use of (1)H nuclear magnetic resonance (NMR) for 3D mapping of the relative density distribution in pharmaceutical tablets manufactured under controlled conditions. The tablets are impregnated with a compatible liquid. The technique involves imaging of the presence of liquid which occupies the open pore space. The method does not require special calibration as the signal is directly proportional to the porosity for the imaging conditions used. The NMR imaging method is validated using uniform density flat faced tablets and also by direct comparison with X-ray computed tomography. The results illustrate (1) the effect of die wall friction on density distribution by compressing round, curved faced tablets using clean and pre-lubricated tooling, (2) the evolution of density distribution during compaction for both clean and pre-lubricated die wall conditions, by imaging tablets compressed to different compaction forces, and (3) the effect of tablet image on density distribution by compressing two complex shape tablets in identical dies to the same average density using punches with different geometries.

  13. NMR assessment on bone simulated under microgravity

    NASA Astrophysics Data System (ADS)

    Ni, Q.; Qin, Y.

    Introduction Microgravity-induced bone loss has been suggested to be similar to disuse-osteoporosis on Earth which constitutes a challenging public health problem No current non-destructive method can provide the microstructural changes in bone particularly on cortical bone Recently the authors have applied low field nuclear magnetic resonance NMR spin-spin relaxation technique and computational analysis method to determine the porosity pore size distribution and microdamage of cortical bone 1-3 The studies by the authors have shown that this technology can be used to characterize microstructural changes as well as bone water distribution bound and mobile water changes of weightless treated simulating a microgravity condition turkey and mouse cortical bone We further determinate that the NMR spin-spin relaxation time T 2 spectrum derived parameters can be used as descriptions of bone quality e g matrix water distribution and porosity size distributions and alone or in combination with current techniques bone mineral density measurements more accurately predict bone mechanical properties Methods underline Bone sample preparation Two kinds of animal samples were collected and prepared for designed experiments from SUNY Cortical bones of the mid-diaphyses of the ulnae of 1-year-old male turkeys were dissected from freshly slaughtered animals Eight samples were categorized from normal or control and four samples were 4-week disuse treated by functionally isolated osteotomies disuse A total of 12

  14. NMR studies of protein-ligand interactions.

    PubMed

    Maurer, Till

    2005-01-01

    Interaction between biological macromolecules or of macromolecules with low-molecular-weight ligands is a central paradigm in the understanding of function in biological systems. It is also the major goal in pharmaceutical research to find and optimize ligands that modulate the function of biological macromolecules. Both technological advances and new methods in the field of nuclear magnetic resonance (NMR) have led to the development of several tools by which the interaction of proteins or DNA and low molecular weight-ligands can be characterized at an atomic level. Information can be gained quickly and easily with ligand-based techniques. These need only small amounts of nonisotope labeled, and thus readily available target macromolecules. As the focus is on the signals stemming only from the ligand, no further NMR information regarding the target is needed. Techniques based on the observation of isotopically labeled biological macromolecules open the possibility to observe interactions of proteins with low-molecular-weight ligands, DNA or other proteins. With these techniques, the structure of high-molecular-weight complexes can be determined. Here, the resonance signals of the macromolecule must be identified beforehand, which can be time consuming but with the benefit of obtaining more information with respect to the target ligand complex.

  15. Assessment of Bone Microstructural Changes by NMR

    NASA Astrophysics Data System (ADS)

    Ni, Qingwen; Wang, Xiaodu

    2008-03-01

    Previous studies have shown that age related increases in bone porosity without significant changes in bone mineral density (BMD) (without bone microstructural information) result in a decrease in bone strength. Bone fracture toughness is also significantly correlated to changes in porosity, microarchitecture, collagen integrity, microdamage, and water distribution, all of which are measures of bone quality. Unfortunately, current technology does not allow the non-destructive and non-invasive detection of bone water distribution or other measures of bone quality including microporosity. On the other hand, Nuclear Magnetic Resonance (NMR) proton spin-spin (T2) relaxation time measurements and computational analytical method have been used to determine microstructural characteristics of various types of fluid filled porous materials. The study in here is to demonstrate that non-destructive and non-invasive NMR proton spin-spin (T2) relaxation techniques has been developed and applied to quantify the porosity, pore size distribution and water distribution in human cortical bone. This new bone microstructural information can then be used as descriptions of bone quality and, along or in combination with existing method (BMD) to more accurately assess bone fracture risk, and the results could help doctors and researchers to detect osteoporosis and other conditions related to weak bones in persons.

  16. Line-narrowing in proton-detected nitrogen-14 NMR

    NASA Astrophysics Data System (ADS)

    Cavadini, Simone; Vitzthum, Veronika; Ulzega, Simone; Abraham, Anuji; Bodenhausen, Geoffrey

    2010-01-01

    In solids spinning at the magic angle, the indirect detection of single-quantum (SQ) and double-quantum (DQ) 14N spectra ( I = 1) via spy nuclei S = 1/2 such as protons can be achieved in the manner of heteronuclear single- or multiple-quantum correlation (HSQC or HMQC) spectroscopy. The HMQC method relies on the excitation of two-spin coherences of the type T11IT11S and T21IT11S at the beginning of the evolution interval t1. The spectra obtained by Fourier transformation from t1 to ω1 may be broadened by the homogenous decay of the transverse terms of the spy nuclei S. This broadening is mostly due to homonuclear dipolar S- S' interactions between the proton spy nuclei. In this work we have investigated the possibility of inserting rotor-synchronized symmetry-based C or R sequences and decoupling schemes such as Phase-Modulated Lee-Goldburg (PMLG) sequences in the evolution period. These schemes reduce the homonuclear proton-proton interactions and lead to an enhancement of the resolution of both SQ and DQ proton-detected 14N HMQC spectra. In addition, we have investigated the combination of HSQC with symmetry-based sequences and PMLG and shown that the highest resolution in the 14N dimension is achieved by using HSQC in combination with symmetry-based sequences of the R-type. We show improvements in resolution in samples of L-alanine and the tripeptide ala-ala-gly (AAG). In particular, for L-alanine the width of the 14N SQ peak is reduced from 2 to 1.2 kHz, in agreement with simulations. We report accurate measurements of quadrupolar coupling constants and asymmetry parameters for amide 14N in AAG peptide bonds.

  17. CARBON-RICH PRESOLAR GRAINS FROM MASSIVE STARS: SUBSOLAR {sup 12}C/{sup 13}C AND {sup 14}N/{sup 15}N RATIOS AND THE MYSTERY OF {sup 15}N

    SciTech Connect

    Pignatari, M.; Zinner, E.; Hoppe, P.; Jordan, C. J.; Gibson, B. K.; Trappitsch, R.; Herwig, F.; Fryer, C.; Hirschi, R.; Timmes, F. X.

    2015-08-01

    Carbon-rich grains with isotopic anomalies compared to the Sun are found in primitive meteorites. They were made by stars, and carry the original stellar nucleosynthesis signature. Silicon carbide grains of Type X and C and low-density (LD) graphites condensed in the ejecta of core-collapse supernovae. We present a new set of models for the explosive He shell and compare them with the grains showing {sup 12}C/{sup 13}C and {sup 14}N/{sup 15}N ratios lower than solar. In the stellar progenitor H was ingested into the He shell and not fully destroyed before the explosion. Different explosion energies and H concentrations are considered. If the supernova shock hits the He-shell region with some H still present, the models can reproduce the C and N isotopic signatures in C-rich grains. Hot-CNO cycle isotopic signatures are obtained, including a large production of {sup 13}C and {sup 15}N. The short-lived radionuclides {sup 22}Na and {sup 26}Al are increased by orders of magnitude. The production of radiogenic {sup 22}Ne from the decay of {sup 22}Na in the He shell might solve the puzzle of the Ne-E(L) component in LD graphite grains. This scenario is attractive for the SiC grains of type AB with {sup 14}N/{sup 15}N ratios lower than solar, and provides an alternative solution for SiC grains originally classified as nova grains. Finally, this process may contribute to the production of {sup 14}N and {sup 15}N in the Galaxy, helping to produce the {sup 14}N/{sup 15}N ratio in the solar system.

  18. Dual element ((15)N/(14)N, (13)C/(12)C) isotope analysis of glyphosate and AMPA by derivatization-gas chromatography isotope ratio mass spectrometry (GC/IRMS) combined with LC/IRMS.

    PubMed

    Mogusu, Emmanuel O; Wolbert, J Benjamin; Kujawinski, Dorothea M; Jochmann, Maik A; Elsner, Martin

    2015-07-01

    To assess sources and degradation of the herbicide glyphosate [N-(phosphonomethyl) glycine] and its metabolite AMPA (aminomethylphosphonic acid), concentration measurements are often inconclusive and even (13)C/(12)C analysis alone may give limited information. To advance isotope ratio analysis of an additional element, we present compound-specific (15)N/(14)N analysis of glyphosate and AMPA by a two step derivatization in combination with gas chromatography/isotope ratio mass spectrometry (GC/IRMS). The N-H group was derivatized with isopropyl chloroformate (iso-PCF), and remaining acidic groups were subsequently methylated with trimethylsilyldiazomethane (TMSD). Iso-PCF treatment at pH <10 gave too low (15)N/(14)N ratios indicating an incomplete derivatization; in contrast, too high (15)N/(14)N ratios at pH >10 indicated decomposition of the derivative. At pH 10, and with an excess of iso-PCF by 10-24, greatest yields and accurate (15)N/(14)N ratios were obtained (deviation from elemental analyzer-IRMS: -0.2 ± 0.9% for glyphosate; -0.4 ± 0.7% for AMPA). Limits for accurate δ(15)N analysis of glyphosate and AMPA were 150 and 250 ng injected, respectively. A combination of δ(15)N and δ(13)C analysis by liquid chromatography/isotope ratio mass spectrometry (LC/IRMS) (1) enabled an improved distinction of commercial glyphosate products and (2) showed that glyphosate isotope values during degradation by MnO2 clearly fell outside the commercial product range. This highlights the potential of combined carbon and nitrogen isotopes analysis to trace sources and degradation of glyphosate.

  19. The RGB and AGB Star Nucleosynthesis in Light of the Recent 17O(p, α)14N and 18O(p, α)15N Reaction-rate Determinations

    NASA Astrophysics Data System (ADS)

    Palmerini, S.; Sergi, M. L.; La Cognata, M.; Lamia, L.; Pizzone, R. G.; Spitaleri, C.

    2013-02-01

    In recent years, the Trojan Horse Method (THM) has been used to investigate the low-energy cross sections of proton-induced reactions on A = 17 and A = 18 oxygen isotopes, overcoming extrapolation procedures and enhancement effects due to electron screening. In particular, the strengths of the 20 keV and 65 keV resonances in the 18O(p, α)15N and 17O(p, α)14N reactions, respectively, have been extracted, as well as the contribution of the tail of the broad 656 keV resonance in the 18O(p, α)15N reaction inside the Gamow window. The strength of the 65 keV resonance in the 17O(p, α)14N reaction, measured by means of the THM, has been used to renormalize the corresponding resonance strength in the 17O + p radiative capture channel. As a result, more accurate reaction rates for the 18O(p, α)15N, 17O(p, α)14N, and 17O(p, γ)18F processes have been deduced, devoid of systematic errors due to extrapolation or the electron screening effect. Such rates have been introduced into state-of-the-art red giant branch and asymptotic giant branch (AGB) models for proton-capture nucleosynthesis coupled with extra-mixing episodes. The predicted abundances have been compared with isotopic compositions provided by geochemical analysis of presolar grains. As a result, an improved agreement is found between the models and the isotopic mix of oxide grains of AGB origins, whose composition is the signature of low-temperature proton-capture nucleosynthesis. The low 14N/15N found in SiC grains cannot be explained by the revised nuclear reaction rates and remains a serious problem that has not been satisfactorily addressed.

  20. Heteronuclear Multidimensional Protein NMR in a Teaching Laboratory

    ERIC Educational Resources Information Center

    Wright, Nathan T.

    2016-01-01

    Heteronuclear multidimensional NMR techniques are commonly used to study protein structure, function, and dynamics, yet they are rarely taught at the undergraduate level. Here, we describe a senior undergraduate laboratory where students collect, process, and analyze heteronuclear multidimensional NMR experiments using an unstudied Ig domain (Ig2…

  1. Probe for high resolution NMR with sample reorientation

    DOEpatents

    Pines, A.; Samoson, A.

    1990-02-06

    An improved NMR probe and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise orientationally disordered samples. The apparatus mechanically varies the orientation of the sample such that the time average of two or more sets of spherical harmonic functions are zero. 8 figs.

  2. Structure calculation, refinement and validation using CcpNmr Analysis

    PubMed Central

    Skinner, Simon P.; Goult, Benjamin T.; Fogh, Rasmus H.; Boucher, Wayne; Stevens, Tim J.; Laue, Ernest D.; Vuister, Geerten W.

    2015-01-01

    CcpNmr Analysis provides a streamlined pipeline for both NMR chemical shift assignment and structure determination of biological macromolecules. In addition, it encompasses tools to analyse the many additional experiments that make NMR such a pivotal technique for research into complex biological questions. This report describes how CcpNmr Analysis can seamlessly link together all of the tasks in the NMR structure-determination process. It details each of the stages from generating NMR restraints [distance, dihedral, hydrogen bonds and residual dipolar couplings (RDCs)], exporting these to and subsequently re-importing them from structure-calculation software (such as the programs CYANA or ARIA) and analysing and validating the results obtained from the structure calculation to, ultimately, the streamlined deposition of the completed assignments and the refined ensemble of structures into the PDBe repository. Until recently, such solution-structure determination by NMR has been quite a laborious task, requiring multiple stages and programs. However, with the new enhancements to CcpNmr Analysis described here, this process is now much more intuitive and efficient and less error-prone. PMID:25615869

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

    SciTech Connect

    George J. Hirasaki; Kishore K. Mohanty

    2005-09-05

    The objective of this report is to characterize the fluid properties and fluid-rock interactions that are needed for formation evaluation by NMR well logging. The advances made in the understanding of NMR fluid properties are summarized in a chapter written for an AAPG book on NMR well logging. This includes live oils, viscous oils, natural gas mixtures, and the relation between relaxation time and diffusivity. Oil based drilling fluids can have an adverse effect on NMR well logging if it alters the wettability of the formation. The effect of various surfactants on wettability and surface relaxivity are evaluated for silica sand. The relation between the relaxation time and diffusivity distinguishes the response of brine, oil, and gas in a NMR well log. A new NMR pulse sequence in the presence of a field gradient and a new inversion technique enables the T{sub 2} and diffusivity distributions to be displayed as a two-dimensional map. The objectives of pore morphology and rock characterization are to identify vug connectivity by using X-ray CT scan, and to improve NMR permeability correlation. Improved estimation of permeability from NMR response is possible by using estimated tortuosity as a parameter to interpolate between two existing permeability models.

  4. NMR-Metabolic Methodology in the Study of GM Foods

    Technology Transfer Automated Retrieval System (TEKTRAN)

    The 1H NMR methodology used in the study of genetically modified (GM) foodstuff is discussed. The study of transgenic lettuce (Lactuca sativa cv "Luxor") over-expressing the KNAT1 gene from Arabidopsis is presented as a novel study-case. The 1H NMR metabolic profiling was carried out. Twenty-two wat...

  5. 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...

  6. Two-dimensional NMR spectroscopy. Applications for chemists and biochemists

    SciTech Connect

    Croasmun, W.R.; Carlson, R.M.K.

    1987-01-01

    Two-dimensional nuclear magnetic resonance spectroscopy (2-D NMR) has become a very powerful class of experiments (in the hands of an adept scientist) with broad adaptability to new situations. It is the product of a happy marriage between modern pulse FT-NMR technology, with its large memory and high-speed computers, and the physicists and chemists who love to manipulate spin systems. Basic 2-D experiments are now a standard capability of modern NMR spectrometers, and this timely book intends to make 2-D NMR users of those who are familiar with normal 1-D NMR. The 2-D NMR goal is correlation of the lines of the observed NMR spectrum with other properties of the system. This book deals with applications to high-resolution spectrum analysis, utilizing either coupling between the NMR-active nuclei or chemical exchange to perform the correlation. The coupling can be scalar (through bonds) or direct through space (within 5 A). The coupling may be homonuclear (between like nuclei) or heteronuclear.

  7. Probe for high resolution NMR with sample reorientation

    DOEpatents

    Pines, Alexander; Samoson, Ago

    1990-01-01

    An improved NMR probe and method are described which substantially improve the resolution of NMR measurements made on powdered or amorphous or otherwise orientationally disordered samples. The apparatus mechanically varies the orientation of the sample such that the time average of two or more sets of spherical harmonic functions are zero.

  8. Chemical Equilibrium in Supramolecular Systems as Studied by NMR Spectrometry

    ERIC Educational Resources Information Center

    Gonzalez-Gaitano, Gustavo; Tardajos, Gloria

    2004-01-01

    Undergraduate students are required to study the chemical balance in supramolecular assemblies constituting two or more interacting species, by using proton NMR spectrometry. A good knowledge of physical chemistry, fundamentals of chemical balance, and NMR are pre-requisites for conducting this study.

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

    PubMed

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

    2014-10-01

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

  10. CHARACTERIZATION OF METABOLITES IN SMALL FISH BIOFLUIDS AND TISSUES BY NMR SPECTROSCOPY

    EPA Science Inventory

    Nuclear magnetic resonance (NMR) spectroscopy has been utilized for assessing ecotoxicity in small fish models by means of metabolomics. Two fundamental challenges of NMR-based metabolomics are the detection limit and characterization of metabolites (or NMR resonance assignments...

  11. The acquisition of multidimensional NMR spectra within a single scan

    PubMed Central

    Frydman, Lucio; Scherf, Tali; Lupulescu, Adonis

    2002-01-01

    A scheme enabling the complete sampling of multidimensional NMR domains within a single continuous acquisition is introduced and exemplified. Provided that an analyte's signal is sufficiently strong, the acquisition time of multidimensional NMR experiments can thus be shortened by orders of magnitude. This could enable the characterization of transient events such as proteins folding, 2D NMR experiments on samples being chromatographed, bring the duration of higher dimensional experiments (e.g., 4D NMR) into the lifetime of most proteins under physiological conditions, and facilitate the incorporation of spectroscopic 2D sequences into in vivo imaging investigations. The protocol is compatible with existing multidimensional pulse sequences and can be implemented by using conventional hardware; its performance is exemplified here with a variety of homonuclear 2D NMR acquisitions. PMID:12461169

  12. Understanding multi-quantum NMR through secular approximation.

    PubMed

    Srivastava, Deepansh; SubbaRao, R Venkata; Ramachandran, Ramesh

    2013-05-14

    With the development of technology and improved understanding of nuclear spin-spin interactions and their behavior in static/oscillating magnetic fields, NMR spectroscopy has emerged as a powerful tool for characterizing molecular structure in a wide range of systems of chemical, physical and biological relevance. Here in this article, we revisit the important connection between "Secular-Approximation" (a well-known fundamental concept) and NMR spectroscopy. Employing recent experimental results as the background, an alternate interpretation of the secular approximation is presented for describing and understanding the nuances of Multi-Quantum (MQ) NMR spectroscopy of quadrupolar nuclei. Since MQ NMR spectroscopy of quadrupolar nuclei forms the basis of the structural characterization of inorganic solids and clusters, we believe that the analytic theory presented herein would be beneficial both in the understanding and design of MQ NMR experiments. Additionally, the analytic results are corroborated with rigorous numerical simulations and could be employed in the quantitative interpretation of experimental results.

  13. A review of blind source separation in NMR spectroscopy.

    PubMed

    Toumi, Ichrak; Caldarelli, Stefano; Torrésani, Bruno

    2014-08-01

    Fourier transform is the data processing naturally associated to most NMR experiments. Notable exceptions are Pulse Field Gradient and relaxation analysis, the structure of which is only partially suitable for FT. With the revamp of NMR of complex mixtures, fueled by analytical challenges such as metabolomics, alternative and more apt mathematical methods for data processing have been sought, with the aim of decomposing the NMR signal into simpler bits. Blind source separation is a very broad definition regrouping several classes of mathematical methods for complex signal decomposition that use no hypothesis on the form of the data. Developed outside NMR, these algorithms have been increasingly tested on spectra of mixtures. In this review, we shall provide an historical overview of the application of blind source separation methodologies to NMR, including methods specifically designed for the specificity of this spectroscopy. PMID:25142734

  14. Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy.

    PubMed

    Ardenkjaer-Larsen, Jan-Henrik; Boebinger, Gregory S; Comment, Arnaud; Duckett, Simon; Edison, Arthur S; Engelke, Frank; Griesinger, Christian; Griffin, Robert G; Hilty, Christian; Maeda, Hidaeki; Parigi, Giacomo; Prisner, Thomas; Ravera, Enrico; van Bentum, Jan; Vega, Shimon; Webb, Andrew; Luchinat, Claudio; Schwalbe, Harald; Frydman, Lucio

    2015-08-01

    In the Spring of 2013, NMR spectroscopists convened at the Weizmann Institute in Israel to brainstorm on approaches to improve the sensitivity of NMR experiments, particularly when applied in biomolecular settings. This multi-author interdisciplinary Review presents a state-of-the-art description of the primary approaches that were considered. Topics discussed included the future of ultrahigh-field NMR systems, emerging NMR detection technologies, new approaches to nuclear hyperpolarization, and progress in sample preparation. All of these are orthogonal efforts, whose gains could multiply and thereby enhance the sensitivity of solid- and liquid-state experiments. While substantial advances have been made in all these areas, numerous challenges remain in the quest of endowing NMR spectroscopy with the sensitivity that has characterized forms of spectroscopies based on electrical or optical measurements. These challenges, and the ways by which scientists and engineers are striving to solve them, are also addressed. PMID:26136394

  15. Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy.

    PubMed

    Ardenkjaer-Larsen, Jan-Henrik; Boebinger, Gregory S; Comment, Arnaud; Duckett, Simon; Edison, Arthur S; Engelke, Frank; Griesinger, Christian; Griffin, Robert G; Hilty, Christian; Maeda, Hidaeki; Parigi, Giacomo; Prisner, Thomas; Ravera, Enrico; van Bentum, Jan; Vega, Shimon; Webb, Andrew; Luchinat, Claudio; Schwalbe, Harald; Frydman, Lucio

    2015-08-01

    In the Spring of 2013, NMR spectroscopists convened at the Weizmann Institute in Israel to brainstorm on approaches to improve the sensitivity of NMR experiments, particularly when applied in biomolecular settings. This multi-author interdisciplinary Review presents a state-of-the-art description of the primary approaches that were considered. Topics discussed included the future of ultrahigh-field NMR systems, emerging NMR detection technologies, new approaches to nuclear hyperpolarization, and progress in sample preparation. All of these are orthogonal efforts, whose gains could multiply and thereby enhance the sensitivity of solid- and liquid-state experiments. While substantial advances have been made in all these areas, numerous challenges remain in the quest of endowing NMR spectroscopy with the sensitivity that has characterized forms of spectroscopies based on electrical or optical measurements. These challenges, and the ways by which scientists and engineers are striving to solve them, are also addressed.

  16. Synchronous Spin Exchange Optical Pumping for Precision NMR

    NASA Astrophysics Data System (ADS)

    Korver, Anna; Weber, Josh; Thrasher, Daniel; Walker, Thad

    2016-05-01

    We present the successful execution of synchronous spin exchange optical pumping for precision NMR. In this novel form of NMR, the bias field is applied as a sequence of alkali 2 π pulses; the resulting transverse alkali polarization is then modulated at the NMR frequency and spin exchange collisions build up a transverse precessing noble gas polarization. As compared to longitudinally pumped NMR, this method suppresses the alkali frequency shift by over a factor of 2500. We also discuss how we use synchronous spin exchange optical pumping to excite two noble gas species simultaneously. With dual species operation, we are able to use one species to lock the magnetic field while the other is left to detect nonmagnetic interactions. This method promises to achieve NMR frequency uncertainties of 100nHz/√{ Hz}. Research supported by the NSF and Northrop-Grumman Corp.

  17. Two-Dimensional NMR Lineshape Analysis

    PubMed Central

    Waudby, Christopher A.; Ramos, Andres; Cabrita, Lisa D.; Christodoulou, John

    2016-01-01

    NMR titration experiments are a rich source of structural, mechanistic, thermodynamic and kinetic information on biomolecular interactions, which can be extracted through the quantitative analysis of resonance lineshapes. However, applications of such analyses are frequently limited by peak overlap inherent to complex biomolecular systems. Moreover, systematic errors may arise due to the analysis of two-dimensional data using theoretical frameworks developed for one-dimensional experiments. Here we introduce a more accurate and convenient method for the analysis of such data, based on the direct quantum mechanical simulation and fitting of entire two-dimensional experiments, which we implement in a new software tool, TITAN (TITration ANalysis). We expect the approach, which we demonstrate for a variety of protein-protein and protein-ligand interactions, to be particularly useful in providing information on multi-step or multi-component interactions. PMID:27109776

  18. NMR Measurements of Granular Flow and Compaction

    NASA Astrophysics Data System (ADS)

    Fukushima, Eiichi

    1998-03-01

    Nuclear magnetic resonance (NMR) can be used to measure statistical distributions of granular flow velocity and fluctuations of velocity, as well as spatial distributions of particulate concentration, flow velocity, its fluctuations, and other parameters that may be derived from these. All measurements have been of protons in liquid-containing particles such as mustard seeds or pharmaceutical pills. Our favorite geometry has been the slowly rotating partially filled rotating drum with granular flow taking place along the free surface of the particles. All the above-mentioned parameters have been studied as well as a spatial distribution of particulate diffusion coefficients, energy dissipation due to collisions, as well as segregation of non-uniform mixtures of granular material. Finally, we describe some motions of granular material under periodic vibrations.

  19. NMR applications to low porosity carbonate stones.

    PubMed

    Alesiani, M; Capuani, S; Maraviglia, B

    2003-09-01

    The purpose of this paper is to investigate NMR applications to porous materials widely employed in artistic and historical monuments and largely studied in the Cultural Heritage conservation field. Carrara marble, Candoglia marble and travertine samples were studied and data from relaxation times measurements were compared. Very interesting results from treated samples are reported and explained under the structure related spin lattice relaxation time point of view. Images of Carrara marble aged sample (XIX century), coming from the Florence Cathedral obtained for short absorption time of water by capillary rise and for relatively small thickness slices together show the fluid's spatial distribution within the stone. Comparative images showing untreated sample with the treated ones were obtained suggesting very useful applications for the determination of treatment effectiveness. PMID:14559345

  20. Spatially resolved spectroscopy using tapered stripline NMR

    NASA Astrophysics Data System (ADS)

    Tijssen, Koen C. H.; Bart, Jacob; Tiggelaar, Roald M.; Janssen, J. W. G. (Hans); Kentgens, Arno P. M.; van Bentum, P. Jan M.

    2016-02-01

    Magnetic field B0 gradients are essential in modern Nuclear Magnetic Resonance spectroscopy and imaging. Although RF/B1 gradients can be used to fulfill a similar role, this is not used in common practice because of practical limitations in the design of B1 gradient coils. Here we present a new method to create B1 gradients using stripline RF coils. The conductor-width of a stripline NMR chip and the strength of its radiofrequency field are correlated, so a stripline chip can be tapered to produce any arbitrary shaped B1 field gradient. Here we show the characterization of this tapered stripline configuration and demonstrate three applications: magnetic resonance imaging on samples with nL-μL volumes, reaction monitoring of fast chemical reactions (10-2-101 s) and the compensation of B0 field gradients to obtain high-resolution spectra in inhomogeneous magnetic fields.

  1. NMR local coil with adjustable spacing

    SciTech Connect

    Dembinski, G.T.

    1988-03-22

    A local coil assembly for use in NMR imaging is described which comprises: a base; a first local coil module mounted to the base and extending upward therefrom; sockets disposed in the base, each at a different distance from the first local coil module; a second local coil module having a connector therein which mates with each of the sockets to enable the second local coil module to be connected to the base at any one of the sockets; and a set of reactive components. The values of the respective reactive components are selected such that the second local oil module may be connected to any of the sockets without any substantial change in the resonant frequency of the assembly.

  2. NMR and pulsed field gradient NMR approach of water sorption properties in Nafion at low temperature.

    PubMed

    Guillermo, Armel; Gebel, Gérard; Mendil-Jakani, Hakima; Pinton, Eric

    2009-05-14

    The water uptake and the water self-diffusion coefficient were measured in Nafion membranes at subzero temperatures. NMR spectroscopy was used to precisely quantify the actual concentration of water in membranes as a function of the temperature and their hydration rates at room temperature. We find that below 273 K the water concentration decreases with temperature to reach, at around 220 K, a limit value independent of the initial concentration. This regime is observed if the concentration at room temperature is higher than 10%. Below this concentration no membrane deswelling was observed. The water self-diffusion coefficient, measured by pulsed field gradient NMR in function of the temperature, is determined by the actual concentration C(T) whatever the concentration at room temperature. The concentration variation is attributed to a decrease in the relative humidity RH(T) of the water vapor surrounding the membrane induced by the simultaneous presence of supercooled water inside the membrane and ice outside the membrane.

  3. Solid state NMR study of bone mineral

    SciTech Connect

    Wu, Y.

    1992-01-01

    In high field (9.4 T) CP MASS (cross polarization magic angle sample spinning) studies, in contrast to the scheme in the literature that infers the presence of minor constituents in spectra, we developed a new scheme to suppress the main part of the spectra to show the minor constituents. In order to perform in vivo solid state NMR studies, a double tuned two port surface coil probe was constructed. This probe is a modified version of the traditional Cross probe, which utilizes two 1/4 wave length 50 ohm transmission line, one with open ended and the other with shorted end, to isolate the high and low frequency circuits. The two resonance frequencies in Cross probe were proton and carbon. Our probe is designed to resonate at the proton and phosphorus frequencies, which are much closer to each other and hence more difficult to be tuned and matched simultaneously. Our approach to solve this problem is that instead of using standard 50 ohm transmission lines, we constructed a low capacity open end coaxial transmission line and low inductance shorted end coaxial transmission line. The Q of the phosphorus channel is high. We developed a short contact time cross polarization technique for non-MASS spectroscopy which reduces the signal of the major component of bone mineral to emphasize the minor component. By applying this technique on intact pork bone samples with our home made surface coil, we observed the wide line component, acid phosphate, for the first time. Hydroxyapatite, brushite and octacalcium are considered in the literature to be the model compounds for bone mineral. Cross polarization dynamics has been studied on hydroxyapatite and brushite, which yielded an NMR value for the distance between proton and phosphorus. One and two dimensional CP MASS spectroscopy of octacalcium phosphate were also studied, which revealed the different cross polarization rates and anisotropic channel shifts of acid phosphate and phosphate ions in octacalcium phosphate.

  4. Solid-state NMR structures of integral membrane proteins.

    PubMed

    Patching, Simon G

    2015-01-01

    Solid-state NMR is unique for its ability to obtain three-dimensional structures and to measure atomic-resolution structural and dynamic information for membrane proteins in native lipid bilayers. An increasing number and complexity of integral membrane protein structures have been determined by solid-state NMR using two main methods. Oriented sample solid-state NMR uses macroscopically aligned lipid bilayers to obtain orientational restraints that define secondary structure and global fold of embedded peptides and proteins and their orientation and topology in lipid bilayers. Magic angle spinning (MAS) solid-state NMR uses unoriented rapidly spinning samples to obtain distance and torsion angle restraints that define tertiary structure and helix packing arrangements. Details of all current protein structures are described, highlighting developments in experimental strategy and other technological advancements. Some structures originate from combining solid- and solution-state NMR information and some have used solid-state NMR to refine X-ray crystal structures. Solid-state NMR has also validated the structures of proteins determined in different membrane mimetics by solution-state NMR and X-ray crystallography and is therefore complementary to other structural biology techniques. By continuing efforts in identifying membrane protein targets and developing expression, isotope labelling and sample preparation strategies, probe technology, NMR experiments, calculation and modelling methods and combination with other techniques, it should be feasible to determine the structures of many more membrane proteins of biological and biomedical importance using solid-state NMR. This will provide three-dimensional structures and atomic-resolution structural information for characterising ligand and drug interactions, dynamics and molecular mechanisms of membrane proteins under physiological lipid bilayer conditions.

  5. Solid-state NMR structures of integral membrane proteins.

    PubMed

    Patching, Simon G

    2015-01-01

    Solid-state NMR is unique for its ability to obtain three-dimensional structures and to measure atomic-resolution structural and dynamic information for membrane proteins in native lipid bilayers. An increasing number and complexity of integral membrane protein structures have been determined by solid-state NMR using two main methods. Oriented sample solid-state NMR uses macroscopically aligned lipid bilayers to obtain orientational restraints that define secondary structure and global fold of embedded peptides and proteins and their orientation and topology in lipid bilayers. Magic angle spinning (MAS) solid-state NMR uses unoriented rapidly spinning samples to obtain distance and torsion angle restraints that define tertiary structure and helix packing arrangements. Details of all current protein structures are described, highlighting developments in experimental strategy and other technological advancements. Some structures originate from combining solid- and solution-state NMR information and some have used solid-state NMR to refine X-ray crystal structures. Solid-state NMR has also validated the structures of proteins determined in different membrane mimetics by solution-state NMR and X-ray crystallography and is therefore complementary to other structural biology techniques. By continuing efforts in identifying membrane protein targets and developing expression, isotope labelling and sample preparation strategies, probe technology, NMR experiments, calculation and modelling methods and combination with other techniques, it should be feasible to determine the structures of many more membrane proteins of biological and biomedical importance using solid-state NMR. This will provide three-dimensional structures and atomic-resolution structural information for characterising ligand and drug interactions, dynamics and molecular mechanisms of membrane proteins under physiological lipid bilayer conditions. PMID:26857803

  6. Improving the resolution in proton-detected through-space heteronuclear multiple quantum correlation NMR spectroscopy

    NASA Astrophysics Data System (ADS)

    Shen, Ming; Trébosc, J.; Lafon, O.; Pourpoint, F.; Hu, Bingwen; Chen, Qun; Amoureux, J.-P.

    2014-08-01

    ammonium 14N sites in L-histidineṡHClṡH2O.

  7. Photochemical pump and NMR probe: chemically created NMR coherence on a microsecond time scale.

    PubMed

    Torres, Olga; Procacci, Barbara; Halse, Meghan E; Adams, Ralph W; Blazina, Damir; Duckett, Simon B; Eguillor, Beatriz; Green, Richard A; Perutz, Robin N; Williamson, David C

    2014-07-16

    We report pump-probe experiments employing laser-synchronized reactions of para-hydrogen (para-H2) with transition metal dihydride complexes in conjunction with nuclear magnetic resonance (NMR) detection. The pump-probe experiment consists of a single nanosecond laser pump pulse followed, after a precisely defined delay, by a single radio frequency (rf) probe pulse. Laser irradiation eliminates H2 from either Ru(PPh3)3(CO)(H)2 1 or cis-Ru(dppe)2(H)2 2 in C6D6 solution. Reaction with para-H2 then regenerates 1 and 2 in a well-defined nuclear spin state. The rf probe pulse produces a high-resolution, single-scan (1)H NMR spectrum that can be recorded after a pump-probe delay of just 10 μs. The evolution of the spectra can be followed as the pump-probe delay is increased by micro- or millisecond increments. Due to the sensitivity of this para-H2 experiment, the resulting NMR spectra can have hydride signal-to-noise ratios exceeding 750:1. The spectra of 1 oscillate in amplitude with frequency 1101 ± 3 Hz, the chemical shift difference between the chemically inequivalent hydrides. The corresponding hydride signals of 2 oscillate with frequency 83 ± 5 Hz, which matches the difference between couplings of the hydrides to the equatorial (31)P nuclei. We use the product operator formalism to show that this oscillatory behavior arises from a magnetic coherence in the plane orthogonal to the magnetic field that is generated by use of the laser pulse without rf initialization. In addition, we demonstrate how chemical shift imaging can differentiate the region of laser irradiation thereby distinguishing between thermal and photochemical reactivity within the NMR tube.

  8. Introducing the gNMR Program in an Introductory NMR Spectrometry Course to Parallel Its Use by Spectroscopists

    ERIC Educational Resources Information Center

    Rummey, Jackie M.; Boyce, Mary C.

    2004-01-01

    An approach that is useful to any introductory nuclear magnetic resonance (NMR) spectroscopy course is developed. This approach to teaching NMR spectrometry includes spectral simulation along with the traditional elements of hands-on instrument use and structure elucidation to demonstrate the connection between simulating a spectrum and structure…

  9. NMR at cryogenic temperatures: A {sup 13}C NMR study of ferrocene

    SciTech Connect

    Orendt, A.M.; Facelli, J.C.; Jiang, Y.J.; Grant, D.M.

    1998-09-24

    A new cryogenic apparatus is described that can be used to obtain NMR spectra at temperatures down to 8--10 K. The static solid {sup 13}C NMR spectrum of ferrocene is recorded at that temperature. Spectra recorded at higher temperatures show that ferrocene is still freely rotating about its 5-fold symmetry axis on the {sup 13}C NMR time scale at 45--50 K. A comparison of the principal values of the {sup 13}C chemical-shift tensor obtained from the room- and low-temperature spectra of ferrocene indicates that the lowest frequency chemical shift principal component, {delta}{sub 33}, is tilted off this symmetry axis by approximately 12{degree}. Quantum chemical calculations of the chemical-shift tensor, completed on structures of ferrocene from the literature as well as on optimized structures with the cyclopentadienyl rings locked in both the staggered and eclipsed arrangements, predict the angle between the {delta}{sub 33} direction and the rotation axis to be between 11 and 15{degree}, depending upon the geometry used in the calculation. The calculations also predict the sign of the angular perturbation, information not obtained from the experiment. An explanation of this angular change in the {delta}{sub 33} direction is provided by the composition of the molecular orbitals.

  10. Improved nuclear magnetic resonance apparatus having semitoroidal rf coil for use in topical NMR and NMR imaging

    DOEpatents

    Fukushima, E.; Roeder, S.B.W.; Assink, R.A.; Gibson, A.A.V.

    1984-01-01

    An improved nuclear magnetic resonance (NMR) apparatus for use in topical magnetic resonance (TMR) spectroscopy and other remote sensing NMR applications includes a semitoroidal radio frequency (rf) coil. The semitoroidal rf coil produces an effective alternating magnetic field at a distance from the poles of the coil, so as to enable NMR measurements to be taken from selected regions inside an object, particularly including human and other living subjects. The semitoroidal rf coil is relatively insensitive to magnetic interference from metallic objects located behind the coil, thereby rendering the coil particularly suited for use in both conventional and superconducting NMR magnets. The semitoroidal NMR coil can be constructed so that it emits little or no excess rf electric field associated with the rf magnetic field, thus avoiding adverse effects due to dielectric heating of the sample or to any other interaction of the electric field with the sample.

  11. NMR and SAXS characterization of the denatured state of the chemotactic protein CheY: implications for protein folding initiation.

    PubMed

    Garcia, P; Serrano, L; Durand, D; Rico, M; Bruix, M

    2001-06-01

    The denatured state of a double mutant of the chemotactic protein CheY (F14N/V83T) has been analyzed in the presence of 5 M urea, using small angle X-ray scattering (SAXS) and heteronuclear magnetic resonance. SAXS studies show that the denatured protein follows a wormlike chain model. Its backbone can be described as a chain composed of rigid elements connected by flexible links. A comparison of the contour length obtained for the chain at 5 M urea with the one expected for a fully expanded chain suggests that approximately 25% of the residues are involved in residual structures. Conformational shifts of the alpha-protons, heteronuclear (15)N-[(1)H] NOEs and (15)N relaxation properties have been used to identify some regions in the protein that deviate from a random coil behavior. According to these NMR data, the protein can be divided into two subdomains, which largely coincide with the two folding subunits identified in a previous kinetic study of the folding of the protein. The first of these subdomains, spanning residues 1-70, is shown here to exhibit a restricted mobility as compared to the rest of the protein. Two regions, one in each subdomain, were identified as deviating from the random coil chemical shifts. Peptides corresponding to these sequences were characterized by NMR and their backbone (1)H chemical shifts were compared to those in the intact protein under identical denaturing conditions. For the region located in the first subdomain, this comparison shows that the observed deviation from random coil parameters is caused by interactions with the rest of the molecule. The restricted flexibility of the first subdomain and the transient collapse detected in that subunit are consistent with the conclusions obtained by applying the protein engineering method to the characterization of the folding reaction transition state.

  12. NMR and SAXS characterization of the denatured state of the chemotactic protein Che Y: Implications for protein folding initiation

    PubMed Central

    Garcia, Pascal; Serrano, Luis; Durand, Dominique; Rico, Manuel; Bruix, Marta

    2001-01-01

    The denatured state of a double mutant of the chemotactic protein CheY (F14N/V83T) has been analyzed in the presence of 5 M urea, using small angle X-ray scattering (SAXS) and heteronuclear magnetic resonance. SAXS studies show that the denatured protein follows a wormlike chain model. Its backbone can be described as a chain composed of rigid elements connected by flexible links. A comparison of the contour length obtained for the chain at 5 M urea with the one expected for a fully expanded chain suggests that ∼25% of the residues are involved in residual structures. Conformational shifts of the α-protons, heteronuclear 15N-{1H} NOEs and 15N relaxation properties have been used to identify some regions in the protein that deviate from a random coil behavior. According to these NMR data, the protein can be divided into two subdomains, which largely coincide with the two folding subunits identified in a previous kinetic study of the folding of the protein. The first of these subdomains, spanning residues 1–70, is shown here to exhibit a restricted mobility as compared to the rest of the protein. Two regions, one in each subdomain, were identified as deviating from the random coil chemical shifts. Peptides corresponding to these sequences were characterized by NMR and their backbone 1H chemical shifts were compared to those in the intact protein under identical denaturing conditions. For the region located in the first subdomain, this comparison shows that the observed deviation from random coil parameters is caused by interactions with the rest of the molecule. The restricted flexibility of the first subdomain and the transient collapse detected in that subunit are consistent with the conclusions obtained by applying the protein engineering method to the characterization of the folding reaction transition state. PMID:11369848

  13. The use of a selective saturation pulse to suppress t1 noise in two-dimensional (1)H fast magic angle spinning solid-state NMR spectroscopy.

    PubMed

    Robertson, Aiden J; Pandey, Manoj Kumar; Marsh, Andrew; Nishiyama, Yusuke; Brown, Steven P

    2015-11-01

    A selective saturation pulse at fast magic angle spinning (MAS) frequencies (60+kHz) suppresses t1 noise in the indirect dimension of two-dimensional (1)H MAS NMR spectra. The method is applied to a synthetic nucleoside with an intense methyl (1)H signal due to triisopropylsilyl (TIPS) protecting groups. Enhanced performance in terms of suppressing the methyl signal while minimising the loss of signal intensity of nearby resonances of interest relies on reducing spin diffusion--this is quantified by comparing two-dimensional (1)H NOESY-like spin diffusion spectra recorded at 30-70 kHz MAS. For a saturation pulse centred at the methyl resonance, the effect of changing the nutation frequency at different MAS frequencies as well as the effect of changing the pulse duration is investigated. By applying a pulse of duration 30 ms and nutation frequency 725 Hz at 70 kHz MAS, a good compromise of significant suppression of the methyl resonance combined with the signal intensity of resonances greater than 5 ppm away from the methyl resonance being largely unaffected is achieved. The effectiveness of using a selective saturation pulse is demonstrated for both homonuclear (1)H-(1)H double quantum (DQ)/single quantum (SQ) MAS and (14)N-(1)H heteronuclear multiple quantum coherence (HMQC) two-dimensional solid-state NMR experiments.

  14. NMR data visualization, processing, and analysis on mobile devices.

    PubMed

    Cobas, Carlos; Iglesias, Isaac; Seoane, Felipe

    2015-08-01

    Touch-screen computers are emerging as a popular platform for many applications, including those in chemistry and analytical sciences. In this work, we present our implementation of a new NMR 'app' designed for hand-held and portable touch-controlled devices, such as smartphones and tablets. It features a flexible architecture formed by a powerful NMR processing and analysis kernel and an intuitive user interface that makes full use of the smart devices haptic capabilities. Routine 1D and 2D NMR spectra acquired in most NMR instruments can be processed in a fully unattended way. More advanced experiments such as non-uniform sampled NMR spectra are also supported through a very efficient parallelized Modified Iterative Soft Thresholding algorithm. Specific technical development features as well as the overall feasibility of using NMR software apps will also be discussed. All aspects considered the functionalities of the app allowing it to work as a stand-alone tool or as a 'companion' to more advanced desktop applications such as Mnova NMR. PMID:25924947

  15. Can NMR solve some significant challenges in metabolomics?

    NASA Astrophysics Data System (ADS)

    Nagana Gowda, G. A.; Raftery, Daniel

    2015-11-01

    The field of metabolomics continues to witness rapid growth driven by fundamental studies, methods development, and applications in a number of disciplines that include biomedical science, plant and nutrition sciences, drug development, energy and environmental sciences, toxicology, etc. NMR spectroscopy is one of the two most widely used analytical platforms in the metabolomics field, along with mass spectrometry (MS). NMR's excellent reproducibility and quantitative accuracy, its ability to identify structures of unknown metabolites, its capacity to generate metabolite profiles using intact bio-specimens with no need for separation, and its capabilities for tracing metabolic pathways using isotope labeled substrates offer unique strengths for metabolomics applications. However, NMR's limited sensitivity and resolution continue to pose a major challenge and have restricted both the number and the quantitative accuracy of metabolites analyzed by NMR. Further, the analysis of highly complex biological samples has increased the demand for new methods with improved detection, better unknown identification, and more accurate quantitation of larger numbers of metabolites. Recent efforts have contributed significant improvements in these areas, and have thereby enhanced the pool of routinely quantifiable metabolites. Additionally, efforts focused on combining NMR and MS promise opportunities to exploit the combined strength of the two analytical platforms for direct comparison of the metabolite data, unknown identification and reliable biomarker discovery that continue to challenge the metabolomics field. This article presents our perspectives on the emerging trends in NMR-based metabolomics and NMR's continuing role in the field with an emphasis on recent and ongoing research from our laboratory.

  16. Can NMR solve some significant challenges in metabolomics?

    PubMed

    Nagana Gowda, G A; Raftery, Daniel

    2015-11-01

    The field of metabolomics continues to witness rapid growth driven by fundamental studies, methods development, and applications in a number of disciplines that include biomedical science, plant and nutrition sciences, drug development, energy and environmental sciences, toxicology, etc. NMR spectroscopy is one of the two most widely used analytical platforms in the metabolomics field, along with mass spectrometry (MS). NMR's excellent reproducibility and quantitative accuracy, its ability to identify structures of unknown metabolites, its capacity to generate metabolite profiles using intact bio-specimens with no need for separation, and its capabilities for tracing metabolic pathways using isotope labeled substrates offer unique strengths for metabolomics applications. However, NMR's limited sensitivity and resolution continue to pose a major challenge and have restricted both the number and the quantitative accuracy of metabolites analyzed by NMR. Further, the analysis of highly complex biological samples has increased the demand for new methods with improved detection, better unknown identification, and more accurate quantitation of larger numbers of metabolites. Recent efforts have contributed significant improvements in these areas, and have thereby enhanced the pool of routinely quantifiable metabolites. Additionally, efforts focused on combining NMR and MS promise opportunities to exploit the combined strength of the two analytical platforms for direct comparison of the metabolite data, unknown identification and reliable biomarker discovery that continue to challenge the metabolomics field. This article presents our perspectives on the emerging trends in NMR-based metabolomics and NMR's continuing role in the field with an emphasis on recent and ongoing research from our laboratory. PMID:26476597

  17. Theoretical Modeling of (99)Tc NMR Chemical Shifts.

    PubMed

    Hall, Gabriel B; Andersen, Amity; Washton, Nancy M; Chatterjee, Sayandev; Levitskaia, Tatiana G

    2016-09-01

    Technetium-99 (Tc) displays a rich chemistry due to its wide range of accessible oxidation states (from -I to +VII) and ability to form coordination compounds. Determination of Tc speciation in complex mixtures is a major challenge, and (99)Tc nuclear magnetic resonance (NMR) spectroscopy is widely used to probe chemical environments of Tc in odd oxidation states. However, interpretation of (99)Tc NMR data is hindered by the lack of reference compounds. Density functional theory (DFT) calculations can help to fill this gap, but to date few computational studies have focused on (99)Tc NMR of compounds and complexes. This work evaluates the effectiveness of both pure generalized gradient approximation and their corresponding hybrid functionals, both with and without the inclusion of scalar relativistic effects, to model the (99)Tc NMR spectra of Tc(I) carbonyl compounds. With the exception of BLYP, which performed exceptionally well overall, hybrid functionals with inclusion of scalar relativistic effects are found to be necessary to accurately calculate (99)Tc NMR spectra. The computational method developed was used to tentatively assign an experimentally observed (99)Tc NMR peak at -1204 ppm to fac-Tc(CO)3(OH)3(2-). This study examines the effectiveness of DFT computations for interpretation of the (99)Tc NMR spectra of Tc(I) coordination compounds in high salt alkaline solutions. PMID:27518482

  18. NMR data visualization, processing, and analysis on mobile devices.

    PubMed

    Cobas, Carlos; Iglesias, Isaac; Seoane, Felipe

    2015-08-01

    Touch-screen computers are emerging as a popular platform for many applications, including those in chemistry and analytical sciences. In this work, we present our implementation of a new NMR 'app' designed for hand-held and portable touch-controlled devices, such as smartphones and tablets. It features a flexible architecture formed by a powerful NMR processing and analysis kernel and an intuitive user interface that makes full use of the smart devices haptic capabilities. Routine 1D and 2D NMR spectra acquired in most NMR instruments can be processed in a fully unattended way. More advanced experiments such as non-uniform sampled NMR spectra are also supported through a very efficient parallelized Modified Iterative Soft Thresholding algorithm. Specific technical development features as well as the overall feasibility of using NMR software apps will also be discussed. All aspects considered the functionalities of the app allowing it to work as a stand-alone tool or as a 'companion' to more advanced desktop applications such as Mnova NMR.

  19. Benchmarking NMR experiments: A relational database of protein pulse sequences

    NASA Astrophysics Data System (ADS)

    Senthamarai, Russell R. P.; Kuprov, Ilya; Pervushin, Konstantin

    2010-03-01

    Systematic benchmarking of multi-dimensional protein NMR experiments is a critical prerequisite for optimal allocation of NMR resources for structural analysis of challenging proteins, e.g. large proteins with limited solubility or proteins prone to aggregation. We propose a set of benchmarking parameters for essential protein NMR experiments organized into a lightweight (single XML file) relational database (RDB), which includes all the necessary auxiliaries (waveforms, decoupling sequences, calibration tables, setup algorithms and an RDB management system). The database is interfaced to the Spinach library ( http://spindynamics.org), which enables accurate simulation and benchmarking of NMR experiments on large spin systems. A key feature is the ability to use a single user-specified spin system to simulate the majority of deposited solution state NMR experiments, thus providing the (hitherto unavailable) unified framework for pulse sequence evaluation. This development enables predicting relative sensitivity of deposited implementations of NMR experiments, thus providing a basis for comparison, optimization and, eventually, automation of NMR analysis. The benchmarking is demonstrated with two proteins, of 170 amino acids I domain of αXβ2 Integrin and 440 amino acids NS3 helicase.

  20. NMR velocity mapping of gas flow around solid objects.

    PubMed

    Han, Song-I; Pierce, Kimberly L; Pines, Alexander

    2006-07-01

    We present experimental visualizations of gas flow around solid blunt bodies by NMR imaging. NMR velocimetry is a model-free and tracer-free experimental means for quantitative and multi-dimensional flow visualization. Hyperpolarization of (129)Xe provided sufficient NMR signal to overcome the low density of the dilute gas phase, and its long coherence time allows for true velocity vector mapping. In this study, the diverging gas flow around and wake patterns immediately behind a sphere could be vectorally visualized and quantified. In a similar experiment, the flow over an aerodynamic model airplane body revealed a less disrupted flow pattern.

  1. NMR velocity mapping of gas flow around solid objects

    NASA Astrophysics Data System (ADS)

    Han, Song-I.; Pierce, Kimberly L.; Pines, Alexander

    2006-07-01

    We present experimental visualizations of gas flow around solid blunt bodies by NMR imaging. NMR velocimetry is a model-free and tracer-free experimental means for quantitative and multi-dimensional flow visualization. Hyperpolarization of Xe129 provided sufficient NMR signal to overcome the low density of the dilute gas phase, and its long coherence time allows for true velocity vector mapping. In this study, the diverging gas flow around and wake patterns immediately behind a sphere could be vectorally visualized and quantified. In a similar experiment, the flow over an aerodynamic model airplane body revealed a less disrupted flow pattern.

  2. Quantitative structure parameters from the NMR spectroscopy of quadrupolar nuclei

    SciTech Connect

    Perras, Frederic A.

    2015-12-15

    Here, nuclear magnetic resonance (NMR) spectroscopy is one of the most important characterization tools in chemistry, however, 3/4 of the NMR active nuclei are underutilized due to their quadrupolar nature. This short review centers on the development of methods that use solid-state NMR of quadrupolar nuclei for obtaining quantitative structural information. Namely, techniques using dipolar recoupling as well as the resolution afforded by double-rotation are presented for the measurement of spin–spin coupling between quadrupoles, enabling the measurement of internuclear distances and connectivities.

  3. Characterization of a chiral nematic mesoporous organosilica using NMR

    NASA Astrophysics Data System (ADS)

    Manning, Alan; Shopsowitz, Kevin; Giese, Michael; MacLachlan, Mark; Dong, Ronald; Michal, Carl

    2012-10-01

    Using templation with nanocrystalline cellulose, a mesoporous organosilica film with a chiral nematic pore structure has recently been developed. [1] We have used a variety of Nuclear Magnetic Resonance (NMR) techniques to characterize the pore structure. The pore size distribution has been found by analyzing the freezing point depression of absorbed water via NMR cryoporometry. The effective longitudinal and transverse pore diameters for diffusing water were investigated with Pulsed-Field Gradient (PFG) NMR and compared to a 1-D connected-pore model. Preliminary data on testing imposed chiral ordering in absorbed liquid crystals is also presented. [4pt] [1] K.E. Shopsowitz et al. JACS 134(2), 867 (2012)

  4. NMR imaging of components and materials for DOE application

    SciTech Connect

    Richardson, B.R.

    1993-12-01

    The suitability for using NMR imaging to characterize liquid, polymeric, and solid materials was reviewed. The most attractive applications for NMR imaging appear to be liquid-filled porous samples, partially cured polymers, adhesives, and potting compounds, and composite polymers/high explosives containing components with widely varying thermal properties. Solid-state NMR line-narrowing and signal-enhancing markedly improve the imaging possibilities of true solid and materials. These techniques provide unique elemental and chemical shift information for highly complex materials and complement images with similar spatial resolution, such as X-ray computed tomography (CT).

  5. NMR studies of metallic tin confined within porous matrices

    SciTech Connect

    Charnaya, E. V.; Tien, Cheng; Lee, M. K.; Kumzerov, Yu. A.

    2007-04-01

    {sup 119}Sn NMR studies were carried out for metallic tin confined within synthetic opal and porous glass. Tin was embedded into nanoporous matrices in the melted state under pressure. The Knight shift for liquid confined tin was found to decrease with decreasing pore size. Correlations between NMR line shapes, Knight shift, and pore filling were observed. The melting and freezing phase transitions of tin under confinement were studied through temperature dependences of NMR signals upon warming and cooling. Melting of tin within the opal matrix agreed well with the liquid skin model suggested for small isolated particles. The influence of the pore filling on the melting process was shown.

  6. Structural biology applications of solid state MAS DNP NMR

    NASA Astrophysics Data System (ADS)

    Akbey, Ümit; Oschkinat, Hartmut

    2016-08-01

    Dynamic Nuclear Polarization (DNP) has long been an aim for increasing sensitivity of nuclear magnetic resonance (NMR) spectroscopy, delivering spectra in shorter experiment times or of smaller sample amounts. In recent years, it has been applied in magic angle spinning (MAS) solid-state NMR to a large range of samples, including biological macromolecules and functional materials. New research directions in structural biology can be envisaged by DNP, facilitating investigations on very large complexes or very heterogeneous samples. Here we present a summary of state of the art DNP MAS NMR spectroscopy and its applications to structural biology, discussing the technical challenges and factors affecting DNP performance.

  7. NMR contributions to structural dynamics studies of intrinsically disordered proteins☆

    PubMed Central

    Konrat, Robert

    2014-01-01

    Intrinsically disordered proteins (IDPs) are characterized by substantial conformational plasticity. Given their inherent structural flexibility X-ray crystallography is not applicable to study these proteins. In contrast, NMR spectroscopy offers unique opportunities for structural and dynamic studies of IDPs. The past two decades have witnessed significant development of NMR spectroscopy that couples advances in spin physics and chemistry with a broad range of applications. This article will summarize key advances in basic physical-chemistry and NMR methodology, outline their limitations and envision future R&D directions. PMID:24656082

  8. Characterisation of triacetone triperoxide (TATP) conformers using LC-NMR.

    PubMed

    Haroune, Nicolas; Crowson, Andrew; Campbell, Bill

    2011-06-01

    Previous studies [1,2] have reported the existence of two conformers of TATP. This study demonstrates the ability of LC-NMR to separate and characterise the individual conformers. The NMR data is consistent with the proposed structures for the two conformers. Re-equilibration can be followed by NMR and the kinetics of the process studied. Over the past decade the use of the explosive TATP in terrorist devices has increased. Therefore, the ability to analyse and characterise this material has assumed greater importance. PMID:21605825

  9. NMR studies on polyphosphide Ce6Ni6P17

    NASA Astrophysics Data System (ADS)

    Koyama, T.; Yamada, H.; Ueda, K.; Mito, T.; Aoyama, Y.; Nakano, T.; Takeda, N.

    2016-02-01

    We report the result of 31P nuclear magnetic resonance (NMR) studies on Ce6Ni6P17. The observed NMR spectra show a Lorentzian-type and an asymmetric shapes, reflecting the local symmetry around each P site in the cubic unit cell. We have identified the observed NMR lines corresponding to three inequivalent P sites and deduced the temperature dependence of the Knight shift for each site. The Knight shifts increase with decreasing temperature down to 1.5 K, indicating a localized spin system of Ce6Ni6P17. Antiferromagnetic correlation between 4f spins is suggested from the negative sign of the Weiss-temperature.

  10. Solid-State NMR Studies of Amyloid Fibril Structure

    NASA Astrophysics Data System (ADS)

    Tycko, Robert

    2011-05-01

    Current interest in amyloid fibrils stems from their involvement in neurodegenerative and other diseases and from their role as an alternative structural state for many peptides and proteins. Solid-state nuclear magnetic resonance (NMR) methods have the unique capability of providing detailed structural constraints for amyloid fibrils, sufficient for the development of full molecular models. In this article, recent progress in the application of solid-state NMR to fibrils associated with Alzheimer's disease, prion fibrils, and related systems is reviewed, along with relevant developments in solid-state NMR techniques and technology.

  11. A simple low-cost single-crystal NMR setup.

    PubMed

    Vinding, Mads S; Kessler, Tommy O; Vosegaard, Thomas

    2016-08-01

    A low-cost single-crystal NMR kit is presented along with a web-based post-processing software. The kit consists of a piezo-crystal motor and a goniometer for the crystal, both embedded in a standard wide-bore NMR probe with a 3D printed scaffold. The NMR pulse program controls the angle setting automatically, and the post-processing software incorporates a range of orientation-angle discrepancies present in the kit and other single-crystal setups. Results with a NaNO3 single-crystal show a high degree of reproducibility and excellent agreement with previous findings for the anisotropic quadrupolar interaction.

  12. A simple low-cost single-crystal NMR setup

    NASA Astrophysics Data System (ADS)

    Vinding, Mads S.; Kessler, Tommy O.; Vosegaard, Thomas

    2016-08-01

    A low-cost single-crystal NMR kit is presented along with a web-based post-processing software. The kit consists of a piezo-crystal motor and a goniometer for the crystal, both embedded in a standard wide-bore NMR probe with a 3D printed scaffold. The NMR pulse program controls the angle setting automatically, and the post-processing software incorporates a range of orientation-angle discrepancies present in the kit and other single-crystal setups. Results with a NaNO3 single-crystal show a high degree of reproducibility and excellent agreement with previous findings for the anisotropic quadrupolar interaction.

  13. Fragment-Based Drug Discovery Using NMR Spectroscopy

    PubMed Central

    Harner, Mary J.; Frank, Andreas O.; Fesik, Stephen W.

    2013-01-01

    Nuclear magnetic resonance (NMR) spectroscopy has evolved into a powerful tool for fragment-based drug discovery over the last two decades. While NMR has been traditionally used to elucidate the three-dimensional structures and dynamics of biomacromolecules and their interactions, it can also be a very valuable tool for the reliable identification of small molecules that bind to proteins and for hit-to-lead optimization. Here, we describe the use of NMR spectroscopy as a method for fragment-based drug discovery and how to most effectively utilize this approach for discovering novel therapeutics based on our experience. PMID:23686385

  14. NMR Studies of Protein Structure and Dynamics

    NASA Astrophysics Data System (ADS)

    Li, Xiang

    Available from UMI in association with The British Library. Requires signed TDF. This thesis describes applications of 2D homonuclear NMR techniques to the study of protein structure and dynamics in solution. The sequential assignments for the 3G-residue bovine Pancreatic Polypeptide (bPP) are reported. The secondary and tertiary structure of bPP in solution has been determined from experimental NMR data. bPP has a well defined C-terminal alpha-helix and a rather ordered conformation in the N-terminal region. The two segments are joined by a turn which is poorly defined. Both the N- and the C-terminus are highly disordered. The mean solution structure of bPP is remarkably similar to the crystal structure of avian Pancreatic Polypeptide (aPP). The average conformations of most side-chains from the alpha-helix of bPP in solution are closely similar to those of aPP in the crystalline state. A large number of side-chains of bPP, however, show significant conformational averaging in solution. The 89-residue kringle domain of urokinase from both human and recombinant sources has been investigated. Sequential assignments based primarily on the recombinant sample and the determination of secondary structure are presented. Two helices have been identified; one of these corresponds to that reported for t-PA kringle 2, but does not exist in other kringles with known structures. The second helix is thus far unique to the urokinase kringle. Three antiparallel beta-sheets and three tight turns have also been identified. The tertiary fold of the molecule conforms broadly to that found for other kringles. Three regions in the urokinase kringle exhibit high local mobility; one of these, the Pro56-Pro62 segment, forms part of the proposed binding site. The other two mobile regions are the N- and C-termini which are likely to form the interfaces between the kringle and the other two domains (EGF and protease) in urokinase. The differential dynamic behaviours of the kringle and

  15. NMR Methods, Applications and Trends for Groundwater Evaluation and Management

    NASA Astrophysics Data System (ADS)

    Walsh, D. O.; Grunewald, E. D.

    2011-12-01

    Nuclear magnetic resonance (NMR) measurements have a tremendous potential for improving groundwater characterization, as they provide direct detection and measurement of groundwater and unique information about pore-scale properties. NMR measurements, commonly used in chemistry and medicine, are utilized in geophysical investigations through non-invasive surface NMR (SNMR) or downhole NMR logging measurements. Our recent and ongoing research has focused on improving the performance and interpretation of NMR field measurements for groundwater characterization. Engineering advancements have addressed several key technical challenges associated with SNMR measurements. Susceptibility of SNMR measurements to environmental noise has been dramatically reduced through the development of multi-channel acquisition hardware and noise-cancellation software. Multi-channel instrumentation (up to 12 channels) has also enabled more efficient 2D and 3D imaging. Previous limitations in measuring NMR signals from water in silt, clay and magnetic geology have been addressed by shortening the instrument dead-time from 40 ms to 4 ms, and increasing the power output. Improved pulse sequences have been developed to more accurately estimate NMR relaxation times and their distributions, which are sensitive to pore size distributions. Cumulatively, these advancements have vastly expanded the range of environments in which SNMR measurements can be obtained, enabling detection of groundwater in smaller pores, in magnetic geology, in the unsaturated zone, and nearby to infrastructure (presented here in case studies). NMR logging can provide high-resolution estimates of bound and mobile water content and pore size distributions. While NMR logging has been utilized in oil and gas applications for decades, its use in groundwater investigations has been limited by the large size and high cost of oilfield NMR logging tools and services. Recently, engineering efforts funded by the US Department of

  16. The PAW/GIPAW approach for computing NMR parameters: a new dimension added to NMR study of solids.

    PubMed

    Charpentier, Thibault

    2011-07-01

    In 2001, Mauri and Pickard introduced the gauge including projected augmented wave (GIPAW) method that enabled for the first time the calculation of all-electron NMR parameters in solids, i.e. accounting for periodic boundary conditions. The GIPAW method roots in the plane wave pseudopotential formalism of the density functional theory (DFT), and avoids the use of the cluster approximation. This method has undoubtedly revitalized the interest in quantum chemical calculations in the solid-state NMR community. It has quickly evolved and improved so that the calculation of the key components of NMR interactions, namely the shielding and electric field gradient tensors, has now become a routine for most of the common nuclei studied in NMR. Availability of reliable implementations in several software packages (CASTEP, Quantum Espresso, PARATEC) make its usage more and more increasingly popular, maybe indispensable in near future for all material NMR studies. The majority of nuclei of the periodic table have already been investigated by GIPAW, and because of its high accuracy it is quickly becoming an essential tool for interpreting and understanding experimental NMR spectra, providing reliable assignments of the observed resonances to crystallographic sites or enabling a priori prediction of NMR data. The continuous increase of computing power makes ever larger (and thus more realistic) systems amenable to first-principles analysis. In the near future perspectives, as the incorporation of dynamical effects and/or disorder are still at their early developments, these areas will certainly be the prime target.

  17. In-Cell Biochemistry Using NMR Spectroscopy

    PubMed Central

    Burz, David S.; Shekhtman, Alexander

    2008-01-01

    Biochemistry and structural biology are undergoing a dramatic revolution. Until now, mostly in vitro techniques have been used to study subtle and complex biological processes under conditions usually remote from those existing in the cell. We developed a novel in-cell methodology to post-translationally modify interactor proteins and identify the amino acids that comprise the interaction surface of a target protein when bound to the post-translationally modified interactors. Modifying the interactor proteins causes structural changes that manifest themselves on the interacting surface of the target protein and these changes are monitored using in-cell NMR. We show how Ubiquitin interacts with phosphorylated and non-phosphorylated components of the receptor tyrosine kinase (RTK) endocytic sorting machinery: STAM2 (Signal-transducing adaptor molecule), Hrs (Hepatocyte growth factor regulated substrate) and the STAM2-Hrs heterodimer. Ubiquitin binding mediates the processivity of a large network of interactions required for proper functioning of the RTK sorting machinery. The results are consistent with a weakening of the network of interactions when the interactor proteins are phosphorylated. The methodology can be applied to any stable target molecule and may be extended to include other post-translational modifications such as ubiquitination or sumoylation, thus providing a long-awaited leap to high resolution in cell biochemistry. PMID:18626516

  18. Dynamic NMR study of trans-cyclodecene

    SciTech Connect

    Pawar, D.M.; Noe, E.A.

    1996-12-18

    The slow-exchange {sup 13}C spectrum of trans-cyclodecene at -154.9{degree}C shows eight peaks of the olefinic carbons, and these are interpreted in terms of five conformations. Three of the conformations are of C{sub 1} symmetry, and two are of C{sub 2} symmetry. Further evidence for the number of conformations and their symmetries came from a proton NMR spectrum of the olefinic hydrogens taken at -154.9{degree}C with decoupling the allylic hydrogens. Populations ranged from 3.0% to 37.6% with the least-populated conformation having a free energy of 0.59 kcal/mol, relative to the most stable conformer. The conformations studied by Saunders and Jimenez-Vazquez using Allinger`s MM3 force field are described, and the calculated strain energies and populations are discussed. Energies for six conformations were also obtained from ab initio calculations at the HF/6-311G{sup *} level. 22 refs., 4 figs., 3 tabs.

  19. The Doppler effect in NMR spectroscopy.

    PubMed

    Guéron, Maurice

    2003-02-01

    An NMR sample may be subject to motions, such as those due to sample spinning or to liquid flow. Is the spectrum of such a sample affected by the Doppler effect? The question arises because, instrumental dimensions being much shorter than the wavelength, it is the near-field of the precessing magnetic moment which couples to the receiver coil, rather than the radiated far-field. We expand the near-field into plane propagating waves. For each such wave there is another one with the same amplitude, propagating in the opposite direction. The Doppler shifts are therefore equal and opposite. In the model case of a small fluid sample moving with constant velocity, this leads to a distribution of Doppler shifts which is symmetrical with respect to the unshifted frequency: there is no net spectral shift. We examine the possibility of observing the Doppler distribution in this case. We also consider the case of thermal motion of a gas. We draw attention to the resolved Doppler splitting of molecular rotational transitions in a supersonic burst as observed in a microwave resonator. We also mention briefly the Doppler effect in molecular beam spectroscopy.

  20. A multinuclear static NMR study of geopolymerisation

    SciTech Connect

    Favier, Aurélie; Habert, Guillaume; Roussel, Nicolas; D'Espinose de Lacaillerie, Jean-Baptiste

    2015-09-15

    Geopolymers are inorganic binders obtained by alkali activation of aluminosilicates. While the structure of geopolymers is now well understood, the details of the geopolymerisation reaction and their impact on the rheology of the paste remain uncertain. In this work, we follow the elastic properties of a paste made with metakaolin and sodium silicate solution. After the first sharp increase of elastic modulus occurring a few hundred of seconds after mixing and related to the heterogeneous formation of an alumina–silicate gel with a molar ratio Si/Al < 4 located at the grains boundaries, we focus on the progressive increase in elastic modulus on a period of few hours during the setting of the geopolymer. In this study, we combine the study of rheological properties of the paste with {sup 23}Na, {sup 27}Al and {sup 29}Si static NMR measurement in order to better understand the origin of this second increase in elastic modulus. Our results show that, after a few hours, Al and Na evolution in the liquid phase are concomitant. This suggests the precipitation of an aluminosilicate phase where Al is in tetrahedral position and Na compensates the charge. Furthermore, Si speciation confirms this result and allows us to identify the precipitation of a product, which has a chemical composition close to the final composition of geopolymer. This study provides strong evidence for a heterogeneous formation of an aluminosilicate glass directly from the first gel and the silicate solution without the need for a reorganisation of Gel 1 into Gel 2.